Composite antibacterial odor-reducing sanitary towel and preparation method thereof

Abstract

The invention relates to a composite antibacterial odor-reducing sanitary napkin and a preparation method thereof, and belongs to the technical field of personal hygiene care product manufacturing, and the preparation method comprises the following steps: polymerizing a hydrophilic monomer in a nitrogen atmosphere to prepare a hydrophilic spacer arm modified polymer; meanwhile, a vacuum impregnation and wall material coating process is adopted, and a porous carrier and antibacterial factors are combined to prepare a core-shell structure compound; mixing the two components with a cross-linking agent, a catalyst and the like, and performing ultrasonic dispersion and standing defoaming to prepare finishing liquid; the finishing liquid is sprayed to the surface of a sanitary napkin base material under the low-humidity condition, drying and curing are conducted through gradient heating, and finally the composite antibacterial odor-reducing sanitary napkin is prepared, continuous antibacterial activity and excellent interface compatibility are ensured, and micro-crack falling of a functional layer is avoided when the base material deforms.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of personal hygiene care products, in particular to a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof. BACKGROUND

[0002] With the increasing demand for women's menstrual health and comfort, sanitary napkins with composite antibacterial and odor-reducing functions have gradually become the focus of attention. Existing products of this type usually need to build a functional layer on the surface of the fiber substrate to achieve specific functions. However, traditional processes rely mainly on ordinary hydrophobic adhesives or simple physical mixing methods. Although this approach can provide certain functions in the early stage, it has significant defects in actual use. On the one hand, the rigid hydrophobic film layer hinders the rapid infiltration of liquid, resulting in poor surface air permeability, easy to produce a stuffy and sticky feeling, and when the substrate is deformed under stress, the functional layer is prone to micro-cracks or peeling due to the lack of flexibility, resulting in functional failure. On the other hand, the direct addition of active factors lacks effective loading and slow-release protection, and is prone to rapid release in a humid environment, resulting in rapid decay of antibacterial and odor-reducing effects, and even may stimulate sensitive skin due to instantaneous high concentration. Therefore, how to enhance the interface bonding strength of the functional layer and the substrate while solving the problem of stuffiness caused by hydrophobic adhesives and achieving long-term and mild release of active factors has become a problem that needs to be solved in this field.

[0003] The above information disclosed in the above background section is only used to strengthen the understanding of the background of the present disclosure, and therefore it can include information that does not constitute prior art known to those of ordinary skill in the art. SUMMARY

[0004] The present application aims to provide a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof to solve the problems raised in the above background.

[0005] The technical solution of the present application is a preparation method of a composite antibacterial and odor-reducing sanitary napkin, which comprises mixing a hydrophilic spacer arm modified polymer, a core-shell structure antibacterial and odor-reducing composite, a crosslinking agent and a solvent, adding a catalyst and stirring, ultrasonic dispersion, standing and defoaming to obtain a composite functional finishing liquid;

[0006] Under the conditions of room temperature and relative humidity of air less than 60%, the composite functional finishing liquid is applied on the surface of the fiber substrate of the sanitary napkin by spraying to form a uniform liquid thin layer;

[0007] The fiber substrate of the sanitary napkin with the liquid thin layer is placed in an oven for gradient temperature drying, solidification to obtain a composite antibacterial and odor-reducing sanitary napkin;

[0008] The preparation of the hydrophilic spacer arm modified polymer comprises the following steps:

[0009] The hydrophilic long-chain monomer, the active grafting monomer and deionized water are mixed, stirred, an initiator is added in a nitrogen atmosphere, and a reflux reaction is carried out for 4-8 hours. After the reaction is completed, a precipitant selected from diethyl ether or acetone is added, and the mixture is left to stand, filtered, washed and dried to obtain the hydrophilic spacer arm modified polymer.

[0010] The preparation of the core-shell structure antibacterial and odor-removing composite includes the following steps:

[0011] Step 1: The porous inorganic carrier is added to an antibacterial and odor-removing factor solution, vacuum impregnated, centrifuged and dried to obtain a loaded inner core.

