JPH0446304B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a di-copper-containing bisazo compound and a method for dyeing or printing using the same. More particularly, the present invention relates to a copper bisazo compound and a method for dyeing or printing textile materials in navy color using the same as a fiber-reactive dye. Reactive dyes having a copper-containing monoazo or copper-containing bisazo skeleton in the molecular structure of the dye are known, but they have poor fastness properties such as sweat resistance, sunlight resistance, chlorine water resistance, peroxide washing fastness, etc. Performance was inadequate and there were unresolved technical points. For these reasons, the inventors of the present invention have made extensive studies and have found that a novel di-copper-containing bisazo compound can solve the above-mentioned problems, leading to the completion of the present invention. That is, the present invention is based on the following general formula () [Wherein, X is a halogen atom, R is a hydrogen atom, or hydroxy, cyano, alkoxy, halogen, carboxy, carbamoyl, alkoxycarbonyl,
a lower alkyl group optionally substituted with alkylcarbonyloxy, sulfo or sulfamoyl, A is methyl, ethyl, methoxy, ethoxy,
A phenylene group optionally substituted with one or two substituents or a naphthylene group optionally substituted with one sulfo group selected from the group of chlorine, bromine and sulfo, Y is -SO ₂ CH=CH ₂ Or-
SO ₂ CH ₂ CH ₂ Z (Z represents a group that is eliminated by the action of an alkali), and n represents 0 or 1. ] The present invention provides a di-copper-containing bisazo compound or a salt thereof, and a method for dyeing or printing using the same. In the general formula (), the halogen atom represented by X includes fluorine, chlorine, and bromine atoms, and preferably fluorine and chlorine atoms. A substituent other than a hydrogen atom represented by R, i.e.
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 group, a carboxy group, a carbamoyl group, and an alkoxycarbonyl group. , an alkylcarbonyloxy group, a sulfo group, and a sulfamoyl group are preferred. Particularly preferable examples of R include hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, 2-hydroxyethyl group, 2-hydroxy Propyl 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, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-3-methoxypropyl group, chloromethyl group, bromomomethyl 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-carbomoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 3-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, 3-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfamoylethyl group, 3
Examples include -sulfamoylpropyl group and 4-sulfamoylbutyl group. In the general formula (), A is preferably
Methyl group, ethyl group, methoxy group, ethoxy group,
selected from the group of chlorine, bromine and sulfonic acid groups,
A phenylene group optionally substituted with one or two substituents or a naphthylene group optionally substituted with one sulfonic acid group, such as

