JPS62199656A - Azo compound and dyeing using said compound - Google Patents

Abstract

NEW MATERIAL:A compound in the form of a free acid expressed by formula I (R1 is CH3 or C2H5; R2 and R3 are H, Cl or CH3; X is formula II or III). EXAMPLE:A compound expressed by formula IV. USE:A dye capable of dyeing cellulosic fibers and fibrous materials containing cellulosic fibers to scarlet color with improved fastness (solubility) and dyeing mixed spun fabrics of polyester fibers/cotton in one bath and one stage. PREPARATION:4-Hydroxy-7-acetylamino-naphthalene-2-sulfonic acid is coupled with a diazo compound of 4-methoxy-aniline-2-sulfonic acid and the resultant compound is then hydrolyzed to give a compound expressed by formula V, which is further reacted with a compound expressed by formula VI and cyanuric chloride in an optional order to afford a compound expressed by formula VII. The resultant compound expressed by formula VII is reacted with nicotinic acid or isonicotinic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an azo compound and a method for dyeing cellulose fibers or fibrous materials containing cellulose fibers using the azo compound.

Conventional technology In dyeing cellulose fibers, reactive dyes are currently used in large quantities because they have superior clarity and various fastness properties compared to other dyes □ For example, dichlorotriazinyl, monochlorotriazinyl , fluorochloropyrimidinyl, dichlorotriazinyl, sulfatoethylsulfonyl, etc. using a reactive dye having a reactive group, or a substance that releases an acid binder by the action of heat (e.g., sodium carbonate, potassium carbonate, Sodium hydroxide, potassium hydroxide/sodium metasilicate, trisodium phosphate, tripotassium phosphate, potassium pyrophosphate, sodium pyrophosphate, sodium bicarbonate, sodium trichloroacetate) can be used alone or in combination of two or more. The pH value of the bath is 1
Cellulose fibers are dyed with reactive dyes at a temperature of 100° C. or lower in the presence of a neutral electrolyte such as sodium chloride or sodium sulfate, which is adjusted to a temperature of 0 or higher.

On the other hand, mixed fiber materials (blends) containing cellulose fibers are increasingly used as fiber materials for clothing, and blends of polyester fibers and cotton (hereinafter referred to as T/C blends) are suitable for clothing and are economical. It came to be used in large quantities because of its superior properties. Furthermore, T/C blends are usually dyed using reactive dyes and disperse dyes in the following manner.

(■) One-bath two-step method First, the polyester fiber side is dyed with a disperse dye using a carrier dyeing method, a high temperature dyeing method, etc., and then the cotton side is dyed with a reactive dye in the same bath. Or stain in the reverse order.

(2) Two-bath method First, the polyester fiber side is dyed using the method described above, and then the cotton side is dyed in a separate bath.

Or stain in the reverse order.

(IID 1-bath, 1-step method: Dyeing the polyester fiber side and the cotton side in the same bath in one dyeing operation.

Among the above-mentioned methods, the following dyes are known as reactive dyes of cotton color suitable for dyeing T/C mixture in one bath and one stage.

Problems to be Solved by the Invention The dyes described above, which are known as reactive dyes suitable for T/C mixed one-bath dyeing, are not sufficient in terms of color yield, various fastnesses, solubility, etc. (especially in terms of color yield). The quality is not satisfactory.

Means to solve the problems Developed a scarlet reactive dye that is sufficiently suitable for the T/C mixed one-bath one-stage dyeing method and has improved the above-mentioned problems (color yield, various fastnesses, solubility) As a result of intensive research, we have arrived at the present invention. That is, the present invention can be used in the form of a free acid of the formula +]) (In formula (1), R1 is CHa or C2H5,
No. 3 provides a method for dyeing fiber materials containing R1 fibers or cellulosic fibers. The azo compound represented by formula (1) is prepared by using a bath containing a disperse dye in the presence of an acid binder at pH 5-
T/C at temperatures between 95 and 150°C in the presence of disperse dyes, simply by the presence of a slow-acting agent that maintains the temperature at 95-150°C.
It has extremely advantageous characteristics for a one-bath, one-step dyeing method in that it can dye a mixture uniformly. Of course, excellent effects can be obtained even when applied to fiber materials consisting only of cellulose fibers, not just T/C mixtures. Further, the azo compound represented by formula (1) of the present invention can be used for polyester fibers and rayon;
For dyeing blended products of cotton or rayon with triacetate fibers, polyacrylonitrile fibers, modified polyacrylonitrile fibers, polyamide fibers, wool, silk, etc., in combination with disperse dyes, acidic metal-containing dyes, cationic dyes, etc. However, you can get excellent results.

The azo compound represented by formula (1) of the present invention is synthesized, for example, by the following method.

