Antibacterial deodorant regenerated cellulose fiber and method for producing the same

Abstract

The application provides an antibacterial and deodorizing regenerated cellulose fiber and a preparation method thereof, and relates to the field of modified cellulose fibers. The preparation method of the antibacterial and deodorizing regenerated cellulose fiber comprises the following steps: preparing a composite antibacterial and deodorizing dispersion system, preparing a blending spinning stock solution, spinning, and post-treatment. The preparation of the composite antibacterial and deodorizing dispersion system comprises the following steps: preparing a porous adsorption powder, chitosan modification treatment, zinc alginate modification treatment, and mixing preparation. The antibacterial and deodorizing regenerated cellulose fiber can fully exert the function of the antibacterial and deodorizing effective components in the fiber, has excellent antibacterial performance, can simultaneously eliminate acidic and alkaline odors, and can effectively avoid the loss of the antibacterial and deodorizing effective components in the fiber during subsequent use.

Description

Technical Field

[0001] This invention relates to the field of modified cellulose fibers, and in particular to an antibacterial and deodorizing regenerated cellulose fiber and its preparation method. Background Technology

[0002] Various bacteria and molds, such as Staphylococcus aureus, Escherichia coli, Aspergillus flavus, and Candida albicans, exist in nature. Under certain environmental conditions, they can multiply rapidly on textiles such as clothing, making the textiles susceptible to degradation and discoloration due to their acidic or alkaline metabolites. These metabolites also produce volatile, foul-smelling substances such as acetic acid and ammonia, which can easily trigger skin diseases and become unbearable in poorly ventilated, high-temperature public places. Therefore, antibacterial and deodorizing fibers and related textiles have emerged. These fibers can inhibit the growth of these bacteria and molds within a limited space, while simultaneously eliminating, reducing, or weakening impurities and unpleasant odors in the air. They possess enormous market potential and have become a sought-after product.

[0003] In recent years, cellulose fiber products have gained widespread application due to their excellent moisture absorption, breathability, and comfortable wear. With the improvement of people's living standards, the development of healthy, environmentally friendly products and green, multifunctional cellulose fibers has become the industry's development direction. Correspondingly, various regenerated cellulose fibers with antibacterial and deodorizing functions are constantly emerging. Existing technologies disclose various regenerated cellulose fibers with antibacterial and deodorizing functions and their preparation methods, but they still have the following defects: 1) During the preparation of regenerated cellulose fibers, the stability of the effective antibacterial and deodorizing components is poor, especially during fiber forming, where the effective components are severely damaged, directly leading to a reduction in fiber functionality; 2) The effective components inside existing regenerated cellulose fibers are difficult to exert their effects, resulting in a waste of antibacterial and deodorizing components; 3) During subsequent use, the effective antibacterial and deodorizing components of existing regenerated cellulose fibers are easily lost, failing to stably exert their antibacterial and deodorizing effects within the fiber; 4) The deodorizing function of existing regenerated cellulose fibers is singular, usually only effective against one of acidic or alkaline odors, unable to simultaneously eliminate both acidic and alkaline odors, resulting in unsatisfactory deodorizing effects.

[0004] Based on this, a method for preparing antibacterial and deodorizing regenerated cellulose fiber is provided. This method effectively improves the stability of the effective antibacterial and deodorizing components during the regenerated cellulose fiber preparation process, thereby enhancing the fiber's antibacterial and deodorizing functionality. It also effectively prevents the loss of these effective antibacterial and deodorizing components during subsequent use, ensuring long-term stable antibacterial and deodorizing performance. Furthermore, the method provides an antibacterial and deodorizing regenerated cellulose fiber prepared using the aforementioned method, in which the effective antibacterial and deodorizing components can fully exert their effects; and it can simultaneously eliminate both acidic and alkaline odors, exhibiting comprehensive deodorizing functionality. This method has significant technical importance and research value. Summary of the Invention

[0005] To address the technical problems existing in the prior art, this invention provides a method for preparing antibacterial and deodorizing regenerated cellulose fiber. This method can effectively improve the stability of the effective antibacterial and deodorizing components during the preparation of regenerated cellulose fiber, thereby enhancing the antibacterial and deodorizing functionality of the fiber. It can also effectively prevent the loss of the effective antibacterial and deodorizing components in the fiber during subsequent use, enabling it to maintain stable antibacterial and deodorizing performance over a long period of time.

[0006] This invention also provides an antibacterial and deodorizing regenerated cellulose fiber prepared by the aforementioned method, in which the effective antibacterial and deodorizing components can fully exert their function; and it can simultaneously eliminate acidic and alkaline odors, providing comprehensive deodorizing functionality. To solve the above technical problems, the technical solution adopted by the present invention is as follows: A method for preparing antibacterial and deodorizing regenerated cellulose fiber includes the following steps: preparing a composite antibacterial and deodorizing dispersion system, preparing a blending spinning solution, spinning, and post-treatment; The preparation of the composite antibacterial and deodorizing dispersion system includes the following steps: preparing porous adsorption powder, chitosan modification treatment, zinc alginate modification treatment, and mixed formulation; The method for preparing porous adsorbent powder involves grinding inorganic porous materials to a particle size D. 90 ≤1.655μm, resulting in porous adsorption powder; The chitosan modification method is as follows: after the porous adsorption powder is placed in a chitosan solution for adsorption, it is placed in an aqueous bath containing sodium hydroxide and ethanol and stirred to obtain a chitosan modified porous adsorption powder dispersion system. The method for modifying zinc alginate is as follows: after the porous adsorption powder is placed in a sodium alginate solution for adsorption, it is placed in a zinc chloride solution and stirred to obtain a zinc alginate modified porous adsorption powder dispersion system. The method for preparing the mixed formulation is to mix the chitosan-modified porous adsorption powder dispersion system, the zinc alginate-modified porous adsorption powder dispersion system, and the thickener evenly to obtain a composite antibacterial and deodorizing dispersion system. The composite antibacterial and deodorizing dispersion system is mixed with the spinning solution to form a blended spinning solution. After spinning and post-treatment, antibacterial and deodorizing regenerated cellulose fibers are obtained.

[0007] Preferably, in the chitosan modification treatment, the chitosan solution is an aqueous solution of chitosan in acetic acid, and the concentration of the chitosan solution is 1-2 wt%. The weight ratio of porous adsorbent powder to chitosan solution is 1:10-20; The water-based bath solution containing sodium hydroxide and ethanol has a sodium hydroxide mass fraction of 2-3 wt%, an ethanol mass fraction of 1-2 wt%, and the balance is deionized water.

[0008] Preferably, in the chitosan modification process, after the porous adsorbent powder is placed in the chitosan solution for adsorption, a porous adsorbent powder with adsorbed chitosan is obtained, which is then placed in an aqueous bath containing sodium hydroxide and ethanol, and the oven-dry mass fraction of the porous adsorbent powder with adsorbed chitosan is controlled to be 20-30 wt%.

[0009] Preferably, in the zinc alginate modification treatment, the concentration of the sodium alginate solution is 4-6 wt%. The weight ratio of porous adsorption powder to sodium alginate solution is 1:10-20; The concentration of the zinc chloride solution is 6-8 wt%.

