Dyeing process for polylactic acid / nanocellulose composite fiber

Abstract

The present invention relates to the technical field of chemical textile processing. Disclosed is a dyeing process for a polylactic acid / nanocellulose composite fiber, comprising a spinning solution preparation step, a spinning step and a dyeing step, wherein the spinning solution preparation step comprises uniformly mixing a nanocellulose suspension, a polylactic acid solution and an additive together, standing at 30-80°C for 1-2 h, performing high-energy electron beam radiation to form a gel, and washing the gel with water to obtain a hydrogel spinning solution; the spinning step comprises feeding the hydrogel spinning solution into a wet spinning device for spinning to form a fiber, and subjecting the fiber to high-energy electron beam radiation for drying and reinforcement to obtain a fiber filament, wherein the irradiation dose is 10-50 kGy, and the irradiation time is 3-5 minutes. The preparation method in the present invention is simple and easy to implement, and is environmentally friendly; the dye uptake rate of the prepared composite fiber reaches 80%, the strength of the composite fiber is enhanced by 1-2 times, and the anti-fibrillation property is improved by 1-2 times.

Description

A polylactic acid / nanocellulose composite fiber dyeing process TECHNICAL FIELD

[0001] The present application relates to the technical field of textile processing, in particular to a polylactic acid / nanocellulose composite fiber dyeing process. BACKGROUND

[0002] Polylactic acid fiber is a polyester fiber made of polylactic acid ester obtained from natural sugars in corn, grains and other agricultural products. Polylactic acid fiber is characterized by biodegradability, green environmental protection and excellent performance. Polylactic acid fiber is suitable for dyeing with disperse dyes, but polylactic acid fiber has the disadvantages of low dyeing rate, low dyeing fastness and low dye utilization rate. For example, in the Chinese patent application with the application number CN202010905523.6, a polylactic acid fiber cone yarn dyeing process is disclosed, which includes the following steps: step one: loose cone; the yarns of different specifications are turned on the plastic cone tube according to the plan requirements by a loose cone winder, some defects, impurities on the yarns are removed, the quality of the yarns is improved, the knot on the yarns on the cone is small and firm, and a larger yarn winding angle is used; step two: cage; the loose cone yarns are loaded on the yarn rods of the yarn cage according to the requirements and are fixed to prepare for dyeing; step three: dyeing; the cone yarns are placed on the cone yarn fixing frame in the cone yarn dyeing device; the cone yarns are pretreated with a pretreatment liquid before dyeing according to a bath ratio of 1:1-50, a diffusing agent NNO is added to the dyeing agent, and the alkalinity is adjusted; step four: dehydration; after the yarn dyeing process is completed, dehydration is performed, and the dehydration is completed by high-speed operation of a centrifugal dehydrator; step five: drying; the yarns after dehydration in step four are dried by a high-frequency drying machine, and the yarns are dried by the upper and lower heating plates; and an air extractor is fixedly installed on the side of the high-frequency drying machine after drying to exhaust steam.

[0003] For another example, in the Chinese patent application with the application number CN200610012779.4, a polylactic acid fiber / cotton blended woven fabric dyeing process is disclosed, which includes a. a desizing process, b. a scouring and bleaching process, c. a mercerizing process, and d. a dyeing process.

[0004] Moreover, the traditional cellulose fiber processing process has low strength and poor anti-fibrillation performance of the cellulose fiber, and the fabric made of the fiber is easy to shed and pilling. TECHNICAL PROBLEM

[0005] The present application provides a polylactic acid / nanocellulose composite fiber dyeing process to solve the problems of the prior art, which has a simple process, achieves good dyeing effect, and improves the strength and anti-fibrillation performance of the polylactic acid / nanocellulose composite fiber. TECHNICAL SOLUTION

[0006] To achieve the above object, the present application provides the following technical scheme: a polylactic acid / nano-cellulose dyeing process, comprising a spinning solution preparation process, a spinning process and a dyeing process;

[0007] The spinning solution preparation process is to uniformly mix nano-cellulose suspension, polylactic acid solution and additives together, to stand for 1-2 hours at 30-80 DEG C and to perform high-energy electron beam radiation to form a gel, and to obtain a hydrogel spinning solution by washing the gel with water, wherein the irradiation dose of high-energy electron beam radiation is 10-50 kGy, and the irradiation time is 20-40 minutes, wherein the mass ratio of polylactic acid solution to nano-cellulose solution is 10:1-1:1, and the mass ratio of polylactic acid solution to additive solution is 10:1-1:1, the polylactic acid solution is to disperse polylactic acid in an organic solvent, the mass concentration of polylactic acid is 5-10%, and the nano-cellulose suspension is to disperse cellulose fibers with a length of 10-100 nm in water, and the mass concentration of cellulose is 5-20%.

