JPS63199269A - Trisazo compound and dyeing process using same - Google Patents

Abstract

NEW MATERIAL:The compound expressed by formula I (X1-X3 are CH3, OCH3, OC2H5, Cl, COOH, etc.; X4 and X5 are OCH3, OC2H5, -NHCOCH3 or CH3; X6 is CH3, C2H5 or phenyl; X7 and X8 are SO3H COOH, CH3, Cl, NO2 or H; R is group of formula II, III, etc.) as free acid. EXAMPLE:The compound of formula IV. USE:A dye for dyeing a cellulosic fiber in deep blue color having excellent fastness to chlorine water and combined action of sweat and sun light. PREPARATION:A compound of formula V is diazotized and coupled with a compound of formula VI in acidic state and the reaction product is hydrolyzed. Separately, a compound of formula VII is diazotized and coupled with a compound of formula VIII and the product is diazotized. The hydrolysis product is coupled with the diazotization product and the product is made to react with a compound of formula R-Cl, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a trisazo compound and a conventional technique for dyeing cellulose fibers using the same.In recent years, there has been an increasing trend toward differentiation and luxury of textile products. Regarding the reactive dyes that are often used for dyeing cellulose fibers, there is a desire to develop dyes with excellent chlorine water fastness and sweat/sunlight composite fastness, and this demand is particularly strong for azo dark blue dyes. Examples of typical dark blue reactive dyes are shown below, but these known dyes cannot meet the above requirements.

C, 1, Reactive Black 5 (The hue of the dyed product is dark blue) C, 1, Reactive Bl
ue 194C, 1, Reactive Bl
ue 184C, 1, Reactive Bl
ue 171C, 1, Reactive Bl
ue 112 Problems to be Solved by the Invention Currently, a large number of navy blue reactive dyes are in use, but no reactive dye has been found that satisfies both chlorine water fastness and sweat/sunlight composite fastness.

Therefore, there is a strong demand for the development of a dark blue reactive dye having such properties.

Means for Solving the Problems The present inventors have conducted extensive research to develop a dark blue reactive dye that has improved the above-mentioned problems (chlorine, sweat and sunlight combined fastness), and have developed the present invention. It has been very busy. That is, the present invention provides free acid forms (in formula (1), XI, X2 and N are each independently H, C) Ia, OCH3, OC2H5,
CL, C0OH, -OH.

-8O, H, -No□, NHCOCH3, NHCO
NH2, SO2NH2゜-8O2C) Ia or -802
CHt CH20H, X, and are each independently 10C
H3, -0C2Hs, -NHCOCHa or -CH3, -〇HI, C mountain or one, X7 and h each independently -8OaH, COOH, CH3, C4NO2kyl-substituted amino group, lower alkanol-substituted amino group, -N
HCHCONH203H, -NHCH2C0OH, -N
几.

and Xll are each independent VC-H, -OH, -8O3H,
-CHl.

-COOH, -Ct, -CN or -8O2CH2CH
20SO3H respectively). ] respectively. ) A trisazo compound represented by the following and a method for dyeing cellulose fibers using the same are provided.

The present invention will be described in detail.

The trisazo compound represented by formula (1) of the present invention can be synthesized, for example, by the following method. That is, a compound represented by the above formula (3) (Xt and for have the same meanings as above)
1 mole was diazotized at a temperature of 0-40'C for 1-3 hours,
Acidic coupling is performed with 1 mol of a compound represented by the following formula (4) <Xa has the same meaning as above) in water at pH 2-5.5 and temperature 0-40°C for 5-20 hours to obtain the formula Compound (5) is obtained. Then, under strong acidity at a temperature of 80 to 100°C,
Hydrolysis is carried out for 10 hours to obtain a compound of formula (6).

・Diazotize 1 mole of the compound (XI, X2 and N have the same meanings as above) to form the compound (Xt
A coupling reaction is carried out with 1 mol of the compound (and and n have the same meanings as above) in water, for example, at a pH of 1-5 and a temperature of 5-40°C for 10-20 hours to obtain a compound represented by formula (9). Next, 1 mol of the compound of formula (9) was added at a temperature of 5-30°.
diazotized with C for 1-3 hours, and reacted (coupling reaction) with 1 mol of the compound of formula (6) in water, for example, at pH 8-11 and temperature 5-30°C for 1-5 hours (coupling reaction).
Compound (Xt, Xs, Xs, Xt, Xs, '
Xs, Xt, and X have the same meanings as above).

