Lyocell fiber with antibacterial, heat-storage and temperature-regulation functions and preparation method of Lyocell fiber

Abstract

The invention discloses a preparation method of lyocell fibers with antibacterial, heat-storage and temperature-regulation functions. The preparation method comprises the steps of pulp oxidation, phase change microcapsule preparation and fiber spinning post-treatment. The preparation method comprises the following steps: firstly, preparing graphene oxide dispersion liquid and phase change microcapsules with proper particle sizes, oxidizing cotton pulp to form a stable cross-linking effect with an antibacterial extract, then dissolving and co-spinning the cotton pulp into the lyocell fiber with the antibacterial, heat-storage and temperature-regulation functions, and weaving the fiber into a fabric which has the properties of repelling mosquitoes, absorbing moisture, ventilating, regulating temperature and storing heat, so that the antibacterial, heat-storage and temperature-regulation functions are realized. Meanwhile, excellent antibacterial performance and washing performance are achieved. According to the preparation method of the lyocell fiber with the antibacterial, heat-storage and temperature-adjusting functions, provided by the invention, the temperature-adjusting and antibacterial effects are lasting, the preparation process is green, simple and convenient, industrial production is facilitated, and the lyocell fiber can be widely applied to the fields of close-fitting household textile articles, medical textile articles and the like; wide market application prospects are realized, and certain market requirements are met.

Description

Technical Field

[0001] The invention belongs to the field of functional textiles, and specifically relates to a lyocell fiber with antibacterial, heat-storing and temperature-regulating functions and a preparation method thereof. Background Art

[0002] With the improvement of social living standards and quality, people's requirements for the health, environmental protection and safety of fiber textiles are also constantly increasing. In daily life, there are many pathogens that are harmful to the human body, which pose potential hazards to human health, especially infants, pregnant women and the elderly, who have weak resistance and are easily infected by pathogens if they are not careful. At the same time, various new types of clothing have been developed, among which clothing with heat storage and heating functions are increasingly favored by people. This type of clothing is mainly suitable for wearing in cold climates. It has good thermal insulation function and can also store the heat released by the human body. Therefore, the development of fiber textiles with excellent antibacterial, thermal insulation and heat storage properties is of great significance to the healthy growth of infants and young children and the high-quality development of the living standards of the aging population.

[0003] At present, most of the antibacterial agents used in antibacterial yarn fabrics on the market are chemical antibacterial agents. Wearing textiles woven with them for a long time will cause potential harm to skin health. Moreover, the yarn fabrics soaked in antibacterial agents have poor skin-friendly effects and are not suitable for close-fitting household textiles. Chinese invention patent application No. 201010620582.5 discloses a lightweight thermal insulation fabric, which is made by imitating the thermal insulation concept of a thermos bottle using a hollow polyester fiber yarn with a hollow rate of 10% to 80%. However, these methods are too complicated and costly to manufacture, and their thermal insulation function is easily lost after long-term use. Therefore, it is urgent to find a heat storage and thermal insulation fiber that is efficient, convenient, low-cost and durable, which is a problem that needs to be solved urgently.

[0004] As a traditional Chinese herbal medicine, the stems, leaves and extracts of mugwort have antibacterial, antibacterial, detoxification and allergy treatment functions. Therefore, the reasonable addition of mugwort extracts in the spinning solution can not only give the fiber excellent antibacterial properties, but also repel mosquitoes and increase the added value of the product. The fabrics made from aloe vera have good hygroscopicity, skin affinity, antibacterial and radiation resistance, and have the health care effects of moisturizing the skin and protecting the skin. At present, it is mainly used in underwear, baby and maternity products.

[0005] Lyocell fiber is a new type of lyocell fiber, which is prepared by spinning process by directly dissolving spinning pulp with N-methylmorpholine-N-oxide as solvent. Lyocell fiber has the hygroscopicity, dyeability, comfort of wearing of natural fiber and the high strength, durability and other properties of synthetic fiber. The production process of lyocell fiber is pollution-free to the environment, and it can be naturally degraded by itself, and is called as the revolutionary fiber of the 21st century. The present invention uses n-octadecane and graphene oxide as phase change materials, has the advantages of non-toxicity, low price, phase change temperature suitable for human body temperature, high latent heat value, excellent thermal conductivity, etc., uses natural antibacterial agent wormwood / aloe vera, has little toxic and side effects on the body, is non-irritating, graphene oxide has chemical stability, and the preparation process of phase change microcapsules is less green chemical residue, can ensure the antibacterial heat storage and warmth-keeping functionality of people's underwear, and is harmless to health, meeting people's demand for green textiles. Summary of the invention

[0006] The present invention provides a method for preparing lyocell fiber with antibacterial heat storage and temperature regulation functions, which can solve the problems in the above-mentioned background technology.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A method for preparing antibacterial heat storage and temperature regulating function lyocell fiber comprises the following steps:

[0009] Step S1: Preparation of graphene oxide dispersion: After dissolving chitosan, allyl polyoxyethylene ether and acetic acid solution, graphene oxide is added to the mixed solution, and after ultrasonic dispersion, the graphene oxide dispersion is obtained;

[0010] Step S2: Preparation of oxidized cotton pulp: adding cotton pulp to a TEMPO / NaClO aqueous solution, then slowly adding a NaClO solution, and after the reaction, filtering by suction to obtain oxidized cotton pulp;

[0011] Step S3: Preparation of polyurethane / octadecane microcapsules: under N2 atmosphere, isophorone diisocyanate and polypropylene glycol are mixed, and a transparent polyurethane prepolymer is obtained by water bath reaction. Meanwhile, octadecane is mixed with the polyurethane prepolymer under water bath conditions, and then a surfactant is added. After stirring and emulsification, a chain extender is slowly added dropwise, and the temperature is gradually increased at 60 to 80°C for 4 to 8 hours. After suction filtration, elution, and drying, the polyurethane / octadecane microcapsules are obtained;

