Thermal-insulation bacteria-cleaning cotton cloth material and preparation method thereof

Abstract

The invention discloses a thermal-insulation bacteria-cleaning cotton cloth material and a preparation method thereof, and relates to the technical field of textiles. The invention discloses a heat-preservation bacteria-cleaning cotton cloth material. The invention discloses a water-based antibacterial fabric, which is prepared from the following raw materials in parts by weight: 20 to 30 parts of modified bamboo fiber, 5 to 8 parts of modified nano zinc oxide, 40 to 50 parts of cotton fiber, 3 to 5 parts of polyvinyl alcohol, 2 to 4 parts of sodium carboxymethyl cellulose, 1 to 3 parts of glycerinum, 0.5 to 1.5 parts of tea tree essential oil, 2 to 5 parts of chitosan, 0.3 to 0.8 part of citric acid, 1 to 2 parts of silane coupling agent KH-550, 1 to 3 parts of nano silicon dioxide, 2 to 4 parts of polyethylene glycol 400, 80 to 120 parts of deionized water and 4 to 6 parts of ethyl alcohol. And 1.5-3 parts of diluted hydrochloric acid. The thermal-insulation bacteria-cleaning cotton cloth material has the remarkable advantages that the modified bamboo fibers, the cotton fibers and the like are used as raw materials, and the thermal-insulation bacteria-cleaning cotton cloth material has good thermal insulation and bacteria-cleaning effects through multi-step modification and a preparation process. The preparation method is scientific in raw material matching, rigorous in preparation process, capable of ensuring stable material performance, high in process operability and suitable for popularization and application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of textiles, in particular to a heat-retaining and bacteria-removing cotton fabric material and a preparation method thereof. BACKGROUND

[0002] In the field of textile fabric applications, although traditional cotton fabric materials occupy an important position due to excellent skin-friendliness and air permeability, they have significant limitations in the comprehensive performance of heat retention and antibacterial properties. The fibers of ordinary cotton fabric are arranged loosely, and the internal air retention capacity is weak. Heat is easily conducted and dissipated through the gaps between the fibers, resulting in that the heat retention performance of the cotton fabric can only meet the basic needs and is difficult to be applied in low-temperature environments or scenarios with high requirements for warmth, such as infant clothing and medical care products.

[0003] At the same time, the porous structure of cotton fabric fibers makes them easily absorb moisture, oil and microorganisms in the environment. Under humid conditions, pathogenic bacteria such as Escherichia coli and Staphylococcus aureus can easily multiply in large numbers, not only causing unpleasant odors and mold phenomena in the fabric, reducing the service life, but also possibly causing skin infections, allergies and other health risks through contact.

[0004] The existing improvement methods have obvious drawbacks: heat retention enhancement is usually achieved by increasing the thickness of the fabric or adding chemical fillers, which results in a decrease in air permeability and a hardening of the fabric, losing its original comfortable characteristics; antibacterial treatment usually involves directly mixing silver ions, quaternary ammonium salts and other chemical antibacterial agents, which can have a short-term effect, but such substances are easily lost with an increase in the number of washes, and the antibacterial effect has poor durability. In addition, some chemicals may irritate the skin and have questionable biological safety.

[0005] In addition, materials such as bamboo fibers and nano-zinc oxide that have potential heat-retaining and antibacterial functions have poor interfacial compatibility with cotton fibers when not scientifically modified, and are prone to agglomeration in the fabric, making it difficult to achieve uniform dispersion, resulting in large fluctuations in the overall performance of the material and making it difficult to achieve a synergistic improvement in heat retention and bacteria removal. Therefore, it is an urgent need for the industry to develop a cotton fabric material that can simultaneously solve the problems of insufficient heat retention, poor antibacterial durability, and the need to balance comfort and safety. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a heat-retaining and bacteria-removing cotton fabric material and a preparation method thereof, which solves the problems of poor heat retention, easy bacterial growth, poor compatibility of natural fibers with cotton fibers, and insufficient dispersion of nano-antibacterial agents in traditional cotton fabrics.

[0007] To achieve the above purpose, the present application is implemented by the following technical solutions: A heat preservation and sterilization cotton material, comprising the following raw materials by weight: 20-30 parts of modified bamboo fiber, 5-8 parts of modified nano zinc oxide, 40-50 parts of cotton fiber, 3-5 parts of polyvinyl alcohol, 2-4 parts of sodium carboxymethyl cellulose, 1-3 parts of glycerol, 0.5-1.5 parts of tea tree essential oil, 2-5 parts of chitosan, 0.3-0.8 parts of citric acid, 1-2 parts of silane coupling agent KH-550, 1-3 parts of nano silicon dioxide, 2-4 parts of polyethylene glycol 400, 80-120 parts of deionized water, 4-6 parts of ethanol, and 1.5-3 parts of dilute hydrochloric acid.

