JPS6086169A - Azo compound and dyeing of fiber material using the same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [A is benzene ring having 1-2 sulfonic acid groups or carboxyl groups and optionally methyl, methoxy or chlorine as substituent, or naphthalene ring having 1-3 sulfonic acid groups; R1-R3 are H or methyl; n is 1 or 2; X is group of formula II, Cl or F; B is -(CH2)m- (m is 2 or 3), -C2H4OC2H4-, or group of formula III, etc.] as free acid. EXAMPLE:The compound of formula IV. USE:Dye for dyeing cellulosic fibers such as cotton, rayon, flaxen, etc. or a blend of polyester fiber and cotton in orange-red color having excellent fastness to moisture, chlorine water, light, sunlight and sweat. PREPARATION:The objective compound can be produced e.g. by reacting the compound of formula V as free acid with cyanuric chloride, coupling the product with a diazotized compound of formula A-NH2, and reacting the coupled product successively with the compound of formula VI and nicotinic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble azo compound and a method for dyeing textile materials using the same. More specifically, in the form of a free acid, formula (1) [formula (1) has one or two sulfonic acid groups or carboxyl groups and may further have a methyl group, methoxy group or chlorine atom. Benzene nucleus; ・A naphthalene nucleus having 1 to 3 sulfonic acid groups, R, R2, R3 each independently represents a hydrogen atom, a mechlorine atom, or a fluorine atom, and B represents -(CH2)+rr-(m represents 2 or 3)
, -C21-140C2l-14.

(independently excluding hydrogen atom, methyl group, sulfonic acid group or A),
This invention relates to a water-soluble azo compound represented by O and a monthly dyeing method for cellulose fibers or cellulose fiber-containing fibers using the same.

Reactive dyes are currently used in large quantities in the dyeing of cellulose fibers because they are superior in brightness and various fastnesses compared to other dyes. For example, dichlortriazinyl,
Monochlorotriazinyl, fluorochlorohyrimidinyl,
A reactive dye having a reactive group such as cycloquinoxazinyl, methylsulfonylpyrimidinyl, vinylsulfonyl, or sulfatoethylsulfonyl is used as an acid binder or a substance that releases the acid binder by the action of Bano heat (e.g. Sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate,
The pi-1 value of the dyebath can be adjusted by using 3-111Ium phosphate (Pyro 11 Sosaiben-h II Uum Pyro 11 Sosodium decathorium, sodium bicarbonate, sodium trichloroacetate) alone or in combination on two inserts. Reactive dyeing of cellulose fibers is carried out at a temperature of 100° C. or lower in the presence of a neutral electrolyte such as sodium chloride or sodium sulfate. On the other hand, mixed fiber materials (blends) containing cellulose fibers are often used as textile materials for clothing, and among them, blends of polyester fiber and cotton (hereinafter abbreviated as T/C blends) are suitable for clothing and have excellent economic efficiency. It came to be used in large quantities because of its

T/C blends are usually dyed using reactive dyes and disperse dyes in the following manner.

(1) 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.

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

Or stain in the reverse order.

However, from the viewpoint of shortening dyeing time, streamlining the dyeing process, and saving energy, it has become impossible to use the T/C mixture in the same bath and finish dyeing polyester fibers and cotton in one dyeing operation (one bath, one step method). , has come to be. But,
1 bath of T/C mixture with reactive dye and disperse dye
There are several obstacles to dyeing with f-di using high temperature methods. For example, acid binders or substances that release acid binders, which are essential for dyeing with reactive dyes, aggregate or decompose disperse dyes coexisting in the dye bath, while for example, 1:30 for dyeing polyester fibers. In an aqueous medium at a high temperature such as °C, reactive dyes are hydrolyzed by acid binders and the like, and do not dye cotton. Therefore T
There has been a strong demand for the development of a reactive dye that can dye a /C mixture in a one-bath, one-step process.

The inventors of the present invention have carried out extensive research in response to these requests, and have discovered that the compound represented by formula (1) is extremely suitable for the T/C mixed one-bath, one-stage dyeing method. This led to the invention.

The compound represented by formula (1) is not only suitable for dyeing by a one-bath one-stage method carried out in the presence of an acid binder, but also is suitable for dyeing silk in dye baths of pl-J 4 to 10, especially 5 to 9. It is extremely suitable for the one-bath, one-stage dyeing method in that it can uniformly dye T/C blends at temperatures of 100 to 150°C in the presence of dispersed dyes simply by coexisting with a chemical that has a buffering effect. ing.