[0012] Step S4: Cross-linking reaction between oxidized pulp in spinning solution and antimicrobial active substance: adding oxidized cotton pulp and graphene dispersion into NMMO aqueous solution, then adding stabilizer and cross-linking agent, then adding antimicrobial extract and polyurethane / octadecane microcapsules, and after cross-linking reaction, obtaining primary spinning solution;

[0013] Step S5: subjecting the primary spinning solution to ultrasonic treatment and then stirring and dissolving the solution to obtain a secondary spinning solution;

[0014] Step S6: filtering and spinning the secondary spinning solution to obtain spun fibers, immersing the newly spun fibers in the antibacterial extract, drying, immersing them in the antibacterial extract again, drying, and then washing the dried spun fibers with alcohol, water, oiling, and drying in sequence to obtain antibacterial, heat-storing, and temperature-regulating lyocell fibers.

[0015] Further, in S1, the mass ratio of chitosan, allyl polyoxyethylene ether, and acetic acid solution is 10:3:50;

[0016] The mass ratio of graphene oxide to the mixed liquid is 1:40 to 80;

[0017] The concentration of the acetic acid solution is 2%;

[0018] The particle size of graphene oxide ranges from 200 to 500 nm;

[0019] The time condition of ultrasonic dispersion treatment is 20 to 30 minutes.

[0020] Further, in S2, after cotton pulp, TEMPO and NaBr are dissolved in deionized water, NaClO solution is added to obtain TEMPO / NaClO solution; wherein, in parts by mass, cotton pulp:TEMPO:NaBr:deionized water:NaClO solution = 50:1-3:10:200:50, the concentration of NaClO solution is 0.02-0.10 mmol / L, the pH of TEMPO / NaClO solution is 10-11, and the reaction time is 20-40 min.

[0021] Further, in S3, the mass ratio of isophorone diisocyanate to polypropylene glycol is 1:3;

[0022] The temperature condition of the water bath reaction is 80-85°C and the time condition is 1-3h;

[0023] The mass ratio of octadecane to polyurethane prepolymer is 3:1;

[0024] The surfactant is xylene, and the mass ratio of the surfactant to polypropylene glycol is 2:3;

[0025] The chain extender is ethylene glycol, and the mass ratio of the chain extender to isophorone diisocyanate is 1:2.

[0026] Further, in S4, in S4, the stabilizer is propyl gallate and the cross-linking agent is cysteine;

[0027] In terms of mass ratio, oxidized cotton pulp: graphene dispersion = 1:10-50;

[0028] Propyl gallate accounts for 0.03-0.05% of the mass of oxidized cotton pulp;

[0029] Cysteine ​​accounts for 0.5-2% of the mass of oxidized cotton pulp;

[0030] The antibacterial extract is wormwood / aloe antibacterial extract, and the antibacterial extract accounts for 3-10% of the mass of the oxidized cotton pulp;

[0031] The polyurethane / octadecane microcapsules account for 10-40% of the mass of the oxidized cotton pulp;

[0032] The temperature condition of the cross-linking reaction is 50-60°C and the time condition is 30-60min;

[0033] The oxidized cotton pulp in the primary spinning solution accounts for 4-10% of the mass of the NMMO aqueous solution, and the mass of NMMO in the NMMO aqueous solution accounts for 50-70%; the temperature condition of the cross-linking reaction is 50-60°C, and the time condition is 30-60min.

[0034] Further, in S5, the ultrasonic treatment power is 200-300 W, the ultrasonic frequency is 50-60 KHz, and the ultrasonic treatment time is 2-4 h; the stirring and dissolving conditions are negative pressure 0.09-0.1 MPa, temperature 85-105° C., and time conditions are 1-3 h.

[0035] Further, in S6, the temperature condition for spinning the secondary spinning solution is 95-110°C;

[0036] The air gap length of the spinning system is 2-3 cm, the spinning speed is 30-50 m / min, the spinneret aperture is 15-115 μm, and the capillary length is 300-400 μm;

[0037] The coagulation treatment is carried out in a NMMO aqueous solution having a temperature of 25 to 50° C. and a concentration of 15 to 40 wt %.

[0038] Further, in S6, the bath ratio of the spun fiber in the antibacterial extract for the first time is 1:20-30, the temperature condition is 50-60°C, the concentration condition of the antibacterial extract is 2-8 mg / mL, the time condition is 1-2 hours, and the temperature condition of the first drying is 80-90°C, and the time condition is 10-30 minutes;

[0039] The bath ratio of the spun fiber for the second immersion in the antibacterial extract is 1:20-30, the temperature condition is 60-80°C, the concentration condition of the antibacterial extract is 6-10 mg / mL, the time condition is 2-4h, and the temperature condition of the second drying is 30-40°C.

[0040] The antibacterial, heat-storing and temperature-regulating lyocell fiber obtained by the preparation method of the antibacterial, heat-storing and temperature-regulating lyocell fiber.

[0041] The present invention has the following beneficial effects:

[0042] (1) The present invention makes full use of the antibacterial components of wormwood and aloe vera, organically combines the antibacterial components in wormwood and aloe vera with lyocell fibers, and uses oxidized pulp and cysteine ​​crosslinking agent to fix the antibacterial active ingredients in lyocell fibers, and soaks them in low-concentration antibacterial agents for crosslinking and adsorption just after spinning and before shaping. At the same time, in view of the difficulty in uniformly combining graphene with lyocell fibers, a reasonable dispersion method is formulated to make graphene oxide evenly distributed in the spinning solution, thereby achieving uniform distribution of graphene oxide in lyocell fibers, and graphene oxide and phase change microcapsules cooperate to absorb heat and adjust the temperature.

[0043] The pure natural mugwort / aloe vera composite antibacterial heat storage and temperature regulation function Lyocell fiber is produced, which has excellent antibacterial health care effects and good washing resistance. After being woven into fabric, it has moisture absorption and breathability properties, and also has excellent antibacterial temperature regulation and heat storage properties.

