A textile dye and its preparation and dyeing methods

Abstract

This invention provides a textile dye and its preparation and dyeing methods. The preparation method of the textile dye includes the following steps: S1, ultra-finely pulverizing a natural extract into particles with a diameter of 2-10 μm to obtain extract powder; S2, uniformly mixing the extract powder with modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres to obtain a material; S3, adding the material to water, stirring, solidifying, drying, and pulverizing to obtain the dye. This invention, through the compounding of natural extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres, is green, environmentally friendly, and safe. The resulting dye exhibits strong stability, high dyeing rate, uniform dyeing effect, strong affinity for textiles, excellent color fastness, high light stability, and resistance to fading, making it of significant value for widespread application.

Description

Technical Field

[0001] This invention relates to the field of textile chemical technology, and in particular to a textile dye and its preparation and dyeing methods. Background Technology

[0002] Most natural dyes are extracted from plants and are non-toxic, harmless, and environmentally friendly. They are renewable and pollution-free. Using natural pigments to dye fabrics is an ancient method, but due to their poor wash fastness and less vibrant colors, they have gradually been replaced by synthetic dyes. Currently, with economic and cultural development and a growing awareness of environmental protection, health, and green living, the potential safety risks of synthetic dyes have caused widespread concern. More and more people are pursuing natural textile materials while also paying increasing attention to the safety of dyes used. Natural dyes are regaining attention due to their environmental and health benefits; therefore, developing safe, economical, and effective natural dyes is imperative.

[0003] Therefore, the current methods of dyeing textiles with natural dyes need to overcome problems such as low dye uptake rate, poor dyeing uniformity, low color fastness of finished products, poor light stability, and unsuitability for actual industrial production. Summary of the Invention

[0004] In view of this, the present invention proposes a textile dye and its preparation and dyeing methods, which comprehensively solve the above-mentioned technical problems.

[0005] The technical solution of this invention is implemented as follows:

[0006] A method for preparing a textile dye, comprising the following steps:

[0007] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0008] S2. Mix the extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres evenly to obtain the material.

[0009] The metal salt-grafted cellulose whiskers are prepared by ultrasonically stirring cellulose whiskers and a metal salt solution.

[0010] The modified dextran is prepared by mixing dextran with 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at 40-60°C for 4-6 hours.

[0011] S3. Add the material to water, stir, solidify, dry and pulverize to obtain the dye.

[0012] Furthermore, in step S1, the method for preparing the natural extract includes:

[0013] (1) The raw materials are subjected to steam explosion treatment. The mixture after explosion is added to phosphate buffer to adjust the pH to 6.8-7.4 to obtain slurry;

[0014] (2) The slurry was subjected to ultrasonic low-oxygen extraction to obtain filter residue and extract. The extract was concentrated to obtain powder a, which was stored at low temperature.

[0015] (3) Add the filter residue to the bacterial liquid for mixed fermentation, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0016] Furthermore, in step (1), the raw material is any one of red beet, cocoa peel, blueberry or orange peel; the steam explosion is performed at 130-150℃ and 0.2-0.4MPa for 30-60s.

[0017] In step (2), the ultrasonic hypoxia extraction is performed under the conditions of 2%-4% oxygen content, 30-45℃, and 20-30kHz for 20-30 minutes.

[0018] In step (3), the ratio of filter residue to bacterial solution is 1:5-7 g / mL; the bacterial solution is composed of Bacillus subtilis and Candida oleifera in a mass ratio of 1-3:1; the fermentation is carried out at 25-28℃ for 6-10 hours.

[0019] Furthermore, in step S2, the mass ratio of the extract powder to the modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres is 1:0.2-0.4:1-3:0.1-0.3.

[0020] Furthermore, in step S2, the solid-liquid ratio of the cellulose whiskers and the metal salt solution is 1:6-8 mg / mL; the concentration of the metal salt solution is 1-3 mol / L, comprising zinc chloride, cerium nitrate, and silver nitrate in a mass ratio of 1:2-4:0.2-0.5; and the ultrasonic stirring is performed at 200-300 W and 50-70 °C for 5-7 h.