Of course, it is fully applicable not only to T/C mixtures but also to fiber materials made only of cellulose fibers. Formula (1)
The compound represented by the formula dyes cellulose fibers orange to red, and the dyed product has excellent fastness to wet, chlorine water, 4-light, sweat and sunlight.

The compound of the present invention has the most remarkable effect when used for dyeing cellulose fibers such as cotton, rayon, hemp, and 'J'/C blends, but it can also be used to dye polyester fibers such as trayon, cotton or rayon, and triacetate fibers. Disperse dyes, basic dyes, cationic dyes, acid dyes O-1, acidic metal-containing dyes for dyeing blended products with polyacrylonitrile fibers, modified polyacrylonitrile fibers, polyamide fibers, wool, silk, etc. 4. Excellent effects can be obtained by staining using the following methods.

The compound represented by (1) of the present invention is synthesized, for example, as follows.

[In formula (2), n and R have the same meanings as above] 7. By reacting with 1 mole of cyanuric oxide or cyanuric fluoride in water, for example, at 10°C or lower, a compound expressed by the formula (3) [In formula (3), Xl represents a chlorine atom or a fluorine atom, and n represents the same meaning as above] is obtained. Then, 1 mole of the compound represented by A N1-12 (A represents the same meaning as above) was diazotized to obtain the compound of the formula (
The compound represented by formula (4) is obtained by coupling to the compound of formula (3).

1 Then, 05 mol of a compound represented by the formula (-11N-13-NI-], (n, , R, and 13 represent the same 12R3 meanings as above) is added to the formula (4 ) to obtain a compound represented by formula (5).

Nicotinic acid or isonicotinic acid 1 to 1 to the compound of formula (5)
A compound of formula (1) is obtained by reacting 3 moles in aqueous solution at a temperature of 60 DEG to 100 DEG C.

No( used in producing the compound of formula (1)
(2) (Canogring component), A-Nil□ (Specific examples of the diazo compound are shown below.

Example of a compound represented by formula (2): 503I (Example of a compound represented by A, -N, H2: C113.
Shizuki 3 Next, a method for dyeing fiber yarn using the compound represented by formula (1) of the present invention will be described.

First, when dyeing a fiber material consisting only of cellulose fibers by the meji dyeing method, prepare a dye bath using the compound of the present invention, an inorganic salt (for example, sodium sulfate, sodium chloride, etc.), and immerse the fiber at a temperature of 50 to 90 degrees. After dyeing with C for 10 to 60 minutes, an acid binder is added and further dyeing is carried out at the same temperature for 20 to 60 minutes.In this case, the acid binder is added to the dye bath from the beginning and dyeing is carried out, first, the compound of the present invention is dyed. It is also possible to adopt a method in which the material is treated with a dye bath consisting of only a dye, and then treated with a bath consisting of an acid binder and an inorganic salt for dyeing.

In addition to the dyeing method, it is also possible to perform dyeing by a padding dyeing method or a printing method according to a conventional method.

Next, when dyeing the T/C mixture, use the compound of the present invention, a disperse dye, an inorganic salt, a buffer to maintain the pH value between 5 and 9, and if necessary, a surfactant, a reduction inhibitor, etc. Prepare a dye bath and immerse the fibers in it to 100-150°c”c-
Perform staining for 120-90 minutes. In this case, dyeing is also possible by a method of dyeing in the presence of a usual acid binder.

Blends other than T/C blends can also be dyed by methods similar to those described above, depending on the type of dye used.

The compound of the present invention can be used alone or in combination with two inserts. Also, as an acid binder, sodium carbonate,
Potassium carbonate, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, potassium birophosphate, sodium birophosphate, sodium bicarbonate,
Sodium trichloroacetate and the like are used as buffering agents, such as acetic acid-sodium acetate, potassium phosphate-disodium phosphate, monosodium phosphate-disodium phosphate, and the like.

The compound of the present invention is prepared using a mixture of ']'/C in combination with a disperse dye in one bath and one bath.
This makes it possible to dye by punching, and its economic effects are extremely significant in terms of reducing dyeing time, streamlining the dyeing process, and saving energy.

Next, the present invention will be specifically explained with reference to Examples.

