Preparation method of long-acting antibacterial anti-perspective functional lyocell fiber

Abstract

The invention relates to a preparation method of a long-acting antibacterial anti-perspective functional lyocell fiber, and belongs to the technical field of textile fibers. The method comprises the following steps: step SS1: firstly, mixing and infiltrating nano zirconium phosphate silver-zinc-loaded antibacterial powder with a small amount of water, and slowly adding wetted antibacterial agent slurry into a dispersant aqueous solution to obtain an antibacterial agent dispersion liquid; step SS2, adding rutile type nano titanium dioxide into deionized water to obtain titanium dioxide dispersion liquid; step SS3, respectively adding the antibacterial agent dispersion liquid, the titanium dioxide dispersion liquid and the antioxidant into the NMMO solution, and mixing under stirring; step SS4, premixing cellulose pulp with an NMMO (N-methylmorpholine-N-oxide) mixed solution containing an antibacterial agent and titanium dioxide to prepare pulp porridge; and step SS5, carrying out decompression dehydration on the slurry congee to prepare a spinning solution, extruding the spinning solution from a spinneret plate, and carrying out coagulating bath cooling, drafting and forming to obtain the long-acting antibacterial anti-perspective functional lyocell fiber. According to the invention, collaborative optimization of long-acting antibacterial property, high anti-perspective property and comprehensive performance of the fiber is realized.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of long-acting antibacterial anti-see-through lyocell fiber, and belongs to the technical field of textile fibers. BACKGROUND

[0002] With the increasing improvement of living standards, people have higher and higher requirements for the comfort and functionality of garment fabrics. The surface of conventional lyocell fiber is smooth and delicate, which can bring a cool and comfortable experience in summer, but summer light-colored and thin garments made of conventional lyocell fiber, especially white fabrics, have the problems of underwear and skin exposure, unattractive appearance and the like, and cannot meet the performance requirements of light weight and visual shielding.

[0003] Two key problems exist in conventional lyocell fiber: one is weak anti-see-through performance, especially in the application scene of summer light-colored and thin fabrics, the visible light transmittance is high, and it is difficult to meet the demand of consumers for privacy protection; the other is weak antibacterial property, pathogenic bacteria such as escherichia coli and staphylococcus aureus are easy to breed in a humid environment, which causes fabric odor, skin allergy and the like, and limits its application in medical, outdoor and other special scenes.

[0004] In order to further expand the application field of lyocell fiber in the downstream industry, the development of differentiated and functional lyocell fiber has attracted widespread attention. For antibacterial function, the mainstream technology is to attach antibacterial agents to the surface of the fiber through post-dipping, coating and other processes, the bonding force between the fiber and the antibacterial agent is poor, and the antibacterial agent is easy to fall off during washing, which cannot achieve long-acting antibacterial effect; for anti-see-through function, rutile type nano titanium dioxide, zinc oxide and other light shielding aids are usually coated, but the coating layer has poor bonding force with the fiber, is easy to fall off after washing and rubbing, leading to the attenuation of the anti-see-through performance, and the soft hand feeling and air permeability of the fiber are also damaged. In recent years, although some researches have tried to combine single functional additives with lyocell fiber, there is still no technical solution to solve the stability of anti-see-through and long-acting antibacterial performance at the same time, and the compatibility of functional additives with lyocell spinning system and the balance of fiber comprehensive performance.

[0005] According to the literature investigation, the antibacterial property of lyocell fiber has attracted widespread attention, for example, Chinese patent CN116837475A discloses a preparation method of antibacterial lyocell fiber, which first dissolves cellulose quaternary ammonium salt in NMMO solvent, and then dissolves cellulose pulp. Although the method can effectively improve the antibacterial property of lyocell fiber, the cellulose quaternary ammonium salt is not resistant to high temperature and is easy to decompose in the high-temperature spinning process, which weakens its antibacterial property.

[0006] Patent CN105177746A discloses an antibacterial Lyocell fiber and a preparation method thereof, the application obtains an NMMO solution containing ZnO by mixing nano-ZnO after surface modification treatment with NMMO aqueous solution, then dissolving cellulose pulp, and spinning to prepare antibacterial Lyocell fiber, wherein the mass content of nano-ZnO is 0.1-10%, the content of antibacterial agent is high, and the production cost is high.

