Non-elution type antibacterial spun-bonded non-woven fabric, preparation process and application thereof

Abstract

This invention belongs to the field of nonwoven technology, and relates to a non-leaching antibacterial spunbond nonwoven fabric, its preparation process, and its application. The nonwoven fabric is prepared by spunbonding polypropylene, antibacterial modified montmorillonite, and a silane coupling agent as the main raw materials. The antibacterial modified montmorillonite is obtained by mechanically grinding montmorillonite, inserting a cationic antibacterial agent, polypropylene grafted with maleic anhydride, and polypropylene powder between its layers. It possesses antibacterial properties, with an inhibition rate of >65% against Staphylococcus aureus, >65% against Escherichia coli, and >50% against Candida albicans, and a cell survival rate >92%. It also exhibits excellent mechanical strength, with a transverse elongation of 95-110% and a transverse breaking force of 40-47 N; a longitudinal elongation of 75-85% and a longitudinal breaking force of 90-100 N. This nonwoven fabric is prepared by superimposing and laminating it with meltblown nonwoven fabric, breathable membrane and coating layer to obtain antibacterial spunbond meltblown composite nonwoven fabric, antibacterial coated nonwoven fabric and antibacterial coated nonwoven fabric.

Description

Technical Field

[0001] This invention belongs to the field of nonwoven technology, and relates to a spunbond nonwoven fabric, particularly to a non-leaching antibacterial spunbond nonwoven fabric and its preparation process and application. Background Technology

[0002] The main materials of spunbond nonwoven fabrics include polyester and polypropylene, with polypropylene spunbond nonwoven fabrics being the most common in medical and hygiene products. Polypropylene spunbond nonwoven fabric, also known as polypropylene spunbond nonwoven fabric, is a new generation of environmentally friendly material, characterized by water repellency, breathability, flexibility, non-flammability, non-toxicity, non-irritation, and a wide range of colors. During the pandemic, ordinary protective products cannot meet the needs for resisting bacteria and viruses, and consumables such as masks and protective clothing may become new sources of infection after use. With the increasing application of spunbond nonwoven fabrics, the demand for safe, efficient, durable, and non-leaching antibacterial spunbond nonwoven fabrics is also growing rapidly.

[0003] The existing antibacterial spunbond nonwoven fabrics have the following problems: 1. Antibacterial agents are difficult to be compatible with polypropylene, resulting in poor dispersibility of the blended system; 2. Most antibacterial spunbond nonwoven fabrics on the market achieve temporary antibacterial effects by spraying / soaking antibacterial agent solutions, resulting in low production efficiency and difficulty in ensuring long-lasting antibacterial effects; 3. Coating-type antibacterial agents are easy to fall off the surface of nonwoven fabrics and may cause cytotoxicity to normal cells.

[0004] To address the above issues, Chinese invention patent CN111424432B discloses a non-leaching, long-lasting antibacterial protective nonwoven fabric, its preparation method, and its application. The method involves uniformly spraying an antibacterial liquid onto the nonwoven fabric or immersing the nonwoven fabric in the antibacterial liquid. After organosilicon molecular polymerization, the bonding force between the nonwoven fabric fibers and the antibacterial active substances is enhanced. High-temperature setting then oriented and loads ammonium salts and nano-silver, among other antibacterial active substances, onto the surface of the nonwoven fabric, thus producing an antibacterial protective nonwoven fabric. This technology achieves antibacterial properties through the preparation of nonwoven fabric and antibacterial liquid, spraying or immersing in the antibacterial liquid, and high-temperature setting. However, this process is excessive, resource-intensive, and the coating is prone to peeling off during use, resulting in low production efficiency and hindering widespread application.

[0005] Chinese invention patent CN111172749A discloses an antibacterial and antiviral nonwoven fabric and its preparation method, as well as a mask containing the same. The method involves preparing a sol by combining inorganic antibacterial agents such as titanium dioxide and nano-zinc oxide with organic antibacterial agents such as chitosan and quaternary ammonium salts. The second layer of the mask, treated with organic fluorine, is then immersed in the sol to prepare the antibacterial and antiviral nonwoven fabric. This nonwoven fabric is then combined with a first fabric layer, an anti-smog filter layer, and a second fabric layer to prepare the mask. However, the sol-soaking method is inefficient, and adding a new fabric layer to the existing mask structure complicates the manufacturing process, potentially affecting the original mask's air resistance. This results in low production efficiency and difficulty in mass production.

[0006] Chinese invention patent CN113968585A discloses a modified nano-montmorillonite, a nano-tackifier, and their preparation methods and applications. It describes how long-chain active groups are introduced between the nano-montmorillonite sheets via an intercalation reaction in solution, altering the hydrophilicity and hydrophobicity of the nano-montmorillonite itself. This patent demonstrates the feasibility of modifying montmorillonite in solution, but the process is complex, time-consuming, and yields low output, making it unsuitable for industrial production.

[0007] Chinese invention patent CN100519415C discloses a method for preparing sheet-exfoliated nano-montmorillonite, which uses a mechanochemical method to prepare nano-montmorillonite. Sodium-based montmorillonite is organically intercalated and modified by mechanochemical method to obtain sheet-exfoliated nano-montmorillonite powder. The process is simple and suitable for industrial production. However, the method does not specify the application scenarios and requires separate development of related processes for different products.

[0008] Organic modification of montmorillonite is currently a hot research topic. Surfactant treatment can alter the microenvironment of montmorillonite. Quaternary ammonium salts, as surfactants, can undergo ion exchange with cations in montmorillonite in solvents, entering the interlayer spaces and increasing the interlayer spacing, thus improving the performance of montmorillonite. The alkyl chains outside the layers further enhance the oleophilicity of montmorillonite, strengthening the affinity between montmorillonite layers and resin molecular chains, reducing the surface energy of montmorillonite, and making it easier for resin monomers or molecular chains to insert into the interlayer spaces to form nanocomposites. Quaternary ammonium salt-intercalated modified montmorillonite exhibits certain antibacterial properties and can improve the strength of polypropylene; however, its compatibility with polypropylene needs careful consideration. The addition of maleic anhydride grafted onto polypropylene can improve its compatibility, but the dispersibility of polypropylene grafted with maleic anhydride with polypropylene and modified montmorillonite also needs to be considered.

[0009] Modified montmorillonite and polypropylene matrix can be firmly bonded through intercalation via nano-effects during melt blending modification. The melt intercalation method only requires mixing polypropylene and montmorillonite, and then uniformly mixing them in an extruder to obtain a nanocomposite material. Polymer molecules can intercalate into the lamellar spaces of montmorillonite, improving the toughness, thermal stability, aging resistance, and tensile strength of the polypropylene material itself. This process requires minimal solvents, is simple to operate, and only requires conventional equipment such as screw extruders and mixers. Organic modification and grafting maleic anhydride onto polypropylene can improve the compatibility of montmorillonite and polypropylene. Currently, most polypropylene-montmorillonite nanocomposites focus on reinforcing polypropylene; however, this robust intercalation method, while ensuring the stability of cationic modifiers using montmorillonite as a carrier in polypropylene, has not been extensively addressed.

[0010] In view of the shortcomings of existing technologies, there is an urgent need to develop a new type of antibacterial spunbond nonwoven fabric that can firmly bond the antibacterial unit with the spunbond nonwoven fabric, and has a simple production process that can be continuously produced on a large scale, which is conducive to its promotion and application. Summary of the Invention

[0011] Based on this, the purpose of the present invention is to provide a non-leaching antibacterial spunbond nonwoven fabric and its preparation process, so as to overcome the shortcomings of the prior art.

[0012] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a non-leaching antibacterial spunbond nonwoven fabric, characterized in that it is prepared by spunbonding a process using polypropylene, antibacterial modified montmorillonite, and silane coupling agent as the main raw materials; the antibacterial modified montmorillonite is obtained by inserting a cationic antibacterial agent, polypropylene grafted with maleic anhydride, and polypropylene powder between its layers through mechanical grinding.