[0044] (2) The present invention makes full use of the natural ingredients of aloe vera - amino acids, which have a good moisturizing effect on the skin; polysaccharides, which have anti-inflammatory and anti-aging effects on the skin; so that the fabric has multiple effects such as health care, antibacterial, anti-inflammatory, and skin-friendly.

[0045] (3) The preparation process of the present invention is simple, the cost is low, and it is suitable for industrial production. It can be widely used in the fields of close-fitting household textile materials and medical textile materials, and has broad market application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 It is a flow chart of a method for preparing lyocell fiber with antibacterial heat storage and temperature regulation function according to the present invention;

[0047] Figure 2 The reaction formula is the oxidation of cotton pulp and the graft cross-linking of the oxidized pulp and the antibacterial extract;

[0048] Figure 3 ac are polarization comparison diagrams of the antibacterial heat storage and temperature regulating regenerated cellulose secondary spinning solutions prepared in Example Ⅰ, Example Ⅱ and Example Ⅲ of the present invention, respectively;

[0049] Figure 4 a is a lyocell fiber, b-d are the antibacterial heat storage and temperature regulating function lyocell fibers prepared in Examples I-III respectively, e and f are scanning electron microscope comparison pictures of the cross section of the lyocell fiber and the cross section of the antibacterial heat storage and temperature regulating function lyocell fiber prepared in Example III respectively;

[0050] Figure 5ac are EDS element analysis diagrams of the antibacterial heat storage and temperature regulating functional lyocell fibers prepared in Examples I to III, respectively;

[0051] Figure 6 The antibacterial effect diagram of common yarn fiber and yarn fiber prepared in Examples Ⅰ to Ⅲ on Escherichia coli; wherein a represents common yarn fiber; b represents antibacterial heat storage and temperature regulation Lyocell fiber in Example Ⅰ; c represents antibacterial heat storage and temperature regulation Lyocell fiber in Example Ⅱ; d represents antibacterial heat storage and temperature regulation Lyocell fiber in Example Ⅲ;

[0052] Figure 7 The antibacterial effect diagram of common yarn fiber and yarn fiber prepared in Examples Ⅰ to Ⅲ on Staphylococcus aureus; wherein a represents common yarn fiber; b represents antibacterial heat storage and temperature regulation Lyocell fiber in Example Ⅰ; c represents antibacterial heat storage and temperature regulation Lyocell fiber in Example Ⅱ; d represents antibacterial heat storage and temperature regulation Lyocell fiber in Example Ⅲ;

[0053] Figure 8 This is the DSC test chart of the antibacterial, heat-storing and temperature-regulating lyocell fiber prepared in Examples Ⅰ to Ⅲ. DETAILED DESCRIPTION

[0054] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings. If no specific technology or conditions are indicated in the embodiments, the technology or conditions described in the literature in this field or the product instructions are used. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional products that can be obtained commercially.

[0055] It should be noted that the polypropylene glycol of the present invention is polypropylene glycol-500, the antibacterial extract is a mixture of wormwood extract and aloe composite extract, and the mixing ratio of wormwood extract and aloe composite extract is 1:3.

[0056] The aloe vera compound extract is commercially available from Sigma-Aldrich Company, and its English name is Aloin or Barbaloin, CAS: 1415-73-2.

[0057] The wormwood extract is extracted in the laboratory and its purity is about 80%.

[0058] like Figure 1 As shown, the present invention provides a method for preparing lyocell fiber with antibacterial heat storage and temperature regulation function, comprising the following steps:

[0059] Step S1: Preparation of graphene oxide dispersion: After dissolving chitosan, allyl polyoxyethylene ether and acetic acid solution, graphene oxide is added to the mixed solution, and after ultrasonic dispersion, a graphene oxide dispersion is obtained; wherein, in parts by mass, chitosan: allyl polyoxyethylene ether: acetic acid solution = 10:3:50; in parts by mass, graphene oxide: mixed solution = 1:40-80; the concentration of the acetic acid solution is 2%; the particle size range of graphene oxide is 200-500nm; the time condition of ultrasonic dispersion treatment is 20-30min.

[0060] Step S2: Preparation of oxidized cotton pulp: After dissolving cotton pulp, TEMPO and NaBr in deionized water, add NaClO solution to obtain TEMPO / NaClO solution, and after reaction, filter to obtain oxidized cotton pulp. In which, by mass, cotton pulp: TEMPO: NaBr: deionized water: NaClO solution = 50:1-3:10:200:50, the concentration of NaClO solution is 0.02-0.10 mmol / L, the pH of TEMPO / NaClO solution is 10-11, and the reaction time is 20-40 min.

[0061] Step S3: Preparation of polyurethane / octadecane microcapsules: under N2 atmosphere, isophorone diisocyanate and polypropylene glycol are mixed, and a transparent polyurethane prepolymer is obtained by water bath reaction. At the same time, octadecane is mixed with the polyurethane prepolymer under water bath conditions, and then a surfactant is added. After stirring and emulsification, a chain extender is slowly added dropwise, and the temperature is increased by 60 to 80°C for 4 to 8 hours. After suction filtration, elution, and drying, polyurethane / octadecane microcapsules are obtained. Among them, in S3, the mass ratio of isophorone diisocyanate to polypropylene glycol is 1:3; the temperature condition of the water bath reaction is 80 to 85°C, and the time condition is 1-3 hours; the mass ratio of octadecane to polyurethane prepolymer is 3:1; the surfactant is xylene, and the mass ratio of the surfactant to polypropylene glycol is 2:3; the chain extender is ethylene glycol, and the mass ratio of the chain extender to isophorone diisocyanate is 1:2.

