Antibacterial alginate fiber and preparation method thereof

Abstract

This application discloses a method for preparing antibacterial alginate fiber material, comprising: spun out a sodium alginate solution through a spinneret, passing it sequentially through an antibacterial solution, and then solidifying it through a coagulation liquid to obtain antibacterial alginate fiber; the antibacterial solution contains 1-5% polylysine and 1-3% calcium chloride solution. Compared with traditional alginate fiber, the prepared fiber has bactericidal properties, better liquid absorption properties, and better mechanical properties, showing promising application prospects in the health and medicine field. Furthermore, the preparation method is simpler and suitable for industrial production.

Description

Technical Field

[0001] This application relates to the field of antibacterial fiber materials, specifically an antibacterial alginate fiber and its preparation method. Background Technology

[0002] Alginate fiber, also known as calcium alginate fiber, is obtained by metal substitution between sodium alginate and calcium ions. Alginate is mainly extracted from seaweed. Alginate is a natural polysaccharide with excellent biocompatibility. At the same time, alginate fiber has excellent liquid absorption and flame retardant properties, making it an ideal medical fiber material.

[0003] Alginic acid fiber has a high moisture regain rate and excellent water absorption. After absorbing wound exudate, which contains sodium ions, the fiber transforms into a gel state, promoting wound healing. Therefore, alginate fiber is often used as a high-end medical dressing. Because alginate fiber itself lacks antibacterial elements and cannot kill bacteria, its primary function as a medical dressing is to form a gel to prevent the flow of fluids and bacteria, thus providing an antibacterial effect, but lacking bactericidal or sterilizing properties.

[0004] Amino acids, also known as polypeptides, are a type of biomaterial. They are formed by the dehydration condensation of three or more amino acid molecules, exhibiting superior biocompatibility and being easily absorbed by the human body. Furthermore, some amino acids, after binding with bacteria, may affect bacterial membrane properties, thus possessing certain antibacterial properties.

[0005] Existing technologies, such as Jin Fangyu et al., Preparation and Performance Study of Sodium Alginate / Polylysine Composite Fiber [J], *New Chemical Materials*, September 2022, Vol. 50, No. 9, pp. 134-138, disclose the preparation and performance study of sodium alginate / polylysine composite fiber. Specifically, it discloses the use of glycerol as a plasticizer, through the interaction of -COO- in sodium alginate (SA) molecules with -NH3- easily formed in polylysine (PL) molecules. + Composite fibers were prepared by salt-linked crosslinking. This method involves mixing lysine and alginate in the raw materials. Since the two react during mixing and are immiscible, the fiber preparation process involves using tweezers to grip the traction film and attach it to a roller. As the roller winds at a uniform speed, the film is drawn into a fibrous shape, and the composite fiber is continuously produced at the liquid interface. However, this method yields coarse fibers, is inefficient, and the resulting product has no promising industrial applications.

[0006] The authorized invention patent with publication number CN111996616B also discloses a size-controllable sodium alginate / polylysine self-assembled fiber. It discloses the formation of a polymer film at the interface between a sodium alginate solution and a polylysine solution using electrostatic self-assembly. Under external force, the film continuously polymerizes at the interface to form fibers. Example 1 discloses the following steps: "Sodium alginate / polylysine mixing: 1 wt% sodium alginate and 2 wt% polylysine solutions prepared above are added sequentially to a beaker with an inner diameter of 35.1 mm in a 3:1 ratio. A self-assembled polymer film is formed at the interface of the two solutions within 0.5 minutes; Fiber preparation: The self-assembled polymer film is uniformly drawn upwards at a speed of 50 cm / min to form fibers, and then dried at room temperature to obtain sodium alginate / polylysine self-assembled fibers." Therefore, this method still uses the film formed at the interface between sodium alginate and polylysine to produce fibers. This method faces insurmountable technical problems in actual industrial production.

[0007] The present disclosure aims to prepare an alginate fiber with excellent biocompatibility, and the fiber material can be applied in the field of health and medical care. The preparation method is simpler and suitable for industrial production. Summary of the Invention

[0008] This invention is based on existing antibacterial alginate fiber materials as a research foundation, aiming to prepare a functionally modified fiber of natural polysaccharides with excellent biocompatibility and antibacterial properties. This functionally modified alginate fiber can be industrially produced and applied in the medical and health field, such as being made into high-value-added products like face masks, medical dressings, and biological sutures. It also has high potential in the daily consumer goods field.