[0021] Furthermore, in step S2, the solid-liquid ratio of the dextran and 3-aminopropyltriethoxysilane, hexadecyltriethoxysilane is (10-30) mg:(4-6) mL:(3-5) mL.

[0022] A textile dye is prepared by the above-described preparation method.

[0023] A dyeing method for textiles, comprising the following steps:

[0024] (1) Pre-treat the textiles to be dyed and set aside;

[0025] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste, and then bake them for later use;

[0026] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, and after completion, they are left to stand at normal pressure and then washed with soap.

[0027] Furthermore, in step (1), the pretreatment is carried out at 40-60℃ and 40-55% relative humidity for 1-2 hours.

[0028] Furthermore, in step (3), the ultra-high pressure treatment is performed at 100MPa for 60-80 minutes, or at 300MPa for 40-50 minutes, or at 500MPa for 20-30 minutes.

[0029] Compared with the prior art, the beneficial effects of the present invention are:

[0030] 1. This invention uses a combination of natural extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres. It is green, environmentally friendly, and safe, and the resulting dye has strong stability, high dyeing rate, uniform dyeing effect, strong affinity to textiles, and excellent color fastness, high light stability, and is not easy to fade. It has important application value.

[0031] 2. The natural extract powder of the present invention is obtained by steam explosion treatment of raw materials, ultrasonic low oxygen and bacterial fermentation to maximize the extraction of the required natural extracts, and the powder obtained by ultra-fine grinding can effectively increase the solubility and stability of dyes, can uniformly dye, and dye bright colors.

[0032] 3. The reactive groups on the modified dextran of this invention can combine with the surface of textile fibers, enhancing the adhesion and stability of dyes. Simultaneously, the modified dextran disperses better, preventing precipitation and resulting in more uniform dyeing. The cellulose whiskers grafted with metals Zn, Ce, and Ag of this invention increase the lightfastness, odor resistance, and antibacterial properties of dyed textiles. The metal-grafted cellulose whiskers possess high specific surface area and excellent mechanical properties, forming stable complexes on the textile fiber surface, increasing durability. The polylactic acid microspheres of this invention exhibit good biodegradability, allowing for control of dyeing speed, improved uniformity, and enhanced dyeing effect.

[0033] 4. The dyeing method of the present invention improves the color fastness of dyeing. The ultra-high pressure treatment allows the dye to penetrate the fiber uniformly, shortens the dyeing time and the amount of dye used, achieves good dyeing effect at a lower temperature, improves production efficiency, saves energy, and improves color stability, and has great promotional value. Detailed Implementation

[0034] To better understand the technical content of this invention, specific embodiments are provided below to further illustrate the invention.

[0035] Unless otherwise specified, the experimental methods used in the embodiments of this invention are all conventional methods.

[0036] Unless otherwise specified, all materials and reagents used in the embodiments of this invention are commercially available.

[0037] The polylactic acid microspheres of the present invention are one or more of PLGA, PLGA-PEG, and PLLG-PEG microspheres;

[0038] The Bacillus subtilis strain of this invention was purchased from Guangzhou Weiyuan Biotechnology Co., Ltd.; the Candida oliguria strain was purchased from Nuoan Gene Technology Co., Ltd.

[0039] The raw material for the natural extract of this invention can be any one of red beet, cocoa peel, blueberry or orange peel.

[0040] Example 1

[0041] The preparation method of textile dyes in this embodiment includes the following specific steps:

[0042] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0043] The preparation methods for natural extracts include:

[0044] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 140℃ and 0.3MPa for 45s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0045] (2) The slurry was subjected to ultrasonic low-oxygen extraction, specifically: extraction was performed at 3% oxygen content, 40℃, and 25kHz for 25 min to obtain filter residue and extract. The extract was concentrated to obtain powder a, which was then stored at low temperature.

