Environment-friendly cashmere galling process adopting natural plant pigment for printing and dyeing

Abstract

The invention discloses an environment-friendly cashmere galling process for printing and dyeing with natural plant pigments, and relates to the technical field of cashmere product processing. The invention discloses environment-friendly cashmere printed and dyed by natural plant pigments. The fabric is prepared from the following raw materials in parts by weight: 10 to 30 parts of natural plant pigment, 100 parts of cashmere fiber, 5 to 15 parts of sodium alginate, 3 to 8 parts of citric acid, 4 to 10 parts of modified chitosan, 2 to 6 parts of glycerol, 2 to 5 parts of sodium bicarbonate, 3 to 7 parts of soybean protein, 1 to 3 parts of nano titanium dioxide, 2 to 5 parts of polyethylene glycol, 0.5 to 1.5 parts of modified cellulase, 1 to 3 parts of calcium chloride, 200 to 500 parts of distilled water, 2 to 6 parts of tea polyphenol and 3 to 8 parts of corn starch. Natural plant pigments are adopted in the process, the process is environmentally friendly and harmless, various modified materials and ultrasonic and microwave technologies are matched, the printing and dyeing effect and the fiber performance are improved, the treated cashmere product is high in wool density, appropriate in length and good in color fastness, the anti-ultraviolet and antibacterial functions are achieved, and the process is environmentally friendly and efficient.

Description

Technical Field

[0001] The invention relates to the technical field of cashmere product processing, in particular to an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing. Background Art

[0002] Amidst the rapid development of the textile industry, the drawbacks of traditional cashmere processing techniques are becoming increasingly prominent. On the one hand, chemical synthetic dyes release harmful substances such as formaldehyde and azo compounds during the printing and dyeing process, which not only cause excessive COD levels in textile wastewater but can also trigger allergic reactions in humans through skin contact and even pose a risk of cancer. According to statistics, traditional printing and dyeing processes generate approximately 200 tons of wastewater containing heavy metals and aromatic amines for every ton of cashmere products produced, causing irreversible damage to the aquatic ecosystem. On the other hand, conventional napping processes rely on strong acid and alkali additives to destroy the fiber's surface scale structure. While this improves the adhesion of the fleece, it reduces the fiber's breaking strength by over 30%, increasing the pilling rate and shortening the product's service life.

[0003] At the same time, global environmental regulations are becoming increasingly stringent. The EU's REACH regulation has restricted the use of over 100 textile chemicals, and my country's "Water Pollutant Discharge Standard for Textile Dyeing and Finishing Industries" has also lowered the COD emission limit to 50 mg / L. Consumer demand for "ecological textiles" is exploding. The global organic cashmere product market is expected to reach $8.7 billion in 2024, with a compound annual growth rate exceeding 15%. However, existing natural dye printing and dyeing processes face technical bottlenecks such as poor color fastness and weak wool binding. Traditional enzyme treatment processes are susceptible to temperature and pH changes, resulting in insufficient production stability. Achieving high-performance cashmere products while meeting environmental requirements has become a key challenge for the industry. Summary of the Invention

[0004] In response to the shortcomings of the existing technology, the present invention provides an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing, which solves the problems of large chemical dye pollution, serious fiber damage, insufficient product performance, single function and poor process stability in the traditional cashmere printing and dyeing napping process.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0006] The environmentally friendly cashmere printed and dyed with natural plant pigments contains the following raw materials in parts by weight: 10-30 parts of natural plant pigments, 100 parts of cashmere fibers, 5-15 parts of sodium alginate, 3-8 parts of citric acid, 4-10 parts of modified chitosan, 2-6 parts of glycerol, 2-5 parts of sodium bicarbonate, 3-7 parts of soy protein, 1-3 parts of nano-titanium dioxide, 2-5 parts of polyethylene glycol, 0.5-1.5 parts of modified cellulase, 1-3 parts of calcium chloride, 200-500 parts of distilled water, 2-6 parts of tea polyphenols, and 3-8 parts of corn starch.

[0007] Furthermore, the natural plant pigment is a plant pigment selected from indigo, madder red, wormwood, and green tea.

[0008] Furthermore, the modified chitosan is prepared in the following steps:

[0009] A1. Add acetic acid solution to a reactor containing chitosan, place the reactor in a constant temperature water bath, start stirring and heat to 40°C, maintain stirring at this temperature for 2 hours; after the chitosan is completely dissolved, slowly add glyoxal, continue to maintain stirring, and react at 40°C for 3 hours; filter the hydroformylated chitosan solution to obtain a pure hydroformylated chitosan solution;

[0010] A2. Pour the hydroformylated chitosan solution into a reactor, add sodium hydroxide solution, and stir in a constant temperature water bath at 35°C for 1.5 hours. After stirring, slowly add nano-silica and transfer the reactor to an ultrasonic disperser for 30 minutes. Remove the complex solution from the ultrasonic disperser and let it stand at room temperature for 1 hour to obtain a stable nano-silica-hydroformylated chitosan complex solution.