[0007] Patent CN118563558 A discloses a multifunctional anti-see-through fiber for textiles and a preparation method thereof, which is to dip polylactic acid (PLA) fibers into a dispersion liquid of titanium dioxide nanoparticles, doped rare earth zinc oxide nanoparticles and silver nanoparticles and tea tree oil in sequence for coating treatment, and then perform cross-linking treatment in glutaraldehyde solution. Finally, the treated fibers are spun and woven to form a fabric. The coating layer of the method has weak bonding force with the fibers, is easy to fall off after washing and rubbing, and causes the anti-see-through performance to attenuate. SUMMARY

[0008] The existing organic antibacterial agent has the characteristics of quick-acting and excellent antibacterial effect, but its poor heat resistance and durability, high toxicity and other shortcomings limit its wide application; the safety of the natural antibacterial agent is very high, but its poor heat resistance and short antibacterial effect duration limit its use; the current research and development of antibacterial agents at home and abroad focuses on silver, copper and zinc inorganic antibacterial agents, which have high safety, good heat resistance, high antibacterial efficiency, long-lasting antibacterial property and wide application, and the widely used ones are silver-zeolite, silver-silica gel antibacterial agent and silver-loaded zirconium phosphate. However, the traditional inorganic silver-loaded antibacterial agent is prone to discoloration, has poor compatibility with materials, and when added to materials, the large particle size of the antibacterial agent affects the performance and processing performance of the materials, and the antibacterial effect is poor.

[0009] In view of the shortcomings and deficiencies of the prior art, the primary purpose of the present application is to provide a preparation method of long-acting antibacterial and anti-see-through lyocell fiber, which is suitable for the research and production of medical protective fabrics, outdoor clothes, close-fitting clothes and other products that require both fiber hiding and antibacterial properties, and can promote the development of green textile materials in the direction of multifunctional and high added value.

[0010] The present application specifically adopts the following technical scheme: a preparation method of long-acting antibacterial and anti-see-through lyocell fiber, comprising the following steps: Step SS1: preparing an antibacterial agent dispersion liquid: first, mix nano-zirconium phosphate silver-loaded zinc antibacterial powder with a small amount of water for soaking, then prepare a water solution with a mass content of 1%-2% of dispersant, slowly add the wet antibacterial agent slurry to the dispersant aqueous solution while stirring, then use an ultrasonic dispersing instrument for oscillation treatment to obtain an antibacterial agent dispersion liquid; Step SS2: Preparation of dispersion liquid of titanium white: Rutile nano titanium white powder is added into deionized water and dispersed under high-speed stirring; then ultrasonic dispersing instrument is used for oscillation treatment to obtain titanium white dispersion liquid; Step SS3: The antibacterial agent dispersion liquid, titanium white dispersion liquid and antioxidant are added into NMMO solution respectively and mixed under stirring; Step SS4: Cellulose pulp and NMMO mixed liquid containing antibacterial agent and titanium white are premixed to prepare pulp; Step SS5: The pulp is subjected to pressure reduction dehydration to prepare spinning solution, the spinning dope is extruded from a spinneret, cooled and drawn in a coagulation bath to form a long-acting antibacterial and anti-see-through functional lyocell fiber.

[0011] As a preferred embodiment, the particle size of the nano zirconium phosphate silver zinc antibacterial powder in step SS1 is 30-50 nm.

[0012] As a preferred embodiment, the stirring time in step SS1 is 5-10 minutes; and the oscillation treatment time is 20-40 minutes.

[0013] As a preferred embodiment, the particle size of the rutile nano titanium white powder in step SS2 is <300 nm.

[0014] As a preferred embodiment, step SS2 further comprises: dispersing under high-speed stirring at 2000-3000 r / min for 10-15 minutes; and then oscillation treatment is performed using an ultrasonic dispersing instrument for 20-40 minutes.

[0015] As a preferred embodiment, the mass fraction of the NMMO solution in step SS3 is 60-70%.

[0016] As a preferred embodiment, step SS3 further comprises: mixing under stirring at 1000-2000 r / min for 20-30 minutes.

[0017] As a preferred embodiment, the mass ratio of the cellulose pulp to the NMMO solution in step SS4 is 1:10-15.

[0018] As a preferred embodiment, the cellulose concentration of the spinning solution in step SS5 is 7-12 wt%.