[0010] Preferably, in the zinc alginate modification treatment, after the porous adsorbent powder is placed in the sodium alginate solution for adsorption, a porous adsorbent powder adsorbed with sodium alginate is obtained, which is then placed in a zinc chloride solution, and the oven-dry mass fraction of the porous adsorbent powder adsorbed with sodium alginate is controlled to be 20-30 wt%.

[0011] Preferably, in the mixed formulation, the chitosan-modified porous adsorbent powder dispersion system and the zinc alginate-modified porous adsorbent powder dispersion system are mixed in equal volumes. The amount of thickener added is 0.5-1.5% of the total dry weight of chitosan-modified porous adsorbent powder and zinc alginate-modified porous adsorbent powder in the composite antibacterial and deodorizing dispersion system.

[0012] Furthermore, the method for preparing the blended spinning solution is to mix a spinning solution with a cellulose content of 8.5-9.3 wt% with a composite antibacterial and deodorizing dispersion system and a pore-forming agent solution evenly to obtain the blended spinning solution. The weight of the composite antibacterial and deodorizing dispersion system should be 6-15% of the weight of chitosan in the spinning solution. The pore-forming agent solution is a sodium carbonate solution or a sodium bicarbonate solution; the weight of the pore-forming agent solution added is 5-8% of the weight of sodium carbonate or sodium bicarbonate in the regenerated cellulose fiber spinning solution.

[0013] Preferably, the spinning solution is made from cellulose pulp and has a falling ball viscosity of 36-55s; The spinning solution also contains sodium hydroxide and a modifier; the modifier is a mixture of polyethylene glycol and urea; the sodium hydroxide content in the spinning solution is 4.5-5.6 wt%; the weight of the modifier is 2.0-3.5% of the weight of methyl cellulose in the spinning solution.

[0014] Furthermore, the method for preparing porous adsorbent powder involves grinding and dispersing inorganic porous materials, dispersants, and defoamers in deionized water until the particle size D is reached. 90 ≤1.655μm, a porous adsorption powder dispersion system with a solid content of 30-50wt% was obtained; the pH was adjusted to neutral, the solids were separated and collected, and dried to obtain the porous adsorption powder.

[0015] Preferably, the weight of the dispersant added is 3.0-5.0% of the dry basis weight of the inorganic porous material; the weight of the defoamer added is 3.5-5.5% of the dry basis weight of the inorganic porous material.

[0016] Preferably, the inorganic porous material is zeolite or kaolin; The dispersant is one of the following: sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium styrene maleic anhydride, or sodium hexametaphosphate; The defoamer is either an organosilicon defoamer or a polyether defoamer.

[0017] Furthermore, the spinning method involves using a blended spinning solution to spin the fibers through a coagulation bath at 45-50°C. After the nascent fiber bundle is drawn, a shaped fiber bundle with a semi-open structure in the cross-section of the fiber is obtained. The coagulation bath contains the following components: 100-110 g / L sulfuric acid and 290-310 g / L sodium sulfate. Zinc sulfate is not used.

[0018] Furthermore, the post-processing method involves subjecting the spun filament bundle to desulfurization modification, oiling treatment, dehydration treatment, irradiation treatment, and opening treatment to obtain antibacterial and deodorizing regenerated cellulose fibers.

[0019] The desulfurization modification is carried out using a desulfurization bath containing Na2SO3 and a cationic modifier; the cationic modifier is one of the following: hexadecyltrimethylammonium chloride, cationic polyacrylamide, 3-acrylamido-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride; Preferably, in the desulfurization modification, the Na2SO3 content in the desulfurization bath is 5.0-8.5 g / L, and the cationic modifier content is 35-45 g / L.

[0020] In the oiling process, a mixed solution of an oiling agent and a weak acid at 55-65℃ is used for oiling, and the oil content of the antibacterial and deodorizing regenerated cellulose fiber is controlled to be 0.21-0.35wt%, and the pH is 6.7-6.9. Preferably, in the mixed solution containing oil and weak acid, the concentration of oil is 3.0-6.0 g / L, the concentration of weak acid is 4.0-8.0 g / L, and the pH value is 6.0-6.5; the weak acid is a polycarboxylic acid or citric acid.

[0021] In the dehydration process, the water is first pressed and dehydrated using a high-pressure rolling mill until the moisture regain is 120-135%, and then vacuum dried until the moisture regain is 11.6-13.8%. Preferably, the pressing and dehydration pressure is controlled at 0.35-0.4 MPa; the vacuum degree of vacuum drying is controlled at 0.03-0.09 MPa, and the temperature is controlled at 45-48℃.

[0022] In the irradiation treatment, the irradiation dose is controlled at 20-70 kGy and the irradiation time is 60-120 s.

[0023] An antibacterial and deodorizing regenerated cellulose fiber is prepared using the aforementioned method.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The method for preparing the antibacterial and deodorizing regenerated cellulose fiber of the present invention involves adsorbing chitosan and sodium alginate using porous adsorption materials, and using a molding process to form the effective components (chitosan and zinc alginate) within the pores of the porous adsorption materials to form a protective layer, thereby improving the stability of the antibacterial and deodorizing effective components and producing a composite antibacterial and deodorizing dispersion system.

[0025] Then, through spinning and finishing, the fiber is endowed with good and lasting functionality. Specifically, by combining the spinning process and the pore-forming agent added to the blending spinning solution, the formed fiber matrix presents a semi-open structure with more pores in the transverse and longitudinal sections, thereby increasing the fiber's adsorption of cationic modifiers and weak acids during post-treatment; and through irradiation cross-linking reaction, the stability and functionality of the fiber structure are further improved.

[0026] The aforementioned technical methods work together synergistically to effectively improve the stability of antibacterial and deodorizing active ingredients and enhance the antibacterial and deodorizing functionality of the fiber during the preparation of regenerated cellulose fiber. They also effectively prevent the loss of antibacterial and deodorizing active ingredients in the fiber during subsequent use, enabling it to maintain stable antibacterial and deodorizing performance over a long period. At the same time, the antibacterial and deodorizing regenerated cellulose fiber prepared in this way allows the antibacterial and deodorizing active ingredients inside to fully exert their effects and can simultaneously eliminate both acidic and alkaline odors, providing comprehensive deodorizing functionality.

[0027] (2) The antibacterial and deodorizing regenerated cellulose fiber of the present invention has a semi-open matrix structure with some pores in the transverse and longitudinal sections; according to the test, the antibacterial and deodorizing regenerated cellulose fiber has excellent antibacterial and deodorizing functions, with an inhibition rate of up to 95.8% against Staphylococcus aureus, up to 94.3% against Escherichia coli, and up to 96.7% against Candida albicans; its ammonia reduction rate is up to 95.2%, its acetic acid reduction rate is up to 96.1%, and its isovaleric acid reduction rate is up to 97%. 0.2%; at the same time, zinc has anti-allergic effects and good health benefits; furthermore, the antibacterial and deodorizing regenerated cellulose fiber has good functional durability and washability. After 20 washes, the inhibition rate against Staphylococcus aureus can still reach 89.8%, the inhibition rate against Escherichia coli can still reach 89.7%, and the inhibition rate against Candida albicans can still reach 90.5%; its reduction rate against ammonia can still reach 90.1%, the reduction rate against acetic acid can still reach 90.3%, and the reduction rate against isovaleric acid can still reach 92.8%.