[0011] A3. Pour the nano-silica-formylated chitosan complex solution and the polyvinyl alcohol solution into the reactor together, place the reactor in a constant temperature water bath, heat it to 50°C, maintain this temperature and stir for 2 hours. After the reaction is completed, cool the modified chitosan solution to room temperature and seal it for storage.

[0012] Furthermore, in step A1, the mass ratio of chitosan, acetic acid solution, and glyoxal is 1:10:0.1, the mass fraction of the acetic acid solution is 5%, and the stirring speed is 150 r / min.

[0013] Furthermore, in step A2, the mass ratio of the hydroformylated chitosan solution, the sodium hydroxide solution, and the nano-silica is 8:1:1.2, the mass fraction of the sodium hydroxide solution is 2%, the stirring speed is 150 r / min, and the ultrasonic power is 500 W.

[0014] Furthermore, in step A3, the mass ratio of the nano-silica-formylated chitosan complex solution to the polyvinyl alcohol solution is 5:1, the mass fraction of the polyvinyl alcohol solution is 3%, and the stirring speed is 120 r / min.

[0015] After being dissolved in acetic acid, chitosan reacts with glyoxal to hydroformylate and increase active groups. It is then compounded with nano-silica through ultrasonic dispersion. The excellent properties of nano-silica are used to improve the performance of the composite. Finally, it is mixed with polyvinyl alcohol solution. Through intermolecular interactions, the film-forming property, stability and functionality of chitosan are improved, allowing it to play a better role in cashmere processing, such as enhancing the bonding strength of fibers.

[0016] Furthermore, the modified cellulase is specifically prepared in the following steps:

[0017] B1. Add calcium chloride solution to the conical flask containing cellulase, shake the conical flask to mix the two evenly, and then place the conical flask in a constant temperature incubator at 30°C for 1 hour. After the standing period, shake the solution evenly to obtain the first modified cellulase solution;

[0018] B2. Pour the first modified cellulase solution into a reaction vessel, place the reaction vessel in a constant temperature water bath at 25°C, place it on a magnetic stirrer, start stirring, slowly add β-cyclodextrin, and continue stirring for 2 hours. After the reaction is completed, filter to obtain a pure β-cyclodextrin-cellulase inclusion complex solution;

[0019] B3. Pour the β-cyclodextrin-cellulase inclusion complex solution and the sodium alginate solution into the reactor together, place the reactor in a constant temperature water bath, turn on the stirrer, raise the temperature to 35°C, maintain the temperature and stir for 1.5 hours to obtain a modified cellulase solution; after the reaction is completed, cool the modified cellulase solution to room temperature, transfer it to a sterile storage container, seal it, and store it in a refrigerator at 4°C to maintain its activity.

[0020] Furthermore, in step B1, the mass ratio of cellulase to calcium chloride solution is 1:6, and the mass fraction of calcium chloride solution is 1%.

[0021] Furthermore, in step B2, the mass of β-cyclodextrin is 8% of the mass of cellulase, and the stirring speed is 120 r / min.

[0022] Furthermore, in step B3, the mass ratio of the β-cyclodextrin-cellulase inclusion complex solution to the sodium alginate solution is 4:1, the mass fraction of the sodium alginate solution is 2%, and the stirring speed is 100 r / min.

[0023] Cellulase is first treated with calcium chloride solution, which may stabilize the structure of the enzyme through ionic action. Then it is included with β-cyclodextrin. The inclusion effect of β-cyclodextrin is used to protect the active center of the enzyme and reduce the influence of external factors on the enzyme. Finally, it is mixed with sodium alginate solution. Sodium alginate may play a role in protecting and stabilizing the enzyme, thereby improving the stability and activity of cellulase and making it easier to treat fibers.

[0024] The environmentally friendly cashmere preparation method using natural plant pigments for printing and dyeing specifically comprises the following steps:

[0025] S1. Add distilled water to the reactor and heat it to 40-50°C. Then add sodium alginate and polyethylene glycol in sequence. Turn on the ultrasonic equipment, set the ultrasonic frequency and power, and start the microwave device at the same time, adjust the power, and continue the treatment for 15-25 minutes under this synergistic effect.

[0026] S2, adding citric acid and sodium bicarbonate to the above solution, adjusting the pH value of the solution to 5-7, then adding natural plant pigments, stirring evenly to form a printing and dyeing solution;

[0027] S3. Place modified chitosan, soy protein, nano-titanium dioxide, glycerol, calcium chloride, tea polyphenols, and corn starch into a supercritical reactor, introduce supercritical carbon dioxide fluid, control the pressure and temperature in the reactor, and maintain the conditions for 30-40 minutes to prepare a mixed slurry; soak cashmere fiber in the mixed slurry, set electrode plates on both sides of the soaking container, apply a pulsed electric field, and soak at 30-40° C. for 1-2 hours;

[0028] S4. Place the soaked cashmere fiber in the reaction chamber of the plasma treatment equipment, introduce argon as the working gas, and process for 3-5 minutes. After the surface of the cashmere fiber is etched and activated, the cashmere fiber is placed in the printing and dyeing liquid and subjected to printing and dyeing treatment at a temperature of 45-55°C for 1-1.5 hours to obtain environmentally friendly cashmere printed and dyed with natural plant pigments.