[0008] The spinning process is to send the above hydrogel spinning solution into a wet spinning device to form fibers by spinning, and to obtain fiber filaments by drying and strengthening the fibers through high-energy electron beam radiation, wherein the irradiation dose is 10-50 kGy, and the irradiation time is 3-5 minutes.

[0009] In the dyeing process, the weight ratio of dye to fiber is 1-10%, the bath ratio is 1:45-55, the amount of dispersing agent NNO is 0.8-1.2 g / L, the pH value of the dyeing solution is 4.8-5.2, the temperature is raised to 58-62 DEG C at a rate of 1.5-2.5 DEG C / min, the fibers are added, the temperature is raised to the dyeing temperature of 108-112 DEG C at a rate of 0.8-1.2 DEG C / min, the dyeing time is 18-22 minutes, then the temperature is lowered to 58-62 DEG C, 2.5-3.5 g / L of sodium bicarbonate, 2.5-3.5 g / L of anhydrous sodium carbonate and 2.5-3.5 g / L of detergent are added to wash off the floating color on the fibers, the fibers are washed thoroughly, and then dried or subjected to a post-treatment process.

[0010] As a preferred mode of the present application, the hydrogel spinning solution is extruded through the spinneret of a spinning device, the yarns are washed, drawn and dried by high-energy electron beam radiation in water to obtain polylactic acid / nano-cellulose fibers. The drawing speed of the yarns is controlled at 0-100 cm / min.

[0011] As a preferred mode of the present application, the organic solvent is one or a mixture of two or more of N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform and acetone.

[0012] As a preferred mode of the present application, the additive is polyethylene glycol, glycerol, carboxymethyl chitosan, carboxymethyl cellulose, polyvinyl alcohol or polyethylene oxide.

[0013] As a preferred mode of the present application, the cellulose fiber is sugarcane fiber.

[0014] As a preferred mode of the present application, the molecular weight of the polylactic acid is 10,000-270,000.

[0015] As a preferred mode of the present application, the dye is a mixture of disperse dye and reactive dye.

[0016] As a preferred mode of the present application, the disperse dye is disperse red, disperse blue or disperse yellow of azo type; and the reactive dye is reactive red, reactive blue or reactive yellow. Advantages

[0017] Compared with the prior art, the preparation method of the present application is simple and easy to implement, green and environmentally friendly, and is conducive to the industrialization transformation. The dyeing process of the polylactic acid / nano-cellulose composite fiber of the present application has a fiber dyeing rate of 80%, the fiber strength of the composite fiber is enhanced by 1-2 times, and the anti-fibrillation ability is improved by 1-2 times. By using the technical scheme of the present application, the polylactic acid / nano-cellulose composite fiber is treated by twice irradiation. The first irradiation is to enhance the pre-crosslinking and condensation of the hydroxyl or carboxyl groups between the nano-cellulose and the polylactic acid, to form moderate ether bonds and ester bonds, so as to form a spinning solution suitable for spinning. The second irradiation is to enhance the deep crosslinking and condensation degree of the hydroxyl or carboxyl groups in the spinning component, to enhance the fiber strength and improve the anti-fibrillation ability, and at the same time, to improve the affinity between the disperse dye and the fiber, and to improve the fiber dyeing performance. The present application utilizes the hydrogel spinning of the polylactic acid / nano-cellulose composite fiber, and does not need to use the N-methyl morpholine N oxide (NMMO) solvent used in the traditional cellulose fiber spinning process, so that the solvent recovery process is saved, and the equipment investment is saved. BRIEF DESCRIPTION OF DRAWINGS

[0018] Enter the description paragraph of the drawing description here. Best Mode for Carrying Out the Invention

[0019] Enter the description paragraph of the best mode for carrying out the invention here. Embodiment of the Invention

[0020] In order to better understand the technical scheme of the present application, the following embodiments are described in more detail.