(al Formula obtained by coupling a diazotide of 4-methoxy (or 4-ethoxy)-aniline-2-sulfonic acid to 4-hydroxy-7-acetylamino-naphthalene-2-sulfonic acid and then hydrolyzing it. (2) (In formula (2), R1 represents the same meaning as above.) and the compound represented by formula (3) (R2 and R3 represent the same meanings as above). react with cyanuric chloride in the order (
(first combination, second combination) A compound represented by formula (4) (in formula (4), R1, R2, and R3 represent the same meanings as above) is obtained.

Next, the compound represented by formula (4) and nicotinic acid or
React with isonicotinic acid (tertiary combination) to obtain an azo compound represented by (1).

(b) 4-hydroxy-7-amino-naphthalene-2-
A sulfonic acid and a compound represented by formula (3) are reacted with cyanuric chloride in any order (first combination, second combination) to form formula (5) (in formula (5), R2 and R3 are (has the same meaning as ) is obtained. Then the formula (5
) is coupled with a diazotized product of 4-methoxy-aniline-2-sulfonic acid or 4-ethoxy-aniline-2-sulfonic acid to form an azo compound represented by (4). Then, a tertiary combination is carried out in the same manner as described in (al) to obtain an azo compound represented by formula (1).

(c) 4-hydroxy-7-amino-naphthalene-2-
Sulfonic acid and cyanuric chloride are reacted (first combination), and then 4-methoxy-aniline-2-sulfonic acid or a diazotized product of 4-ethoxy-aniline-2-sulfonic acid is coupled to form the formula (6) A compound represented by (in formula (6), R represents the same meaning as above) is obtained. Next, the compound represented by formula (3) is reacted (secondary combination) to obtain the compound represented by formula (4), and then a third combination is performed in the same manner as described in (al) to obtain the formula A compound represented by (1) is obtained.

Specific examples of the compound represented by formula (3) used in molding the azo compound of formula (1) include the following.

In the above, the first deletion condensation is performed at a temperature of 0 to 25°C and a pH of 2 to
7 Preferably temperature 5-15°C, pH 4-6.5, 2nd deletion condensation temperature 30-60°C and pH 4-8 Preferably temperature 40-50°C, pH 6-7, W, 3 deletion condensation 70-10
It is carried out at a temperature of 0° C. and p)i 5 to 7, preferably at a temperature of 80 to 90° C. and a pH of 5.5 to 6.5.

The diazotization reaction is carried out by a known method, for example, by dropping an aqueous solution of sodium nitrite in a mineral acid such as hydrochloric acid or sulfuric acid at 5°C or lower, and the coupling reaction is similarly carried out, for example, at 10°C or lower under neutral or slightly acidic conditions. be exposed.

Next, a method for dyeing cellulose fibers or fiber materials containing cellulose fibers using the azo compound represented by formula (1) of the present invention will be explained.

When dyeing a fiber material consisting only of cellulose fibers by dip dyeing, a dye bath is prepared from the azo compound of the present invention, inorganic salts (e.g. sodium sulfate, sodium chloride, etc.), the fibers are immersed, After dyeing at ℃ for 10 to 60 minutes, add an acid binder if necessary, and dye for 20 minutes at the same temperature.
Perform staining for ~60 minutes. In this case, it is also possible to adopt a method in which the acid binder is added to the dye bath from the beginning and dyeing is carried out. In addition to the dyeing method, it is also possible to carry out dyeing by a padding dyeing method or a textile printing method according to a conventional method.

One-bath one-stage dyeing of T/C mixture using the azo compound and disperse dye of the present invention is carried out, for example, as follows.

an azo compound represented by formula (1) of the present invention, a dispersion cross-linking agent),
A dye bath consisting of a reduction inhibitor is prepared, the T/C mixture is immersed in this, and dyeing is carried out at 95 to 150°C for 20 to 90 minutes. In this case, it is also possible to carry out dyeing in the presence of a conventional acid binder by using a disperse dye that has sufficient resistance to alkali.

Blends other than T/C blends, such as blends of cellulose fibers and polyamide fibers (nylon, wool, silk, etc.), polyacrylic fibers, acid-modified polyester fibers, etc., are also expressed by formula (1) of the present invention. Dyeing can be carried out in the same manner as described above using a combination of an azo compound, an acid dye, a basic dye, etc. The compounds represented by Bunmu (1) can also be used in combination of two or more thereof.

When an acid binder is present in the above dyeing method,
Sodium carbonate, potassium carbonate, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, potassium birophosphate, sodium pyrophosphate, sodium bicarbonate, sodium trichloroacetate, etc., and when a buffer is present. For example, acetic acid-sodium acetate, monosodium phosphate-disodium phosphate, maleic acid-borax, etc. are used.