[0029] Furthermore, in the step S1, the temperature is raised to 40-50°C, the ultrasonic frequency is 20-40kHz, the power is 300-500W, and the power of the microwave device is adjusted to 200-400W.

[0030] Furthermore, in the step S3, the pressure in the reactor is 10-20 MPa, the temperature is 35-45° C., the electric field strength is 10-20 kV / cm, the pulse frequency is 10-50 Hz, and the pulse width is 100-500 μs.

[0031] Furthermore, in the step S4, the air pressure is controlled to be 10-100 Pa and the power is controlled to be 50-150 W.

[0032] The environmentally friendly cashmere brushing process using natural plant pigments for printing and dyeing has the following specific steps:

[0033] Y1. Take out the cashmere fibers that have been printed and dyed, place them in clean water, and rinse them 3-5 times in a countercurrent manner, with each rinse lasting 5-10 minutes to ensure that the residual printing and dyeing liquid on the fiber surface is fully removed. After rinsing, place the cashmere fibers in a centrifugal dehydrator, set the speed, and dehydrate for 3-5 minutes to complete the dehydration process;

[0034] Y2. Place the dehydrated cashmere fiber into an ultrasonic treatment container, add clean water to completely immerse the fiber, turn on the ultrasonic equipment, set the ultrasonic frequency and power, and the treatment time is 10-15 minutes;

[0035] Y3. Place the dehydrated cashmere fibers into the diluted modified cellulase solution, ensuring that the fibers are completely immersed. Pretreat at 30-35°C for 0.5-1 hour, gently stirring every 15-20 minutes to ensure full contact between the solution and the fibers. After the pretreatment, remove the fibers and rinse them with clean water 2-3 times to remove any residual enzyme solution on the surface, then drain briefly.

[0036] Y4. Start the drum-type napping machine and preheat the equipment to 30-35°C. Place the pretreated cashmere fibers evenly into the drum, set the drum speed, start the plasma equipment simultaneously, and introduce helium as the working gas. The napping time is 15-25 minutes.

[0037] Y5. Spread the brushed cashmere fibers flat on the tray of the steam setting equipment. After the equipment is sealed, introduce saturated steam and maintain the steam environment for 10-15 minutes to obtain steam-set environmentally friendly cashmere.

[0038] Furthermore, in the Y1 step, the rotation speed is 1000-1500 r / min.

[0039] Furthermore, in the Y2 step, the ultrasonic frequency is 30-40 kHz and the power is 300-500 W.

[0040] Furthermore, in the Y3 step, the mass fraction of the modified cellulase solution is 0.3-0.8%.

[0041] Furthermore, in the Y4 step, the drum speed is 80-120 r / min, the air pressure is controlled at 20-80 Pa, and the power is 80-120 W.

[0042] Furthermore, in the Y5 step, the steam temperature is 100-110° C. and the pressure is 0.1-0.2 MPa.

[0043] The present invention provides an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing, which has the following beneficial effects:

[0044] 1. Use natural plant pigments such as indigo and madder red to replace traditional chemical synthetic dyes, cutting off the introduction of harmful substances such as aromatic amines and heavy metals from the raw material end. During the production process, the COD and BOD indicators of printing and dyeing wastewater are significantly improved, and can be directly reused in the production process, significantly reducing water treatment costs. The composite system of modified chitosan and nano-silica controls the formaldehyde content of the finished product to an extremely low level through physical encapsulation, far exceeding the national standard. The natural antibacterial system formed by tea polyphenols and corn starch avoids the biological toxicity of traditional quaternary ammonium salt antibacterial agents, has a significant inhibitory effect on common pathogens, and is washable, achieving a dual improvement in environmental protection and health performance.

[0045] 2. Supercritical carbon dioxide fluid processing technology promotes uniform penetration of soy protein and nano-titanium dioxide into the fiber, significantly increasing the density and length of the down, while also improving the uniformity of the tips. A pulsed electric field-assisted soaking process promotes the formation of a stable hydrogen bond network between modified chitosan and cashmere fibers, effectively enhancing the fiber's breaking strength. Furthermore, the composite film composed of nano-titanium dioxide and polyvinyl alcohol imparts UV resistance to the product, while process optimization ensures the highest level of color fastness in the industry, maintaining color stability even after prolonged friction and washing, fundamentally addressing the pain points of fiber strength loss and fading in traditional processes.

[0046] 3. Cellulase modified through β-cyclodextrin inclusion technology significantly expands the range of active temperature and pH values, reducing energy consumption for temperature control in industrial production while improving the stability of the enzyme treatment process. A plasma etching process precisely controls the fiber surface microstructure, doubling the dyeing solution adsorption rate, significantly improving dye utilization, and reducing raw material waste and production costs. The steam setting process utilizes saturated steam treatment with specific parameters, effectively solving the problem of hair lodging in traditional napping processes. This results in an extremely high hair fixation rate in the finished product, ensuring consistent quality in large-scale production.

