JPS6090265A - Disazo compound and dyeing of fibrous material using it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [X is phenyl which may be replaced with sulfonic, carboxyl, etc., naphthyl which may be replaced with 1-3 sulfonic groups, 1-3C alkyl which may be replaced with carboxyl, or sulfonic, or H; one or both of Z1 and Z2 are group shown by the formula II (COOH is linked in 3- or 4-position), and the other is Cl, or F; A<-> is amion; m is 1, or 2]. EXAMPLE:A compound shown by the formula III. USE:Dye for dyeing cellulose fiber, especially mixed fabric of polyester fiber and cotton with improved fastness to wetting, chlorine, and light in dark blue-dark green. PREPARATION:For example, 1mol diamine shown by the formula IV is condensed with 1mol amine shown by the formula V and 1mol compound shown by the formula VI (Z3 is Cl, or F), diazotized, and coupled with 0.5mol 1-amino- 8-naphthol-3,6-disulfonic acid to give a disazo compound shown by the formula VII. This compound is further reacted with 1mol (iso)nicotinic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble disazo compound and a method for dyeing textile materials using the same. More specifically, formula (1) [wherein X is a sulfonic acid group, a carboxyl group, a methyl group,
A phenyl group optionally substituted with a methoxy group or a chlorine atom; a naphthyl group substituted with 1 to 3 sulfonic acid groups; an 01-C3 alkyl group optionally substituted with a carboxyl group or a sulfonic acid group; In the hydrogen atom, 1t represents a hydrogen atom or bonded to the 4-position, 1 represents a chlorine atom or a fluorine atom, A- represents an anion, and m represents 1 or 2. The present invention relates to a disazo compound represented by the following formula and a method for dyeing cellulose fibers or cellulose fiber-containing fiber materials using the disazo compound.

Reactive dyes for cellulose fibers are used in large quantities because they have superior fastness and brightness compared to other dyes for cellulose fibers.

For example, reactive dyes with reactive groups such as dichlorotri(cinyl, monochlorotrinidinyl, fluorochloropyrimidinyl, cycloquinoxacinyl, methylsulfonylchlorohyrimidinyl, vinylsulfonyl, sulfatoethylsulfonyl) are used as acid binders. or substances that release acid binders by the action of heat (e.g., sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, sodium pyrophosphate, birophosphate) By using potassium, sodium bicarbonate, sodium trichloroacetate alone or in combination of two or more, the pH of the dye bath can be adjusted to 10.
Cellulose fibers are dyed at temperatures below 100° C. in the presence of neutral electrolytes such as sodium chloride and sodium sulfate.

On the other hand, mixed fiber materials (blends) containing cellulose fibers are increasingly used as textile materials for clothing, and among them, blends of polyester fibers and cellulose fibers, particularly cotton (hereinafter abbreviated as T/C blends), are suitable for clothing. It has come to be widely used for reasons such as excellent durability and economical efficiency. The following method has generally been used to dye T/C blends using reactive dyes and disperse dyes.

(1) - Two-bath method First, the polyester fiber side is dyed with a disperse dye by a carrier dyeing method, a high temperature dyeing method, etc., and then, in □, the cellulose fiber side is dyed with a reactive dye in the same bath.

Or by the reverse method.

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

Or by the reverse method.

However, recently, from the viewpoint of shortening the dyeing time, streamlining the dyeing process, and saving energy, efforts have been made to use the T/C mixture in the same bath and finish the dyeing in one dyeing process (-one-bath method). .

However, there are several obstacles to dyeing T/C blends with reactive dyes and disperse dyes in a single step in a sea bath using a high temperature method or the like. For example, acid binders or substances releasing acid binders necessary for dyeing reactive dyes aggregate or disperse disperse dyes in the dyebath. In addition, in an aqueous medium at a high temperature such as 130°C for dyeing the polyester fiber side, reactive dyes are hydrolyzed by acid binders, etc.
For example, it does not stain cellulose fibers.

Therefore, there has been a strong demand for the development of a reactive dye that enables dyeing of T/C mixtures in one step in one bath.

As a result of intensive research to meet these demands, the present inventors discovered that the compound represented by formula (1) has extremely high suitability for the T/C mixed one-bath one-step dyeing method. There are two.

