JPS6220314B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for improving the color fastness of a dyed material made of cellulose fibers or other fibers dyed using reactive dyes or vat dyes. Reactive dyes have shown remarkable growth 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 , dye comes off due to moisture, and appears as contamination of 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. When treated with the polyamines that have been developed to date, although the purpose of preventing aging can be achieved, the dyes become more susceptible to the action of chlorine in tap water, which actually promotes discoloration and fading. This is often the case. Therefore, countermeasures against this problem are required. In addition, with respect to the color fastness of dyed products made with vat dyes, there is relatively no problem with other fastness properties, but as with reactive dyes, chlorine fastness is low and easily stained with tap water. Causes discoloration and fading. 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, polyethylene polyamine () represented by the general formula NH ₂ -(CH ₂ CH ₂ NH) _o H (wherein n is 1 to 5) and the general formula (In the formula, R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 18 carbon atoms, or a hydroxyethyl group, respectively) and epihalohydrin (). This results in
The charging molar ratio of () and () is 0.01 to 5, and the charging molar ratio of () + () to () is 0.5 to 5.
It has been discovered that a polymer falling within the range of No. 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. It is about how to improve. The acid hydrolysis resistance of dyed products treated with the polymer of the present invention is excellent, and the dye has the advantage of being effective with about 1/2 the amount compared to conventional treatment agents. It also has good performance in terms of fastness to chlorine, and by treating it with the method of the present invention, discoloration and fading due to chlorine can be significantly improved compared to the untreated case. This is in contrast to conventional polyamine treatment, which actually promotes discoloration and fading due to chlorine. Furthermore, it has good performance in terms of fastness to water, fastness to washing, and fastness to sweat. The method for producing the polymer used in the present invention is specifically shown in the reference examples below, and it can be obtained by heating a mixture of the above-mentioned polyethylene polyamine, primary or secondary amine, and epihalohydrin in water or a polar solvent. . These polymers are easily soluble in water. 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, the concentration of the polymer
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, synthetic examples of polymers used in the present invention are shown as reference examples,
Next, examples will be shown. Reference Example 1 Add 25 g of ethylenediamine, 70% to a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, and thermometer.
Add 27 g of ethylamine aqueous solution and 55 g of water, stir to dissolve uniformly, and then maintain the temperature at 20°C.
Add epichlorohydrin from the dropping funnel to this mixture.
77g was added dropwise over 4 hours. 30 minutes after the addition was completed, the temperature was raised to 70℃, and the temperature was kept constant for 4 more hours.
Allowed time to react. The viscosity of the reaction solution gradually increases,
It can be seen that the condensation progresses. After the reaction was completed, 10 g of the reaction solution was poured into 500 ml of acetone to produce a white precipitate. Filter the precipitate through a glass filter at 60°C.
After drying for 24 hours, 6.7 g of white solid polymer was obtained. The yield was 97%. Reference Example 2 Ethylenediamine 45 was prepared in the same manner as Reference Example 1.
g, 16 g of a 70% aqueous ethylamine solution, and 93 g of epichlorohydrin were reacted by adding 94 g of water. After the reaction was completed, 10 g of the reaction solution was taken and treated in the same manner as in Reference Example 1 to obtain 5.5 g of a white solid polymer. Yield 90%
It was hot. Reference Example 3 Ethylenediamine 21 was prepared in the same manner as Reference Example 1.
83 g of water was added to 42 g of 70% ethylamine aqueous solution and 92 g of epichlorohydrin and reacted. After the reaction was completed, 10 g of the reaction solution was taken and treated in the same manner as in Reference Example 1 to obtain 5.9 g of a white solid polymer. Yield 94%
It was hot. Reference Examples 4 to 12 In place of ethylamine in Reference Example 1, other primary or secondary amines as shown in Table 1 were used and reacted with ethylenediamine and epichlorohydrin in water in the same manner as in Reference Example 1. A white solid polymer was obtained. However, depending on the type of each amine, the dropwise addition time of epichlorohydrin and the temperature of the reaction system during the dropwise addition are slightly different. These reaction conditions and the yield of the obtained polymer are summarized in Table 1.

[Table] Example 1 A 0.5 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 12 above was prepared, and then dyed by dipping at a concentration of 4% (based on fiber weight) using the following reactive dye. The dyed cloth 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 air-dried. The dyes used were Leverfix Golden Yellow EG manufactured by Bayer AG (hereinafter abbreviated as Bayer), Leverfix Brilliant Red E-4B manufactured by Bayer, and Leverfix Brilliant Red E-2B manufactured by Bayer. Next, the acid hydrolysis resistance of this treated dyed fabric was examined using the following method and compared with that of an untreated dyed fabric. After immersing the test piece in a solution containing 10 g of lactic acid, it is squeezed using a squeezing machine to a squeezing rate of 80%, and dried at 120°C for 4 minutes. After the specimen is dry, it is sandwiched between two attached white cloths (silk and cotton) and roughly sewn together to prepare a composite specimen. After that, the water fastness test method (JIS
-L-0846). The results are shown in Table 2. In the case of untreated dyed fabrics, considerable staining was observed on the attached white cloth for all dyeings, but in the case of dyed fabrics treated using the polymer of the present invention, almost no staining was observed on the attached white cloth. .

[Table] Example 2 A 0.5 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 12 above was prepared, and then the following reactive dye was used at a concentration of 4% (based on the fiber weight) by dipping or printing. A dyed cotton fabric dyed by the 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 Levafix 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 tested using the following method and compared with that of an untreated dyed cotton fabric. The test piece was immersed in a buffer solution with a pH of 8.0 ± 0.2 containing 50 ppm of available chlorine (bath ratio 1:100), and was heated at 25°C for 4 hours.
For an hour, put it in a JIS-L-0821 washing test machine. Thereafter, it was washed under running water for 10 minutes, dehydrated, and dried. The results are shown in Table 3. In the case of untreated dyed cotton fabrics, all showed significant discoloration, whereas the dyed cotton fabrics treated with the polymer shown in the reference example showed almost no discoloration and fading and had good chlorine fastness. I understand.

[Table] Example 3 A 0.5 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 12 above was prepared, and dyed cotton cloth was then dyed at a concentration of 2% (based on fiber weight) using the following vat dyes. to the polymer aqueous solution at a bath ratio of 1:20 and a temperature of
It was immersed at 50°C for 20 minutes, washed with water, and air-dried.
The stains 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 with those of the untreated dyed cotton fabric. The results are shown in Table 4. In the case of untreated dyed cotton fabrics, all dyes exhibited discoloration accompanied by significant discoloration, but dyed cotton fabrics treated with the polymer shown in the reference example showed almost no discoloration and fading, and vat dyes It can be seen that it also has good chlorine fastness.

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Claims (1)

[Claims] 1 0.01 to 5 mol 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) and the general formula [In the formula, R ₁ and R ₂ are each hydrogen, carbon number 1 to 18
is an alkyl group or hydroxyethyl group]
Using a polymer produced by condensing 0.5 to 2 moles of epihalohydrin () to 1 mole of a mixture of 1 mole of primary or secondary amine () represented by 1. A method for improving the color fastness of a dyed product, which comprises treating a dyed product obtained by dyeing a fiber material made of fibers using a reactive dye or a vat dye.