[0012] Step 2: The loaded inner core is dispersed in a film-forming wall material solution containing 1%-2% acetic acid by volume fraction, high-speed sheared, an interfacial modifier is added, and the mixture is reacted and incubated for 2-4 hours. The mixture is filtered, washed and dried to obtain the core-shell structure antibacterial and odor-removing composite.

[0013] Preferably, the mass ratio of the hydrophilic spacer arm modified polymer, the core-shell structure antibacterial and odor-removing composite, the crosslinking agent, the solvent and the catalyst is (12-24):(5-15):(2-6):(60-120):(0.5-1.5).

[0014] Preferably, the solvent is any one of deionized water, anhydrous ethanol or a 1%-2% acetic acid solution by volume fraction; the catalyst is sodium dihydrogen phosphate or sodium hypophosphite; and the crosslinking agent is any one of citric acid or glutaraldehyde.

[0015] Preferably, the gradient temperature drying is specifically: first, pre-drying at 45-55°C for 15-30 minutes, then heating to C for 3-8 minutes.

[0016] Preferably, the mass ratio of the hydrophilic long-chain monomer, the active grafting monomer, deionized water, the initiator and the precipitant is (20-40):(5-10):(100-200):(0.1-0.3):(50-100).

[0017] Preferably, the hydrophilic long-chain monomer is polyethylene glycol methacrylate; and the active grafting monomer is any one of acrylic acid or methacrylic acid.

[0018] Preferably, the mass ratio of the porous inorganic carrier and the antibacterial and odor-removing factor solution is (5-10):(40-80); the vacuum degree of the vacuum impregnation is -0.08 MPa to -0.1 MPa, and the impregnation time is 2-4 hours.

[0019] Preferably, the porous inorganic carrier is any one of mesoporous silica or nano zeolite; and the antibacterial and odor-removing factor solution is a nano silver solution or a plant polyphenol extract.

[0020] Preferably, the mass ratio of the supported core, the film-forming wall material solution, and the interface modifier is (8-12):(50-100):(1-3).

[0021] Preferably, the solute in the film-forming wall material solution is chitosan or sodium alginate; the interface modifier is glycidyloxypropyltrimethoxysilane or methylacryloyloxypropyltrimethoxysilane; when using methylacryloyloxypropyltrimethoxysilane, an initiator with a mass fraction of 0.1%-0.5% needs to be added to the reaction system to initiate the double bond polymerization grafting.

[0022] The present application provides a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof by improving the prior art, which has the following improvements and advantages compared with the prior art:

[0023] 1. The hydrophilic spacer arm modified polymer prepared by the present application uses a hydrophilic long-chain monomer to construct a flexible spacer layer, effectively solving the problem of surface stickiness and liquid infiltration blockage caused by the rigid hydrophobic film layer formed by ordinary resins in the prior art. The polymer forms a three-dimensional network on the fiber surface, which not only firmly anchors the antibacterial factors, but also exposes the antibacterial sites after liquid absorption through the swing of the spacer arm. This structure can quickly guide the liquid to infiltrate when a large amount of liquid is poured, reducing surface residue, thereby maintaining a dry and breathable surface layer while ensuring continuous antibacterial activity and excellent interfacial compatibility, and avoiding micro-cracks and shedding of the functional layer during deformation of the substrate.

[0024] 2. The present application uses a core-shell structure antibacterial and odor-removing compound, which loads the antibacterial and odor-removing factors inside the porous inorganic carrier through vacuum impregnation and wraps them with a film-forming wall material. This structure uses the dual action of physical adsorption and chemical bonding to achieve controlled release of functional factors, effectively preventing the irritation of the skin caused by rapid migration of the factors. Compared with the method of directly adding active factors, this compound can avoid the rapid release of active ingredients in a humid environment, ensuring that the sanitary napkin still has durable and stable antibacterial and odor-removing properties in a long-wearing or high-humidity environment at night.