[0009] Based on this, the present invention proposes to prepare antibacterial alginate fibers using a wet spinning process. The raw materials for preparing antibacterial alginate fibers include sodium alginate, polylysine, and calcium chloride.

[0010] The prepared antibacterial alginate fiber has industrial production prospects and also possesses good antibacterial properties, biocompatibility, water absorption and dyeability.

[0011] Furthermore, the antibacterial alginate fiber prepared in this disclosure has a water absorption capacity of more than 15 g / g, and more preferably more than 17 g / g.

[0012] Furthermore, the antibacterial alginate fiber prepared in this disclosure has an absorption capacity of more than 20 g / g for physiological saline, more preferably more than 22 g / g;

[0013] Furthermore, the antibacterial alginate fiber prepared in this disclosure has an ethanol absorption capacity greater than 5 g / g, preferably greater than 8 g / g.

[0014] In some embodiments, the antibacterial rate of the antibacterial alginate fiber prepared according to this disclosure is greater than 70%, preferably greater than 80%, and more preferably greater than 90%.

[0015] In some embodiments, the antibacterial alginate fiber prepared according to this disclosure has a fiber diameter of less than 200 micrometers;

[0016] Preferably, the antibacterial alginate fiber prepared in this disclosure has a diameter of less than 150 micrometers, more preferably less than 100 micrometers;

[0017] In some embodiments, the antibacterial alginate fiber prepared according to this disclosure has a strength greater than 1.8 cN / dtex, preferably greater than 2.0 cN / dtex, more preferably greater than 2.6 cN / dtex, and even more preferably greater than 3.0 cN / dtex.

[0018] In some experiments, this disclosure also provides a method for preparing an antibacterial alginate fiber material, comprising the following steps:

[0019] (1) Prepare sodium alginate solution;

[0020] (2) Prepare antibacterial solution;

[0021] (3) Prepare solidified liquid;

[0022] (4) Wet spinning to prepare antibacterial alginate fiber.

[0023] In step (1), the sodium alginate solution is sprayed out through a spinneret, passes through an antibacterial solution, and is then solidified by a coagulation liquid to obtain antibacterial seaweed fiber.

[0024] The sodium alginate solution is prepared by dissolving sodium alginate in water, wherein the sodium alginate content is 1-6%, preferably 2-5%, and more preferably 4%.

[0025] Furthermore, the sodium alginate solution is degassed to remove air bubbles from the sodium alginate solution;

[0026] The degassing includes static degassing and / or negative pressure degassing;

[0027] In some embodiments, the preparation of the antibacterial solution involves weighing out an antibacterial agent, dissolving it in water, and stirring.

[0028] The antibacterial agent is polylysine, and the molecular weight of the polylysine is 3000-5000, preferably 3500-4500, and more preferably 3500-3600.

[0029] Furthermore, the antibacterial solution contains 1-5% polylysine by weight, preferably 1-4%, and more preferably 2-4%.

[0030] Furthermore, a curing agent, namely calcium chloride solution, is also added to the antibacterial solution.

[0031] Furthermore, the content of the calcium chloride solution is 1-5%, preferably 1-3%, and more preferably 1-2%.

[0032] In some embodiments, the content of antibacterial agent to curing agent in the antibacterial solution is 2-4:1-2, and preferably the content of antibacterial agent to curing agent is 2:1.

[0033] In some embodiments, the preparation of the coagulation liquid involves adding a curing agent to water and stirring, wherein the curing agent is calcium chloride;

[0034] Furthermore, the calcium chloride content in the coagulation liquid is 5-10% by weight, preferably 5-8%, and more preferably 6%.

[0035] In some embodiments, the wet spinning is to use a screw wet spinning machine to spin the sodium alginate solution in step (1).

[0036] Furthermore, the sodium alginate solution passes through a spinneret into an antibacterial solution tank for antibacterial finishing, resulting in nascent fibers.

[0037] Furthermore, the nascent fibers, after passing through the antibacterial solution tank, are further cured in a curing tank containing a coagulating liquid to obtain antibacterial fibers.

[0038] Furthermore, the ratio of the stretching rate of the solidification tank of the coagulation liquid to the stretching rate of the antibacterial liquid tank of the antibacterial solution is greater than 2, and more preferably the stretching ratio is greater than 3.

[0039] The diameter of the spinneret's spinneret orifice is less than 100 μm, and more preferably, the diameter of the spinneret's spinneret orifice is less than 75 μm.