[0046] (3) Add the filter residue to the bacterial solution (Bacillus subtilis and Candida oleifera in a mass ratio of 2:1) according to the material-liquid ratio of 1:6 g / mL, mix, ferment at 27°C for 8 hours, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0047] S2. Mix the extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres in a mass ratio of 1:0.3:2:0.2 evenly to obtain the material.

[0048] The preparation method of metal salt grafted cellulose whiskers is as follows: cellulose whiskers are added to a 2 mol / L metal salt (zinc chloride, cerium nitrate and silver nitrate in a mass ratio of 1:3:0.4) solution at a solid-liquid ratio of 1:7 mg / mL, and ultrasonically stirred at 250 W and 60 °C for 6 h.

[0049] The modified dextran was prepared by adding dextran to 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at a solid-liquid ratio of 20mg:5mL:4mL and mixing at 50℃ for 5h.

[0050] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0051] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0052] (1) The textiles to be dyed are pretreated at 50°C and 45% relative humidity for 1.5 hours and then set aside.

[0053] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste and pad them, bake at 50°C for 4 hours, and set aside.

[0054] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, specifically: under 100MPa conditions for 60-80 minutes, and then left to stand at normal pressure. The textiles are then soaped.

[0055] Example 2

[0056] The preparation method of textile dyes in this embodiment includes the following specific steps:

[0057] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0058] The preparation methods for natural extracts include:

[0059] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 130℃ and 0.2MPa for 30s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0060] (2) The slurry was subjected to ultrasonic low-oxygen extraction, specifically: extraction was performed for 20 min at an oxygen content of 2%, 30°C, and 20 kHz. The slurry was then filtered to obtain a residue and extract. The extract was concentrated to obtain powder a, which was stored at low temperature.

[0061] (3) Add the filter residue to the bacterial solution (Bacillus subtilis and Candida oleifera in a mass ratio of 1:5 g / mL) according to the material-liquid ratio of 1:5 g / mL, mix, ferment at 25°C for 6 h, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0062] S2. Mix the extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres in a mass ratio of 1:0.2:1:0.1 evenly to obtain the material.

[0063] The preparation method of metal salt grafted cellulose whiskers is as follows: cellulose whiskers are added to a 1 mol / L metal salt (zinc chloride, cerium nitrate and silver nitrate in a mass ratio of 1:2:0.2) solution at a solid-liquid ratio of 1:6 mg / mL, and ultrasonically stirred at 200 W and 50 °C for 5 h.

[0064] The modified dextran was prepared by adding dextran to 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at a solid-liquid ratio of 10mg:4mL:3mL and mixing at 40℃ for 4h.

[0065] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0066] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0067] (1) The textiles to be dyed are pretreated at 40°C and 40% relative humidity for 1 hour and then set aside.

[0068] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste and pad them, bake at 60°C for 5 hours, and set aside.

[0069] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, specifically: treated at 300MPa for 40-50 minutes, and then left to stand at normal pressure. The textiles are then soaped.

[0070] Example 3

[0071] The preparation method of textile dyes in this embodiment includes the following specific steps:

[0072] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0073] The preparation methods for natural extracts include:

[0074] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 150℃ and 0.4MPa for 60s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0075] (2) The slurry was subjected to ultrasonic low-oxygen extraction, specifically: extraction was performed at 45°C and 30kHz for 30 minutes to obtain filter residue and extract. The extract was concentrated to obtain powder a, which was then stored at low temperature.

[0076] (3) Add the filter residue to the bacterial solution (Bacillus subtilis and Candida oleifera in a mass ratio of 3:1) according to the material-liquid ratio of 1:7 g / mL, mix, ferment at 28℃ for 10 h, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0077] S2. Mix the extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres in a mass ratio of 1:0.4:3:0.3 evenly to obtain the material.

[0078] The preparation method of metal salt grafted cellulose whiskers is as follows: cellulose whiskers are added to a 3 mol / L metal salt (zinc chloride, cerium nitrate and silver nitrate in a mass ratio of 1:4:0.5) solution at a solid-liquid ratio of 1:8 mg / mL, and ultrasonically stirred at 300 W and 70 °C for 7 h.