[0019] The application has the advantages that: the application adopts the method of adding the "zirconium phosphate nano silver zinc antibacterial agent + rutile type nano titanium white powder" dual functional additive stock solution to prepare lyocell fibers, realizes long-acting antibacterial and anti-see-through dual functions. The zirconium phosphate nano has a layered microporous structure similar to zeolite, can firmly fix silver and zinc ions in its crystal lattice like a "cage", greatly reduces the free and migration of metal ions, and makes the toxicity risk of the human body skin and environment far lower than that of traditional silver ion or zinc oxide antibacterial agent. The addition of the rutile type nano titanium white powder in the stock solution can make the titanium white powder uniformly dispersed in the fibers, avoid the problems of additive falling off and fiber performance degradation caused by the finishing process, and through the optimization of the additive amount (the mass fraction of the rutile type nano titanium white powder is 4%-10%, and the content of the silver zinc antibacterial agent is 0.1%-0.2%), the basic performances of the fibers such as dry breaking strength, wet breaking strength and elongation are ensured on the premise of ensuring excellent functional indexes, and the long-acting antibacterial, high anti-see-through and fiber comprehensive performance are synergistically optimized. DETAILED DESCRIPTION

[0020] The following examples are only used to more clearly illustrate the technical solutions of the application, and cannot be used to limit the protection scope of the application. Example 1:

[0021] (1) The zirconium phosphate nano silver zinc antibacterial agent is mixed and soaked with a small amount of water, the antibacterial agent is 0.05% of the mass of the pulp, a water solution containing 1% of the dispersant is prepared, the wet antibacterial agent slurry is slowly added into the dispersant water solution, and stirring is performed for 5 minutes; then an ultrasonic dispersing instrument is used for oscillation treatment for 30 minutes to obtain an antibacterial agent dispersion liquid; the dispersant is one or two of sodium polyacrylate, sodium hexametaphosphate and sodium silicate.

[0022] (2) The rutile type nano titanium white powder is added into deionized water, the titanium white powder is 4% of the mass of the pulp, and is dispersed for 10 minutes under the condition of 2000-3000r / min high-speed stirring; then an ultrasonic dispersing instrument is used for oscillation treatment for 30 minutes to obtain a titanium white powder dispersion liquid.

[0023] (3) The antibacterial agent dispersion liquid, the titanium white powder dispersion liquid and the antioxidant are respectively added into 60% NMMO water solution, and are mixed for 30 minutes under the condition of 1500r / min stirring to obtain an NMMO mixed slurry. The antioxidant is a phenolic compound, the molecular structure of the antioxidant contains active groups such as phenolic hydroxyl groups, these groups can provide hydrogen atoms to combine with free radicals, make the free radicals lose activity, prevent the further oxidation reaction, prevent the degradation of the solvent and cellulose at high temperature, and thus the stability of the spinning stock solution is maintained.

[0024] (4) The cellulose pulp and NMMO mixed slurry is premixed to prepare a pulp. In this step, the mass ratio of cellulose pulp and NMMO solution is 1:14.

[0025] (5) The pulp is dehydrated under reduced pressure to prepare a spinning solution with a cellulose concentration of 9wt%. The spinning dope is extruded from a spinneret, cooled and drawn in a coagulation bath to form a long-acting antibacterial and anti-see-through Lyocell fiber.

[0026] Example 2: (1) The amount of nano-zirconium phosphate loaded silver zinc antibacterial agent is 0.1% of the mass of the pulp; (2) The amount of nanometer rutile is 5% of the mass of the pulp; the remaining steps are the same as in Example 1.

[0027] Example 3: (1) The amount of nano-zirconium phosphate loaded silver zinc antibacterial agent is 0.2% of the mass of the pulp; (2) The amount of nanometer rutile is 6% of the mass of the pulp; the remaining steps are the same as in Example 1.

[0028] Example 4: (1) The amount of nano-zirconium phosphate loaded silver zinc antibacterial agent is 0.2% of the mass of the pulp; (2) The amount of nanometer rutile is 7% of the mass of the pulp; the remaining steps are the same as in Example 1.

[0029] Comparative Example 1 The nano-zirconium phosphate loaded silver zinc antibacterial agent is mixed with a small amount of water to soak, and the amount of antibacterial agent is 0.1% of the mass of the pulp; a water solution containing 1% of the dispersant is prepared, and the soaked antibacterial agent slurry is slowly added to the dispersant water solution while stirring for 5 minutes; then an ultrasonic dispersing instrument is used for oscillation treatment for 30 minutes to obtain an antibacterial agent dispersion; the remaining steps are the same as in Example 1.

[0030] The above antibacterial and anti-see-through Lyocell fiber is subjected to opening, carding, drawing, roving, spinning, and winding processes to prepare a 40 English Lyocell yarn, and then subjected to sizing, beaming, threading, weaving, desizing, and drying processes to obtain a 20cm x 30cm antibacterial and anti-see-through Lyocell fabric with a fabric weight of 150-170 g / cm 2 . Table 1 shows the characterization data and effect data of the products of the examples and comparative examples.