[0040] More preferably, during the antibacterial finishing process of the sodium alginate solution entering the antibacterial solution tank through the spinneret, the finishing time is less than 30 seconds, preferably less than 20 seconds, and more preferably less than 10 seconds.

[0041] Preferably, the sodium alginate solution enters the antibacterial solution tank through the spinneret for antibacterial finishing, and the finishing time is greater than 5 seconds.

[0042] Preferably, the nascent fibers in the antibacterial solution tank are subjected to deep curing in a curing tank containing a coagulating liquid, and the curing time is greater than 10s, preferably greater than 20s, and more preferably greater than 40s.

[0043] Specifically, a method for preparing an antibacterial alginate fiber material is further disclosed, including the following steps;

[0044] (1) Prepare sodium alginate solution;

[0045] Weigh out sodium alginate and add it to water, stir to prepare a solution with a sodium alginate content of 1-6%, and let it stand and / or remove bubbles under vacuum to obtain a sodium alginate spinning solution.

[0046] (2) Prepare antibacterial solution;

[0047] Weigh out the antibacterial agent and add it to water, stir, and prepare a solution with an antibacterial agent content of 1-5%, preferably 2-4%;

[0048] The antibacterial agent is polylysine, and the molecular weight of polylysine is 3000-5000.

[0049] A curing agent, namely calcium chloride, may also be added to the antibacterial solution. The amount of calcium chloride used is 1-5%, preferably 1-2%.

[0050] (3) Prepare solidified liquid.

[0051] Weigh out the curing agent and add it to the water, stir, and prepare a solidified liquid with a curing agent content of 5-10%.

[0052] (4) Wet spinning;

[0053] The sodium alginate in step (1) was wet-spun using a screw spinning machine.

[0054] Specifically, the sodium alginate solution prepared in step (1) is placed into the spinning solution spinning tank, the antibacterial solution prepared in step (2) is added into the antibacterial solution tank, and the coagulation liquid prepared in step (3) is added into the solidification tank.

[0055] The sodium alginate solution in step (1) is sprayed out through a spinneret, passed through an antibacterial solution, and then solidified through a coagulation liquid to obtain antibacterial seaweed fiber.

[0056] The diameter of the spinneret's spinneret holes is less than 100 μm.

[0057] The ratio of the fiber's stretching rate in the curing tank of the coagulation solution to the stretching rate in the antibacterial solution tank is greater than 2, and more preferably greater than 3.

[0058] In the wet spinning process, the sodium alginate solution enters the antibacterial solution tank through the spinneret for antibacterial finishing. The finishing time is 5-30 seconds, preferably 10-20 seconds.

[0059] The nascent fibers in the antibacterial solution tank are subjected to deep curing in a curing tank containing a coagulating liquid, wherein the curing time is greater than 10s, preferably greater than 20s, and more preferably greater than 40s.

[0060] Compared with existing technologies, the antibacterial alginate fiber material prepared by this invention has at least the following beneficial effects:

[0061] 1. Compared with traditional alginate fiber, the antibacterial fiber prepared in this disclosure has bactericidal properties. Specifically, it utilizes the antibacterial agent polylysine, which has excellent biological properties and can bind to the cell membrane of bacteria, affecting bacterial metabolism and achieving the purpose of sterilization.

[0062] 2. Unlike other antibacterial agents that are post-treated onto alginate fibers during spinning, this disclosure involves direct treatment during the spinning process, resulting in high treatment efficiency, excellent antibacterial properties, and superior fixation of the antibacterial agent, leading to long-lasting antibacterial performance.

[0063] 3. Compared with traditional alginate fiber and antibacterial alginate fiber, the antibacterial alginate fiber disclosed herein has excellent mechanical properties and liquid absorption properties, and has good application prospects in the health and medicine field.

[0064] 4. Compared with other finishing and spinning methods for alginate fibers, the preparation method disclosed herein is simpler and can be applied to industrial production. Attached Figure Description

[0065] Figure 1 : Schematic diagram of the preparation process of the present invention.

[0066] The components include: 1 spinneret, 2 antibacterial solvent solution tank, 3 guide roller, 4 curing tank, 5 drying oven, and 6 winding roller.

[0067] Figure 2 : Schematic diagram of the reaction of the fibers of the present invention in the antibacterial liquid tank and the curing tank. Detailed Implementation

[0068] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0069] Specifically, this disclosure provides a method for preparing an antibacterial alginate fiber material, comprising the following steps:

[0070] (1) Prepare sodium alginate solution;

[0071] Weigh out sodium alginate and add it to water, stir to prepare a solution with a sodium alginate content of 1-6%, and let it stand and / or remove bubbles under vacuum to obtain a sodium alginate spinning solution.

