JPS6114276B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for post-treatment of dyed cellulosic fibers. More specifically, the present invention relates to a method for improving the color fastness of a dyed product obtained by dyeing cellulosic fibers or a fibrous material composed of cellulosic fibers and other fibers with a reactive dye by post-treating the dyed product. Conventionally, there is a method to improve the wet fastness of dyed cellulose fibers by using a wet fastness enhancer, and a polyamine-based cationic resin type obtained by condensing a polyalkyl polyamine with dicyandiamide, etc. Most commonly used. Examples of polyamine-based cationic resins include condensation resins obtained by heating and condensing polyethylene polyamine and dicyandiamide as already described in U.S. Pat. No. 2,649,354, and polyethylene polyamine, dicyandiamide, There is a tripartite condensation resin of urea.
All of these are excellent in improving wet fastness. However, reactive dye dyeings post-treated with polyamine-based cationic resins
It is often observed that the sharpness of hue, which is the most characteristic of reactive dyes, is impaired (hue change). Furthermore, the phenomenon of discoloration and fading of dyed products due to chlorine ions contained in tap water or pool water (poor chlorine fastness) was often observed, and furthermore, the fastness to sunlight was also poor. In order to overcome the drawbacks of these polyamine-based cationic resins, a method has recently been developed in which dyed products are post-treated with a cationic polymer obtained by the reaction of dialkylamine and epihalohydrin. However, when dyed items are post-treated with this cationic polymer, the disadvantages of polyamine-based cationic resins, such as hue change and poor sunlight fastness, are almost eliminated; It is considerably inferior to resins, and its chlorine fastness is also insufficient. For this reason, at present, polyamine-based cationic resins are used for dyed products that require high wet fastness, and cationic polymers are used for dyed products that do not require such high wet fastness. be. The inventors of the present invention improved the conventional drawbacks and conducted extensive research into an excellent post-treatment agent that does not need to be used selectively.As a result, we found that certain cationic polymers impair the sharpness of the hue of dyed products. The present invention was completed based on the discovery that it exhibits a good wet fastness enhancing effect without any problems, and has excellent chlorine fastness and sunlight fastness. That is, according to the present invention, dyeings of cellulose fibers or fiber materials made of cellulose fibers and other fibers with reactive dyes are dyed with a homopolymer and/or a copolymer of an acid salt or a quaternary salt of vinylimidazole. It is characterized by post-treatment using a post-treatment agent consisting of a copolymer with a possible comonomer, or a mixture of the homopolymer and/or copolymer and a cationic polymer represented by the following general formula (2). A post-treatment of dyed cellulose fibers is provided. In the above formula, R ₃ and R ₄ may be the same or different and each represents a lower alkyl group, and
represents a halogen atom or HSO ₄ . The acids constituting the vinyl imidazole acid salt according to the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid, formic acid, and butyric acid. Examples of quaternizing agents include methyl chloride, benzyl chloride, dimethyl sulfate, diethyl sulfate, and ethylene chlorohydrin. Further, all of the neutralization or quaternization reactions can be performed by known methods. As the compound to be copolymerized with the acid salt or quaternary salt of vinylimidazole, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, hydroxyethyl methacrylate, vinyl acetate, acrylamide, alkyl methacrylate, chloromethylated styrene, vinylpyridine, etc. can be used. However, it is not limited to these. These comonomers can be used in any proportion.
