JPS59174652A - Bisazo compound and dyeing or textile printing using the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is halogen; R1 is (substituted) lower alkyl; R2 is H or (substituted) lower alkyl; R3 is H, methyl, or sulfonic acid; Z1-Z3 are each H, Cl, methyl, carboxylic acid, etc.; Z4 and Z5 are such that either of them is amino, the other being OH; A is (substituted) phenylene, or naphthylene; Y is -SO2CH=CH2, etc.] and its salt. EXAMPLE:A compound of formula II. USE:Dye for dyeing hydroxyl- or carbonamide group-contg. fibrous material, esp. cellulose one, navy blue with excellent humidity and light resistance and sweat resistance under sunlight. PREPARATION:For example, an aromatic sulfonic acid of formula III or its salt and a compound of formula IV are subjected, in an aqueous medium to condensation with a trihalogenotriazine of formula V to prepare a compound of formula VI or its salt. The compound obtained from the above one by diazotization and the compound derived from a compound of formula VII by diazotization are made to react in an aqueous medium, with a 1-amino-8-hydroxynaphthalene-3,6- disulfonic acid (salt).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hisazo compound and a method of dyeing or printing using the same. More particularly, the present invention relates to a compound having fiber reactivity and capable of dyeing or printing fibers in a 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 relates to the following general formula (I) [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, and R3 is hydrogen Atom, methyl group or sulfonic acid group, Zl+ 22 + 23 each independently represents a hydrogen atom, chlorine atom, methyl group, methoxy group, ethyl group, ethoxy group, sulfonic acid group or carboxylic acid group, Z4
, Z5 is an amino group on one side and a hydroxyl group on the other, A is a phenylene group or a phthylene group which may have a substituent, Y is -5O2CH=CH2 or -8OzCHzC
Hzf and Z represent groups that are 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.

Of the general formula (I), the following general formula (I-1) (
l [wherein, R1+ 22. z3. Z4, Zs +
A and H Y H have the above meanings. ] A bisazo compound or a salt thereof represented by these is preferred.

In the general formula (I), X represents a chlorine atom, a fluorine atom or a bromine atom, the former two being preferred, and a chlorine atom being particularly preferred. 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 (II) [wherein R2 and R3 have the above-mentioned meanings]. ] Aromatic sulfonic acid or its salt represented by the following general formula "RI IN-AY (2) [wherein, R1, A and Y have the above-mentioned meanings.
] The compounds represented by ゛ are added in any order in an aqueous medium to pH'l to p at a temperature of -10°C to 40°C.
Since the temperature is adjusted to H9, the secondary temperature is θ°C to 70°C.
While adjusting the pH to 2 to 9 with the following general formula (I
V)X [wherein, X has the above meaning. [In the formula, R11R2, R3, A, X and Y have the above-mentioned meanings. ] or a salt thereof is obtained.

A compound obtained by diazotizing this by a conventional method and the following general formula (W) 1 [wherein Zl, Z2 and Z3 have the above-mentioned meanings.

] A compound obtained by diazotizing the compound shown by a conventional method in an aqueous medium in any order, and then at a temperature of -1.
React with ■-Amino-8-hydroxynaphthalene-8,6-disulfonic acid or its salt at a temperature of 0°C to 40°C and a pH of 4, and secondarily at a temperature of -10°C to 40°C and a pH of 8 to 9. It can be manufactured by

Alternatively, the compounds represented by the general formula (]I) and (IVII) are condensed at a temperature of -10 to 40°C and a pH of 1 to 9, and then diazotized, and this and the compound represented by the general formula (V'll and l-amino- 8-Hydroxynaphthalene-3,6-disulfonic acid or a salt thereof is reacted stepwise by the method described above, and then condensed with a compound represented by the general formula at a temperature of 0°C to 70°C and a pH of 2-9. It can also be manufactured by

In the general formula (IJ), the lower alkyl group represented by R1 and R2 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, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, and a sulfamoyl group.

