JPS6344867B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to concentrated solutions of metal complex dyes. More particularly, the present invention relates to concentrated solutions of chromium or cobalt complex dyes having sulfonic acid groups. Metal complex dyes having sulfonic acid groups are used in dyeing and printing in textile, leather, woodworking, and metal dyeing industries, but when used in powder form, they scatter during handling, worsening the working environment. For this reason, it is desirable to provide this type of dye as a solution. The properties of the dye solution are required to be stable during long-term storage, safe for the human body, highly concentrated, and have good performance in use. The present inventors have completed the present invention as a result of repeated research for this purpose. That is, the present invention provides (a) a metal complex dye having a sulfonic acid group, and (b) the following general formula: {In the formula, R is a saturated or unsaturated carbon number of 12 to
18 alkyl group or formula

[Formula] (In the formula, R' represents a saturated or unsaturated alkyl group having 10 to 16 carbon atoms), and x and y are in a relationship such that the total of x and y is 2 to 40. is an integer that satisfies } This is a concentrated solution of a metal complex dye characterized by comprising an oxyamine derivative represented by the following and (c) an organic solvent selected from lower alcohols, polyhydric alcohols, and their ethers. This concentrated solution is a highly concentrated solution never before seen in the wool dyeing industry, has low toxicity to the human body, and is stable for long periods of storage over a wide temperature range from -20°C to 60°C. , and easy to use. Furthermore, compared to powdered dyes, it has higher dyeability during wool dyeing, and has almost no residual metal (eg, chromium) concentration in the residual bath, reducing the burden of wastewater treatment on dyeing factories. Furthermore, when used for coloring leather, the water resistance of the colored surface is significantly improved. Examples of chromium or cobalt complex dyes having sulfonic acid groups suitable for use in the present invention include the following dyes:

[Table] The amine derivative used in the present invention is represented by the following structural formula, for example, and is usually liquid. Examples of lower alcohols, polyhydric alcohols, their ethers or esters, or polyethers include ethanol, n-propanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoacetate. , diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, polyethylene glycol and dithioethylene glycol. The proportions of (a) the metal complex dye having a sulfonic acid group, (b) the above-mentioned oxyamine derivative, and (c) the above-mentioned organic solvent are 30 to 60%, respectively, based on the weight of the target concentrated solution. 5 to 40%, 20 to 50%, and if necessary, water may be added to this concentrated dye solution, or if necessary, a hydrophilic organic solvent such as butyrolactone or dioxane may be added. The organic solvent and oxyamine derivative used in the present invention are selected from those with low toxicity to the human body. In order to produce the concentrated solution of the present invention, a dried product of a metal complex dye having a sulfonic acid group, a wet cake, or a reaction solution in which metal complex formation has been completed is dissolved in the above-mentioned amine derivative and a solvent at room temperature or under heating. . The concentrated solution of the present invention has a concentration 2 to 3 times that of conventional dye solutions for wool dyeing, and also has a concentration of 50 to 70% relative to powder dyes. Furthermore, it has excellent cold stability, and even when stored for long periods in a -20°C freezer, it does not gel or solidify, and no dye precipitation is observed. In addition, no change in hue or density was observed in a heat abuse test at 60°C, indicating extremely excellent stability from low to high temperatures. This concentrated solution can be used as it is or diluted for dyeing or printing natural or synthetic polyamides, cellulose, and metals such as aluminum. Particularly in the dyeing of wool fibers, this concentrated solution has high permeability and good dyeability, and is advantageously used for one-bath one-step dyeing, one-bath two-step dyeing, or two-step dyeing of blended fabrics of wool fibers and other fibers. I can do it.
For example, if you try to dye a blended product of acrylonitrile fiber and wool fiber with a cationic dye and a metal complex dye having a sulfonic acid group at the same time, the disadvantage is that complexes will be generated between these dyes and they will settle. However, since the concentrated solution of the present invention does not easily generate complexes even when used simultaneously with a cationic dye, dyeing could be carried out in one step in one bath. Also, the metal concentration in the remaining bath after dyeing,
For example, the chromium concentration is reduced from one-tenth to one-hundredth of that of powdered products, to around 0.02 ppm, which greatly reduces the burden of chromium wastewater treatment in dyeing factories. In the dyeing of leather, this concentrated solution can be diluted with water or any desired suitable solvent in any proportion without forming deposits in the diluted solution. For this reason, it is very advantageous over leather dyeing methods using spray guns. In addition, leather colored with this concentrated solution has excellent water resistance compared to leather colored with a conventional metal complex dye solution containing sulfonic acid groups, and the water permeability test shows that the colored surface does not bleed or darken. The unevenness is significantly improved. Furthermore, the surface of the leather after coloring is generally treated with a water-soluble or water-diluted emulsion such as casein or water-based acrylic emulsion, but the leather colored with the concentrated solution of the present invention is treated with a water-soluble or water-diluted emulsion. There was no contamination of the surface-treated paint film. Among the concentrated solutions of the present invention, an amine derivative with a total number of ethylene oxide chains (total of x and y) of 5 to 50 is selected for dyeing wool fibers, and an amine derivative with a total number of ethylene oxide chains of 2 to 10 is selected for leather dyeing. It is preferable to do so. As described above, it is important to select the amine derivative for the concentrated solution of the present invention according to its intended use, and by doing so, great practical effects can be obtained. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. Example 1 40 parts of dye C.I18761 was prepared using the following formula. The mixture was added to a solution consisting of 10 parts of oxyamine represented by the following formula, 25 parts of ethylene glycol, 15 parts of alcohol, and 10 parts of water, stirred and dissolved at room temperature for about 60 minutes, and trace amounts of undissolved matter were removed by filtration. The concentrated solution thus obtained has extremely excellent storage stability over a temperature range of -20°C to 70°C without causing dye precipitation, gelation, change in concentration, or change in hue. Furthermore, it has the same hue as powder C.I18761 and exhibits excellent dyeing properties for wool yarn, and the chromium concentration in the dyeing residual bath is
100 compared to staining used in powder form.
It decreased to one-fold. Note that when oxyamine was excluded from the above solvent composition, only 20 parts of C.I18761 was dissolved. Example 2 40 parts of dye C.I18735 was mixed with the following formula in a solution consisting of 30 parts of oxyamine, 15 parts of ethylene glycol, and 15 parts of alcohol;
Stir and dissolve at 50°C for minutes. Thereafter, the mixture was cooled to room temperature, and insoluble materials were removed by filtration. The concentrated solution thus obtained is Example 1
It had similar performance. Example 3 40 parts of dye C.I13901 was mixed with the following formula of oxyamine and 35 parts of ethylene glycol monomethyl ether.
Stir and dissolve at 50°C for minutes. The concentrated dye solution is then cooled to room temperature and traces of residue are removed by filtration. The concentrated solution thus obtained had similar performance to Example 1. Example 4 40 parts of C.I15711 was used as a dye according to the following formula. The mixture is added to a mixed solution consisting of 33 parts of oxyamine represented by the formula and 46 parts of ethylene glycol monomethyl ether, and stirred and dissolved at 70°C for 60 to 90 minutes. Thereafter, it was cooled to room temperature, and trace amounts of undissolved matter were removed by filtration. The concentrated solution thus obtained has similar performance to Example 1. This concentrated solution is particularly suitable for dyeing leather. For example, 10 parts of this concentrated solution was diluted with 63 parts of water and 27 parts of ethylene glycol monoethyl ether and used for spray dyeing. This colored leather, which was air-dried for a day and a night after dyeing, had excellent level dyeing properties and water drip tests. Also, no change is observed when boiling in water.
No contamination of the coating film was observed in a coating test using the aqueous acrylic emulsion as a surface finishing agent. still,
For comparison, when leather was colored with a solution that did not contain the amine derivative, the dye leaked out when it was immersed in water, staining the solution in a deep color even when exposed to cold water. Example 5 40 parts of dye C.I18761 was mixed with the following formula 10 parts of oxyamine, 25 parts of ethylene glycol,
It was added to a mixed solution consisting of 15 parts of alcohol and 10 parts of water, stirred and dissolved at room temperature for about 60 minutes, and trace amounts of undissolved matter were removed by filtration. The concentrated solution thus obtained had similar performance to Example 1. Example 6 40 parts of C.I18761 was added as a dye according to the following formula. Add to a mixture of 10 parts of oxyamine represented by, 20 parts of ethylene glycol, 20 parts of alcohol, and 10 parts of water, stir and dissolve at room temperature for about 60 minutes,
Trace amounts of undissolved matter were removed by filtration. The concentrated solution thus obtained had similar performance to Example 1. Example 7 30 parts of CI15711 was used as a dye according to the following formula. The mixture was added to a mixed solution consisting of 10 parts of oxyamine represented by the formula and 57 parts of ethylene glycol monomethyl ether, stirred and dissolved at 70°C for about 70 minutes, and trace amounts of undissolved matter were removed by filtration. The concentrated solution thus obtained had similar performance to Example 1. An example of cheese dyeing a blended yarn of acrylonitrile fiber/wool fiber (blend ratio 70/30) using this concentrated solution in one step in one bath will be described below. 30.0 parts of the concentrated solution of this example, 17.5 parts of Eisenkatyron Black AWH Liquid (Hodogaya Chemical Co., Ltd. product), 10 parts of Kathylon Salt W New Conc (nonionic surfactant, Hodogaya Chemical Co., Ltd. product)
Ospin 100K (dyeing aid, Tokai Oil Co., Ltd. product)
30 parts, 25 parts of acetic acid, 5 parts of sodium acetate and warm water
A dye bath was prepared from 10,000 parts. As an example of an acrylonitrile fiber/wool blend yarn, 1000 parts of cashmilon/wool (70/30) 52 count cheese single yarn was dyed in the above dye bath using a cheese dyeing machine using a one-bath one-step dyeing method. . After dyeing, it was washed with water and then soaped with a soaping liquid (bath ratio 1:10) consisting of 0.1% Neugen HC (surfactant, product of Daiichi Kogyo Seiyaku Co., Ltd.) and 0.05% acetic acid. Next, Buryan TW-45 (softening agent, Matsumoto Yushi Co., Ltd. product)
The material was softened with a 4% aqueous solution (solution ratio 1:10), washed with water, and dried. The cheese single yarn thus obtained was uniformly dyed in both the inner and outer layers, and the wet friction fastness of both the inner and outer layers of the cheese was grade 4.

Claims (1)

[Scope of Claims] 1 (a) a metal complex dye having a sulfonic acid group; (b) the following general formula: {wherein R represents a saturated alkyl group having 12 to 22 carbon atoms, or a group represented by the formula, [formula] (wherein R' represents a saturated alkyl group having 10 to 20 carbon atoms), x and y are integers such that the sum of x and y satisfies a relationship of 2 to 50. }; and (c) an organic solvent selected from lower alcohols, polyhydric alcohols, and their ethers.