The compound of the present invention not only shows excellent suitability for T/C mixed one-bath one-step dyeing method, but also has sufficient suitability for dyeing cellulose fibers by ordinary methods, but it should be noted that , the novel compounds of the invention can be used in the absence of an acid binder or a substance that releases an acid binder, or when the dyebath is
■4-10 In the presence of disperse dyes, 100-1
The advantage is that T/C blend can be dyed in one step in one bath at a dyeing temperature of 50°C. When the compound (dye) of the present invention is used in a one-bath, one-step dyeing method with T/C mixed with a disperse dye, the T/C mixed color does not cause aggregation of the disperse dye or decomposition of the disperse dye or reactive dye. can be dyed uniformly. The compound of the present invention dyes cellulose fibers in navy blue or dark green hues, and the dyed products have excellent wet fastness, chlorine fastness, and light fastness.

The compound of the present invention has the most remarkable effect when used for dyeing cotton, recycled viscose fiber, cellulose fiber such as hemp, and T/C blend, but it can also be used to dye cellulose fiber, triacetate fiber, polyester fiber, etc. It can be applied to dyeing mixed fiber materials with acrylonitrile fibers, modified polyacrylic fibers, polyamide fibers, wool, silk, etc., and excellent effects can be obtained even when dyeing cellulose fibers.

In these cases, by using disperse dyes, basic dyes, cationic dyes, acid dyes, acidic metal-containing dyes, etc., it is possible to obtain a dyed blend in which each fiber forming the blend is uniformly dyed.

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

1 mol of diamine of formula (2), and 1 mol of amine of formula (3) I-], N-X 1(3) 几 (in the formula, X and R represent the same meanings as above),
The compound of formula (5) is condensed with 1 mol of the compound of formula (5) (in the formula, Z3 represents a chlorine atom or a fluorine atom) in any order.

Next, the compound of formula (5) was diazotized by a conventional method, acidic coupled with 0.5 mol of 1-amino-8-naphthol-3,6-disulfonic acid using 1) I-124, and then further p
By performing alkali coupling with H4-9, the formula (6
) to obtain a disazo compound. In this case, a coupling promoter such as urea or thiourea may also be added. Furthermore, the compound of formula (6) and nicotinic acid or isonicotinic acid 1
mol is reacted in water at 50-100°C to obtain a compound of formula (1).

To obtain the compound of Bunmu (6), diamine 1 of formula (2)
After condensing 1 mol of the compound represented by formula (4) with 1 mol of the compound represented by formula (4), diazotization is performed by a conventional method, and 1-
After coupling with amino-8-naphthol-3,6-disulfonic acid, it is condensed with an amine represented by formula (3), or a disazo compound represented by formula (7)0
．． 5 moles and 1 mole of the amine represented by the formula (3) are combined with the formula (
It can also be obtained by condensation with 1 mol of the compound represented by 4) in any order.

To obtain the target product from the reaction solution, a conventional salting out method or acid precipitation method is used. Alternatively, the reaction solution can be directly spray-dried.

Next, specific examples of the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (4) used in producing the compound of formula (1) are listed.

Compound represented by formula (2); 1.3-phenylenediamine-4-sulfonic acid 1.4-
Phenylenediamine-2-sulfonic acid compound represented by formula (3); NH3,N(2CH3, Nl-1(CHa)2,
NHz C1-1z CHhNH□CH2Cl-12C
l-13, N1-12 Cl-12C0OH,, N1-
1□Cl-12CI-1□COO1,lN1-1□C)
I2CI-12SO3I-1, Nl(□C1-1(Cl
-13) 2 Compounds represented by formula (4); 1,3.5-trichlorotriazine 1.3.5-) lifluorotriazine; The negative charge required to balance the positive charge of the nitrogen atom of the pyridine nucleus causes the OH''-, C1-C in the molecule to be removed from the reaction solution.
It may be oo-, 80M.

Next, a method for dyeing cellulose fibers and cellulose fiber-containing fiber materials (blends) using the compound of the present invention will be described.

When dyeing cellulose fibers using the compounds of the invention by a batch dyeing process, the dyebath is usually prepared with an inorganic salt such as sodium sulfate or sodium chloride and the compounds of the invention, and the fibers are immersed and heated to 50-90°C. Under heating 10-60
After staining for minutes, acid binders such as sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, sodium birophosphate,
Potassium birophosphate and sodium trichloroacetate are added singly or in a mixture of two or more, and further
Perform staining for minutes.

In this case, the acid binder may be added to the dye bath from the beginning, or
It is also possible to treat the dye in a separate bath containing an acid binder and an inorganic salt after dyeing in a neutral state.