[0013] Furthermore, the nonwoven fabric possesses antibacterial properties, with an inhibition rate of >65% against Staphylococcus aureus, >65% against Escherichia coli, and >50% against Candida albicans, and a cell survival rate of >92%. It also exhibits excellent mechanical strength, with a transverse elongation of 95-110% and a transverse breaking force of 40-47N; a longitudinal elongation of 75-85% and a longitudinal breaking force of 90-100N.

[0014] This invention further provides a process for preparing a non-leaching antibacterial spunbond nonwoven fabric, characterized by comprising the following steps: S1, add montmorillonite alcohol solution A and cationic antibacterial agent alcohol solution B to a ball mill in proportion and grind and react for a period of time. Then add polypropylene powder and polypropylene grafted maleic anhydride in proportion and continue grinding. After drying and pulverizing, antibacterial modified montmorillonite is obtained. S2, the antibacterial modified montmorillonite, polypropylene powder and silane coupling agent described in S1 are mixed in proportion, and then extruded and slit by an extruder to form antibacterial masterbatch; S3, after mixing the antibacterial masterbatch, polypropylene and color masterbatch mentioned in S2 in a certain proportion, the mixture is melted, spun, initially pressed and hot rolled to obtain a non-leaching antibacterial spunbond nonwoven fabric.

[0015] Further, in S1, the ratio of montmorillonite to solvent in the montmorillonite alcohol solution A is 1:5-10, and the amount of montmorillonite added is 3-5 parts; in the antibacterial agent alcohol solution B, the ratio of cationic antibacterial agent to solvent is 1:3-5, and the amount of cationic antibacterial agent added is 1-6 parts; the amount of polypropylene powder added is 1 part; the amount of polypropylene grafted with maleic anhydride added is 1.5-3 parts; wherein the raw material components are in parts by weight.

[0016] Further, the montmorillonite in S1 includes sodium-based montmorillonite with an ion exchange capacity of 100-200 meq / 100g; the cationic antibacterial agent includes any one or more of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, hexadecylpyridine bromide, hexadecylpyridine chloride, tetradecyl dimethyl benzyl ammonium chloride, and hexadecyl dimethyl benzyl ammonium chloride; the solvent includes any one or more of anhydrous ethanol and methanol.

[0017] Further, the ratio of the antibacterial modified montmorillonite, polypropylene powder, and silane coupling agent in S2 is 1:0.8-1.2:0.03-0.05; the coupling agent mainly includes any one or two of γ-methacryloyloxypropyltrimethoxysilane (KH560, CAS No.: 2530-85-0) and γ-glycidoxypropyltrimethoxysilane (KH570, CAS No.: 2530-83-8); wherein the raw material components are in parts by weight.

[0018] Furthermore, the ratio of the antibacterial masterbatch, polypropylene, and color masterbatch added in S3 is 1:6-10:0-0.3; wherein the raw material components are in parts by weight.

[0019] Furthermore, in S1, the mass ratio of large, medium, and small agate balls used in the ball mill is 10-20:25-40:40-65; the overall ball-to-material ratio is 70-80:20-30; the ball milling speed is 400-500 rpm; after mixing solutions A and B, the cumulative ball milling time is 1-2 hours for forward rotation and 1-2 hours for reverse rotation; after adding polypropylene grafted maleic anhydride and polypropylene powder, the cumulative ball milling time is 1-2 hours for reverse rotation and 1-2 hours for forward rotation; after ball milling, drying takes 6-8 hours at a drying temperature of 80-90℃.

[0020] Furthermore, the extrusion parameters of the antibacterial masterbatch mentioned in S2 include: low-speed stirring in a high-speed mixing pot for 1 min; feeding the stirred raw material into a twin-screw extruder, with the temperatures of the ten zones of the twin-screw extruder as follows: Zone 1 140±10℃, Zone 2 145±10℃, Zone 3 155±5℃, Zone 4 180±10℃, Zone 5 195±5℃, Zone 6 200±5℃, Zone 7 205±10℃, Zone 8 205±10℃, Zone 9 205±10℃, and die head 205±10℃; feeding speed 12±2 rpm / min; main machine speed 120±15 rpm / min; and pelleting speed 370±20 rpm / min.

[0021] Furthermore, the extrusion parameters for the non-leaching antibacterial spunbond nonwoven fabric described in S3 include: the spunbond process temperatures in zones one through six are 185±10℃ in zone one, 225±10℃ in zone two, 235±10℃ in zone three, 235±10℃ in zone four, 235±10℃ in zone five, and 235±10℃ in zone six; the cooling, stretching, and blowing parameters are: melt cooling air 6±2℃; monomer 550±50 rpm / min; metering pump 24±1 Hz; suction 1150±100 rpm / min; and web forming speed 215±15m / min.

[0022] The present invention also provides an application of non-leaching antibacterial spunbond nonwoven fabric, characterized in that antibacterial spunbond meltblown composite nonwoven fabric, antibacterial coated nonwoven fabric, and antibacterial coated nonwoven fabric are prepared by superimposing and compounding with meltblown nonwoven fabric, breathable membrane and coating layer.

[0023] The beneficial effects of this invention are: 1. The preparation process provided by this invention involves tightly intercalating a cationic antibacterial agent into sodium-based montmorillonite through a mechanical grinding process, followed by the addition of polypropylene powder and polypropylene-grafted maleic anhydride. During the ball milling stage, the montmorillonite sheets gradually increase in size, and the polypropylene molecular chains and polypropylene-grafted maleic anhydride molecular chains become entangled inside and outside the montmorillonite sheets. The maleic anhydride groups in the sheets can also form hydrogen bonds with the nitrogen ions in the intercalated quaternary ammonium salt antibacterial agent, resulting in a strong bond. This process also improves the compatibility and interfacial bonding between montmorillonite and the organic polymer polypropylene.

[0024] 2. The preparation process provided by this invention, by adding a coupling agent, can further promote the mixing of montmorillonite and polypropylene. The polypropylene molecular chains are inserted into the montmorillonite sheets, which further increase in size and improve compatibility with polypropylene, resulting in an antibacterial montmorillonite-polypropylene nanocomposite material. The quaternary ammonium salt cations intercalated between the montmorillonite sheets, through the composite material formed by montmorillonite and polypropylene, not only achieve antibacterial function but also further improve the bond between the antibacterial agent and polypropylene, resulting in a non-leaching antibacterial masterbatch, ensuring the safety of downstream products.

[0025] 3. The preparation process provided by this invention, in which the montmorillonite antibacterial masterbatch is prepared by ball milling combined with melt extrusion, due to the ball milling dispersion, organic matter intercalation and other processes, the coupling agent, polypropylene grafted with maleic anhydride, and polypropylene mutually promote each other, resulting in nano-montmorillonite masterbatch with high compatibility with polypropylene. It can not only exhibit the rigidity of nano-montmorillonite itself, but also promote the crystallization of nonwoven fibers during the nonwoven fabric melting, cooling and stretching process, making the molecular chain arrangement more regular and improving the strength of nonwoven fabric.

[0026] 4. The non-leaching antibacterial spunbond nonwoven fabric provided by this invention has an inhibition rate of >65% against Staphylococcus aureus, >65% against Escherichia coli, and >50% against Candida albicans, with a cell survival rate of >92%; it also has excellent mechanical strength, with a transverse elongation of 95-110% and a transverse breaking force of 40-47N; a longitudinal elongation of 75-85% and a longitudinal breaking force of 90-100N.

[0027] 5. The antibacterial spunbond nonwoven fabric, antibacterial spunbond meltblown composite nonwoven fabric, antibacterial coated nonwoven fabric, and antibacterial laminated nonwoven fabric provided by the present invention can be widely used in products such as medical surgical masks, medical isolation gowns, medical protective clothing, disposable inner sheets, disposable surgical gowns, disposable nursing pads, disposable diapers, and disposable travel clothing. Attached Figure Description

[0028] To more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Appendix Figure 1 This is a schematic diagram of the intercalation and modification process of antibacterial modified montmorillonite.

[0030] Appendix Figure 2 This is a schematic diagram of the granulation process for antibacterial masterbatch.

