KR920000699B1 - Process for the preparation of disazo compounds - Google Patents

Abstract

No content.

Description

Method of Preparation of Diazo Compound

The present invention relates to a method for producing a diazo compound, and also to a method for dyeing cellulose fibers using the diazo compound. In particular, furthermore, the diazo compound of the present invention is in the form of a free acid,

Belonging to a diazo compound represented by a copper salt compound thereof, wherein X is a hydroxyl or methoxy group, and Y and Z are each within the range provided that the total number of sulfonic acid groups in general formula (1) is 3 or 4 Hydrogen, chlorine, methyl and sulfonic acid groups. The present invention also relates to a method for dyeing cellulose fibers using the diazo compound as described above.

Numerous direct dyes have been disclosed in the patent specification and have been commonly used by many people to enable cellulose fiber dyeing in blue or dark blue shades with good washing and light fastness. However, these dyes sometimes encounter the following difficulties when used in combination with disperse dyes for dyeing polyester / cellulose blend fibers in a single step under high temperature and acidic conditions.

1) The dyeing power of the direct dye is significantly reduced, and 2) the direct dye is solidified in the salt bath, making it impossible to obtain uniform dyeing.

Therefore, in the polyester / cellulose blend fiber dyeing, an undesirable bathing or single bath two-stage dyeing method was applied in view of energy saving and power reduction. Under these circumstances, the development of a blue or dark blue direct dye having a high dyeing affinity for cellulose fibers, especially cotton fibers at high temperature under acidic conditions and excellent washing fastness has been urgently required.

It is an object of the present invention to provide a dye having the properties that meet the above requirements, i.e., pure blue or dark blue shade by polyester / cellulose at high temperature under acidic conditions by a single step dyeing method in combination with a disperse dye. It is to make it possible to dye to oz blend fiber.

The diazo compound of Formula (1) and its copper salt are generally diazotized to two kinds of amines represented by the following general formula

Where X, Y, Z are as above, coupling the resulting diazonium salt with di (5-hydroxy-7-sulfonnaphthyl-2) amine in any order and, if necessary, a base such as ammonia Obtained by operating the diazo compound produced in combination with a activating agent in the presence of

The amines (diazo components) represented by the formulas (2) and (3) include the following compounds (as free acid forms):

2-Amino-6-nitrophenol-4-sulfonic acid, 2-amino-4-nitrophenol-6-sulfonic acid, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 2-amino- 5-nitro-4-chlorophenol, 2-methoxy-4-nitroaniline-5-sulfonic acid, 4-methyl-2-methoxy-3-nitroaniline and the like.

Industrially useful conditions for preparing the compound of formula (1) and its operating salt are as follows.

The diazonium salt solution obtained by diazotizing one molar ratio of any one of the amines (primary diazo component) of the above formulas (2) and (3) was adjusted to weak acidity using an alkaline agent such as a dilute sodium carbonate solution, and the solution was adjusted to pH. 1 mole ratio solution of di (5-hydroxy-7-sulfonafphyl-2-) amine of 4 to 8 (primary coupling) and another amine (secondary dia) of the above formulas (2) and (3) Crude component) The diazonium salt solution obtained by diazotizing 1 mol ratio is added to the monoazo solution of pH 7-9 obtained by primary coupling.

[Secondary coupling]

Diazolation of amines of formulas (2) and (3) proceeds easily with sodium nitrite in aqueous solutions of inorganic acids such as hydrochloric acid and sulfuric acid at temperatures below 15 ° C.

The amount of diazonium salt obtained by diazotizing each of the amines of the general formulas (2) and (3) used is 1 mol or 1 mol per 1 mol of the di (5-hydroxy-7-sulfonnaphthyl-2) amine. Excess is preferred.