Next, 1 mol of the compound represented by R-C/ or R-F (R represents the same meaning as above) is added to, for example, O to 3o in water.
The compound of formula (10) was reacted with the compound of formula (10) at pH 5-s for 1-5 hours, and 1 mol of the compound represented by Y-H (Y represents the same meaning as above) was added to the thus obtained compound as necessary. The reaction is carried out at a temperature of 30-70°C and a pH of 4-10 for 3-10 hours to obtain the compound of formula (1).

Depending on the type of compound represented by KR, the following nine synthetic methods may be more advantageous than the above synthetic methods.

That is, a compound represented by Y-H (Y represents the same meaning as above), for example, is reacted in water at O to 30°C for 1 to 5 hours at H5-8, and a compound of formula (11) (Y and Z are (same meaning as above) to obtain B.

Next, 1 mol of the compound represented by the formula (12) (Xt and N have the same meanings as above) was added to water at 30-70°C, for example.
The reaction is carried out at pH 5-9 for 5-20 hours to obtain a compound of formula (13).

The compound of formula (13) is diazotized, and the compound represented by formula (4) is diazotized, for example, in water at pH 2-5.5 and temperature 0-
Acidic coupling was performed at 40°C for 5-20 hours to obtain the formula (1
Compound 4) (Z, Y, Xs, Xt and h have the same meanings as above) is obtained.

The compound of formula (9) was diazotized in the same manner as above to give the compound of formula (14
) is reacted in the same manner as above to obtain formula (15) (% formula % represents the same meaning as above).

Formula (3), Formula (12), Formula (4), Formula (7), Formula (
8), specific compounds represented by Y-H include the following.

Compound of formula (3): Compound of formula (12); Compound of formula (4); Compound of formula (7); Compound of formula (8); Y-H compound; ,NHtCH,acH,OH,NHCHa
C) TltOH,NH(C几CH20H)z, NHs
C le C le 5 OIH, N quick C le C0OH, N le.

Next, a method for staining cellulose fibers using the trisazo compound of the present invention will be explained.

The trisazo compound of the present invention is suitable for dyeing natural and regenerated cellulosic fibers as well as blended fibers containing these fibers and fibers other than cellulosic fibers.Dyeing methods include dip dyeing, pad dyeing, and printing using conventional reactive dyes. Methods used for staining can be applied.

First, when applying the compound (dye) of the present invention under relatively high bath ratio conditions such as the dyeing method, the compound (dye) of the present invention may be heated for several minutes to several tens of minutes in the presence of an inorganic salt such as sodium chloride or sodium sulfate. After dyeing for a few minutes, an acid binder is added, and if necessary, dyeing is further carried out under heating for several minutes to several tens of minutes.

In this case, an acid binder is added from the beginning of dyeing, and when the compound (dye) of the present invention is applied, the dye, acid binder, and if necessary, a penetrant, urea as a solubilizer, and alginic acid as a migration preventive agent. After padding the fibers in a pad bath prepared from soda etc. and squeezing them (or without squeezing them)
The dye is fixed by steaming or dry heat treatment.

Furthermore, in the textile printing method, a color paste is prepared by using alginic acid, emulsion paste, etc. as a base paste, and adding dyes, acid binders, urea, etc. to this, and printing this on the fiber as needed. After intermediate drying, steam or dry heat treatment is performed to fix the dye. In this case, the fibers impregnated with the acid binder solution are printed with a colored paste that does not contain an acid binder, or the colored paste that does not contain an acid binder is printed, and then a solution containing an acid binder is used. The dye may be fixed by treatment in the same manner as described above.

The acid binders used in the above dyeing methods include, for example, sodium hydrogen carbonate, sodium metaphosphate, triphosphoric acid
Examples include sodium, ortho- or metasilicate, sodium carbonate, and sodium hydroxide.

Tables 1 and 2 show conditions for the more preferable dyeing method for each reactive group for the dyeing method using the compound of the present invention.