The middle part of the examples is expressed in parts by weight, and the sulfonic acid group in each formula is expressed in free form.

Example 1 22 parts of chlorotriazinyl dye represented by 300 parts of water
To this was added a solution of 6 parts of nicotinic acid dissolved in 70 parts of water and 2 parts of sodium hydroxide. The temperature of this mixed solution was raised to 80°C, and the reaction was continued at the same temperature for 10 hours, followed by salting out with common salt, filtration, and drying. Obtained.

The λInaX of this mixture was 543 [in water].

The composition ratio of the mixture was measured by high performance liquid chromatography.

The dye represented by formula (6) was synthesized as follows.

Add 1-amino-8-hydroxynaphthalene-3,6- to a solution of 7.6 parts of cyanuric chloride suspended in 50 parts of ice.
10 parts of a solution consisting of 13.6 parts of disulfonic acid and 50 parts of water
It was added at ℃ and allowed to react for 1 hour.

Next, a diazonium salt solution prepared by diazotizing 10 parts of 2-aminobenzenesulfonic acid by a conventional method was added, pi-1 was adjusted to 7 with an aqueous solution of caustic soda, and the mixture was coupled at 5° C. for 2 hours. After coupling, p-phenylenediamine 2
1 part was added thereto, and the mixture was reacted at 40° C. for 2 hours while keeping I)I at 6 to 7 with an aqueous caustic soda solution.

Add 100 parts of common salt to the reaction solution and salt out excessively.6) Dye 3
I got 5 copies.

Example 2 2 parts of the compound (mixture) obtained in Example 1, Glauber's salt (50
Part, N221 (Po4・121-1202 part and J(1
A dye bath was prepared consisting of 20.5 parts of -+2 PO, 1 part of sodium metanitrobenzenesulfonate, and 9345 parts of water.

The 'dyebath pl-1 value at this time was 7. Put 50 parts of scoured and bleached non-mercerized cotton stockinette into the dye bath,
The mixture was heated at 13 o'ct for 30 minutes with stirring, and dyed at the same temperature for 60 minutes. The pH value after staining was 7, the same as before the start of staining. Next, it was washed with water, soaped with 1,000 parts of an aqueous solution containing 2 parts of anionic surfactant at 100°C for 10 minutes, and then washed with water and dried to obtain a dark red dyed product.

This product has excellent fastness to chlorinated water, 4 light, and sweat and sunlight.

Example 3 05 parts of the compound (mixture) obtained in Example 1, 1 gu ay
alon Poyester Ligbi It, c
d I) with a buffer consisting of acetic acid and sodium acetate containing 1 part of BL-8E' (Nippon Kayakutan Disperse Dye), 60 parts of Glauber's Salt, 1 part of sodium metanitrobenzenesulfonate, and 2 parts of a formalin condensate of naphthalene sulfonic acid. I-16
, the dye bath of 1o o o i1+ adjusted to 5,
Polyester fiber/cotton (65/35) blended fabric (T/C
50 parts of the mixture was added, heated to 130°C for 20 minutes, and dyed at the same temperature for 60 minutes. After washing with water, 100% in 1000 parts of water containing 2 parts of anionic surfactant and 2 parts of soda ash.
'C soaped for 20 minutes. The dyed product was then washed with water and dried to obtain a dyed product in which both the polyester fiber side and the cotton side were uniformly dyed in deep red.

Example 4 chloro) l) 21 parts of azinyl dye and 3 parts of water
00 parts and added 6 parts of nicotinic acid. then l'l
Adjust to 1) I-15,5 with an aqueous sodium hydroxide solution, raise the temperature to 90°C, and during the reaction at the same temperature, add an aqueous sodium chloride solution as necessary to 1) II 6-65. The reaction was allowed to proceed for 8 hours while holding (1). It was salted out with common salt, filtered and dried to obtain 24 parts of Wasarel compound represented by the following formula (10).
; IX 485 parts m (9 in water) The dye of formula (9) was synthesized as follows.

Dissolve 169 parts of Zo compound in 300 parts of water, add ice and stir at 0°C.
Then, 7.6 parts of cyanuric chloride was added.

5° while keeping pl-1 at 5 to 6 with aqueous caustic soda solution.
The reaction was carried out at C for 2 hours. Next, 41 parts of 2,6-diamitluene-4-sulfonic acid was processed, heated to 508CK, and reacted for 3 hours while keeping the pH at 5 to 7 with an aqueous solution of caustic soda. Add 70 parts of common salt to the reaction solution and filter by salting out.
9) and obtained 30 copies of Rusomeo El.