[0031] Appendix Figure 3 The XRD patterns of antibacterial modified montmorillonite before and after modification are shown.

[0032] Appendix Figure 4 Infrared spectra of antibacterial modified montmorillonite.

[0033] Appendix Figure 5 The figure shows the transverse fracture force and displacement curve for Example 3.

[0034] Appendix Figure 6 The longitudinal fracture force versus displacement curve is shown in Example 3.

[0035] Appendix Figure 7 The results are for the non-leaching test of antibacterial spunbond nonwoven fabric. Detailed Implementation

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. All mentioned embodiments are implemented based on the technical solutions of the present invention, and detailed implementation processes are given. However, it should be stated that the scope of protection of the present invention is not limited to the following embodiments. Example 1

[0037] Preparation of a non-leaching antibacterial spunbond nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: Weigh 100 parts of sodium montmorillonite (100 meq / 100g) and add 500 parts of anhydrous ethanol, stirring continuously to obtain suspension A; weigh 57.6 parts of hexadecyl pyridine bromide (1.5 times the cation exchange capacity) and add it to 200 parts of anhydrous ethanol solvent, stirring with a magnetic stirrer to prepare mixed solution B; place grinding balls in a planetary ball mill, pour in mixed solutions A and B, the ratio of grinding balls is large (D14), medium (D10), small (D6) = 10:25:65, the ball-to-material ratio is 80:20 and the mill is sealed; open the ball mill and run at 500... Grind at rpm / min, rotating forward for 1 hour and rotating backward for 2 hours. Then, add 50 parts of polypropylene grafted maleic anhydride and 30 parts of polypropylene powder to the ball mill jar and continue grinding at 500 rpm / min, rotating backward for 1 hour and rotating forward for 2 hours. Filter the mixed slurry taken from the ball mill and dry it in a vacuum drying oven at 80℃ for 8 hours to obtain highly compatible antibacterial modified montmorillonite; a total of more than 5 kg was prepared. (2) Preparation of antibacterial masterbatch: Weigh 20 parts of spunbond polypropylene powder, 1 part of KH570, and 20 parts of the highly compatible antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; then feed the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 139℃, Zone 2 142℃, Zone 3 157℃, Zone 4 177℃, Zone 5 196℃, Zone 6 205℃, Zone 7 209℃, Zone 8 208℃, Zone 9 210℃, and the die head 209℃. The feeding speed is 12.2 rpm / min, the main machine speed is 117 rpm / min, and the pelletizing speed is 359 rpm / min. (3) Preparation of antibacterial spunbond nonwoven fabric: Ten parts of montmorillonite antibacterial masterbatch, 80 parts of spunbond polypropylene granules, and 1 part of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 192℃ in zone one, 232℃ in zone two, 244℃ in zone three, 245℃ in zone four, 241℃ in zone five, and 242℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 6℃; monomer 570 rpm / min; metering pump 23.2 Hz; suction 1230 rpm / min. The web forming speed was 219 m / min. The prepared antibacterial spunbond nonwoven fabric was subjected to performance tests such as appearance, width, weight, and tensile strength. Example 2

[0038] Preparation of a non-leaching antibacterial spunbond nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: Weigh 100 parts of sodium montmorillonite (200 meq / 100g) and add 450 parts of anhydrous methanol, stirring continuously to obtain suspension A; weigh 118.8 parts of hexadecylbenzyldimethylammonium chloride (1.5 times the cation exchange capacity) and add it to 400 parts of anhydrous ethanol solvent, stirring with a magnetic stirrer to prepare mixed solution B; place grinding balls in a planetary ball mill, pour in mixed solutions A and B, the ratio of grinding balls is large (D14), medium (D10), small (D6) = 15:30:55, the ball-to-material ratio is 75:25 and the mill is sealed; open the ball mill and run at 450... Grind at rpm / min, rotating forward for 1.5 hours and then rotating in reverse for 1 hour. Then, add 50 parts of polypropylene grafted maleic anhydride and 20 parts of polypropylene powder to the ball mill jar and continue grinding at 500 rpm / min, rotating in reverse for 1.5 hours and then rotating forward for 1.5 hours. Filter the mixed slurry taken from the ball mill and dry it in a vacuum drying oven at 90℃ for 6 hours to obtain highly compatible antibacterial modified montmorillonite; a total of more than 5 kg was prepared. (2) Preparation of antibacterial masterbatch: Weigh 20 parts of spunbond polypropylene powder, 0.8 parts of KH570, and 18 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 136℃, Zone 2 139℃, Zone 3 156℃, Zone 4 176℃, Zone 5 197℃, Zone 6 200℃, Zone 7 196℃, Zone 8 197℃, Zone 9 198℃, and the die head 199℃. The feeding speed is 13.2 rpm / min, the main machine speed is 133 rpm / min, and the pelletizing speed is 375 rpm / min. (3) Preparation of antibacterial spunbond nonwoven fabric: Ten parts of montmorillonite antibacterial masterbatch, 90 parts of spunbond polypropylene granules, and 2 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 185℃ in zone one, 227℃ in zone two, 239℃ in zone three, 241℃ in zone four, 241℃ in zone five, and 243℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 7℃; monomer 550 rpm / min; metering pump 24.1 Hz; suction 1150 rpm / min. The web forming speed was 201 m / min. The prepared antibacterial spunbond nonwoven fabric was subjected to performance tests such as appearance, width, weight, and tensile strength. Example 3

[0039] Preparation of a non-leaching antibacterial spunbond nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: Weigh 100 parts of sodium montmorillonite (200 meq / 100g) and add 500 parts of anhydrous ethanol, stirring continuously to obtain suspension A; weigh 112.4 parts of hexadecylpyridine chloride (twice the cation exchange capacity) and add it to 500 parts of anhydrous methanol solvent, stirring with a magnetic stirrer for 1 hour to prepare mixed solution B; place grinding balls in a planetary ball mill, pour in mixed solutions A and B, with the ratio of large (D14), medium (D10), and small (D6) grinding balls being 10:40:50, and the ball-to-material ratio being 70:30, then seal the mill; open the ball mill and run it at 500... Grind at rpm / min for 1 hour in forward rotation, then add 45 parts of polypropylene grafted maleic anhydride and 20 parts of polypropylene powder to the ball mill jar, continue grinding at 500 rpm / min, continue grinding at 450 rpm / min, reverse rotation for 1.5 hours, forward rotation for 1.5 hours; filter the mixed slurry taken from the ball mill and dry it in a vacuum drying oven at 90℃ for 6 hours to obtain highly compatible antibacterial modified montmorillonite; more than 5 kg were prepared in total; (2) Preparation of antibacterial masterbatch: Weigh 20 parts of spunbond polypropylene powder, 0.6 parts of KH570, and 24 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 132℃, Zone 2 136℃, Zone 3 153℃, Zone 4 173℃, Zone 5 194℃, Zone 6 203℃, Zone 7 193℃, Zone 8 194℃, Zone 9 196℃, and the die head 198℃. The feeding speed is 14 rpm / min, the main machine speed is 116 rpm / min, and the pelletizing speed is 375 rpm / min. (3) Preparation of antibacterial spunbond nonwoven fabric: Ten parts of montmorillonite antibacterial masterbatch, 60 parts of spunbond polypropylene granules, and 3 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 181℃ in zone one, 223℃ in zone two, 235℃ in zone three, 237℃ in zone four, 238℃ in zone five, and 240℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 5.5℃; monomer 580 rpm / min; metering pump 23.8 Hz; suction 1130 rpm / min. The web forming speed was 198 m / min. The prepared antibacterial spunbond nonwoven fabric was subjected to performance tests such as appearance, width, weight, and tensile strength. Example 4