[0008] Further, the mass fraction of the dilute hydrochloric acid is 5%; the sodium carboxymethyl cellulose is food-grade sodium carboxymethyl cellulose, and the viscosity of its aqueous solution is 600-800 mPa・s at 25℃ and a concentration of 2%; the polyvinyl alcohol has an alcoholysis degree of 86-90% and a polymerization degree of 1700-1800; and the nano silicon dioxide is gas-phase-prepared nano silicon dioxide with a specific surface area of 180-220 m 2 / g and an average particle size of 20-25 nm.

[0009] Further, the modified bamboo fiber is prepared according to the following steps: A1, put the bamboo fiber into a 8% sodium hydroxide solution, stir at 80℃ in a constant-temperature water bath at 150r / min for 40min, then take it out, wash it with deionized water until it is neutral, squeeze it dry, then immerse it in a 4% silane coupling agent KH-560 aqueous solution containing sodium dodecyl benzene sulfonate, adjust the pH to 5.0 with dilute hydrochloric acid, and then stand for immersion at 30℃ for 3h, stirring every 30min during the period; after that, wash it with 60℃ warm water twice, then lay it flat in a 50℃ oven for drying for 6h, turning it over every 2h; thus, the first modified bamboo fiber is obtained; A2, take the first modified bamboo fiber, immerse it in a 3% carboxymethyl chitosan aqueous solution, add 10% citric acid dropwise, adjust the pH to 5.5, and then stir at 40℃ for 2.5h; then take it out, immerse it in a 1.5% tea polyphenol ethanol aqueous solution with an ethanol concentration of 30%, and then stand for immersion at 35℃ for 3h, stirring every 40min during the period; after that, wash it with 30% ethanol solution twice, then wash it with deionized water until the filtrate is colorless, and then dry it at 45℃ with air blowing for 5h; thus, the second modified bamboo fiber is obtained; A3, taking sodium lignosulfonate, dissolved in deionized water, 600 r / min stirring 30 min to completely dissolved, then add ammonium persulfate, continue to stir 15 min to get precursor solution; take the second modified bamboo fiber, immersed in the precursor solution, 80℃ constant temperature water bath with 200 r / min stirring reaction 2h, every 30 min turn over once, after the end of the fiber, immersed in the mass fraction 1% of chitosan acetic acid solution, containing acetic acid, with sodium hydroxide to adjust pH to 5.5, room temperature static crosslinking 1h, every 20 min light stirring once, after the end of the deionized water washing to the filtrate is neutral, squeezed dry after 50℃ air drying 3h, every 40 min turn over once, to get modified bamboo fiber.

[0010] Further, the A1 in the bamboo fiber, sodium hydroxide solution, silane coupling agent KH-560 aqueous solution, sodium dodecyl benzene sulfonate dosage ratio is 100g: 800g: 500g: 0.3g.

[0011] Further, the A2 in the first modified bamboo fiber, carboxymethyl chitosan aqueous solution, tea polyphenol ethanol aqueous solution dosage ratio is 100g: 500g: 300g.

[0012] Further, the A3 in the sodium lignosulfonate, deionized water, ammonium persulfate dosage ratio is 50g: 450g: 0.25g, the second modified bamboo fiber, precursor solution, chitosan acetic acid solution dosage ratio is 100g: 500g: 300g, 300g chitosan acetic acid solution contains 3.6g acetic acid.

[0013] Further, the A3 in the sodium lignosulfonate and ammonium persulfate mass ratio is 200: 1, and the precursor solution and the second modified bamboo fiber mass ratio is 5: 1, by the ratio control to achieve the uniform grafting of sodium lignosulfonate on the surface of bamboo fiber.

[0014] Further, the modified nano zinc oxide, the specific preparation steps are as follows: B1, taking the particle size of 50-80nm nano zinc oxide, added to deionized water to make 15% suspension, 800 r / min stirring 30 min, then add aluminum sulfate and ammonium dihydrogen phosphate in turn, stirring 15 min, then adjust the pH to 7.5 with ammonia water, 70℃ water bath reaction 1.5h, during the period of 150 r / min stirring, stop stirring after the reaction, static precipitation 30 min, pour off the supernatant, washed the precipitate with deionized water 3 times, 60℃ oven drying 6h, and crush through 100 mesh sieve, to get the first modified nano zinc oxide; B2, the first modified nano zinc oxide is taken and added into a 2% sodium alginate aqueous solution, stirred at room temperature for 1 h, filtered and drained, added into a 2% chitosan acetic acid solution, stirred at 200 r / min for 1 h, repeated alternately for 3 times, filtered from the chitosan acetic acid solution in the last time, washed with deionized water until neutral, dried in a 50℃ oven for 4 h, to obtain the second modified nano zinc oxide; B3, the second modified nano zinc oxide is taken and added into a 2% phytic acid aqueous solution, stirred at 60℃ at 200 r / min for 1 h, then added into a 3% persimmon tannin aqueous solution, adjusted to pH 3.5 with dilute hydrochloric acid, heated to 80℃ and continued to stir for 2 h, after the reaction, precipitated for 20 min, the supernatant was discarded, washed with deionized water for 4 times, dried in a 50℃ oven for 5 h, and crushed through a 200 mesh sieve, to obtain the modified nano zinc oxide.

