JPH0556389B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a monoazo compound and a method for dyeing or printing using the same. Reactive dyes are widely used for dyeing and printing textile materials, but at present, the known orange to scarlet reactive dyes are still not satisfactory in terms of high requirements regarding build-up and fastness. Therefore, it is strongly desired to provide a further improved reactive dye. For example, in Japanese Patent Publication No. 39-18184, the following formula The dyes shown are listed. However, these dyes not only have low solubility and poor build-up properties, making it impossible to obtain dyed products with high density, but also have the disadvantage of extremely poor wash-off properties, so they have little practical value. . Furthermore, the latter dyes are particularly poor in light fastness. As a result of intensive research to improve the shortcomings of known dyes and develop a dye that satisfies various requirements for dye properties, the inventors of the present invention have developed an orange to scarlet dye with excellent build-up properties, fixation rate, and fastness. We have discovered a compound that gives dyed products with high density and completed the present invention. The present invention has the following general formula () in the form of a free acid: [In the formula, X represents chlorine, fluorine or carboxypyridinio group. Z is a group -CH= _CH2 or a group -
Represents CH ₂ CH ₂ A. A is a group that leaves with an alkali. Y represents a hydrogen atom or a sulfonic acid group. R ₁ represents a methyl group, an ethyl group, a methoxy group, or an ethoxy group. R ₂ is a hydrogen atom, a methyl group, or a group -
CH ₂ CH ₂ R ₆ (wherein R ₆ represents a hydrogen atom, a carboxylic acid group, a carbamoyl group, or a cyano group),
R ₃ represents a hydrogen atom or a methyl group. R ₄ and
R ₅ each independently represents a hydrogen atom or a sulfonic acid group. ] The present invention relates to a monoazo compound represented by the following or a salt thereof, and a method for dyeing or printing a fiber material using the same. The compound represented by the general formula () of the present invention can be produced, for example, in the following manner. General formula () [In the formula, R ₁ and R ₅ have the above meanings.] ] The compound represented by is diazotized at -10℃ to 40℃ to form the general formula () [In the formula, R ₃ and R ₄ have the above-mentioned meanings. ] A compound represented by the general formula () is coupled with a compound represented by the general formula () at a temperature of -10°C to 50°C, more preferably at a temperature of 0°C to 20°C, while adjusting the pH to 5 to 12, more preferably 6 to 10. [In the formula, R ₁ , R ₃ , R ₄ and R ₅ have the above meanings. ] A compound represented by is obtained. Alternatively, a similar coupling reaction is performed using an N-acylated product of general formula (), and then the acyl group is hydrolyzed at a temperature of 50 to 100 °C in the presence of an acid or alkali to form an N-acylated product of general formula (). Compounds can also be obtained. Then, the compound of general formula () is mixed in an aqueous medium at a temperature of -10°C to 50°C, more preferably 0°C to
A dichlorotriazinyl compound or a difluorotriazinyl compound is obtained by primary condensation with cyanuric chloride or cyanuric fluoride while adjusting the pH to PH2 to PH10, more preferably PH3 to 7 at 30°C, and then the general formula () [In the formula, Y, Z and R ₂ have the above meanings.] ] The reaction components shown are secondarily condensed at a temperature of 20°C to 80°C, more preferably 30°C to 50°C, while adjusting the pH to 2 to 9, more preferably 4 to 6, so that X is chlorine or fluorine. A compound of the general formula () can be obtained. Alternatively, as another method, the reaction components of the general formula () are mixed with cyanuric chloride or primary condensation with cyanuric fluoride,
Then the temperature is 0°C to 70°C, more preferably 20°C.
to 50℃, PH2 to PH9, more preferably
It can also be obtained by secondary condensation of the compound of general formula () while adjusting the pH to 4 to 6. On the other hand, for the compound of general formula () where X is a carboxypyridinio group, carboxypyridine is added to the compound of general formula () where X is chlorine or fluorine at 20°C.