[0040] Preparation of a non-leaching antibacterial spunbond nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: Weigh 100 parts of sodium montmorillonite (100 meq / 100g) and add 600 parts of anhydrous ethanol, stirring continuously to obtain suspension A; weigh 49.63 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (1 cation exchange capacity) and add it to 290 parts of anhydrous ethanol solvent, stirring with a magnetic stirrer to prepare mixed solution B; place grinding balls in a planetary ball mill, pour in mixed solutions A and B, the ratio of grinding balls is large (D14), medium (D10), small (D6) = 20:40:40, the ball-to-material ratio is 80:20 and the mill is sealed; open the ball mill and start at 500... Grind at rpm / min for 1 hour in forward rotation, then for 2 hours in forward rotation. Subsequently, 50g of polypropylene grafted with maleic anhydride and 20g of polypropylene powder are added to the ball mill jar, and grinding continues at 500r / min, reverse rotation for 2 hours, and forward rotation for 1 hour. The mixed slurry taken out of the ball mill is filtered and dried in a vacuum drying oven at 90℃ for 6 hours to obtain highly compatible antibacterial modified montmorillonite; a total of more than 7kg is prepared. (2) Preparation of antibacterial masterbatch: Weigh 20 parts of spunbond polypropylene powder, 1 part of KH560, and 20 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 130℃, Zone 2 135℃, Zone 3 150℃, Zone 4 170℃, Zone 5 191℃, Zone 6 195℃, Zone 7 195℃, Zone 8 196℃, Zone 9 196℃, and the die head 197℃. The feeding speed is 13.8 rpm / min, the main machine speed is 118 rpm / min, and the pelletizing speed is 381 rpm / min. (3) Preparation of antibacterial spunbond nonwoven fabric: Ten parts of montmorillonite antibacterial masterbatch and 60 parts of spunbond polypropylene granules were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 180℃ in zone one, 220℃ in zone two, 230℃ in zone three, 230℃ in zone four, 230℃ in zone five, and 235℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 4.2℃; monomer 530 rpm / min; metering pump 23.0 Hz; suction 1120 rpm / min. The web forming speed was 215 m / min. The prepared antibacterial spunbond nonwoven fabric was subjected to performance tests such as appearance, width, weight, and tensile strength.

[0041] In step (3), the temperature range can fluctuate by 10°C, and spunbond nonwoven fabric can be prepared stably in all cases. Example 5

[0042] Preparation of a non-leaching antibacterial spunbond nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: Weigh 100 parts of sodium montmorillonite (100 meq / 100g) and add 400 parts of anhydrous ethanol, stirring continuously to obtain suspension A; weigh 36.8 parts of tetradecyl dimethyl benzyl ammonium chloride (1 cation exchange capacity) and add it to 120 parts of anhydrous ethanol solvent, stirring with a magnetic stirrer to prepare mixed solution B; place grinding balls in a planetary ball mill, pour in mixed solutions A and B, with the ratio of large (D14), medium (D10), and small (D6) grinding balls = 1. The ball-to-material ratio was 77:23 (0:30:60, sealed); the ball mill was turned on and ground at 450 rpm / min for 2 hours, then ground again for 1 hour. Then, 75 parts of polypropylene grafted maleic anhydride and 25 parts of polypropylene powder were added to the ball mill jar, and grinding continued at 500 rpm for 1 hour in reverse rotation and 1 hour in forward rotation. The mixed slurry taken from the ball mill was filtered and dried in a vacuum drying oven at 80°C for 8 hours to obtain highly compatible antibacterial modified montmorillonite; a total of over 5 kg was prepared. (2) Preparation of antibacterial masterbatch: Weigh 20 parts of spunbond polypropylene powder, 1 part of KH560, and 22 parts of the highly compatible antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; then feed the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 137℃, Zone 2 142℃, Zone 3 158℃, Zone 4 177℃, Zone 5 199℃, Zone 6 203℃, Zone 7 209℃, Zone 8 210℃, Zone 9 210℃, and the die head 209℃. The feeding speed is 12.1 rpm / min, the main machine speed is 115 rpm / min, and the pelletizing speed is 361 rpm / min. (3) Preparation of antibacterial spunbond nonwoven fabric: Ten parts of montmorillonite antibacterial masterbatch, 60 parts of spunbond polypropylene granules, and 1.5 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 194℃ in zone one, 232℃ in zone two, 240℃ in zone three, 241℃ in zone four, 243℃ in zone five, and 245℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 6℃; monomer 550 rpm / min; metering pump 23.1 Hz; suction 1210 rpm / min. The web forming speed was 221 m / min. The prepared antibacterial spunbond nonwoven fabric was subjected to performance tests such as appearance, width, weight, and tensile strength. Example 6

[0043] Preparation of a non-leaching antibacterial spunbond nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: 100 parts of sodium montmorillonite (100 meq / 100g) were weighed and added to 450 parts of anhydrous ethanol, and the mixture was stirred continuously to obtain suspension A. 29.7 parts of hexadecylbenzyldimethylammonium chloride and 37.22 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (1.5 times the cation exchange capacity) were weighed and added to 250 parts of anhydrous ethanol solvent, and stirred with a magnetic stirrer to prepare mixed solution B. Grinding balls were placed in a planetary ball mill, and mixed solutions A and B were poured in. The ratio of grinding balls was large (D14), medium (D10), and small (D6) = 15:30:60, and the ball-to-material ratio was 74:26. ​​The mill was then sealed. The mill was opened and the flow rate was 500 rpm. Grind at rpm / min, rotating forward for 1 hour and rotating backward for 1.5 hours. Then, add 45 parts of polypropylene grafted maleic anhydride and 30 parts of polypropylene powder to the ball mill jar and continue grinding at 500 rpm / min, rotating backward for 1 hour and rotating forward for 1 hour. Filter the mixed slurry taken from the ball mill and dry it in a vacuum drying oven at 80℃ for 8 hours to obtain highly compatible antibacterial modified montmorillonite; a total of more than 5 kg was prepared. (2) Preparation of antibacterial masterbatch: Weigh 20 parts of spunbond polypropylene powder, 0.9 parts of KH560, and 19 parts of the highly compatible antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; then introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 137℃, Zone 2 140℃, Zone 3 155℃, Zone 4 176℃, Zone 5 193℃, Zone 6 201℃, Zone 7 205℃, Zone 8 207℃, Zone 9 209℃, and the die head 209℃. The feeding speed is 14 rpm / min, the main machine speed is 135 rpm / min, and the pelletizing speed is 356 rpm / min. (3) Preparation of antibacterial spunbond nonwoven fabric: Ten parts of montmorillonite antibacterial masterbatch, 100 parts of spunbond polypropylene granules, and 3 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 189℃ in zone one, 228℃ in zone two, 244℃ in zone three, 245℃ in zone four, 241℃ in zone five, and 242℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 6℃; monomer 600 rpm / min; metering pump 24 Hz; suction 1250 rpm / min. The web forming speed was 225 m / min. The prepared antibacterial spunbond nonwoven fabric was subjected to performance tests such as appearance, width, weight, and tensile strength. Example 7

[0044] Preparation of a non-leaching antibacterial spunbond nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: Weigh 100 parts of sodium montmorillonite (200 meq / 100g) and add 500 parts of anhydrous ethanol, stirring continuously to obtain suspension A; weigh 42.26 parts of hexadecylpyridine chloride and 41.4 parts of tetradecyl dimethyl benzyl ammonium chloride (1.5 times the cation exchange capacity) and add them to 400 ml of anhydrous ethanol solvent, stirring with a magnetic stirrer to prepare mixed solution B; place grinding balls in a planetary ball mill, pour in mixed solutions A and B, the ratio of grinding balls being large (D14), medium (D10), and small (D6) = 12:26:62, and the ball-to-material ratio being 79:21 and seal; open the ball mill and run at 500... Grind at rpm / min, forward rotation for 1 hour, reverse rotation for 2 hours, then add 50 parts of polypropylene grafted maleic anhydride and 20 parts of polypropylene powder to the ball mill jar, continue grinding at 500 rpm / min, reverse rotation for 1.5 hours, forward rotation for 1.5 hours; filter the mixed slurry taken from the ball mill and dry it in a vacuum drying oven at 90℃ for 6 hours to obtain highly compatible antibacterial modified montmorillonite; more than 5 kg were prepared in total; (2) Preparation of antibacterial masterbatch: Weigh 20 parts of spunbond polypropylene powder, 0.9 parts of KH560, and 18 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; then feed the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 136℃, Zone 2 139℃, Zone 3 156℃, Zone 4 176℃, Zone 5 197℃, Zone 6 200℃, Zone 7 196℃, Zone 8 197℃, Zone 9 198℃, and the die head 199℃. The feeding speed is 10 rpm / min, the main machine speed is 115 rpm / min, and the pelletizing speed is 355 rpm / min. (3) Preparation of antibacterial spunbond nonwoven fabric: Ten parts of montmorillonite antibacterial masterbatch, 90 parts of spunbond polypropylene granules, and 1.5 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by forced air. The spunbond process temperatures in zones one through six were 185℃ in zone one, 227℃ in zone two, 239℃ in zone three, 241℃ in zone four, 241℃ in zone five, and 243℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced air were: melt cooling air 7℃; monomer 550 rpm / min; metering pump 24.1 Hz; suction 1150 rpm / min. The web forming speed was 201 m / min. The prepared antibacterial spunbond nonwoven fabric was subjected to performance tests such as appearance, width, weight, and tensile strength.