An aqueous solution of 1 to 3 moles of copper salts such as copper sulfate, copper acetate or copper chloride (II) contains diazo compounds at 20 to 95 ° C., if necessary, in the presence of ammonia, diethanolamine or N-methylethanolamine. Is added to the obtained reaction solution. If Y and Z in the formulas (2) and (3) are represented by the same atom or group, the diazo compound of formula (1) and its covalent salt also diazotize about 2 molar ratios of the amine represented by the following formula and

Where X and Y (or Z) are as described above and di (5-hydroxy-7-sulfonnaphthyl-2 at a temperature below 10 ° C., pH 8-9, to obtain a diazo compound represented by the following general formula: Coupling the resulting diazonium salt with 1 molar ratio of

Wherein X and Y (or Z) are as described above and are obtained by the co-homolation of the diazo compound produced according to the above-mentioned method.

The amount of amine used of the diazonium salt obtained by diazotizing the amine of the general formula (4) to be used is preferably 2 moles or 2 molar excesses per mole of the di (5-hydroxy-7-sulfonnaphthyl-2) amine. .

The new diazo compound of the present invention and its copper salt are conventional dyeing methods in which natural or regenerated cellulose fibers are dyed by dyeing, continuous dyeing or printing and polyester fibers are dispersed using dyes, for example, high temperature and high pressure dyeing. It can be used under the general dyeing conditions applied by dyeing method which is dyed by carrier dyeing, dermasol dyeing or printing and acrylic fiber is dyeing by using cationic dye, for example by dyeing or printing. Dyed dyestuffs have a clear blue or dark blue tint and are excellent in washing and daylight fastness.

Blended fibers such as cellulose fibers and polyester / cellulose blend fibers in a mixture using a dye bath or printing paste containing the diazo compound of the present invention alone or in a mixture with another dye such as a disperse dye are known methods. Can be dyed and printed.

The biggest feature of the present invention is that by using the dye of the present invention, polyester / cellulose blend fibers can be uniformly dyed with high consumption in combination with the disperse dyes in one step dyeing method under the dyeing conditions for disperse dyes. .

The invention is further illustrated in the following examples. In the examples, part (s) is given by weight and sulfonic acid groups are shown in free acid form.

Example 1

The pH and temperature of the solution obtained by dissolving 46.1 parts of 4,4'-dihydroxy-6,6'-disulfodinaphthyl-2,2'-amine in 800 parts of water were adjusted below pH 7 and 10 ° C, respectively. . 24.6 parts of 6-nitro-2-aminophenol-4-sulfonic acid were diazotized in a usual manner and a solution of the diazonium salt obtained by adjusting to pH 4.5 was poured down into the solution while stirring.

The coupling reaction was carried out with about 4 parts of sodium carbonate at a temperature below 10 ° C. for 3 hours while maintaining the pH of the reaction solution at 6.5 to 7.0 (first coupling).

24 parts of sodium carbonate were added to the reaction solution, and the diazonium salt solution obtained by diazotizing 23.4 parts of 4-nitro-2-aminophenol-6-sulfonic acid in the usual manner was poured therein, and the mixture was then stirred for 8 hours at pH 8-9. The reaction was completed at a temperature below 10 ° C. to complete the coupling reaction (second coupling).

A reaction solution containing a compound having the following general formula was obtained.

54.2 parts of copper sulfate pentahydrate aqueous solution was added there, and the pH of the mixture was adjusted to pH 7 with about 6 parts of sodium carbonate. 100 parts of 30% aqueous ammonia solution was added and the mixture was stirred at 30 ° C. for 2 hours. Then, crystals formed by adding 10% sodium chloride to the reaction solution were filtered and dried to obtain a compound having the following general formula.

(Purity determined by liquid chromatography: 95%)

λmax 587 nm (in 10% aqueous pyridine solution; then equally applicable)

The compound of the above general formula is also used for diazonium salt of 4-nitro-2-aminophenol-6-sulfonic acid and 4,4'-dihydroxy-6,6'-disulfodinaphthyl-2,2'- This is obtained by coupling the amine and then coupling with 6-nitro-2-aminophenol-4-sulfonic acid and then homogenizing the resulting product under the above conditions.