[0072] The sodium alginate content can be 1%, 3%, 4%, or 6%.

[0073] The process of removing bubbles from sodium alginate can be carried out by standing, vacuum degassing, or a combination of standing and vacuum degassing.

[0074] (2) Prepare antibacterial solution;

[0075] Weigh out the antibacterial agent and add it to the water, stir, and prepare a solution with an antibacterial agent content of 1-5%.

[0076] The antibacterial agent is polylysine, and the molecular weight of polylysine is 3000-5000.

[0077] The molecular weight of the polylysine is any one of 3800, 4200, or 4800.

[0078] The amount of polylysine used can be 1%, 2%, 3%, 4%, or 5%.

[0079] A curing agent, namely calcium chloride, may also be added to the antibacterial solution, and the amount of calcium chloride used is 1-5%.

[0080] The amount of calcium chloride used can be 1%, 2%, 4%, or 5%.

[0081] Furthermore, the ratio of polylysine to calcium chloride is 2:1, 3:2, 4:1, or 5:2.

[0082] The amount of calcium chloride used is less than the amount of polylysine.

[0083] Because calcium chloride and alginate solidify very quickly, when the amount of calcium chloride used is high, calcium chloride will quickly form a dense solidified state on the surface of alginate during the solidification process, thereby preventing the solidification reaction of other substances (polylysine) with sodium alginate and affecting the finishing effect of antibacterial components.

[0084] In step (2), this disclosure uses polylysine as an antibacterial material. Polylysine is a linear polymer. When it comes into contact with the cell membrane, it disrupts the integrity of the cell membrane, easily causing cell membrane rupture and inducing microbial death. Moreover, its antibacterial properties are different from inorganic antibacterial agents or other polymeric antibacterial agents, and it has bioincompatible properties. Polylysine exhibits excellent biocompatibility.

[0085] In addition, since polylysine is positively charged, when sodium alginate passes through a lysine solution, alginic acid can quickly combine with lysine through ionic forces. This combination is fast and achieves pre-curing of alginic acid, giving the nascent fibers an antibacterial effect.

[0086] Because polylysine and sodium alginate are bonded by ionic bonds, the antibacterial agent content in the antibacterial solution increases rapidly during the finishing process. Therefore, the antibacterial solution needs to be continuously replenished during the spinning process. This spinning process will first cause differences in the performance of the spun fibers (the antibacterial agent content on the spun fibers is unstable before and after the process), and waste of antibacterial agent. In addition, due to the rapid absorption of polylysine, the dispersion of polylysine will be very uneven. At the same time, due to the uneven solidification of the nascent fibers, the fibers are prone to breakage, which may lead to spinning failure in severe cases.

[0087] To address the aforementioned problems in production practice, this invention incorporates a curing agent into the antibacterial solution. The added curing agent is calcium chloride. Calcium chloride contains small calcium ions with high activity. The addition of calcium chloride significantly buffers the adsorption effect of polylysine, resulting in more uniform adsorption of polylysine on the nascent fibers. This prevents significant localized curing of the fibers and ensures a relatively uniform distribution of the antibacterial agent. The spinning process is greatly simplified, and the fiber properties become more stable. Furthermore, the addition of calcium chloride allows the fibers to withstand a higher draw ratio, thereby obtaining finished fibers with higher orientation and improving the mechanical properties of the fibers.

[0088] The content of curing agent in the antibacterial liquid, specifically the ratio of antibacterial agent to curing agent, directly affects the antibacterial and mechanical properties. The inventors found that when the amount of curing agent is less than that of antibacterial agent, the fiber exhibits better antibacterial and mechanical properties. In particular, when the amount of curing agent is less than half or even more than that of antibacterial agent, the overall performance of the fiber is optimal.

[0089] (3) Prepare solidified liquid;

[0090] Weigh out the curing agent and add it to the water, stir, and prepare a solidified liquid with a curing agent content of 5-10%.

[0091] The curing agent is one or more of calcium chloride, copper sulfate, and calcium sulfate.

[0092] The preferred curing agent is calcium chloride, wherein the amount of calcium chloride used can be 5%, 8%, 9%, or 10%.

[0093] In the coagulation bath, divalent metal ions can be selected for curing. Since the nascent fiber has already undergone pre-curing, the concentration of the curing agent in the coagulation bath is significantly increased, ensuring that sufficient ion exchange occurs during the fiber stretching process in the coagulation bath, resulting in high-performance fibers that are insoluble in water.

