JPH0469190B2 - - 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. For more details, see the general formula () [In the formula, D is 1, 2 or 3 substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, halogen atom, acetylamino group, propionylamino group, nitro group, sulfo group and carboxyl group represents a phenyl group substituted by a group. X is a halogen atom, Y is -SO ₂ CH
=CH ₂ or -SO ₂ CH ₂ CH ₂ Z, Z is a group that is eliminated by the action of an alkali, A is a phenylene group or naphthylene group that may have a substituent, R ₁ ,
_R2 is each independently a hydrogen atom or an optionally substituted lower alkyl group, _R3 is an optionally substituted alkyl group, aralkyl group, or cyclohexyl group, _R4 is an alkyl group, an aralkyl group, or a cyclohexyl group, W is a direct bond, −CH ₂
-or

[Formula] Group (indicated by an asterisk) The bond is

[Formula] means a bond that leads to a group. ). ] The present invention relates to a monoazo compound or a salt thereof, and a method of dyeing or printing using the monoazo compound or a salt thereof. In the general formula (), the halogen atom represented by X is particularly preferably chlorine, bromine or fluorine. Examples of the group represented by Z which is eliminated by the action of an alkali include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, and a halogen atom. The compounds of the invention are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the soda, potassium and calcium salts. The compound of the present invention can be produced, for example, in the following manner. General formula below () (In the formula, R ₂ , R ₃ , R ₄ , and W have the above-mentioned meanings.) A pyridone derivative or a salt thereof represented by the following general formula () (In the formula, R ₁ , A, and Y have the above-mentioned meanings.) In an arbitrary order, the compounds represented by the formula are initially mixed in an aqueous medium at a temperature of -10°C to 40°C with a pH of 2 to 9.
while adjusting the pH at 0℃ to 70℃.
While adjusting the pH to 2 to 9, use the following general formula () (In the formula, X has the above meaning.) By condensing with a trihalogenotriazine represented by the following general formula () (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, W, X, and Y have the above-mentioned meanings.) A compound or a salt thereof is obtained. Next, an aromatic amine or a salt thereof represented by the following general formula () D-NH ₂ () (wherein D has the above-mentioned meaning) and a temperature of -10
A compound of general formula () or a salt thereof can be obtained by coupling at a temperature of 50°C to 50°C while adjusting the pH to 4 to 10. Alternatively, a pyridone derivative represented by the general formula () or a salt thereof and a trihalogenotriazine represented by the general formula () are mixed in an aqueous medium at a temperature of -10 to
After condensation at 40°C while adjusting the pH to 2 to 9, the aromatic amine represented by the general formula () or a salt thereof diazotized by a conventional method and a temperature of -10°C.
Coupling is carried out at a temperature of 0°C to 50°C while adjusting the pH to 4 to 10, and then a compound represented by the general formula () is coupled at a temperature of 0°C to 70°C with a pH of 2 to PH2.