[0062] Step S4: Cross-linking reaction between oxidized pulp in spinning liquid and antimicrobial active substance: adding oxidized cotton pulp and graphene dispersion into NMMO (4-methylmorpholine-N-oxide) aqueous solution, then adding stabilizer and cross-linking agent, followed by adding antimicrobial extract and polyurethane / octadecane microcapsules, and after cross-linking reaction, obtaining primary spinning liquid. Among them, in terms of mass ratio, oxidized cotton pulp: graphene dispersion = 1:10-50; in terms of the mass of oxidized cotton pulp, the stabilizer is propyl gallate, the mass proportion of propyl gallate is 0.03-0.05%, the cross-linking agent is cysteine, the mass proportion of cysteine ​​is 0.5-2%, the mass proportion of antibacterial extract is 3-10%, and the mass proportion of polyurethane / octadecane microcapsules is 10-40%; the temperature condition of the cross-linking reaction is 50-60°C, and the time condition is 30-60min; the oxidized cotton pulp in the primary spinning solution accounts for 4-10% of the mass of the NMMO aqueous solution, and the cross-linking reaction is carried out at 50-60°C in the NMMO solution for 30-60min, so that the active substance is fully cross-linked in the spinning solution to prevent precipitation in the coagulation bath, wherein the mass proportion of NMMO in the NMMO aqueous solution is 50-70%.

[0063] Step S5: ultrasonically treat the first spinning solution, and then stir and dissolve it to obtain a second spinning solution. The ultrasonic treatment power is 200-300W, the ultrasonic frequency is 50-60KHz, and the ultrasonic treatment time is 2-4h; the stirring and dissolving conditions are negative pressure of 0.09-0.1MPa, temperature of 85-105°C, and time of 1-3h.

[0064] Step S6: filtering and spinning the secondary spinning solution to obtain spun fibers, immersing the spun fibers in the antibacterial extract, drying, and then immersing them in the antibacterial extract again, drying, and then washing the dried spun fibers with alcohol, water, oiling, and drying in sequence to obtain antibacterial, heat-storing, and temperature-regulating lyocell fibers.

[0065] Among them, the temperature condition for spinning the secondary spinning solution is 95-110°C; the air gap length of the spinning system is 2-3cm, the spinning speed is 30-50m / min, the spinneret aperture is 15-115μm, and the pore capillary length is 300-400μm; the coagulation treatment is carried out in a NMMO aqueous solution with a temperature of 25-50°C and a concentration of 15-40wt%.

[0066] The first immersion of the spinning fiber in the antibacterial extract has a bath ratio of 1:20-30, a temperature condition of 50-60°C, a concentration condition of 2-8 mg / mL of the antibacterial extract, a time condition of 1-2 hours, and a temperature condition of 80-90°C for the first drying, and a time condition of 10-30 minutes.

[0067] The bath ratio of the spun fiber in the antibacterial extract for the second time is 1:20-30, the temperature condition is 60-80°C, the concentration condition of the antibacterial extract is 6-10 mg / mL, the time condition is 2-4h, and the temperature condition of the second drying is 30-40°C.

[0068] The present invention also provides a fiber fabric with antibacterial heat storage and temperature regulation effect, which is obtained by adopting the preparation method of the antibacterial heat storage and temperature regulation function lyocell fiber.

[0069] The present invention also provides a fiber fabric with antibacterial heat storage and temperature regulation effect, and the preparation method thereof is as follows:

[0070] The antibacterial, heat-storing and temperature-regulating lyocell fibers and polylactic acid fibers obtained by the above-mentioned preparation method are subjected to the processes of cleaning, carding, drawing, roving, spun yarn, winding, doubling and twisting to obtain yarns, and the obtained blended yarns are subjected to the processes of warping, sizing and reeding, and then woven on a jet loom to produce fiber fabrics with antibacterial, heat-storing and temperature-regulating effects.

[0071] Among them, it should be noted that the processes of cotton cleaning, carding, drawing, coarse yarn, spun yarn, winding, doubling, doubling process, warping, sizing, reeding process, weaving, etc. of the present invention all belong to the prior art, and the present invention will not elaborate on their specific process methods.

[0072] <Example I>

[0073] A method for preparing antibacterial heat storage and temperature regulating function lyocell fiber comprises the following steps:

[0074] Step S1: Preparation of graphene oxide dispersion: chitosan, allyl polyoxyethylene ether, and 2% acetic acid solution are dissolved in a ratio of 10:3:50, a certain amount of graphene oxide is weighed and first ground with a ball mill to a particle size range of 200 to 500 nm, and then mixed with the above mixed solution in a ratio of 1:50 by mass, and after ultrasonic dispersion for 20 to 30 minutes, a graphene oxide dispersion is obtained;

[0075] Step S2: oxidizing pulp: dissolving cotton pulp, TEMPO and NaBr in 200 parts of deionized water at a ratio of 50:1:10, heating to 45°C, preparing 50 parts of 0.02-0.10 mmol / L NaClO solution, and dropping 1 part of low-concentration HCl dissolved in the TEMPO / NaClO solution, reacting for 30 minutes, maintaining the pH of the TEMPO / NaClO solution at 10-11, and filtering to obtain oxidized cotton pulp.