Polymers of acid salts or quaternary salts of vinylimidazole and copolymers with other comonomers can be produced by conventionally known methods. For example, it can be easily obtained by polymerizing a mixed solution in which an acid salt or quaternary salt of vinylimidazole and water coexist in the presence of a polymerization catalyst such as potassium persulfate. The cationic polymer of general formula (2) used in the present invention has the following general formula (3). It can be produced by polymerizing a compound represented by the formula (wherein R ₃ , R ₄ and X are the same as defined above) by a known method. For example, it can be easily obtained by cyclopolymerizing a mixture of diallyldimethylammonium chloride and water in the presence of a polymerization catalyst such as potassium persulfate. The homopolymer and/or copolymer of vinylimidazole acid salt or quaternary salt and/or copolymer with other comonomers and the cationic polymer represented by general formula (2) can be blended in any proportion, but the former It is preferable to use as the main component. The processing method of the present invention can be carried out in a manner similar to that used for conventionally known wet fastness enhancers. The concentration of post-treatment agent used in the present invention is 0.01%
The content may range from 5% to 5%, but preferably from 0.05 to 2%. For dyed products, a range of 1% to 10% is good. Note that the PH of the treatment liquid can be freely selected within the range of PH3 to 11, but is preferably PH7 to 9. Further, the temperature during treatment may be 20 to 70°C, and the time may be 10 to 30 minutes. Drying after treatment may be either natural drying or heat drying. Cellulose fibers and mixed fibers of these fibers and other fibers to which the present invention is applied include cotton, viscose rayon, mixed fibers of cotton and polyester, mixed fibers of cotton and polyamide fibers, and viscose rayon and polyester fibers. Examples include mixed fibers with cotton and acrylic fibers, and mixed fibers with cotton and acrylic fibers.
Further, examples of reactive dyes include organic dyes having a vinyl sulfone group, a dichlorotriazine group, a monochlorotriazine group, a dichloroquinoxaline group, a monochlorodifluoropyrimidine group, a sulfate ethyl sulfonamide group, and the like. The present invention will be explained below by giving examples, but the present invention is not limited to these. Further, parts and % in the examples indicate parts by weight and % by weight, respectively. Synthesis Example 1 85 g of 1-vinylimidazole (0.904
mol) and add 111.8g while being careful not to generate heat.
(0.886 mol) of dimethyl sulfate was added dropwise over 2 hours while maintaining the temperature at 55-60°C. After dripping, 55
Continue the stirring reaction at ~60°C for 1 hour, then add 130g of water to bring the temperature to 80-85°C and add 1.5g of potassium persulfate.
Polymerization was carried out with stirring in the presence of nitrogen gas for 4 hours to obtain a yellowish brown viscous substance. this product
200 g was poured into 200 ml of acetone to form a pale yellow precipitate, which was separated and washed twice with 300 ml of acetone to yield 117.6 g of a hygroscopic pale yellow solid polymer. This pale yellow solid polymer
40g was dissolved in 160g of water to obtain Product A (transparent yellow, slightly viscous liquid). Synthesis Example 2 64.5 g of 1-vinylimidazole was placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel.
(0.686 mol) and 28 g (0.17 mol) of dimethylaminoethyl methacrylate, and while being careful not to generate heat, 107 g (0.84 mol) of dimethyl sulfuric acid was added to 55 to 60 g of dimethyl sulfate.
Dropped at a temperature of ℃ for 2 hours, after dropping 55 ~
The reaction was continued with stirring at 60°C for 1 hour. Next, 200 g of water was added and the temperature was raised to 80 to 85° C., and polymerization was carried out with stirring for 4 hours while passing nitrogen gas in the presence of 1.5 g of potassium persulfate to obtain a yellowish brown viscous material. This viscous substance 200
Pour g into 200 ml of acetone to obtain a pale yellow precipitate. Separate this precipitate and wash it twice with 300 ml of acetone to form a hygroscopic pale yellow solid polymer99.
g was obtained. Add 40g of this pale yellow solid polymer to water.
It was dissolved in 160 g to give product B (yellow transparent viscous liquid). Synthesis Example 3 43 g (0.45 mol) of 1-vinylimidazole and 56 g of dimethylaminoethyl methacrylate were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel.
(0.357 mol), being careful not to generate heat.
100.5g (0.797mol) dimethyl sulfate at 55-60℃
It took 2 hours to drip while maintaining the temperature of
The reaction was continued with stirring at 55-60°C for 1 hour. then 200
Add 1.5g of water and bring to 80-85℃, add 1.5g of potassium persulfate.
Polymerization was carried out with stirring for 4 hours while passing nitrogen gas in the presence of 100 g, to obtain a yellowish brown viscous substance. this viscous substance
When 200 g was poured into 2000 ml of acetone, a pale yellow precipitate formed. Separate the precipitate and wash twice with 300ml of acetone to obtain a hygroscopic light yellow solid polymer.