The compound of the general formula () or a salt thereof can also be obtained by condensation while adjusting the amount of 9. Or N- of the compound represented by the general formula ()
The acylated product is coupled with a diazotized aromatic amine represented by the general formula () or its salt at a temperature of -10°C to 50°C while adjusting the pH to 4 to 10, and then 50°C in the presence of an acid or alkali.
Hydrolyzing the acyl group at a temperature of 100℃ to 100℃,
A compound represented by the following general formula () is obtained. (In the formula, R ₂ , R ₃ , R ₄ , D, and W have the above-mentioned meanings.) Next, the compound of formula () or a salt thereof and the compound represented by general formula () are mixed in an arbitrary order into an aqueous solution. In the medium, initially at a temperature of -10℃ to 40℃, PH2
While adjusting the pH to 9, the temperature is adjusted to 0℃.
The compound of the general formula () or a salt thereof can also be obtained by condensation with a trihalogenotriazine represented by the general formula () while adjusting the pH to 2 to 9 at 70°C to 70°C. The diazo component represented by the general formula () is:
For example, 2-aminobenzenesulfonic acid 2-amino-5-methylbenzenesulfonic acid 2-amino-5-ethylbenzenesulfonic acid 2-amino-5-methoxybenzenesulfonic acid 2-amino-5-ethoxybenzenesulfonic acid 2-amino -5-chlorobenzenesulfonic acid 2-amino-5-bromobenzenesulfonic acid 2-amino-5-acetylaminobenzenesulfonic acid 2-amino-5-propionylaminobenzenesulfonic acid 2-amino-5-nitrobenzenesulfonic acid 2-amino -4-chloro-5-methylbenzenesulfonic acid 2-amino-5-chloro-4-methylbenzenesulfonic acid 2-amino-4-methoxybenzenesulfonic acid 2-amino-4-methoxybenzenesulfonic acid 3-amino-4 -Methylbenzenesulfonic acid 3-amino-4-ethylbenzenesulfonic acid 3-amino-4-methoxybenzenesulfonic acid 3-amino-4-ethoxybenzenesulfonic acid 3-amino-4-chlorobenzenesulfonic acid 3-amino-4-bromo Benzenesulfonic acid 4-amino-3-methylbenzenesulfonic acid 4-amino-3-ethylbenzenesulfonic acid 4-amino-3-methoxybenzenesulfonic acid 4-amino-3-ethoxybenzenesulfonic acid 4-amino-3-chlorobenzenesulfone Acid 4-amino-3-nitrobenzenesulfonic acid 2-aminobenzene-1,4-disulfonic acid 2-aminobenzene-1,5-disulfonic acid 2-aminobenzoic acid 2-amino-4-methoxybenzoic acid 2-amino- 5-methoxybenzoic acid 2-amino-4-acetylaminobenzoic acid 2-amino-5-acetylaminobenzoic acid 2-amino-4-sulfobenzoic acid 2-amino-5-sulfobenzoic acid 4-amino-2,5 -dimethylbenzenesulfonic acid 4-amino-2,5-diethylbenzenesulfonic acid 4-amino-2,5-dimethoxybenzenesulfonic acid 4-amino-2,5-diethoxybenzenesulfonic acid 4-amino-2,5-dimethylbenzenesulfonic acid Chlorobenzenesulfonic acid 4-amino-2,5-dibromobenzenesulfonic acid 4-amino-2-methyl-5-methoxybenzenesulfonic acid 4-amino-2-methyl-5-ethoxybenzenesulfonic acid 2-amino-5-methyl Benzene-1,4-disulfonic acid 2-amino-5-ethylbenzene-1,4-disulfonic acid 2-amino-5-methoxybenzene-1,4-
2-amino-5-ethoxybenzene-1,4-disulfonic acid
2-amino-5-acetylaminobenzene disulfonic acid
1,4-disulfonic acid 2-amino-5-propionylaminobenzene-
Examples include 1,4-disulfonic acid. A is preferably one phenylene group or sulfo group optionally substituted with one or two substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfo group. A naphthylene group which may be substituted with, for example, the following.