[0047] 4. This process achieves the integration of antibacterial, UV-resistant, and high colorfastness properties through the coordinated design of material modification and process parameters. The synergistic antibacterial system of tea polyphenols and modified chitosan not only protects against a wide range of fungi but also offers long-lasting efficacy. The photocatalytic properties of nano-titanium dioxide impart air purification capabilities to the product, decomposing formaldehyde. The moisturizing film formed by corn starch and glycerin enhances the softness and drape of cashmere products, ensuring they meet both environmental standards and the tactile and functional requirements of high-end apparel. This paves the way for the expansion of cashmere products into specialized applications such as medical and outdoor applications. DETAILED DESCRIPTION

[0048] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0049] Example 1, an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing, the specific steps are as follows:

[0050] S1. Add 200 parts of distilled water to the reactor, raise the temperature to 40°C, add 5 parts of sodium alginate and 2 parts of polyethylene glycol in sequence, turn on the ultrasonic equipment, set the ultrasonic frequency to 20 kHz and the power to 300 W, and start the microwave device at the same time, adjust the power to 200 W, and continue the treatment under this synergistic effect for 15 minutes;

[0051] S2. Add citric acid and sodium bicarbonate to the above solution to adjust the pH value of the solution to 5, then add 10 parts of indigo pigment and stir evenly to form a printing solution;

[0052] S3. Place 4 parts of modified chitosan, 3 parts of soy protein, 1 part of nano-titanium dioxide, 2 parts of glycerol, 1 part of calcium chloride, 2 parts of tea polyphenols and 3 parts of corn starch into a supercritical reactor, introduce supercritical carbon dioxide fluid, control the pressure in the reactor to 10 MPa and the temperature to 35°C, maintain the conditions for 30 minutes, and prepare a mixed slurry; soak cashmere fiber in the mixed slurry, set electrode plates on both sides of the soaking container, apply a pulsed electric field with an electric field strength of 10 kV / cm, a pulse frequency of 10 Hz, and a pulse width of 100 μs, and soak at 30°C for 1 hour;

[0053] S4. Place the soaked cashmere fiber in a reaction chamber of a plasma treatment device, introduce argon as a working gas, control the gas pressure at 10 Pa, the power at 50 W, and the treatment time at 3 min to complete the etching and activation of the cashmere fiber surface; after completion, place the cashmere fiber in a printing and dyeing solution and perform a printing and dyeing treatment at a temperature of 45° C. for 1 h to obtain environmentally friendly cashmere dyed with natural plant pigments;

[0054] Y1. Take out the cashmere fibers that have been printed and dyed, place them in clean water, and rinse them three times using a countercurrent rinse method, with each rinse lasting 5 minutes to ensure that the printing and dyeing liquid remaining on the fiber surface is fully removed. After rinsing, place the cashmere fibers in a centrifugal dehydrator, set the speed to 1000 r / min, and the dehydration time to 3 minutes to complete the dehydration process;

[0055] Y2. Place the dehydrated cashmere fiber into an ultrasonic treatment container, add clean water to completely immerse the fiber, turn on the ultrasonic equipment, set the ultrasonic frequency to 30kHz, the power to 300W, and the treatment time to 10min;

[0056] Y3. Place the dehydrated cashmere fibers into a diluted 0.3% modified cellulase solution, ensuring that the fibers are completely immersed. Pretreat at 30°C for 0.5 h, gently stirring every 15 min to ensure full contact between the solution and the fibers. After pretreatment, remove the fibers, rinse them twice with clean water to remove any residual enzyme solution on the surface, and then drain briefly.

[0057] Y4. Start the drum-type napping machine and preheat the equipment to 30°C. Place the pretreated cashmere fibers evenly into the drum. Set the drum speed to 80 rpm. Simultaneously start the plasma equipment and introduce helium as the working gas. Control the pressure at 20 Pa, the power at 80 W, and the napping time for 15 minutes.

[0058] Y5. Spread the brushed cashmere fibers flat on the tray of the steam setting equipment. After the equipment is sealed, introduce saturated steam with a temperature of 100°C and a pressure of 0.1 MPa. Maintain the steam environment for 10 minutes to obtain steam-set environmentally friendly cashmere.

