JPH0751676B2 - Water-soluble formazan dye - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-soluble formazan dye that is a blue dye, and more specifically, it is a formazan that is excellent in reaction stickiness to cellulose and nitrogen-containing fibers in a low pH region. It is about dyes.

[Conventional technology]

As a dye for dyeing cellulose or nitrogen-containing fibers, a water-soluble reactive dye is usually used,
Dyes with various structures have been proposed. Typically,
When the above-mentioned fibers are dyed by the dip dyeing method using this type of dye, a relatively low temperature of about 60 to 70 ° C. is adopted as the temperature of the dyeing bath.

In recent years, with the diversification of fiber materials, for example, mixed fibers of cellulose fibers and polyester fibers have been used, and as a method for dyeing such mixed fibers, conventionally, using a disperse dye, 120 A so-called two-step method is employed in which polyester fibers are dyed at a high temperature of about 140 ° C and then cellulose fibers are dyed with a reactive dye at a low temperature of about 60 ° C to 70 ° C. However, recently, using a reactive dye and a disperse dye together, 120
A method of dyeing cellulose and polyester fibers at the same time in a high-temperature dyeing bath of ~ 140 ° C has been proposed. Regarding the dye, for example, a reactive dye composed of a formazan compound represented by the following structural formula (a) is known. Has been. (JP-A-60-90264) [Problems to be Solved by the Invention] However, when dyeing a cellulose fiber with a conventionally known reactive dye in such a high-temperature dyeing bath, the reaction fixation ratio of the dye to the fiber is And the build-up property was poor, and a good dyed product could not be obtained.

Further, for example, in the case of a reactive dye composed of a formazan compound represented by the structural formula (a), which is proposed as a dye for improving such problems, a high temperature dye bath (for example, 130 ° C.) When dyed with, although some effects can be obtained, 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 an even better reaction fixation ratio to cellulose fibers even under the dyeing conditions of polyester fibers. is there.

[Means for solving problems]

 The above object of the present invention is to provide a compound represented by the following general formula [I] in the form of a free acid.[In the formula, Y¹And Y²Is a hydrogen atom, a lower alkyl group,
Phonic acid group, carboxyl group, sulfamoyl group, carba
Represents a moyl group or a hydroxyethyl group, n is 1 to
Represents an integer of 2, A Represents an anion)
This is achieved by the water-soluble formazan dye.

Hereinafter, the present invention will be described in detail.

In the water-soluble formazan dye represented by the above general formula [I], the lower alkyl group represented by Y ¹ and Y ² usually has 1 to 1 carbon atoms such as methyl, ethyl, propyl and butyl.
4 straight-chain or branched alkyl groups can be mentioned.

n represents a positive number of 1 to 2, and the case of 1 is particularly preferable.

A Balances the positive charge of the nitrogen atom of the pyridine nucleus
Is a negative charge required for, for example, OH , Cl , F Etc.
Can be mentioned.

The formazan dye represented by the general formula [I] shown above can be produced as follows. For example, the following general formula [I
I] (Wherein n is the same as the above definition) 1 mole ratio of the formazan compound and the following formula [III] (Wherein Y ¹ and Y ² are the same as defined above) 1 mole ratio of the pyridine compound is reacted in an aqueous medium at 60 ° to 90 ° C. and pH 4 to 6 to give the compound represented by the general formula [I]. Formazan dyes can be produced. Although an ordinary salting-out method is used to obtain the desired product from the reaction solution, the reaction solution can be directly spray-dried.

INDUSTRIAL APPLICABILITY The formazan dye of the present invention can be widely used as dyes for dyeing fibers, cloths, papers, dyes for coloring synthetic resins, and inks for inkjet printers, and especially as dyes. Excellent suitability.

When the formazan dye of the present invention is used as a dye,
The target fibers are cotton, viscose rayon,
Cupra ammonium rayon, cellulosic fibers such as hemp, and further nitrogen-containing fibers such as polyamide, wool and silk are preferred, and cellulose fibers are desirable, and the cellulose fibers are, for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate. Is particularly desirable.

When the mixed fiber of cellulose and polyester is dyed using the formazan dye of the present invention, for example, Color
The disperse dyes for polyester fibers described in Index (Third Edition) can be used at the same time for dyeing in one step and one bath.