In addition, when the compound (dye) of the present invention is used to color T/C mixed delicate fibers by dyeing, the compound disperse dye of the present invention and an inorganic salt may be added as necessary to adjust the dye bath pl-1 value from 5 to 9-9. Buffers (e.g. mixtures of acetic acid and sodium acetate, mixtures of monopotassium phosphate and disodium phosphate, mixtures of monosodium phosphate and dibasic phosphate), surfactants, reduction inhibitors, etc. A dye bath is prepared from the above, the fibers are immersed in this dye bath, heated to 100 to 150°C, and dyed for 20 to 90 minutes. It is also possible to dye only cellulose fibers using the method described above.

The compound of the present invention makes it possible to dye T/C mixtures in one step in one bath with the coexistence of disperse dyes, and its economic effects are extremely significant in terms of shortening dyeing time, streamlining the dyeing process, and saving energy. Hey.

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

In the examples, "part" means "part by weight", "%" means "% by weight", sulfonic acid group and carboxyl group are represented in free form, and the positive charge of the nitrogen atom of the pyridine nucleus is expressed in the solution or molecule. OH-, C1- or coo7. in the molecule. Assume that it has been neutralized by sob.

Example 1 11.4 parts of the disazo compound represented by formula (8) was dissolved in 250 parts of water, and a solution consisting of 2.5 parts of nicotinic acid, 25 parts of water, and 0.9 parts of sodium hydroxide was added to this solution. added. This mixed solution was heated to 90°C and reacted for 10 hours. By salting out the reaction solution with sodium chloride and drying the resulting crystals at 80°C, a mixture of dark blue disazo compounds (λma
12.3 parts of x 61 Q um (in water) were obtained.

The result of high-performance liquid chromatography analysis of the compound representing the metal atom was a mixture of 68% (9) and 10,131% (10,131%).The disazo compound of formula (8) used in the above example was obtained as follows. It was done.

Add 3.9 parts of cyanuric chloride and a small amount of surfactant to 50 parts of cold water and disperse well. Add 3-9 parts of 1°3-phenylenediamine-4-sulfone e' to this suspension and 30 parts of water.
The solution dissolved in 1 part was added dropwise over 30 minutes.

Next, with a 10% aqueous sodium carbonate solution I) I-16
, 0, and stirred for 1 hour while adding ice and maintaining the temperature at 5-10°C. Ice was added to the resulting reaction solution to bring the temperature to 0-5℃, and the temperature was increased to 4℃.
Add 3.7 parts of 0% sodium nitrite aqueous solution. Add 4.3 parts of concentrated hydrochloric acid to this mixture and stir at 5-10°C for 1 hour. Next, excess nitrous acid is decomposed with sulfamino acid to obtain a diazonium salt solution.

1-Amino-8-naphthol-3,6-disulfic acid 3
A solution prepared by dissolving 4 parts in 40 parts of water at 5.5-6.0 pg) was added to the above diazonium salt solution with ice to give 5-10 pg.
Add dropwise over 1 hour while keeping at ℃. During this time, a 10% sodium carbonate aqueous solution was simultaneously added dropwise to maintain the pH at 2.5-3.0. After the dropwise addition is completed, the coupling reaction (acidic coupling) is completed by further stirring for 2 hours. Then, by adding a 10% sodium carbonate aqueous solution, I) I-17,0~
Step 7.5: Stir for 1 hour and perform alkaline springing.

Next, 2.9 parts of 4-aminobenzoic acid was added to 15 parts of water at pH 6.
,0-7,0 is added to the above reaction solution,
Do not keep pH 7.0-8.0 50-6. '0'
Stir at C for 2 hours.

Salting out with sodium chloride was performed, and the precipitate was separated from E and dried at 80°C to obtain 19 parts of the disazo compound of formula (8).

Example 2゜2 parts of the compound obtained in Example 1 (mixture of formula (9) and formula (1o)), 60 parts of Glauber's salt, 2 parts of disodium phosphate, 0.5 part of monopotassium phosphate, metanitrobenzene A dyebath consisting of 1 part sodium sulfonate and 934.5 parts water was used. The pH value of the dye bath at this time was 7. Fifty parts of scouring and bleaching non-silcut cotton knitted fabric was placed in this dye bath, and the temperature was raised to 130° C. over 30 minutes while stirring, and dyeing was carried out at that temperature for 60 minutes. The pI-I value after staining was 7, which was different from before the start of staining.

