JPS63168465A - Water-soluble formazan dye and dyeing method using the same - Google Patents

Abstract

NEW MATERIAL:Compds. of formula I [wherein R is H or a (substd.)lower alkyl; X is (substd.)phenylene or naphthylene; Y is a group of formula II or III; W is a group which can be removed by the action of an alkali; Z is phenylamino having a sulfo and/or carboxyl group or naphthylamino having a sulfo and/or carboxyl group]. EXAMPLE:Compd. of formula IV. USE:Water-soluble magenta dyes which dye cellulosic fibers and nitrogen-contg. fibers blue and colors paper, synthetic resins, etc. PREPARATION:One mol of a compd. of formula V is condensed with one mol of an amino compd. of formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a blue water-soluble formazan dye having a novel structure and a dyeing method using the dye. The present invention relates to a formazan dye having an excellent reactive fixation property particularly to cellulose and nitrogen-containing fibers, and a method for dyeing cellulose fibers or fibers containing nitrogen-containing fibers using the formazan dye.

2. Description of the Related Art For example, water-soluble reactive dyes are usually used as dyes for dyeing cellulose or nitrogen-containing fibers, and dyes having various structures have been proposed.

Generally, when the various dyes are used to dye the above-mentioned fibers by dip dyeing, the temperature of the dye bath is relatively low, for example, about 60 to 70°C.

In recent years, with the diversification of fiber materials, for example, mixed fibers of cellulose fibers and polyester fibers have been used. Conventionally, the dyeing method for such mixed fibers has been to dye 120% by using a disperse dye in advance. A so-called two-stage method is employed in which polyester fibers are dyed at a high temperature of about 140° C. and then cellulose fibers are dyed using a reactive dye at a low temperature of about 60 to 70° C. However, recently, a method has been proposed in which cellulose and polyester fibers are simultaneously dyed using a reactive dye and a disperse dye in a high-temperature dye bath of 120 to 140 degrees Celsius in one step. For example, reactive dyes made of formazan compounds represented by the following structural formula [A] are known. (Refer to Japanese Unexamined Patent Publication No. 60-90264) Problems to be Solved by the Invention However, when cellulose fibers are dyed using conventionally known reactive dyes in such a high-temperature dye bath, The reaction fixation rate of the dye to the fiber was low, the build-up property was also poor, and it was not possible to obtain a good dyed product.

Also, for example, in the case of a reactive dye consisting of a formazan compound represented by the above structural formula [A], which has been proposed as a dye to improve such problems, a high temperature dye bath (e.g. 130°C) is used. Although a certain degree of effect can be obtained when dyeing with this method, there is a problem that the dyeing rate and build-up property are still insufficient.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water-soluble dye that exhibits a better reaction fixation rate for cellulose fibers even under dyeing conditions for polyester fibers. There is a particular thing. Another object of the present invention is to provide a method for dyeing fibers containing cellulose or nitrogen-containing fibers.

Means for Solving the Problems The above object of the present invention is to obtain the following general formula [1] in the form of a free acid: [wherein R represents a hydrogen atom or an optionally substituted lower alkyl group, and X represents a substituted represents a phenylene group or naphthylene group which may have a group, and Y is -8O2
CH=CH2 group or -802C2H4W group (where,
W represents a group which is eliminated by the action of an alkali), and Z represents a phenyl7mino group or a naphthylamino group having one or two groups selected from a sulfonic acid group and a carboxylic acid group. This can be achieved by producing a water-soluble formazan dye represented by the following formula, and by dyeing fibers containing cellulose or nitrogen-containing fibers using a dye.

The present invention will be explained in detail below.

First, to explain the water-soluble formazan dye of the first invention, in the water-soluble formazan dye represented by the general formula fI, one or two groups selected from a sulfonic acid group and a carboxylic acid group represented by Z are Specific examples of the phenylamino group or naphthyleneamino group include:
For example, the following are required.

Among these, a phenylamino group having one sulfonic acid group is particularly preferred.