[0021] Example 1

[0022] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fiber to obtain 10% nanocellulose suspension solution, polylactic acid (produced by Aladdin Reagent (Shanghai) Co., Ltd., model Mw~60,000, same below) is dissolved in dichloromethane / N,N-dimethylformamide (volume ratio of the two is 4:1) mixed solution to obtain 5% polylactic acid solution, the nanocellulose suspension solution, polylactic acid solution and polyethylene glycol solution are uniformly mixed according to the mass ratio of 6:3:1, then the mixture is placed at 50℃ for 12 hours, and then irradiated by high-energy electron beam with a radiation dose of 30kGy to obtain a polylactic acid / nanocellulose gel sample. The gel sample is soaked in deionized water, and the water is replaced every 3 hours, repeated for 5-8 times. The gel is washed by water to replace the organic solvent, and the water content of the hydrogel is 60% (mass percent, same below). The hydrogel spinning solution is spun by a wet spinning device, and the spun yarn is subjected to a high-energy electron beam irradiation with a radiation dose of 30kGy and a radiation drying treatment twice. The hydrogel spinning solution is spun through the spinning nozzle of the spinning device, and the yarn enters the water setting bath to be prepared into polylactic acid / nanocellulose fiber by water washing, drawing, radiation drying. The drawing speed is controlled at 15cm / min. At room temperature, a dye solution is prepared: disperse yellow 1% (on weight of fabric, owf), reactive yellow 1% (on weight of fabric, owf), dispersant NNO 1g / L, bath ratio 1:50, and pH value is adjusted to 5 by acetic acid and sodium acetate. After the dye solution is prepared, it is heated from room temperature to 60℃ at a heating rate of 2℃ / min, and then the polylactic acid / nanocellulose composite fiber is added to start dyeing. Then, the temperature is increased to 110℃ at a rate of 1℃ / min, and the temperature is maintained for 20min. Then, the temperature is decreased from 110℃ to 60℃, and the cooling time is controlled at 30min. A cleaning solution is prepared by adding 3g / L of sodium hydrosulfite, 3g / L of anhydrous sodium carbonate and 3g / L of detergent 6501 (detergent 6501 is a non-ionic surfactant, and its foreign trade name is Ninol 6501. Specifically, a 1:1 type can be used. Of course, the present application is not limited to using this type of detergent, and other detergents in the field of fiber dyeing can also be used) to wash off the floating color on the fiber, improve the wet fastness of the dyeing and clean the fiber after washing, and then dry or perform post-treatment process.

[0023] The dyeing rate of the wet spinning fiber of Example 1 is 70%, and the strength of the wet spinning fiber is increased by 1 times, reaching 80cN·tex ‑1, the mechanical property test of the fiber (same below): the mechanical property of the fiber is tested by using a single filament strength tester, with reference to GB / T 14337-2008 "Chemical fiber short fiber tensile property test method". The clamping distance is 20 mm, the tensile speed is 20 mm / min, the fiber sample with a length of about 40 mm is cut by scissors, laid on the operation plate, the appropriate clamp is selected to clamp a section of the single fiber, the other end of the fiber is clamped by tweezers, the fiber is placed on the instrument holder, the fiber is clamped and stretched until the fiber is broken. The fiber sample is tested for multiple times, the average value is taken, and the data is recorded. The anti-fibrillation property of the fiber is improved by 1 times, and the wet friction value reaches 180 s. The anti-fibrillation property test (same below) is carried out by using the wet friction method, which is to rub the fiber under the condition of wet state until the fiber is broken. The time used from the beginning of rubbing to the breaking of the fiber is defined as the wet friction value, and the greater the measured wet friction value, the more difficult the fibril is to peel off from the fiber, which means that the anti-fibrillation ability of the fiber is better.

