JPH0420948B2 - - Google Patents

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. For more details, use formula (1) (In formula (1), X is a hydrogen atom, a methyl group, a methoxy group, or a 2-methoxyethoxy group, and Y is a hydrogen atom,
a methyl group, a methoxy group, an acetylamino group or a ureido group, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, n is a number of 2 or 3, and Z ₁ is a group

[Formula] (assuming that the carboxyl group is bonded to the 3- or 4-position) chlorine atom or fluorine atom, B is -(CH ₂ ) m- (m is 2 or 3)
): −C ₂ H ₄ OC ₂ H ₄ −:

[Formula] P-phenylenediamine residue or m-phenylenediamine residue optionally substituted with a methyl group, methoxy group, sulfonic acid group, carboxylic acid or chlorine atom:

[Formula] (Q represents -O-, -SO ₂ -, -NHCO-, or -NH-)

【formula】

[Formula] or

Represents [formula]. However, the carboxyl group of the pyridine nucleus is bonded to the 3- or 4-position. ) and a method for dyeing cellulose or cellulose-containing fiber materials using the water-soluble azo compound. Reactive dyes for cellulose fibers are used in large quantities because they have superior fastness and sharpness compared to other dyes for cellulose fibers. For example, reactive dyes with reactive groups such as dichlorotriazinyl, monochlorotriazinyl, fluorochloropyrimidinyl, dichloroquinoxazinyl, methylsulfonylchloropyrimidinyl, vinylsulfonyl, sulfatoethylsulfonyl, etc. 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, triphosphate)
Adjust the pH of the dye bath to 10 or higher using potassium, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, sodium trichloroacetate, alone or in combination, and add sodium chloride, sodium sulfate, etc. 100 in the presence of neutral electrolytes
Cellulose fibers are dyed at temperatures below ℃. On the other hand, mixed fiber materials (blends) containing cellulose fibers are increasingly used as textile materials for clothing, especially blends of polyester fibers and cellulose fibers, especially blends of polyester fibers and cotton (hereinafter referred to as T/C blends). (abbreviated)) has come to be widely used because it is suitable for clothing and is economical. The following method is generally used to dye T/C blends using reactive dyes and disperse dyes. (i) One-bath two-step 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 the cellulose fiber side is dyed with a reactive dye in the same bath. Or in the reverse order. (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, in the reverse order. On the other hand, from the viewpoints of shortening 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 dyeing in one dyeing process (one-bath, one-step method). Ta. By the way, there are several obstacles to dyeing T/C blends with reactive dyes and disperse dyes in one bath and one step using a high temperature method or the like. For example, acid binders necessary for dyeing with reactive dyes or substances that release acid binders due to heat or the like often cause the disperse dyes in the dye bath to aggregate or decompose. In addition, when dyeing polyester fibers in an aqueous medium at a high temperature such as 130° C., reactive dyes are hydrolyzed by acid binding agents and do not dye cellulose fibers. Therefore, there is a strong demand for the development of a reactive dye that makes it possible to dye T/C mixtures in one step in one bath. As a result of extensive 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. This led to the present invention. The compound of the present invention not only shows high suitability for T/C mixed one-bath one-step dyeing method, but also has sufficient suitability for dyeing cellulose fibers by ordinary dyeing methods such as dyeing method, printing method, and packing method. However, it is noteworthy that the novel compounds of the present invention do not use acid binders or substances that release acid binders;
Alternatively, by simply coexisting with a buffering agent necessary to maintain the dye bath at a pH of 4 to 10, especially 5 to 9, the T/C mixture can be dyed in one bath at a dyeing temperature of 100 to 150°C in the presence of disperse dyes. It can be dyed. When the compound of the present invention is used in one-bath one-step dyeing of a T/C mixture together with a disperse dye, the T/C mixture is dyed uniformly without causing aggregation of the disperse dye or decomposition of the disperse dye or reactive dye. can do. The compound of the present invention dyes cellulose fibers in a yellow hue, and the dyed product has excellent wet fastness, chlorine fastness, light fastness, and sweat/sunlight fastness. The compound of the present invention can be applied to cotton, recycled viscose fiber,
The most remarkable effect is obtained when used for dyeing cellulose fibers such as hemp and T/C blends, but it is also used for dyeing cellulose fibers, triacetate fibers, polyacrylonitrile fibers, modified polyacrylic fibers, polyamide fibers, and wool. It is applied to the dyeing of mixed fiber materials with silk, etc., and excellent effects can be obtained even when dyeing the cellulose fiber side. In these cases, basic dyes, cationic dyes,
By using acidic dyes, acidic metal-containing dyes, etc. in combination, it is possible to obtain uniformly dyed fiber materials made of different types of fibers. The compound represented by formula (1) of the present invention can be synthesized, for example, by the following method. First, equation (2) (In formula (2), n represents the same meaning as above)
1 mole of the compound of formula (3) is diazotized by a conventional method. (X and Y in formula (3) have the same meanings as above) is coupled to 1 mol of the compound of formula (4). and then formula (5) (Z ₂ in formula (5) represents a chlorine atom or a fluorine atom) is reacted with 1 mole of the compound of formula (6) in water. The compound is obtained. then