[0028] (3) The preparation method of the antibacterial and deodorizing regenerated cellulose fiber of the present invention is easy to control, the process is stable and reliable, the raw materials are easy to obtain, and it is conducive to industrial-scale production. Attached Figure Description

[0029] Figure 1 A cross-sectional micrograph of the antibacterial and deodorizing regenerated cellulose fiber prepared in Example 3.

[0030] Figure 2 Micrograph of the longitudinal section of the antibacterial and deodorizing regenerated cellulose fiber prepared in Example 3. Detailed Implementation

[0031] To provide a clearer understanding of the technical features, objectives, and effects of this invention, specific embodiments are now described. It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0032] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments of the present invention. As used herein, "first," "second," etc., are used to distinguish similar objects and are not used to describe a particular order or sequence. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0033] This invention provides a method for preparing antibacterial and deodorizing regenerated cellulose fiber, comprising the following steps: preparing a composite antibacterial and deodorizing dispersion system, preparing a blending spinning solution, spinning, and post-treatment.

[0034] The preparation of the composite antibacterial and deodorizing dispersion system includes the following steps: preparing porous adsorption powder, chitosan modification treatment, zinc alginate modification treatment, and mixed formulation.

[0035] The method for preparing porous adsorbent powder involves using zirconium oxide as the grinding medium, dispersing inorganic porous materials in deionized water using a sand mill disperser, and adding a dispersant (3.0-5.0% by dry weight of the inorganic porous materials) and an antifoamer (3.5-5.5% by dry weight of the inorganic porous materials) to assist in the grinding and dispersion. The grinding speed is controlled at 2000-3000 r / min. During the grinding process, cooling water at a temperature of 10-20℃ is circulated for cooling, and the particle size of the inorganic porous materials is monitored until the particle size reaches D. 90 ≤1.655μm, to obtain a porous adsorption powder dispersion system with a solid content of 30-50wt%; adjust the pH of the porous adsorption powder dispersion system to neutral, filter and collect the solids, and dry the solids under forced air conditions at 90-100℃ to obtain dry porous adsorption powder.

[0036] In the preparation of the porous adsorbent powder, the inorganic porous material is selected from silicate minerals such as zeolite and kaolinite, which have porous structures; the particle size D90 of the inorganic porous material is ≤5.236μm. The dispersant is one of the following: sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium styrene maleic anhydride, or sodium hexametaphosphate; the defoamer is an organosilicon defoamer or a polyether defoamer.

[0037] The chitosan modification method involves dissolving chitosan (degree of deacetylation ≥ 95%, viscosity 100-200 mPa·s) in an aqueous acetic acid solution at 30-40℃ with a mass fraction of 2-3 wt% to obtain a chitosan solution with a mass fraction of 1-2 wt%. Then, under stirring at 600-800 r / min, the prepared porous adsorbent powder is added to 10-20 times its weight of the chitosan solution. After stirring and adsorption at room temperature for 30-60 min, the solid is collected by filtration to obtain a porous adsorbent powder containing adsorbed chitosan. The chitosan-modified porous adsorbent powder was then added to an aqueous bath (i.e., a deionized aqueous solution containing sodium hydroxide and ethanol) with a sodium hydroxide mass fraction of 2-3 wt% and an ethanol mass fraction of 1-2 wt% under stirring at 200-300 r / min. The oven-dry mass fraction of the chitosan-adsorbed porous adsorbent powder was controlled at 20-30 wt%, and the mixture was stirred for 20-50 min to allow the chitosan adsorbed in the pores to solidify, thus obtaining a chitosan-modified porous adsorbent powder dispersion system protected by the porous adsorbent powder. This system exhibits good antibacterial properties and also provides excellent deodorization for acidic odors.

[0038] The method for modifying zinc alginate involves dissolving biological sodium alginate in deionized water at 25-30°C to obtain a sodium alginate solution with a mass concentration of 4-6 wt%. Under stirring conditions of 600-800 r / min, the prepared porous adsorbent powder is added to 10-20 times its weight of the sodium alginate solution, and the mixture is stirred at room temperature for 30-50 min to ensure complete adsorption of sodium alginate. The solid is then collected by filtration to obtain porous adsorbent powder adsorbed with sodium alginate. Then, under stirring conditions of 200-300 r / min, the porous adsorbent powder containing adsorbed sodium alginate was added to an aqueous bath (i.e., zinc chloride aqueous solution) with a zinc chloride mass fraction of 6-8 wt%. The oven-dry mass fraction of the porous adsorbent powder containing adsorbed sodium alginate was controlled at 20-30 wt%. The mixture was stirred for 30-50 min, causing the sodium alginate adsorbed in the pores to be converted into zinc alginate, thus obtaining a zinc alginate modified porous adsorbent powder dispersion system protected by the porous adsorbent powder. This system has good antibacterial properties and also provides good deodorization for alkaline odors.

[0039] The method for preparing the mixed formulation is as follows: equal volumes of the chitosan-modified porous adsorbent powder dispersion system and the zinc alginate-modified porous adsorbent powder dispersion system are mixed, and a thickener accounting for 0.5-1.5% of the dry basis mass of all effective components (chitosan-modified porous adsorbent powder and zinc alginate-modified porous adsorbent powder) is added. The mixture is then mixed evenly, and the pH value is adjusted to 7.5-8.5 to obtain a composite antibacterial and deodorizing dispersion system for later use.

[0040] In the mixed formulation, the thickener is one of the following: sodium hydroxyethyl cellulose, sodium carboxymethyl cellulose, or sodium carboxyethyl cellulose. By adding the thickener, the viscosity of the composite antibacterial and deodorizing dispersion system is increased, thereby reducing the impact of the composite antibacterial and deodorizing dispersion system on the subsequent preparation of the blended spinning solution.

[0041] The method for preparing the blended spinning solution is as follows: using cellulose pulp (preferably wood pulp, cotton pulp, or bamboo pulp) as raw material, a regenerated cellulose fiber spinning solution with a falling ball viscosity of 36-55s is prepared by conventional viscose preparation process (composition: methyl cellulose, sodium hydroxide, and denaturant); using a pre-spinning injection device, a composite antibacterial and deodorizing dispersion system and a pore-forming agent solution are added to the regenerated cellulose fiber spinning solution to obtain the blended spinning solution.

[0042] In the preparation of the blended spinning solution, the regenerated cellulose fiber spinning solution contains 8.5-9.3 wt% methyl cellulose and 4.5-5.6 wt% sodium hydroxide; the added weight of the modifier in the regenerated cellulose fiber spinning solution is 2.0-3.5% of the weight of methyl cellulose; the modifier is a mixture of polyethylene glycol and urea in any proportion.

[0043] In the preparation of the blended spinning solution, the weight of the composite antibacterial and deodorizing dispersion system is added according to the weight of chitosan being 6-15% of the weight of cellulose A in the regenerated cellulose fiber spinning solution. The pore-forming agent solution is added at a weight of 5-8% of the weight of the pore-forming agent (sodium carbonate or sodium bicarbonate) in the regenerated cellulose fiber spinning solution; the pore-forming agent solution is preferably a sodium carbonate solution or sodium bicarbonate solution with a mass fraction of 30-40%.