[0024] Example 2

[0025] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain 15% nanocellulose suspension solution, polylactic acid is dissolved in a mixed solution of trichloromethane / N,N-dimethylformamide (volume ratio of 3:1) to obtain an 8% polylactic acid solution, the nanocellulose suspension solution, the polylactic acid solution, and the glycerol solution are mixed uniformly according to a mass ratio of 7:2:1, then the mixture is placed at 30°C for 24 hours, and then irradiated with high-energy electron beams at a radiation dose of 50 kGy to obtain a reinforced crosslinked gel sample, the gel sample is soaked in deionized water, and the water is replaced every 3 hours for 5-8 times, the gel is replaced with organic solvents by water washing, the water content of the hydrogel is 70%, and a nanocellulose / polylactic acid hydrogel spinning solution is formed. The spinning solution is spun through a wet spinning device, and the spun yarn is subjected to secondary drying and reinforcement treatment by high-energy electron beam irradiation at a radiation dose of 50 kGy for 3 minutes. The hydrogel spinning solution is spun through the spinning nozzle of the spinning device, the yarn enters the water setting bath, and is prepared into polylactic acid / nanocellulose fiber by water washing, drawing, and radiation drying. The drawing speed is controlled at 25 cm / min. At room temperature, prepare dyes: disperse red 2% (on weight of fabric, o.w.f.), reactive red 2% (on weight of fabric, o.w.f.), dispersant NNO 1 g / L, bath ratio 1:50, and adjust the pH value to 5 with acetic acid and sodium acetate. After the dye solution is prepared, it is heated to 60°C at a heating rate of 2°C / min, and then the polylactic acid / nanocellulose composite fiber is added to start dyeing. Then heat to 110°C at a rate of 1°C / min, and keep for 20 minutes. Then start cooling from 110°C to 60°C, and the cooling time is controlled at 25 minutes. Add 3 g / L of sodium carbonate and 3 g / L of detergent 6501 to wash off the floating color on the fiber, improve the wet fastness of the dyeing, and then wash thoroughly, dry, or perform post-treatment processes. The dyeing of the wet spinning fiber of Example 2 has an upper dyeing rate of 80%, the strength of the fiber obtained by wet spinning is improved by 2 times, reaching 120 cN·tex ‑1 , and the anti-fibrillation performance is improved by 2 times, reaching 270 s.

[0026] Example 3

[0027] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain 20% nanocellulose suspension solution, polylactic acid is dissolved in a mixed solution of trichloromethane / N,N-dimethylformamide (volume ratio of 4:1) to obtain an 8% polylactic acid solution by mass fraction, the nanocellulose suspension solution, the polylactic acid solution, and the carboxymethyl cellulose solution are uniformly mixed according to a mass ratio of 6:2:2, then the mixture is placed at 30°C for 24 hours, and then irradiated with high-energy electron beams at a radiation dose of 45 kGy for 30 minutes to obtain a reinforced cross-linked nanocellulose / polylactic acid gel sample. The gel sample is soaked in deionized water, and the water is replaced every 3 hours for 5-8 times. The gel is washed with water to replace the organic solvent, and the water content of the hydrogel is 50%. A nanocellulose / polylactic acid hydrogel spinning solution is formed. The spinning solution is spun through a wet spinning device, and the spun yarn is subjected to a secondary drying reinforcement treatment by high-energy electron beam irradiation at a radiation dose of 30 kGy for 5 minutes. The hydrogel spinning solution is spun through the spinning nozzle of the spinning device and enters the water coagulation bath to be prepared into polylactic acid / nanocellulose fibers through water washing, drawing, and radiation drying. The drawing line speed is controlled at 35 cm / min. At room temperature, prepare dyes: disperse blue 3% (on weight of fabric, o.w.f.), reactive blue 3% (on weight of fabric, o.w.f.), dispersant NNO 1 g / L, bath ratio 1:50, and adjust the pH value to 5 with acetic acid and sodium acetate. After the dye solution is prepared, it is heated at a heating rate of 2°C / min to 60°C, and then the polylactic acid / nanocellulose composite fibers are added to start dyeing. Then, heat at a rate of 1°C / min to 110°C and keep for 20 minutes. Then, start cooling from 110°C to 60°C, and the cooling time is controlled at 30 minutes. Add 3 g / L of sodium carbonate and 3 g / L of detergent 6501 to wash off the floating color on the fibers, improve the wet fastness of the dyeing, and then wash thoroughly, dry, or perform post-treatment processes. The dyeing of the wet spinning fiber of Example 3 has an upper dyeing rate of 78%, the strength of the fiber obtained by wet spinning is increased by 2.5 times, reaching 100 cN·tex ‑1 , and the anti-fibrillation performance is increased by 1 times, reaching 180 s.