The compound was dissolved in water to form a reddish blue solution, and the cellulose fibers were dyed to a reddish blue tint with excellent washing and light fastness.

Example 2

46.1 parts of 4,4'-dihydroxy-6,6'-disulfodinaphthyl-2,2'-amine were added in the same manner as in Example 1 to 24.6 parts of 6-nitro-2-aminophenol-4-sul Coupling with the diazonium salt obtained by diazotizing the phonic acid (first coupling), the product was then subjected to 24.9 parts of 4-nitro-2-methoxyaniline-5-sulfonic acid at a temperature below 10 ° C., pH 8-9. Coupling with the diazonium salt obtained by diazotization (second coupling). 54.2 parts of copper sulfate pentahydrate and 18.3 parts of monoethanolamine were added to the reaction solution containing a compound having the following general formula.

The temperature of the mixture was raised to 90 ° C.-95 ° C. and the mixture was stirred for 4 hours at that temperature. Sodium chloride was added to it in 15% by weight of the reaction solution for salting. Thus, the precipitated crystals were filtered to obtain a compound having the following general formula, which was dissolved in water to give a reddish blue solution.

This compound stained the cellulose fibers with a reddish blue color with a more reddish tint than in Example 1. The color fastness to washing was very good.

Example 3

48 parts sodium carbonate was added to 46.1 parts 4,4'-dihydroxy-6,6'-disulfodinaphthyl-2,2'-amine aqueous solution in 800 parts water. Usually, the diazonium salt obtained by diazotizing 48.2 parts of 6-nitro-2-aminophenol-4-sulfonic acid was poured into the solution while maintaining at a temperature below 10 ° C. A reaction solution containing a compound having the following general formula was obtained.

After stirring for 3 hours, 54.2 parts of copper sulfate pentahydrate and 23 parts of aqueous monomethylethanolamine solution were added thereto. The quenching reaction was carried out at 30 to 40 ° C. for 3 hours. After completion of the reaction, sodium chloride was added thereto in an amount of 15% to the reaction solution to salt it. The crystals were filtered and dried to give a compound having the following general formula.

This compound stained cellulose fibers in a reddish blue tint with a bluer toun than in Example 1. Color fastness to washing was very good.

The copper complex or copper chloride (II) chloride was used in place of the above-mentioned copper sulfate pentahydrate to repeat a similar complexation reaction with the above-mentioned method to obtain a compound having the following general formula.

Example 4-14

Compounds of the present invention were synthesized in a similar manner as in Examples 1 to 3 using the first and second diazo components shown in the following table. They showed good fastness to washing and vividly dyed cellulose fibers in dark blue or blue. The following table shows the first and second diazo components, the amount of copper sulphate used in the immobilization reaction, and λ max of the resulting compound.

Note on the chart:

^{* 1} The amount of copper sulfate in the table indicates the number of moles of copper sulfate used per mole of 4,4'-dihydroxy-6,6'-disulfodinaphthyl-2,2'-amine. It had two mobilizers in the same molecule as in Example 1.

^{* 2} determined in 10% aqueous pyridine solution.

^{* 3} According to high performance liquid chromatography analysis, the copper compound (mixture) has the following constitution.

Copper-glass diazo compound: 25%

Diazo compound containing one mobilizer: 50%

Diazo compound containing two mobilizers: 25%

^{* 4} According to high performance liquid chromatography analysis, the compound (mixture) had the following composition.