Note that Table 1 is for the dyeing method, and Table 2 is for the pad dyeing method.

Specific examples of cellulose fibers to which the compound of the present invention is applied include cotton, mercerized cotton, viscose rayon,
Examples include cufflar rayon, hemp, etc., and blends of these materials with wool, silk, polyamide fibers such as nylon, polyester fibers, or polyacrylic fibers may also be used. Further, the fiber may be in any form such as cotton, thread, knitted fabric, or woven fabric.

The trisazo compound represented by formula (1) of the present invention has a high affinity for cellulose fibers, reducing the amount of neutral salt used in dyeing with existing reactive dyes to less than half. Not only is it extremely economical, showing excellent color yield and build-up properties, but it also has excellent wet fastness such as sunlight fastness and washing fastness, and has recently become a popular choice for chlorinated water. Provides an extremely excellent dark blue color that is both fastness and combined fastness to sweat and sunlight.

EXAMPLES Next, the present invention will be explained in more detail with reference to examples. In the examples, parts are parts by weight and % is weight Bariponox NA (
Product name: Made by Lion Oil, part heated to 45-50℃ 3
After adding 10% caustic soda dissolved in 0 parts to this reaction solution, the temperature was raised to 60°C over 30 minutes while maintaining pH 6.5 ± 0.2 with 10% soda ash solution. The temperature was raised. A reaction solution was obtained by reacting at the same temperature for 5 hours. Next, ice was added to this reaction solution to bring the temperature to 15°C, 1.5 parts of sodium nitrite was added to dissolve it, and then 4 parts of hydrochloric acid was added and diazotization was carried out at a temperature of 20 ± 2°C for 2 hours. went. Then excess NO with sulfamino acid
; Ions were extinguished to obtain a diazotized solution.

An aqueous solution prepared by dissolving 50 parts of the diazotized solution with 10% caustic soda while adjusting the pH to 6.5±0.2 was added to the diazotized solution over a period of 30 minutes. After addition, adjust the pH to 4 with 10% soda ash solution.
Neutralized to 5. After reacting for 15 hours at the same pH 1 temperature of 20 ± 2 °C, the temperature was raised to 50 °C, and 35% of sodium chloride was added.
After stirring for 30 minutes, filtration and separation were carried out to obtain the formula (17
) was obtained (25 parts of hydrated compound).

A solution consisting of 0.5 part of SNA aqueous solution was added and stirred for 1 hour to obtain a dispersion. 3.5 parts of hydrochloric acid was added to this dispersion over 10 minutes, and the temperature was brought to 10° C. with ice. Furthermore, a solution of 1.4 parts of sodium nitrite dissolved in 20 parts of water was added over 30 minutes, and diazotization was carried out at the same temperature for 1 hour.

Next, excess NO2 ions were quenched with sulfamino acid to obtain a diazotized solution.

The temperature was raised to 70°C, the mixture was completely melted, 3.8 parts of hydrochloric acid was added to dissolve the mixture, and ice was added to bring the temperature to 30°C, and the liquid was added all at once to the diazotized liquid. pH 3 with 10% soda ash solution,
Neutralize to 5 ± 0.2, at a temperature of 20 ± 2°C and at the same pH.
After reacting for an hour, the temperature was raised to 60°C and pu
After neutralization to 2.5 and stirring for 30 minutes, the product was obtained. This compound 3.
2 parts were added to 70 parts of water, heated to 60°C, and 10% caustic soda solution was added to adjust the pH to 8.5 to dissolve. Next, add ice to bring the temperature to 15°C, add 0.75 parts of sodium nitrite, then add 2.8 parts of hydrochloric acid and bring the temperature to 20-25°C.
Time diazotized. Then excess NO with sulftimic acid
; Ions were extinguished to obtain a diazotized solution. Separately, 7.2 parts of the compound of formula (17) was added to 80 parts of water, and the mixture was adjusted to pH 9.5 with 10% caustic soda solution and dissolved. Next, 4 parts of soda ash was added and dissolved, then ice was added to bring the temperature to 10 parts at 2°C, the diazotized solution was added over 30 minutes, and 5 parts at the same temperature.
Allowed time to react. Then, the temperature was raised to 50°C, 35 parts of sodium chloride was added, and the mixture was separated, filtered, and dried.
30 parts of the compound were obtained.