100℃ to 100℃, more preferably 40℃ to 80℃
It can be obtained by reacting at a pH of 2 to 9, more preferably 4 to 7. The diazo component represented by the general formula () is
For example, 2-amino-5-methylbenzenesulfonic acid 2-amino-5-ethylbenzenesulfonic acid 2-amino-5-methoxybenzenesulfonic acid 2-amino-5-ethoxybenzenesulfonic acid 2-amino-5-methylbenzene- 1,4-disulfonic acid 2-amino-5-ethylbenzene-1,4-disulfonic acid 2-amino-5-methoxybenzene-1,4-
Disulfonic acid 2-amino-5-ethoxybenzene-1,4-
Examples include disulfonic acid. Examples of the reaction components represented by the general formula () include: [In the formula, the bond indicated with an asterisk is HR ₂ | N - group (in the formula,
R ₂ has the meaning given above. ) means a bond that leads to Z has the meaning given above. ] etc. can be raised. Preferred fiber materials that can be applied in the present invention include cellulose fibers such as cotton, viscose rayon, cuprammonium rayon, hemp, and polyesters containing cellulose fibers, triacetate, polyacrylonitrile, modified polyacrylonitrile, polyamide, wool, It is applicable to mixed fiber materials such as silk (cellulose-containing fiber materials) in any form such as yarn, fabric, skein, loose fiber, etc. In the case of the exhaust method, the dyeing of the present invention is carried out at a relatively low temperature in a dye bath containing Glauber's salt or common salt in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, or caustic soda. Dyeing can also be done by a textile printing method. For example, a color paste containing an acid binder such as bicarbonate of soda, soda carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, is printed on the fiber, and after intermediate drying, 100% This is done by steaming or dry heating at ~200°C. Furthermore, the dyeing of the present invention may be carried out by a continuous method, or cold patch batch dyeing is also possible. The compound of the present invention obtained in this manner has good build-up properties, and the dyed product has good chlorine fastness and
It has excellent sweat fastness to sunlight and good acid stability. In addition, the compound of the present invention has good alkali stability and shows a high exhaustion rate and fixation rate in exhaust dyeing, and also shows a high fixation rate in textile printing, so it is not only possible to obtain dyed products with high density. At the same time, it has excellent wash-off properties and has the great advantage that unfixed dye can be easily removed. Furthermore, the compound of the present invention has the unique ability to be hardly affected by changes in dyeing temperature, alkali agent, inorganic salt addition amount, and bath ratio in exhaust dyeing, and allows dyeing to be carried out with extremely high reproducibility. In addition, the compound of the present invention exhibits excellent build-up properties and excellent alkali stability in cold batch up dyeing, and shows almost no difference in density or hue between fixation at low temperatures and fixation at 25°C, and also shows excellent alkali stability. It has the ability to be resistant to hydrolysis by agents. Next, the present invention will be explained with reference to examples. In the text,
Parts represent parts by weight. Example 1 9.2 parts of cyanuric chloride is added to a solution in which 0.1 part of a nonionic surfactant is dissolved in 100 parts of water at 0 to 5°C and dispersed. To this, add 11.3 parts of J acid to 100 parts of water, pH 7.
The solution dissolved in step 8 is added dropwise at 0 to 5°C over 1 hour. After the addition is complete, 20% aqueous sodium carbonate solution is added to adjust the pH to 3, and the mixture is further stirred for 2 hours. Then 2-N-cyanoethylaminonaphthalene-6-
Add 19 parts of β-hydroxyethylsulfone sulfate and raise the temperature to 40° C. while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution, and stir at the same temperature for 6 hours. Then, after cooling again to 0-5°C, 12.6 parts of sodium bicarbonate are added. To this, 2-amino-
A solution obtained by diazotizing 9.6 parts of 5-methoxybenzenesulfonic acid in a conventional manner is added at 0 to 5°C over 1 hour. After stirring at the same temperature for 2 hours, adjust the pH to 5 with hydrochloric acid.