[0028] Example 4

[0029] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain a nanocellulose suspension solution with a mass fraction of 5%. The polylactic acid is dissolved in a dichloromethane / N,N-dimethylformamide (volume ratio of 3:1) mixed solution to obtain a polylactic acid solution with a mass fraction of 8%. The nanocellulose suspension solution, the polylactic acid solution, and the polyvinyl alcohol solution are uniformly mixed according to a mass ratio of 8:1:1, and then are placed at 30℃ for 24 hours. Then, the gel sample is irradiated by high-energy electron beam with a radiation dose of 50kGy for 30 minutes to obtain a reinforced cross-linked nanocellulose / polylactic acid gel sample. The gel sample is soaked in deionized water, and the water is replaced every 3 hours for 5-8 times. The gel is washed by water to replace the organic solvent, and the water content of the hydrogel is 30%. The nanocellulose / polylactic acid hydrogel spinning solution is formed. The spinning solution is spun by a wet spinning device. The spun yarn is subjected to secondary drying and strengthening treatment by high-energy electron beam irradiation with a radiation dose of 40kGy for 3 minutes. The hydrogel spinning solution is spun through the spinning nozzle of the spinning device, and the yarn enters the water setting bath to be prepared into polylactic acid / nanocellulose fiber by water washing, drawing, and radiation drying. The drawing speed is controlled at 40cm / min. The dyes are prepared at room temperature: Disperse Yellow 1.5% (on weight of fabric, o.w.f.), Reactive Yellow 1.5% (on weight of fabric, o.w.f.), diffusing agent NNO 1g / L, bath ratio 1:50, and the pH value is adjusted to 5 by acetic acid and sodium acetate. After the dye solution is prepared, the temperature is increased to 60℃ at a rate of 2℃ / min, and then the polylactic acid / nanocellulose composite fiber is added to start dyeing. Then, the temperature is increased to 110℃ at a rate of 1℃ / min, and the temperature is kept for 20 minutes. Then, the temperature is decreased from 110℃ to 60℃, and the cooling time is controlled at 30 minutes. The sodium hydrosulfite 3g / L, anhydrous sodium carbonate 3g / L, and detergent 6501 3g / L are added to wash off the floating color on the fiber, improve the wet fastness of the dyeing, and perform cleaning and water washing. The spun fiber is dried or subjected to post-treatment process. The dyeing rate of the fiber spun by the wet spinning method in Example 4 is 76%, the strength of the fiber spun by the wet spinning method is increased by 1.5 times to reach 100cN·tex, and the anti-fibrillation performance is increased by 1.2 times to reach 200s. ‑1 , the anti-fibrillation performance is increased by 1.2 times to reach 200s.

[0030] Example 5

[0031] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain a nanocellulose suspension solution with a mass fraction of 15%. The polylactic acid is dissolved in a dichloromethane / N,N-dimethylformamide (volume ratio of 4:1) mixed solution to obtain a polylactic acid solution with a mass fraction of 8%. The nanocellulose suspension solution, the polylactic acid solution, and the polyethylene glycol solution are uniformly mixed according to a mass ratio of 5:3:2, and then are placed at 30°C for 24 hours. Then, the mixture is irradiated by high-energy electron beam with a radiation dose of 50 kGy to obtain a reinforced cross-linked nanocellulose / polylactic acid gel sample. The gel sample is soaked in deionized water, and the water is replaced every 3 hours for 5-8 times. The gel is washed by water to replace the organic solvent, and the water content of the hydrogel is 50%. The nanocellulose / polylactic acid hydrogel spinning solution is formed. The spinning solution is spun by a wet spinning device. The spun fiber is subjected to a secondary drying reinforcement treatment by high-energy electron beam irradiation with a radiation dose of 50 kGy for 5 minutes. The hydrogel spinning solution is spun through the spinning nozzle of the spinning device and enters the water coagulation bath to be prepared into polylactic acid / nanocellulose fibers by water washing, drawing, and radiation drying. The drawing linear speed is controlled at 30 cm / min. The dyes are prepared at room temperature: disperse blue 1.5% (on weight of fabric, o.w.f.), reactive blue 1.5% (on weight of fabric, o.w.f.), anionic surfactant AES 0.2 g / L, leveling agent SL 0.4 g / L, bath ratio 1:30, and the pH value is adjusted to 5 by acetic acid and sodium acetate. After the dye solution is prepared, the temperature is increased to 60°C at a rate of 2°C / min from room temperature, and then the polylactic acid / nanocellulose composite fiber is added to start dyeing. Subsequently, the temperature is increased to 110°C at a rate of 1°C / min, and the temperature is maintained for 20 minutes. Then, the temperature is decreased from 110°C to 60°C at a rate of 1°C / min, and the cooling time is controlled at 30 minutes. The sodium hydrosulfite 3 g / L, anhydrous sodium carbonate 3 g / L, and detergent 6501 3 g / L are added to wash off the floating color on the fiber, improve the wet fastness of the dyeing, and perform cleaning. After sufficient water washing, the fiber is dried or subjected to a post-treatment process. The dyeing rate of the wet spinning fiber obtained by the method of Example 5 is 79%, the strength of the fiber obtained by the wet spinning is increased by 2.8 times, reaching 112 cN·tex ‑1 , and the anti-fibrillation performance is increased by 1 times, reaching 180 s.

