JPS63178168A - Water-soluble monoazo dye - Google Patents

Abstract

NEW MATERIAL:Water-soluble monoazo dyes in the free form of formula I (wherein X is halogen; Y is -OR', a group of formula II or a substd. aliph. or arom. residue; R<1> is a lower alkyl or the like; R<2> is a lower alkylene; R<3> is a lower alkyl; m is 2-6; Z is -CH=CH2, -CH2CH2Cl or -CH2CH2OSO3H; W<1> and W<2> are methoxy or ethoxy) (e.g. a compd. of formula III). USE:Reactive dyes which dye cellulosic fibers and nitrogen-contg. fibers deeply and uniformly, has excellent temperature sensitivity and fastness to sunlight, chlorine, perspiration, etc., and are greenish yellow dyes. PREPARATION:One mol of a triazine compd. of formula IV is condensed with one mol of a compd. of formula V in an aq. medium. The resulting compd. of formula VI is coupled with a diazotized product of a compd. of formula VII to obtain a water-soluble monoazo dye of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel greenish-yellow water-soluble monoazo dye. This invention relates to a water-soluble monoazo-reactive dye which is particularly excellent for dyeing cellulose or nitrogen-containing fibers.

(Prior art) When dyeing fibers containing cellulose or nitrogen-containing fibers, water-soluble reactive dyes are usually used. ,
It is required that the dyed object can be dyed deeply and that the waxiness of various types of dyed objects is also good. The properties of such reactive dyes vary slightly depending on the dye's basic skeleton, substituents, reactive groups, and combinations of these.In the past, dyes with various structures have been proposed, and at present they have been developed to a fairly satisfactory level. Good dyes have been put into practical use.

(Problems to be Solved by the Invention) However, among the reactive dyes, among the greenish yellow dyes, no dye having excellent dyeing properties in all respects is known yet. For example, greenish-yellow reactive dyes with good level dyeing properties have the problem of insufficient fastness against sunlight, chlorine, sweat, sunlight, etc.; Most of them have problems in that they have poor thermal sensitivity and level dyeing properties.

The object of the present invention is to provide a novel greenish-yellow water-soluble monoazo-reactive dye that can solve the above conventional problems and has excellent dyeing properties in all respects.

(Means for Solving the Problems) The present inventors have conducted various studies to achieve the above object, and as a result, have arrived at the present invention. That is, the present invention provides compounds of the general formula (1) [wherein, X represents a halogen atom, and Y represents an -OR' group (
However, R1 represents a hydroxyl group, a cyano group, or a lower alkyl group which may be substituted with a halogen atom. ), -〇+R
20 R3 group (however, R2 represents a lower alkylene group and R
3 represents a lower alkyl group, and m represents an integer of 2 to 6.

) or an aliphatic or aromatic amino residue substituted with 1 to 2 sulfonic acid groups or carboxylic acid groups t-
Table wa L, Z bar CH=CH2 group, -CH2CH2(J
group or -CH2CH20SO3H group, Wl, W
2 represents a methoxy group or an ethoxy group, and benzene iA may be further substituted with a methyl group, an ethyl group, a methoxy group, or an ethoxy group at the same time as the Wl and -8O2z groups. ] This paper focuses on water-soluble monoazo dyes shown in the following.

In the following, the present invention will be described in detail. In the water-soluble monoazo dye of the present invention, the halogen atom represented by X in the general formula (1) usually includes a fluorine atom, a chlorine atom, and a bromine atom. In particular, fluorine atoms and chlorine atoms are preferred.

In addition, one OR' group represented by Y and -〇+R2-0+
Examples of the lower alkyl group represented by R1 and R3 in the mR3 group include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group. Moreover, in the case of the lower alkyl group represented by R1, it may be substituted with a hydroxyl group, a cyan group, or a halogen atom, and specific examples thereof include, for example, a 2-hydroxyethyl group, a 4-hydroxybutyl group, 2-cyanoethyl group, cyanmethyl group, 3-
Examples include chloropropyl group. Further, as the lower alkylene group represented by R2, for example, a methylene group,
Ethylene group, propylene group, butylene group has 1 to 4 carbon atoms
Examples include alkylene groups. Furthermore, m is particularly preferably an integer of 2 to 4.

Furthermore, specific examples of aliphatic or aromatic amino residues substituted with 1 to 2 sulfonic acid groups or carbon 12 groups substituted by Y include the following formula: % Formula % etc. Things can be mentioned.

The water-soluble monoazo dye of the present invention exists in the form of a free acid or a salt thereof, and salts usually include alkali metal salts and alkaline earth metal salts, particularly lithium salts,
Sodium salts and potassium salts are preferred.

The monoazo dye of the present invention represented by the forepaw general formula (1) is:
It can be manufactured by the following method.

For example, 1 mole of triazide/compound represented by the following general formula (II) (wherein X and Y are the same as the definitions in the front foot general formula (1)) in the form of a free acid, and Formula (Ill)0cH3 (wherein, W2 is the same as the definition in the forepaw general formula (1).

) in an aqueous medium,
A compound represented by the following general formula (IV) ocH3 (wherein, X, Y and W2 are the same as defined in the front paw general formula (1)) is obtained in the form of a free acid. On the other hand, in the form of a free acid, the following general formula (V) (wherein Wl, Z and benzene ring A are represented by the front foot general formula (1)
Same as the definition in . The desired monoazo dye can be produced by diazotizing 1 mole of the compound represented by ) by a conventional method and coupling it with 1 mole of the compound represented by the general formula (IV). Note that the usual salting out method is used to obtain the target product from the reaction solution, but
The reaction solution can also be spray dried.