[0059] Example 2, an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing, the specific steps are as follows:

[0060] S1. Add 500 parts of distilled water to the reactor, raise the temperature to 50°C, add 15 parts of sodium alginate and 5 parts of polyethylene glycol in sequence, turn on the ultrasonic equipment, set the ultrasonic frequency to 40 kHz and the power to 500 W, and simultaneously start the microwave device and adjust the power to 400 W. Continue the treatment under this synergistic effect for 25 minutes;

[0061] S2, adding citric acid and sodium bicarbonate to the above solution, adjusting the pH value of the solution to 7, then adding 30 parts of madder red pigment, stirring to form a printing solution;

[0062] S3. Place 10 parts of modified chitosan, 7 parts of soy protein, 3 parts of nano-titanium dioxide, 6 parts of glycerol, 3 parts of calcium chloride, 6 parts of tea polyphenols and 8 parts of corn starch into a supercritical reactor, introduce supercritical carbon dioxide fluid, control the pressure in the reactor to 20 MPa and the temperature to 45°C, maintain the conditions for 40 minutes, and prepare a mixed slurry; place 100 parts of cashmere fibers into the mixed slurry and soak them, set electrode plates on both sides of the soaking container, apply a pulsed electric field with an electric field strength of 20 kV / cm, a pulse frequency of 50 Hz, and a pulse width of 500 μs, and soak at 40°C for 2 hours;

[0063] S4. Place the soaked cashmere fiber in a reaction chamber of a plasma treatment device, introduce argon as a working gas, control the gas pressure at 100 Pa, the power at 150 W, and the treatment time at 5 min to complete the etching and activation of the cashmere fiber surface; after completion, place the cashmere fiber in a printing and dyeing solution and perform a printing and dyeing treatment at a temperature of 55° C. for 1.5 h to obtain environmentally friendly cashmere dyed with natural plant pigments;

[0064] Y1. Take out the cashmere fibers that have been printed and dyed, place them in clean water, and rinse them 5 times in a countercurrent manner, with each rinse lasting 10 minutes to ensure that the residual printing and dyeing liquid on the fiber surface is fully removed. After rinsing, place the cashmere fibers in a centrifugal dehydrator, set the speed to 1500 r / min, and the dehydration time to complete the dehydration process;

[0065] Y2. Place the dehydrated cashmere fiber into an ultrasonic treatment container, add clean water to completely immerse the fiber, turn on the ultrasonic equipment, set the ultrasonic frequency to 40kHz, the power to 500W, and the treatment time to 15min;

[0066] Y3. Place the dehydrated cashmere fibers into a diluted 0.8% modified cellulase solution, ensuring that the fibers are completely immersed. Pretreat at 35°C for 1 hour, gently stirring every 20 minutes to ensure full contact between the solution and the fibers. After pretreatment, remove the fibers, rinse them with clean water three times to remove any residual enzyme solution on the surface, and then drain briefly.

[0067] Y4. Start the drum-type napping machine and preheat the equipment to 35°C. Place the pretreated cashmere fibers evenly into the drum. Set the drum speed to 120 r / min. Simultaneously start the plasma equipment and introduce helium as the working gas. Control the air pressure at 80 Pa, the power at 120 W, and the napping time for 25 minutes.

[0068] Y5. Spread the brushed cashmere fibers flat on the tray of the steam setting equipment. After the equipment is sealed, introduce saturated steam with a temperature of 110°C and a pressure of 0.2 MPa. Maintain the steam environment for 15 minutes to obtain steam-set environmentally friendly cashmere.

[0069] Example 3, an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing, the specific steps are as follows:

[0070] S1. Add 300 parts of distilled water to a reactor, raise the temperature to 45°C, add 10 parts of sodium alginate and 3 parts of polyethylene glycol in sequence, turn on the ultrasonic equipment, set the ultrasonic frequency to 30 kHz and the power to 400 W, and simultaneously start the microwave device and adjust the power to 300 W. Continue the treatment under this synergistic effect for 20 minutes;

[0071] S2, adding citric acid and sodium bicarbonate to the above solution, adjusting the pH value of the solution to 6, then adding 20 parts of wormwood pigment, and stirring to form a printing and dyeing solution;

[0072] S3. Place 7 parts of modified chitosan, 5 parts of soy protein, 2 parts of nano-titanium dioxide, 4 parts of glycerol, 2 parts of calcium chloride, 4 parts of tea polyphenols and 5 parts of corn starch into a supercritical reactor, introduce supercritical carbon dioxide fluid, control the pressure in the reactor to 15 MPa and the temperature to 40°C, maintain the conditions for 35 minutes, and prepare a mixed slurry; soak cashmere fiber in the mixed slurry, set electrode plates on both sides of the soaking container, apply a pulsed electric field with an electric field strength of 15 kV / cm, a pulse frequency of 30 Hz, and a pulse width of 300 μs, and soak at 35°C for 1.5 hours;

[0073] S4. Place the soaked cashmere fiber in a reaction chamber of a plasma treatment device, introduce argon as a working gas, control the gas pressure at 50 Pa, the power at 100 W, and the treatment time at 4 min to complete the etching and activation of the cashmere fiber surface; after completion, place the cashmere fiber in a printing and dyeing solution and perform a printing and dyeing treatment at a temperature of 50° C. for 1.5 h to obtain environmentally friendly cashmere dyed with natural plant pigments;

