JPH0425311B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a bisazo compound and a method of dyeing or printing using the same. For more details,
The present invention relates to a compound that has fiber reactivity and is capable of dyeing or printing fibers in navy color, and to dyeing or printing fibers using the compound. Conventionally, known reactive dyes that give navy colors used for this purpose have been insufficient in terms of dyeing performance and fastness. As a result of intensive studies aimed at improving these points, the present inventors have discovered that a compound having a specific structure or a salt thereof has excellent performance, and has completed the present invention. The present invention is based on the following general formula () [Wherein, X is a halogen atom, _R1 is an optionally substituted lower alkyl group, _R2 is a hydrogen atom or an optionally substituted lower alkyl group, _R3 is a hydrogen atom or a methyl group, _Z1 , Z ₂ and Z ₃ are each independently a hydrogen atom, a chlorine atom, a methyl group, a methoxy group,
Ethyl group, ethoxy group, sulfonic acid group or carboxylic acid group, Z ₄ and Z ₅ are amino groups on one side and hydroxyl groups on the other side, A is phenylene group or naphthylene group which may have a substituent, 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. ] The present invention relates to a bisazo compound or a salt thereof, and a method of dyeing or printing using the same. Among the above general formulas (), especially the following general formula (-1) [In the formula, R ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , A and Y have the above-mentioned meanings. ] A bisazone compound or a salt thereof represented by these is preferred. In the general formula (), X is a chlorine atom, a fluorine atom or a bromine atom, and the former two are preferred;
Particularly preferred is a chlorine atom. 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 and potassium salts. The compound of the present invention can be produced by a known method or in accordance therewith. For example, the following general formula () [In the formula, R ₁ and R ₃ have the above meanings. ] Aromatic sulfonic acid or its salt and the following general formula () [In the formula, R ₁ , A and Y have the above meanings.] ] in an aqueous medium in any order,
Primarily, PH1 to PH at a temperature of -10℃ to 40℃
While adjusting the temperature to
While adjusting the pH to 2 to 9 at °C, use the following general formula () [In the formula, X has the above meaning. ] Condensation with the trihalogenotriazine represented by the following general formula () [In the formula, R ₁ , R ₂ , R ₃ , A, X and Y have the above-mentioned meanings. ] or a salt thereof is obtained. A compound obtained by diazotizing this using a conventional method,
General formula below () [In the formula, Z ₁ , Z ₂ and Z ₃ have the above meanings. ] A compound obtained by diazotizing the compound shown by a conventional method in an aqueous medium in any order, firstly at a temperature of -10 to 40°C and a pH of 0 to 4, and secondarily at a temperature of - It can be produced by reacting with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid or a salt thereof at 10-40°C and pH 3-9. Alternatively, the compounds represented by the above general formulas () and () are condensed at a temperature of -10 to 40°C and a pH of 1 to 9, and then diazotized, and this is combined with the above general formulas () and 1-amino-8-hydroxynaphthalene. -3,6-disulfonic acid or its salt is reacted stepwise by the method described above, and then the compound represented by the general formula () is reacted at a temperature of 0°C to 70°C, PH
It can also be produced by condensing 2 to 9. In the general formula (), the lower alkyl group represented by R ₁ and R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the optionally substituted groups include a hydroxy group, a cyano group,
Preferred are an alkoxy group, a halogen group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, and a sulfamoyl group. Particularly preferable examples of R ₁ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, 2-hydroxyethyl group, 2-hydroxyethyl group, and 2-hydroxyethyl group. Roxypropyl 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, 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, methoxy Carbonylmethyl 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- Examples include sulfamoylethyl group, 3-sulfamoylpropyl group, 4-sulfamoylbutyl group, and the like. Particularly preferable examples of R ₂ include hydrogen and the above-mentioned substituted or unsubstituted alkyl groups exemplified for R ₁ . A is a phenylene group or a sulfonic acid group optionally substituted with one or two substituents, preferably selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfonic acid group. A naphthylene group which may be substituted with one group, for example,