[0076] Step S3: Preparation of polyurethane / octadecane microcapsules: under N2 atmosphere, isophorone diisocyanate and polypropylene glycol are added to a three-necked flask at a ratio of 1:3 by mass, and the mixture is heated in a water bath at 80°C for 2 hours to obtain a transparent polyurethane prepolymer; under water bath conditions, octadecane / prepolymer are mixed at a ratio of 3:1 by mass, and then xylene is added, with the ratio of xylene to polypropylene glycol being 2:3. After stirring and emulsifying, a chain extender is slowly added dropwise, with the ratio of ethylene glycol to isophorone diisocyanate being 1:2. The mixture is heated at a gradient of 60 to 80°C for 8 hours, and the polyurethane / octadecane microcapsules are obtained by suction filtration, elution, and drying;

[0077] Step S4: mixing oxidized cotton pulp, graphene dispersion and 50% NMMO aqueous solution in a mass ratio of 1:25:25, then adding 0.03% of propyl gallate and 0.5% of cysteine ​​based on the mass of oxidized cotton pulp, followed by adding 5% of antibacterial extract based on the mass of oxidized cotton pulp and 30% of polyurethane / octadecane microcapsules based on the mass, and performing cross-linking reaction in a reactor at 50° C. for 30 minutes to obtain a primary spinning solution;

[0078] Step S5: subjecting the primary spinning solution to ultrasonic treatment at a power of 200 W, an ultrasonic frequency of 60 KHz, and an ultrasonic treatment time of 2 hours, and then heating to 90° C. and dissolving under vacuum stirring for 1.5 hours to obtain a secondary spinning solution;

[0079] Step S6: adding the secondary spinning solution to a screw extruder, further dissolving it at 95°C, then filtering it, and entering the spinning system for spinning. The ejected silk threads are vertically stretched in the air and enter the coagulation bath. The air gap length of the spinning system is 2 cm, the spinning speed is 37 m / min, the spinneret aperture is 115 μm, the capillary length is 350 μm, and the coagulation bath contains a 20 wt% NMMO aqueous solution at a temperature of 45°C;

[0080] Step S7: immersing the fiber spun in step S6 in a 6 mg / mL antibacterial extract at 50° C. for 2 hours with a bath ratio of 1:20, and then drying the fiber at 80° C. for 10 minutes;

[0081] Step S8: Immerse the fiber prepared in S7 in an antibacterial extract at a concentration of 6 mg / mL at 60°C for 2 hours with a bath ratio of 1:25, then take out the fiber with liquid and dry it at 35°C, finally wash the fiber with alcohol, wash with water, oil and dry it to obtain Lyocell fiber with antibacterial, heat storage and temperature regulation functions.

[0082] A method for preparing an antibacterial heat storage and temperature regulating fiber fabric comprises the following steps:

[0083] The antibacterial, heat-storing and temperature-regulating lyocell fibers and polylactic acid fibers prepared in this embodiment are subjected to the steps of cleaning, carding, drawing, roving, spun yarn, winding, doubling and twisting to obtain yarns, and the obtained blended yarns are subjected to the steps of warping, sizing and reeding, and then woven on a jet loom to produce fiber fabrics with antibacterial, heat-storing and temperature-regulating effects.

[0084] <Example II>

[0085] A method for preparing antibacterial heat storage and temperature regulating function lyocell fiber comprises the following steps:

[0086] Step S1: Preparation of graphene oxide dispersion: chitosan, allyl polyoxyethylene ether, and 2% acetic acid solution are dissolved in a ratio of 10:3:50, a certain amount of graphene oxide is weighed and first ground with a ball mill to a particle size range of 200 to 500 nm, and then mixed with the above solution in a ratio of 1:50, and after ultrasonic dispersion for 20 to 30 minutes, a graphene oxide dispersion is obtained;

[0087] Step S2: oxidizing pulp: dissolve cotton pulp, TEMPO and NaBr in 200 parts of deionized water at a ratio of 50:1:10, heat to 45°C, prepare 50 parts of 0.05 mmol / L NaClO solution, and drop 1 part of low-concentration HCl dissolved in the TEMPO / NaClO solution, react for 30 minutes, maintain the pH of the TEMPO / NaClO solution at 10-11, and filter to obtain oxidized cotton pulp.

[0088] Step S3: Preparation of polyurethane / octadecane microcapsules: Under N2 atmosphere, add isophorone diisocyanate and polypropylene glycol in a ratio of 1:3 into a three-necked flask, heat in a water bath at 85°C for 2h to obtain a transparent polyurethane prepolymer. Under water bath conditions, octadecane and prepolymer are mixed in a ratio of 3:1 by mass, and then xylene is added, with the ratio of xylene to polypropylene glycol being 2:3. After stirring and emulsification, ethylene glycol is slowly added dropwise, with the ratio of ethylene glycol to isophorone diisocyanate being 1:2. The temperature is gradually increased from 60 to 80°C for 6h, and the polyurethane / octadecane microcapsule sample is obtained by filtration, elution, and drying;

[0089] Step S4: mixing oxidized cotton pulp, graphene dispersion and 50% NMMO aqueous solution in a mass ratio of 1:20:25, then adding 0.03% of propyl gallate and 1% of cysteine ​​based on the mass of oxidized cotton pulp, then adding 8% of antibacterial extract based on the mass of oxidized cotton pulp and 15% of polyurethane / octadecane microcapsules to the spinning solution, and performing cross-linking reaction in a reactor at 50° C. for 40 minutes;

[0090] Step S5: subjecting the reacted spinning solution to ultrasonic treatment at a power of 300 W and an ultrasonic frequency of 60 KHz; subjecting the solution to ultrasonic treatment for 2 hours, and then heating the solution to 90° C. and dissolving the solution under vacuum stirring for 1.5 hours to obtain a lyocell composite plant antibacterial heat storage and temperature regulating regenerated cellulose spinning solution;

[0091] Step S6: adding the spinning solution to a screw extruder, further dissolving it at 95°C, then filtering it, and entering the spinning system for spinning. The ejected silk threads are vertically stretched in the air and enter the coagulation bath. The air gap length of the spinning system is 2 cm, the spinning speed is 35 m / min, the spinneret aperture is 15-115 μm, the capillary length is 350 μm, and the coagulation bath contains a 20 wt% NMMO aqueous solution at a temperature of 45°C;

[0092] Step S7: immersing the fiber spun in step S6 in a 6 mg / mL antibacterial extract at 50° C. for 2 hours with a bath ratio of 1:20, and then drying the fiber at 80° C. for 30 minutes;

[0093] Step S8: immersing the antibacterial heat storage and temperature regulation function lyocell fiber prepared in S7 in an antibacterial extract with a concentration of 8 mg / mL at 80° C. for 2 hours, with a bath ratio of 1:25, then taking out the fiber with liquid and drying it at 40° C., and finally washing the antibacterial heat storage and temperature regulation function lyocell fiber with alcohol washing, water washing, oiling, and drying;

[0094] A method for preparing an antibacterial heat storage and temperature regulating fiber fabric comprises the following steps:

[0095] The antibacterial, heat-storing and temperature-regulating lyocell fibers and polylactic acid fibers prepared in this embodiment are subjected to the steps of cleaning, carding, drawing, roving, spun yarn, winding, doubling and twisting to obtain yarns, and the obtained blended yarns are subjected to the steps of warping, sizing and reeding, and then woven on a jet loom to produce fiber fabrics with antibacterial, heat-storing and heat-insulating effects.