[0079] The modified dextran was prepared by adding dextran to 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at a solid-liquid ratio of 30mg:6mL:5mL and mixing at 60℃ for 6h.

[0080] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0081] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0082] (1) The textiles to be dyed are pretreated at 60°C and 55% relative humidity for 2 hours and then set aside.

[0083] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste, and then bake them for later use;

[0084] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, specifically: treated at 500MPa for 20-30 minutes, and then left to stand at normal pressure. The textiles are then soaped.

[0085] Comparative Example 1

[0086] The difference from Example 1 is that conventional commercially available dyes (purchased from Shenzhen Baoan District Haitongyuan Fine Chemical Processing Plant) were used, and conventional dyeing methods were employed for dyeing.

[0087] Comparative Example 2

[0088] The difference from Example 1 is that the preparation method of the natural extract lacks ultrasonic low-oxygen extraction, but otherwise it is the same as Example 1.

[0089] The preparation method of the textile dye in this comparative example includes the following specific steps:

[0090] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0091] The preparation methods for natural extracts include:

[0092] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 140℃ and 0.3MPa for 45s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0093] (2) According to the ratio of the mixture after blasting to the bacterial liquid as 1:6 g / mL, the slurry was added to the bacterial liquid (Bacillus subtilis and Candida oleifera in a mass ratio of 2:1) and mixed. The mixture was fermented at 27°C for 8 hours. Ethanol was added to the fermentation liquid, and the mixture was precipitated at low temperature. The mixture was then filtered and concentrated to obtain powder b. Powder a and powder b were mixed evenly to obtain the natural extract.

[0094] S2. Mix the extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres in a mass ratio of 1:0.3:2:0.2 evenly to obtain the material.

[0095] The preparation method of metal salt grafted cellulose whiskers is as follows: cellulose whiskers are added to a 2 mol / L metal salt (zinc chloride, cerium nitrate and silver nitrate in a mass ratio of 1:3:0.4) solution at a solid-liquid ratio of 1:7 mg / mL, and ultrasonically stirred at 250 W and 60 °C for 6 h.

[0096] The modified dextran was prepared by adding dextran to 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at a solid-liquid ratio of 20mg:5mL:4mL and mixing at 50℃ for 5h.

[0097] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0098] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0099] (1) The textiles to be dyed are pretreated at 50°C and 45% relative humidity for 1.5 hours and then set aside.

[0100] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste and pad them, bake at 50°C for 4 hours, and set aside.

[0101] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, specifically: under 100MPa conditions for 60-80 minutes, and then left to stand at normal pressure. The textiles are then soaped.

[0102] Comparative Example 3

[0103] The difference from Example 1 is that the metal salt grafted cellulose whiskers are replaced with metal salts, otherwise it is the same as Example 1.

[0104] The preparation method of the textile dye in this comparative example includes the following specific steps:

[0105] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0106] The preparation methods for natural extracts include:

[0107] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 140℃ and 0.3MPa for 45s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0108] (2) The slurry was subjected to ultrasonic low-oxygen extraction, specifically: extraction was performed at 3% oxygen content, 40℃, and 25kHz for 25 minutes to obtain filter residue and extract. The extract was concentrated to obtain powder a, which was then stored at low temperature.

[0109] (3) Add the filter residue to the bacterial solution (Bacillus subtilis and Candida oleifera in a mass ratio of 2:1) according to the material-liquid ratio of 1:6 g / mL, mix, ferment at 27°C for 8 hours, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0110] S2. Mix the extract powder, modified dextran, metal salts (zinc chloride, cerium nitrate, and silver nitrate in a mass ratio of 1:0.3:2:0.2, and polylactic acid microspheres evenly to obtain the material.

[0111] The modified dextran was prepared by adding dextran to 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at a solid-liquid ratio of 20mg:5mL:4mL and mixing at 50℃ for 5h.