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

[Formula] means a bond that leads to a group). And Y is a group -SO ₂ CH=CH ₂ or a group -
Represents SO ₂ CH ₂ CH ₂ Z, where Z is a group that is eliminated with an alkali, such as a sulfate ester group,
This includes a thiosulfate group, a phosphate group, an acetate group, a halogen atom, and the like. The compound of the present invention can be produced by a known method or in accordance with a known method. For example, as the free acid, the formula (In the formula, n has the above meaning.) A compound represented by the following general formula () [In the formula, Y, A and R have the above meanings. ] in an aqueous medium in any order,
Primarily at -10 to 40℃ and PH1 to 9, secondarily at 0 to 70℃ and PH2 to 9, the following general formula () [In the formula, X has the above meaning. ] It can be produced by condensation with the trihalogenotriazine shown below. Depending on the reaction conditions, the starting compounds mentioned are used in the form of acids and/or salts, in particular alkali metal or alkaline earth metal salts. The compounds of the invention may exist in the form of free acids, but are preferably alkali metal or alkaline earth metal salts, especially sodium or potassium salts. In order to use the compound of the present invention as a desired counterion,
This can be done by selecting the type of counter ion of the starting compound, the type of alkaline agent used to neutralize the acid during the production process, or the type of electrolyte used in salting out and isolation if necessary. The di-copper-containing bisazo compound produced according to the present invention may be made into a liquid product by removing the inorganic salt and adding a stabilizer or a dyeability improver if necessary, or the liquid product may be made into a liquid product. Alternatively, the reaction solution can be made into a powder product by evaporation, for example, by spray drying, and can also be made into a liquid or powder product through salting out separation by addition of an electrolyte using a generally known method. 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. The cellulosic fiber material is preferably cotton, but also other vegetable fibers such as linen, hemp, juute 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 present 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, 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 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. Thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used in the printing pastes, 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 acidic or weakly acidic dyeing and PH.
This can be done by controlling the exhaustion and then changing the PH value to a neutral, or even alkaline, value for fixation. Dyeing can usually be 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.
It is particularly suitable for dyeing cellulose fiber materials, and has good light resistance and excellent sweat resistance, sunlight resistance, chlorine water resistance, and peroxide washing fastness. 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 distinctive in that it can be obtained. The present invention will be explained in detail below with reference to Examples. In the examples, parts and % indicate parts by weight and % by weight, respectively. Example 1 4.61 parts of cyanuric chloride and 1-N-ethylaminobenzene-3-β-sulfatoethyl sulfone
7.64 parts in 50 parts of water for about 3 hours at 5±3℃, PH5±
1, and then in the form of the free acid, the following formula Add 24.66 parts of the compound shown in 30~ for about 6 hours.
The second condensation is carried out by keeping at 40℃ and pH5±1, and in the form of free acid, the following formula (λmax=590 nm, however, measured in an aqueous solvent) A compound represented by the following was obtained. Dissolve 0.1, 0.3 and 0.6 parts of this compound in 200 parts of water, add 10 parts of Glauber's salt and 10 parts of cotton, heat to 60°C, add 4 parts of soda carbonate and dye for 1 hour. Washing with water, soaping, washing with water and drying yielded a navy colored dyed product which was excellent in various fastnesses, particularly sweat, sunlight, chlorine water and peroxide washing fastnesses, and had extremely good build-up properties. This compound also had excellent solubility, and showed good level dyeing and dyeing reproducibility. Example 2 In Example 1, in place of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone, equivalent moles of the following amines were used, and the corresponding copper-containing bisazo compound was prepared in the same manner. Obtained.

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[Table] Example 3 Each of the invention compounds described in Example 2 was dyed according to the method described in Example 1, and the same performance as that of the compound described in Example 1 was exhibited. Example 4 The compounds described in Examples 1 and 2 were synthesized in the same manner as in Example 1, except that an equimolar amount of cyanuric fluoride was used instead of the cyanuric chloride used in the synthesis, and the corresponding compounds were synthesized in the same manner as in Example 1. A copper-containing bisazo compound was obtained. These compounds showed similar performance to the compounds described above.

Claims (1)

[Claims] 1. The following general formula () [Wherein, X is a halogen atom, R is a hydrogen atom, or hydroxy, cyano, alkoxy, halogen, carboxy, carbamoyl, alkoxycarbonyl,
a lower alkyl group optionally substituted with alkylcarbonyloxy, sulfo or sulfamoyl, A is methyl, ethyl, methoxy, ethoxy,
A phenylene group optionally substituted with one or two substituents or a naphthylene group optionally substituted with one sulfo group selected from the group of chlorine, bromine and sulfo, Y is -SO ₂ CH=CH ₂ Or-
SO ₂ CH ₂ CH ₂ Z (Z represents a group that is eliminated by the action of an alkali), and n represents 0 or 1. ] A di-copper-containing bisazo compound or a salt thereof. 2 General formula below [Wherein, X is a halogen atom, R is a hydrogen atom, or hydroxy, cyano, alkoxy, halogen, carboxy, carbamoyl, alkoxycarbonyl,
a lower alkyl group optionally substituted with alkylcarbonyloxy, sulfo or sulfamoyl, A is methyl, ethyl, methoxy, ethoxy,
A phenylene group optionally substituted with one or two substituents or a naphthylene group optionally substituted with one sulfo group selected from the group of chlorine, bromine and sulfo, Y is -SO ₂ CH=CH ₂ Or-
SO ₂ CH ₂ CH ₂ Z (Z represents a group that is eliminated by the action of an alkali), and n represents 0 or 1. ] A method of dyeing or printing using the di-copper-containing bisazo compound or its salt.