JPS6220313B2 - - 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. The amount of reactive dyes used has increased significantly 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. Reactive dyes are
During dyeing, covalent bonds are formed and strongly bonded to the fibers, but over time, these bonds are hydrolyzed and broken due to the influence of acids, etc., and as a result, the dye falls off due to moisture. , appearing 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. Although treatment with the polyamines developed to date can achieve the purpose of preventing aging,
On the contrary, the dye becomes more susceptible to the action of chlorine in tap water, which often promotes discoloration and fading. 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, the fastness to chlorine is low and is easily washed away by tap water. The color changes and fades. 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, a polymer () produced by the condensation of polyethylene polyamine and _{epihalohydrin} represented by the general formula _NH2- ( _CH2CH2NH ) _-oH (wherein n is 1 to 5)
and the general formula or [In the formula, R ₁ , R ₂ , R ₃ are each H, carbon number 1 to
12 alkyl groups or

[Formula] and X is Cl, Br or I, Y is Cl, NO ₃ , 1/2SO ⁻ ₄ or C _o H _2o+1 COO (in the formula, n = 1 to 6)] The present inventors have discovered that a reaction product with a compound having the above-mentioned properties has the ability to achieve the above object, and as a result, the present invention has been completed. That is, the present invention relates to improving the color fastness of a dyed product dyed with a reactive dye or a vat dye, which is characterized by treating the dyed product with 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. Furthermore, it 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. Next, a method for producing the polymer used in the present invention will be explained. Taking the case of ethylenediamine with n=1 as an example, the polymer () produced by the condensation of polyethylene polyamine and epihalohydrin is It is thought to have the following structure, and has a secondary amine and a small amount of tertiary amine in its structure. The compound () can be obtained by reacting the hydrochloride of a secondary amine or tertiary amine with epihalohydrin, and the compound () can be produced by reacting the compound () with an alkali. As mentioned above, since the polymer () has a secondary amine in its structure, it easily reacts with () which is an alkyl halide or has an epoxy group, for example, It is thought that a compound having the following structure is produced. A specific manufacturing method will be described in the following reference example. 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 Mix 361g of ethylenediamine and 392g of water,
℃, add 255 g of epichlorohydrin under stirring.
Drip in time. Thirty minutes after the completion of the dropwise addition, the temperature was raised to 80°C, and the reaction was continued for 4 hours to obtain an ethylenediamine/epichlorohydrin polymer. 55g of this solution and 50% of 3-chloro-2-hydroxypropyltrimethylammonium chloride
94 g of aqueous solution is mixed, and 20 g of 50% caustic soda aqueous solution is added dropwise thereto at room temperature. After the dropwise addition was completed, heating was continued at 80°C for 3 hours, and the pH gradually decreased to 6.5. A portion of this solution was taken and precipitated in acetone, passed through a glass filter, and dried under reduced pressure to obtain a yield of 90%. Reference Examples 2 to 3 In the same manner as in Reference Example 1, the reaction between the ethylenediamine/epichlorohydrin polymer and 3-chloro-2-hydroxypropyltrimethylammonium chloride (CTA) was carried out by changing the molar ratio of the charges. The results are shown in Table 1.

[Table] Reference Example 4 85 g of a 60% aqueous solution of ethylenediamine/epichlorohydrin polymer and 152 g of a 33% aqueous solution of 2,3-epoxypropyltrimethylammonium chloride were mixed, kept at room temperature for 1 hour, and then reacted at 70°C for 3 hours. . The yield was measured in the same manner as in Reference Example 1.
It was 92%. Reference Example 5 Another 3-chloro-2-hydroxypropylamine derivative was used in place of the 3-chloro-2-hydroxypropyltrimethylammonium chloride used in Reference Example 1, and a combination of this and ethylenediamine/epichlorohydrin used in Reference Example 1 was used. The polymer was reacted in the same manner as in Reference Example 1. The results are shown in Table 2.

【table】

[Table] Example 1 A 0.7 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 10 above was prepared, and then dyed by dipping at a concentration of 4% (based on fiber weight) using the following reactive dye. The dyed cotton 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 then 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 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 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. Once the test piece is dry, place it between two attached white cloths (silk and cotton) and roughly sew them together.
Prepare composite specimens. After that, test according to the water fastness test method (JIS-L-0846). The results are shown in Table 3. In the case of untreated dyed cotton fabrics, considerable staining was observed on the attached white cloth for all dyes, but in the case of dyed cotton fabrics treated using the polymer according to the present invention, almost no staining was observed on the attached white cloth. Nakatsuta.

【table】

[Table] Example 2 A 0.5 g/aqueous solution of each of the polymers obtained in Reference Examples 1 to 10 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. The dyed cotton cloth dyed by this 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 Lebafix 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, and Ciba. Cibacron Brilliant Blue BR-P manufactured by
(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 cotton fabric. The test piece is immersed in a buffer solution with a pH of 8.0±0.2 containing 50 ppm of available chlorine (bath ratio 1:100) and subjected to a JIS-L-0821 washing tester at 25°C for 4 hours. Thereafter, it was washed under running water for 10 minutes, dehydrated, and dried. The results are shown in Table 4. While the untreated dyed cotton fabrics all showed significant discoloration, the dyed fabrics treated with the polymer shown in the reference examples showed almost no discoloration and fading, indicating that they had good chlorine fastness. I understand.

[Table] Example 3 A 0.5 g/aqueous solution of the polymer obtained in the above reference example was prepared, and then a 2% solution was prepared using the following vat dye.
A dyed cotton fabric dyed at a concentration (based on fiber weight) was immersed in an aqueous polymer solution at a bath ratio of 1:20 and a temperature of 50° C. for 20 minutes, washed with water, and then air-dried. 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. . Next, the chlorine fastness of this treated dyed cotton fabric was measured in Example 2.
The results were compared with those of untreated dyed cotton fabrics. The result is the fifth
Shown in the table. In the case of untreated dyed cotton fabrics, all dyes exhibited discoloration accompanied by significant discoloration, but dyed fabrics treated with the polymer shown in the reference example showed almost no discoloration and fading. It can be seen that the dye also has good chlorine fastness.

【table】

Claims (1)

_{[ Claims} ] _{1. A} polymer ( )
and the general formula A reaction product with a compound represented by or the polymer (), [Formula and in, R ₁ , R ₂ , R ₃ are each,
H, an alkyl group having 1 to 12 carbon atoms, or [Formula], X is Cl, Br, or I, and Y is Cl, NO ₃ , 1/2SO ₄ or C _o H _2o+1 COO
(In the formula, n = 1 to 6)] Using the reaction product with the compound represented by, cellulose fiber or a fiber material consisting of this and other fibers is produced using a reactive dye or a vat dye. A method for improving the color fastness of a dyed product, which comprises treating the dyed product.