[0025] 3. The present application realizes in-situ crosslinking and stable assembly of functional materials on the surface of the sanitary napkin fiber substrate by introducing a crosslinking agent and an optimized gradient temperature drying process. The hydrophilic spacer arm modified polymer and the core-shell structure compound form a firm chemical bond, which, combined with the use of an interface modifier, significantly improves the adhesion and deformation resistance of the functional layer. This crosslinked network effectively prevents the shedding of the functional layer during the menstrual period, solving the technical problem of easy shedding of the functional layer in existing products, and also avoiding the blockage of fiber pores due to excellent interfacial compatibility, achieving the synergy of antibacterial and odor-removing properties and breathability and heat dissipation.

[0026] 4、The prepared composite antibacterial and odor-reducing sanitary napkin realizes synergistic effect of liquid absorption and guidance, long-acting bacteriostasis, and rapid odor removal; in complex scenes such as simulated menstrual wetness, exercise sweating, or summer high temperature and high humidity, the hydrophilic spacer arm on the surface can quickly guide the infiltration of liquid and keep dry, and the odor-removing factor in the core-shell structure can quickly neutralize odor molecules; the product not only overcomes the sticky feeling of traditional hydrophobic coatings, but also builds a safer protective barrier by optimizing the microstructure while ensuring breathability, providing a fresh experience and health protection for the user throughout the menstrual period, and is especially suitable for application scenes with high requirements for breathability and comfort. DETAILED DESCRIPTION

[0027] To make the purpose, technical solutions and advantages of the present application clearer, the present application is further described in detail below with specific examples.

[0028] Example 1

[0029] The present embodiment provides a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof, aiming to solve the problems of easy peeling of the functional layer and stuffiness caused by hydrophobic adhesives in existing products, comprising the following steps: mixing a hydrophilic spacer arm modified polymer, a core-shell structure antibacterial and odor-removing compound, a crosslinking agent, and a solvent, adding a catalyst for stirring, ultrasonic dispersion, standing for defoaming, to obtain a composite functional finishing liquid; under the condition of room temperature and air relative humidity less than 60%, the composite functional finishing liquid is applied on the surface of the sanitary napkin fiber substrate by spraying to form a uniform liquid thin layer;

[0030] The sanitary napkin fiber substrate with the applied liquid thin layer is placed in an oven for gradient temperature drying, specifically: first pre-drying at 45℃ for 30 minutes, then heating to 80℃ for curing for 10 minutes, to obtain a composite antibacterial and odor-reducing sanitary napkin; in the simulated wet environment of female menstrual period, the three-dimensional network constructed by the hydrophilic spacer arm modified polymer effectively anchors the antibacterial factor, while keeping the surface dry and breathable, and persistently inhibiting the growth of bacteria and reducing odor;

[0031] The mass ratio of the hydrophilic spacer arm modified polymer, the core-shell structure antibacterial and odor-removing compound, the crosslinking agent, the solvent, and the catalyst is 12:5:2:60:0.5; the solvent is deionized water; the catalyst is sodium hypophosphite; and the crosslinking agent is citric acid;

[0032] The preparation of the hydrophilic spacer arm modified polymer comprises the following steps: mixing a hydrophilic long-chain monomer, an active grafting monomer and deionized water, stirring, adding an initiator in a nitrogen atmosphere, carrying out a reflux reaction for 4 hours, after the reaction is completed, adding a precipitant selected from diethyl ether or acetone, standing, suction filtration, washing, drying, and obtaining the hydrophilic spacer arm modified polymer; the mass ratio of the hydrophilic long-chain monomer, the active grafting monomer, the deionized water, the initiator and the precipitant is 20:5:100:0.1:50; the hydrophilic long-chain monomer is polyethylene glycol methacrylate; and the active grafting monomer is acrylic acid;