[0044] The spinning method involves using a blended spinning solution to spin the fibers through a coagulation bath at 45-50°C. After the nascent fiber bundle is drawn, a shaped fiber bundle is obtained. The existing spinning forming process ensures that the fiber matrix of the prepared shaped fiber bundle has a semi-open structure, and the pore-forming agent makes the transverse and longitudinal sections of the fiber matrix of the shaped fiber bundle contain more pores to facilitate the adsorption of additives in subsequent processing.

[0045] In the spinning process, the coagulation bath contains the following components: 100-110 g / L sulfuric acid and 290-310 g / L sodium sulfate, but zinc sulfate is not used.

[0046] The post-processing method involves sequentially subjecting the formed filament bundle to desulfurization modification, oiling treatment, dehydration treatment, and irradiation treatment to further improve the functionality of the fiber, ensuring the functionality of the fiber from both spinning and fiber finishing aspects; finally, after opening treatment, antibacterial and deodorizing regenerated cellulose fiber is obtained.

[0047] In the post-treatment, desulfurization modification is carried out using a desulfurization bath at 60-85℃. The desulfurization bath contains Na2SO3 and a cationic modifier, wherein Na2SO3 is 5.0-8.5 g / L and the cationic modifier is 35-45 g / L. The cationic modifier is one of the following: hexadecyltrimethylammonium chloride, cationic polyacrylamide, 3-acrylamido-2-hydroxypropyltrimethylammonium chloride, or 3-chloro-2-hydroxypropyltrimethylammonium chloride. Desulfurization modification not only improves the stability of the fiber but also enhances its deodorizing effect against acidic odors.

[0048] In the post-treatment, the oiling process is carried out using a mixed solution of an oil-containing agent and a weak acid at 55-65℃; the concentration of the oil agent in the mixed solution is 3.0-6.0 g / L, the concentration of the weak acid is 4.0-8.0 g / L, and the pH value is 6.0-6.5; the weak acid is a polycarboxylic acid or citric acid. Through the oiling treatment, the oil content of the final fiber product is 0.21-0.35 wt%, and the fiber pH is 6.7-6.9.

[0049] In the post-processing, the dehydration treatment first uses a high-pressure rolling mill for pressing and dehydration, controlling the pressing and dehydration pressure at 0.35-0.4 MPa, and the moisture regain of the fiber after pressing and dehydration is 120-135%; then vacuum drying is carried out, controlling the vacuum degree at 0.03-0.09 MPa and the vacuum drying temperature at 45-48℃, until the moisture regain of the fiber is 11.6-13.8%.

[0050] In the post-processing, the irradiation treatment involves irradiating the dehydrated fibers with an electron beam, controlling the irradiation dose at 20-70 kGy and the irradiation time at 60-120 s. Through irradiation treatment, the hydroxyl groups on the regenerated cellulose fibers react with polycarboxylic acids or citric acid, improving the stability of the active ingredients and simultaneously enhancing the fiber's deodorizing effect against alkaline odors.

[0051] The present invention also provides antibacterial and deodorizing regenerated cellulose fibers prepared by the aforementioned method.

[0052] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described below in conjunction with some specific embodiments.

[0053] Example 1 This embodiment provides a method for preparing antibacterial and deodorizing regenerated cellulose fiber with a specification of 1.33 dtex × 38 mm. The specific steps are as follows: 1. Preparation of a composite antibacterial and deodorizing dispersion system 1) Preparation of porous adsorbent powder Zirconia was used as the grinding media, and zeolite (particle size D) was dispersed by a sand mill disperser. 90=5.236μm) was ground and dispersed in deionized water, with 3.0% (by dry weight of inorganic porous material) of dispersant (sodium dodecylbenzene sulfonate) and 3.5% (by dry weight of inorganic porous material) of defoamer (organosilicone defoamer) added to assist in grinding and dispersion. The grinding speed was controlled at 2000 r / min. During the grinding process, cooling water at 20℃ was circulated to cool the inorganic porous material and the particle size was monitored until the particle size reached D 90 =1.655μm, a porous adsorption powder dispersion system with a solid content of 30wt% was obtained; the pH of the porous adsorption powder dispersion system was adjusted to neutral, the solids were collected by filtration, and the solids were dried under 90℃ forced air conditions to obtain dry porous adsorption powder.

[0054] 2) Chitosan modification treatment Chitosan (degree of deacetylation 95%, viscosity 150 mPa·s) was dissolved in an aqueous solution of acetic acid at 30℃ with a mass fraction of 3 wt% to obtain a chitosan solution with a mass fraction of 1 wt%. Then, under stirring at 600 r / min, the prepared porous adsorbent powder was added to 20 times its weight of the chitosan solution. After stirring and adsorption at room temperature for 30 min, the solid was collected by filtration to obtain porous adsorbent powder with adsorbed chitosan. Then, under stirring at 200 r / min, the porous adsorbent powder with adsorbed chitosan was added to an aqueous bath solution with a mass fraction of 2 wt% sodium hydroxide and a mass fraction of 1 wt% ethanol. The oven-dry mass fraction of the porous adsorbent powder with adsorbed chitosan was controlled to be 20 wt%. The mixture was stirred and reacted for 20 min to obtain a chitosan-modified porous adsorbent powder dispersion system.

[0055] 3) Zinc alginate modification treatment Biological sodium alginate was dissolved in deionized water at 25°C to obtain a sodium alginate solution with a mass concentration of 4 wt%. Under stirring at 600 r / min, the prepared porous adsorbent powder was added to 20 times its weight of the sodium alginate solution, and stirred at room temperature for 30 min to allow for full adsorption of sodium alginate. The solid was then collected by filtration to obtain porous adsorbent powder with adsorbed sodium alginate. Then, under stirring at 200 r / min, the porous adsorbent powder with adsorbed sodium alginate was added to an aqueous bath solution with a mass fraction of 6 wt% zinc chloride, and the oven-dry mass fraction of the porous adsorbent powder with adsorbed sodium alginate was controlled to be 20 wt%. The mixture was stirred for 30 min to obtain a zinc alginate modified porous adsorbent powder dispersion system.

[0056] 4) Mixed formulations Equal volumes of chitosan-modified porous adsorbent powder dispersion system and zinc alginate-modified porous adsorbent powder dispersion system were mixed, and a thickener (sodium hydroxyethyl cellulose) of 0.5% by dry weight of all effective components (chitosan-modified porous adsorbent powder and zinc alginate-modified porous adsorbent powder) was added. The mixture was stirred evenly, and the pH was adjusted to 7.5 to obtain a composite antibacterial and deodorizing dispersion system for later use.

[0057] 2. Preparation of blend spinning solution Using cellulose pulp (wood pulp) as raw material, a regenerated cellulose fiber spinning solution with a falling ball viscosity of 36s was prepared (composition: methyl cellulose, sodium hydroxide, and denaturant). Using a pre-spinning injection device, a composite antibacterial and deodorizing dispersion system and a pore-forming agent solution were added to the regenerated cellulose fiber spinning solution to obtain a blended spinning solution.