~ 6, add 40 parts of sodium chloride to precipitate crystals, suction filtrate, wash and dry at 60°C to obtain the following formula (1) in the form of free acid: A monoazo compound represented by (λmax 502 nm) was obtained. Example 2 2-Amino-
A compound obtained by carrying out the same operation as in Example 1 except that 14.4 parts of 1-sulfonaphthalene-6-β-hydroxyethylsulfone was used was added in 500 parts of 100% sulfuric acid at a temperature of 5 to 20°C. Add the mixture over time and stir at the same temperature for 3 hours. Next, the mixture is slowly distilled into 1200 parts of ice, and the precipitated crystals are separated. The obtained crystals were dispersed in 400 parts of water, and sodium carbonate was added to adjust the pH to 5 to 6. After dissolving, 60 parts of sodium chloride was added to precipitate the crystals again. After washing by suction, the crystals were heated at 60°C. In the dry free acid form, the formula (2) below: A monoazo compound represented by (λmax505nm) was obtained. Example 3 In Example 1, in place of 2-amino-5-methoxybenzenesulfonic acid, the compound () in the second column of the table below was used, in place of J acid, the compound () in the third column was used, and in place of the J acid, the compound () in the third column was used. Cyanuric chloride or cyanuric fluoride shown in the column (in the column, Cl indicates cyanuric chloride, F indicates cyanuric fluoride) in place of 2-N-cyanoethylaminonaphthalene-6-β-hydroxyethylsulfonic acid sulfate, Synthesized in the same manner as in Example 1 using the compound () in column 5,
Monoazo compounds (1) to (27) were obtained.

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[Table] Example 4 2-amino-5-ethoxybenzene-1,4-
7-Amino-4-hydroxy-3- synthesized from 13 parts of disulfonic acid diazonium salt and 12 parts of J acid
While maintaining the pH of (2-sulfo-4-ethoxyphenylazo)naphthalene-2-sulfonic acid at 4 to 5 with a 20% aqueous sodium carbonate solution over 1 hour, 9.2 parts of cyanuric fluoride was added dropwise to the solution at a temperature of 0 to 10. Stir at ℃ for 2 hours. Subsequently, 20 parts of 2-N-carbamoylethylaminonaphthalene-6-β-hydroxyethylsulfone sulfate was added, and the temperature was raised to 50°C while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution. Stir for an hour. Then, 40 parts of sodium chloride was added to precipitate crystals, which were suctioned, filtered, washed, and dried at 60°C to give the following formula (3) in the form of free acid: A monoazo compound represented by (λmax503nm) was obtained. Example 5 Example 4 was carried out using the compounds in columns 2 to 5 of the table below.
Monoazo compounds (1) to (27) were obtained in the same manner as above.

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[Table] Example 6 9.2 parts of cyanuric chloride is added to a solution in which 0.1 part of a nonionic surfactant is dissolved in 100 parts of water at 0 to 5°C and dispersed. To this, 15.1 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid was added to water.
A solution prepared by dissolving 200 parts at pH 7 to 8 is added dropwise at 0 to 5°C over 1 hour. After the addition is complete, 20% aqueous sodium carbonate solution is added to adjust the pH to 3, and the mixture is further stirred for 2 hours. Then, add 14 parts of sodium bicarbonate. A solution obtained by diazotizing 9.6 parts of 2-amino-5-methoxybenzenesulfonic acid in a conventional manner is added to this at 0 to 5°C over 1 hour. After stirring at the same temperature for 4 hours, the pH was adjusted to 5-6 with hydrochloric acid, and then 2 hours.
-N-methylaminonaphthalene-6-sulfo-8
-β-Hydroxyethylsulfone sulfate ester
Add 19.7 parts and raise the temperature to 40℃ while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution.