[0096] <Example III>

[0097] A method for preparing antibacterial heat storage and temperature regulating function lyocell fiber comprises the following steps:

[0098] Step S1: Preparation of graphene oxide dispersion: chitosan, allyl polyoxyethylene ether, and 2% acetic acid solution are dissolved in a ratio of 10:3:50, a certain amount of graphene oxide is weighed and first ground with a ball mill to a particle size range of 200 to 500 nm, and then mixed with the above solution in a ratio of 1:60, and after ultrasonic dispersion for 20 to 30 minutes, a graphene oxide dispersion is obtained;

[0099] Step S2: oxidizing pulp: dissolve cotton pulp, TEMPO and NaBr in 200 parts of deionized water at a ratio of 50:1:10, heat to 50°C, prepare 50 parts of 0.05 mmol / L NaClO solution, and drop 1 part of low-concentration HCl dissolved in the TEMPO / NaClO solution, react for 30 minutes, maintain the pH of the TEMPO / NaClO solution at 10-11, and filter to obtain oxidized cotton pulp.

[0100] Step S3: Preparation of polyurethane / octadecane microcapsules: Under N2 atmosphere, add isophorone diisocyanate and polypropylene glycol in a ratio of 1:3 into a three-necked flask, heat in a water bath at 85°C for 2h to obtain a transparent polyurethane prepolymer. Under water bath conditions, octadecane and prepolymer are mixed in a mass ratio of 3:1, and then xylene is added, and the ratio of xylene to polypropylene glycol is 2:3. After stirring and emulsification, ethylene glycol is slowly added dropwise, and the ratio of ethylene glycol to isophorone diisocyanate is 1:2. The temperature is gradually increased from 60 to 80°C for 8h, and the polyurethane / octadecane microcapsule sample is obtained by filtration, elution, and drying;

[0101] Step S4: mixing oxidized cotton pulp, graphene dispersion and 50% NMMO aqueous solution at a mass ratio of 1:30:25, then adding 0.05% of propyl gallate and 1% of cysteine ​​based on the mass of oxidized cotton pulp, then adding 10% of antibacterial extract based on the mass of oxidized cotton pulp and 35% of polyurethane / octadecane microcapsules to the spinning solution, and performing cross-linking reaction at 60° C. in a reactor for 50 minutes;

[0102] Step S5: subjecting the reacted spinning solution to ultrasonic treatment at a power of 300 W and an ultrasonic frequency of 60 KHz; subjecting the solution to ultrasonic treatment for 2 hours, and then heating the solution to 90° C. and dissolving the solution under vacuum stirring for 1.5 hours to obtain a lyocell composite plant antibacterial heat storage and temperature regulating regenerated cellulose spinning solution;

[0103] Step S6: adding the spinning solution to a screw extruder, further dissolving it at 95°C, then filtering it, and entering the spinning system for spinning. The ejected silk threads are vertically stretched in the air and enter the coagulation bath. The air gap length of the spinning system is 3 cm, the spinning speed is 35 m / min, the spinneret aperture is 100 μm, the capillary length is 400 μm, and the coagulation bath contains a 14 wt% NMMO aqueous solution at a temperature of 45°C.

[0104] Step S7: immersing the fiber spun in step S6 in a 6 mg / mL antibacterial extract at 50° C. for 2 hours with a bath ratio of 1:25, and then drying the fiber at 90° C. for 30 minutes;

[0105] Step S8: immersing the antibacterial heat storage and temperature regulation function lyocell fiber prepared in S7 in an antibacterial extract with a concentration of 10 mg / mL at 80° C. for 2 hours, with a bath ratio of 1:30, then taking out the fiber with liquid and drying it at 40° C., and finally washing the antibacterial heat storage and temperature regulation function lyocell fiber with alcohol washing, water washing, oiling, and drying;

[0106] A method for preparing an antibacterial heat storage and temperature regulating fiber fabric comprises the following steps:

[0107] The antibacterial, heat-storing and temperature-regulating lyocell fibers and polylactic acid fibers prepared in this embodiment are subjected to the steps of cleaning, carding, drawing, roving, spun yarn, winding, doubling and twisting to obtain yarns, and the obtained blended yarns are subjected to the steps of warping, sizing and reeding, and then woven on a jet loom to produce fiber fabrics with antibacterial, heat-storing and temperature-regulating effects.

[0108] Polarizing microscope test and conclusion: Figure 3 ac are polarized contrast diagrams of the antibacterial heat storage and temperature regulating regenerated cellulose spinning solution obtained in step S5 of the preparation method described in Example Ⅰ, Example Ⅱ and Example Ⅲ of the present invention respectively; Figure 3 It can be seen that the oxidized pulp and the antibacterial active substances of mugwort / aloe are dissolved, while the phase change microcapsules and graphene oxide are evenly dispersed in the spinning solution, ensuring that the spinning can proceed smoothly, and the core-shell structure of the phase change microcapsules is complete, and there is no leakage of the phase change material, ensuring that the prepared antibacterial heat storage and temperature regulation function Lyocell fiber can stably and durably regulate the temperature.