[0094] The preferred curing agent in this invention is calcium chloride, which has high ion exchange efficiency and is more suitable for high draw ratio process conditions, enabling the fiber to have better mechanical properties.

[0095] (4) Wet spinning;

[0096] The sodium alginate in step (1) was wet-spun using a screw spinning machine.

[0097] Wet spinning is a relatively mature method for preparing alginate fibers. However, the performance of the fibers produced varies greatly depending on the different process parameters in the wet spinning method. This invention uses a screw extrusion wet spinning machine to extrude sodium alginate spinning solution into an antibacterial solution tank through a screw, and then mechanically pulls it into a coagulation bath. After that, the antibacterial alginate fiber material is obtained through a subsequent winding device.

[0098] Specifically, the sodium alginate solution prepared in step (1) is placed into the spinning solution spinning tank, the antibacterial solution prepared in step (2) is added into the antibacterial solution tank, and the coagulation liquid prepared in step (3) is added into the solidification tank.

[0099] The sodium alginate solution in step (1) is sprayed out through a spinneret, passed through an antibacterial solution, and then solidified through a coagulation liquid to obtain antibacterial seaweed fiber.

[0100] The diameter of the spinneret's spinneret orifice is less than 100 μm;

[0101] The diameter of the spinneret orifice can be 35μm, 50μm, 75μm, or 100μm.

[0102] The spinneret determines the fiber thickness and mechanical properties. The larger the spinneret orifice, the greater the fiber draw ratio. Under these conditions, the fiber orientation is higher, and the mechanical properties of the fiber are significantly improved.

[0103] The ratio of the fiber's stretching rate in the curing tank of the coagulation solution to the stretching rate in the antibacterial solution tank is greater than 2, and more preferably greater than 3.

[0104] The ratio of the stretching rate of the curing tank to the stretching rate of the antibacterial liquid tank can be 2, 3, or 4.

[0105] More specifically, in other embodiments, the antibacterial alginate fibers prepared according to the above method of this disclosure have excellent properties.

[0106] The antibacterial alginate fiber prepared in this disclosure has a water absorption capacity of more than 15 g / g.

[0107] Specifically, it can be 16g / g, 17g / g, 18g / g, 19g / g, or 20g / g.

[0108] The water absorption of fibers is determined by the gaps between fibers and the density of fibers. The antibacterial alginate fibers prepared in this disclosure are insoluble in water. Alginate fibers have a lot of hydrophilic groups, and sodium alginate is not completely cured during the curing process. Therefore, alginate fibers have excellent water absorption rate, which is controlled by the curing agent and the stretch ratio in the coagulation bath.

[0109] Furthermore, the antibacterial alginate fiber prepared in this disclosure has an absorption capacity of more than 20 g / g for physiological saline, more preferably more than 22 g / g;

[0110] The volume of physiological saline absorbed can be 20g / g, 22g / g, 25g / g, or 30g / g.

[0111] The antibacterial alginate fiber prepared in this disclosure has the property of absorbing physiological saline gelation. This property is mainly due to the replacement of sodium ions in physiological saline with calcium ions in alginate, which increases the sodium alginate content in the fiber, making the fiber have higher liquid absorption performance and gelation.

[0112] Furthermore, the antibacterial alginate fiber prepared in this disclosure has an ethanol absorption capacity greater than 5 g / g, preferably greater than 8 g / g.

[0113] Alcohol is a non-polar solvent. Alcohol and antibacterial alginate fiber are immiscible, and alginate fiber absorbs little alcohol from nearby sources, making it difficult to fix alcohol.

[0114] In some embodiments, the antibacterial alginate fiber prepared according to this disclosure has an antibacterial rate of greater than 70%, preferably greater than 80%, and more preferably greater than 90%.

[0115] In some embodiments, the antibacterial alginate fiber prepared according to this disclosure has a fiber diameter of less than 200 micrometers;

[0116] Preferably, the antibacterial alginate fiber prepared in this disclosure has a diameter of less than 150 micrometers, more preferably less than 100 micrometers;

[0117] In some embodiments, the antibacterial alginate fiber prepared according to this disclosure has a strength greater than 1.8 cN / dtex, preferably greater than 2.0 cN / dtex, and more preferably greater than 2.6 cN / dtex.