[Formula] (R ₁ , R ₂ and B have the same meanings as above) 0.5 mol is reacted with the compound of formula (6) to form the compound of formula (7) This is reacted with 1 mole of nicotinic acid or isonicotinic acid in water at 50 to 100°C to obtain the compound of formula (1). To obtain the desired product from the reaction solution, ordinary salting-out methods and acid precipitation methods are used, but the reaction solution can also be spray-dried as it is. Next, the compound represented by formula (2) used in producing the compound of formula (1), the compound represented by formula (3),

A specific example of the compound represented by the formula is given below. However, all shall be expressed in the form of free acid. Compound represented by formula (2): Compound represented by formula (3):

Compound represented by the formula: H ₂ NCH ₂ CH ₂ NH ₂ H ₂ NCH ₂ CH ₂ CH ₂ NH ₂
H ₂ NCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ NH ₂ Next, a method for dyeing cellulose fibers and cellulose-containing fiber materials (blended fibers) using the compound of the present invention will be described. When cellulose fibers are dyed by the batch dyeing method using the compounds of the present invention, the dye bath is usually prepared with an inorganic salt such as sodium sulfate or sodium chloride and the compound of the present invention, and the fibers are immersed.
After staining at 50-90℃ for 10-60 minutes, acid-acid binders such as sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, triphosphate Potassium, sodium pyrophosphate, potassium pyrophosphate, and sodium trichloroacetate are added singly or in combination of two or more, and dyeing is further carried out at the same temperature for 20 to 60 minutes. In this case, the acid binder may be added to the dye bath from the beginning, or
It is also possible to carry out fixing in a separate bath containing an acid binder and an inorganic salt after dyeing in a neutral condition. In addition, when dyeing a T/C mixture by dip dyeing using the compound of the present invention, the compound of the present invention, a disperse dye, an inorganic salt, and, if necessary, a buffer to maintain the pH value of the dye bath at 5 to 9. (For example, a mixture of acetic acid and sodium acetate, a mixture of monopotassium phosphate and disodium phosphate, a mixture of monosodium phosphate and disodium phosphate), a surfactant, a reduction inhibitor, etc. to prepare a dye bath. , immerse the T/C mixture in this dye bath,
Heat to 100-150℃ and stain for 20-90 minutes. Furthermore, 100% cellulose fibers can also be dyed in the same manner as described above. The compound of the present invention makes it possible to dye T/C mixtures in one step in one bath by coexisting with a disperse dye, and its economic effects are extremely large in terms of shortening 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 is expressed in free form. Example 1 Formula (8) 8.3 parts of the chlortriazinyl compound represented by was dissolved in 200 parts of water, and a solution consisting of 2 parts of nicotinic acid, 0.7 parts of sodium hydroxide, and 2 parts of water was added thereto. This mixed solution was heated to 90°C and reacted for 10 hours. Then, salting out with common salt, filtering and drying, formula (9), formula
19 parts of a triazinyl compound (mixture λmax 396 nm (in water)) represented by (10) was obtained. The results of high performance liquid chromatography analysis revealed that it was a mixture of (9)48% and (10)45.0%. The compound represented by formula (8) was produced as follows. 2-naphthylamine-4,8-disulfonic acid
Dissolve 14.4 parts in 90 parts of water at pH 6.5, add 30 parts of ice,
Then 13 parts of concentrated hydrochloric acid were added. Next, a solution consisting of 3.4 parts of sodium nitrite and 5 parts of water was added to diazotize the mixture at 10°C for 1 hour. Add this diazonium salt solution to water.
The mixture was added to a solution consisting of 150 parts of 3-acetylaminoaniline, 7.1 parts of 3-acetylaminoaniline, and 8 parts of soda ash over 30 minutes while maintaining the temperature at 10°C. The reaction was continued at the same temperature for 1 hour. Next, 8.1 parts of cyanuric chloride was added, and the mixture was reacted for 1 hour at 10° C. or lower while maintaining the pH at 6.0 to 6.5 using sodium carbonate. Then, 4,4′-diaminostilbene-2,
After adding 7.6 parts of 2'-disulfonic acid and reacting at 50°C for 2 hours, salt was added to the mixture for salting out, followed by filtering and drying.
30 parts of a compound represented by formula (8) was obtained. Example 2 A dye consisting of 2 parts of the compound (mixture) obtained in Example 1, 60 parts of Glauber's salt, 2 parts of disodium phosphate, 0.5 part of monopotassium phosphate, 1 part of sodium metanitrobenzenesulfonate, and 934.5 parts of water. A bath was prepared. The pH value of the dye bath at this time was 7. Unsilced cotton stockinette that has been scoured and bleached in this dye bath.
50 parts were added, the temperature was raised to 130°C over 30 minutes while stirring, and dyeing was carried out at that temperature for 60 minutes. The PH value of the dye bath after dyeing was 7, the same as before the start of dyeing. After dyeing, wash with water and prepare an aqueous solution containing 2 parts of anionic surfactant.
Using 1000 parts, soaping was carried out at 100°C for 10 minutes, followed by washing with water and drying to obtain a yellow dyed product. This product had excellent wet fastness, chlorine fastness, light fastness, and sweat/sunlight fastness. Example 3 1 part of the compound (mixture) obtained in Example 1, 640.5 parts of Color Index Disperse Yellow,