[0109] EDS element analysis: Figure 5 ac are the EDS element analysis diagrams of the antibacterial heat storage and temperature regulating Lyocell fibers prepared in Examples Ⅰ to Ⅲ respectively; Figure 5 It can be seen that the main elements in Lyocell fiber are C, O, N, and S, and the main elements in the phase change material n-octadecane are C and H. It can be seen that the O element decreases in the protruding parts of the Lyocell fiber surface, so it is judged that the protruding parts of the fiber are phase change microcapsules, and the phase change microcapsules are preliminarily judged to exist in the fiber.

[0110] Scanning electron microscope test and conclusion: Figure 4 It can be seen that the SU-5000 field emission scanning electron microscope is used to explore the microscopic morphology changes of the antibacterial, heat-storing and temperature-regulating lyocell fibers prepared in Examples Ⅰ to Ⅲ. The surface of ordinary lyocell fibers is relatively smooth and flat, while the surface of the antibacterial, heat-storing and temperature-regulating lyocell fibers prepared in Examples Ⅰ to Ⅲ has a large number of protrusions. Auxiliary EDS element analysis shows that this is because some phase change microcapsules are attached to the fiber surface, which destroys the surface flatness and makes it uneven. There are voids inside the fiber after adding the microcapsules, which is caused by the microcapsules embedded in it. This also well illustrates that the microcapsules can stably exist inside the fiber.

[0111] Antibacterial test and conclusion: The present invention takes ordinary lyocell fiber as a control, selects Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus as experimental strains, and slightly improves on the basis of GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method" to study the antibacterial properties of the prepared yarn fiber.

[0112] The specific operation is as follows: weigh a certain mass of fiber, sterilize it under ultraviolet light for 30 minutes, and after sterilization, add 5mL LB culture solution, 10μL activated bacteria (OD600≈0.5~0.6), and 0.1g antibacterial yarn fiber to the sterilized conical flask in turn, seal the sterilized conical flask with a stopper, and put it into a constant temperature shaking incubator for 48h, with the speed set to 120rmp and the temperature set to 37℃. After the incubation time is over, draw 100μL from each mixed culture solution into a sterile centrifuge tube, and then draw 900μL sterile water into the same centrifuge tube to complete a dilution, and so on, dilute to 10-4, 10-5, and finally take 100μL of the diluted mixed culture solution and evenly spread it on the agar medium, let it stand for 0.5h with the front side facing up, and then put it upside down in a 37℃ constant temperature incubator for 24h, and count the single colonies on the medium. Each group of experiments was repeated three times, and the average of the three antibacterial rates was taken.

[0113] according to Figure 6 , 7 The functional lyocell fibers prepared in Examples I to III have a good antibacterial effect compared to the original sample. The experimental data are shown in the following table by counting the number of lyocell fibers according to the following formula:

[0114]

[0115] Table 1 Statistics of antibacterial rates of different bacterial species in common yarn fibers and fibers prepared in Examples I to III

[0116] sample Ordinary yarn fiber Example I Example II Example III Escherichia coli - 97.3％ 98.6％ 100％ Staphylococcus aureus - 99.9％ 100％ 100％

[0117] DSC test and conclusion: Figure 8 The heat absorption and release of the antibacterial, heat-storing and temperature-regulating lyocell fibers prepared in different embodiments are measured using a 204F1 differential scanning calorimeter under the same test conditions. Figure 8 It can be seen that the fiber has obvious heat absorption and release phenomenon in the process of heating and cooling. In Figure a, it is the heating stage, and the temperature range of the phase change microcapsules in the fiber for endothermic liquefaction is 23 to 33°C; in Figure b, it is the cooling stage, and the temperature range of the phase change microcapsules for exothermic solidification is 10 to 23°C, indicating that with the change of temperature, the fiber has the function of bidirectional temperature regulation.

[0118] The thermal insulation performance of the functional fabric formed by weaving the lyocell fiber with antibacterial heat storage and temperature regulation function prepared in the above specific embodiments Ⅰ to Ⅲ of the present invention was tested, and the thermal insulation value was tested using a JIS L1096 KES thermal insulation testing machine. The thermal insulation value can reflect its thermal insulation effect. The test results are shown in Table 2.

[0119] Table 2 Thermal insulation properties of fabrics made from Examples I to III and purchased Lyocell fibers

[0120] sample Example I Example II Example III Lyocell fiber Insulation value 0.77 0.74 0.79 0.41

[0121] Generally, the larger the heat preservation Kroger value, the better the heat preservation performance of the fabric. As can be seen from Table 2, the heat preservation Kroger value of the antibacterial heat storage and temperature regulation Lyocell fibers prepared in Examples 1 to 3 reaches above 0.74, indicating that the prepared antibacterial heat storage and temperature regulation Lyocell fibers play an important role.