[0033] The preparation of the core-shell structure antibacterial and odor-removing composite comprises the following steps: step 1, adding a porous inorganic carrier into an antibacterial and odor-removing factor solution, vacuum impregnating at a vacuum degree of-0.08 MPa for 4 hours, centrifuging, and drying to obtain a loaded inner core; step 2, dispersing the loaded inner core in a film-forming wall material solution containing 1% (by volume fraction) of an interface modifier, and carrying out high-speed shearing at a rotational speed of 10,000 rpm for 15 minutes, and then carrying out a reaction and keeping warm at 60°C for 3 hours; suction filtering, washing, and drying to obtain the core-shell structure antibacterial and odor-removing composite; the mass ratio of the porous inorganic carrier and the antibacterial and odor-removing factor solution is 5:40; the mass ratio of the loaded inner core, the film-forming wall material solution and the interface modifier is 8:50:1; the porous inorganic carrier is mesoporous silica; the antibacterial and odor-removing factor solution is a nano-silver solution; the solute in the film-forming wall material solution is chitosan; and the interface modifier is silane coupling agent KH-560. The preparation of the core-shell structure antibacterial and odor-removing composite comprises the following steps: step 1, adding a porous inorganic carrier into an antibacterial and odor-removing factor solution, vacuum impregnating at a vacuum degree of-0.08 MPa for 4 hours, centrifuging, and drying to obtain a loaded inner core; step 2, dispersing the loaded inner core in a film-forming wall material solution containing 1% (by volume fraction) of an interface modifier, and carrying out high-speed shearing at a rotational speed of 10,000 rpm for 15 minutes, and then carrying out a reaction and keeping warm at 60°C for 3 hours; suction filtering, washing, and drying to obtain the core-shell structure antibacterial and odor-removing composite; the mass ratio of the porous inorganic carrier and the antibacterial and odor-removing factor solution is 5:40; the mass ratio of the loaded inner core, the film-forming wall material solution and the interface modifier is 8:50:1; the porous inorganic carrier is mesoporous silica; the antibacterial and odor-removing factor solution is a nano-silver solution; the solute in the film-forming wall material solution is chitosan; and the interface modifier is silane coupling agent KH-560.

[0034] Example 2:

[0035] The present embodiment provides a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof. The interface compatibility is improved by introducing a long-chain hydrophilic spacer arm, and the method comprises the following steps: mixing a hydrophilic spacer arm modified polymer, a core-shell structure antibacterial and odor-removing composite, a crosslinking agent and a solvent, adding a catalyst and stirring, ultrasonic dispersion, standing and defoaming to obtain a composite functional finishing liquid; under the conditions of room temperature and an air relative humidity of less than 60%, the composite functional finishing liquid is applied on the surface of a sanitary napkin fiber substrate in a spraying manner to form a uniform liquid thin layer.

[0036] The sanitary napkin fiber substrate to which the liquid thin layer is applied is placed in an oven for gradient temperature drying, specifically, pre-drying at 48°C for 26 minutes, and then solidifying at 84°C for 9 minutes to obtain a composite antibacterial and odor-reducing sanitary napkin. The preparation method makes the surface layer of the sanitary napkin still be able to expose antibacterial sites through the swing of the spacer arm after absorbing liquid, which is suitable for use in scenarios with large amounts of exercise and more sweating, and ensures continuous bacteriostasis and fresh experience.

[0037] ​The mass ratio of the hydrophilic spacer arm modified polymer, the core-shell structure antibacterial and odor-removing compound, the crosslinking agent, the solvent and the catalyst is 15:8:3:75:0.8; the solvent is anhydrous ethanol; the catalyst is sodium dihydrogen phosphate; and the crosslinking agent is glutaraldehyde.

[0038] The preparation of the hydrophilic spacer arm modified polymer comprises the following steps: mixing a hydrophilic long-chain monomer, an active grafting monomer and deionized water, stirring, adding an initiator in a nitrogen atmosphere, performing reflux reaction for 5 hours, adding a precipitant selected from diethyl ether or acetone after the reaction is completed, standing, suction filtration, washing, drying, and obtaining the hydrophilic spacer arm modified polymer; the mass ratio of the hydrophilic long-chain monomer, the active grafting monomer, the deionized water, the initiator and the precipitant is 25:6:125:0.15:60; the hydrophilic long-chain monomer is polyethylene glycol methacrylate; and the active grafting monomer is methacrylic acid.