97.6g was obtained. 40g of this pale yellow solid polymer
was dissolved in 160 g of water to obtain Product C (light yellow, transparent, viscous liquid). Synthesis Example 4 97.2 g (11 mol) of diallylamine was added to a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel, and 123.7 g (0.98 mol) was added while being careful not to generate heat.
dimethyl sulfuric acid was added dropwise over a period of 2 hours while maintaining the temperature at 55-60°C, and after the dropwise addition, the stirring reaction was continued at 55-60°C for 1 hour. Next, 95 g of water was added, the temperature was raised to 50-55°C, and polymerization was carried out with stirring for 8 hours while passing nitrogen gas in the presence of 1.7 g of potassium persulfate, to obtain a pale yellow viscous substance. When 200 g of this viscous material was poured into 2000 ml of acetone, a white precipitate formed. The precipitate was separated and washed twice with 300 ml of acetone to obtain 97.3 g of a hygroscopic white solid polymer. 40 g of this white solid polymer was dissolved in 160 g of water to obtain Product D (colorless and transparent, slightly viscous liquid). Formulation Example 1 30g of pale yellow solid polymer obtained in Synthesis Example 1
and 10 g of the white solid polymer obtained in Synthesis Example 4 were dissolved in 160 g of water to obtain Compound E (yellow transparent, slightly viscous liquid). Formulation Example 2 20g of the pale yellow solid polymer obtained in Synthesis Example 1 and 20g of the white solid polymer obtained in Synthesis Example 4 were mixed with water.
It was dissolved in 160 g to give Formulation F (yellow transparent, slightly viscous liquid). Formulation Example 3 30 g of the pale yellow solid polymer obtained in Synthesis Example 3 and 10 g of the white polymer obtained in Synthesis Example 4 were mixed with 160 g of water.
g to give Formulation G (pale yellow transparent viscous liquid). Test Example 1 The color fastness of the product of the present invention applied to cotton cloth dyed with a reactive dye was tested in accordance with the following method. (1-1) Preparation of dyed product Cotton knitted fabric was dyed with a reactive dye according to a conventional method, and then dyed with a 2 g/aqueous solution of Lipotol RK-5 (manufactured by Nicca Chemical Co., Ltd.) at 90°C for 10 minutes. After washing for a minute,
Washed with water and dried.

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[Table] (1-2) Fastness enhancer treatment The products of the present invention and comparative products were used in an amount of 5% based on the weight of the dyed product, treated at a bath ratio of 1:30 for 20 minutes at approximately 60°C, and washed with water. Then it was dried. (1-3) Fastness test method (a) Dyeing fastness test against washing JIS L-0844 Method A-3 (b) Dyeing fastness test against sweat JIS L-0848 Method A Alkaline (c) Dyeing after aging Fastness test The test fabric was steamed for 60 minutes at 115°C using an HP steamer, and then subjected to a color fastness test against water according to JIS L-0846 Method A. (d) Chlorine fastness test Available chlorine 20ppm (using sodium hypochlorite)
The test cloth is immersed in this solution at a bath ratio of 1:200 for 2 hours at room temperature. (e) Sunlight fastness test Test fabric at 63°C in a fade-o-meter.
Expose for 20 hours. (1-4) Judgment method Color fastness was determined by evaluating the degree of contamination of the attached white cloth (cotton and silk) using a gray scale for contamination. In the chlorine fastness test and the sunlight fastness test, the degree of fading was evaluated using a gray scale for fading. (1-5) Test results <Color fastness test>

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[Table] As shown above, it can be seen that the method according to the present invention is superior to the conventional method in terms of various fastnesses and hue changes.

Claims (1)

[Scope of Claims] 1. Dyeing of cellulose fibers or fiber materials made of cellulose fibers and other fibers with reactive dyes by copolymerizing them with homopolymers and/or quaternary salts of vinylimidazole. post-treatment using a post-treatment agent consisting of a copolymer with a functional monomer, or a mixture of the homopolymer and/or copolymer and a cationic polymer represented by the following general formula (2). A method for post-processing dyed cellulose fibers, characterized by: In the above formula, R ₃ and R ₄ may be the same or different and each represents a lower alkyl group, and
represents a halogen atom or HSO ₄ .