[0045] Comparative Example 1 Preparation of a nonwoven fabric (1) Preparation of spunbond nonwoven fabric: 39.88 parts of polypropylene and 0.12 parts of color masterbatch are added to the corresponding hopper and mixed evenly as the material is fed in. The mixture is then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced air. The spunbond process temperatures in zones one through six are as follows: zone one 186℃, zone two 224℃, zone three 235℃, zone four 236℃, zone five 237℃, and zone six 239℃, respectively. Cooling, stretching, and forced air parameters are: melt cooling air 7℃; monomer 600 rpm / min; metering pump 23.1 Hz; suction 950 rpm / min. The web forming speed is 225 m / min. (2) Antibacterial modification: The spunbond nonwoven fabric obtained in step (1) is soaked in an aqueous solution of 1% dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride for 30 min and then dried at 80°C.

[0046] The prepared nonwoven fabric products will be tested for properties such as appearance, width, weight, and tensile strength.

[0047] Comparative Example 2 Preparation of a nonwoven fabric (1) Preparation of modified montmorillonite: 100 parts of sodium-based montmorillonite (200 meq / 100g) were weighed and added to 500 parts of anhydrous ethanol. The mixture was stirred continuously to obtain suspension A. Grinding balls were placed in a planetary ball mill, and mixed solution A was poured in. The ratio of grinding balls was large (D14), medium (D10), and small (D6) = 10:25:65, with a ball-to-material ratio of 80:20. The mill was sealed and operated at 500 rpm / min for 1 hour. Then, mixed solution A, 50 parts of polypropylene-grafted maleic anhydride, and 20 parts of polypropylene powder were added to the mill jar. Grinding continued at 500 rpm / min, reversed for 1.5 hours, and then forward for 1.5 hours. The mixed slurry removed from the mill was dried in a vacuum drying oven at 90℃ for 6 hours to obtain modified montmorillonite. A total of over 5 kg was prepared. (2) Masterbatch preparation: Weigh 20 parts of spunbond polypropylene powder, 0.9 parts of KH560, and 18 parts of modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 140℃, Zone 2 143℃, Zone 3 157℃, Zone 4 178℃, Zone 5 198℃, Zone 6 205℃, Zone 7 200℃, Zone 8 199℃, Zone 9 199℃, and the die head 200℃. The feeding speed is 14 rpm / min, the main machine speed is 122 rpm / min, and the pelletizing speed is 355 rpm / min. (3) Nonwoven fabric preparation: Ten parts of montmorillonite masterbatch, 45 parts of spunbond polypropylene granules, and 1.5 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by forced air. The spunbond process temperatures in zones one through six were 191℃ in zone one, 228℃ in zone two, 237℃ in zone three, 239℃ in zone four, 240℃ in zone five, and 243℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced air were: melt cooling air 7℃; monomer 590 rpm / min; metering pump 24 Hz; suction 1250 rpm / min. The web forming speed was 209 m / min. The prepared nonwoven fabric products are subjected to performance tests such as appearance, width, weight, and tensile strength.

[0048] Comparative Example 3 Preparation of a nonwoven fabric (1) Masterbatch preparation: Weigh 82.5 parts of spunbond polypropylene powder, 2 parts of sodium montmorillonite, 6 parts of PP-G-MAH, 8 parts of cetylpyridine chloride antibacterial agent powder, and 1.5 parts of KH560 and stir at low speed for 1 hour in a high-speed mixing pot; pour the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 138℃, Zone 2 142℃, Zone 3 157℃, Zone 4 176℃, Zone 5 185℃, Zone 6 185℃, Zone 7 195℃, Zone 8 198℃, Zone 9 198℃, and the die head 197℃. The feeding speed is 14 rpm / min, the main machine speed is 122 rpm / min, and the pelletizing speed is 355 rpm / min. (2) Nonwoven fabric preparation: Ten parts of montmorillonite antibacterial masterbatch, 45 parts of spunbond polypropylene granules, and 1 part of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by forced air. The spunbond process temperatures in zones one through six were 186℃ in zone one, 228℃ in zone two, 229℃ in zone three, 230℃ in zone four, 230℃ in zone five, and 230℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced air were: melt cooling air 7℃; monomer 590 rpm / min; metering pump 24 Hz; suction 1250 rpm / min. The web forming speed was 209 m / min. The prepared nonwoven fabric products are subjected to performance tests such as appearance, width, weight, and tensile strength.

[0049] Comparative Example 4 Preparation of a nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: 100 parts of sodium montmorillonite (100 meq / 100g) were weighed and added to 500 parts of anhydrous ethanol, and the mixture was stirred continuously to obtain suspension A. 36.8 parts of tetradecyl dimethyl benzyl ammonium chloride (1 times the cation exchange capacity) were weighed and added to 120 parts of anhydrous ethanol solvent, and stirred with a magnetic stirrer to prepare mixed solution B. Grinding balls were placed in a planetary ball mill, and mixed solutions A and B were poured in. The ratio of grinding balls was large (D14), medium (D10), and small (D6) = 10:25:65, and the ball-to-material ratio was 80:20. The mill was sealed and operated at 500 rpm / min, rotating forward for 1 hour and then rotating in reverse for 2 hours. Subsequently, 80 parts of polypropylene powder were added to the mill jar, and grinding was continued at 500 rpm / min, rotating in reverse for 1 hour and then rotating forward for 1 hour. The mixed slurry taken from the mill was filtered and dried in a vacuum drying oven at 80°C for 8 hours to obtain antibacterial modified montmorillonite. More than 5 kg were prepared in total. (2) Masterbatch preparation: Weigh 20 parts of spunbond polypropylene powder, 0.8 parts of KH570, and 18 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 136℃, Zone 2 140℃, Zone 3 148℃, Zone 4 167℃, Zone 5 189℃, Zone 6 193℃, Zone 7 201℃, Zone 8 205℃, Zone 9 205℃, and Die head 205℃. The feeding speed is 12.1 rpm / min, the main machine speed is 115 rpm / min, and the pelletizing speed is 361 rpm / min. (3) Nonwoven fabric preparation: Ten parts of montmorillonite antibacterial masterbatch, 90 parts of spunbond polypropylene granules, and 2 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 185℃ in zone one, 225℃ in zone two, 235℃ in zone three, 235℃ in zone four, 235℃ in zone five, and 235℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 6℃; monomer 550 rpm / min; metering pump 23.1 Hz; suction 1210 rpm / min. The web forming speed was 221 m / min. The prepared nonwoven fabric products are subjected to performance tests such as appearance, width, weight, and tensile strength.