Particularly preferred examples of R1 include methyl group, ethyl, l, n-7'rovir! 4.1so-propyl group, n
-butyl group, 1so-butyl group, 5ec-]f group, 2
-Hydroxyethyl group, 2-hydroxypropyl group, 3
-Hydroxypropyl group, 2-hydroxybutyl group, 3
-Hydroxybutyl group, 4-hydroxytyl 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-ethquinethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-8-methoxypropyl group, chloromethyl group, bromomethyl group, 2-10 loethyl group, 2-bromoethyl group , 8-chloropropyl group, 8-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, 3-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group , 4-methoxycarbonylbutyl group, 4-ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 8-methylcarbonyloxypropyl group , 8-ethylcarbonyloxyprobyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group,
Sulfomethyl group, 2-sulfoethyl group, 8-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfamoylethyl group, 8-sulfamoylpropyl group, 4-sulfamoylbutyl group, etc. I can give it to you. Particularly preferable R2 is hydrogen or R2.
, the above-mentioned substituted or unsubstituted alkyl groups can be mentioned.

A is a phenylene group or sulfone optionally substituted with one or two substituents, preferably selected from the group of methyl, ethyl, methoxy, ethoxy, salts, bromine and sulfonic acid groups. It is a naphthylene group which may be substituted with one acid group, and means, for example, the same bond. ), etc.

And Y is the group 5O2CH= CH2 or the group -5O2C
Represents H2CH2Z, 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.

Depending on the reaction conditions, the starting compounds mentioned are used in the form of acids and/or salts, in particular alkali metal salts or A/L/potassium earth metal salts.

□ In order to obtain the 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 manufacturing process, or the salting-out isolation method as necessary. This is possible by selecting the type of electrolyte.

The bisazo compound produced according to the present invention can be made into a liquid product by removing the inorganic salt 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 blinding of 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. Cellulose fiber materials include cotton, as well as other vegetable fibers such as linen, hemp,
Jute and ramie fibers are preferred. Regenerated cellulose fibers are, for example, viscose staple and filament viscose.

Materials containing carbonamide groups include, 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.

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, in the case of exhaust dyeing 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, a solubilizer is added. , use a penetrant or leveling agent together,
It is carried out at relatively low temperatures. 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,
After padding and drying at room temperature or elevated temperature, it can be fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, either in one phase, e.g. by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-160°C, or in two phases, e.g. Printing can be carried out by printing with an acidic or weakly acidic printing paste, passing it through a hot electrolyte-containing alkaline group, or by overpadding with an alkaline electrolyte-containing padding liquid and 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, and sodium chloride acetate.

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 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 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, and wash-off properties, as well as good solubility and high exhaustion and fixation properties, making it possible to produce dyed products of stable quality that are less affected by fluctuations in dyeing temperature and dye bath ratio. It is characterized by the fact that it is

Among them, in the general formula (I), Z4 is an amino group,
When Z5 is a hydroxyl group, the compound has excellent chlorine water resistance and chlorine bleaching resistance, and in particular, the compound represented by the general formula (I-1) has excellent formalin resistance and formalin-light fastness. It has extremely excellent characteristics.

Hereinafter, the present invention will be explained in detail with reference to Examples. In the examples, parts and weights indicate parts by weight and weight j1%, respectively.

Example 1 4-methylaniline-2-sulfonic acid was added to 25 parts of ice water.
71 parts and 3.7 parts of concentrated hydrochloric acid were added to form an 85% sodium nitrite solution at 0 to 5°C. Diazotization is carried out by injecting lI. After eliminating excess nitrous acid, 7.81 parts of l-amino-8-hydroxyna; talene-3,6-disulfonic acid monosodium salt was injected at 0-10°C over a period of about 1 hour. Coupling is carried out at pH 0.5-1.5.