[0118] Figure 1 The diagram shown is a process schematic of an embodiment of the present invention. This process is not a schematic diagram of a specific production workshop. In this process, the seaweed fiber bundle is ejected through the spinneret 1, first undergoes initial coagulation in the antibacterial solvent solution tank 2, and adsorbs the antibacterial agent. Then, the fiber is stretched by the guide roller 3 and introduced into the curing tank 4 for coagulation and stretching. After fiber formation, it is sent to the drying box 5 for drying by the guide roller. Finally, the dried fiber is collected on the winding roller 6.

[0119] In actual production processes, curing tanks and antibacterial solvent solution tanks can be stacked depending on the actual situation. This is mainly used to control the travel distance of the fiber in the curing tank and antibacterial solvent solution tank, thereby controlling the performance of the fiber prepared by spinning.

[0120] Figure 2 This demonstrates the process of sodium alginate nascent fibers being cured by adsorption of substances into the fibers in an antibacterial solvent solution tank and a curing tank. In the antibacterial solvent solution tank, calcium chloride and antibacterial agents are simultaneously adsorbed onto and react with the fibers. Due to the smaller volume of calcium chloride, adsorption is faster, slowing down the adsorption rate of the antibacterial agent and effectively improving the uniformity of adsorption. In the curing tank, the fibers are subjected to significant stretching, becoming thinner, while calcium chloride in the coagulation bath is further adsorbed and cured into the fibers, thereby improving the mechanical properties of the fibers.

[0121] Example 1

[0122] Sodium alginate solutions were prepared at concentrations of 3%, 4%, and 5%. The prepared sodium alginate solutions were then placed in a vacuum apparatus for vacuum degassing to obtain sodium alginate spinning solutions of three concentrations.

[0123] To prepare antibacterial solutions, add polylysine to water and stir to prepare 2%, 4%, and 5% solutions respectively.

[0124] In addition, take a certain amount of the polylysine solution prepared above, add 2% calcium chloride to 2% and 4% polylysine solutions, add 1% calcium chloride to 2% polylysine, add 2% or 5% calcium chloride to 5% polylysine solution, and add 8% calcium chloride to 4% polylysine solution to obtain an antibacterial solution.

[0125] To prepare coagulation solutions, add calcium chloride to water to prepare coagulation baths with concentrations of 3%, 5%, 8%, and 10%.

[0126] Example 2

[0127] Sodium alginate was wet-spun using a screw spinning machine.

[0128] The sodium alginate solution prepared in Example 1 was placed into the spinning solution spinning tank, the antibacterial solution was prepared and added to the antibacterial solution tank, and the coagulation liquid was prepared and added to the curing tank.

[0129] Sodium alginate solution is sprayed out through a spinneret, passes through an antibacterial solution, and then solidifies through a coagulation liquid to obtain antibacterial seaweed fiber.

[0130] The diameters of the spinneret orifices were selected as 50μm, 75μm, and 100μm, respectively.

[0131] The ratios of the stretching rate of the curing tank to the stretching rate of the antibacterial liquid tank were set to 1, 1.5, 2, 3, and 4, respectively.

[0132] Example 3

[0133] Specifically, regarding the solutions provided in Examples 1 and 2, a method for preparing an antibacterial alginate fiber material is described, comprising the following steps:

[0134] (1) Prepare sodium alginate solution;

[0135] (2) Prepare antibacterial solution;

[0136] (3) Prepare solidified liquid;

[0137] (4) Wet spinning;

[0138] The nascent spun fibers are immersed in the antibacterial finishing solution for 10 seconds and in the coagulation bath for 40 seconds.

[0139] The time the fiber spends in the antibacterial solution tank and the curing tank is determined by the length of the fiber immersed in the solution.

[0140] Based on the parameter selection designed in Examples 1 and 2, specific examples are shown in the table below.

[0141]

[0142] The antibacterial material obtained by AK in the above experiment was tested, including appearance testing, infrared testing, etc., as follows:

[0143] Prepare physiological saline solution, place the prepared fiber bundle in the solution (test water, physiological saline and alcohol respectively) to fully absorb the liquid, weigh the change in fiber mass after full absorption, and obtain the amount of liquid absorbed;

[0144] The mechanical properties of the fibers were analyzed using an electronic monofilament tensile testing machine.

[0145] The antibacterial properties of fibers are evaluated according to the national standard "Evaluation of Antibacterial Properties of Textiles".