This compound exhibited a maximum absorption wavelength of 592 nm.

(In a 20% pyridine aqueous solution...the same applies hereinafter) Example 2 The same operation as in Example 1 was carried out except that 2.9 parts were used, and the formula (
25 parts of compound 18) were obtained. This compound exhibited a maximum absorption wavelength of 591 nm.

To Example 3 38° The compounds shown in Table 3 were synthesized by a method similar to Example 1. For those labeled with "hue", dyeing was carried out by the cotton dip dyeing method according to the example described later.

Add 75 parts of λtAs to Example 39, dissolve it by adjusting the pH to 7.5 with 10% caustic soda solution, add 2.1 parts of sodium nitrite, cool the temperature to 5°C by adding ice, and add 5.5 parts of hydrochloric acid. I added the second part all at once.

Diazotization was carried out at a temperature of 10° C. and 2° C. for 1 hour.

Excess N6 ions were eliminated with sulfamic acid to obtain a diazotized solution.

In addition, the pu was adjusted to 6.5±0.2 with 10% caustic soda solution. This liquid was added to the above diazotized liquid over a period of 30 minutes, and then the pH was adjusted to 4.5 with 10% soda ash solution.

After reacting for 15 hours at a pH of 4.5 and a temperature of lO±2°C, 15 parts of hydrochloric acid was added to make it strongly acidic, hydrolysis was carried out at 95°C for 4 hours, and the temperature was lowered to 80°C. Concentrated caustic soda solution (48%)
The pH was adjusted to 8.5. After salting out with 50 parts of IJum and stirring for 30 minutes, it was filtered and separated, and the formula (20
) was obtained (35 parts of hydrated compound).

3.2 parts of the solution was diazotized in the same manner as in Example 1 to obtain a diazotized liquid.

4.9 parts of the compound of formula (20) was added to 50 parts of water at 60°C.
At the same temperature, the solution was adjusted to pH 8.5 with a 10% caustic soda solution and dissolved. 3.0 parts of soda ash was added to the resulting solution and dissolved, and then the above diazotized solution, which had been cooled to 10°C to 2°C by adding ice, was added over 30 minutes and reacted at the same temperature for 5 hours. A reaction solution containing the compound of formula (21) was obtained.

It was added to a solution consisting of 0.5 part of Liponox NA aqueous solution and stirred to obtain a dispersion. Next, the above formula (21) is applied to this dispersion.
The reaction solution containing the compound was adjusted to pH 6.0 with 10% soda ash solution.
-6pH6 added over 30 minutes while maintaining pH6.5
, 0-6,5, after reacting for 5 hours at a temperature of 20 ± 2°C, the temperature was raised to 50°C, salted out with 35 parts of sodium chloride, and 30
After stirring for several minutes, filtration, separation, and drying Examples 40 to 43 According to Example 39, the compounds shown in the structural formula column of Table 4 were synthesized and their maximum absorption wavelengths were measured. Somesekoma Ta. Hue means the hue of the dyed material at that time.

Example 44 First, the compound of formula (21) was synthesized in the same manner as in Example 39.

The mixture was stirred to obtain a dispersion. The above formula (21) is applied to this dispersion.
The compound was added over 30 minutes while maintaining pH 6.0-6.5 with 10% soda ash solution. Then pH 6.0
= 6.5, and the reaction was stirred for 3 hours at a temperature of 10±2°C. (Reaction Solution) The sulfate salt was gradually added to the above reaction solution, and the pH was adjusted to 5.5-6.0 with 10% soda ash solution. While maintaining the same pH, raise the temperature to 50℃, and
The reaction was carried out at 0°C and pH 5.5 to 6.0 for 5 hours. Thereafter, 50 parts of sodium chloride was added to salt out the mixture, stirred for 30 minutes, filtered, separated and dried to obtain 30 parts of the compound of formula (22).

This compound exhibited a maximum absorption wavelength of 592 nm.

Example 45゜To 2.0 parts of the compound of formula (16) obtained in Example 1, 40
After adding 960 parts of boiling water and stirring to dissolve, 960 parts of water was added to prepare a dye bath. 80 parts of anhydrous sodium sulfate and 20 parts of sodium carbonate were added to this dye bath, and after stirring and dissolving, 50 grams of knitted knitted fabric was added to start dyeing.