Stir for an hour. Add 40 parts of sodium chloride to precipitate crystals,
After suction filtering, washing, and drying at 60℃, the following formula (4) is obtained in the form of free acid. A monoazo compound represented by (λmax502nm) was obtained. Example 7 Example 6 using the compounds in columns 2 to 5 of the table below
Monoazo compounds (1) to (9) were obtained in the same manner as above.

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[Table] Example 8 2-Amino-
A compound obtained by carrying out exactly the same operation as in Example 1 except for using 14.4 parts of 1-sulfonaphthalene-6-β-hydroxyethylsulfone was added to 500 parts of 100% sulfuric acid at a temperature of 5 to 20°C for 2 hours. and stirred at the same temperature for 3 hours. Next, the mixture is slowly distilled into 1200 parts of ice, and the precipitated crystals are separated. The obtained crystals were dispersed in 400 parts of water, and sodium carbonate was added to adjust the pH to 5 to 6. After dissolving, 12.3 parts of nicotinic acid was added and the pH was adjusted to 5 to 6 using dilute sulfuric acid at 50 to 60°C. adjust. 3 in the PH range at the same temperature
Stir for an hour. Next, 40 parts of sodium chloride was added to precipitate crystals, which were filtered off by suction and dried at 60°C, resulting in the following formula (5) in the form of free acid: A monoazo compound represented by (λmax505nm) was obtained. Example 9 Example 8 using the compounds in columns 2 to 5 below
Monoazo compounds (1) to (27) were obtained in the same manner as above.

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[Table] Staining example 1 0.3 parts of the monoazo compound (1) obtained in Example 1
Dissolve in 200 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 50°C. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a highly concentrated scarlet dyed product with excellent chlorine fastness, sweat and sunlight fastness, and good build-up properties. Staining example 2 0.3 parts of the monoazo compound (2) obtained in Example 2
Dissolve in 150 parts of water, add 30 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60°C. Then, after 20 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a highly concentrated scarlet dyed product with excellent chlorine fastness, sweat and sunlight fastness, and good build-up properties. Staining example 3 Monoazo compounds (1) to (27) obtained in Example 3
Dissolve 0.3 parts of each in 300 parts of water, add 30 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60°C. Then 20
After 5 minutes, 5 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a highly concentrated scarlet dyed product with excellent chlorine fastness and sweat/sunlight fastness, and good build-up properties. Staining example 4 0.3 parts of the monoazo compound (3) obtained in Example 4
Dissolve in 200 parts of water, add 30 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 50°C. After 30 minutes, 4 parts of tribasic sodium phosphate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a highly concentrated scarlet dyed product with excellent chlorine fastness, sweat and sunlight fastness, and good build-up properties. Dyeing Example 5 Monoazo compounds (1) to (27) obtained in colored paste composition Example 5
5 parts each Urea 5 parts Sodium alginate (5%) Base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts The color paste having the above composition was printed on mercerized cotton broadcloth, and after intermediate drying, 100 parts Steam for 5 minutes at ℃, wash with hot water, soak, wash with hot water, and finish by drying. In this way, a scarlet printed product with a high fixation rate, excellent fastness to chlorine, fastness to sweat and sunlight, and good build-up properties was obtained. Dyeing Example 6 Color paste composition Monoazo compound obtained in Example 6 (4) 4 parts Urea 5 parts Sodium alginate (5%) Base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 14 parts The color paste is printed on mercerized cotton broadcloth, and after intermediate drying, it is steamed at 120°C for 5 minutes, washed with hot water, soaped, washed with hot water, and dried to finish. In this way, an orange printed material with a high fixation rate, excellent chlorine fastness, sweat