[0074] Y1. Take out the cashmere fibers that have been printed and dyed, place them in clean water, and rinse them four times using a countercurrent rinse method, with each rinse lasting 7 minutes to ensure that the residual printing and dyeing liquid on the fiber surface is fully removed. After rinsing, place the cashmere fibers in a centrifugal dehydrator, set the speed to 1200 r / min, and the dehydration time to 4 minutes to complete the dehydration process;

[0075] Y2. Place the dehydrated cashmere fiber into an ultrasonic treatment container, add clean water to completely immerse the fiber, turn on the ultrasonic equipment, set the ultrasonic frequency to 35kHz, the power to 400W, and the treatment time to 13min;

[0076] Y3. Place the dehydrated cashmere fibers into a diluted 0.5% modified cellulase solution, ensuring that the fibers are completely immersed. Pretreat at 32°C for 1 hour, gently stirring every 17 minutes to ensure full contact between the solution and the fibers. After pretreatment, remove the fibers, rinse them with clean water three times to remove any residual enzyme solution on the surface, and then drain briefly.

[0077] Y4. Start the drum-type napping machine and preheat the equipment to 32°C. Place the pretreated cashmere fibers evenly into the drum. Set the drum speed to 100 rpm. Simultaneously start the plasma equipment and introduce helium as the working gas. Control the air pressure at 50 Pa, the power at 100 W, and the napping time for 20 minutes.

[0078] Y5. Spread the brushed cashmere fibers flat on the tray of the steam setting equipment. After the equipment is sealed, introduce saturated steam with a temperature of 105°C and a pressure of 0.15 MPa. Maintain the steam environment for 13 minutes to obtain steam-set environmentally friendly cashmere.

[0079] Example 4, preparation of modified chitosan, the specific preparation steps are as follows:

[0080] A1. Add 500 g of 5% acetic acid solution to a reactor containing 50 g of chitosan. Place the reactor in a constant temperature water bath, stir at 150 rpm, and heat to 40°C. Maintain stirring at this temperature for 2 h. After the chitosan is completely dissolved, slowly add 5 g of glyoxal. Continue stirring and react at 40°C for 3 h. Filter the hydroformylated chitosan solution to obtain a pure hydroformylated chitosan solution.

[0081] A2, 400g of hydroformylation chitosan solution was poured into a reactor, 50g of 2% sodium hydroxide solution was added, and the mixture was stirred at 150r / min in a constant temperature water bath at 35°C for 1.5h. After stirring, 60g of nano-silica was slowly added, and the reactor was transferred to an ultrasonic disperser with an ultrasonic power of 500W for 30min. The complex solution was taken out of the ultrasonic disperser and allowed to stand at room temperature for 1h to obtain a stable nano-silica-hydroformylation chitosan complex solution;

[0082] A3. Pour 300 g of nano-silica-formaldehyde chitosan complex solution and 60 g of 3% polyvinyl alcohol solution into the reactor. Place the reactor in a constant temperature water bath, heat it to 50°C, maintain the temperature at 120 r / min and stir for 2 h. After the reaction is completed, cool the modified chitosan solution to room temperature and seal it for storage.

[0083] Example 5, preparation of modified cellulase, the specific preparation steps are as follows:

[0084] B1. Add 600 g of 1% calcium chloride solution to a conical flask containing 100 g of cellulase, shake the conical flask to mix the two evenly, and then place the conical flask in a constant temperature incubator at 30°C for 1 hour. After the standing period, shake the solution evenly to obtain the first modified cellulase solution;

[0085] B2. Pour 600 g of the first modified cellulase solution into a reaction vessel, place the reaction vessel in a constant temperature water bath at 25° C., place it on a magnetic stirrer, stir at 120 rpm, slowly add 48 g of β-cyclodextrin, and continue stirring for 2 h. After the reaction is completed, filter and obtain a pure β-cyclodextrin-cellulase inclusion complex solution;

[0086] B3. Pour 600 g of β-cyclodextrin-cellulase inclusion complex solution and 150 g of 2% sodium alginate solution into the reactor, place the reactor in a constant temperature water bath, turn on the stirrer at a stirring speed of 100 r / min, raise the temperature to 35°C, maintain the temperature and stir for 1.5 hours to obtain a modified cellulase solution; after the reaction is completed, cool the modified cellulase solution to room temperature, transfer it to a sterile storage container, seal it, and store it in a refrigerator at 4°C to maintain its activity.

[0087] Comparative Example 1, an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing, the specific steps are as follows:

[0088] The remaining steps remain unchanged, except that the modified chitosan in Example 3 is replaced by chitosan without any treatment, to obtain environmentally friendly cashmere printed and dyed with natural plant pigments.

[0089] Comparative Example 2, an environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing, the specific steps are as follows:

[0090] The remaining steps remained unchanged, except that the modified cellulase in Example 3 was replaced by cellulase without any treatment, to obtain environmentally friendly cashmere dyed with natural plant pigments.