While continuing to stir, raise the temperature to 95℃ in 20 minutes and raise the temperature to 60℃ at 95℃.
Stained for minutes. After that, the dyed fabric is taken out from the dye bath, washed under running water, washed with hot water at 90℃, and boiled.The finished dyed fabric shows a deep navy blue color and has the following traces, excellent chlorine water fastness and sweat/sunlight resistance. It had good fastness.

゛Fastness test conditions (common hereafter) Chlorine water fastness (JIS - strong test) Contains effective chlorine amount 20 ppm, pH 7.0 - 0.2
The test cloth is immersed in a test solution that is 200 times the weight of the test cloth and sealed, stirred at 27±2° C. for 30 minutes, dehydrated, and dried at room temperature. The series is determined using the blue scale for the obtained test cloth.

Sweat and Sunlight Composite Fastness After immersing the test fabric in 50 times the weight of the test fabric prepared as shown in the table below for 30 minutes, take it out and set it in a carbon arc lamp lightfastness tester, and after exposing it for 20 hours, wash and dry. do. For the obtained test cloth, determine the series by Buman & Cool.

Example 46 80 parts of boiling water was added to 4.0 parts of the compound obtained in Example 4, and after stirring and dissolving, 920 parts of water was added to prepare a dye bath.

To this dye bath, 30 parts of anhydrous sodium sulfate was added, and after stirring and dissolving, 50 parts of stockinette was added to start dyeing. After raising the temperature to 95° C. over 20 minutes while stirring, 20 parts of dicarbonate was added, and dyeing was continued at 95° C. for 60 minutes. After that, the dyed fabric was taken out of the dye bath and washed under running water, hot water at 90℃, and boiled.The finished dyed fabric has less than half the amount of anhydrous mirabilite than normal salt, and despite the high dyeing temperature, it is extremely It exhibited a high color yield and had excellent chlorine water fastness and sweat/sunlight composite fastness.

Example 47 150 parts to 60 parts of the compound of formula (16) obtained in Example 1
After adding 500 parts of urea and 500 parts of boiling water and dissolving it,
A dyebath was prepared by adding 0 parts of water and 20 parts of sodium carbonate. Using the padding method, this dye bath is padded onto mercerized cotton broadcloth (dye bath pick-up height 70%), dried (120℃ for 2 minutes), then painted (170℃ for 2 minutes), washed with running water, hot water at 90℃, and boiled. The dyed fabric finished with this treatment showed a high color yield, and had excellent chlorine water fastness and sweat/sunlight combined fastness.

Example 48゜To 2.0 parts of the compound of formula (16) obtained in Example 1, 40
After adding 100% of boiling water and stirring to dissolve, add Kay in a separate bath.
Add 20 parts of 50°C warm water to 2.0 parts of acelon Navy Blue E-EX (disperse dye, manufactured by Nippon Kayaku), stir it, add the dispersed disperse dye dispersion and 940 parts of water, and then add 20 parts of the dispersed dye dispersion and 940 parts of water. Anhydrous sodium sulfate was added, and finally acetic acid and sodium acetate were added to adjust the pH to 6.0 to prepare a dye bath. This dye bath is polyester/cotton blend stockinette (50:50)
Add 50 parts and start dyeing.

While continuing to stir, raise the temperature to 130℃ in 40 minutes.
The mixture was kept at 20 minutes, and then cooled to 85° C. over 15 minutes. 85
When the temperature reaches ℃, add 20 parts of sodium carbonate and raise the temperature to 85℃.
Staining was continued for 60 minutes.

The dyed fabric is then taken out of the dye bath, washed under running water, washed in hot water at 90°C, and then subjected to a boiling process.The resulting dyed fabric has an extremely high color even though it uses less than half of the amount of mirabilite used. As shown below, it had excellent chlorine water fastness and sweat/sweat/sunlight composite fastness.