[0015] Further, the amount ratio of the nano zinc oxide, deionized water, aluminum sulfate and ammonium dihydrogen phosphate in B1 is 100 g:567 g:3 g:2 g.

[0016] The amount ratio of the first modified nano zinc oxide, sodium alginate aqueous solution and chitosan acetic acid solution in B2 is 100 g:500 g:500 g, and 5 g of acetic acid is contained in 500 g of the chitosan acetic acid solution.

[0017] The amount ratio of the second modified nano zinc oxide, phytic acid aqueous solution and persimmon tannin aqueous solution in B3 is 100 g:500 g:300 g.

[0018] Further, the mass ratio of the phytic acid aqueous solution to the persimmon tannin aqueous solution in B3 is 5:3, and the pH of the reaction system is controlled at 3.5, which can promote the formation of a stable composite antibacterial layer of phytic acid and persimmon tannin on the surface of the nano zinc oxide.

[0019] A preparation method of a heat-insulating and bacteria-removing cotton cloth material, specifically comprising the following steps: S1, deionized water is poured into a reaction kettle, heated to 60℃, polyvinyl alcohol and sodium carboxymethyl cellulose are added, stirring is started and the stirring speed is maintained at 300 r / min, the stirring is continued for 30 min until the raw materials are completely dissolved to form a transparent viscous liquid; then the system is cooled to 40℃, chitosan, citric acid and silane coupling agent KH-550 are added in sequence, the stirring speed is adjusted to 500 r / min, and the reaction is carried out for 20 min, during which the pH of the system is adjusted to 5.0-5.5 with dilute hydrochloric acid; finally, glycerol and polyethylene glycol 400 are added, and the stirring is continued for 15 min to obtain a mixed base; S2, another beaker is taken, modified bamboo fiber, modified nano zinc oxide and nano silicon dioxide are added, a high-speed dispersion machine is used to pre-disperse at a speed of 1500 r / min for 10 min, so that all particles are free of agglomeration, and the dispersed functional filler is obtained; the dispersed functional filler is slowly poured into the mixed base material, and stirred at a speed of 600 r / min during pouring, and after the addition is completed, the stirring is continued for 40 min, and a uniform slurry is formed; S3, the cotton fiber is taken into a vacuum impregnation tank, the slurry obtained in S2 is poured into the tank, and the cotton fiber is completely immersed, the tank body is closed, vacuum is drawn to a vacuum degree of-0.08 MPa, the state is maintained for 30 min, then the vacuum is released, and then normal pressure soaking is carried out for 2 h, and the cotton fiber is turned over every 30 min during the soaking; after the soaking is completed, the cotton fiber is fished out, and the roller machine is used for rolling under the pressure of 0.3 MPa, the fiber liquid rate is controlled to be 80%, and then the fiber is transferred into an oven, and is pre-dried at 60 DEG C for 30 min until there is no obvious liquid drop on the fiber surface; S4, the pre-dried cotton fiber is laid on a curing frame, and the tea tree oil diluted in advance with ethanol is uniformly sprayed, and the oil is fully penetrated after 10 min; then the fiber is put into a hot air circulating oven, dried at 80 DEG C for 1 h, and then heated to 100 DEG C for curing for 2 h, and the fiber is turned over every 30 min during the curing to ensure uniform heating; after cooling to room temperature, the fiber is combed by a carding machine to remove surface impurities, and finally the heat-insulating and bacteria-removing cotton cloth material is obtained through cutting and winding.

[0020] The application provides a heat-insulating and bacteria-removing cotton cloth material and a preparation method thereof, and has the following beneficial effects: 1、The present application significantly improves the compatibility and synergistic effect between the components of the material by modifying the bamboo fiber and nano zinc oxide in multiple steps. The modified bamboo fiber is pretreated with sodium hydroxide, grafted with silane coupling agent, and then modified with carboxymethyl chitosan, tea polyphenol and sodium lignosulfonate. This not only enhances the bonding force with cotton fiber, but also endows it with better moisture absorption and heat preservation performance. The modified nano zinc oxide is pretreated with aluminum sulfate and ammonium dihydrogen phosphate, and coated with sodium alginate, chitosan, phytic acid and persimmon tannin in multiple layers. This improves the dispersion uniformity in the fiber matrix, prevents the loss of antibacterial components, and realizes the long-term and stable performance of heat preservation and bacteria removal, avoiding the performance fluctuation caused by uneven dispersion or poor compatibility of single functional material.