After dyeing, the dyed product was washed with water, soaped with 1.000 parts of an aqueous solution containing 2 parts of an anionic surfactant at 100° C. for 10 minutes, washed with water, and dried to obtain a silk-colored dyed product.

This product had excellent wet fastness, chlorine fastness, light fastness, and sweat/sunlight fastness.

Example 3 1 part of the compound obtained in Example 1 (mixture of formula (9) and formula (10)), Kayalon polyester, Navy Blue E
X-8F200 (Nippon Kayakutan Disperse Dye) 0.5 parts, Glauber's Salt 80 parts, sodium metanitrobenzenesulfonate 1 part, formalin condensate of naphthalene sulfonic acid (dispersant)
1.2 parts to a dyebath with a total volume of 1000 parts adjusted to pH 7.0 with a buffer consisting of disodium phosphate and monopotassium phosphate. I? +7 ester fiber/cotton (50/5
．． 0') Blending; <I + 50 parts added in 20 minutes to 1
The temperature was raised to 30°C and dyeing was carried out at this temperature for 60 minutes. After washing with water, soaping for 20 minutes at 100°C in 1000 parts of water containing 2 parts of anionic surfactant and 2 parts of sodium carbonate,
Then, it was washed with water and dried.

A dyed product was obtained in which both the polyester fiber side and the cotton side were uniformly dyed in dark blue.

Example 4 Polyester fibers/cotton (
50150) 50 parts of the blended fabric was introduced, heated to 130°C for 20 minutes, and dyed at this temperature for 60 minutes. Next, the same treatment as in Example 3 was carried out to obtain a dyed product in which both the polyester fiber side and the cotton side were uniformly dyed in dark blue.

Example 5.

12.4 parts of a disazo compound represented by the formula (1υ) was dissolved in 300 parts of water, and 5.0 parts of nicotinic acid was added.Then, the pH was adjusted to 6.0 with 5% sodium hydroxide, and the mixture was heated to 90°C. The mixture was stirred at the same temperature for 8 hours while maintaining the pH at 5.5 to 6.0 by adding a 5% aqueous sodium hydroxide solution as necessary.The reaction solution was salted out with sodium chloride, and the precipitate was dissolved in F.
After separation, the mixture was dried under reduced pressure at 60°C to obtain 13.5 parts of a dark green disazo compound represented by formula (12). (λ+nax
6 3 0 nln (Suigetsu) Formula used in the previous example (1
Is it expressed by υ? The suazo compound was obtained as follows.

4-Aminotoluene-2-sulfonic acid9. A small amount of surfactant and 9.2 parts of cyanuric chloride were added to the solution of 2 parts dissolved in 80 parts of water in a neutral state and 20 parts of ice added to bring the temperature to 0-5°C, and then dissolved in a 10% aqueous sodium carbonate solution. Yo! It
The mixture was stirred at 0-5° C. for 2 hours while maintaining the pH at 6.0-7.0.

1,4-]]nylenediamine-2-sulfonic acid 9 0
A neutral solution of 20 parts of water was added to the above reaction solution, and the pH was adjusted to pH 6, 0 using a 10% aqueous sodium carbonate solution.
-6. Stir at 5-10°C for 4 hours while keeping the temperature at 5°C. Ta.

Ice was added to the resulting reaction solution to bring the temperature to 0-5°C, 8.8 parts of a 40% aqueous sodium nitrite solution and 12.0 parts of concentrated hydrochloric acid were added, and the mixture was stirred at 0-10°C for 1 hour. Decomposed with nitric acid and sulfamic acid. Thirty parts of thiourea was added to the viscous diazonium salt solution thus obtained.

1-Amino-8-naphthol-3,6-disulfonic acid 6
．． 2 parts pi-1 in 40 parts water 5. 5-6.
Add the solution dissolved in step 0 to the diazonium salt solution at 20 to 3
It was added dropwise for 0 minutes, and then diluted with a 10% aqueous sodium carbonate solution, pH 3.5-4. The mixture was stirred at 10-15° C. for 5 to 8 hours while maintaining the temperature at 10°C to 15°C. (Acidic coupling then 10
% sodium carbonate aqueous solution 5 pl-1 8. 0
-8, 5 and stirred for 2 hours to perform alkali coupling. After salting out with sodium chloride, the precipitate was separated from F and dried to obtain 21 parts of a disazo compound represented by the formula (1υ).