[0031] Table 1

[0032] As can be seen from Examples 1-4, with the increase of the content of the antibacterial agent, the antibacterial rate of the Lyocell fiber increases, and when the content of the antibacterial agent is ≥0.2%, the antibacterial rate is >99.9%; with the increase of the content of the titanium white powder, the dry breaking strength and the dry elongation of the Lyocell fiber are both significantly decreased, but when the content of the titanium white powder is 7%, the dry breaking strength of the fiber is significantly decreased, which is due to the fact that too much inorganic particles titanium white powder affects the spinning process and the fiber performance.

[0033] As can be seen from Examples 1-4 and Comparative Example 1, when the titanium white powder is added in the Lyocell fiber, the anti-see-through index of the fabric is significantly increased, and with the increase of the content of the titanium white powder, the anti-see-through index of the fabric gradually increases, and the fabric has excellent anti-see-through performance; too little has no effect. Under the premise of ensuring the spinnability and the mechanical performance of the fiber, the application obtains a suitable TiO2 addition amount, and the prepared fabric is not only light, comfortable, moisture-conducting and quick-drying, but also has the anti-see-through effect, and the transmission of the visible light is greatly reduced.

[0034] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the application but not to limit it, although the application has been described in detail with reference to the above examples, those skilled in the art should understand that: the specific embodiments of the application can still be modified or replaced equivalently without departing from the spirit and scope of the application, any modification or equivalent replacement without departing from the spirit and scope of the application should be covered in the protection scope of the claims of the application.

Claims

1. A process for the production of long-lasting antibacterial anti-see-through functional lyocell fibers, characterized in that, It comprises the following steps: Step SS1: preparing the antibacterial agent dispersion liquid: first, mix nano zirconium phosphate silver zinc antibacterial powder with a small amount of water to soak, then prepare a water solution with a mass content of 1%-2% of the dispersant, slowly add the wet antibacterial agent slurry into the dispersant water solution while stirring; then use an ultrasonic dispersing instrument for oscillation treatment to obtain the antibacterial agent dispersion liquid; Step SS2: preparing the dispersion liquid of titanium white powder: add the rutile type nano titanium white powder into deionized water and disperse under high-speed stirring; Then use an ultrasonic dispersing instrument for oscillation treatment to obtain the titanium white powder dispersion liquid; Step SS3: add the antibacterial agent dispersion liquid, titanium white powder dispersion liquid, and antioxidant into the NMMO solution and mix under stirring; Step SS4: prepare the slurry by premixing the cellulose pulp and the NMMO mixed solution containing the antibacterial agent and titanium white powder; Step SS5: perform pressure reduction dewatering on the slurry to obtain a spinning solution, the spinning dope is extruded from the spinneret, cooled and drawn in the coagulation bath to form a long-acting antibacterial and anti-see-through functional lyocell fiber.

2. A process for the preparation of long-lasting antibacterial anti-see-through lyocell fiber according to claim 1, characterized in that, The particle size of the nano zirconium phosphate silver zinc antibacterial powder in step SS1 is 30-50 nm.

3. A process for the preparation of long-lasting antibacterial anti-see-through lyocell fiber according to claim 1, characterized in that, The stirring time in step SS1 is 5-10 minutes; the oscillation treatment time is 20-40 min.

4. The method for preparing a long-lasting antibacterial and anti-seepage lyocell fiber according to claim 1, characterized in that, The particle size of the rutile type nano titanium white powder in step SS2 is <300 nm.

5. The method for preparing a long-lasting antibacterial and anti-seepage lyocell fiber according to claim 1, characterized in that, Step SS2 also comprises: dispersing under high-speed stirring at 2000-3000 r / min for 10-15 min; then using an ultrasonic dispersing instrument for oscillation treatment for 20-40 min.

6. A process for the preparation of long-lasting anti-bacterial, anti-see-through lyocell fiber according to claim 1, characterized in that, The mass fraction of the NMMO solution in step SS3 is 60-70%.

7. A process for the preparation of long-lasting anti-bacterial, anti-see-through lyocell fiber according to claim 1, characterized in that, Step SS3 also comprises: mixing under stirring at 1000-2000 r / min for 20-30 min.

8. A process for the preparation of long-lasting anti-bacterial, anti-see-through lyocell fiber according to claim 1, characterized in that, The mass ratio of the cellulose pulp and the NMMO solution in step SS4 is 1:10-15.

9. A process for the preparation of long-lasting anti-bacterial, anti-see-through lyocell fiber according to claim 1, characterized in that, The cellulose concentration of the spinning solution in step SS5 is 7-12 wt%.

Images