[0021] 2、The heat-preservation and bacteria-removing cotton cloth material fully considers safety and comfort in raw material selection and preparation process. The sodium carboxymethyl cellulose used is food grade, polyvinyl alcohol and chitosan are both biocompatible substances, the introduction of natural ingredients such as tea tree essential oil, tea polyphenol and persimmon tannin replaces part of the chemical antibacterial agents that may cause irritation, and reduces the risk of causing allergy or discomfort when the material contacts the skin. At the same time, through vacuum impregnation, control of liquid rate and gradient drying solidification in the preparation process, the integrity and bulkiness of the fiber structure are ensured, the original soft and skin-friendly properties of cotton fiber are retained, and problems such as stiffness and reduced air permeability caused by functional modification are avoided, meeting the demand for comfortable experience in daily wear and special scenarios.

[0022] 3、The preparation method of the present application has strong operability and stability, which is conducive to realizing large-scale production. The whole process is clear, the reaction conditions of each link are clear and easy to control, in addition, the raw materials used such as bamboo fiber, cotton fiber and nano zinc oxide are all conventional materials that are easy to obtain, without the need for special high-end equipment, which reduces the production threshold and facilitates enterprises to produce in batches according to actual needs, promoting the wide application of the heat-preservation and bacteria-removing cotton cloth material in clothing, household supplies, medical care and other fields.

[0023] 4、The material realizes the synergistic effect of heat preservation and bacteria removal through the synergistic effect of multiple functional components, expanding the application scenarios of cotton cloth material. The composite structure of bamboo fiber and cotton fiber forms more air storage space, which, together with the moisturizing effect of glycerol and polyethylene glycol, effectively reduces heat loss and improves overall heat preservation effect; and the modified nano zinc oxide, chitosan, tea tree essential oil and phytic acid components have a significant inhibitory effect on common pathogenic bacteria such as Escherichia coli and Staphylococcus aureus through physical adsorption, destruction of bacterial cell membranes and other ways, reducing the odor and mold problems caused by bacterial growth. The comprehensive performance of heat preservation, bacteria removal, safety and comfort makes the material not only suitable for ordinary daily clothing, but also meets the needs of special fields such as infant supplies, elderly care supplies and medical protective clothing that have high requirements for heat preservation and antibacterial properties, and has a wide market application prospect. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0025] Example 1, a heat-preservation and bacteria-removing cotton cloth material is prepared, and the specific preparation steps are as follows: S1, take 80 parts of deionized water into the reaction kettle, heat to 60℃, add 3 parts of polyvinyl alcohol and 2 parts of carboxymethyl cellulose sodium, start stirring and maintain the stirring speed at 300r / min, continue stirring for 30min until the raw materials are completely dissolved to form a transparent viscous liquid; then cool the system to 40℃, add 2 parts of chitosan, 0.3 parts of citric acid and 1 part of silane coupling agent KH-550 in turn, adjust the stirring speed to 500r / min, react for 20min, during which adjust the pH of the system to 5.0 with 1.5 parts of dilute hydrochloric acid; finally add 1 part of glycerol and 2 parts of polyethylene glycol 400, continue stirring for 15min to obtain the mixed base; S2, take another beaker, add 20 parts of modified bamboo fiber, 5 parts of modified nano zinc oxide and 1 part of nano silicon dioxide, pre-disperse at a speed of 1500r / min for 10min to ensure that all particles are not agglomerated, and obtain the dispersed functional filler; slowly pour the dispersed functional filler into the mixed base, stir at a speed of 600r / min while pouring, continue stirring for 40min after the addition is completed, and form a uniform slurry; S3, take 40 parts of cotton fiber and put it into a vacuum impregnation tank, pour the slurry obtained in S2 into the tank, make sure the cotton fiber is completely immersed, close the tank and vacuumize to-0.08MPa, keep this state for 30min, then release the vacuum, then soak for 2h under normal pressure, turn the cotton fiber every 30min during the soaking; after soaking, take out the cotton fiber, roll it with a roller machine under a pressure of 0.3MPa, control the fiber liquid rate to be 80%, then transfer it into an oven, pre-dry at 60℃ for 30min until there is no obvious liquid drop on the fiber surface; S4, spread the pre-dried cotton fiber on the curing rack, evenly spray 0.5 parts of tea tree oil diluted with 4 parts of ethanol in advance, and place for 10min to make the essential oil penetrate fully; then put the fiber into a hot air circulating oven, first dry at 80℃ for 1h, then heat to 100℃ for 2h, turn the fiber every 30min during the curing process to ensure uniform heating; after cooling to room temperature, card the fiber with a carding machine to remove the surface stray hair, and finally cut, wind to obtain the heat-insulating and bacteria-removing cotton cloth material.