Total volume 1000 containing 80 parts of Glauber's salt, 1 part of sodium metanitrobenzenesulfonate, and 2 parts of a formalin condensate of naphthalene sulfonic acid (dispersant), adjusted to pH 7.0 with a buffer consisting of disodium phosphate and monopotassium phosphate. 50 parts of T/C (50/50) blended fabric was placed in a dye bath, heated to 130°C over 20 minutes, and dyed at this temperature for 60 minutes. After washing with water, 1000ml of water containing 2 parts of anionic surfactant and 2 parts of sodium carbonate.
Soap at 100°C for 20 minutes in the room, then wash with water,
Dry. A dyed product was obtained in which both the polyester fiber side and the cotton side were uniformly dyed yellow. No dye aggregates, dye decomposition products, etc. were observed in the dye bath after dyeing. Example 4 Formula (11) Add 12 parts of chlorotriazinyl compound represented by
Dissolved in 300 parts of nicotinic acid. Added 5 parts. After adjusting the pH to 6.5 with sodium hydroxide,
The mixture was heated to .degree. C. and reacted at the same temperature for 8 hours while maintaining the pH at 6.0 to 6.5 with a dilute aqueous sodium hydroxide solution. The mixture was then salted out with common salt and overdried to obtain 13 parts of a compound represented by the following formula (12). (λmax445nm (underwater) The compound represented by formula (11) was produced as follows. The following formula (13) 49.5 parts of an aminoazo compound represented by 1 part of water,
After adding 200 parts of ice, 19 parts of cyanuric chloride was added, and the pH was adjusted using sodium carbonate.
The reaction was carried out for 1 hour at 10°C or lower while maintaining the temperature at 6.0 to 6.5. Next, add 3 parts of ethylenediamine and heat at 50°C while maintaining the pH at 5 to 6 using sodium carbonate.
The reaction was carried out for 5 hours. Next, add salt and salt out.
Filtered and dried. 65 parts of a compound represented by formula (11) was obtained. Example 5 1 part of the target compound obtained in Example 4, 0.8 part of Color Index Disperse Yellow 64,
0.1 part of Disperse Thread 60, 60 parts of Glauber's salt, 1 part of sodium metanitrobenzenesulfonate, formalin condensate of naphthalene sulfonic acid (dispersant)
Part 2, Tetrosin K (Carrier manufactured by Yamakawa Pharmaceutical Co., Ltd.) 5
Make up a total of 1,000 parts of dye containing 1,000 parts and adjusted to pH 7.0 with the buffer of Example 3. T/C (50/50)
Add 50 parts of mixed knitted cloth and heat to 100℃.
Dyeing was carried out at the same temperature for 0 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 in golden yellow. This dyed product had excellent wet fastness, light fastness, and chlorine fastness. Example 6 Formula (14) Add 10 parts of chlortriazinyl compound represented by
300 parts, and 3 parts of isonicotinic acid were added.
Next, the pH was adjusted to 6.5 with caustic soda and heated to 80°C. PH6.0 ~ by dilute caustic sozo solution at the same temperature
The reaction was carried out for 15 hours while maintaining the temperature at 6.5. Salting out with common salt and over-drying yielded 12 parts of the compound of formula (15). (λmax410nm (in water)) In addition, the compound of formula (14) was manufactured according to the method described in Examples 1 and 4. Example 7 2 parts of the target compound obtained in Example 6, 80 mg of Glauber's salt
Prepare a dye bath using 1,000 parts of water and 1,000 parts of water.
After 50 parts of cotton stockinette was soaked and dyed at 80° C. for 30 minutes, 20 parts of sodium carbonate was added and dyed subsequently at the same temperature for 60 minutes. A yellow dyed product was obtained by soaping and drying in the same manner as in Example 2. This product had excellent wet fastness, light fastness, and chlorine fastness. Example 8 Formula (16) Add 10 parts of fluorotriazinyl dye represented by
The solution was dissolved in 300 parts, 3 parts of nicotinic acid was added, and then sodium hydroxide was added to adjust the pH to 6.5. Heat this solution to 60℃, add dilute aqueous sodium carbonate solution at the same temperature, and keep the pH at 6.0 to 6.5 for 10 minutes.
Allowed time to react. After salting out with common salt and over-drying, 10 parts of triazinyl compounds (mixture) represented by formulas (17) and (18) were obtained.
(λmax455nm (underwater)) High performance liquid chromatography analysis results (17)
It was a mixture of 68% (18) and 23%. Example 9 1 part of the compound (mixture) obtained in Example 1, Color Index Disperse Yellow 64 0.5
A dye bath containing 1,000 parts of total solution was prepared from 1,000 parts of sodium chloride, 80 parts of Glauber's salt, and water. Its pH value was 6.7. T/ in this dye bath
Add 50 parts of C (50/50) blended fabric and heat to 130℃ for 20 minutes.
The sample was heated to a temperature of 100.degree. C. and dyed at this temperature for 60 minutes. The pH value of the remaining bath after dyeing was 5.8. After dyeing, the fabric was soaped in the same manner as in Example 3 to obtain a dyed product in which both the polyester fiber side and the cotton side were uniformly dyed yellow. Examples 10-42 Compounds were produced and cotton was dyed according to Examples 1, 4, 6, and 8. Compounds represented by formula (2) and compounds represented by formula (3) are shown in the following table.