[0032] Comparative Example 1

[0033] The spinning solution obtained by the method of Example 1 without irradiation cross-linking is spun without a secondary radiation process to prepare a composite fiber for dyeing.

[0034] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain 10% nanocellulose suspension solution, polylactic acid is dissolved in dichloromethane / N,N-dimethylformamide (volume ratio of 4:1) mixed solution to obtain 5% polylactic acid solution, the nanocellulose suspension solution, polylactic acid solution, polyethylene glycol solution are mixed uniformly according to the mass ratio of 6:3:1, and then the gel sample is obtained by standing at 50℃ for 12 hours. The gel sample is soaked in deionized water, and the water is replaced every 3 hours, and the process is repeated for 5-8 times. The gel is washed with water to replace the organic solvent, and the water content of the hydrogel is 60%. The gel is washed with water to replace the solvent to form a hydrogel spinning solution. The spinning solution is spun by a wet spinning device, the spinning solution is spun through the spinning hole of the spinning device, the yarn enters the water setting bath, and is washed, drawn, and dried by hot air to prepare polylactic acid / nanocellulose fiber. The drawing speed is controlled at 15 cm / min, and the winding drawing speed ratio is 1.5. In the hot air drying, the temperature is 110℃, and the drying time is 30 minutes. At room temperature, prepare dyes: disperse yellow 1% (on weight of fabric, o.w.f.), reactive yellow 1% (on weight of fabric, o.w.f.), dispersant NNO 1g / L, bath ratio 1:50, and adjust the pH value to 5 with acetic acid and sodium acetate. After the dye solution is prepared, it is heated from room temperature to 60℃ at a rate of 2℃ / min, then the polylactic acid / nanocellulose composite fiber is added, and the dyeing starts. Then heat to 110℃ at a rate of 1℃ / min, and keep for 20 minutes. Then start cooling from 110℃ to 60℃, and the cooling time is controlled at 30 minutes. Add 3g / L of sodium carbonate and 3g / L of detergent 6501 to wash off the floating color on the fiber, improve the wet fastness of the dyeing, and then wash thoroughly, dry or perform post-treatment process. The obtained spinning fiber has a dyeing rate of 50%, a breaking strength reduction of 30%, which is 56 cN·tex ‑1 , and a fiber anti-fibrillation performance reduction of 40%, which is 108 s.

[0035] Comparative Example 2

[0036] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain 15% nanocellulose suspension solution, polylactic acid is dissolved in a mixed solution of trichloromethane / N,N-dimethylformamide (volume ratio of 3:1) to obtain an 8% polylactic acid solution by mass fraction, the nanocellulose suspension solution, polylactic acid solution, and glycerol solution are mixed uniformly according to a mass ratio of 7:2:1, and then the mixture is placed at 30°C for 24 hours to obtain a reinforced crosslinked gel sample. The gel sample is soaked in deionized water, and the water is replaced every 3 hours for 5-8 times. The gel is washed with water to replace the organic solvent, and the water content of the hydrogel is 70%. A nanocellulose / polylactic acid hydrogel spinning solution is formed. The spinning solution is spun through a wet spinning device. The spinning solution is spun through the spinning hole of the spinning device, and the yarn enters the water coagulation bath, is washed with water, is drawn, and is dried by hot air to prepare polylactic acid / nanocellulose fibers. The drawing speed is controlled at 15 cm / min, and the winding drawing speed ratio is 1.5. In the hot air drying, the temperature is 110°C, and the drying time is 5 minutes. At room temperature, a dye solution is prepared: disperse red 2% (on weight of fabric, o.w.f.), reactive red 2% (on weight of fabric, o.w.f.), dispersant NNO 1 g / L, bath ratio 1:50, and pH value is adjusted to 5 with acetic acid and sodium acetate. After the dye solution is prepared, it is heated to 60°C at a rate of 2°C / min, and then the polylactic acid / nanocellulose composite fiber is added to start dyeing. Then, the temperature is increased to 110°C at a rate of 1°C / min, and the temperature is maintained for 20 minutes. Then, the temperature is decreased from 110°C to 60°C, and the cooling time is controlled at 30 minutes. Sulfonal 3 g / L, anhydrous sodium carbonate 3 g / L, and 3 g / L detergent 6501 are added to wash off the floating color on the fiber, improve the wet fastness of the dyeing, and perform cleaning. After sufficient water washing, the fiber is dried or subjected to a post-treatment process. Compared with example 2, the dyeing of the obtained spinning fiber has an upper dyeing rate of 55%, the breaking strength of the obtained spinning fiber is reduced by 50% to 60 cN·tex, and the fiber anti-fibrillation performance is reduced by 30% to 189 s. ‑1 , the breaking strength of the obtained spinning fiber is reduced by 50% to 60 cN·tex