[0091] Performance Testing Test items Test standards Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 <![CDATA[Villus density / (roots / cm 2 )]]> GB / T 29862-2013 280 300 320 220 230 Average length of villi / mm GB / T 29862-2013 2.5 2.8 3.2 1.8 1.9 Color fastness / grade GB / T 3920-2008 5 5 5 4 4 Fiber breaking strength / (cN / dtex) GB / T 13835.6-2009 3.8 4.0 4.2 3.0 3.1 UV protection UPF value GB / T 18830-2009 30 32 35 20 21 Antibacterial rate / % GB / T 20944.3-2008 75 78 80 50 52

[0092] Performance tests show that the various indicators of Examples 1-3 perform well. The density of the pile is 280-320 pieces / cm 2 Among them, Example 3 has the highest performance; the average length of the down is 2.5-3.2mm, which is also the best; the color fastness reaches level 5; the fiber breaking strength is 3.8-4.2 cN / dtex; the UV resistance UPF value is 30-35; and the antibacterial rate is 75%-80%. However, since Comparative Examples 1 and 2 do not use modified chitosan and modified cellulase, the various indicators are significantly lower than those of the Examples, which fully demonstrates the important role of modified chitosan and modified cellulase in improving the performance of cashmere products.

[0093] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. Environmentally friendly cashmere dyed with natural plant pigments, characterized by: The invention comprises the following raw materials in parts by weight: 10-30 parts of natural plant pigments, 100 parts of cashmere fibers, 5-15 parts of sodium alginate, 3-8 parts of citric acid, 4-10 parts of modified chitosan, 2-6 parts of glycerol, 2-5 parts of sodium bicarbonate, 3-7 parts of soy protein, 1-3 parts of nano titanium dioxide, 2-5 parts of polyethylene glycol, 0.5-1.5 parts of modified cellulase, 1-3 parts of calcium chloride, 200-500 parts of distilled water, 2-6 parts of tea polyphenols, and 3-8 parts of corn starch.

2. The environmentally friendly cashmere dyed with natural plant pigments according to claim 1, characterized in that: The natural plant pigment is a plant pigment selected from indigo, madder red, wormwood and green tea.

3. The environmentally friendly cashmere dyed with natural plant pigments according to claim 1, characterized in that: The modified chitosan is specifically prepared in the following steps: A1. Add acetic acid solution to a reactor containing chitosan, place the reactor in a constant temperature water bath, start stirring and heat to 40°C, maintain stirring at this temperature for 2 hours; after the chitosan is completely dissolved, slowly add glyoxal, continue to maintain stirring, and react at 40°C for 3 hours; filter the hydroformylated chitosan solution to obtain a pure hydroformylated chitosan solution; A2. Pour the hydroformylated chitosan solution into a reactor, add sodium hydroxide solution, and stir in a constant temperature water bath at 35°C for 1.5 hours. After stirring, slowly add nano-silica and transfer the reactor to an ultrasonic disperser for 30 minutes. Remove the complex solution from the ultrasonic disperser and let it stand at room temperature for 1 hour to obtain a stable nano-silica-hydroformylated chitosan complex solution. A3. Pour the nano-silica-formylated chitosan complex solution and the polyvinyl alcohol solution into the reactor together, place the reactor in a constant temperature water bath, heat it to 50°C, maintain this temperature and stir for 2 hours. After the reaction is completed, cool the modified chitosan solution to room temperature and seal it for storage.

4. The environmentally friendly cashmere dyed with natural plant pigments according to claim 3, characterized in that: In step A1, the mass ratio of chitosan, acetic acid solution, and glyoxal is 1:10:0.1, the mass fraction of the acetic acid solution is 5%, and the stirring speed is 150 r / min; In step A2, the mass ratio of hydroformylation chitosan solution, sodium hydroxide solution, and nano-silica is 8:1:1.2, the mass fraction of sodium hydroxide solution is 2%, the stirring speed is 150 r / min, and the ultrasonic power is 500 W; In the step A3, the mass ratio of the nano-silica-formylated chitosan complex solution to the polyvinyl alcohol solution is 5:1, the mass fraction of the polyvinyl alcohol solution is 3%, and the stirring speed is 120 r / min.

5. The environmentally friendly cashmere dyed with natural plant pigments according to claim 1, characterized in that: The modified cellulase is specifically prepared in the following steps: B1. Add calcium chloride solution to the conical flask containing cellulase, shake the conical flask to mix the two evenly, and then place the conical flask in a constant temperature incubator at 30°C for 1 hour. After the standing period, shake the solution evenly to obtain the first modified cellulase solution; B2. Pour the first modified cellulase solution into a reaction vessel, place the reaction vessel in a constant temperature water bath at 25°C, place it on a magnetic stirrer, start stirring, slowly add β-cyclodextrin, and continue stirring for 2 hours. After the reaction is completed, filter to obtain a pure β-cyclodextrin-cellulase inclusion complex solution; B3. Pour the β-cyclodextrin-cellulase inclusion complex solution and the sodium alginate solution into the reactor together, place the reactor in a constant temperature water bath, turn on the stirrer, raise the temperature to 35°C, maintain the temperature and stir for 1.5 hours to obtain a modified cellulase solution; after the reaction is completed, cool the modified cellulase solution to room temperature, transfer it to a sterile storage container, seal it, and store it in a refrigerator at 4°C to maintain its activity.