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

[Formula] means a bond leading to a group). etc. can be given. and Y is the group SO ₂ CH=CH ₂ or the group −SO ₂ CH ₂
It represents CH ₂ Z, where Z is a group that is eliminated with an alkali, such as a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, a halogen atom, and the like. 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. In order to obtain a desired counter ion in the bisazo compound of the present invention, the type of counter ion in the starting compound, the type of alkaline agent used to neutralize the acid during the production process, or the electrolyte used in salting out and isolation as necessary. This is possible by selecting the type of The bisazo compound produced according to the present invention can be made into a liquid product by removing inorganic salts and adding a stabilizer or a dyeability improver as necessary, or this liquid product or reaction solution It can be made into a powder product by evaporation, for example by spray drying, and it 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-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-, polyamide-11 and polyamide-4. . 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 padzink method, it can be padded at room temperature or at an elevated temperature 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 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 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 condensate 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.
Particularly suitable for dyeing cellulose fiber materials,
Good light and sweat resistance, good moisture resistance, such as washing resistance, peroxide washing resistance, sweat resistance, acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and ironing resistance. has. In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility and high exhaustion and fixation properties.
It is characterized by being less susceptible to fluctuations in dyeing temperature and dye bath ratio and producing dyed products of stable quality. Among them, compounds in which Z ₄ is an amino group and Z ₅ is a hydroxyl group in the general formula () have excellent chlorine water resistance and chlorine bleach resistance, and in particular, compounds in the general formula (
The compound represented by -1) also has extremely excellent formalin resistance and formalin-light fastness. Hereinafter, the present invention will be explained in detail with reference to Examples.
In the examples, parts and % indicate parts by weight and % by weight, respectively. Example 1 Add 4.71 parts of 4-methylaniline-2-sulfonic acid and 3.7 parts of concentrated hydrochloric acid to 25 parts of ice water, and heat at 0 to 5°C for 35 minutes.
Diazotization is carried out by injecting 5.1 parts of % sodium nitrite solution. After eliminating excess nitrite, 1-amino-
A neutral solution of 7.81 parts of 8-hydroxynaphthalene-3,6-disulfonic acid monosodium salt was added at 0 to 10°C.
It takes about 1 hour to inject and couple at pH 0.5 to 1.5. After stirring this mixture for several hours, it is neutralized with a caustic soda solution to a pH of 7, and salted out with sodium chloride at 30 to 35°C to obtain a monoazo dye. On the other hand, 4.61 parts of cyanuric chloride and 4.70 parts of m-phenylenediaminesulfonic acid were heated to pH 6-7 in 50 parts of water by keeping at 0-5°C for 1-2 hours to carry out the first condensation, and then 1-N -ethylaminobenzene-3
A second condensation is carried out by adding 7.64 parts of -β-sulfatoethyl sulfone and stirring overnight at 25-30° C. while maintaining the pH at 5-5.5 with 9% sodium bicarbonate solution. Then, after adding 50 parts of ice and 7.1 parts of concentrated hydrochloric acid,
Diazotization is carried out by adding 5.3 parts of % sodium nitrite solution. The diazotized solution from which the residual nitrous acid has been removed is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10°C, and the mixture is stirred for 1 to 2 hours to perform coupling. After adjusting the pH to 5.5 to 6.0 with dilute sulfuric acid and the temperature to 50 to 55°C, add sodium chloride to the solution for salting out, filter, wash, and dry at 60°C. The produced bisazone compound, in the form of free acid, has the following formula: (Maximum input = 600 nm, however, in an aqueous solvent, measured under the same conditions below). Dissolve 0.1, 0.3 and 0.6 parts of the obtained bisazo compounds in 200 parts of water, add 10 parts of Glauber's salt and 10 parts of cotton, raise the temperature to 60°C, add 4 parts of soda carbonate, and dye for 1 hour. After washing with water, soaping, washing with water and drying, a greenish navy with excellent fastness, especially chlorine fastness, formalin fastness, and formalin-light fastness, extremely good build-up properties and good technical dyeing properties. A colored dyeing was obtained. This compound also had excellent solubility and showed good level dyeing and dyeing reproducibility. Examples 2 to 18 The corresponding bisazo compounds were synthesized using the following raw materials in the same manner as in Example 1. The bisazo compounds shown below contain 1-amino-8-hydroxynaphthalene- as the azo component.
Using 3,6-disulfonic acid disodium salt, the diazo component of the monoazo compound [the compound of the above general formula ()]: Column A, the aromatic sulfone constituting the diazo component of the disazo compound [the compound of the above general formula ()] Acid [compound of the above general formula ()]: Column B,
Compound of the above general formula (): Column C, and trihalogenotriazine [compound of the above general formula ()]:
It is characterized by Column D and the color tone of the dyed product obtained by dyeing by the same method as in Example 1: Column E.

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[Table] Example 19 Each was dyed in the same manner as in Example 1 except that the bisazo compound of Example 2-18 was used, and various fastnesses were determined, especially chlorine fastness, formalin fastness, and formalin-light fastness. A dyed product was obtained which had excellent strength and extremely good technical dyeability. These compounds had excellent solubility and showed good level dyeing and dyeing reproducibility. Examples 20 to 35 The corresponding bisazo compounds were synthesized using the following raw materials in the same manner as in Example 1. The bisazo compounds shown below contain 1-amino-8-hydroxynaphthalene- as the azo component.
Using disodium 3,6-disulfonate, the diazo component of the monoazo compound [the compound of the above general formula ()]: Column A, the aromatic sulfonic acid constituting the diazo component of the disazo compound [the compound of the above general formula ()] [Compound of the above general formula ()]: Column B, and compound of the above general formula (): Column C, and trihalogenotriazine [Compound of the above general formula ()]: Column D, and the same method as Example 1. The color tone of the dyed product obtained by dyeing with: Characterized by column E.