[0050] Comparative Example 5 Preparation of a nonwoven fabric (1) Preparation of antibacterial agents: Weigh 57.6 parts of hexadecyl pyridine bromide and add it to 200 parts of anhydrous ethanol solvent. Stir with a magnetic stirrer to prepare mixed solution B. Place grinding balls in a planetary ball mill, pour in mixed solution B, and the ratio of grinding balls is large (D14), medium (D10), and small (D6) = 10:25:65, with a ball-to-material ratio of 80:20. Seal the mill. Turn on the mill and grind at 500 rpm for 1 hour. Then add 50 parts of polypropylene grafted maleic anhydride and 30 parts of polypropylene powder to the mill jar and continue grinding at 500 rpm for 1 hour in reverse and 1 hour in forward. Filter the mixed slurry taken from the mill and dry it in a vacuum drying oven at 80°C for 8 hours to obtain the antibacterial agent. Prepare a total of more than 5 kg. (2) Masterbatch preparation: Weigh 20 parts of spunbond polypropylene powder, 0.8 parts of KH570, and 18 parts of the antibacterial agent obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 135℃, Zone 2 140℃, Zone 3 145℃, Zone 4 175℃, Zone 5 185℃, Zone 6 195℃, Zone 7 195℃, Zone 8 195℃, Zone 9 200℃, and the die head 200℃. The feeding speed is 12.1 rpm / min, the main machine speed is 115 rpm / min, and the pelletizing speed is 361 rpm / min. (3) Nonwoven fabric preparation: Ten parts of antibacterial masterbatch, 90 parts of spunbond polypropylene granules, and 2 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced air. The spunbond process temperatures in zones one through six were 175℃ in zone one, 215℃ in zone two, 225℃ in zone three, 225℃ in zone four, 225℃ in zone five, and 225℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced air were: melt cooling air 6℃; monomer 550 rpm / min; metering pump 23.1 Hz; suction 1210 rpm / min. The web forming speed was 221 m / min. The prepared nonwoven fabric products are subjected to performance tests such as appearance, width, weight, and tensile strength.

[0051] Comparative Example 6 Preparation of a nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: 100 parts of sodium-based montmorillonite (100 meq / 100g) were weighed and added to 500 parts of anhydrous ethanol, and the mixture was stirred continuously to obtain suspension A. 23.5 parts of p-chloro-m-xylenol (1.5 times the cation exchange capacity) were weighed and added to 100 parts of anhydrous ethanol solvent, and stirred with a magnetic stirrer to prepare mixed solution B. Grinding balls were placed in a planetary ball mill, and mixed solutions A and B were poured in. The ratio of grinding balls was large (D14): small (D6) = 15:85, and the ball-to-material ratio was 80:20. The mill was sealed and turned on at 500 rpm / min for 1.5 hours. Then, 50 parts of polypropylene grafted maleic anhydride and 30 parts of polypropylene powder were added to the mill jar, and the milling continued at 500 rpm / min, followed by reverse grinding for 0.5 hours and forward grinding for 0.5 hours. The mixed slurry taken from the mill was filtered and dried in a vacuum drying oven at 80°C for 8 hours to obtain antibacterial modified montmorillonite. A total of more than 5 kg was prepared. (2) Masterbatch preparation: Weigh 20 parts of spunbond polypropylene powder, 0.8 parts of KH570, and 18 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 139℃, Zone 2 144℃, Zone 3 155℃, Zone 4 180℃, Zone 5 199℃, Zone 6 203℃, Zone 7 208℃, Zone 8 208℃, Zone 9 210℃, and the die head 210℃. The feeding speed is 12.1 rpm / min, the main machine speed is 115 rpm / min, and the pelletizing speed is 361 rpm / min. (3) Nonwoven fabric preparation: Ten parts of montmorillonite antibacterial masterbatch, 90 parts of spunbond polypropylene granules, and 2 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 190℃ in zone one, 230℃ in zone two, 241℃ in zone three, 241℃ in zone four, 243℃ in zone five, and 245℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 6℃; monomer 550 rpm / min; metering pump 23.1 Hz; suction 1210 rpm / min. The web forming speed was 221 m / min. The prepared nonwoven fabric products are subjected to performance tests such as appearance, width, weight, and tensile strength.

[0052] Comparative Example 7 Preparation of a nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: Weigh 36.8 parts of tetradecyl dimethyl benzyl ammonium chloride and add it to 200 parts of anhydrous ethanol solvent. Stir with a magnetic stirrer to prepare mixed solution B. Place grinding balls in a planetary ball mill, pour in mixed solution B, and the ratio of grinding balls is large (D14), medium (D10), and small (D6) = 10:25:65, with a ball-to-material ratio of 50:50. Seal the mill. Turn on the mill and grind at 200 rpm for 1 hour in the forward direction and 1 hour in the reverse direction. Then add 50 parts of polypropylene grafted maleic anhydride and 20 parts of polypropylene powder to the mill jar and continue grinding at 300 rpm for 1 hour in the reverse direction and 1 hour in the forward direction. Filter the mixed slurry taken out of the mill and dry it in a vacuum drying oven at 80°C for 8 hours to obtain antibacterial modified montmorillonite. Prepare a total of more than 5 kg. (2) Masterbatch preparation: Weigh 20 parts of spunbond polypropylene powder, 0.8 parts of KH560, and 18 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 143℃, Zone 2 147℃, Zone 3 159℃, Zone 4 179℃, Zone 5 199℃, Zone 6 204℃, Zone 7 209℃, Zone 8 209℃, Zone 9 210℃, and the die head 210℃. The feeding speed is 12.1 rpm / min, the main machine speed is 115 rpm / min, and the pelletizing speed is 361 rpm / min. (3) Nonwoven fabric preparation: Ten parts of montmorillonite antibacterial masterbatch, 90 parts of spunbond polypropylene granules, and 1 part of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by induced airflow. The spunbond process temperatures in zones one through six were 194℃ in zone one, 232℃ in zone two, 240℃ in zone three, 241℃ in zone four, 243℃ in zone five, and 245℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced airflow were: melt cooling air 6℃; monomer 550 rpm / min; metering pump 23.1 Hz; suction 1210 rpm / min. The web forming speed was 221 m / min. The prepared nonwoven fabric products are subjected to performance tests such as appearance, width, weight, and tensile strength.

[0053] Comparative Example 8 Preparation of a nonwoven fabric (1) Preparation of antibacterial modified montmorillonite: 100 parts of sodium-based montmorillonite (100 meq / 100g) were weighed and added to 500 parts of anhydrous ethanol, and the mixture was stirred continuously to obtain suspension A. 39.6 parts of hexadecylbenzyldimethylammonium chloride were weighed and added to 130 parts of anhydrous ethanol solvent, and stirred with a magnetic stirrer to prepare mixed solution B. Grinding balls were placed in a planetary ball mill, and mixed solutions A and B were poured in. The ratio of grinding balls was large (D14), medium (D10), and small (D6) = 10:25:65, and the ball-to-material ratio was 80:20. The mill was sealed and operated at 500 rpm / min, rotating forward for 1 hour and then rotating in reverse for 1.5 hours. Subsequently, 50 parts of polypropylene grafted maleic anhydride and 25 parts of polypropylene powder were added to the mill jar, and grinding was continued at 500 rpm / min, rotating in reverse for 1 hour and then rotating forward for 1 hour. The mixed slurry taken from the mill was filtered and dried in a vacuum drying oven at 80°C for 8 hours to obtain antibacterial modified montmorillonite. More than 5 kg were prepared in total. (2) Masterbatch preparation: Weigh 20 parts of spunbond polypropylene powder and 18 parts of antibacterial modified montmorillonite obtained in step (1) and stir at low speed for 1 min in a high-speed mixing pot; introduce the stirred granules into a twin-screw extruder. The temperatures of the ten zones of the twin-screw extruder are as follows: Zone 1 144℃, Zone 2 149℃, Zone 3 159℃, Zone 4 177℃, Zone 5 199℃, Zone 6 203℃, Zone 7 209℃, Zone 8 209℃, Zone 9 210℃, and the die head 215℃. The feeding speed is 12.1 rpm / min, the main machine speed is 115 rpm / min, and the pelletizing speed is 361 rpm / min. (3) Nonwoven fabric preparation: Ten parts of montmorillonite antibacterial masterbatch, 90 parts of spunbond polypropylene granules, and 1.5 parts of color masterbatch were added to the corresponding hoppers and mixed evenly as the materials were fed in. The mixture was then melt-extruded, cooled by side-blowing air, stretched by forced air, and formed into fabric by forced air. The spunbond process temperatures in zones one through six were 194℃ in zone one, 232℃ in zone two, 240℃ in zone three, 241℃ in zone four, 243℃ in zone five, and 245℃ in zone six, respectively. The relevant parameters for cooling, stretching, and forced air were: melt cooling air 6℃; monomer 550 rpm / min; metering pump 23.1 Hz; suction 1210 rpm / min. The web forming speed was 221 m / min. The prepared nonwoven fabric products are subjected to performance tests such as appearance, width, weight, and tensile strength.