The mixture was stirred for several hours, neutralized with a caustic soda solution to pH 7, and salted out with sodium chloride at ~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 added to 50 parts of water to a pH of 6 to 7.
Perform the first condensation by standing at 0-5°C for ~2 hours,
Next, 64 parts of 1-N-ethylaminobenzene-8-β゛-sulphate ethyl sulfonate was added and the pH was maintained at 5-5.5 with J29% sodium carbonate solution.
The second condensation is carried out by stirring overnight at 0°C.

Next, add 50 parts of ice and 7.1 parts of concentrated hydrochloric acid, and reduce to 85%.
Add 5.8 parts of sodium nitrite solution to carry out diazotization.

The diazotized solution from which excess nitrous acid has been removed is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10 DEG C., and the mixture is stirred for 1 to 2 hours to effect coupling. After adjusting the pH to 5.5 to 6.0 with dilute sulfuric acid and the temperature to 50 to 55°C, 1 part of sodium chloride is added to this solution to salt out, filter, wash, and then dry at 60°C.

The produced bisazo compound, in the form of a free acid, is represented by the following formula (measured at a maximum of -600 nm in an aqueous solvent and under the same conditions hereinafter).

0.1, 0.8 and 0.6 parts of the obtained bisazo compounds were each dissolved in 2 ooiscm of water, and □10 parts of mirabilite and 1 part of cotton were added.
Add 0 parts, raise the temperature to 61°C, add 4 parts of soda carbonate, and
Time staining.

Washing, soaping, washing and drying, various fastness properties,
Among these, a greenish navy dyed product was produced which was particularly excellent in fastness to salt and electricity, fastness to formalin, and fastness to formalin-I light, and had extremely good build-up properties and good technical dyeing properties.

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 l- as the azo component.
Using amino-8-hydrokyleneaphthalene-8,6-disulfonic acid disodium salt, monoazotization and diazo component of metal [the above general formula (compound of Ml)]: Column A, diazo component of the disazo compound [the above general formula Aromatic sulfonic acid constituting the compound of ff) [compound of the general formula (W)]:
Column B, J compound of the above general formula (2): C-, and compound of trihalogenotriazine [the above general formula]: Column D,
The color tone of the dyed product obtained by dyeing in the same manner as in Example 1 is characterized by column E.

Examples 20 to 85 In the same manner as in Example 1, the following raw materials were used to synthesize the corresponding bisazo compounds.

The bisazo compounds shown below contain l- as the azo component.
Using disodium amino-8-hydroxynaphthalene-3,6-disulfonate, the diazo component of the monoazo compound [compound of the above general formula (vIl)]: Column A, the diazo component of the disazo compound [the compound of the above general formula fV] Aromatic sulfonic acids [compounds of the above general formula (Ill)] 2B column, compounds of the above general formula (to): C column, and trihalogenotriazine [compounds of the above general formula (w)]: D
Column, and the color tone of the dyed product obtained by dyeing by the same method as in Example 1: Column E.

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 a dyed product was obtained which had excellent color fastness, especially chlorine fastness, and extremely good wave resistance. I got it.

These compounds had excellent solubility and showed good level dyeing and dyeing reproducibility.

Example 37 First condensation was carried out by combining 4.61 parts of cyanuric chloride and 4.70 parts of m-phenylenediamine sulfonic acid in 50 parts of water at pH 6-7 [1-2 hours at 0-5°C; ni l
7.64 parts of -N-ethylaminobenzene-3-β-sulfatoethyl sulfone were added and stirred overnight at 25-30°C while keeping the pH at 5-5.5 with 9% sodium bicarbonate solution. Perform condensation.

Next, 50 parts of ice and 7.1 parts of concentrated hydrochloric acid were added, followed by 5.3 parts of a 35% sodium nitrite solution to effect diazotization.