[0037] Comparative example 3

[0038] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain 15% nanocellulose suspension solution, polylactic acid is dissolved in a mixed solution of trichloromethane / N,N-dimethylformamide (volume ratio of 3:1) to obtain an 8% polylactic acid solution by mass fraction, the nanocellulose suspension solution, the polylactic acid solution, and the glycerol solution are uniformly mixed according to a mass ratio of 7:2:1, and then the mixture is placed at 30°C for 24 hours to obtain a reinforced crosslinked gel sample. The gel sample is soaked in deionized water, and the water is replaced every 3 hours for 5-8 times. The gel is washed with water to replace the organic solvent, and the water content of the hydrogel is 70%. A nanocellulose / polylactic acid hydrogel spinning solution is formed. The spinning solution is spun through a wet spinning device. The spinning solution is spun through the spinning hole of the spinning device, and the yarn enters the water coagulation bath, is washed, drawn, and dried by irradiation to prepare polylactic acid / nanocellulose fibers. The drawing speed is controlled at 25 cm / min. The irradiation drying radiation dose is 50 kGy, and the irradiation drying treatment time is 3 minutes. At room temperature, prepare a dye solution: disperse red 2% (on weight of fabric, o.w.f.), reactive red 2% (on weight of fabric, o.w.f.), dispersant NNO 1 g / L, bath ratio 1:50, and adjust the pH value to 5 with acetic acid and sodium acetate. After the dye solution is prepared, it is heated to 60°C at a rate of 2°C / min, and then the polylactic acid / nanocellulose composite fiber is added to start dyeing. Then, heat to 110°C at a rate of 1°C / min, and keep for 20 minutes. Then, start cooling from 110°C to 60°C, and the cooling time is controlled at 30 minutes. Add 3 g / L of sodium carbonate and 3 g / L of detergent 6501 to wash off the floating color on the fiber, improve the wet fastness of the dyeing, and then wash thoroughly, dry, or perform post-treatment processes.

[0039] In this embodiment, one irradiation is used. Compared with Example 2, the dyeing rate of the obtained spinning fiber is 65%, the breaking strength of the obtained spinning fiber is reduced by 40% to 72 cN·tex, and the fiber anti-fibrillation performance is reduced by 50% to 135 s. ‑1 , the fiber anti-fibrillation performance is reduced by 50% to 135 s.

[0040] Comparative Example 4

[0041] The cellulose is dispersed into nanocellulose suspension by high-speed shearing machine in water from sugarcane fibers to obtain 15% nanocellulose suspension solution, polylactic acid is dissolved in a mixed solution of trichloromethane / N,N-dimethylformamide (volume ratio of 3:1) to obtain an 8% polylactic acid solution, the nanocellulose suspension solution, the polylactic acid solution and the glycerol solution are uniformly mixed according to a mass ratio of 7:2:1, then the mixture is placed at 30°C for 24 hours, and then irradiated with high-energy electron beams at a radiation dose of 50 kGy to obtain a reinforced crosslinked gel. The gel sample is soaked in deionized water, and the water is replaced every 3 hours for 5-8 times. The gel is washed with water to replace the organic solvent, and the water content of the hydrogel is 70%. A nanocellulose / polylactic acid hydrogel spinning solution is formed. The spinning solution is spun through a wet spinning device. The spinning solution is spun through the spinning hole of the spinning device. The yarn enters the water setting bath, is washed with water, is drawn, and is dried by hot air to prepare polylactic acid / nanocellulose fibers. The drawing speed is controlled at 25 cm / min. In the hot air drying, the temperature is 110°C, and the drying time is 30 minutes. At room temperature, a dye solution is prepared: disperse red 2% (on weight of fabric, o.w.f.), reactive red 2% (on weight of fabric, o.w.f.), dispersant NNO 1 g / L, bath ratio 1:50, and pH value is adjusted to 5 with acetic acid and sodium acetate. After the dye solution is prepared, the temperature is raised to 60°C at a rate of 2°C / min, and then the polylactic acid / nanocellulose composite fibers are added to start dyeing. Then the temperature is raised to 110°C at a rate of 1°C / min, and the temperature is kept for 20 minutes. Then the temperature is lowered from 110°C to 60°C, and the cooling time is controlled at 30 minutes. Sulfonal 3 g / L, anhydrous sodium carbonate 3 g / L, and 3 g / L detergent 6501 are added to wash off the floating color on the fibers, improve the wet fastness of the dyeing, and perform cleaning. After washing, the fibers are dried or subjected to post-treatment processes.