[0054] Implementation effect

[0055] The nonwoven fabrics obtained from the above embodiments and comparative examples were subjected to the following performance tests, and the test results are shown in Table 1 and Table 2.

[0056] 1. Biological performance testing (1) Antibacterial test, the test shall be conducted in accordance with GB / T 15979 "Hygienic Standard for Disposable Sanitary Products".

[0057] (2) Cytotoxicity test, refer to GB / T 16886.5-2017 "Biological evaluation of medical devices - Part 5: In vitro cytotoxicity test".

[0058] Table 1. Results of antibacterial rate and cytotoxicity tests for nonwoven fabric examples and comparative examples.

[0059] The test results show that the antibacterial spunbond nonwoven fabric obtained by the preparation process provided by the present invention has good antibacterial properties and low cytotoxicity. This is mainly because the cationic antibacterial agent can be firmly fixed in the montmorillonite intercalation and uniformly dispersed in the resin matrix without dissolving or falling off. The processing temperature range is relatively wide, mainly because the antibacterial modified montmorillonite has high thermal stability and can be uniformly dispersed in the resin matrix. Comparative Example 1 used a post-processing method to prepare antibacterial spunbond nonwoven fabric. The resulting nonwoven fabric had antibacterial properties but high cytotoxicity and poor antibacterial effect. This was mainly because the antibacterial agent was mainly on the surface of the spunbond nonwoven fabric after soaking in the solution, and the antibacterial agent was easily detached and dissolved. Comparative Example 2 only added sodium montmorillonite and did not perform cationic antibacterial agent intercalation. The resulting spunbond nonwoven fabric had no antibacterial properties. Comparative Example 3 directly blended polypropylene with antibacterial agent to prepare antibacterial masterbatch. The prepared material had relatively low antibacterial properties. This was mainly because the antibacterial agent was not fully intercalated into montmorillonite, resulting in poor compatibility and uneven dispersion. Some antibacterial agent accumulated at the screw pre-filter and was filtered out during processing. In addition, the antibacterial agent partially decomposed during high-temperature processing, resulting in low antibacterial properties and high cytotoxicity. In Comparative Example 4, PP-G-MAH was not added during the preparation of the antibacterial modified montmorillonite. This resulted in PP-G-MAH not being intercalated into the montmorillonite, preventing the inorganic montmorillonite from effectively dispersing and compatibility with the PP resin matrix. This led to montmorillonite aggregation, causing pore blockage during spinning and the filtration of most of the antibacterial components. In Comparative Example 5, montmorillonite was not added during the preparation of the antibacterial modified montmorillonite, preventing the antibacterial agent from being embedded in the intercalation layer and from receiving the protection of the montmorillonite intercalation. This made it prone to decomposition during high-temperature processing, resulting in loss of antibacterial properties and significant cytotoxicity from the decomposition produced. In Comparative Example 6, the grinding balls used in the preparation of the antibacterial modified montmorillonite consisted only of large and small balls, resulting in insufficient grinding. This led to incomplete and insufficient contact between the montmorillonite and the antibacterial agent, with most of the antibacterial agent failing to intercalate into the montmorillonite layers. Furthermore, since the antibacterial agent was non-cationic, it could not fully form ion exchange with sodium-based montmorillonite, thus failing to completely and effectively intercalate into the montmorillonite layers. Consequently, both its antibacterial and biosafety performance did not meet the target effects. In Comparative Example 7, the grinding rate and ball-to-material ratio during the preparation of the antibacterial modified montmorillonite were low, resulting in insufficient and incomplete contact between the montmorillonite and the antibacterial agent. Most of the antibacterial agent failed to intercalate into the montmorillonite layers, and both its antibacterial and biosafety performance did not meet the target effects. In Comparative Example 8, the antibacterial masterbatch lacked a coupling agent during preparation, which limited the dispersion and compatibility of the antibacterial modified montmorillonite in the PP resin, leading to montmorillonite agglomeration. This, in turn, caused pore blockage and the filtration of some antibacterial components during the spinning process.

[0060] Furthermore, as can be seen from the processing techniques of the examples and comparative examples, the processing temperature range of Examples 1-7 is wider, while the processing temperature range of the comparative examples is relatively smaller. Comparative Examples 3, 5, 6, and 7, where the antibacterial agent was not fully or completely intercalated into montmorillonite, require lower processing temperatures to reduce the decomposition of the antibacterial agent. However, lowering the temperature cannot completely inhibit the decomposition of the antibacterial agent, and low-temperature processing affects spinning stability. The preparation method provided by this invention uses antibacterial modified montmorillonite, which has good compatibility with polypropylene and is less sensitive to processing techniques.

[0061] Figure 1 The diagram shows the modification mechanism of montmorillonite. Taking the chain-like quaternary ammonium salt molecule as an example, the lamellar structure of montmorillonite is easier to separate during ball milling in a solution environment. The Na ions in the lamellar structure exchange ions with the N ions of the quaternary ammonium salt cation. The quaternary ammonium salt molecules enter between the lamellar structures of montmorillonite, increasing the interlayer spacing and remaining between the lamellar structures. The grinding time is extended, and the polypropylene and polypropylene-grafted maleic anhydride portions enter the lamellar structures.

[0062] from Figure 3 and Figure 4 It can be seen that after ball milling and intercalation, the diffraction angle of the (001) plane of nano-montmorillonite decreased from a minimum of 7.08° to 2.52°, and the interlayer spacing increased from 1.45 nm to 3.50 nm, with broadening and the appearance of mixed peaks. This indicates that a large amount of quaternary ammonium salt antibacterial agent was intercalated into the interlayer of montmorillonite, significantly altering the interlayer spacing and reducing interlayer regularity. After the addition of PP and PP-G-MAH, the interlayer spacing of montmorillonite further increased, with the diffraction angle of the (001) plane decreasing from a minimum of 2.52° to 2.28°, and the interlayer spacing further increasing to 3.87 nm. This may be due to some PP molecular chains entering the layers, further expanding the layers. After quaternary ammonium salt intercalation, the interlayer spacing was 2917.45 cm⁻¹. -1 2849.23cm -1 CH stretching vibration peaks of -CH2 and -CH3 were observed, at 1467.02 cm⁻¹. -1 The presence of in-plane bending vibration peaks for -CH2 and -CH3 indicates that the quaternary ammonium salt antibacterial agent has been successfully intercalated into the montmorillonite layers.

[0063] Figure 2A schematic diagram of the granulation mechanism of the antibacterial masterbatch is provided. During melt extrusion of cationic modified montmorillonite and polypropylene molecular chains, more long-chain polypropylene molecular chains enter the spaces between the layers, further increasing the interlayer spacing of polypropylene. The exposed polypropylene, grafted with maleic anhydride and coupling agent, promotes the compatibility between polypropylene and montmorillonite. Because quaternary ammonium salts replace the interlayer cations and connect with the interlayer molecules, the cationic antibacterial agents in montmorillonite with enlarged or partially peeled layers can be stably fixed. Furthermore, the entanglement between organic molecular chains further increases the stability of the antibacterial agent. Therefore, quaternary ammonium salt molecules are uniformly and firmly bound between the polypropylene layers.

[0064] The antibacterial spunbond nonwoven fabric provided by this invention has excellent antibacterial properties while ensuring biocompatibility. The antibacterial properties are shown in Table 2 and... Figure 7 As shown.