[0026] Example 2, prepare a heat-insulating and bacteria-removing cotton cloth material, the specific preparation steps are as follows: S1, pour 120 parts of deionized water into the reaction kettle, heat to 60℃, add 5 parts of polyvinyl alcohol and 4 parts of carboxymethyl cellulose sodium, start stirring and maintain the stirring speed at 300r / min, continue stirring for 30min until the raw materials are completely dissolved to form a transparent viscous liquid; then cool the system to 40℃, add 5 parts of chitosan, 0.8 parts of citric acid and 2 parts of silane coupling agent KH-550 in turn, adjust the stirring speed to 500r / min, react for 20min, and adjust the pH of the system to 5.5 with 3 parts of dilute hydrochloric acid during the reaction; finally add 3 parts of glycerol and 4 parts of polyethylene glycol 400, continue stirring for 15min to obtain the mixed base; S2, take another beaker, add 30 parts of modified bamboo fiber, 8 parts of modified nano zinc oxide and 3 parts of nano silicon dioxide, pre-disperse at a speed of 1500r / min for 10min to ensure that all particles are not agglomerated, and obtain the dispersed functional filler; slowly pour the dispersed functional filler into the mixed base, stir at a speed of 600r / min during pouring, continue stirring for 40min after the addition is completed, and form a uniform slurry; S3, take 50 parts of cotton fiber and put it into a vacuum impregnation tank, pour the slurry obtained in S2 into the tank, make sure the cotton fiber is completely immersed, close the tank and vacuumize to-0.08MPa, keep this state for 30min, then release the vacuum, and then soak for 2h under normal pressure, turn the cotton fiber every 30min during the soaking; after soaking, take out the cotton fiber, roll it with a roller machine under a pressure of 0.3MPa, control the fiber liquid rate to be 80%, then transfer it to an oven, pre-dry at 60℃ for 30min until there is no obvious liquid drop on the fiber surface; S4, lay the pre-dried cotton fiber on the curing rack, evenly spray 1.5 parts of tea tree oil diluted with 6 parts of ethanol in advance, and place for 10min to allow the oil to penetrate fully; then put the fiber into a hot air circulating oven, first dry at 80℃ for 1h, then heat to 100℃ for 2h, turn the fiber every 30min during the curing process to ensure uniform heating; after cooling to room temperature, card the fiber with a carding machine to remove the surface stray hair, and finally cut, wind to obtain the heat-insulating and bacteria-removing cotton cloth material.

[0027] Example 3, prepare a heat-insulating and bacteria-removing cotton cloth material, the specific preparation steps are as follows: S1, take 100 parts of deionized water into the reaction kettle, heat to 60℃, add 4 parts of polyvinyl alcohol and 3 parts of carboxymethyl cellulose sodium, start stirring and maintain the stirring speed at 300r / min, continue stirring for 30min until the raw materials are completely dissolved to form a transparent viscous liquid; then cool the system to 40℃, add 3 parts of chitosan, 0.5 parts of citric acid and 2 parts of silane coupling agent KH-550 in turn, adjust the stirring speed to 500r / min, react for 20min, during which adjust the pH of the system to 5.5 with 2 parts of dilute hydrochloric acid; finally add 2 parts of glycerol and 3 parts of polyethylene glycol 400, continue stirring for 15min to obtain the mixed base; S2, take another beaker, add 25 parts of modified bamboo fiber, 6 parts of modified nano zinc oxide and 2 parts of nano silicon dioxide, pre-disperse at a speed of 1500r / min for 10min to ensure that all particles are not agglomerated, and obtain the dispersed functional filler; slowly pour the dispersed functional filler into the mixed base, stir at a speed of 600r / min while pouring, continue stirring for 40min after the addition is completed, and form a uniform slurry; S3, take 45 parts of cotton fiber and put it into a vacuum impregnation tank, pour the slurry obtained in S2 into the tank, make sure the cotton fiber is completely immersed, close the tank and vacuumize to-0.08MPa, keep this state for 30min, then release the vacuum, then soak for 2h under normal pressure, turn the cotton fiber every 30min during the soaking; after soaking, take out the cotton fiber, roll it with a roller machine under a pressure of 0.3MPa, control the fiber liquid rate to be 80%, then transfer it into an oven, pre-dry at 60℃ for 30min until there is no obvious liquid drop on the fiber surface; S4, spread the pre-dried cotton fiber on the curing rack, evenly spray 1 part of tea tree oil diluted with 5 parts of ethanol, and let it stand for 10min to make the essential oil penetrate fully; then put the fiber into a hot air circulating oven, first dry at 80℃ for 1h, then heat to 100℃ for 2h, turn the fiber every 30min during the curing process to ensure uniform heating; after cooling to room temperature, card the fiber with a carding machine to remove the surface stray hair, and finally cut, wind to obtain the heat-preserving and bacteria-removing cotton cloth material.