The lower alkyl group which may have a substituent represented by R is, for example, a C1 to C4 linear or branched unsubstituted alkyl group, or hydroxymethyl,
Included are alkyl groups substituted with a hydroxyl group, a cyano group, a halogen atom, or an alkoxy group, such as 2-hydroxyethyl, 2-cyanoethyl, cyanomethyl, 2-chloroethyl, and 2-methoxyethyl.

Examples of the phenylene group or naphthylene group which may have a substituent represented by Examples include phenylene groups or naphthylene mAζ substituted with one or two substituents selected from lower alkoxy groups such as, halogen atoms such as chlorine atoms and bromine atoms, and sulfonic acid groups.

Specific examples of the group represented by the general formula 1\-X- composed of R and X include the following.

03H Furthermore, the group represented by W which is eliminated by the action of an alkali usually includes a sulfuric acid ester group, a diosulfuric acid ester group, a phosphoric acid ester group, an acetic acid ester group, or a halogen atom, and particularly preferably 1a Nisder group is mentioned.

The water-soluble formazan dyes of the present invention exist in pre-liberated form or in the form of their salts, which are usually alkali metal salts and alkaline earth metal salts, especially lithium salts, sodium salts, potassium salts, etc. Salt is preferred.

The water-soluble formazan dye represented by the general formula [I] is
It can be manufactured as follows.

For example, 1 molar proportion of the compound represented by the following general formula [I[] (wherein Z is the same as defined above) and the following general formula [III]H
-N-X-Y [I[I] (wherein R,
, and Y is the same as defined above) The water-soluble formazan dye represented by the general formula [I] can be produced by condensing 1 molar proportion of the amino compound represented by the formula [I].

The water-soluble formazan dye of the present invention can be used as a dye for dyeing fibers and cloth, a dye for coloring paper, and synthetic resins.
Although it can be widely used as a pigment for inkjet printers, it is especially suitable as a dye.

Next, the dyeing method of the second invention will be explained.

When the water-soluble formazan dye of the present invention is used 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. Examples include fibers, with cellulose fibers being particularly preferred. Further, these fibers may be mixed fibers of polyester, triacetate, polyacrylonitrile, and the like. In the fiber dyeing method using the water-soluble formazan dye of the present invention, dyes necessary for dyeing non-cellulose fibers, such as Co1orIndex, are used.
(3rd edition) can be added to the dye bath at the same time for dyeing.

When dyeing cellulose fibers using the water-soluble formazan dye of the present invention, for example, the water-soluble formazan dye represented by the above general formula
) Buffer necessary to maintain H5 to 10 (for example, acids such as carbonic acid, boric acid, phosphoric acid, acetic acid, citric acid, etc., and sodium salts or potassium salts of these acids, singly or in mixtures, usually 0.5 ~5.0q/Ω) and, if necessary, an electrolyte (sodium chloride or sodium sulfate, etc.)
~150g/! degree, particularly preferably 40 to 807/
Good dyeing can be achieved by preparing a dye bath containing Ω), adding cellulose fibers to the dye bath, and heating at a temperature of 100 to 150° C. for 30 to 60 minutes.

In addition, in order to dye blended fabrics, blended knitted fabrics, etc. produced by mixing cellulose fibers with other fibers, such as polyester fibers, water-soluble Formazan dye and the above Co1or Ind
By adding the disperse dye described in Ex. In this case, it is preferable to maintain the pH of the dye bath at 7 to 9. Especially I)H 8
It is preferable to keep it at 9.

In addition, when dyeing blended fabrics, blended knitted fabrics, etc., as described above, the conventional one-bath two-step method in which one fiber is dyed and then the other fiber is dyed in the same bath is used. Furthermore, the dyeing method using the water-soluble formazan dye of the present invention and the dyeing method for fibers other than cellulose fibers may be combined to dye cellulose fibers and other fibers from separate baths. It is also possible to adopt a two-bath method.