Example 6.

2 parts of the disazo compound of formula (Engineering 2) obtained in Example 5,
80 parts of Glauber's salt, water i. Prepare a dye bath in the ooo section, soak 50 parts of cotton stockinette in the dye bath, dye it at 80°C for 30 minutes, add carbon dioxide (20 parts), and continue dyeing at the same temperature for 60 minutes. did.

The dyed product was then treated and dried in the same manner as in Example 2 to obtain a dark green dyed product, which had excellent wet fastness and light fastness.

Example 7 12.8 parts of the disazo compound represented by formula (13) was dissolved in 300 parts of water, 3.7 parts of isonicotinic acid was added, and the pH was adjusted to 6.5 with a 5% aqueous sodium hydroxide solution. Stirred at -80°C for 24 hours. The reaction solution was salted out with sodium chloride,
The precipitate was separated from F and dried to obtain 13.8 parts of the compound of formula (14). (λmax 610 nm (Mizuno formula (14)) Note that the compound of formula (13) was produced according to the method described in Example 1.

Dyeing was performed using the disazo compound of formula (14) according to Example 2 to obtain a dark blue dyed product. It had excellent wet fastness, chlorine fastness, light fastness, and sweat fastness to light.

Example 8゜4 parts of the disazo compound of formula (14) obtained in Example 7,
Kayalon Polyester Navy Blue EX-81”20
02 parts, 80 parts of Glauber's salt, 2 parts of sodium benzenesulfonate, 2 parts of formalin condensate of naphthalene sulfonic acid, and pl (7,0 Full details adjusted to 10
00 parts of the solution was injected into a cheese dyeing machine (manufactured by Nippon Senzo Kikai@). 100 parts of polyester fiber/cotton (5o15o) blended yarn was introduced and the temperature was raised to 130° C. in 30 minutes, and dyed at this temperature for 30 minutes. It was then treated in the same manner as in Example 3, washed with water and dried.

Both the polyester fiber side and the cotton side were dyed uniformly dark blue.

Example 9 135 parts of the disazo compound represented by formula (15) was dissolved in 300 parts of water, 2.5 parts of nicotinic acid was added, and the solution was adjusted to pi-16.5 with a 5% aqueous sodium hydroxide solution.

This solution was heated to 60° C. and stirred for 10 hours while maintaining the pH at 6,0 to 65 with 10 cycles of an aqueous sodium carbonate solution. The reaction solution was salted out with sodium chloride, and the precipitate was separated from F and dried under vacuum at 40°C to form a mixture of dark blue disazo compounds (λrnax) represented by formulas (16) and (17).
610 nm (H2O), 14.3 parts were obtained.

The result of high performance liquid chromatography analysis (formula (16) and formula (17) representing elementary atoms) was a mixture consisting of 73% of formula (16) and 20% of formula (17).

Examples 10-62 According to Example 1.5.7.8, a disazo compound of formula (18) was prepared and cotton was dyed.

The following table shows the compound represented by formula (2) used in producing the compound of formula (18), the compound represented by formula (3), the bonding position of the carboxyl group in the pyridine nucleus, the λmax (water) of the compound, It shows the hue when cotton is dyed.

Claims (1)

[Scope of Claims] A phenyl group optionally substituted with a methyl group, a methoxy group, or a chlorine atom: A naphthyl group substituted with 1 to 3 sulfonic acid groups; A phenyl group substituted with a carboxyl group or a sulfonic acid group; C3 to C3 alkyl group or hydrogen atom, 几 represents a hydrogen atom or a methyl group, and the sil group of Zl and Z2 is bonded to the 3 or 4 position), and the other represents a chlorine atom Or represents a fluorine atom. A- represents an anion, and m represents 1 or 2.] A disazo compound represented by: [In the formula, X is a sulfonic acid group, a carboxyl group, a methyl group,
Phenyl group optionally substituted with methoxy group or chlorine atom; Naphthyl group substituted with 1 to 3 sulfonic acid groups; C1-C3 alkyl group optionally substituted with carboxyl group or sulfonic acid group or a hydrogen atom, with the R xyl group bonded to the 3 or 4 position], the other represents a chlorine atom or a fluorine atom, or represents an anion, and m represents 1 or 2. ] A method for dyeing cellulose fibers or fiber materials containing cellulose fibers, characterized by using a disazo compound represented by the following.