[0028] Example 4, preparation of modified bamboo fiber, the specific preparation steps are as follows: A1, take 100g bamboo fiber, put into 800g mass fraction 8% sodium hydroxide solution, in 80℃ constant temperature water bath 150r / min stirring treatment 40min, after the end of fishing, washing with deionized water to neutral, squeeze dry after immersion in 500g mass fraction 4% silane coupling agent KH-560 aqueous solution, containing 0.3g sodium dodecyl benzene sulfonate, then adjust pH to 5.0 with dilute hydrochloric acid, 30℃ static immersion 3h, during every 30min stirring 1 time, after washing with 60℃ warm water 2 times, again in 50℃ oven flat dry 6h, every 2h turn over once, get the first modified bamboo fiber; A2, take the first modified bamboo fiber 100g, immerse in 500g mass fraction 3% carboxymethyl chitosan aqueous solution, drop 10% mass fraction citric acid, adjust pH to 5.5, 40℃ stirring reaction 2.5h; fishing after immersion in 300g mass fraction 1.5% tea polyphenol ethanol aqueous solution, ethanol concentration is 30%, 35℃ constant temperature immersion 3h, every 40min stirring 1 time; after soaking end with 30% ethanol solution washing 2 times, again with deionized water washing to filtrate colorless, 45℃ air drying 5h, get the second modified bamboo fiber; A3, take 50g sodium lignosulfonate, dissolved in 450g deionized water, 600r / min stirring 30min to completely dissolved, then add 0.25g ammonium persulfate, continue to stir 15min to get precursor solution; take 100g second modified bamboo fiber, immerse in 500g precursor solution, 80℃ constant temperature water bath with 200r / min stirring reaction 2h, every 30min turn over once, after fishing, immerse in 300g mass fraction 1% chitosan acetic acid solution, containing 3.6g acetic acid, adjust pH to 5.5 with sodium hydroxide, room temperature static crosslinking 1h, every 20min light stirring, after washing with deionized water to filtrate neutral, squeeze dry after 50℃ air drying 3h, every 40min turn over once, get modified bamboo fiber.

[0029] Example 5, preparation of modified nano zinc oxide, the specific preparation steps are as follows: B1, take 100g particle size 50-80nm nano zinc oxide, add 567g deionized water to make 15% suspension, 800r / min stirring 30min, then add 3g aluminum sulfate and 2g ammonium dihydrogen phosphate in turn, stirring 15min, then adjust pH to 7.5 with ammonia water, 70℃ water bath reaction 1.5h, during keeping 150r / min stirring, after reaction stop stirring, static sedimentation 30min, pour off the supernatant, wash the precipitate with deionized water 3 times, dry in 60℃ oven 6h, and crush through 100 mesh sieve, get the first modified nano zinc oxide; B2, take the first modified nano zinc oxide 100 g, add 500 g of 2% by mass sodium alginate aqueous solution, stir at room temperature for 1 h, filter and drain, add 500 g of 2% by mass chitosan acetic acid solution, stir for 1 h, repeat the alternate soaking for 3 times, in the last time, filter from the chitosan acetic acid solution, wash with deionized water until neutral, dry in the oven at 50℃ for 4 h, to obtain the second modified nano zinc oxide; B3, take the second modified nano zinc oxide 100 g, add 500 g of 2% by mass phytic acid aqueous solution, stir at 60℃ for 1 h, add 300 g of 3% by mass persimmon tannin aqueous solution, adjust the pH to 3.5 with dilute hydrochloric acid, continue to stir at 80℃ for 2 h, after the end, stand for 20 min, pour off the supernatant, wash with deionized water for 4 times, dry in the oven at 50℃ for 5 h, crush through 200 mesh sieve, to obtain the modified nano zinc oxide.

[0030] Comparative Example 1, prepare the heat preservation bacteria-free cotton cloth material, the specific preparation steps are as follows: The rest of the steps are unchanged, only the modified bamboo fiber of Example 3 is replaced with bamboo fiber without any treatment, to prepare the heat preservation bacteria-free cotton cloth material.

[0031] Comparative Example 2, prepare the heat preservation bacteria-free cotton cloth material, the specific preparation steps are as follows: The rest of the steps are unchanged, only the modified nano zinc oxide of Example 3 is replaced with nano zinc oxide without any treatment, to prepare the heat preservation bacteria-free cotton cloth material.

[0032] Performance test:

[0033] From the performance test results, the heat preservation bacteria-free cotton cloth material of Examples 1-3 is excellent in thermal resistance (0.082-0.088 m 2 K / W), antibacterial rate (99.2%-99.7% for escherichia coli, 99.0%-99.6% for staphylococcus aureus), air permeability (846-860 mm / s), breaking strength (386-398 N), moisture absorption and retention (moisture regain 8.2%-8.8%), softness (8.0-8.6 mm), acid and alkali stability (pH difference before and after washing 0.2-0.3), and skin irritation (0); while the performance of Comparative Example 1 in heat preservation, air permeability, breaking strength, moisture absorption and retention, softness, acid and alkali stability is decreased, and the antibacterial rate of Comparative Example 2 is greatly reduced and has skin irritation.

[0034] The above content is only an example and description of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as it does not deviate from the invention or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.