[0058] The regenerated cellulose fiber spinning solution contains 8.5 wt% methyl cellulose and 4.5 wt% sodium hydroxide; the added modifier in the regenerated cellulose fiber spinning solution is 2.0% of the weight of methyl cellulose; the modifier is an equal weight mixture of polyethylene glycol and urea.

[0059] The weight of the composite antibacterial and deodorizing dispersion system is 6% of the weight of chitosan in the regenerated cellulose fiber spinning solution.

[0060] The pore-forming agent solution is added at a weight of 5% of the weight of the pore-forming agent (sodium carbonate) in the regenerated cellulose fiber spinning solution, which is a sodium carbonate solution with a mass fraction of 30 wt%.

[0061] 3. Spinning The blended spinning solution is used to spin the fibers through a coagulation bath at 45°C. After the nascent fiber bundle is drawn, a shaped fiber bundle is obtained. The fiber matrix of the shaped fiber bundle is controlled to have a semi-open structure.

[0062] The coagulation bath contains the following components: 100g / L sulfuric acid and 290g / L sodium sulfate, but zinc sulfate is not used.

[0063] 4. Post-processing The formed filaments are successively subjected to desulfurization modification, oiling treatment, dehydration treatment, irradiation treatment and opening treatment to obtain antibacterial and deodorizing regenerated cellulose fibers.

[0064] The desulfurization modification was carried out using a desulfurization bath at 60°C. The desulfurization bath contained Na2SO3 and a cationic modifier (hexadecyltrimethylammonium chloride), with Na2SO3 at 5.0 g / L and the cationic modifier at 35 g / L.

[0065] The oiling treatment was carried out using a mixed solution of an oil-containing agent and a weak acid at 55℃; the concentration of the oil-containing agent in the mixed solution was 3.0 g / L, the concentration of the weak acid was 4.0 g / L, and the pH value was 6.0; the weak acid was a polycarboxylic acid. Through the oiling treatment, the oil content of the final fiber product was 0.21 wt%, and the fiber pH was 6.7.

[0066] The dehydration process begins with pressing and dehydration using a high-pressure rolling mill, with the pressing pressure controlled at 0.35 MPa. After pressing and dehydration, the moisture regain of the fiber is 120%. Then, vacuum drying is performed, with the vacuum level controlled at 0.03 MPa and the vacuum drying temperature at 45°C, until the moisture regain of the fiber reaches 11.6%.

[0067] Irradiation treatment involves using an electron beam to irradiate the dehydrated fibers, controlling the irradiation dose at 20 kGy and the irradiation time at 120 s.

[0068] This embodiment also provides antibacterial and deodorizing regenerated cellulose fibers prepared using the aforementioned method. The antibacterial and deodorizing regenerated cellulose fiber matrix prepared in Example 1 exhibits a semi-open structure with some pores in its transverse and longitudinal sections. Testing showed that the antibacterial and deodorizing regenerated cellulose fiber possesses excellent antibacterial and deodorizing functionality, with an inhibition rate of 87.6% against Staphylococcus aureus, 86.5% against Escherichia coli, and 89.3% against Candida albicans; its ammonia reduction rate is 86.2%, its acetic acid reduction rate is 88.5%, and its isovaleric acid reduction rate is 90.7%; simultaneously, zinc has anti-allergic effects and good health benefits. Furthermore, the antibacterial and deodorizing regenerated cellulose fiber exhibits good functional durability and washability. After 20 washes (using the washing conditions and procedures specified in standard GB / T 8629-2017 "Testing Procedures for Household Washing and Drying of Textiles"), the inhibition rate against Staphylococcus aureus remains at 85.2%, against Escherichia coli at 83.6%, and against Candida albicans at 84.9%. Its reduction rates against ammonia remain at 81.1%, against acetic acid at 82.0%, and against isovaleric acid at 85.3%.

[0069] Example 2 This embodiment provides a method for preparing antibacterial and deodorizing regenerated cellulose fiber with a specification of 1.67 dtex × 38 mm. The specific steps are as follows: 1. Preparation of a composite antibacterial and deodorizing dispersion system 1) Preparation of porous adsorbent powder Zirconia was used as the grinding media, and zeolite (particle size D) was dispersed by a sand mill disperser. 90=4.925μm) was ground and dispersed in deionized water, with 4.0% of the inorganic porous material's dry weight as a dispersant (sodium styrene maleic anhydride) and 4.5% of the inorganic porous material's dry weight as an defoamer (polyether defoamer) added to assist in grinding and dispersion. The grinding speed was controlled at 2500 r / min. During the grinding process, cooling water at 15℃ was circulated to lower the temperature, and the particle size of the inorganic porous material was monitored until the particle size reached D 90 =1.326μm, a porous adsorption powder dispersion system with a solid content of 40wt% was obtained; the pH of the porous adsorption powder dispersion system was adjusted to neutral, the solids were collected by filtration, and the solids were dried under 95℃ forced air conditions to obtain dry porous adsorption powder.

[0070] 2) Chitosan modification treatment Chitosan (degree of deacetylation 95%, viscosity 150 mPa·s) was dissolved in an aqueous solution of acetic acid at 35℃ with a mass fraction of 2.5 wt% to obtain a chitosan solution with a mass fraction of 1.5 wt%. Then, under stirring at 700 r / min, the prepared porous adsorbent powder was added to 15 times its weight of the chitosan solution. After stirring and adsorption at room temperature for 45 min, the solid was collected by filtration to obtain porous adsorbent powder with adsorbed chitosan. Then, under stirring at 250 r / min, the porous adsorbent powder with adsorbed chitosan was added to an aqueous bath with a mass fraction of 2.5 wt% sodium hydroxide and a mass fraction of 1.5 wt% ethanol. The oven-dry mass fraction of the porous adsorbent powder with adsorbed chitosan was controlled to be 25 wt%. The mixture was stirred and reacted for 35 min to obtain a chitosan-modified porous adsorbent powder dispersion system.

[0071] 3) Zinc alginate modification treatment Biological sodium alginate was dissolved in deionized water at 28°C to obtain a sodium alginate solution with a mass concentration of 5 wt%. Under stirring at 700 r / min, the prepared porous adsorbent powder was added to 15 times its weight of the sodium alginate solution and stirred at room temperature for 45 min to allow for full adsorption of sodium alginate. The solid was then collected by filtration to obtain porous adsorbent powder with adsorbed sodium alginate. Then, under stirring at 250 r / min, the porous adsorbent powder with adsorbed sodium alginate was added to an aqueous bath solution with a mass fraction of 7 wt% zinc chloride. The oven-dry mass fraction of the porous adsorbent powder with adsorbed sodium alginate was controlled to be 25 wt%, and the mixture was stirred for 40 min to obtain a zinc alginate modified porous adsorbent powder dispersion system.

[0072] 4) Mixed formulations Equal volumes of chitosan-modified porous adsorbent powder dispersion system and zinc alginate-modified porous adsorbent powder dispersion system were mixed, and a thickener (sodium carboxymethyl cellulose) of 1.0% by dry weight of all effective components (chitosan-modified porous adsorbent powder and zinc alginate-modified porous adsorbent powder) was added. The mixture was stirred evenly, and the pH was adjusted to 8.0 to obtain a composite antibacterial and deodorizing dispersion system for later use.