[0112] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0113] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0114] (1) The textiles to be dyed are pretreated at 50°C and 45% relative humidity for 1.5 hours and then set aside.

[0115] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste and pad them, bake at 50°C for 4 hours, and set aside.

[0116] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, specifically: under 100MPa conditions for 60-80 minutes, and then left to stand at normal pressure. The textiles are then soaped.

[0117] Comparative Example 4

[0118] The difference from Example 1 is that the modified dextran is missing; otherwise, it is the same as Example 1.

[0119] The preparation method of the textile dye in this comparative example includes the following specific steps:

[0120] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0121] The preparation methods for natural extracts include:

[0122] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 140℃ and 0.3MPa for 45s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0123] (2) The slurry was subjected to ultrasonic low-oxygen extraction, specifically: extraction was performed at 3% oxygen content, 40℃, and 25kHz for 25 minutes to obtain filter residue and extract. The extract was concentrated to obtain powder a, which was then stored at low temperature.

[0124] (3) Add the filter residue to the bacterial solution (Bacillus subtilis and Candida oleifera in a mass ratio of 2:1) according to the material-liquid ratio of 1:6 g / mL, mix, ferment at 27°C for 8 hours, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0125] S2. Mix the extract powder, metal salt-grafted cellulose whiskers, and polylactic acid microspheres in a mass ratio of 1:2:0.2 evenly to obtain the material.

[0126] The preparation method of metal salt grafted cellulose whiskers is as follows: cellulose whiskers are added to a 2 mol / L metal salt (zinc chloride, cerium nitrate and silver nitrate in a mass ratio of 1:3:0.4) solution at a solid-liquid ratio of 1:7 mg / mL, and ultrasonically stirred at 250 W and 60 °C for 6 h.

[0127] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0128] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0129] (1) The textiles to be dyed are pretreated at 50°C and 45% relative humidity for 1.5 hours and then set aside.

[0130] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste and pad them, bake at 50°C for 4 hours, and set aside.

[0131] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, specifically: under 100MPa conditions for 60-80 minutes, and then left to stand at normal pressure. The textiles are then soaped.

[0132] Comparative Example 5

[0133] The difference from Example 1 is that polylactic acid microspheres are missing; otherwise, they are the same as in Example 1.

[0134] The preparation method of textile dyes in this embodiment includes the following specific steps:

[0135] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0136] The preparation methods for natural extracts include:

[0137] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 140℃ and 0.3MPa for 45s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0138] (2) The slurry was subjected to ultrasonic low-oxygen extraction, specifically: extraction was performed at 3% oxygen content, 40℃, and 25kHz for 25 minutes to obtain filter residue and extract. The extract was concentrated to obtain powder a, which was then stored at low temperature.

[0139] (3) Add the filter residue to the bacterial solution (Bacillus subtilis and Candida oleifera in a mass ratio of 2:1) according to the material-liquid ratio of 1:6 g / mL, mix, ferment at 27°C for 8 hours, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0140] S2. Mix the extract powder, modified dextran, and metal salt-grafted cellulose whiskers in a mass ratio of 1:0.3:2 evenly to obtain the material.

[0141] The preparation method of metal salt grafted cellulose whiskers is as follows: cellulose whiskers are added to a 2 mol / L metal salt (zinc chloride, cerium nitrate and silver nitrate in a mass ratio of 1:3:0.4) solution at a solid-liquid ratio of 1:7 mg / mL, and ultrasonically stirred at 250 W and 60 °C for 6 h.

[0142] The modified dextran was prepared by adding dextran to 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at a solid-liquid ratio of 20mg:5mL:4mL and mixing at 50℃ for 5h.

[0143] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0144] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0145] (1) The textiles to be dyed are pretreated at 50°C and 45% relative humidity for 1.5 hours and then set aside.

[0146] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste and pad them, bake at 50°C for 4 hours, and set aside.

[0147] (3) The textiles treated in step (2) are subjected to ultra-high pressure treatment, specifically: under 100MPa conditions for 60-80 minutes, and then left to stand at normal pressure. The textiles are then soaped.