The monoazo dye of the present invention can be widely used as a dye for dyeing fibers and cloth, a dye for coloring paper and synthetic resins, and a dye for inkjet printers. Excellent aptitude.

When using the monoazo dye of the present invention as a dye, target fibers include cellulose fibers such as cotton, viscose rayon, cuproammonium rayon, and hemp, as well as nitrogen-containing fibers such as polyamide, wool, and silk. cellulose fibers are particularly preferred. Furthermore, these fibers may be used as mixed fibers of polyester, triacetate, polyacrylonitrile, and the like.

In order to dye cellulose or nitrogen-containing fibers using the monoazo dye of the present invention, an acid binder consisting of an inorganic alkali such as sodium bicarbonate or soda carbonate, or an organic base such as triethylamine is usually used. In its presence, staining can be carried out according to conventional methods.

As the dyeing method of the present invention, dip dyeing is particularly suitable, and the dyeing temperature is usually preferably about 40 to 80°C.

Furthermore, the monoazo dye of the present invention can also be applied to other dyeing methods to which vinyl sulfone type reactive dyes can be applied, such as cold pad patch method, pad steam method, and textile printing method.

(Example) Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples as long as they do not exceed the gist thereof.

Example 1 After diazotizing 1 mole of a compound represented by the following structural formula in the form of a free acid with 1 mole of an amine compound represented by the following structural formula in the form of a free acid according to a conventional method, pH 7-8 at a temperature of 0-5°C in aqueous media
The coupling was carried out under the following conditions.

After the coupling was completed, the mixture was salted out with potassium chloride, filtered, and dried to obtain a monoazo dye having the following structural formula (shown in free acid form) and maximum absorption wavelength.

Add 0.22% of the monoazo dye obtained as above to 22% of water.
00 mJ, added Glauber's Salt 109, immersed unmercerized cotton stockinette 102 in the prepared dye bath, and
It took several minutes to raise the temperature to 60°C. Next, carbonated soda 3
．． After adding Of and dyeing at 60° C. for 1 hour, washing with water, soaping, washing with water, and drying were performed to obtain a greenish-yellow dyed product.

The dyed products obtained with this dye are uniformly dyed, extremely dense, and have a light fastness rating (JIS L-084).
2) is excellent at grade 6, and has excellent chlorine fastness (JIS
In accordance with L-0884, the effective salt level ($20ppm) is very good at grade 4-5, and the sweat and sunlight fastness (JIS L-0
888A method alkali) was grade 4, which was very good.

Example 2 In Example 1, dye source 1i 60°C was changed to 40°C or 80°C.
Dyeing was carried out in the same manner as in Example 1 except that the temperature was changed to
was at the same level.

From these results, it was found that the monoazo dye of the present invention was
It can be seen that almost the same results are obtained when dyeing at either temperature of 0° C. or 80° C., indicating excellent thermal sensitivity.

Example 3 0.22 of a monoazo dye represented by the following structural formula in the form of a free acid was dissolved in 200 mjl of water, 8 f of Glauber's salt was added, and 10 f of unmercerized cotton knitted fabric was immersed in the prepared dye bath. It takes 5 minutes
The temperature was raised to 0°C. Next, 3.02% of sodium carbonate was added and dyed at 50° C. for 1 hour, followed by washing, soaping, washing and drying to obtain a greenish-yellow dyed product.

The dyed products obtained using this dye are uniformly dyed, have a deep color after being stirred, and have a light fastness rating (JIS L-084).
2) is excellent at grade 6, and has excellent chlorine fastness (JIS
Based on L-0884, effective chlorine zoppm) is 4-
It is very good at grade 5, and also has sweat and sunlight fastness (JIS L).
-0888A method alkali) was grade 4, which was very good.

The monoazo dye used in this example was produced according to Example 1.

Example 4 A4-1 to A whose respective structural formulas are shown in the free acid form in Table 1 below
When the monoazo dye of the present invention of 10 fi of 410 was synthesized according to the method of Example 1 and cotton cloth was dyed in the same manner as in Example 1, a rich greenish-yellow dyed product was obtained in each 6-yen color. Ta.

The results are shown in Table 1 below. Furthermore, the light fastness of these dyed products was 6th grade, the chlorine fastness was 4-5th grade, and the sweat and sunlight fastness was 4th grade, all of which were good.

(Effects of the Invention) The water-soluble monoazo dye of the present invention is a novel greenish-yellow monoazo dye having both a vinyl sulfone type reactive δ and a monohalogenotriazine type reactive group in the molecule, and is It is a greenish-yellow color that not only can dye fibers thickly and uniformly, but also has excellent temperature sensitivity, good fastness to light, chlorine, sweat, sunlight, etc., and has all the dyeing characteristics. As a reactive dye, it exhibits a remarkable effect that has unprecedented industrial value.

Claims (1)

[Claims] (1) In the form of free acid, general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I
[In the formula, X represents a halogen atom, and Y represents a -OR^1 group (wherein, R^1 represents a hydroxyl group, a cyano group, or a lower alkyl group which may be substituted with a halogen atom), -
O-(R^2O)-_mR^3 group (wherein, R^2 represents a lower alkylene group, R^3 represents a lower alkyl group, and m represents an integer of 2 to 6) or 1 to 2 represents an aliphatic or aromatic amino residue substituted with sulfonic acid groups or carboxylic acid groups, and Z is -CH=CH_
2 groups, -CH_2CH_2Cl group or -CH_2CH_
2OSO_3H group, W^1 and W^2 represent methoxy group or ethoxy group, and benzene ring A is W^
1 and -SO_2Z groups and may be further substituted with a methyl group, ethyl group, methoxy group or ethoxy group. ] Water-soluble monoazo dye.