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【formula】 (In the formula, the bond indicated with an asterisk is

[Formula] means a bond that leads to a group. ) In R ₁ and R ₂ , the lower alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and the optionally substituted groups include a hydroxy group, a cyano group, an alkoxy group, a halogen atom, A carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, and a sulfamoyl group are preferred. Particularly preferable R ₁ and R ₂ include, for example, hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, and
-propyl group, n-butyl group, iso-butyl group,
sec-butyl group, 2-hydroxyethyl group, 2-
Hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group base, 3
-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-3-methoxypropyl group, chloromethyl group , bromomethyl group,
2-chloroethyl group, 2-bromoethyl group, 3-
Chloropropyl group, 3-bromopropyl group, 4-
Chlorobutyl group, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group,
1,2-dicarboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 3-carbamoylpropyl group, 4-carbamoylbutyl group,
Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group,
2-ethoxycarbonylethyl group, 8-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group,
4-ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group,
2-ethylcarbonyloxyethyl group, 3-methylcarbonyloxypropyl group, 3-ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group,
Examples include 3-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfamoylethyl group, 3-sulfamoylpropyl group, and 4-sulfamoylbutyl group. The alkyl group represented by R ₃ and R ₄ is
Examples include linear or branched unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, nonyl group, and dodecyl group, and substituted alkyl groups represented by R ₃ Examples include hydroxyalkyl groups such as hydroxyethyl group and hydroxypropyl group, and alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, methoxypropyl group and butoxyethyl group. Examples of the aralkyl group represented by R ₃ and R ₄ include a benzyl group and a phenethyl group. Furthermore, R ₃ and R ₄ may each be a cyclohexyl group. The compound of the present invention has fiber reactivity and can be used for dyeing or printing hydroxy group-containing or carbonamide group-containing materials. The material is in the form of a fibrous material;
Alternatively, it is preferably used in the form of a blended material thereof. Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol. The cellulosic fiber material is preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose staple and filament viscose. Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4. It is. The compounds of the invention can be dyed or printed on the above-mentioned materials, in particular on the above-mentioned fiber materials, in a manner depending on their physical and chemical properties. For example, when exhaust dyeing is carried out on cellulose fibers, in the presence of an acid binder such as soda carbonate, sodium phosphate, or caustic soda, a neutral salt, such as mirabilite or common salt, is optionally added and, if desired, dissolved. It is carried out at relatively low temperatures using auxiliaries, penetrants or leveling agents. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after the actual dyeing temperature has been reached, or even before then, optionally in portions. When dyeing cellulose fibers according to the padding method, they can be padded at room temperature or at elevated temperatures and, after drying, fixed by steaming or dry heat. When printing is carried out on cellulose fibers, it can be carried out in one phase, for example by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-160°C, or in two phases. For example, it can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot alkaline bath containing an electrolyte, or overpadding with a padding liquid containing an alkaline electrolyte, followed by steaming or dry heat treatment. In the printing pastes, pastes or emulsifiers, such as, for example, sodium alginate or starch ethers, are used, if desired in combination with customary printing auxiliaries and/or dispersants, such as, for example, urea. Suitable acid binders for fixing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heated conditions. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Examples of such acid binders include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary, or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate, and the like. Dyeing of synthetic and natural polyamide and polyurethane fibers begins with an acidic or weakly acidic dye bath.
This can be done by controlling the exhaustion and then changing the pH value to a neutral, or even alkaline, value for fixation. Dyeing is usually carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as a condensation product of cyanuric chloride and 3 times the mole of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, addition products of stearylamine and ethylene oxide can also be used. The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials.
Particularly suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, sweat resistance, acid hydrolysis resistance and alkali resistance, Furthermore, it has good abrasion resistance and ironing resistance. In addition, it has excellent build-up properties, level dyeing properties, wash-off properties, good solubility, high exhaustion and fixation properties, and dyed products with stable quality that are not affected by fluctuations in dyeing temperature or dye bath ratio. It is characterized by the fact that it is Next, the present invention will be explained in more detail with reference to Examples. In the text, parts and % indicate parts by weight and % by weight. Example 1 9.2 parts of cyanuric chloride is added to 100 parts of water at 0 to 10°C and dispersed. To this, 1-ethyl-3-amino-
4-Methyl-6-hydroxy-2-pyridone 8.4
100 parts of an aqueous solution containing 100 parts of the solution was added dropwise at 0 to 5°C. After dropping, add 15% sodium carbonate aqueous solution to adjust the pH.
Adjust to 7-8. A diazotized solution of 8.7 parts of orthanilic acid in a conventional manner was added to this at 0 to 5°C for 1 hour, and at the same temperature, PH was added with a 15% aqueous sodium carbonate solution.
Stir until coupling is completed while adjusting the temperature to 5 to 6. Then, 1-N-ethylaminobenzene-3-
Add 15.5 parts of β-sulfatoethyl sulfone,
The temperature was raised to 40° C. while adjusting the pH to 5 to 6, and the mixture was stirred at the same temperature for 5 hours to obtain a monoazo compound having the following structural formula in the form of a free acid. λ _nax = 420 nm (in an aqueous medium, the same applies hereinafter) Example 2 In the same manner as in Example 1, using the diazo component listed in the column instead of ortanilic acid, 1-ethyl-3-
Using pyridone in column 1 instead of amino-4-methyl-6-hydroxy-2-pyridone, 1-N-
Ethylaminobenzene-3-β-sulfatoethylsulfone was replaced with the amine listed in column 1 to give the corresponding monoazo compound.

【table】

[Table] All monoazo compounds had λ _nax =420 nm. Example 3 9.2 parts of cyanuric chloride is added to 100 parts of water at 0 to 10°C and dispersed. To this, 1-aminobenzene-4-β
- Add 14.1 parts of sulfatoethyl sulfone to 0 to 0 while adjusting the pH to 5 to 7 with a 15% aqueous sodium carbonate solution.
Add at 10°C. Further, the mixture was stirred for 2 hours at the same temperature and pH. To this, N-ethyl-4-methyl-6-
A 15% aqueous solution of a pyridone derivative was prepared by reacting 7.6 parts of hydroxy-2-pyridone with a bisulfite adduct of 8.2 parts of 4-acetaminobenzaldehyde, followed by saponification of the acetyl group by boiling in an aqueous hydrochloric acid solution for 2 hours. Add it while adjusting the pH to 6-8 with aqueous sodium carbonate solution, raise the temperature to 30-40℃, and at the same temperature,
The mixture was stirred for 5 hours while adjusting the pH to 6-8. Next, a solution obtained by diazotizing 8.7 parts of orthanilic acid in a conventional manner was added at 0 to 5°C for 1 hour, and at the same temperature, the pH was adjusted to 6-7 with a 15% aqueous sodium carbonate solution until coupling was completed. The mixture was stirred to obtain a monoazo compound having the following structural formula in the form of a free acid. λ _nax = 420 nm Example 4 In the same manner as in Example 3, using the diazo component listed in the column instead of ortanilic acid, N-ethyl-4-
Using pyridone in the column instead of methyl-6-hydroxy-2-pyridone, 1-aminobenzene-
Instead of 4-β-sulfatoethyl sulfone,
The corresponding monoazo compounds were obtained using the amines in column 1.

[Table] All monoazo compounds had λ _nax =420 nm. Example 5 0.1, 0.3 and 0.6 parts of the monoazo compounds described in Example 1 were each dissolved in 200 parts of water, and 10 parts of Glauber's salt and cotton were added.
Add 10 parts, raise the temperature to 85°C, add 4 parts of soda carbonate, and dye for 1 hour. After washing with water, soaping, rinsing with water and drying, a bright yellow dyed product was obtained which was excellent in various fastnesses, especially fastness to sunlight, sweat, sunlight and chlorine, and had excellent build-up properties and good dischargeability. This compound also has excellent solubility, and has good level dyeing and dyeing reproducibility. Example 6 Similar performance is exhibited by dyeing the monoazo compounds described in Examples 2, 3 and 4 according to the method described in Example 5. Example 7 Add 14.1 parts of 1-aminobenzene-4-β-sulfatoethylsulfone to 100 parts of water, adjust the pH to 5-6 with sodium carbonate, and dissolve. Cool to 0°C, add 6.8 parts of 2,4,6-trifluoro-1,3-5-triazine dropwise, and simultaneously maintain the pH at 5-6 with a 15% aqueous sodium carbonate solution. After condensation, 1-ethyl-
Add a suspension of 9.1 parts of 3-aminomethyl-4-methyl-6-hydroxy-2-pyridone in 100 parts of water, adjust the pH to 6 to 8 with an aqueous solution of caustic soda, and adjust the pH with an aqueous solution of 15% sodium carbonate. While maintaining the temperature at 5 to 6, the temperature is raised to 20°C, and condensation is carried out at the same temperature and pH. Next, a diazotized solution of 10.2 parts of 2-amino-5-methoxybenzenesulfonic acid in a conventional manner was added at 0 to 5°C for 1 hour, and the mixture was stirred while adjusting the pH to 5 to 6 until coupling was completed. A monoazo compound having the following structural formula was obtained in the form of a free acid. λ _nax = 420 nm Example 8 In the same manner as in Example 7, using the diazo component in the column instead of 2-amino-5-methoxybenzenesulfonic acid, 1-ethyl-3-aminomethyl-
Using the pyridone in the column in place of 4-methyl-6-hydroxy-2-pyridone and the amine in the column in place of 1-aminobenzene-4-β-sulfatoethylsulfone, the corresponding monoazo compound was prepared. Obtained.

