JPS607073B2 - Dyeing method for hydrophobic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing hydrophobic fibers, especially polyester fibers or acetate fibers, in a strong yellow to greenish-yellow color.

The dye used in the method of the present invention is a monoazo dye represented by the following general formula 01.

(In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and Y represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, a nitro group, or a cyano group.

However, one of X and Y always represents an iodine atom. Z represents a hydrogen atom, a lower alkyl group, or a lower alkoxy lower alkyl group. Here, lower alkyl and lower alkoxy refer to those having 1 to 6 carbon atoms. ) Many dyes similar to the dyes used in the method of the present invention have been reported, but each of these known dyes has its own characteristics and all have various drawbacks.

As a result of intensive research and consideration, the present inventor has determined that the general formula (1)
When hydrophobic fibers, especially polyester fibers or acetate fibers, are dyed and printed using the dyes shown in
The present inventors have discovered that it is possible to obtain a yellow to greenish-yellow dyed product which has excellent fastness properties, particularly light fastness and sublimation fastness, and has completed the present invention.

The coupling component of the present invention is described in Japanese Patent Publication No. 46-19716 and Japanese Patent Publication No. 47-1854, and the diazo component contains a phenyl group substituted with an iodine atom such as the diazo component of the present invention. is not mentioned.

One of the characteristics of the dyes of the present invention is that they have this diazo component, that is, an iodine atom, in the ortho and/or para positions of the azo group, and these dyes have extremely excellent color build-up properties and are fast to sublimation. The quality is extremely high.

Generally speaking, there is a contradictory relationship between improving dye build-up properties and improving sublimation fastness, and either one of them must be sacrificed, or both must be kept to a certain level. Considering that the reality is that this is not the case, this is extremely noteworthy. A comparison of the sublimation fastness between the dye of the present invention and the dye of Japanese Patent Publication No. 47-1854 is shown below.

The structure of the dye shown in the table shall be shown by the formula.

As is clear from the above table, it can be seen that the dyes of the present invention have superior sublimation fastness compared to those of the cited examples.

The dye of general formula '1' used in the method of the present invention can be obtained, for example, as follows. The amine represented by the following formula '2) is diazotized, and the general formula '3'
It can be obtained by coupling with a coupling component represented by

(The meanings of ×, Y, and Z are the same as in the general formula '1].) The amine represented by the general formula is represented by the following formula {4
} amine (where Y is a hydrogen atom, a chlorine atom,
(representing a bromine atom, methyl group, methoxy group, etro group or cyano group) by a known method, and a compound represented by the following formula '5} (wherein X represents a chlorine atom or a bromine atom) It can be obtained by iodizing amine by a known method.

Furthermore, in the general formula (2}, both x and Y are iodine, which can be obtained by diiodinating aniline by a known method.

The coupling component {3' used in the present invention can be prepared by a known method (for example, Berichte 296).
54 (1896)).

That is, acetoacetic acid methyl ester, cyanoacetic acid methyl ester, and the general formula '61 N-Z (6} (the meaning of Z is the same as that in the general formula (1}, {3l).

) is reacted by heating, diluted by adding water after cooling, and then acidified by adding hydrochloric acid or sulfuric acid, and the precipitated crystals are obtained by furnace separation.

The dye of general formula '1} used in the method of the present invention is used by grinding the dye into fine particles in an aqueous medium together with a suitable dispersant when dyeing hydrophobic fibers.

It is preferable to use the dispersed beam agent in the form of a paste or in the form of a powder by spray drying or the like. The beam agent thus obtained is heated in an aqueous medium in which the fibers are soaked under pressure at a temperature of 1060°C or higher, preferably 110°C to 140°C.
It is advantageous to dye at °C. It is also possible to dye at a relatively high temperature, for example, in the boiling state of water, in the presence of a carrier such as O-1 phenylphenol or trichlorobenzene.

Alternatively, pat the dye dispersion onto the cloth and
It is also possible to use the so-called thermosol dyeing method, which involves drying between 3 town sand and 9 present sand at 230 pm C. On the other hand, in the case of printing, the dye dispersion is kneaded with a suitable paste, and the mixture is putted onto cloth and the desired purpose is achieved by steaming or thermosol method.

Next, the present invention will be explained in more detail with reference to Examples.

"Example Middle" means parts by weight. Example 1 1.2 parts of a dye powder of the following formula was finely dispersed in an aqueous medium together with 2.4 parts of a condensate of alkylnaphthalene-sulfonic acid and formalin as a dispersant and 0.4 parts of sodium polyalkylnaphthalenesulfonate as a wetting agent. Crush it into pieces and disperse it.

This dispersion was added to 400$ of water containing 1 part of sodium oleyl sulfate.
10 pieces of polyester fiber (for example, Tetron) are soaked in the liquid added to the dyeing process and dyed in a pressurized container at 130 qo for 60 minutes. If the dyed fibers are post-treated in a conventional manner, a yellow dyed product with good fastness can be obtained. The dye used in this example can be obtained, for example, as follows.