■-Amino 8 is added to the diazotized solution from which excess nitrous acid has been removed.
-Hydroxynaphthalene-3,6-disulfonic acid monosodium salt 7.81 parts of a neutral solution was injected at 0 to 10°C over a period of about 1 hour to complete the coupling at p f (0.5 to 2.0). After stirring the mixture for several hours, the mixture is neutralized to pH 7 with a sodium carbonate solution, and salted out with sodium chloride at 30 to 35°C to obtain a monoazo dye.

10,000, 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 4.71 parts of 4-methylaniline-2-sulfonic acid and 3.7 parts of conc.
Diazotization is carried out by injecting 5.1 parts of a 5% sodium nitrite solution. After eliminating the residual nitrous acid, add this to a suspension of monoazo dye made alkaline with sodium bicarbonate at 5 to 10°C.
and stirred for 1 to 2 hours to perform coupling.

Adjust the pH to 5.5-6.0 with dilute sulfuric acid and increase the temperature to 50-55℃.
After that, sodium chloride is added to this liquid for salting out, filtered, washed, and then dried at 60°C.

The bisazo compound produced is in the form of a free acid with the following formula % Formula % Obtained bisazo compound 0. l, 0.3 and 0.6
10 parts of Glauber's salt and 10 parts of cotton were added, the temperature was raised to 60°C, 4 parts of soda carbonate was added, and dyeing was carried out 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 surfability. A colored dyeing was obtained.

This compound also had excellent solubility and showed good level dyeing and dyeing reproducibility.

Examples 38 to 54 The following raw materials were used in the same manner as in Example 37 to obtain the corresponding bisazo compounds.

The bisazo compounds shown in the table below are based on the azo component [min.
Using disodium amino-8-hydroxynaphthalene-3,6-disulfonate, the diazo component of the monoazo compound [the aromatic sulfonic acid constituting the above general formula (compound of VJ) [the above general formula (compound of Ill]): Column A, Compound 2 of the above general formula (to) Column 2B, and Trihalogenotriazine [Compound of the above general formula (IV)] 2C Column, Diazo component of the disazo compound [Compound of the above general formula (VII)]: D
column, and the color tone of the dyed product obtained by dyeing by the same method as in Example 37: column E.

Example 55 Dyeing was carried out in the same manner as in Example 87 except that the bisazo compounds of Examples 38 to 54 were used.1. A dyed product was obtained which was excellent in various fastnesses, particularly in chlorine fastness, formalin fastness, and formalin-light fastness, and had extremely good wave riding.

This compound also had excellent solubility and good level dyeing and dyeing reproducibility.

Claims (1)

[Scope of Claims] l) The following general formula (II Alkyl group, R3 is a hydrogen atom, methyl group or sulfonic acid group, Zl l Zz + Zs are each independently a hydrogen atom, chlorine atom, methyl group, methic acid group or carboxylic acid group, Z4, Zs are one of amino groups, The other is a hydroxyl group, A is a phenylene group or naphthylene group which may have a substituent, Y is -5O2CH= CH2 or -5O2
CH2CH2Z and Z represent groups that are eliminated by the action of an alkali. ] A bisazo compound or a salt thereof. 2) The following general formula (I-1) C [wherein, R1, Zz, Z3, Z4, Zs,
A and HY have the same meaning as stated in claim 1). ] A bisazo compound or a salt thereof according to claim 1). 8) The following general formula (I+ [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, a methyl group or sulfonic acid group, Zl, Z2, Z3 are each
Hydrogen atom, chlorine atom, methyl group, methoxy group, ethyl group, ethoxy group, sulfonic acid group or carboxylic acid group, Z4
．． Z5 is an amine group on one side, a hydroxyl group on the other side, A is a phenylene group or a naphthylene group that may have a substituent, and Y is -5O2CH= CH2 or -8O2CH2CH2Z
, Z represents a group that is eliminated by the action of an alkali. ] A method of dyeing or printing using a bisazo compound or a salt thereof.