[0146] The specific fiber properties obtained from the tests are shown in the table below:

[0147]

[0148] Based on the test results above, in Scheme A, the polylysine content is low, and the antibacterial finishing tank lacks calcium chloride. During the experiment, we observed frequent fiber breakage in the antibacterial solution, hindering smooth spinning. This is likely due to insufficient curing of polylysine onto sodium alginate and uneven adsorption of polylysine. Conversely, adding 2% calcium chloride curing agent to the antibacterial solution significantly improved the spinning process, noticeably reducing fiber breakage in the antibacterial solution.

[0149] In Scheme C, the antibacterial liquid contains 5% polylysine and 5% calcium chloride. The antibacterial liquid tank contains a large amount of curing components, and the concentrations of calcium chloride and polylysine in the antibacterial liquid tank are relatively high. This will cause uneven curing. In the subsequent stretching process, due to the large stretching ratio, the fibers will break significantly after entering the coagulation bath.

[0150] Regarding the spinning situation in Scheme E, when sodium alginate enters the antibacterial solution coagulation bath, the calcium chloride content in the antibacterial solution tank is relatively high, and the sodium alginate spinning solution will form rapidly. When the fiber enters the coagulation solution, because the calcium chloride content in the coagulation solution is lower than that in the antibacterial solution, the fiber is prone to breakage in the coagulation bath at high draw speeds. In addition, it was also found in the experiment that if the draw ratio is further increased, the fiber is more prone to breakage in the coagulation bath, making the spinning process unsuccessful.

[0151] In Scheme I, spinning is more difficult than in Schemes A and F. This may be due to the increased concentration of sodium alginate, which causes a sharp increase in the viscosity of the spinning solution. Although the amount of polylysine in the antibacterial agent was increased, the antibacterial agent could not make the high-viscosity sodium alginate form relatively stable nascent fibers in the antibacterial solution tank, resulting in large-area fiber breakage in the antibacterial solution tank.

[0152] From a comprehensive perspective on spinning, while the antibacterial agent polylysine can solidify sodium alginate, the solidification effect is not as good as that of an antibacterial solution containing calcium chloride. This also indicates that when the viscosity of sodium alginate increases, polylysine may not be able to quickly form nascent fibers, making spinning difficult. Regarding spinning performance, spinning is generally smoother when calcium chloride is present in the antibacterial bath. However, based on the results of scheme E, the amount of calcium chloride also affects fiber breakage during drawing. When the calcium chloride content in the antibacterial solution is too high, the nascent fibers solidify more thoroughly in the antibacterial bath, making them prone to breakage during subsequent drawing, resulting in unclear orientation and severely impacting the fiber's mechanical properties.

[0153] Regarding antibacterial properties, the table shows that the overall effect is greatly influenced by the content of antibacterial agents, but it is also affected by the ratio in the antibacterial solution.

[0154] As seen in the tests of schemes A, B, H, and J, scheme J was not tested because it was difficult to form fibers. Regarding schemes A and B, the addition of calcium chloride in scheme B helps improve antibacterial properties. This may be because the polylysine in scheme A, due to its large molecular weight, has a relatively uneven distribution based on molecular and ionic forces, resulting in reduced overall antibacterial properties of the fiber. The calcium chloride introduced in scheme B indirectly acts as a slow adsorption agent, allowing the antibacterial agent to be more evenly adsorbed onto the sodium alginate nascent fiber, thus contributing to improved antibacterial performance.

[0155] Compared to Scheme B, Scheme H has a lower calcium chloride content and a higher sodium alginate viscosity, resulting in a relatively higher overall antibacterial performance. This is mainly because the solidification rate of sodium alginate in the antibacterial solution tank is related to the solidification rate of calcium chloride and sodium alginate. When the solidification rate of calcium chloride and sodium alginate is too fast, the surface of the nascent fiber becomes dense, which will prevent the adsorption of antibacterial agents and thus affect the antibacterial performance.

[0156] The absorption of liquid is mainly affected by the density of the fiber and the concentration of the spinning solution. Generally speaking, the higher the concentration of sodium alginate in the spinning solution, the smaller the fiber draw ratio, or the coarser the spinneret, the higher the liquid absorption is likely to be. This may be determined by the sodium alginate content in the fiber.

[0157] Looking at schemes D, G, H, and K, scheme D's liquid absorption capacity is inferior to that of schemes G, H, and K. However, the liquid absorption performance of schemes G, H, and K is similar. This is mainly due to their coagulation conditions and the similar concentrations of sodium alginate solutions, which result in similar fiber spinning effects.

[0158] Regarding mechanical properties, they are related to both fiber forming and stretching. The speed and extent of coagulation formation affect the microstructure of the nascent fiber, while stretching affects the fiber orientation, which in turn affects the fiber properties.