[Table] All monoazo compounds had λ _nax =420 nm. Example 9 Add 15.5 parts of 1-(N-ethylamino)-benzene-3-β-sulfatoethylsulfone to 200 parts of water, adjust the pH to 5-6 with sodium carbonate, and dissolve.
Cool to 0°C and add 2,4,6-trifluoro-
6.8 parts of 1,3,5-triazine was added dropwise at the same time.
% sodium carbonate aqueous solution to maintain the pH at 5-6. After condensation, N-ethyl-4-methyl-6-hydroxy-
An aqueous solution of a pyridone derivative prepared by reacting 7.6 parts of 2-pyridone with a bisulfite adduct of 8.2 parts of 3-acetaminobenzaldehyde and then boiling in an aqueous hydrochloric acid solution for 2 hours to saponify the acetyl group was
% sodium carbonate aqueous solution while adjusting the pH to 6-8, the temperature was raised to 30-40°C, and the mixture was stirred at the same temperature for 5 hours while adjusting the pH to 6-8. Next, a solution obtained by diazotizing 10.2 parts of 2-amino-5-methoxybenzenesulfonic acid in a conventional manner,
The mixture was added at 0 to 5°C for 1 hour, and stirred at the same temperature while adjusting the pH to 6 to 7 with a 15% aqueous sodium carbonate solution until coupling was completed to obtain a monoazo compound with the following structural formula in the form of a free acid. . λ _nax = 420 nm Example 10 In the same manner as in Example 9, using the diazo component in the column instead of 2-amino-5-methoxybenzenesulfonic acid, N-ethyl-4-methyl-6-hydroxy-2 - Using pyridone in the column instead of pyridone, 1-(N-ethylamino)-benzene-
The corresponding monoazo compound was obtained by substituting the amine in column 3 for 3-β-sulfatoethyl sulfone.

[Table] All monoazo compounds had λ _nax =420 nm. Example 11 0.1, 0.3 and 0.6 parts of each of the monoazo compounds described in Examples 7, 8, 9 and 10 were dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, and the temperature was raised to 60°C. Warm, add 4 parts of soda carbonate, and dye at the same temperature for 1 hour. Next, by washing, soaping, rinsing, and drying, a bright yellow dyed product with high build-up properties and excellent fastness is obtained, which has excellent discharge properties, and is less affected by dyeing temperature fluctuations and is stable. They are also excellent in providing quality products.

Claims (1)

[Claims] 1. The following general formula [In the formula, D is 1, 2 or 3 substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, halogen atom, acetylamino group, propionylamino group, nitro group, sulfo group and carboxyl group represents a phenyl group substituted by a group. X is a halogen atom, Y is -SO ₂ CH
=CH ₂ or -SO ₂ CH ₂ CH ₂ Z, Z is a group that is eliminated by the action of an alkali, A is a phenylene group or naphthylene group that may have a substituent, R ₁
and R ₂ are each independently a hydrogen atom or an optionally substituted lower alkyl group, R ₃ is an optionally substituted alkyl group, aralkyl group, or cyclohexyl group, and R ₄ is an alkyl group, an aralkyl group, or a cyclohexyl group. , W is a direct bond,
Represents -CH ₂ - or a [formula] group (the bond indicated by an asterisk means a bond that is connected to the [formula] group). ] A monoazo compound or a salt thereof. 2 General formula below [In the formula, D is 1, 2 or 3 substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, halogen atom, acetylamino group, propionylamino group, nitro group, sulfo group and carboxyl group represents a phenyl group substituted by a group. X is a halogen atom, Y is -SO ₂ CH
=CH ₂ or -SO ₂ CH ₂ CH ₂ Z, Z is a group that is eliminated by the action of an alkali, A is a phenylene group or naphthylene group that may have a substituent, R ₁
and R ₂ are each independently a hydrogen atom or an optionally substituted lower alkyl group, R ₃ is an optionally substituted alkyl group, aralkyl group, or cyclohexyl group, and R ₄ is an alkyl group, an aralkyl group, or a cyclohexyl group. , W is a direct bond,
Represents -CH ₂ - or a [formula] group (the bond indicated by an asterisk means a bond that is connected to the [formula] group). ] A method of dyeing or printing using a monoazo compound or a salt thereof.