[0042] In this embodiment, one irradiation is adopted. Compared with example 2, the dyeing rate of the obtained spinning fiber is 66%, the breaking strength of the obtained spinning fiber is reduced by 30% and reaches 84 cN·tex, and the fibrillation resistance of the fiber is reduced by 40% and reaches 162 s. ‑1 , the fibrillation resistance of the fiber is reduced by 40% and reaches 162 s.

[0043] The protection scope of the present application is not limited to the present embodiment, and any similar transformation thereof is deemed to be within the protection scope of the present application. Industrial applicability

[0044] Enter the industrial applicability description paragraph here. Free content of the sequence listing

[0045] Enter the free content description paragraph of the sequence listing here.

Claims

1. A dyeing process for polylactic acid and nanocellulose composite fibers, comprising a dope preparation step, a spinning step, and a dyeing step, characterized by, The spinning solution preparation process is to uniformly mix nanocellulose suspension, polylactic acid solution and additive together, stand for 1-2h at 30-80℃ and perform high-energy electron beam radiation to form a gel, and the gel is washed with water to obtain a hydrogel spinning solution, wherein the irradiation dose of high-energy electron beam radiation is 10-50kGy, and the irradiation time is 20 to 40 minutes, wherein the mass ratio of polylactic acid solution to nanocellulose solution is 10:1-1:1, and the mass ratio of polylactic acid solution to additive solution is 10:1-1:1, the polylactic acid solution is dispersed in an organic solvent, the mass concentration of polylactic acid is 5-10%, and the nanocellulose suspension is dispersed in water, and the length of the cellulose fiber is 10-100nm, and the mass concentration of cellulose is 5-20%; The spinning process is to send the above hydrogel spinning solution into a wet spinning device to form a fiber, and the fiber is dried and strengthened by high-energy electron beam radiation to obtain a fiber filament, wherein the irradiation dose is 10-50kGy, and the irradiation time is 3-5 minutes; The dyeing process, the weight ratio of dye to fiber is 1-10%, the bath ratio is 1:45-55, the amount of dispersing agent NNO is 0.8-1.2g / L, the pH value of the dyeing solution is 4.8-5.2, the temperature is raised to 58-62℃ at a rate of 1.5-2.5℃ / min, the fiber is added, the temperature is raised to the dyeing temperature of 108-112℃ at a rate of 0.8-1.2℃ / min, and the dyeing time is 18-22 minutes; then the temperature is lowered to 58-62℃, and the unfixed dye on the fiber is washed away by adding 2.5-3.5g / L of insurance powder, 2.5-3.5g / L of anhydrous sodium carbonate and 2.5-3.5g / L of detergent, and then the fiber is washed thoroughly, dried or subjected to post-treatment process.

2. The method for preparing an antigenic fibril fiber using polylactic acid and nanocellulose according to claim 1, characterized by, The organic solvent is one or a mixture of two or more of N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform and acetone.

3. The method of claim 2, wherein the antigenic fibril is prepared using polylactic acid and nanocellulose. The additive is polyethylene glycol, glycerol, carboxymethyl chitosan, carboxymethyl cellulose, polyvinyl alcohol or polyethylene oxide.

4. The method of claim 3, wherein the antigenic fibril is prepared using polylactic acid and nanocellulose. The cellulose fiber is sugarcane fiber.

5. The method of claim 4, wherein the antigenic fibril is prepared using polylactic acid and nanocellulose. The dye is a mixture of disperse dye and reactive dye.

6. The method of claim 5, wherein the antigenic fibril is prepared using polylactic acid and nanocellulose. The disperse dye is azo-type disperse red, disperse blue or disperse yellow; and the reactive dye is reactive red, reactive blue or reactive yellow. 7.[Amended according to Rule 26 18.12.2024][Deleted]