2-nitro-4-yodoaniline obtained by iodizing 0-nitroaniline by a known method5. Thoroughly knead 5 parts of hydrochloric acid and 5 parts of hydrochloric acid in a mortar, add 5 parts of hydrochloric acid and 10 parts of water to form a suspension, and stir under ice cooling for 0 to 3 hours.
A solution consisting of 1.4 parts of sodium nitrate and 1 part of water is added dropwise at .

After stirring for 2 hours at 0 to 3°C, a small amount of sulfamic acid is added to prepare a diazo solution.

On the other hand, 1-n-butyl-3-cyano-4-methyl-6-hydroxypyrido-2-one 4. Gunbe, caustic soda 4.
0 parts, 5.4 parts of soda carbonate, and 300 parts of water were dissolved to prepare a coupling solution.

Three portions of the diazo solution are added dropwise into this coupling solution at 0° C. to 10 qo.

After 30 minutes at the same temperature, raise the temperature to approximately 70 qo for 30 minutes.
If you wash it with hot water and dry it, it will turn into yellow crystals.'7
) Dye represented by formula 8. A group part is obtained. Example 2 1.2 parts of a dye powder of the following formula was dispersed by adding a dispersant and finely pulverized in the same manner as in Example 1, and the dispersion was mixed with a commercially available carrier (Carrierant 323-Toho Chemical Products). ) 5 parts, surfactant (Monogen Daiichi Kogyo Pharmaceutical Products) 5 parts, and water 150 parts
In addition to the dyeing consisting of the anchor part, 100 parts of the Tetron fabric were soaked to raise the liangsu to the boiling point in 30 minutes and held at this temperature for 60 minutes.

Further, if the dyed product is post-treated by a conventional method, a green-yellow dyed product with good fastness can be obtained. The dye used in this example can be obtained as follows.

5.1 parts of 2-chloro-4-iodoaniline obtained by iodizing 0-chloroaniline by a known method, 1 part of hydrochloric acid, and 10 parts of water were mixed and heated at about 60 oo for 30 minutes.

After cooling, a solution consisting of 1.4 parts of sodium nitrite and 1 part of water was added dropwise at 0 to 3° C. over 30 minutes, and after stirring for 1 hour at 0 to 300° C., a small amount of sulfamic acid was added to prepare a diazo solution. On the other hand 1-
A coupling liquid was prepared by dissolving 4.5 parts of (r-methoxypropyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one, 15 parts of sodium acetate, and 30 parts of water.

Add 60% diazo solution to this coupling solution at 0°C to 500°C.
Drips in minutes. After 30 minutes at the same temperature, raise the temperature to approx.
After brewing the sake at qC for 1 hour, removing it from the oven, washing the scratches, and drying, 9.6 parts of the dye represented by the formula (8) is obtained as yellow crystals.Example 3 An example was carried out using the dye of the following formula. Polyester fibers can be dyed yellow with good fastness in the same manner as in Example 1 or Example 2.

To use this dye for textile printing, it is dispersed in the same manner as in Example 1, and then a colored paste is prepared according to the following composition.

■ Formula dispersed dye 1 part lukewarm water
27.8 parts Carpoxymethyl cellulose glue 6 parts Tartaric acid
0.2 parts leveling agent (Improver 800
) 2 parts (*manufactured by Yokohama Polymer Research Institute) total
10 anchor parts Using this color paste, ink lacquer, drying, steaming with superheated steam at 175°C for 5 minutes, washing with water, descaling, reduction washing, washing with water and drying.

To use this dye in the thermosol dyeing method, after dispersing it in the same manner as in Example 1, add 10 parts of the dispersed and dissolved dye to a pad tank and add 1 part of sodium alginate as a migration inhibitor. A pad solution is used to pad a polyester/cotton blend cloth at room temperature, and the weight increase rate is reduced to 65%.

After performing intermediate drying, dry heat fixation of 200q0, 9 town sand is performed.

Next, it is subjected to reduction cleaning, washing with water and drying. In both the above-mentioned printing and thermosol methods, a yellow dyed product with excellent fastness was obtained. The dye used here was 1-ethyl-3-cyano instead of 1-n-butyl-3-cyano-4-methyl-6-hydroxy-pyrid-2-one used in producing the dye used in Example 1. -4-methyl-6-
It can be obtained in the same manner as in Example 1 using hydroxypyrid-2-one. Dye used in Example 1 1. Instead of Yukuni, it is represented by the following general formula, and its X, Y, Z
By applying the same method as in Example 1 using 1.2 parts of each dye having the structure shown in the following table, dyed products with the tones shown in the right column of the following table all had good fastness. can get.

Next, the m. p. Or input max is shown in the table below.

Claims (1)

[Scope of Claims] 1. A method for dyeing hydrophobic fibers, characterized by using a water-insoluble monoazo dye represented by the following general formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and Y represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, a nitro group, or a cyano atom. Represents a group. However, one of X and Y always represents an iodine atom. Z represents a hydrogen atom, a lower alkyl group, or a lower alkoxy lower alkyl group. Here, lower alkyl and lower alkoxy mean a group having 1 or more carbon atoms. (It represents six things.)