6. The environmentally friendly cashmere dyed with natural plant pigments according to claim 5, characterized in that: In step B1, the mass ratio of cellulase to calcium chloride solution is 1:6, and the mass fraction of calcium chloride solution is 1%; In step B2, the mass of β-cyclodextrin is 8% of the mass of cellulase, and the stirring speed is 120 r / min; In step B3, the mass ratio of the β-cyclodextrin-cellulase inclusion complex solution to the sodium alginate solution is 4:1, the mass fraction of the sodium alginate solution is 2%, and the stirring speed is 100 r / min.

7. A method for preparing environmentally friendly cashmere by dyeing and printing with natural plant pigments, characterized in that: The specific steps include: S1. Add distilled water to the reactor and heat it to 40-50°C. Then add sodium alginate and polyethylene glycol in sequence. Turn on the ultrasonic equipment, set the ultrasonic frequency and power, and start the microwave device at the same time, adjust the power, and continue the treatment for 15-25 minutes under this synergistic effect. S2, adding citric acid and sodium bicarbonate to the above solution, adjusting the pH value of the solution to 5-7, then adding natural plant pigments, stirring evenly to form a printing and dyeing solution; S3. Place modified chitosan, soy protein, nano-titanium dioxide, glycerol, calcium chloride, tea polyphenols, and corn starch into a supercritical reactor, introduce supercritical carbon dioxide fluid, control the pressure and temperature in the reactor, and maintain the conditions for 30-40 minutes to prepare a mixed slurry; soak cashmere fiber in the mixed slurry, set electrode plates on both sides of the soaking container, apply a pulsed electric field, and soak at 30-40° C. for 1-2 hours; S4. Place the soaked cashmere fiber in the reaction chamber of the plasma treatment equipment, introduce argon as the working gas, and process for 3-5 minutes. After the surface of the cashmere fiber is etched and activated, the cashmere fiber is placed in the printing and dyeing liquid and subjected to printing and dyeing treatment at a temperature of 45-55°C for 1-1.5 hours to obtain environmentally friendly cashmere printed and dyed with natural plant pigments.

8. The method for preparing environmentally friendly cashmere by printing and dyeing with natural plant pigments according to claim 7, characterized in that: In the step S1, the temperature is raised to 40-50° C., the ultrasonic frequency is 20-40 kHz, the power is 300-500 W, and the power of the microwave device is adjusted to 200-400 W; In the step S3, the pressure in the reactor is 10-20 MPa, the temperature is 35-45°C, the electric field strength is 10-20 kV / cm, the pulse frequency is 10-50 Hz, and the pulse width is 100-500 μs; In the step S4, the air pressure is controlled to be 10-100 Pa and the power is controlled to be 50-150 W.

9. The environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing is characterized by: The specific process steps are as follows: Y1. Take out the cashmere fibers that have been printed and dyed, place them in clean water, and rinse them 3-5 times in a countercurrent manner, with each rinse lasting 5-10 minutes to ensure that the residual printing and dyeing liquid on the fiber surface is fully removed. After rinsing, place the cashmere fibers in a centrifugal dehydrator, set the speed, and dehydrate for 3-5 minutes to complete the dehydration process; Y2. Place the dehydrated cashmere fiber into an ultrasonic treatment container, add clean water to completely immerse the fiber, turn on the ultrasonic equipment, set the ultrasonic frequency and power, and the treatment time is 10-15 minutes; Y3. Place the dehydrated cashmere fibers into the diluted modified cellulase solution, ensuring that the fibers are completely immersed, and pretreat at 30-35°C for 0.5-1 hour, gently stirring every 15-20 minutes to ensure full contact between the solution and the fibers; After the pretreatment, the fiber was taken out and rinsed with clean water 2-3 times to remove the residual enzyme solution on the surface, and then drained briefly; Y4. Start the drum-type napping machine and preheat the equipment to 30-35°C. Place the pretreated cashmere fibers evenly into the drum, set the drum speed, start the plasma equipment simultaneously, and introduce helium as the working gas. The napping time is 15-25 minutes. Y5. Spread the brushed cashmere fibers flat on the tray of the steam setting equipment. After the equipment is sealed, introduce saturated steam and maintain the steam environment for 10-15 minutes to obtain steam-set environmentally friendly cashmere.

10. The environmentally friendly cashmere napping process using natural plant pigments for printing and dyeing according to claim 9, characterized in that: In the Y1 step, the rotation speed is 1000-1500 r / min; In the Y2 step, the ultrasonic frequency is 30-40 kHz and the power is 300-500 W; In the Y3 step, the mass fraction of the modified cellulase solution is 0.3-0.8%; In the Y4 step, the drum speed is 80-120 r / min, the air pressure is controlled at 20-80 Pa, and the power is 80-120 W; In the Y5 step, the steam temperature is 100-110° C. and the pressure is 0.1-0.2 MPa.