JPS6220312B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for improving the color fastness of a dyed product obtained by dyeing cellulose fibers or fiber materials made of cellulose fibers and other fibers using reactive dyes or vat dyes. Reactive dyes have shown remarkable growth in usage in recent years due to their excellent color clarity and wet fastness. However, there are two problems regarding the color fastness of dyeings made with reactive dyes. One is acid hydrolysis resistance. During dyeing, reactive dyes form covalent bonds with fibers and form strong bonds; however, over time after dyeing, these bonds undergo hydrolysis and break due to the influence of acids, etc., resulting in moisture loss. This causes the dye to fall off and contaminate other clothing. As a countermeasure to this problem, the dyed product is treated with a dilute aqueous solution of a specific polyamine after dyeing, and this method has been shown to be quite effective. The second problem is the fastness to chlorine. This is a phenomenon in which dyes are oxidized by the action of chlorine contained in the tap water used when washing dyed products, causing fading or discoloration of dyed products. Although treatment with the polyamines developed to date can achieve the purpose of preventing aging,
In many cases, the dye becomes more susceptible to the action of chlorine in tap water, which actually promotes discoloration and fading. Therefore, countermeasures against this problem are required. Regarding the color fastness of dyed products using vat dyes, there is relatively no problem with other fastness properties, but as with reactive dyes, chlorine fastness is low and easily altered by tap water. Causes discoloration. In view of this current situation, the present inventor has developed a method for improving the chlorine fastness of reactive dyes while maintaining various fastness properties such as acid hydrolysis resistance, washing resistance, water resistance, and sweat resistance. In particular, in the case of vat dyes, various studies have been conducted with the aim of improving their chlorine fastness. As a result, it is produced by the condensation of polyethylene polyamine () represented by the general formula _NH2- ( _CH2CH2NH ) _-oH (wherein n is 1 to 5 ₎ and epihalohydrin ().
It has been found that a polymer having a molar ratio of () to () of 0.5 to 2 has the ability to achieve the above object, and has thereby completed the present invention. That is, the present invention relates to improving the color fastness of a dyed product dyed using a reactive dye or a vat dye, which is characterized by treating the dyed product using the above-mentioned polymer. Regarding improvement methods. The acid hydrolysis resistance of dyed products treated with the polymer of the present invention is excellent, and because the polymer has a high charge density, it is about 1/2 that of conventional processing agents.
It has the advantage of being effective in small amounts. Furthermore, it has extremely good performance in terms of chlorine fastness, and by treatment according to the method of the present invention, it can be improved to such an extent that discoloration and fading due to chlorine is hardly observed. This is in sharp contrast to conventional polyamines, which actually promote discoloration and fading due to chlorine. It also has good performance in terms of fastness to water, fastness to washing, and fastness to sweat. However, in the case of treatment with the polymer of the present invention, discoloration due to treatment may be observed exceptionally with a few dyes such as Leverfix Navy Blue E-RA, but in such cases, the treatment solution PH of 4
This can be prevented by maintaining the following. The method for producing the polymer used in the present invention will be specifically shown in the following reference examples, and it can be obtained by heating the above-mentioned mixture of polyethylene polyamine and epihalohydrin in water or an organic solvent at a temperature in the range of 30 to 100°C. These polymers are easily soluble in water and have a pH of
It is stable as an aqueous solution in all regions of 1 to 14. There are no particular limitations on the method for treating dyed articles using the polymer according to the present invention, and conventionally known methods can be used as appropriate. For example, if the polymer is
The dyed article to be treated may be immersed in an aqueous solution of 0.1 to 2 g for a predetermined period of time, then washed with water and dried. The bath ratio is usually 1:10 to 20, the treatment temperature is usually room temperature to 80°C, and the treatment time is usually 5 to 20 minutes. In order to further clarify the present invention, synthesis examples of polymers used in the present invention are shown below as reference examples, and then examples are shown. Reference Example 1 361 g of ethylenediamine was placed in a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, and thermometer.
Add 392g of water and stir to dissolve uniformly, then heat to raise the temperature to 50℃. Add 555 g of epichlorohydrin from the dropping funnel to this mixture.
was added dropwise over 2 hours. 30 minutes after finishing dropping, lower the temperature to 80
℃ and react for 3 hours under stirring. It can be seen that the viscosity of the reaction solution gradually increases, and condensation progresses. After the reaction was completed, 10 g of the reaction solution was taken and poured into 500 ml of acetone to produce a white precipitate. The precipitate was filtered through a glass filter and dried under reduced pressure at 60° C. for 24 hours to obtain 6.8 g of a white solid polymer. Yield is 97
It was %. Reference Example 2 In the same manner as Reference Example 1, ethylenediamine 60
g, 139 g of epichlorohydrin was reacted in 200 g of water. After the reaction is complete, take 10g of the reaction solution and use it as reference example 1.
The same treatment as above was carried out to obtain 4.8 g of a white solid polymer. The yield was 98%. Reference Examples 3 to 6 In place of ethylenediamine in Reference Example 1, diethylenetriamine, triethylenetetramine,
In the same manner as in Reference Example 1 using tetraethylenepentamine and pentaethylenehexamine, respectively,
A white solid polymer was obtained by reaction with epichlorohydrin in water. The results are shown in Table 1.