and sunlight fastness, and good build-up properties was obtained. Dyeing Example 7 25 parts each of the monoazo compounds (1) to (9) obtained in Example 7 are dissolved in hot water and cooled to 25°C. Immediately after adding 5.5 parts of a 32.5% caustic soda aqueous solution and 150 parts of water glass at 50 degrees Baumé and further adding water to bring the total volume to 1000 parts at 25°C, this liquid was used as a padding liquid to wind up a cotton fabric. , Seal with polyethylene film and store indoors at 20℃. Cotton fabrics padded in the same manner, rolled up and sealed with polyethylene film are stored indoors at 5°C. After each padding cloth has been left for 20 hours, the dyeing is washed in cold and then hot water, soaped in boiling detergent, washed in cold water and dried. When we investigated the differences in density hue and density between dyed products left at 20°C for 20 hours and dyed products left at 5°C for 20 hours, almost no differences were observed. In addition, a dyed product with good build-up properties was obtained by cold batch up dyeing. Dyeing Example 8 Using 25 parts of the monoazo compound (5) obtained in Example 8, dyeing was carried out by the cold batch up method in the same manner as in Dyeing Example 7 to obtain a dyed product with good build-up properties, and further at 20°C. When the difference in density and hue of the dyed product left at 5° C. and the dyed product left at 5° C. were examined, almost no difference was observed. Staining example 9 Monoazo compounds (1) to (27) obtained in Example 9
Dissolve 25 parts of each in hot water and cool to 25°C. Immediately after adding 10 parts of a 32.5% caustic soda aqueous solution and 30 parts of anhydrous sodium sulfate and further adding water to bring the total amount to 1000 parts at 25°C, this liquid was used as a padding liquid to pad a viscose rayon fabric. do. The padded viscose rayon fabric is rolled up, sealed with polyethylene film and stored indoors at 20°C. In a similar manner, viscose rayon fabrics sealed with padded rolled polyethylene film are stored indoors at 5°C. After each padding cloth has been left for 20 hours, the dyeing is washed in cold and then hot water, soaped in boiling detergent, washed in cold water and dried. When we examined the differences in density hue and density between the dyed product left at 20°C for 20 hours and the dyed product left at 5°C for 20 hours, almost no differences were observed. Staining example 10 Monoazo compounds (1) to (27) obtained in Example 3
Using 20 parts of each of When the difference in density and the difference in density and hue were examined, almost no difference was observed.

Claims (1)

[Claims] 1 The following general formula () in the form of a free acid: [In the formula, X represents chlorine, fluorine or carboxypyridinio group. Z is a group -CH= _CH2 or a group -
It represents CH ₂ CH ₂ A, where A is a group that is eliminated with an alkali. Y represents a hydrogen atom or a sulfonic acid group. R ₁ represents a methyl group, an ethyl group, a methoxy group, or an ethoxy group. R ₂ is a hydrogen atom, a methyl group,
or a group -CH ₂ CH ₂ R ₆ (in the formula, R ₆ represents a hydrogen atom, a carboxylic acid group, a carbamoyl group, or a cyano group), and R ₃ represents a hydrogen atom or a methyl group.
R ₄ and R ₅ each independently represent a hydrogen atom or a sulfonic acid group. ] A monoazo compound or a salt thereof. 2 The following general formula () in the form of free acid: [In the formula, X represents chlorine, fluorine or carboxypyridinio group. Z is a group -CH= _CH2 or a group -
Represents CH ₂ CH ₂ A. A is a group that leaves with an alkali. Y represents a hydrogen atom or a sulfonic acid group. R ₁ represents a methyl group, an ethyl group, a methoxy group, or an ethoxy group. R ₂ is a hydrogen atom, a methyl group,
or a group -CH ₂ CH ₂ R ₆ (in the formula, R ₆ represents a hydrogen atom, a carboxylic acid group, a carbamoyl group, or a cyano group), and R ₃ represents a hydrogen atom or a methyl group.
R ₄ and R ₅ each independently represent a hydrogen atom or a sulfonic acid group. ] A method for dyeing or printing textile materials, characterized by using a monoazo compound represented by the following or a salt thereof.