Example 49゜To 4.0 parts of the compound of formula (16) obtained in Example 1, 80
After adding 960 parts of boiling water and stirring to dissolve, 960 parts of water was added to prepare a dye bath. To this dye bath, 40 parts of anhydrous sodium sulfate and 20 parts of sodium carbonate were added, stirred and dissolved, and then 50 parts of cotton knitted fabric was added to start dyeing. The temperature was raised to 95° C. over 20 minutes while stirring, and dyeing was continued at 5° C. for 60 minutes. After that, the dyed fabric was taken out from the dye bath and washed under running water, followed by boiling at 90°C.The dyed fabric finished with the normal fix treatment (Nippon Kasou Stock % Formula % 20:1) has less anhydrous sodium sulfate than usual. In addition, it shows an extremely high color yield despite the high dyeing temperature, and not only has excellent sunlight fastness and washing fastness, but also excellent chlorine water fastness and sweat fastness, as shown below. It had sunlight composite fastness.

Example 50° 40° to 2.0 parts of the compound of formula (18) obtained in Example 2
After adding 960 parts of boiling water and stirring to dissolve, 960 parts of water was added to prepare a dye bath. 2.0 parts of anhydrous sodium sulfate and 15 parts of sodium carbonate were added to this dye bath, and after stirring and dissolving, 50 parts of cotton stockinette was added.
and start dyeing. 60℃ with continuous stirring
The temperature was raised to 10 minutes, and staining was carried out at 60° C. for 60 minutes. Thereafter, the dyed fabric was taken out of the dye bath, washed under running water, and then boiled and washed in hot water at 90° C. The finished dyed fabric had excellent chlorine water fastness and sweat/sweat/sunlight composite fastness.

Example 51゜To 2.0 parts of the compound of formula (19) obtained in Example 39, 4
After adding 0 parts of boiling water and stirring to dissolve, 960 parts of water was added to prepare a dye bath. To this dye bath, 20 parts of anhydrous sodium sulfate and 15 parts of IJ carbonate were added, and after stirring and dissolving, 50 parts of cotton knitted fabric was added to start dyeing. While continuing to stir 6.
The temperature was raised to 0°C in 10 minutes and dyed at 60°C for 60 minutes. Thereafter, the dyed fabric was taken out of the dye bath, washed under running water, washed in hot water at 90°C, and then boiled.The finished dyed fabric had excellent fastness to chlorine water and combined fastness to sweat and sunlight.

Example 52゜To 2.0 parts of the compound of formula (22) obtained in Example 44, 4
After adding 0 parts of boiling water and stirring to dissolve, 960 parts of water was added to prepare a dye bath. 20 parts of anhydrous sodium sulfate was added to this dye bath, and after stirring and dissolving, 50 parts of knitted knitted cloth was added to start dyeing. While continuing to stir, raise the temperature to 70℃ in 10 minutes to 7'O℃.
After stirring for 20 minutes at , 15 parts of sodium carbonate were added, followed by dyeing at 70° C. for 60 minutes. Thereafter, the dyed fabric was taken out from the dye bath, washed under running water, washed in hot water at 90°C, and then boiled.The finished dyed fabric had excellent chlorine water fastness and shed light composite fastness.

Example 53 To 2.0 parts of the compound obtained in Example 42, 40 parts of boiling water was added, stirred and dissolved, and then 960 parts of water was added to prepare a dye bath. 20 parts of anhydrous sodium sulfate was added to this dye bath, and after stirring and dissolving, 50 parts of knitted knitted cloth was added to start dyeing. While stirring, the temperature was raised to 70°C in 10 minutes, and after stirring at 40°C for 20 minutes, 15 parts of sodium carbonate was added, and then the temperature was raised to 70°C for 6 minutes at 40°C.
Stained for 0 minutes. Thereafter, the dyed fabric was taken out from the dye bath, washed under running water, washed in hot water at 90°C, and then boiled.The finished dyed fabric had excellent chlorine water fastness and shed light composite fastness.

Example 54 80 parts of boiling water was added to 4.0 parts of the compound obtained in Example 40, and 920 parts of condensate, which was dissolved with stirring, was added to prepare a dye bath. 40 parts of anhydrous sodium sulfate and 20 parts of sodium carbonate are added to this dye bath, and after stirring and dissolving, 50 parts of knitted knitted cloth are added to start dyeing. The temperature was raised to 95°C over 20 minutes while stirring, and dyeing was carried out at 95°C for 60 minutes. After that, the dyed fabric was taken out of the dye bath and washed under running water.The finished dyed fabric was washed with hot water at 90℃ and then boiled.The finished dyed fabric contains half the amount of anhydrous sodium sulfate that is normally used, and is extremely high despite the high dyeing temperature. It exhibited color yield and had excellent chlorine water fastness and shed light composite fastness.

