阅读说明：本技术 一种牛奶蛋白纤维的染色工艺 (Dyeing process of milk protein fiber ) 是由 王振永 暨剑侠 孙前程 于 2021-09-14 设计创作，主要内容包括：本申请的目的是提供一种牛奶蛋白纤维的染色工艺,具有上染率高、缓染的优点,该染色工艺,包括以下步骤：(1)将壳聚糖和2wt％醋酸水溶液按质量比1～1.5:1.5混合,25～35℃下超声分散均匀,得改性液；将牛奶蛋白纤维放入改性液中,浴比为1:13～16,48～52℃下搅拌反应12～16min,取牛奶蛋白纤维,水洗、38～42℃下烘干；(2)配制1.8～2.1g/L阳离子染料的染浴,25～35℃下放入牛奶蛋白纤维,浴比为24～26:1,水浴升温至50～90℃,保温55～75min,取出牛奶蛋白纤维,水洗、38～42℃下烘干；染色过程中用2wt％硫酸水溶液调节染浴pH为5～6。(The application aims at providing a dyeing process of milk protein fibers, which has the advantages of high dye uptake and slow dyeing, and comprises the following steps: (1) mixing chitosan and 2 wt% acetic acid aqueous solution according to the mass ratio of 1-1.5: 1.5, and performing ultrasonic dispersion uniformly at the temperature of 25-35 ℃ to obtain a modified solution; putting the milk protein fiber into the modifying liquid, stirring and reacting at 48-52 ℃ for 12-16 min at a bath ratio of 1: 13-16, taking the milk protein fiber, washing with water, and drying at 38-42 ℃; (2) preparing a dye bath of 1.8-2.1 g/L cationic dye, putting the milk protein fiber at 25-35 ℃ in a bath ratio of 24-26: 1, heating the milk protein fiber to 50-90 ℃ in a water bath, keeping the temperature for 55-75 min, taking out the milk protein fiber, washing with water, and drying at 38-42 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.)

1. A dyeing process of milk protein fibers is characterized by comprising the following steps:

(1) mixing chitosan and 2 wt% acetic acid aqueous solution according to the mass ratio of 1-1.5: 1.5, and performing ultrasonic dispersion uniformly at the temperature of 25-35 ℃ to obtain a modified solution; putting the milk protein fibers into the modifying liquid, stirring and reacting at 48-52 ℃ for 12-16 min at a bath ratio of 1: 13-16, taking the milk protein fibers, washing with water, and drying at 38-42 ℃;

(2) preparing a dye bath of 1.8-2.1 g/L cationic dye, putting the milk protein fiber treated in the step (1) at 25-35 ℃, heating to 50-90 ℃ in a water bath at a bath ratio of 24-26: 1, preserving heat for 55-75 min, taking out the milk protein fiber, washing with water, and drying at 38-42 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

2. A process according to claim 1 for dyeing milk protein fibres, comprising the steps of:

(1) mixing chitosan and 2 wt% acetic acid aqueous solution according to the mass ratio of 1.2:1.5, performing ultrasonic dispersion uniformly at 30 ℃, adding alpha-amino-1H-indole-5-acetic acid and pentanediol, stirring and reacting for 45min at 55 ℃, filtering to obtain clear liquid, concentrating at 55 ℃ to remove the solvent completely to obtain a modifier, mixing the modifier and water according to the mass ratio of 1:5, and performing ultrasonic dispersion uniformly to obtain a modified solution; putting the milk protein fiber into the modified solution at a bath ratio of 1:15, stirring and reacting at 50 ℃ for 15min, taking the milk protein fiber, washing with water, and drying at 40 ℃;

(2) preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber treated in the step (1) at the temperature of 30 ℃, wherein the bath ratio is 25:1, heating the milk protein fiber to 50-60 ℃ in a water bath, keeping the temperature for 55-65 min, taking out the milk protein fiber, washing with water, and drying at the temperature of 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

3. A process according to claim 2, wherein the chitosan has a degree of deacetylation of not less than 90%.

4. A process according to claim 3, comprising the steps of:

(1) mixing chitosan and 2 wt% acetic acid aqueous solution according to the mass ratio of 1.2:1.5, performing ultrasonic dispersion uniformly at 30 ℃, adding alpha-amino-1H-indole-5-acetic acid and pentanediol, stirring and reacting for 45min at 55 ℃, filtering to obtain clear liquid, concentrating at 55 ℃ to remove the solvent completely to obtain a modifier, mixing the modifier and water according to the mass ratio of 1:5, and performing ultrasonic dispersion uniformly to obtain a modified solution; putting the milk protein fiber into the modified solution at a bath ratio of 1:15, stirring and reacting at 50 ℃ for 15min, taking the milk protein fiber, washing with water, and drying at 40 ℃;

(2) preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber treated in the step (1) at the temperature of 30 ℃, wherein the bath ratio is 25:1, heating the milk protein fiber to 55 ℃ in a water bath, keeping the temperature for 60min, taking out the milk protein fiber, washing with water, and drying at the temperature of 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

5. The process for dyeing milk protein fiber according to claim 4, wherein the milk protein fiber is milk protein/modacrylic fiber.