When the cellulose-containing fiber is dyed using the formazan dye of the present invention, for example, a buffering agent necessary for maintaining the pH of the dyeing bath at 5 to 8, preferably pH 5.5 to 7.5 (for example,
Acid such as carbonic acid, phosphoric acid, acetic acid, citric acid, boric acid, etc. and a sodium salt or potassium salt of those acids, usually 0.5 to 5.0 g / a single or mixture, and optionally an electrolyte (sodium chloride). Or sodium sulfate etc. is usually 1 to 15
It is desirable to prepare the dyebath using 0 g / about, particularly preferably 40-80 g /). The dyeing temperature at this time is 100 to 150 ° C., and the dyeing time is 30 to 50 minutes.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples and the like.

Example 1 The following structural formula in the form of a free acid (anion component is chlorine ion) Formazan pigment 0.2 g, Glauber's salt 160 g, Na ₂ B ₄ O ₇ · 10H ₂ O 0.1 g and KH ₂ PO ₄ 0.4 g as a buffer 200 ml of water
Add 10 g of unmercerized cotton knitted fabric to the prepared bath and heat up to 120 ° C for 30 minutes, dye at the same temperature for 60 minutes, then wash with water, soap, wash with water and dry to dye a blue dyed product. Got In addition, the pH of this dyeing bath before and after dyeing
Was 6.0. The dyed product obtained was extremely dense.

The formazan dye used in this example is The formazan compound represented by is dissolved in water, 1.5 mol of nicotinic acid is added to the solution, and the mixture is reacted at 90 ° C. and pH = 7 for 7 hours. Then, the reaction solution is salted out with sodium chloride to obtain crystals. And then dried to obtain the formazan dye.

Example 2 In the form of the free acid, the following formula (the anion component is fluoride ion) Formazan dye represented by 0.2g Glauber's salt 16g N as a buffer
aHPO ₄ · 12H ₂ O to 0.4g and KH ₂ PO ₄ 0.2 g placed non mercerized cotton knitted 10g dyebath prepared added to water 200 ml 30
The temperature was raised to 120 ° C. over a period of time, and dyeing was carried out at the same temperature for 60 minutes, followed by washing with water, soaping, washing with water and drying to obtain a blue dyed product. The pH of this dyeing bath was 7 before and after dyeing. The dyed product obtained was extremely dense.

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

Example 3 0.5 g of the formazan dye prepared in Example 1 and the following structural formula Known polyester anthraquinone dyes shown in 0.
Using a mixed dye consisting of 3g, which the salt cake 12g, the _{Na 2 HPO 4 · 12H 2 O} 0.4g and KH ₂ PO ₄ 0.1 g as a buffering agent, water 20
In addition to 0 ml, the adjusted dyebath contains polyester / cotton = 50:
Put 10 g of 50 blended cloth, raise the temperature to 130 ° C over 30 minutes, dye at the same temperature for 60 minutes, then wash with water, soap,
It was washed with water and dried to obtain a blue dyed product with good color uniformity.
The dye bath had a pH of 8 before and after dyeing.

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

Example 4 According to the method described in Example 1, the formazan dyes shown in Tables 1 and 2 (both represented in the form of a free acid, and the anion component is a chloride ion) were synthesized, and these compounds were synthesized. When the cotton cloth and the polyester / cotton blended cloth were dyed with the above dye according to the method described in Examples 1 and 3, the dyes were deeply dyed and had good build-up properties.

The color tone and λmax of the obtained dyed fabric are shown in Table 1 and Table 2
The results were as shown in the table.

[Effects of the Invention] The formazan dye of the present invention is a water-soluble formazan dye having a triazine-type reactive group having a pyridine ring bonded in the structure, and is useful as a dye having a blue color tone. In particular, when this compound is used for dyeing fibers containing cellulose or nitrogen-containing fibers, various fastnesses are good, and
It has the effect of having excellent dyeability. Then, this effect can be obtained at a high temperature of 120 to 140 ° C. which has been conventionally adopted as a dyeing condition for polyester, and under a dyeing condition in a low pH region. Therefore, the dye of the present invention can be prepared by using, for example, a polyester / cellulose or a mixed fiber with a nitrogen-containing fiber together with a water-soluble disperse dye,
It is particularly suitable as a reactive dye for simultaneous dyeing in a single bath.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-90264 (JP, A) JP-A-61-40367 (JP, A) JP-A-60-181373 (JP, A) JP-A-59- 58059 (JP, A)

Claims (1)

[Claims] 1. The following general formula [I] in the form of a free acid.[In the formula, Y¹And Y²Is a hydrogen atom, a lower alkyl group,
Fonate group, carboxyl group, sulfamoyl group, carba
Represents a moyl group or a hydroxyethyl group, n is 1 to
Represents an integer of 2, A Represents an anion)
A water-soluble formazan dye.