The azo compound of formula (1) of the present invention has excellent solubility and excellent color yield for cellulose fibers or cellulose fibers among cellulose fiber-containing fiber materials.
It provides various fastness properties and is particularly effective in terms of color yield.

Example The present invention will be explained in more detail with reference to Examples.

In the examples, parts are by weight, and sulfonic acid groups in each formula are expressed in the form of free acid.

Example 1 5.1 parts of the compound represented by formula (7) was dissolved by heating in 150 parts of water, and 50 parts of ice was added to obtain ]O'C. 10 in this aqueous solution
% Liponox NA (Lion Oil Co., Ltd., dispersant) aqueous solution and 3.8 parts of cyanuric chloride were added and reacted with stirring (first combination). At this time, the pH value was maintained at 4-7 with 10% sodium carbonate. Then 4-
A neutral aqueous solution of 4.4 parts of chloro-aniline-3-sulfonic acid dissolved in 44 parts of water was added, and the temperature was raised to 45°C to conduct a reaction (second combination). .8 parts was added and reacted at 90°C for 8 hours while keeping the pH slightly acidic (pH 5 to 6) (third combination).Next, 10% potassium chloride was added to the reaction solution to perform salting out and precipitate. The crystals were separated from each other to obtain 21.0 parts of an azo compound represented by the following formula (8). (λmax: 503 nm, 20% pyridine aqueous solution (the same applies hereinafter)) I The obtained compound was analyzed by high performance liquid chromatography, and the following results were obtained. Got the results.

Compound shown by Risou 8) 85.9
%I+) Precursor of the compound represented by formula 81 (the following formula)
4.3% Unknown component 9.8% I Example 2 3.8 parts of cyanuric chloride was added to 50 parts of ice water, 10
% Liponox NA aqueous solution in the presence of 0.5 part. In this, add 3.5 parts of aniline-3-sulfonic acid and 35 parts of water.
A neutral aqueous solution was added dropwise to the mixture, and the mixture was reacted with a 10% aqueous solution of sodium carbonate at a temperature of 5° C. or lower while keeping the J)H value between 4 and 7 (first combination). Furthermore, 4-hydroxy-7-amino-naphthalene-2-
A neutral aqueous solution of 4.7 parts of sulfonic acid dissolved in 70 parts of water was added dropwise, and the mixture was reacted at 45° C. while maintaining the pH value at 3 to 5 with a 10% aqueous sodium carbonate solution. (Second Combination) Next, a diazonium salt aqueous solution obtained by diazotizing 4.0 parts of 4-methoxy-aniline-2-sulfonic acid by a conventional method was added to this reaction solution at a temperature of 10°C or less. Coupling was carried out with a 10% aqueous sodium carbonate solution while maintaining a pH value of ~7 to obtain a reaction solution containing the compound represented by formula (9).

I Then, 3.7 parts of isonicotinic acid was added to this reaction solution, and 10 parts of isonicotinic acid was added.
% hydrochloric acid aqueous solution to 5.5%, the temperature was raised to 95°C, and the reaction was carried out at the same temperature for 7 hours (third combination).
% of sodium chloride was added. The precipitated crystals were dried one by one to obtain 23.5 parts of the compound represented by formula (10).

(λmax 505 nm) Example 3 4.8 parts of 4-hydroxy-7-amino-naphthalene-2-sulfonic acid were dissolved in 100 parts of water at a pH value of 6 to obtain a solution. This solution was cooled to below 5°C with ice for 10
% Liponox NA 0.5 part and cyanuric chloride 3
．． 8 parts were added and the reaction was carried out at pH 2-4 (first combination)
. Then 4-ethoxy-aniline-2-sulfonic acid4.
An aqueous solution of diazonium salt obtained by diazotizing 3 parts by a conventional method was added thereto, and coupling was carried out while keeping the pH value at 6 to 7 using IJium bicarbonate. After the coupling is complete, 2-methyl-aniline-4-sulfonic acid 3,9
The temperature was raised to 50°C, and the reaction was carried out while keeping the pH value at 6 to 7 with sodium carbonate (secondary combination).
A reaction solution containing the compound represented by 1) was obtained.

CI Next, 3.2 parts of nicotinic acid was added to this reaction solution, and 1.0
% sodium carbonate aqueous solution to 6 to 7, the temperature was raised to 90°C, and the reaction was carried out at the same temperature for 7 hours (3rd
Next union). Salting out with 10% of the liquid volume of sodium chloride,
When the precipitated crystals were dried in an oven, 21 parts of an azo compound represented by formula (2) was obtained.

(Extreme absorption wavelength 505 nm) Examples 4 to 14 Azo compounds shown in Table 1 were obtained by the same method as in Examples 1 to 3. In the table, R11R21RatX is represented by the formula (1
) corresponds to R1, R2+ Rs, X. "Hue" indicates the hue when cotton is dyed. In addition, a, b, and C in the column of "synthesis method" are based on (aJ, (
b) and (c) are shown.