The compound represented by [Formula], the bonding position of the carboxyl group in the pyridine nucleus, the λmax (in water) of the compound, and the hue when cotton was dyed with the produced compound are shown.

【table】

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Claims (1)

[Claims] 1 Formula (1) in the form of free acid (In formula (1), X is a hydrogen atom, methyl group, methoxy group, or 2-methoxyethoxy group, Y is a hydrogen atom,
methyl group, methoxy group, acetylamino group or ureido group, R ₁ and R ₂ each independently represent a hydrogen atom or methyl group, n represents a number of 2 or 3, Z ₁ represents a group [Formula] (carboxyl group) is bonded at the 3- _or 4-position), chlorine atom or fluorine atom, B is -( _CH2 )m- (m represents 2 or 3): _{-C2H4OC 2} H ₄ −:
[Formula] p-phenylenediamine residue or m-phenylenediamine residue optionally substituted with a methyl group, methoxy group, sulfonic acid group, carboxylic acid group, or chlorine atom:
[Formula] (Q represents -O-, -SO ₂ -, -NHCO- or -NH-):
[Formula] Represents [Formula] or [Formula], respectively. However, the carboxyl group of the pyridine nucleus is 3- or 4-
It is assumed that they are connected to the position. ) A water-soluble azo compound represented by 2 Formula (1) in free acid form (In formula (1), X is a hydrogen atom, methyl group, methoxy group, or 2-methoxyethoxy group, Y is a hydrogen atom,
methyl group, methoxy group, acetylamino group or ureido group, R ₁ and R ₂ each independently represent a hydrogen atom or methyl group, n represents a number of 2 or 3, Z ₁ represents a group [Formula] (carboxyl group) is bonded at the 3- _or 4-position), chlorine atom or fluorine atom, B is -( _CH2 )m- (m represents 2 or 3): _{-C2H4OC 2} H ₄ −
[Formula] p-phenylenediamine residue or m-phenylenediamine residue optionally substituted with a methyl group, methoxy group, sulfonic acid group, carboxylic acid group, or chlorine atom:
[Formula] (Q represents -O-, -SO ₂ -, -NHCO- or -NH-):
[Formula] Represents [Formula] or [Formula], respectively. However, the carboxyl group of the pyridine nucleus is 3- or 4-
It is assumed that they are connected to the position. ) A method for dyeing cellulose or cellulose-containing fibrous materials, characterized by using a water-soluble azo compound represented by: