JPH0149304B2 - - 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, X is a chlorine atom or _a fluorine atom, Y is _-SO2CH = _{CH2 or -SO2CH2CH2Z} , Z is a group that is eliminated by the action of an alkali, A is a methyl group, Ethyl group, methoxy group, ethoxy group, chlorine,
a phenylene group optionally substituted with one or two substituents selected from the group of bromine and sulfo groups, or a naphthylene group optionally substituted with one sulfo group, R ₁ is a hydroxy group, a cyano group,
An alkyl group having 1 to 4 carbon atoms optionally substituted with a methoxy group, a chlorine atom, a carboxy group, a carbamoyl group, a sulfo group or a sulfamoyl group, R ₃ is a hydrogen atom, a methyl group or a sulfo group, R ₄ is a hydrogen atom, a cyano group, a carbamoyl group, a sulfo group, a sulfomethyl group, or a sulfoethyl group, and _R5 is a methyl group, an ethyl group, a phenethyl group, a cyclohexyl group, or a memethyl group, a methoxy group, a dimethylamino group, a diethylamino group, and a chlorine atom represents a benzyl group optionally substituted with a substituent selected from the group of ] 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 (), Y is a group -SO ₂ CH
=CH ₂ or a group -SO ₂ CH ₂ CH ₂ Z, where Z is a group that is eliminated by the action of an alkali, such as a sulfate group, a thiosulfate group, a phosphate group, an acetic acid ester group, Ester groups, halogen atoms, etc. fall under this category. A is substituted with one phenylene group or sulfo group, which may be substituted with one or two substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfo group. is a naphthylene group which may be

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

[Formula] means a bond that leads to a group. ), etc. R ₁ is an optionally substituted alkyl group having 1 to 4 carbon atoms, and the groups optionally substituted with this alkyl group include a hydroxy group, a cyano group, a methoxy group, a chlorine atom, carboxy group,
These are carbamoyl group, sulfo group, and sulfamoyl group. Particularly preferred R ₁ include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group. 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, 3-cyanopropyl group, methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2-hydroxy-
3-methoxypropyl group, chloromethyl group, 2-
Chloroethyl group, 3-chloropropyl group, 4-chlorobutyl 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, sulfomethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4 -sulfobutyl group, sulfamoylmethyl group, 2-sulfamoylethyl group, 3-sulfamoylpropyl group, 4-sulfamoylbutyl group, and the like. R ₅ is a methyl group, an ethyl group, a phenethyl group,
It is a cyclohexyl group or a benzyl group which may be substituted, and the groups which may be substituted with the benzyl group are a methyl group, a methoxy group, a dimethylamino group, a diethylamino group, and a chlorine atom. The optionally substituted benzyl group represented by R ₅ is a benzyl group, p-methylbenzyl group, m-methylbenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, p-dimethylamino or diethylaminobenzyl group. and p-chlorobenzyl group. 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, potash, calcium salts. The compound of the present invention can be produced, for example, as follows. General formula below () (In the formula, R ₃ has the above meaning.) An aromatic sulfonic acid or a salt thereof represented by the following general formula () (In the formula, R ₁ , A, and Y have the above meanings.)
In an arbitrary order, the compounds represented by are initially mixed in an aqueous medium at a temperature of -10°C to 40°C with a pH of 2 to 9.
The temperature should be adjusted to 0°C to 70°C.
While adjusting the PH2 to PH9, 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 ₃ , A, X, and Y have the above-mentioned meanings.) A compound or a salt thereof is obtained. Next, the compound of general formula () or its salt is diazotized in an aqueous medium by a conventional method to obtain the following general formula (). (In the formula, R ₄ and R ₅ have the above-mentioned meanings.) The pyridone derivative or its salt represented by
By coupling at 10℃ to 50℃ while adjusting the pH to 4 to 10, the general formula ()
or a salt thereof can be obtained. Alternatively, an aromatic sulfonic acid or a salt thereof represented by the general formula () and a trihalogenotriazine represented by the general formula () are condensed in an aqueous medium at a temperature of -10°C to 40°C while adjusting the pH to 2 to 9. After that, it is diazotized by a conventional method and coupled with a pyridone derivative 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 the general formula ()
The compound represented by PH2 at a temperature of 0℃ to 70℃
The compound of the general formula () or a salt thereof can also be obtained by condensation while adjusting the pH to 9 to 9. Alternatively, a monoacylated compound represented by the general formula () is diazotized and coupled with a pyridone derivative represented by the general formula () or a salt thereof at a temperature of -10°C to 50°C while adjusting the pH to 4 to 10, and then 50℃ in the presence of acid or alkali
Hydrolyzing the acyl group at a temperature of 100℃ to 100℃,
General formula below () (In the formula, R ₃ , R ₄ and R ₅ have the above-mentioned meanings.) A compound or a salt thereof is obtained. Then,
A compound of formula () or a salt thereof and general formula ()
The compounds represented by are mixed in an aqueous medium in any order, firstly at a temperature of -10°C to 40°C to adjust the pH to PH2 to PH9, and secondarily at a temperature of 0°C to 70°C to adjust the pH to PH2 to PH9. 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 trihalogenotriazine. 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. Preferably, the material is used in the form of a fibrous material or a blend 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. Preferably, the cellulosic fiber material is cotton or other vegetable fibers such as linen, hemp, juute and mirror fibers. Regenerated cellulose fiber is
Examples are 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-11. It is 4. The compounds of the present invention can be dyed or printed on the above-mentioned materials, especially 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 triphosphate, caustic soda, etc., 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 temperature and, after drying, fixed by steaming or dry heat. When printing is carried out on cellulose fibers, it can be done 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. This can be carried out, for example, 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. Thickening agents or emulsifiers, such as sodium alginate or starch ethers, are used in the printing pastes, if desired in combination with customary printing auxiliaries and/or dispersants, such as urea, for example. 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 that liberate alkali when heated. be. 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. Such acid binders include, for example, caustic soda, caustic potash, baking soda, soda carbonate, sodium formate, potassium carbonate,
Examples include secondary or tertiary sodium phosphate, sodium silicate, and sodium trichloroacetate. The dyeing of synthetic and natural polyamide and polyurethane fibers involves first exhaustion under pH control from an acidic or slightly acidic dye bath, and then changing to a neutral or even alkaline pH value for fixation. This can be done by 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 molar amount 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. Especially suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, chlorine water resistance, chlorine bleaching resistance, sweat resistance , has acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and ironing resistance. Also has excellent build up properties,
It is characterized by level dyeing and wash-off properties, good solubility, high exhaustion and fixation properties, and the ability to obtain dyed products of stable quality that are not affected by fluctuations in dyeing temperature or dye bath ratio. . The present invention will be explained in detail below with reference to Examples. In the examples, parts and % mean parts by weight and % by weight, respectively. Example 1 10.1 parts of cyanuric chloride is added to 100 parts of water at 0 to 10°C and dispersed. A suspension of 9.4 parts of 2,5-diaminobenzenesulfonic acid and 100 parts of water, adjusted to pH 6-9 with an aqueous solution of caustic soda, was added dropwise at 0-5°C. After dropping, add 20% sodium carbonate aqueous solution to adjust the pH.
Adjust to 7-8. Then sodium nitrite 3.5
12.7 parts of concentrated hydrochloric acid was added at 0 to 5°C to diazotize the mixture. This diazo suspension was added to a suspension of 11.8 parts of 1-ethyl-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone and 100 parts of water, adjusted to pH 5 to 6 with an aqueous solution of caustic soda. Add another 5 parts of sodium bicarbonate and stir until coupling is complete. Then 1-N-ethylaminobenzene-3-β
- Add 17.0 parts of sulfatoethyl sulfone, and PH
Raise the temperature to 40℃ while adjusting the temperature to 5 to 6, and then increase the temperature to 5
The mixture was stirred for a period of time to obtain a monoazo compound having the following structural formula. (λmax = 422 nm, however, in an aqueous solvent, measured under the same conditions below) Example 2 In the same manner as in Example 1, 1-ethyl-3-carbamoyl-4-methyl-6-hydroxy-2-
Use pyridone in the following table column instead of pyridone,
Using the diamine in the following table column instead of 2,5-diaminobenzenesulfonic acid, and using the amine in the following table column in place of 1-N-ethylaminobenzene-3-β-sulfatoethyl sulfone, The corresponding monoazo compound was obtained.

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[Table] Example 3 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, soaping, rinsing and drying, a bright yellow dyed product was obtained which had excellent fastness to sunlight, sweat, sunlight and chlorine, and had very good build-up and discharge properties. This compound also has excellent solubility, and has good level dyeing and dyeing reproducibility. Example 4 A similar performance is exhibited by using the monoazo compound described in Example 2 and dyeing according to the method described in Example 3. Example 5 Add 9.4 parts of 2,5-diaminobenzenesulfonic acid to 100 parts of water, adjust the pH to 5-6 with aqueous caustic soda solution, and dissolve. Cool to 0°C, add 7.4 parts of 2,4,6-trifluoro-1,3,5-triazine dropwise, and simultaneously maintain pH 5-6 with 15% aqueous sodium carbonate solution. After condensation, add a suspension of 16.2 parts of 1-N-methylamino-4-β-sulfatoethylsulfone and 100 parts of water, adjusted to pH 4 to 6, and maintain the pH at 5 to 6 with an aqueous sodium carbonate solution. At the same time, the temperature was raised to 20°C, and condensation was carried out at the same temperature and pH. Next, add and dissolve 3.5 parts of sodium nitrite,
Diazotization is carried out by injecting 12.7 parts of concentrated hydrochloric acid at 0 to 5°C, and then 1-ethyl-3-carbamoyl-4-
A suspension of 11.8 parts of methyl-6-hydroxy-2-pyridone and 100 parts of water was adjusted to pH 5-6 with an aqueous solution of caustic soda.
Add the solution adjusted to
While adjusting the pH to 5 to 6, the mixture was stirred until coupling was completed to obtain a monoazo compound having the following structural formula. Example 6 In the same manner as in Example 5, 2,5
- Using diamines listed in the following table column instead of diaminobenzenesulfonic acid, 1-N-methylamino-4
-β-Sulfatoethyl sulfone was replaced with the amine listed in the following table column to obtain the corresponding monoazo compound.

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[Table] Example 7 0.1, 0.8 and 0.6 parts of each of the monoazo compounds described in Examples 5 and 6 were added to water.
Dissolve in 200 parts, add 10 parts of Glauber's salt and 10 parts of cotton, and mix at 60℃.
Add 4 parts of soda carbonate and dye at the same temperature for 1 hour. Next, by washing with water, soaping, rinsing with water and drying, a bright yellow dyed product with high build-up properties and excellent various fastnesses was obtained. It has excellent discharge printing properties, is less susceptible to fluctuations in dyeing temperature, and is also excellent in providing dyed products of stable quality.

Claims (1)

[Claims] 1. The following general formula [In the formula, X is a chlorine atom or _a fluorine atom, Y is _-SO2CH = _{CH2 or -SO2CH2CH2Z} , Z is a group that is eliminated by the action of an alkali, A is a methyl group, Ethyl group, methoxy group, ethoxy group, chlorine,
a phenylene group optionally substituted with one or two substituents selected from the group of bromine and sulfo groups, or a naphthylene group optionally substituted with one sulfo group, R ₁ is a hydroxy group, a cyano group,
An alkyl group having 1 to 4 carbon atoms optionally substituted with a methoxy group, a chlorine atom, a carboxy group, a carbamoyl group, a sulfo group or a sulfamoyl group, R ₃ is a hydrogen atom, a methyl group or a sulfo group, R ₄ is a hydrogen atom, a cyano group, a carbamoyl group, a sulfo group, a sulfomethyl group, or a sulfoethyl group, _R5 is a methyl group, an ethyl group, a phenethyl group,
Represents a cyclohexyl group or a benzyl group optionally substituted with a substituent selected from the group consisting of a methyl group, a methoxy group, a dimethylamino group, a diethylamino group, and a chlorine atom. ] A monoazo compound or a salt thereof. 2 General formula below [In the formula, X is a chlorine atom or _a fluorine atom, Y is _-SO2CH = _{CH2 or -SO2CH2CH2Z} , Z is a group that is eliminated by the action of an alkali, A is a methyl group, Ethyl group, methoxy group, ethoxy group, chlorine,
a phenylene group optionally substituted with one or two substituents selected from the group of bromine and sulfo groups, or a naphthylene group optionally substituted with one sulfo group, R ₁ is a hydroxy group, a cyano group,
An alkyl group having 1 to 4 carbon atoms optionally substituted with a methoxy group, a chlorine atom, a carboxy group, a carbamoyl group, a sulfo group or a sulfamoyl group, R ₃ is a hydrogen atom, a methyl group or a sulfo group, R ₄ is a hydrogen atom, a cyano group, a carbamoyl group, a sulfo group, a sulfomethyl group, or a sulfoethyl group, _R5 is a methyl group, an ethyl group, a phenethyl group,
Represents a cyclohexyl group or a benzyl group optionally substituted with a substituent selected from the group consisting of a methyl group, a methoxy group, a dimethylamino group, a diethylamino group, and a chlorine atom. ] A method for dyeing or printing a hydroxy group-containing or carbonamide group-containing material, the method comprising using a monoazo compound or a salt thereof shown in the following.