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[Table] Example 36 Each was dyed in the same manner as in Example 1 except that the bisazo compounds of Examples 20 to 35 were used, and the dyes were excellent in various fastnesses, especially chlorine fastness, and had extremely good technical dyeing properties. A dyed product was obtained. These compounds had excellent solubility and showed good level dyeing and dyeing reproducibility. Example 37 First condensation is carried out by keeping 4.61 parts of cyanuric chloride and 4.70 parts of m-phenylenediaminesulfonic acid at pH 6-7 in 50 parts of water at 0-5°C for 1-2 hours,
Next, 7.64 parts of 1-N-ethylaminobenzene-3-β-sulfate ethyl sulfone was added, and the pH was kept at 5-5.5 with 9% sodium bicarbonate solution.
A second condensation is carried out by stirring overnight at 30°C. Next, add 50 parts of ice and 7.1 parts of concentrated hydrochloric acid to 35%
Diazotization is carried out by adding 5.3 parts of sodium nitrite solution. Add 1
-amino-8-hydroxynaphthalene-3,6-
A neutral solution of 7.81 parts of disulfonic acid monosodium salt was injected at 0 to 10°C over about 1 hour to obtain a pH of 0.5 to 2.0.
Perform coupling with. After stirring this mixture for several hours, it was neutralized with a sodium carbonate solution to a pH of 7 and 30
At ~35°C, salt out with sodium chloride to obtain a monoazo dye. Meanwhile, add 4.71 parts of 4-methylaniline-2-sulfonic acid and 3.7 parts of concentrated hydrochloric acid to 25 parts of ice water, and add
Diazotization is carried out by injecting 5.1 parts of 35% sodium nitrite solution. After the residual nitrous acid has disappeared, this is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10°C, and the mixture is stirred for 1 to 2 hours to perform coupling. PH 5.5-6.0 with dilute sulfuric acid
After adjusting the temperature to 50 to 55°C, add sodium chloride to the solution for salting out, filter, wash, and dry at 60°C. The produced bisazone compound, in the form of free acid, has the following formula: (maximum input = 620nm) Dissolve 0.1, 0.3 and 0.6 parts of the obtained bisazo compounds in 200 parts of water, add 10 parts of Glauber's salt and 10 parts of cotton, raise the temperature to 60°C, add 4 parts of soda carbonate, and dye for 1 hour. After washing with water, soaping, washing with water and drying, a greenish navy with excellent fastness, especially chlorine fastness, formalin fastness, and formalin-light fastness, extremely good build-up properties and good technical dyeing properties. A colored dyeing was obtained. This compound also had excellent solubility and showed good level dyeing and dyeing reproducibility. Examples 38 to 54 The corresponding bisazo compounds were synthesized in the same manner as in Example 37 using the following raw materials. The bisazo compounds shown in the table below contain 1-amino-8-hydroxynaphthalene- as the azo component.
Using disodium 3,6-disulfonate, aromatic sulfonic acid [compound of the above general formula ()] constituting the diazo component of the monoazo compound [compound of the above general formula ()]: Column A, of the above general formula () Compound: Column B, and trihalogenotriazine [compound of the above general formula ()]: Column C, diazo component of the disazo compound [compound of the above general formula ()]: Column D,
The color tone of the dyed product obtained by dyeing in the same manner as in Example 37: Characterized by column E.

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[Table] Example 55 Dyeing was carried out in the same manner as in Example 37 except that the bisazo compounds of Examples 38 to 54 were used, and various fastnesses were determined, especially chlorine fastness, formalin fastness, and formalin-light fastness. A dyed product with excellent dyeing properties was obtained. This compound also had excellent solubility and good level dyeing and dyeing reproducibility.

Claims (1)

[Claims] 1. The following general formula () [Wherein, X is a halogen atom, R ₁ is an optionally substituted lower alkyl group, R ₂ is a hydrogen atom or an optionally substituted lower alkyl group, R ₃ is a hydrogen atom or a methyl group, R ₁ , Z ₂ and Z ₃ are each independently a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a sulfonic acid group or a carboxylic acid group, and Z ₄ and Z ₅ are one of amino groups and the other of hydroxyl groups, A is a phenylene group or a naphthylene group which may have a substituent, Y is _-SO2CH = _{CH2 or -SO2CH2CH2Z} , and Z represents a group that is eliminated by the action of _an alkali. ] A bisazo compound or a salt thereof. 2 General formula (-1) below [In the formula, R ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , A and Y have the same meaning as described in claim 1. ] A bisazo compound or a salt thereof according to claim 1. 3 General formula below () [Wherein, X is a halogen atom, _R1 is an optionally substituted lower alkyl group, _R2 is a hydrogen atom or an optionally substituted lower alkyl group, _R3 is a hydrogen atom or a methyl group, _Z1 , Z ₂ and Z ₃ are each independently a hydrogen atom, a chlorine atom, a methyl group, a methoxy group,
Ethyl group, ethoxy group, sulfonic acid group or carboxylic acid group, Z ₄ and Z ₅ are amino groups on one side and hydroxyl groups on the other side, A is phenylene group or naphthylene group which may have a substituent, 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. ] Using the bisazo compound or its salt shown in
A method of dyeing or printing.