[0159] From schemes D, G, H, and K, the prepared fibers all exhibit good mechanical properties, with a breaking strength greater than 1.8 cN / dtex, and scheme K exceeding 2.0 cN / dtex. This is mainly due to the smoother coagulation in the antibacterial solution bath and the higher draw ratio. However, schemes B, C, and E have relatively high calcium chloride content in the antibacterial solution bath, resulting in insufficient curing of the nascent fibers and a significant reduction in the mechanical properties of the prepared fibers.

[0160] Example 4

[0161] Using the process parameters of scheme D as a basis, the effects of the immersion time of the fiber in the antibacterial liquid tank and the coagulation bath tank on the fiber properties were studied.

[0162] It can be observed that when the nascent fibers are immersed in the antibacterial liquid bath for more than 30 seconds, they are easily broken when they are drawn with a 3 times draw ratio in the coagulation bath.

[0163] When the time that the nascent fibers spend in the antibacterial solution tank is short, such as less than 10 seconds, the antibacterial properties of the fibers are reduced, an effect that is known to those skilled in the art.

[0164] When the initial fiber spends a short time in the coagulation bath, such as less than 20 seconds, the fiber coagulation and shaping are poor, and the fiber strength is reduced, but the liquid absorption is improved to a certain extent.

[0165] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. An antibacterial alginate fiber, prepared by a wet spinning process, characterized in that, The raw materials for preparing antibacterial alginate fiber include sodium alginate, polylysine, and calcium chloride; The molecular weight of the polylysine is 3000-5000. The antibacterial alginate fiber has a water absorption capacity of more than 15 g / g; The antibacterial alginate fiber has an absorption capacity of more than 20 g / g for physiological saline. The antibacterial alginate fiber has an ethanol absorption capacity of more than 5 g / g; The antibacterial alginate fiber is prepared by wet spinning; The wet spinning process involves extruding a sodium alginate solution through a spinneret, passing it sequentially through an antibacterial solution, and then solidifying it with a coagulation liquid to obtain antibacterial alginate fibers. The concentration of sodium alginate solution is 3-4%; The antibacterial solution contains 2-4% polylysine by weight. The antibacterial solution also contains calcium chloride, and the content of calcium chloride is 1-2%. The ratio of polylysine to calcium chloride in the antibacterial solution is 2-4:1-2; The calcium chloride content in the coagulation solution is 5-10% by weight.

2. An antibacterial alginate fiber as described in claim 1, characterized in that, The antibacterial alginate fiber has an antibacterial rate of greater than 80%. The antibacterial alginate fiber has a fiber diameter of less than 200 micrometers; The antibacterial alginate fiber has a strength greater than 1.8 cN / dtex.

3. A method for preparing an antibacterial alginate fiber material, comprising the following steps: (1) Prepare sodium alginate solution; (2) Prepare antibacterial solution; (3) Prepare solidified liquid; (4) Wet spinning; in, Step (4) involves spraying the sodium alginate solution from step (1) through a spinneret, passing it through an antibacterial solution, and then solidifying it with a coagulation liquid to obtain antibacterial alginate fiber. The sodium alginate solution is prepared by dissolving sodium alginate in water, with a sodium alginate content of 3-4%. The antibacterial solution contains 2-4% polylysine by weight. The antibacterial solution also contains calcium chloride, and the content of calcium chloride is 1-2%. The ratio of polylysine to calcium chloride in the antibacterial solution is 2-4:1-2; The calcium chloride content in the coagulation solution is 5-10% by weight.

4. A method for preparing the antibacterial alginate fiber material as described in claim 3, characterized in that, The ratio of polylysine to calcium chloride in the antibacterial solution is 2:

1.

5. A method for preparing the antibacterial alginate fiber material as described in claim 3, characterized in that, The ratio of the stretching rate of the solidification tank of the coagulation liquid to the stretching rate of the antibacterial solution tank of the antibacterial solution is greater than 2. The diameter of the spinneret's spinneret holes is less than 100 μm.

6. A method for preparing the antibacterial alginate fiber material as described in claim 3, characterized in that, The sodium alginate solution enters the antibacterial solution tank through the spinneret for antibacterial finishing, and the finishing time is less than 30 seconds.

7. A method for preparing the antibacterial alginate fiber material as described in claim 3, characterized in that, The nascent fibers in the antibacterial solution tank are subjected to deep curing in a curing tank containing coagulation liquid, with a curing time of more than 20 seconds.

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