Example 55 40 parts of boiling water was added to 2.0 parts of the compound obtained in Example 43, the mixture was stirred and dissolved, and then 960 parts of water was added to prepare a dye bath. 20 parts of anhydrous sodium sulfate and 15 parts of sodium carbonate are added to this dye bath, and after stirring and dissolving, 50 parts of knitted knitted cloth is added to start dyeing. The temperature was raised to 50°C over 10 minutes while stirring, and dyeing was carried out at 50°C for 60 minutes. Thereafter, the dyed fabric was taken out of the dye bath, washed under running water, washed with hot water at 90°C, and then boiled.The finished dyed fabric had excellent chlorine water fastness and shed light composite fastness.

Comparative Test The results of a comparison between five known dyes and the compound of the present invention are shown below. The optimum dyeing conditions for each dye were adopted.

List of existing dye dyeing conditions (material to be dyed: cotton knitted fabric, bath ratio 20: l, dye density:
4% owf-) staining program is as follows.

Dyeing bath Bath ratio 20:1,60'CX20 (anhydrous sodium sulfate, dye, dyed material) 9) Table 5 Comparative test results It is superior to known dyes in that it has good properties.

Effects of the Invention A reactive dye for braided cellulose fibers having excellent properties in both chlorine water fastness and shed light composite fastness was obtained.

Claims (1)

[Claims] 1. Formula (1) in the form of free acid ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) {In formula (1), X_1, X_2 and X_3 are each independently -H, -CH_3 , -OCH_3, -OC_2H_
5, -Cl, -COOH, -OH, -SO_3H-NO
_2, -NHCOCH_3, -NHCONH_2, -S
O_2NH_2, -SO_2CH_3 or -SO_2C
H_2CH_2OH, X_4 and X_5 are each independently -OCH_3, -OC_2H_5, -NHCOCH_3
Or -CH_3, X_6 is -CH_3, -C_2H_
5 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X_7 and X_8 are each independently -SO_3H, -COOH, -C
H_3, -Cl, -NO_2 or -H, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Z is -F or -Cl, Y is lower alkyl substituted amino group, lower alkanol substituted amino group, -NHCH_2C
H_2SO_3H, -NHCH_2COOH, -NH_
2, -OCH_3 or formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In formula (2), X_9 is -H, -CH_3 or -C
_2H_5, X_1_0 and X_1_1 are each independently -H, -OH, -SO_3H, -CH_3, -COOH
, -Cl, -CN or -SO_2CH_2CH_2OS
0_3H respectively). ] respectively. } Trisazo compound 2, represented by formula (1) in the form of a free acid ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) {In formula (1), X_1, X_2 and X_3 are each independently -H, - CH_3, -OCH_3, -OC_2H_
5, -Cl, -COOH, -OH, -SO_3H, -N
O_2, -NHCOCH_3, -NHCONH_2, -
SO_2NH_2, -SO_2CH_3 or -SO_2
CH_2CH_2OH, X_4 and X_5 are each independently -OCH_3, -OC_2H_5, -NHCOCH_
3 or -CH_3, X_6 is -CH_3, -C_2H
＿5 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X＿7
and X_8 are each independently -SO_3H, -COOH, -
CH_3, -Cl, -NO_2 or -H, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Z is -F or -C
l, Y is a lower alkyl-substituted amino group, a lower alkanol-substituted amino group, -NHCH_2CH_2SO_3H,
-NHCH_2COOH, -NH_2, -OCH_3 or formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In formula (2), X_9 is -H, -CH_3 or -C
_2H_5, X_1_0 and X_1_1 are each independently -H, -OH, -SO_3H, -CH_3, -COOH
, -Cl, -CN or -SO_2CH_2CH_2OS
0_3H respectively). ] respectively. } A dyeing method for cellulose fibers characterized by using a trisazo compound represented by