Technical Field

The invention relates to a dyeing process of milk protein fibers.

Background

The milk protein fiber is prepared by dewatering liquid milk, defatting, preparing milk slurry from protein molecules and acrylonitrile molecules by graft copolymerization, and wet spinning to obtain a linear polymer containing milk protein amino acid macromolecules. Thus, milk protein fiber can be described as a synthetic fiber containing animal protein amino acids.

The milk protein fiber integrates the advantages of natural fibers (cotton, hemp, wool and silk) and chemical fibers, has the properties of high chemical fiber strength, small shrinkage, mildew resistance and moth resistance, and also has the advantages of softness, skin friendliness, moisture absorption, air permeability and the like of the natural fibers. In addition, the milk protein fiber contains various amino acids essential to human body, has good affinity with human skin, and has good health promotion effect.

Therefore, the research on the dyeing process of the milk protein fiber has certain production and application values.

Disclosure of Invention

The invention aims to provide a dyeing process of milk protein fibers, which has the advantages of high dye uptake and slow dyeing.

The technical purpose of the invention is realized by the following technical scheme:

a dyeing process of milk protein fibers comprises the following steps:

(1) mixing chitosan and 2 wt% acetic acid aqueous solution according to the mass ratio of 1-1.5: 1.5, and performing ultrasonic dispersion uniformly at the temperature of 25-35 ℃ to obtain a modified solution; putting the milk protein fibers into the modifying liquid, stirring and reacting at 48-52 ℃ for 12-16 min at a bath ratio of 1: 13-16, taking the milk protein fibers, washing with water, and drying at 38-42 ℃;

(2) preparing a dye bath of 1.8-2.1 g/L cationic dye, putting the milk protein fiber treated in the step (1) at 25-35 ℃, heating to 50-90 ℃ in a water bath at a bath ratio of 24-26: 1, preserving heat for 55-75 min, taking out the milk protein fiber, washing with water, and drying at 38-42 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Further, the method comprises the following steps:

(1) mixing chitosan and 2 wt% acetic acid aqueous solution according to the mass ratio of 1.2:1.5, performing ultrasonic dispersion uniformly at 30 ℃, adding alpha-amino-1H-indole-5-acetic acid and pentanediol, stirring and reacting for 45min at 55 ℃, filtering to obtain clear liquid, concentrating at 55 ℃ to remove the solvent completely to obtain a modifier, mixing the modifier and water according to the mass ratio of 1:5, and performing ultrasonic dispersion uniformly to obtain a modified solution; putting the milk protein fiber into the modified solution at a bath ratio of 1:15, stirring and reacting at 50 ℃ for 15min, taking the milk protein fiber, washing with water, and drying at 40 ℃;

(2) preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber treated in the step (1) at the temperature of 30 ℃, wherein the bath ratio is 25:1, heating the milk protein fiber to 50-60 ℃ in a water bath, keeping the temperature for 55-65 min, taking out the milk protein fiber, washing with water, and drying at the temperature of 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Further, the deacetylation degree of chitosan is not less than 90%.

Further, the method comprises the following steps:

(1) mixing chitosan and 2 wt% acetic acid aqueous solution according to the mass ratio of 1.2:1.5, performing ultrasonic dispersion uniformly at 30 ℃, adding alpha-amino-1H-indole-5-acetic acid and pentanediol, stirring and reacting for 45min at 55 ℃, filtering to obtain clear liquid, concentrating at 55 ℃ to remove the solvent completely to obtain a modifier, mixing the modifier and water according to the mass ratio of 1:5, and performing ultrasonic dispersion uniformly to obtain a modified solution; putting the milk protein fiber into the modified solution at a bath ratio of 1:15, stirring and reacting at 50 ℃ for 15min, taking the milk protein fiber, washing with water, and drying at 40 ℃;

(2) preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber treated in the step (1) at the temperature of 30 ℃, wherein the bath ratio is 25:1, heating the milk protein fiber to 55 ℃ in a water bath, keeping the temperature for 60min, taking out the milk protein fiber, washing with water, and drying at the temperature of 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Furthermore, the milk protein fiber is milk protein/modified polyacrylonitrile fiber.

The technical effects of the invention are mainly reflected in the following aspects:

the milk protein fiber has a plurality of dyeing seats provided by ionizing amino acid-COOH into-COO-, the structure of the fiber is loose, the dye is diffused quickly, the dye is combined too fast, and the dye-uptake rate and the dye-uptake effect are influenced; in order to solve the problem, the prior art adopts a form of adding sodium chloride into a dye bath (the starting point is that Na + and dye cations can compete with each other for a dyeing position after the sodium chloride is added into the dye bath, and the Na + is adsorbed by fibers firstly, occupies the dyeing position and then is replaced by the dye cations to play a role in slow dyeing because the Na + has small volume and large fluidity compared with the dye cations); in the application, the mutually exclusive action of the cations of the chitosan and the cationic dyes in the dye bath is utilized, the time of the dyes entering the dyeing position can be slowed down particularly at the initial stage in the dyeing process, a better slow dyeing effect is achieved, and meanwhile, the method does not occupy the dyeing position and can also guarantee higher dye uptake.