Copper-glass diazo compound: 20%

Diazo compound containing one mobilizer: 50%

Diazo compound containing two mobilizers: 30%

Example 15

0.2 parts of the copper compound obtained in Example 1 were dissolved in 5 parts of hot water. 0.15 parts of 5 parts of water at 50 ° C. Kayalon polyester blue 2R-SF (dispersant, product of Nippon Chemical Co., Ltd.) Dispersion, 90 parts of water and 2 parts of Glauber's salt were added thereto. The pH of the salt bath was adjusted to 5.0 using glacial acetic acid and sodium acetate. A knitted fabric of 10 parts of polyester / cotton blend fibers (50:50) was placed therein to be submerged. The temperature was raised to 130 ° C. in 40 minutes. After maintaining this temperature for 30 minutes, the dye bath was slowly cooled to 90 ° C. and maintained at that temperature for 15 minutes to complete dyeing.

After dyeing, wash the cloth in water, and then use San-fix 555 (manufactured by Nippon Sanyo Chemical Industries, Ltd.) to fix it as usual. Got it.

Example 16

0.28 parts of the compound obtained in Example 8 was dissolved in 20 parts of hot water. To 5 parts of 50 ° C. water, a dispersion of 0.26 parts of Kayalon Polyester Navy Blue EX-SF 200 (dispersant, product of Nippon Chemical Co., Ltd.), 75 parts of water and 2 parts of manganese were added thereto. The pH of the resulting salt bath was adjusted to 5.0 using glacial acetic acid and sodium acetate. Ten parts of spun polyester / rayon fibers (65:35) were placed in it to be submerged. The temperature rose to 130 ° C. in 40 minutes. After maintaining this temperature for 30 minutes, the dye bath was slowly cooled to 90 ° C. and maintained at that temperature for 15 minutes to complete dyeing.

After completion of dyeing, the fibers were washed with water and treated with San-fix 555 to fix them in the same manner as usual.

Example 17

0.4 part of the copper compound obtained in Example 3 was dissolved in 10 parts of hot water. 90 parts water and 2 parts forget-me-not were added thereto. Ten parts of non-mercerized cotton fabric were placed in it for submersion. The temperature was raised to 90 ° C. in 30 minutes and the dyeing proceeded for 30 minutes.

After the dyeing was completed, the cloth was washed with water and treated with San-fix 555 by usual method to obtain a vivid dye with a reddish blue color with excellent daylight and washfastness.

Example 18

The non mercerized knitted cotton fabric was obtained in Example 1 in the same manner as in Example 17, and then dyed with a diazo compound to obtain a medium blue dye.

After completion of the dyeing, the cloth was washed with water and treated with San-fix 555 in the same manner as in Example 17 to obtain dyeing having excellent daylight and washing fastnesses.

Claims (7)

Diazonium salt obtained by diazotizing two types of amines represented by the following formulas (2) and (3)

Coupling with the compound di (5-hydroxy-7-sulfonafphyl-2) amine represented by the following formula

Method for producing a water-soluble azo compound in the form of a free acid, characterized in that the compound of formula

Wherein X is a hydroxyl or methoxy group, Y and Z are hydrogen, chlorine, methyl and sulfonic acid groups, provided that the total number of sulfonic acid groups in Structural Formula (1) is 3 or 4, respectively. The diazonium salt obtained by diazotizing the amine represented by any one of Formulas (2) and (3) is coupled with di (5-hydroxy-7-sulfonafphyl-2) amine to give the compound of Formula (1) Method for producing a water-soluble azo compound in the form of a free acid, characterized in that for making. A method for producing a copper salt of a water-soluble azo compound, wherein the compound of formula (1) is quenched with a water-soluble copper-complexing agent to form a copper salt of the compound of formula (1). The method for producing a water-soluble azo compound in the form of a free acid and a copper salt thereof according to claim 1, which is represented by the following formula.

The method for producing a water-soluble azo compound in the form of a free acid and a copper salt thereof according to claim 1, which is represented by the following formula.

The process for producing a water-soluble azo compound in the form of a free acid and a copper salt thereof according to claim 2, wherein the water-soluble azo compound is represented by the following formula

The method of claim 1, wherein the water-soluble azo compound in the form of free sulfonic acid is represented by the following formula.