Example 5 05 parts of the compound of the formula (10), 1 part of Color Index Disverse Yellow-671I, 6005 parts of Tisfu ζ-Zurenod, 60 parts of Glauber's salt, 1 part of sodium metanitrobenzenesulfonate, 2 parts of formalin condensate of naphthalene sulfonic acid. , Tetrosin 1 (manufactured by Yamakawa Pharmaceutical Co., Ltd.). A dye bath containing 95 parts of carrier and adjusted to pl-1, 7 with the buffer of Example 3 is prepared with a total volume of 1.000 parts. Add T/C to this dye bath.
, (50/50) Add 50 parts of blended knitted cloth 1
The temperature was raised to 00°C and dyeing was carried out at the same temperature for 60 minutes. After dyeing, it was washed by the method of Example 3 to obtain a dyed product in which both the polyester fiber side and the cotton side were uniformly dyed orange.

Example 6 20 parts of the chlorotriazinyl dye represented by: 30 parts of water
0 parts and added 6 parts of isonicotinic acid.

Next, the pH was adjusted to 6.0 with aqueous caustic soda solution, and the temperature was adjusted to 90°C.
The temperature rose to . If necessary, add Inari soda aqueous solution to adjust the pH.
The reaction was carried out for 10 hours while maintaining the temperature at 6.0±0.2. The mixture was salted out with common salt, filtered and dried to obtain 27 parts of a compound A1 represented by formula (12). λmax 513 nm (in water)
The dye of formula (11) was synthesized according to the method for producing the dye of formula (9) described in Example 4.

Example 7 2 parts of the target compound obtained in Example 6, 80 parts of anhydrous sodium sulfate,
Prepare a dyebath using 1.000 parts of water, soak 50 parts of cotton and stockinette in this dyebath and treat at 80°C for 0 minutes, add 20 parts of sodium carbonate, and then
Staining was carried out at the same temperature for minutes. After washing with water, it was soaped in the same manner as in Example 2, washed with water, and dried to obtain a dark red dyed product.

“It showed excellent wet, 4-light, and chlorine water fastness.

21 parts of the fluorotriazinyl dye shown in Example 8 was dissolved in 200 parts of water, and 6 parts of nicotinic acid was added. Next, sodium hydroxide was added to give pi-1, 6, and 5. 60% of this solution
℃ and allowed to react for 10 hours. It was salted out with common salt, filtered, and dried.

25 parts of triazinyl compounds (mixture) represented by formulas (14) and (15) were obtained. (λmax 543 nm
(In water)) Examples 9 to 42 [Example] A compound represented by formula (16) was synthesized according to 4.6. Then, according to the method of Example 2, wood [A, I%2. It, 3, and B have the same meanings as above, but do not represent coupler residues] The following table shows the diazo component (A-NI-12), force, and pulling component H.
N -B-Nl-1 (K-1-I), cross-linking agent (i21I (,3), λn]aX in water of the compound in which the bonding position of the carboxyl group in the pyridine nucleus was determined and the hue of the dyed product were shown. .

Claims (2)

[Claims] (1) Formula (1) in the form of a free acid [Formula (1) has one or two sulfonic acid groups or carboxyl groups and may further have a methyl group, methoxy group or chlorine atom Benzene nucleus; Naphthalene nucleus having 1 to 3 sulfonic acid groups, Rt, I(,2, R
:+ each independently represents a hydrogen atom or a methyl group; n represents 1 or 2; XRs and R6 each independently represent a hydrogen atom, a methyl group, a sulfonic acid group or a carboxyl group. Water-soluble azo compound represented by (2) Formula (1) in the form of a free acid [formula (in which A has 1 to 2 sulfonic acid groups or carboxyl groups and may further have a methyl group, methoxy group or chlorine atom) Benzene nucleus: naphthalene nucleus having 1 to 3 sulfonic acid groups, R□, R+2.R3 each independently represents a hydrogen atom or methyl group, n represents 1 or 2, X
Rla each independently represents a hydrogen atom, a methyl group, a sulfonic acid group or a carboxyl group. A method for dyeing cellulose yarn fibers or cellulose fiber-containing fiber materials, characterized by using a water-soluble azo compound represented by