Detailed Description

Example 1: a dyeing process of milk protein fibers comprises the following steps:

(1) mixing chitosan (with deacetylation degree of 92%, from Zhejiang gold Chitosan pharmaceutical Co., Ltd.) and 2 wt% acetic acid aqueous solution at a mass ratio of 1.2:1.5, performing ultrasonic dispersion at 30 ℃, adding alpha-amino-1H-indole-5-acetic acid and pentanediol, stirring and reacting at 55 ℃ for 45min, filtering to obtain a clear solution, concentrating at 55 ℃ to remove the solvent to obtain a modifier, mixing the modifier and water at a mass ratio of 1:5, and performing ultrasonic dispersion to obtain a modified solution; adding milk protein fiber (milk protein/modified polyacrylonitrile fiber, from Shanxi Hengtian New fiber science and technology Co., Ltd., the same below) into the modifying solution at bath ratio of 1:15, stirring at 50 deg.C for reaction for 15min, collecting milk protein fiber, washing with water at 30 deg.C, and oven drying at 40 deg.C;

(2) preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber treated in the step (1) at 30 ℃, wherein the bath ratio is 25:1, heating the milk protein fiber to 55 ℃ in a water bath, keeping the temperature for 60min, taking out the milk protein fiber, washing the milk protein fiber with water at 30 ℃, and drying the milk protein fiber at 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Example 2: a dyeing process of milk protein fibers comprises the following steps:

(1) mixing chitosan (deacetylation degree of 92%, from Zhejiang Chitosan pharmaceutical Co., Ltd.) and 2 wt% acetic acid aqueous solution at a mass ratio of 1.2:1.5, and ultrasonically dispersing at 30 deg.C to obtain modified solution; putting the milk protein fiber into the modified solution at a bath ratio of 1:15, stirring and reacting at 50 ℃ for 15min, taking the milk protein fiber, washing with water at 30 ℃ and drying at 40 ℃;

(2) preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber treated in the step (1) at 30 ℃, wherein the bath ratio is 25:1, heating the milk protein fiber to 55 ℃ in a water bath, keeping the temperature for 60min, taking out the milk protein fiber, washing the milk protein fiber with water at 30 ℃, and drying the milk protein fiber at 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Control group 1: a dyeing process of milk protein fibers comprises the following steps:

preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber at 30 ℃ with a bath ratio of 25:1, heating the water bath to 55 ℃, preserving the heat for 60min, taking out the milk protein fiber, washing with water at 30 ℃ and drying at 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Control group 2: a dyeing process of milk protein fibers comprises the following steps:

preparing a dyeing bath of 2.0g/L cationic dye, putting the milk protein fiber at 30 ℃ with a bath ratio of 25:1, heating the water bath to 90 ℃, preserving the heat for 60min, taking out the milk protein fiber, washing with water at 30 ℃ and drying at 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Control group 3: a dyeing process of milk protein fibers comprises the following steps:

preparing a dye bath of 2.0g/L cationic dye and 0.5g/L sodium chloride, putting the milk protein fiber at 30 ℃, wherein the bath ratio is 25:1, heating the water bath to 90 ℃, keeping the temperature for 60min, taking out the milk protein fiber, washing with water at 30 ℃, and drying at 40 ℃; and in the dyeing process, 2 wt% of sulfuric acid water solution is used for adjusting the pH value of the dye bath to 5-6.

Performance testing

The test was carried out with cationic blue X-GRRL as dye.

1. Percentage of dye uptake

The absorbances of the dye baths before and after dyeing were measured at the maximum absorption wavelength with an ultraviolet-visible spectrophotometer (UV-1700), and the percentage of dyeing was calculated as (1-absorbance of raffinate/absorbance of stock solution after dyeing) × 100%.

2. Soaping fastness according to ISO105-C10:2006 "textile colour fastness test part C10: the fastness to soaping or soaping with soap and soda liquor "standards.

The test results are shown in table 1. Table 1 shows that the final dye-uptake of example 1 and example 2 is higher than that of the control, the dye-uptake is better, and the dye-uptake in different periods is gradually increased, which indicates that the examples 1 and 2 have the slow dye effect compared with the control; the soaping fastness of examples 1 and 2 was also improved.

TABLE 1

3. Antibacterial property test

Test strains: staphylococcus aureus AATCC6538, Escherichia coli AATCC 8099.

Test samples: examples 1 and 2, and examples 1, 2 without dyeing treatment. Uncleaned data was tested.

The test was carried out according to the test method for antibacterial property of fabric FZ-T01021-1992. The parallel test is carried out for 5 times, and the average value is taken.

The test results are shown in table 2. Compared with the antibacterial property of the cloth before and after dyeing, the antibacterial rate after dyeing is reduced but the reduction rate is not large, which indicates that the dyeing is mild and the antibacterial finishing is not greatly damaged.

TABLE 2

The invention is capable of other embodiments and its several details are capable of modifications in various obvious respects, all without departing from the invention.