For example, during dyeing, the water-soluble formazan dye of the present invention has a vinyl sulfone reactive group in its structure.
3O2C2H40S O3H is hydrolyzed, S O
2CH=CH2 and reacts with the fiber.

Examples Below, the water-soluble formazan dye and staining method of the present invention are
The present invention will be further explained in detail with reference to Examples.
The invention is not limited to these examples.

Example 1 Production Example A 1 molar proportion of a formazan compound represented by the following structural formula in the form of a free acid and a 1 molar proportion of a compound represented by the following structural formula were mixed in an aqueous medium at a concentration of 80 to 90%
'C, after condensation at pH 4 to 6, salting out with sodium chloride resulted in the following M4 formula (shown in free acid form).

) and a water-soluble formazan dye of the present invention having analytical values by visible light absorption.

<Dyeing example> The above water-soluble formazan dyes 0.2y, 0.4g and 0.6g were used as dyes, and 16g of Glauber's salt and 0.4g of sodium bicarbonate as a buffer were mixed in 200d of water.
10 g of unmercerized cotton knitted fabric was added to the dye bath, the temperature was raised to 120°C over 30 minutes, and dyeing was carried out at the same temperature for 60 minutes.

Next, washing with water, soaping, washing with water, and drying were performed to obtain a blue dyed product.

In this dyeing test, the reaction fixation rate of the dye to the fibers (81%) was good, and the build-up properties of the dyed product were also good.

Example 2 Water-soluble formazan dye 0.59 produced in Example 1 and a known anthraquinone dye for polyester represented by the following structural formula
Using a mixed dye consisting of 0.29, this and mirabilite 129
, as a buffer Na2 HPO4・12H200,4
g and KH2F) o4o, 19 to 200 d of water to prepare a dye bath, polyester/cotton-50: 5
A blend of $10y of 0 was added, the temperature was raised to 130°C over 30 minutes, and dyeing was carried out at the same temperature for 60 minutes. Next, washing with water, soaping, washing with water, and drying were performed to obtain a blue dyed product with good same color property. In addition, this dyeing bath is 1) H8 throughout before and after dyeing.
Met.

The dyeability of each dye in this dyeing test was very good, and the dyed product obtained was extremely rich.

Example 3 The water-soluble formazan dyes shown in Tables 1 and 2 (all expressed in free acid form) were synthesized according to the method described in Example 1, and these dyes were then treated with Example 1 and When a cotton fabric and a polyester/cotton blend fabric were dyed according to the method described in Example 2, both were deeply dyed and had good build-up properties.

Furthermore, the color tone and λmax of the dyed fabric obtained were as shown in Tables 1 and 2.

Effects of the Invention The water-soluble formazan dye of the present invention is a blue dye having a vinyl sulfone type reactive group as a reactive group in its structure, and has a high temperature range (120 to 14
Excellent reaction adhesion and build-up properties at 0℃).

In particular, it is suitable for dyeing polyester/cellulose mixed fibers in one bath and one step at a temperature of 120 to 140° C. when used in combination with a disperse dye.

Claims (2)

[Claims] (1) In the form of a free acid, the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R represents a hydrogen atom or a lower alkyl group that may be substituted, and X is Represents a phenylene group or naphthylene group which may have a substituent, and Y is -SO_
2CH=CH_2 group or -SO_2C_2H_4W group (where W represents a group that is eliminated by the action of an alkali), and Z is one or two groups selected from a sulfonic acid group and a carboxylic acid group. a phenylamino group or a naphthylamino group having the following. (2) When dyeing fibers containing nitrogen-containing fibers, cellulose is used in the form of a free acid using the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R is hydrogen represents an atom or a lower alkyl group which may be substituted, X represents a phenylene group or naphthylene group which may have a substituent, and Y represents -SO_
2CH=CH_2 group or -SO_2C_2H_4W group (where W represents a group that is eliminated by the action of an alkali), and Z is one or two groups selected from a sulfonic acid group and a carboxylic acid group. A dyeing method characterized by using a water-soluble formazan dye represented by a phenylamino group or a naphthylamino group.