[0148] Comparative Example 6

[0149] The difference from Example 1 is that ultra-high pressure treatment is not used; otherwise, it is the same as Example 1.

[0150] The preparation method of the textile dye in this comparative example includes the following specific steps:

[0151] S1. The natural extract is ultra-finely pulverized into a particle size of 2-10μm to obtain extract powder;

[0152] The preparation methods for natural extracts include:

[0153] (1) The raw materials were subjected to steam explosion treatment, specifically: the mixture was treated at 140℃ and 0.3MPa for 45s, and the pH of the mixture after explosion was adjusted to 7±0.2 in phosphate buffer to obtain slurry;

[0154] (2) The slurry was subjected to ultrasonic low-oxygen extraction, specifically: extraction was performed at 3% oxygen content, 40℃, and 25kHz for 25 minutes to obtain filter residue and extract. The extract was concentrated to obtain powder a, which was then stored at low temperature.

[0155] (3) Add the filter residue to the bacterial solution (Bacillus subtilis and Candida oleifera in a mass ratio of 2:1) according to the material-liquid ratio of 1:6 g / mL, mix, ferment at 27°C for 8 hours, add ethanol to the fermentation liquid, perform low-temperature alcohol precipitation, filter and concentrate to obtain powder b, mix powder a and powder b evenly to obtain natural extract.

[0156] S2. Mix the extract powder, modified dextran, metal salt-grafted cellulose whiskers, and polylactic acid microspheres in a mass ratio of 1:0.3:2:0.2 evenly to obtain the material.

[0157] The preparation method of metal salt grafted cellulose whiskers is as follows: cellulose whiskers are added to a 2 mol / L metal salt (zinc chloride, cerium nitrate and silver nitrate in a mass ratio of 1:3:0.4) solution at a solid-liquid ratio of 1:7 mg / mL, and ultrasonically stirred at 250 W and 60 °C for 6 h.

[0158] The modified dextran was prepared by adding dextran to 3-aminopropyltriethoxysilane and hexadecyltriethoxysilane at a solid-liquid ratio of 20mg:5mL:4mL and mixing at 50℃ for 5h.

[0159] S3. Add the material to water, stir, solidify, dry and pulverize to obtain dye;

[0160] The dyeing method for the above-mentioned textile dyes includes the following specific steps:

[0161] (1) The textiles to be dyed are pretreated at 50°C and 45% relative humidity for 1.5 hours and then set aside.

[0162] (2) Dissolve the dye in water to obtain dye paste, immerse the pretreated textiles to be dyed in the dye paste and pad them, bake at 50°C for 6 hours, and then soap the textiles.

[0163] Test case

[0164] The dyed textile fabrics obtained in Examples 1-3 and Comparative Examples 1-6 were subjected to performance testing.

[0165] Among them, 1. Color fastness to rubbing: The color fastness to rubbing was tested in accordance with GB / T3920-2008, and the test results were analyzed and recorded;

[0166] 2. Water fastness: Water fastness test was conducted in accordance with GB / T5713-2013 (water temperature set at 60℃, test sample placed in water for 30 min, and gray scale used to evaluate the color change grade of the test sample).

[0167] 3. Lightfastness: According to GB / T1710-2008 "Comparison of Lightfastness of Similar Pigments", the light source is a xenon lamp with a quartz cover, wavelength 300-400nm, and irradiance 50±2W / m². 2 The color contrast between the unexposed and fully exposed parts of the test sample was evaluated using a gray scale to determine the lightfastness of the test sample.

[0168] 4. Antibacterial ability test: according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles";

[0169] 5. Other indicators: fixation rate, solubility, K / S value (absorption coefficient / scattering coefficient) and UPF value (ultraviolet protection factor).

[0170] The results are shown in Table 1-2.