[0073] 2. Preparation of blend spinning solution Using cellulose pulp (cotton pulp) as raw material, a regenerated cellulose fiber spinning solution with a falling ball viscosity of 48s was prepared (composition: methyl cellulose, sodium hydroxide, and denaturant). Using a pre-spinning injection device, a composite antibacterial and deodorizing dispersion system and a pore-forming agent solution were added to the regenerated cellulose fiber spinning solution to obtain a blended spinning solution.

[0074] The regenerated cellulose fiber spinning solution contains 8.85 wt% methyl cellulose and 4.9 wt% sodium hydroxide; the added modifier in the regenerated cellulose fiber spinning solution is 3.0% of the weight of methyl cellulose; the modifier is an equal weight mixture of polyethylene glycol and urea.

[0075] The weight of chitosan in the composite antibacterial and deodorizing dispersion system is 12% of the weight of cellulose A in the regenerated cellulose fiber spinning solution.

[0076] The pore-forming agent solution is added at a weight of 6.5% of the weight of the pore-forming agent (sodium bicarbonate) in the regenerated cellulose fiber spinning solution; the pore-forming agent solution is a sodium bicarbonate solution with a mass fraction of 35 wt%.

[0077] 3. Spinning The blended spinning solution is used to spin the fibers through a coagulation bath at 47.5℃. After the nascent fiber bundle is drawn, a shaped fiber bundle is obtained. The fiber matrix of the shaped fiber bundle is controlled to have a semi-open structure.

[0078] The coagulation bath contains the following components: 105 g / L sulfuric acid and 300 g / L sodium sulfate. Zinc sulfate is not used.

[0079] 4. Post-processing The formed filaments are successively subjected to desulfurization modification, oiling treatment, dehydration treatment, irradiation treatment and opening treatment to obtain antibacterial and deodorizing regenerated cellulose fibers.

[0080] The desulfurization modification was carried out using a desulfurization bath at 60°C. The desulfurization bath contained Na2SO3 and a cationic modifier (hexadecyltrimethylammonium chloride), with Na2SO3 at 6.8 g / L and the cationic modifier at 40 g / L.

[0081] The oiling treatment was carried out using a mixed solution of an oil-containing agent and a weak acid at 60℃; the concentration of the oil-containing agent in the mixed solution was 5.0 g / L, the concentration of the weak acid was 6.0 g / L, and the pH value was 6.20; the weak acid was citric acid. Through the oiling treatment, the oil content of the final fiber product was 0.28 wt%, and the fiber pH was 6.8.

[0082] The dehydration process begins with pressing and dehydration using a high-pressure rolling mill, with the pressing pressure controlled at 0.38 MPa. After pressing and dehydration, the moisture regain of the fiber is 126%. Then, vacuum drying is performed, with the vacuum level controlled at 0.05 MPa and the vacuum drying temperature at 47°C, until the moisture regain of the fiber reaches 12.5%.

[0083] Irradiation treatment involves using an electron beam to irradiate the dehydrated fibers, controlling the irradiation dose at 55 kGy and the irradiation time at 85 s.

[0084] This embodiment also provides antibacterial and deodorizing regenerated cellulose fibers prepared using the aforementioned method. The antibacterial and deodorizing regenerated cellulose fiber matrix prepared in Example 2 exhibits a semi-open structure with some pores in its transverse and longitudinal sections. Testing showed that the antibacterial and deodorizing regenerated cellulose fiber possesses excellent antibacterial and deodorizing functionality, with an inhibition rate of 93.2% against Staphylococcus aureus, 92.9% against Escherichia coli, and 94.1% against Candida albicans; its ammonia reduction rate is 92.5%, its acetic acid reduction rate is 93.9%, and its isovaleric acid reduction rate is 94.5%; simultaneously, zinc has anti-allergic effects and good health benefits. Furthermore, the antibacterial and deodorizing regenerated cellulose fiber exhibits good functional durability and washability. After 20 washes (using the washing conditions and procedures specified in standard GB / T 8629-2017 "Testing Procedures for Household Washing and Drying of Textiles"), the inhibition rate against Staphylococcus aureus remains at 87.9%, against Escherichia coli at 87.2%, and against Candida albicans at 88.3%. Its reduction rates against ammonia and acetic acid remain at 89.2%, and against isovaleric acid at 90.6%.

[0085] Example 3 This embodiment provides a method for preparing antibacterial and deodorizing regenerated cellulose fiber with a specification of 2.22 dtex × 38 mm. The specific steps are as follows: 1. Preparation of a composite antibacterial and deodorizing dispersion system 1) Preparation of porous adsorbent powder Zirconia was used as the grinding media, and zeolite (particle size D) was dispersed by a sand mill disperser. 90=3.892μm) was ground and dispersed in deionized water, with 5.0% (by dry weight of inorganic porous material) of dispersant (sodium hexametaphosphate) and 5.5% (by dry weight of inorganic porous material) of defoamer (polyether defoamer) added to assist in grinding and dispersion. The grinding speed was controlled at 3000 r / min. During the grinding process, cooling water at 10℃ was circulated to cool the inorganic porous material and the particle size was monitored until the particle size reached D 90 =1.120μm, a porous adsorption powder dispersion system with a solid content of 50wt% was obtained; the pH of the porous adsorption powder dispersion system was adjusted to neutral, the solids were collected by filtration, and the solids were dried under blast conditions at 100℃ to obtain dry porous adsorption powder.

[0086] 2) Chitosan modification treatment Chitosan (degree of deacetylation 95%, viscosity 150 mPa·s) was dissolved in an aqueous solution of acetic acid at 40℃ with a mass fraction of 2 wt% to obtain a chitosan solution with a mass fraction of 2 wt%. Then, under stirring at 800 r / min, the prepared porous adsorbent powder was added to 10 times its weight of the chitosan solution. After stirring and adsorption at room temperature for 60 min, the solid was collected by filtration to obtain porous adsorbent powder with adsorbed chitosan. Then, under stirring at 300 r / min, the porous adsorbent powder with adsorbed chitosan was added to an aqueous bath solution with a mass fraction of 3 wt% sodium hydroxide and a mass fraction of 2 wt% ethanol. The oven-dry mass fraction of the porous adsorbent powder with adsorbed chitosan was controlled to be 30 wt%. The mixture was stirred and reacted for 50 min to obtain a chitosan-modified porous adsorbent powder dispersion system.

[0087] 3) Zinc alginate modification treatment Biological sodium alginate was dissolved in deionized water at 30°C to obtain a sodium alginate solution with a mass concentration of 6 wt%. Under stirring at 800 r / min, the prepared porous adsorbent powder was added to 10 times its weight of the sodium alginate solution and stirred at room temperature for 50 min to allow for full adsorption of sodium alginate. The solid was then collected by filtration to obtain porous adsorbent powder with adsorbed sodium alginate. Then, under stirring at 300 r / min, the porous adsorbent powder with adsorbed sodium alginate was added to an aqueous bath solution with a mass fraction of 8 wt% zinc chloride. The oven-dry mass fraction of the porous adsorbent powder with adsorbed sodium alginate was controlled to be 30 wt%, and the mixture was stirred for 40 min to obtain a zinc alginate modified porous adsorbent powder dispersion system.