Claims

1. A heat-insulating and antibacterial cotton fabric material, characterized in that: It contains the following raw materials by weight: 20-30 parts modified bamboo fiber, 5-8 parts modified nano zinc oxide, 40-50 parts cotton fiber, 3-5 parts polyvinyl alcohol, 2-4 parts sodium carboxymethyl cellulose, 1-3 parts glycerin, 0.5-1.5 parts tea tree oil, 2-5 parts chitosan, 0.3-0.8 parts citric acid, 1-2 parts silane coupling agent KH-550, 1-3 parts nano silica, 2-4 parts polyethylene glycol 400, 80-120 parts deionized water, 4-6 parts ethanol, and 1.5-3 parts dilute hydrochloric acid.

2. The heat-insulating and antibacterial cotton fabric material according to claim 1, characterized in that: The dilute hydrochloric acid has a mass fraction of 5%; the sodium carboxymethyl cellulose is food-grade sodium carboxymethyl cellulose, and its aqueous solution has a viscosity of 600-800 mPa·s at 25°C and a concentration of 2%; the polyvinyl alcohol has a degree of alcoholysis of 86-90% and a degree of polymerization of 1700-1800; the nano-silica is nano-silica prepared by the gas-phase method, with a specific surface area of ​​180-220 m². 2 / g, with an average particle size of 20-25nm.

3. The heat-insulating and antibacterial cotton fabric material according to claim 1, characterized in that: The modified bamboo fiber is prepared using the following specific steps: A1. Take bamboo fiber and put it into an 8% sodium hydroxide solution. Stir it at 150 r / min for 40 min in a constant temperature water bath at 80℃. After the treatment, take it out, wash it with deionized water until neutral, squeeze it dry, and immerse it in a 4% aqueous solution of silane coupling agent KH-560 containing sodium dodecylbenzene sulfonate. Adjust the pH to 5.0 with dilute hydrochloric acid, and let it stand and soak at 30℃ for 3 h, stirring once every 30 min. After the treatment, wash it twice with 60℃ warm water, and then dry it flat in a 50℃ oven for 6 h, turning it over once every 2 h to obtain the first modified bamboo fiber. A2. Take the first modified bamboo fiber, immerse it in a 3% (w / w) carboxymethyl chitosan aqueous solution, add 10% (w / w) citric acid to adjust the pH to 5.5, and stir at 40℃ for 2.5 hours; after taking it out, immerse it in a 1.5% (w / w) tea polyphenol ethanol aqueous solution with an ethanol concentration of 30%, and soak it at 35℃ for 3 hours, stirring once every 40 minutes; after soaking, wash it twice with a 30% ethanol solution, and then wash it with deionized water until the filtrate is colorless, and dry it at 45℃ for 5 hours to obtain the second modified bamboo fiber; A3. Dissolve sodium lignosulfonate in deionized water and stir at 600 rpm for 30 min until completely dissolved. Add ammonium persulfate and continue stirring for 15 min to obtain the precursor solution. Take bamboo fiber that has undergone the second modification, immerse it in the precursor solution, and stir at 200 rpm in an 80℃ constant temperature water bath for 2 h, turning it over every 30 min. After the reaction, remove the fiber and immerse it in a 1% (w / w) chitosan acetate solution containing acetic acid. Adjust the pH to 5.5 with sodium hydroxide and allow it to crosslink at room temperature for 1 h, stirring gently every 20 min. After the reaction, wash it with deionized water until the filtrate is neutral, squeeze it dry, and dry it at 50℃ for 3 h, turning it over every 40 min to obtain the modified bamboo fiber.

4. The heat-insulating and antibacterial cotton fabric material according to claim 3, characterized in that: The ratio of bamboo fiber, sodium hydroxide solution, silane coupling agent KH-560 aqueous solution, and sodium dodecylbenzenesulfonate in A1 is 100g:800g:500g:0.3g; The ratio of the first modified bamboo fiber, carboxymethyl chitosan aqueous solution, and tea polyphenol ethanol aqueous solution in A2 is 100g:500g:300g; The ratio of sodium lignosulfonate, deionized water, and ammonium persulfate in A3 is 50g:450g:0.25g. The ratio of bamboo fiber, precursor solution, and chitosan acetate solution in the second modification is 100g:500g:300g. 300g of chitosan acetate solution contains 3.6g of acetic acid.