[0171] Table 1

[0172]

[0173] Table 2

[0174]

[0175] As can be seen from Tables 1-2, compared with Comparative Examples 1-6, the textiles obtained by the dyes and dyeing methods of Examples 1-3 of the present invention have high fixation rate, uniform dyeing, high color fastness, and high color depth K / S value, indicating high dyeing rate, and at the same time, excellent antibacterial properties.

[0176] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for the preparation of a textile dye, characterized in that, The specific steps include: S1, the natural extract is ultra-finely pulverized into a particle size of 2-10 µm to obtain an extract powder; The preparation method of the natural extract includes: (1) The raw material is subjected to steam explosion treatment, and the mixture after explosion is added into a phosphate buffer solution to adjust the pH to 6.8-7.4 to obtain a slurry; (2) The slurry is subjected to ultrasonic low-oxygen extraction to obtain a filter residue and an extract liquid, the extract liquid is concentrated to obtain powder a, and the powder a is stored at low temperature; (3) The filter residue is added into a bacterial solution for mixed fermentation, ethanol is added into the fermentation liquor, and low-temperature alcohol precipitation is performed, followed by filtration and concentration to obtain powder b, the powder a and the powder b are uniformly mixed to obtain the natural extract; The bacterial solution is Bacillus subtilis and Candida oleophila at a mass ratio of 1-3:1; S2, the extract powder, modified dextran, metal salt grafted cellulose whiskers, and polylactic acid microspheres are uniformly mixed at a mass ratio of 1:0.2-0.4:1-3:0.1-0.3 to obtain a material; The metal salt grafted cellulose whiskers are prepared by ultrasonic stirring of cellulose whiskers and a metal salt solution; the metal salt includes zinc chloride, cerium nitrate, and silver nitrate at a mass ratio of 1:2-4:0.2-0.5; The modified dextran is prepared by mixing dextran, 3-aminopropyl triethoxysilane, and hexadecyl triethoxysilane at 40-60°C for 4-6 h; S3, the material is added into water for stirring, solidification, drying, and pulverization to obtain a dye.

2. A process for the preparation of a textile dye as claimed in claim 1, characterized in that, In step S1, in step (1), the raw material is any one of red beet, cocoa husk, blue grass, or orange peel; the steam explosion is performed at 130-150°C and 0.2-0.4 MPa for 30-60 s; In step (2), the ultrasonic low-oxygen extraction is performed at an oxygen content of 2%-4%, 30-45°C, and 20-30 kHz for 20-30 min; In step (3), the solid-liquid ratio of the filter residue and the bacterial solution is 1:5-7 g / mL; the fermentation is performed at 25-28°C for 6-10 h.

3. A process for the preparation of a textile dye as claimed in claim 1, wherein, In step S2, the solid-liquid ratio of the cellulose whiskers and the metal salt solution is 1:6-8 mg / mL; the concentration of the metal salt solution is 1-3 mol / L; the ultrasonic stirring is performed at 200-300 W and 50-70°C for 5-7 h.

4. A process for the preparation of a textile dye as claimed in claim 1, wherein, In step S2, the solid-liquid ratio of the dextran, 3-aminopropyl triethoxysilane, and hexadecyl triethoxysilane is (10-30) mg:(4-6) mL:(3-5) mL.

5. A textile dye prepared by the preparation method of any one of claims 1-4.

6. A process for dyeing a textile according to Claim 5 characterised in that, The specific steps include: (1) The textile to be dyed is pretreated for standby; (2) The dye is dissolved in water to obtain a dye liquor, and the pretreated textile to be dyed is immersed in the dye liquor for pad dyeing, and then is baked for standby; (3) The textile treated in step (2) is subjected to ultrahigh pressure treatment, and then is placed at normal pressure for standby, and then is soaped.

7. A process for the dyeing of textile dyestuffs according to claim 6, characterized in that In step (1), the pretreatment is performed at 40-60°C and a relative humidity of 40%-55% for 1-2 h.

8. A process for dyeing a textile according to claim 6, characterised in that, In step (3), the ultra-high pressure treatment is at 100 MPa for 60-80 min, or at 300 MPa for 40-50 min, or at 500 MPa for 20-30 min.

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