[0065] Appendix Figure 7 In the image, the left side shows the results of the inhibition zone of Escherichia coli, the right side shows the results of the inhibition zone of Staphylococcus aureus, the center point shows the non-antimicrobial spunbond nonwoven fabric, and the three positions around the center show the samples of non-leaching antimicrobial spunbond nonwoven fabric. It can be seen from the image that the non-leaching antimicrobial spunbond nonwoven fabric does not have an inhibition zone, which indicates that the antimicrobial nonwoven fabric is non-leaching antimicrobial.

[0066] 2. Physical property testing: The prepared spunbond nonwoven fabric was subjected to tests for properties such as basis weight and tensile strength. The test results are shown in Table 3 and Appendix. Figure 5 Appendix Figure 6 Weight per unit area: GB / T 24218.1-2009 Textiles - Nonwovens - Test Methods - Part 1: Determination of mass per unit area; Tensile properties: GB / T 24218.3-2010 Textiles - Nonwovens - Test Methods - Part 3: Determination of breaking strength and elongation at break. Table 2 shows the test results of the physical properties of the nonwoven fabrics:

[0067] Table 3 shows that the nonwoven fabric prepared using the process provided by this invention exhibits significantly improved mechanical properties, including strength and toughness, compared to conventional nonwoven fabrics, with an improvement rate exceeding 20%. This improvement in mechanical properties is attributed to the modified nano-montmorillonite, which not only promotes compatibility but also enhances the crystallization of polypropylene during stretching, resulting in more complete polypropylene crystallization. The nonwoven fabrics prepared in the comparative examples generally exhibit lower mechanical properties, primarily due to poor compatibility and dispersibility of the various components, as well as the decomposition and degradation of some substances during processing, which affects the quality and stability of the spinning process.

[0068] Combination Figure 5 and Figure 6It can be seen that as spunbond nonwoven fabric is stretched, the slope of the transverse breaking force gradually decreases. After experiencing steady elongation and fiber bonding, it breaks, indicating that the fibers themselves are well-entangled. When the overall strength decreases, the fibers still maintain a certain strength, allowing the material to elongate further. The relatively small longitudinal displacement is due to the sufficient fiber crystallization during the nonwoven fabric production process. The increased strength is primarily due to the addition of nano-montmorillonite, which promotes the crystallization of polypropylene during cooling and stretching, making the molecular chain arrangement more regular and orderly. Secondly, the modified montmorillonite has high compatibility with polypropylene, resulting in overall uniformity and reducing the likelihood of phase separation during stretching. Finally, nano-montmorillonite itself is a rigid inorganic material, and its rigidity also enhances the strength of the nonwoven fabric, which is fully reflected under the premise of good compatibility.

[0069] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A preparation process for a non-leaching antibacterial spunbond nonwoven fabric, characterized in that, The non-leaching antibacterial spunbond nonwoven fabric is prepared by spunbonding process using polypropylene, antibacterial modified montmorillonite and silane coupling agent as the main raw materials. The antibacterial modified montmorillonite is obtained by inserting cationic antibacterial agent, polypropylene grafted with maleic anhydride and polypropylene powder between its layers by mechanical grinding. The preparation process includes the following steps: S1, add montmorillonite alcohol solution A and cationic antibacterial agent alcohol solution B to a ball mill in proportion and grind and react for a period of time. Then add polypropylene powder and polypropylene grafted maleic anhydride in proportion and continue grinding. After drying and pulverizing, antibacterial modified montmorillonite is obtained. S2, the antibacterial modified montmorillonite, polypropylene powder and silane coupling agent described in S1 are mixed in proportion, and then extruded and slit by an extruder to form antibacterial masterbatch; S3, after mixing the antibacterial masterbatch, polypropylene and color masterbatch mentioned in S2 in a certain proportion, the mixture is melted, spun, initially pressed and hot rolled to obtain a non-leaching antibacterial spunbond nonwoven fabric. S1 contains sodium-based montmorillonite with an ion exchange capacity of 100-200 meq / 100g; the cationic antibacterial agent includes any one or more of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, hexadecylpyridine bromide, hexadecylpyridine chloride, tetradecyldimethylbenzylammonium chloride, and hexadecyldimethylbenzylammonium chloride.

2. The preparation process according to claim 1, characterized in that, Non-leaching antibacterial spunbond nonwoven fabric has antibacterial properties, with an inhibition rate of >65% against Staphylococcus aureus, >65% against Escherichia coli, and >50% against Candida albicans, and a cell survival rate of >92%. It also has excellent mechanical strength, with a transverse elongation of 95-110% and a transverse breaking force of 40-47N; a longitudinal elongation of 75-85% and a longitudinal breaking force of 90-100N.

3. The preparation process according to claim 1, characterized in that, In S1, the ratio of montmorillonite to solvent in montmorillonite alcohol solution A is 1:5-10, and the amount of montmorillonite added is 3-5 parts; in the cationic antibacterial agent alcohol solution B, the ratio of cationic antibacterial agent to solvent is 1:3-5, and the amount of cationic antibacterial agent added is 1-6 parts; the amount of polypropylene powder added is 1 part; the amount of polypropylene grafted with maleic anhydride added is 1.5-3 parts; the solvent includes any one or more of anhydrous ethanol and methanol; wherein the raw material components in S1 are in parts by weight.

4. The preparation process according to claim 1, characterized in that, The ratio of antibacterial modified montmorillonite, polypropylene powder and silane coupling agent in S2 is 1:0.8-1.2:0.03-0.05; the coupling agent mainly includes any one or two of γ-methacryloyloxypropyltrimethoxysilane (KH560) and γ-glycidoxypropyltrimethoxysilane (KH570); wherein the raw material components in S2 are in parts by weight.

5. The preparation process according to claim 1, characterized in that, The ratio of antibacterial masterbatch, polypropylene and color masterbatch added in S3 is 1:6-10:0-0.3; wherein the raw material components in S3 are by weight.

6. The preparation process according to any one of claims 3-5, characterized in that, The mass ratio of large, medium, and small agate balls used in the ball milling process described in S1 is 10-20:25-40:40-65; the overall ball-to-material ratio is 70-80:20-30; the ball milling speed is 400-500 rpm; after mixing solutions A and B, the cumulative ball milling time is 1-2 hours for forward rotation and 1-2 hours for reverse rotation; after adding polypropylene grafted maleic anhydride and polypropylene powder, the cumulative ball milling time is 1-2 hours for reverse rotation and 1-2 hours for forward rotation; after ball milling, drying takes 6-8 hours at a temperature of 80-90℃.

7. The preparation process according to claim 6, characterized in that, The extrusion parameters for the antibacterial masterbatch described in S2 include: low-speed mixing in a high-speed mixing tank for 1 min; feeding the mixed raw material into a twin-screw extruder, with the following temperatures for the ten zones of the twin-screw extruder: Zone 1 140±10℃, Zone 2 145±10℃, Zone 3 155±5℃, Zone 4 180±10℃, Zone 5 195±5℃, Zone 6 200±5℃, Zone 7 205±10℃, Zone 8 205±10℃, Zone 9 205±10℃, and die head 205±10℃; feeding speed 12±2 rpm / min; main extruder speed 120±15 rpm / min; and pelleting speed 370±20 rpm / min.

8. The preparation process according to claim 7, characterized in that, The extrusion parameters for the non-leaching antibacterial spunbond nonwoven fabric described in S3 include: the spunbonding process temperatures for zones one through six are 185±10℃ for zone one, 225±10℃ for zone two, 235±10℃ for zone three, 235±10℃ for zone four, 235±10℃ for zone five, and 235±10℃ for zone six, respectively; the cooling, stretching, and blowing parameters are: melt cooling air 6±2℃; monomer 550±50 rpm / min; metering pump 24±1 Hz; suction 1150±100 rpm / min; and web forming speed 215±15 m / min.

9. The application of the preparation process of the non-leaching antibacterial spunbond nonwoven fabric according to claim 1 or 2, characterized in that, The prepared non-leaching antibacterial spunbond nonwoven fabric is combined with meltblown nonwoven fabric, breathable membrane and coating layer to prepare antibacterial spunbond meltblown composite nonwoven fabric, antibacterial coated nonwoven fabric and antibacterial coated nonwoven fabric.

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