[0088] 4) Mixed formulations Equal volumes of chitosan-modified porous adsorbent powder dispersion system and zinc alginate-modified porous adsorbent powder dispersion system were mixed, and a thickener (sodium carboxyethyl cellulose) of 1.5% by dry weight of all effective components (chitosan-modified porous adsorbent powder and zinc alginate-modified porous adsorbent powder) was added. The mixture was stirred evenly, and the pH was adjusted to 8.5 to obtain a composite antibacterial and deodorizing dispersion system for later use.

[0089] 2. Preparation of blend spinning solution Using cellulose pulp (bamboo pulp) as raw material, a regenerated cellulose fiber spinning solution with a falling ball viscosity of 55s was prepared (composition: methyl cellulose, sodium hydroxide, and denaturant). Using a pre-spinning injection device, a composite antibacterial and deodorizing dispersion system and a pore-forming agent solution were added to the regenerated cellulose fiber spinning solution to obtain a blended spinning solution.

[0090] The regenerated cellulose fiber spinning solution contains 9.3 wt% methyl cellulose and 5.6 wt% sodium hydroxide; the added modifier in the regenerated cellulose fiber spinning solution is 3.5% of the weight of methyl cellulose; the modifier is an equal weight mixture of polyethylene glycol and urea.

[0091] The weight of the composite antibacterial and deodorizing dispersion system is added according to the following ratio: chitosan weight is 15% of the weight of cellulose A in the regenerated cellulose fiber spinning solution.

[0092] The pore-forming agent solution is added at a weight of 8% of the weight of the pore-forming agent (sodium carbonate) in the regenerated cellulose fiber spinning solution, which is a sodium carbonate solution with a mass fraction of 40 wt%.

[0093] 3. Spinning The blended spinning solution is used to spin the fibers through a coagulation bath at 50°C. After the nascent fiber bundle is drawn, a shaped fiber bundle is obtained. The fiber matrix of the shaped fiber bundle is controlled to have a semi-open structure.

[0094] The coagulation bath contains the following components: 110 g / L sulfuric acid and 310 g / L sodium sulfate, but does not use zinc sulfate.

[0095] 4. Post-processing The formed filaments are successively subjected to desulfurization modification, oiling treatment, dehydration treatment, irradiation treatment and opening treatment to obtain antibacterial and deodorizing regenerated cellulose fibers.

[0096] The desulfurization modification was carried out using a desulfurization bath at 85℃. The desulfurization bath contained Na2SO3 and a cationic modifier (3-acrylamide-2-hydroxypropyltrimethylammonium chloride), with Na2SO3 at 8.5 g / L and the cationic modifier at 45 g / L.

[0097] The oiling treatment was carried out using a mixed solution of an oil-containing agent and a weak acid at 65℃. The concentration of the oil-containing agent in the mixed solution was 6.0 g / L, the concentration of the weak acid was 8.0 g / L, and the pH value was 6.5. The weak acid was citric acid. Through the oiling treatment, the oil content of the final fiber product was 0.35 wt%, and the fiber pH was 6.9.

[0098] The dehydration process begins with pressing and dehydration using a high-pressure rolling mill, with the pressing pressure controlled at 0.4 MPa. After pressing and dehydration, the moisture regain of the fiber is 135%. Then, vacuum drying is performed, with the vacuum level controlled at 0.09 MPa and the vacuum drying temperature at 48°C, until the moisture regain of the fiber reaches 13.8%.

[0099] Irradiation treatment involves using an electron beam to irradiate the dehydrated fibers, controlling the irradiation dose at 70 kGy and the irradiation time at 60 s.

[0100] This embodiment also provides antibacterial and deodorizing regenerated cellulose fibers prepared using the aforementioned method. For example... Figure 1-2 As shown, the antibacterial and deodorizing regenerated cellulose fiber matrix prepared in Example 3 exhibits a semi-open structure with some pores in its cross-sections. Testing revealed that the antibacterial and deodorizing regenerated cellulose fiber possesses excellent antibacterial and deodorizing properties, with an inhibition rate of 95.8% against Staphylococcus aureus, 94.3% against Escherichia coli, and 96.7% against Candida albicans; its reduction rate for ammonia is 95.2%, for acetic acid 96.1%, and for isovaleric acid 97.2%; simultaneously, zinc has anti-allergic effects and good health benefits. Furthermore, the antibacterial and deodorizing regenerated cellulose fiber exhibits good functional durability and washability. After 20 washes (using the washing conditions and procedures specified in standard GB / T 8629-2017 "Testing Procedures for Household Washing and Drying of Textiles"), the inhibition rate against Staphylococcus aureus remains at 89.8%, against Escherichia coli at 89.7%, and against Candida albicans at 90.5%. Its reduction rates against ammonia and acetic acid remain at 90.1%, 90.3%, and 92.8%, respectively.

[0101] Comparative Example 1 Comparative Example 1 uses the scheme of Example 3, except that in the preparation of the composite antibacterial and deodorizing dispersion system, silica particles with a solid structure of the same particle size are used instead of zeolite with a porous structure; the rest of the process remains unchanged.

[0102] The regenerated cellulose fiber matrix prepared in Comparative Example 1 exhibits a semi-open structure with some pores in its transverse and longitudinal sections. It showed an inhibition rate of 39.2% against Staphylococcus aureus, 40.1% against Escherichia coli, and 38.6% against Candida albicans. Its reduction rates for ammonia were 35.9%, acetic acid 36.2%, and isovaleric acid 37.8%. After 20 washes, the inhibition rates for Staphylococcus aureus and Escherichia coli were 29.8%, 29.5%, and 30.5% against Candida albicans. Its reduction rates for ammonia were 30.2%, acetic acid 30.9%, and isovaleric acid 29.1%.

[0103] As can be seen from Comparative Example 1, the failure to use inorganic porous materials to adsorb and protect the active ingredients will result in a significant weakening of the antibacterial and deodorizing functions of the fibers, as well as poor durability and washability.

[0104] Comparative Example 2 Comparative Example 2 adopts the scheme of Example 3, except that in the zinc alginate modification treatment, a water-based bath solution containing calcium chloride (i.e., calcium chloride aqueous solution) of the same concentration and specification is used to form the porous adsorbent powder containing sodium alginate; the rest of the process remains unchanged.

[0105] The regenerated cellulose fiber matrix prepared in Comparative Example 2 exhibits a semi-open structure with some pores in its transverse and longitudinal sections. It showed an inhibition rate of 86.3% against Staphylococcus aureus, 87.2% against Escherichia coli, and 86.5% against Candida albicans. Its reduction rates for ammonia were 94.4%, acetic acid 95.9%, and isovaleric acid 97.1%. After 20 washes, the inhibition rates against Staphylococcus aureus and Escherichia coli were 83.6%, 83.9%, and 82.8% against Candida albicans. Its reduction rates for ammonia were 90.2%, acetic acid 90.6%, and isovaleric acid 92.9%.

[0106] As can be seen from Comparative Example 2, using calcium chloride instead of zinc chloride to shape porous adsorbent powder containing sodium alginate results in a significant decrease in the antibacterial properties of the prepared fiber, while other functions remain basically unchanged.