[Table] Example 1 A 0.5 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 6 above was prepared, and then dyed by dipping at a concentration of 4% (based on fiber weight) using the following reactive dye. dyed cotton cloth at a bath ratio of 1:20 and a temperature of 50°C.
After soaking for a minute, washing with water, and air drying. The dyes used were Leverfix Golden Yellow EG manufactured by Bayer AG (hereinafter abbreviated as Bayer) and Leverfix Brilliant Red E- manufactured by Bayer.
4B and Bayer's Leverfix Brilliant Red E-2B. Next, the acid hydrolysis resistance of this treated dyed cotton fabric was examined using the following method and compared with that of an untreated dyed cotton fabric.
After immersing the test piece in a solution of 10 g/lactic acid, it is squeezed using a squeezing machine to a squeezing rate of 80%, and dried at 120°C for 4 minutes. Once the test piece is dry, it is sandwiched between two attached white cloths and roughly sewn together to prepare a composite test piece. After that, the water fastness test method (JIS-L
-0846). The results are shown in Table 2. In the case of untreated dyed cotton fabrics, considerable staining of the attached white cloth was observed for all dyes; however, with the dyed fabrics treated using the polymer according to the present invention, no staining of the attached white cloth was observed. Nakatsuta.

[Table] Example 2 A 0.5 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 6 above was prepared, and then the following reactive dye was used at a concentration of 4% (based on the weight of the fiber) using a dipping method or A dyed cotton fabric dyed by the printing method was immersed in an aqueous polymer solution at a bath ratio of 1:20 at a temperature of 50°C for 20 minutes, washed with water, and then air-dried. The dyes used were Leva Fix Golden Yellow G manufactured by Bayer, Cibacron Navy Blue TRBE (dyed by dipping method) manufactured by Ciba Geigy (hereinafter referred to as Ciba), Cibacron Brilliant Blue 3R-P manufactured by Ciba,
Ciba Cibacron Brilliant Blue BR-P
(The above is dyed using the printing method). Next, the chlorine fastness of this treated dyed cotton fabric was examined using the following method and compared with that of an untreated dyed fabric. The test piece was immersed in a buffer solution with a pH of 8.0 ± 0.2 containing 50 p.pm as available chlorine (bath ratio 1:100) and heated at 25°C for 4 hours.
Run it on a JIS L 0821 washing test machine. Thereafter, it was washed under running water for 10 minutes, dehydrated, and dried. The result is the third
Shown in the table. In contrast to the untreated dyed cotton fabrics that all showed significant discoloration, the dyed cotton fabrics treated with the polymer shown in the reference examples showed no discoloration and fading, indicating that they had good chlorine fastness.

【table】

[Table] Example 3 A 0.5 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 6 above was prepared, and then dyed at a concentration of 2% (based on fiber weight) using the following vat dyes. Add cotton cloth to this solution at a bath ratio of 1:20 and a temperature of 50.
After soaking at ℃ for 20 minutes, washing with water, and air drying.
The dyes used were Mikethrene Brilliant Blue R manufactured by Mitsui Toatsu Chemical Co., Ltd. (hereinafter referred to as Mitsui), Mikethrene Brilliant Blue 4G manufactured by Mitsui, Mikethrene Blue 3G manufactured by Mitsui, and Mikethrene Blue RSN manufactured by Mitsui. . The treated dyed cotton fabric was then tested for chlorine fastness using a method similar to that used in Example 2, and the results were compared to the untreated dyed fabric. The result is the fourth
Shown in the table. In the case of untreated dyed cotton fabrics, all dyes exhibited discoloration accompanied by significant discoloration, but in the case of dyed cotton fabrics treated with the polymer shown in the reference example, no discoloration or fading was observed, and in the case of vat dyes. It can be seen that it also has good chlorine fastness.

【table】

Claims (1)

[Claims] 1. Epihalohydrin () per mole of polyethylene polyamine () represented by the general formula NH ₂ -(CH ₂ CH ₂ NH) _o -H (in the formula, n is 1 to 5). It is characterized by treating dyed products obtained by dyeing cellulose fibers or fiber materials consisting of cellulose fibers and other fibers with reactive dyes or vat dyes using 0.5 to 2 moles of a polymer produced by condensation. A method for improving the color fastness of dyed products.