[0122] Although some specific embodiments of the present invention have been described in detail through examples, those skilled in the art should understand that the above examples are for illustration only and are not intended to limit the scope of the present invention. Those skilled in the art to which the present invention belongs may make various modifications or supplements to the specific embodiments described or replace them in a similar manner, but they will not deviate from the direction of the present invention or exceed the scope defined by the attached claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc. made to the above embodiments based on the technical essence of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing antibacterial heat storage and temperature regulating function lyocell fiber, characterized in that: The following steps are involved: Step S1: Preparation of graphene oxide dispersion: After dissolving chitosan, allyl polyoxyethylene ether and acetic acid solution, graphene oxide is added to the mixed solution, and after ultrasonic dispersion, the graphene oxide dispersion is obtained; Step S2: Preparation of oxidized cotton pulp: adding cotton pulp into a TEMPO / NaClO aqueous solution, reacting, and filtering to obtain oxidized cotton pulp; Step S3: Preparation of polyurethane / octadecane microcapsules: under N2 atmosphere, isophorone diisocyanate and polypropylene glycol are mixed, and a transparent polyurethane prepolymer is obtained by water bath reaction. Meanwhile, octadecane is mixed with the polyurethane prepolymer under water bath conditions, and then a surfactant is added. After stirring and emulsification, a chain extender is slowly added dropwise, and the temperature is gradually increased at 60 to 80°C for 4 to 8 hours. After suction filtration, elution, and drying, the polyurethane / octadecane microcapsules are obtained; Step S4: Cross-linking reaction between oxidized cotton pulp and antimicrobial active substance in spinning solution: adding oxidized cotton pulp and graphene dispersion into 4-methylmorpholine-N-oxide aqueous solution, then adding stabilizer and cross-linking agent, and then adding antimicrobial extract and polyurethane / octadecane microcapsules, and after cross-linking reaction, obtaining primary spinning solution; Step S5: subjecting the primary spinning solution to ultrasonic treatment and then stirring and dissolving the solution to obtain a secondary spinning solution; Step S6: filtering and spinning the secondary spinning solution to obtain spun fibers, immersing the spun fibers in the antibacterial extract, drying, immersing them in the antibacterial extract again, drying, and then washing the dried spun fibers with alcohol, water, oiling, and drying in sequence to obtain antibacterial, heat-storing, and temperature-regulating lyocell fibers.

2. The method for preparing the antibacterial heat storage and temperature regulating lyocell fiber according to claim 1, characterized in that: In S1, the mass ratio of chitosan, allyl polyoxyethylene ether, and acetic acid solution is 10:3:50; The mass ratio of graphene oxide to the mixed liquid is 1:40 to 80; The concentration of the acetic acid solution is 2%; The particle size of graphene oxide ranges from 200 to 500 nm; The time condition of ultrasonic dispersion treatment is 20 to 30 minutes.

3. The method for preparing the antibacterial heat storage and temperature regulating lyocell fiber according to claim 1, characterized in that: In S2, cotton pulp, TEMPO and NaBr are dissolved in deionized water, and then NaClO solution is added to obtain TEMPO / NaClO solution; wherein, in parts by mass, cotton pulp:TEMPO:NaBr:deionized water:NaClO solution=50:1-3:10:200:50, the concentration of NaClO solution is 0.02-0.10 mmol / L, the pH of TEMPO / NaClO solution is 10-11, and the reaction time is 20-40 min.

4. The method for preparing the antibacterial heat storage and temperature regulating lyocell fiber according to claim 1, characterized in that: In S3, the mass ratio of isophorone diisocyanate to polypropylene glycol is 1:3; The temperature condition of the water bath reaction is 80-85°C and the time condition is 1-3h; The mass ratio of octadecane to polyurethane prepolymer is 3:1; The surfactant is xylene, and the mass ratio of the surfactant to polypropylene glycol is 2:3; The chain extender is ethylene glycol, and the mass ratio of the chain extender to isophorone diisocyanate is 1:

2.

5. The method for preparing the antibacterial heat storage and temperature regulating lyocell fiber according to claim 1, characterized in that: In S4, the stabilizer is propyl gallate and the cross-linker is cysteine; In terms of mass ratio, oxidized cotton pulp: graphene dispersion = 1:10-50; Propyl gallate accounts for 0.03-0.05% of the mass of oxidized cotton pulp; Cysteine ​​accounts for 0.5-2% of the mass of oxidized cotton pulp; The antibacterial extract is wormwood / aloe antibacterial extract, and the antibacterial extract accounts for 3-10% of the mass of the oxidized cotton pulp; The polyurethane / octadecane microcapsules account for 10-40% of the mass of the oxidized cotton pulp; The temperature condition of the cross-linking reaction is 50-60°C and the time condition is 30-60min; The oxidized cotton pulp in the primary spinning solution accounts for 4-10% of the mass of the 4-methylmorpholine-N-oxide aqueous solution, and the mass of 4-methylmorpholine-N-oxide in the 4-methylmorpholine-N-oxide aqueous solution accounts for 50-70%; the temperature condition of the cross-linking reaction is 50-60°C, and the time condition is 30-60 minutes.

6. The method for preparing the antibacterial heat storage and temperature regulating lyocell fiber according to claim 1, characterized in that: In S5, the ultrasonic treatment power is 200-300 W, the ultrasonic frequency is 50-60 KHz, and the ultrasonic treatment time is 2-4 h; The stirring and dissolving conditions are negative pressure of 0.09 to -0.1 MPa, temperature of 85 to 105°C, and time of 1 to 3 hours.

7. The method for preparing the antibacterial heat storage and temperature regulating lyocell fiber according to claim 1, characterized in that: In S6, the temperature condition for spinning the secondary spinning solution is 95 to 110°C; The air gap length of the spinning system is 2-3 cm, the spinning speed is 30-50 m / min, the spinneret aperture is 15-115 μm, and the capillary length is 300-400 μm; The coagulation treatment is carried out in an aqueous solution of 4-methylmorpholine-N-oxide at a temperature of 25 to 50° C. and a concentration of 15 to 40 wt %.

8. The method for preparing the antibacterial heat storage and temperature regulating lyocell fiber according to claim 1, characterized in that: In S6, the bath ratio of the spun fiber in the antibacterial extract for the first time is 1:20-30, the temperature condition is 50-60°C, the concentration condition of the antibacterial extract is 2-8 mg / mL, the time condition is 1-2 h, and the temperature condition of the first drying is 80-90°C, and the time condition is 10-30 min; The bath ratio of the spun fiber for the second immersion in the antibacterial extract is 1:20-30, the temperature condition is 60-80°C, the concentration condition of the antibacterial extract is 6-10 mg / mL, the time condition is 2-4h, and the temperature condition of the second drying is 30-40°C.

9. Lyocell fiber with antibacterial, heat-storing and temperature-regulating function obtained by the preparation method of Lyocell fiber with antibacterial, heat-storing and temperature-regulating function as claimed in any one of claims 1 to 8.

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