[0107] Comparative Example 3 Comparative Example 3 adopts the scheme of Example 3, with the following differences: 1) In the preparation of the blended spinning solution, the addition of the pore-forming agent solution is omitted; 2) In the spinning process, the conventional solid fiber spinning process is used to prepare solid fibers, so that the main body of the fiber matrix of the formed filament bundle does not present a semi-open structure; the rest of the process remains unchanged.

[0108] The regenerated cellulose fiber matrix prepared in Comparative Example 3 has a serrated solid structure. It exhibits an inhibition rate of 87.6% against Staphylococcus aureus, 86.9% against Escherichia coli, and 87.8% against Candida albicans. Its reduction rates for ammonia are 85.1%, acetic acid 86.3%, and isovaleric acid 86.2%. After 20 washes, the inhibition rates against Staphylococcus aureus and Escherichia coli are 81.8%, 81.1%, and 82.5%, respectively. Its reduction rates for ammonia are 80.1%, acetic acid 81.9%, and isovaleric acid 82.0%.

[0109] As can be seen from Comparative Example 3, omitting the addition of pore-forming agent and not controlling the semi-open structure of the fiber results in a serrated solid structure of the fiber, and the fiber specific surface area is reduced, leading to a significant decrease in antibacterial and deodorizing functions.

[0110] Comparative Example 4 Comparative Example 4 uses the scheme of Example 3, except that the irradiation treatment is omitted in the post-processing; the rest of the process remains unchanged.

[0111] The regenerated cellulose fiber matrix prepared in Comparative Example 4 exhibits a semi-open structure with some pores in its transverse and longitudinal sections. It showed an inhibition rate of 95.6% against Staphylococcus aureus, 94.4% against Escherichia coli, and 96.3% against Candida albicans. Its reduction rates for ammonia were 95.3%, acetic acid 96.0%, and isovaleric acid 96.9%. After 20 washes, the inhibition rates against Staphylococcus aureus and Escherichia coli were 87.6%, 87.2%, and 88.1% against Candida albicans. Its reduction rates for ammonia were 89.2%, acetic acid 88.8%, and isovaleric acid 89.6%.

[0112] As can be seen from Comparative Example 4, the functionality of the prepared fiber, which was not subjected to electron beam irradiation in the post-processing, showed a significant decrease in antibacterial and deodorizing properties after 20 washes compared to the fiber in Example 3, which was subjected to electron beam irradiation.

[0113] Unless otherwise stated, all percentages used in this invention are mass percentages.

[0114] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing antibacterial and deodorizing regenerated cellulose fiber, characterized in that, The process includes the following steps: preparing a composite antibacterial and deodorizing dispersion system, preparing a blending spinning solution, spinning, and post-treatment; The preparation of the composite antibacterial and deodorizing dispersion system includes the following steps: preparing porous adsorption powder, chitosan modification treatment, zinc alginate modification treatment, and mixed formulation; The method for preparing porous adsorbent powder involves grinding inorganic porous materials to a particle size D. 90 ≤1.655μm, resulting in porous adsorption powder; The chitosan modification method is as follows: after the porous adsorption powder is placed in a chitosan solution for adsorption, it is placed in an aqueous bath containing sodium hydroxide and ethanol and stirred to obtain a chitosan modified porous adsorption powder dispersion system. The method for modifying zinc alginate is as follows: after the porous adsorption powder is placed in a sodium alginate solution for adsorption, it is placed in a zinc chloride solution and stirred to obtain a zinc alginate modified porous adsorption powder dispersion system. The method for preparing the mixed formulation is to mix the chitosan-modified porous adsorption powder dispersion system, the zinc alginate-modified porous adsorption powder dispersion system, and the thickener evenly to obtain a composite antibacterial and deodorizing dispersion system. The composite antibacterial and deodorizing dispersion system is mixed with the spinning solution to form a blended spinning solution. After spinning and post-treatment, antibacterial and deodorizing regenerated cellulose fibers are obtained.

2. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, In the chitosan modification treatment, the chitosan solution is an aqueous solution of chitosan in acetic acid, and the concentration of the chitosan solution is 1-2 wt%. The weight ratio of porous adsorbent powder to chitosan solution is 1:10-20; The water-based bath solution containing sodium hydroxide and ethanol has a sodium hydroxide mass fraction of 2-3 wt%, an ethanol mass fraction of 1-2 wt%, and the balance is deionized water.

3. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, In the chitosan modification process, after the porous adsorbent powder is placed in the chitosan solution for adsorption, a porous adsorbent powder with adsorbed chitosan is obtained. The powder is then placed in an aqueous bath containing sodium hydroxide and ethanol, and the oven-dry mass fraction of the porous adsorbent powder with adsorbed chitosan is controlled to be 20-30 wt%.

4. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, In the zinc alginate modification treatment, the concentration of sodium alginate solution is 4-6 wt%. The weight ratio of porous adsorption powder to sodium alginate solution is 1:10-20; The concentration of the zinc chloride solution is 6-8 wt%.

5. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, In the zinc alginate modification process, after the porous adsorbent powder is placed in the sodium alginate solution for adsorption, a porous adsorbent powder with adsorbed sodium alginate is obtained. This powder is then placed in a zinc chloride solution, and the oven-dry mass fraction of the porous adsorbent powder with adsorbed sodium alginate is controlled to be 20-30 wt%.

6. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, In the mixed formulation, chitosan-modified porous adsorption powder dispersion system and zinc alginate-modified porous adsorption powder dispersion system are mixed in equal volumes. The amount of thickener added is 0.5-1.5% of the total dry weight of chitosan-modified porous adsorbent powder and zinc alginate-modified porous adsorbent powder in the composite antibacterial and deodorizing dispersion system.

7. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, The method for preparing the blended spinning solution is to mix a spinning solution with a cellulose content of 8.5-9.3 wt% with a composite antibacterial and deodorizing dispersion system and a pore-forming agent solution evenly to obtain the blended spinning solution. The weight of the composite antibacterial and deodorizing dispersion system should be 6-15% of the weight of chitosan in the spinning solution. The pore-forming agent solution is a sodium carbonate solution or a sodium bicarbonate solution; the weight of the pore-forming agent solution added is 5-8% of the weight of sodium carbonate or sodium bicarbonate in the regenerated cellulose fiber spinning solution.

8. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, The spinning method is to use a blended spinning solution to spin the fibers through a coagulation bath at 45-50℃. After the nascent fiber bundle is drawn, a shaped fiber bundle with a semi-open structure in the cross-section of the fiber is obtained. The coagulation bath contains the following components: 100-110 g / L sulfuric acid and 290-310 g / L sodium sulfate. Zinc sulfate is not used.

9. The method for preparing antibacterial and deodorizing regenerated cellulose fiber according to claim 1, characterized in that, The post-processing method is as follows: the spun filament bundle is subjected to desulfurization modification, oiling treatment, dehydration treatment, irradiation treatment, and opening treatment to obtain antibacterial and deodorizing regenerated cellulose fiber. The desulfurization modification is carried out using a desulfurization bath containing Na2SO3 and a cationic modifier; the cationic modifier is one of the following: hexadecyltrimethylammonium chloride, cationic polyacrylamide, 3-acrylamido-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride; In the irradiation treatment, the irradiation dose is controlled at 20-70 kGy and the irradiation time is 60-120 s.

10. An antibacterial and deodorizing regenerated cellulose fiber, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.

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