5. The heat-insulating and antibacterial cotton fabric material according to claim 4, characterized in that: The mass ratio of sodium lignosulfonate to ammonium persulfate in A3 is 200:1, and the mass ratio of precursor solution to second modified bamboo fiber is 5:

1. By controlling this ratio, sodium lignosulfonate is uniformly grafted onto the surface of bamboo fiber.

6. The heat-insulating and antibacterial cotton fabric material according to claim 1, characterized in that: The modified nano zinc oxide is prepared using the following specific steps: B1. Take nano zinc oxide with a particle size of 50-80nm, add deionized water to prepare a 15% suspension, stir at 800r / min for 30min, then add aluminum sulfate and ammonium dihydrogen phosphate in sequence, stir for 15min, then adjust the pH to 7.5 with ammonia water, react in a 70℃ water bath for 1.5h, and keep stirring at 150r / min during the reaction. After the reaction is completed, stop stirring, let stand for 30min to precipitate, discard the supernatant, wash the precipitate 3 times with deionized water, dry in an oven at 60℃ for 6h, and pulverize through a 100-mesh sieve to obtain the first modified nano zinc oxide; B2. Take the first modified nano zinc oxide and add it to a 2% sodium alginate aqueous solution. Stir at room temperature for 1 hour, filter and drain. Add it to a 2% chitosan acetate solution and stir at 200 r / min for 1 hour. Repeat the alternating soaking 3 times. After filtering it from the chitosan acetate solution for the last time, wash it with deionized water until neutral and dry it in an oven at 50℃ for 4 hours to obtain the second modified nano zinc oxide. B3. Take the second modified nano zinc oxide and add it to a 2% (w / w) phytic acid aqueous solution. Stir at 200 r / min at 60℃ for 1 h. Then add a 3% (w / w) persimmon tannin aqueous solution. Adjust the pH to 3.5 with dilute hydrochloric acid. Heat to 80℃ and continue stirring for 2 h. After the reaction is complete, let it stand for 20 min to precipitate. Pour off the supernatant, wash with deionized water 4 times, dry in an oven at 50℃ for 5 h, and pulverize through a 200-mesh sieve to obtain modified nano zinc oxide.

7. The heat-insulating and antibacterial cotton fabric material according to claim 6, characterized in that: The ratio of nano zinc oxide, deionized water, aluminum sulfate, and ammonium dihydrogen phosphate in B1 is 100g:567g:3g:2g; The ratio of the first modified nano zinc oxide, sodium alginate aqueous solution, and chitosan acetate solution in B2 is 100g:500g:500g, and 500g of chitosan acetate solution contains 5g of acetic acid. The ratio of the second modified nano zinc oxide, phytic acid aqueous solution, and persimmon tannin aqueous solution in B3 is 100g:500g:300g.

8. The heat-insulating and antibacterial cotton fabric material according to claim 7, characterized in that: The mass ratio of phytic acid aqueous solution to persimmon tannin aqueous solution in B3 is 5:3, and the pH of the reaction system is controlled at 3.

5. Under these conditions, phytic acid and persimmon tannin can promote the formation of a stable composite antibacterial layer on the surface of nano zinc oxide.

9. A method for preparing a heat-insulating and antibacterial cotton fabric material, characterized in that: Specifically, it includes the following steps: S1. Pour deionized water into the reactor, heat to 60°C, add polyvinyl alcohol and sodium carboxymethyl cellulose, turn on the stirr and maintain the speed at 300r / min, continue stirring for 30min until the raw materials are completely dissolved and a transparent viscous liquid is formed. The system was then cooled to 40°C, and chitosan, citric acid, and silane coupling agent KH-550 were added sequentially. The stirring speed was adjusted to 500 r / min, and the reaction was carried out for 20 min. During this period, the pH of the system was adjusted to 5.0-5.5 with dilute hydrochloric acid. Finally, glycerol and polyethylene glycol 400 were added, and the mixture was stirred for another 15 min to obtain the mixed base material. S2. In another beaker, add modified bamboo fiber, modified nano zinc oxide and nano silica. Pre-disperse them for 10 minutes using a high-speed disperser at 1500 r / min to ensure that all particles do not agglomerate, thus obtaining the dispersed functional filler. Slowly pour the dispersed functional filler into the mixed base material while stirring at 600 r / min. After the addition is complete, continue stirring for 40 minutes to form a uniform slurry. S3. Place cotton fibers into a vacuum impregnation tank, pour the slurry obtained in S2 into the tank, ensuring that the cotton fibers are completely submerged. After closing the tank, evacuate to a vacuum degree of -0.08MPa, maintain this state for 30 minutes, and then release the vacuum. Subsequently, soak the fibers under normal pressure for 2 hours, turning the cotton fibers over every 30 minutes during this period. After soaking, remove the cotton fibers and roll them with a roller mill at a pressure of 0.3MPa, controlling the fiber liquid content to 80%. Then, transfer them to an oven and pre-dry them at 60℃ for 30 minutes until there are no obvious liquid droplets on the fiber surface. S4. Lay the pre-dried cotton fibers flat on the curing rack, spray them evenly with tea tree oil diluted with ethanol, and let them sit for 10 minutes to allow the oil to fully penetrate. Then, put the fibers into a hot air circulating oven, dry them at 80°C for 1 hour, and then heat them to 100°C for 2 hours. During the curing process, turn the fibers over every 30 minutes to ensure even heating. After cooling to room temperature, comb the fibers with a carding machine to remove surface lint. Finally, cut and wind the fibers to obtain the heat-insulating and antibacterial cotton cloth material.