Example 15 A dyestuff consisting of 4 parts of the compound obtained in Example 1, 80 parts of Glauber's salt, 1 part of Kayaku Buffer p-7 (manufactured by Nippon Kayaku, buffering agent), 1 part of sodium metanitrobenzenesulfonate, and 914 parts of water. A bath was prepared.

The pH value of the dye bath at this time was 7. Add 50 parts of mercerized cotton stockinette with scouring bleach to this dye bath, heat it up to 130°C in 30 minutes while stirring, and
Stained for minutes. The pH value of the dye bath after dyeing was 7, the same as before the start of dyeing.

Then washed with water and aqueous solution 1 containing 2 parts of anionic surfactant.
000 parts and soaping at 100° C. for 15 minutes, followed by washing with water and drying to obtain a bright scarlet dyed product. This dyeing had wet, light, sweat, sunlight and chlorine water fastness.

Example 16゜2 parts of the compound (mixture) obtained in Example 1, disperse dye)
0.7 parts, 80 parts of Glauber's salt, 1 part of sodium metanitrobenzenesulfonate, 2 parts of a formalin condensate of naphthalene sulfonic acid (dispersant), and Kayaku buffer p-71.
Polyester fiber/cotton (50150) blended fabric (T/C blend) was added to a total volume of 1000 parts of the dye bath adjusted to pH 7.
50 parts of the dye was added, the temperature was raised to 130° C. over 30 minutes, and dyeing was carried out at this temperature for 60 minutes. After washing with water, soaping was performed at 100°C for 15 minutes using 1000 parts of an aqueous solution containing 2 parts of anionic surfactant and 2 parts of sodium carbonate, followed by washing with water and drying.

A dyed product with a good color yield and uniformly dyed in bright scarlet on both the polyester fiber side and the cotton side was obtained. This dyed product had excellent moisture fastness, light fastness, sweat/sunlight fastness, and chlorine water fastness.

Example] 7゜A T/C blend was dyed in the same manner as in Example 16 using the target compound obtained in Example 2.3 instead of the compound obtained in Example 1. A dyed product was obtained in which both the fiber side and the cotton side were dyed in a uniform and clear scarlet color. These dyes are wet,
There were concerns about its fastness to light, sweat, sunlight, and chlorine water.

Example 18゜2 parts of the compound obtained in Example 1, Kayaseron Yellow E
-30L 0.4 part, Kayaseron Red E-28L (
Contains 1.7 parts of Nippon Kayaku (manufactured by Nippon Kayaku, disperse dye), 60 parts of Glauber's salt, 5 parts of carrier 430 (manufactured by NICCA CHEMICAL, carrier), 2 parts of a formalin condensate of naphthalene sulfonic acid (dispersant), and Kayak buffer p. -71 parts, a total volume of 1000 parts dyebath adjusted to pH 7 was prepared. Into this T/C (
50150) Fifty parts of the mixed knitted fabric was introduced, heated to 100° C. over 30 minutes, and dyed at this temperature for 60 minutes. After washing with water, soaping was performed at 100° C. for 15 minutes using 1000 parts of an aqueous solution containing 2 parts of anionic surfactant and 2 parts of sodium carbonate, followed by washing with water and drying. A dyed product with a good color yield and uniformly dyed in bright scarlet on both the polyester fiber side and the cotton side was obtained. This dyeing had wet, light, sweat, sunlight and chlorine water fastness.

Example 19゜4 parts of the target compound obtained in Example 1, 80 parts of Glauber's salt, 1 part of water
000 parts of mercerized cotton knitted fabric was immersed in this dye bath, dyed at 80°C for 30 minutes, and then 20 parts of sodium carbonate was added.
Subsequently, dyeing was carried out for 60 minutes at the same temperature. A bright scarlet dyed product was obtained by washing according to the method of Example 15.

Effects of the Invention By using a disperse dye in combination with a T/C mixture, a scarlet-based reactive dye with excellent color variation was obtained, which can be uniformly dyed in one bath.

Claims (1)

[Claims] 1. Formula (1) in the form of a free acid ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In formula (1), R_1 is CH_3 or C_2H_5,
R_2, R_3 represent H, Cl or CH_3, X represents ▲Mathematical formula, chemical formula, table, etc. ▼ or ▲Mathematical formula, chemical formula, table, etc. ▼) Azo compound 2, free acid form Formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In formula (1), R_1 is CH_3 or C_2H_5,
R_2 and R_3 represent H, Cl or CH_3, and X represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, respectively. ) A method for dyeing cellulose fibers or fiber materials containing cellulose fibers, characterized by using an azo compound represented by