[0039] The preparation of the core-shell structure antibacterial and odor-removing compound comprises the following steps: step 1, adding a porous inorganic carrier into an antibacterial and odor-removing factor solution, vacuum impregnating at a vacuum degree of -0.085 MPa for 3.5 hours, centrifuging, drying, and obtaining a loaded inner core; step 2, dispersing the loaded inner core in a film-forming wall material solution containing deionized water, high-speed shearing at a rotating speed of 10,000 rpm for 15 minutes, adding an interface modifier, reacting and incubating at 55℃ for 4 hours; suction filtering, washing, drying, and obtaining the core-shell structure antibacterial and odor-removing compound; the mass ratio of the porous inorganic carrier and the antibacterial and odor-removing factor solution is 6:50; the mass ratio of the loaded inner core, the film-forming wall material solution and the interface modifier is 9:65:1.5; the porous inorganic carrier is nano zeolite; the antibacterial and odor-removing factor solution is a plant polyphenol extract solution; the solute in the film-forming wall material solution is sodium alginate; and the interface modifier is silane coupling agent KH-570. Example 3:

[0040] The present embodiment provides a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof, and focuses on optimizing the stability of the microstructure, comprising the following steps: mixing a hydrophilic spacer arm modified polymer, a core-shell structure antibacterial and odor-removing compound, a crosslinking agent and a solvent, adding a catalyst and stirring, ultrasonic dispersion, standing and defoaming, and obtaining a composite functional finishing liquid; under the conditions of room temperature and air relative humidity less than 60%, applying the composite functional finishing liquid on the surface of a sanitary napkin fiber substrate by spraying to form a uniform liquid thin layer.

[0041]

[0042] ​The sanitary napkin fiber substrate with a liquid thin layer applied is placed in an oven and dried by gradient temperature increase: first, it is pre-dried at 50℃ for 22 minutes, and then the temperature is increased to 88℃ for 7 minutes to obtain a composite antibacterial and odor-reducing sanitary napkin; when worn for a long time at night, this product effectively prevents the migration of functional factors from irritating the skin due to the slow-release effect of the core-shell structure and the strong chemical bonding, while maintaining excellent breathability.

[0043] The mass ratio of the hydrophilic spacer arm modified polymer, the core-shell structured antibacterial and deodorizing complex, the crosslinking agent, the solvent, and the catalyst is 18:10:4:90:1.0; the solvent is deionized water; the catalyst is sodium hypophosphite; and the crosslinking agent is citric acid.

[0044] The preparation of the hydrophilic spacer arm modified polymer includes the following steps: mixing a hydrophilic long-chain monomer, an active graft monomer, and deionized water, stirring, adding an initiator under a nitrogen atmosphere, and refluxing for 6 hours. After the reaction, adding a precipitant selected from diethyl ether or acetone, allowing to stand, filtering, washing, and drying to obtain the hydrophilic spacer arm modified polymer; the mass ratio of the hydrophilic long-chain monomer, active graft monomer, deionized water, initiator, and precipitant is 30:7.5:150:0.2:75; the hydrophilic long-chain monomer is polyethylene glycol methacrylate; and the active graft monomer is acrylic acid.

[0045] The preparation of the core-shell structured antibacterial and deodorizing complex includes the following steps: Step 1: A porous inorganic carrier is added to an antibacterial and deodorizing factor solution. Vacuum impregnation is performed at a vacuum degree of -0.09 MPa for 3 hours, followed by centrifugation and drying to obtain a supported core. Step 2: The supported core is dispersed in a solution containing 1%- In the film-forming wall material solution of acetic acid, The mixture was sheared at high speed for 15 minutes, an interface modifier was added, and the reaction was carried out at 65°C for 2.5 hours. After filtration, washing, and drying, a core-shell structured antibacterial and deodorizing complex was obtained. The mass ratio of the porous inorganic carrier to the antibacterial and deodorizing factor solution was 7.5:60. The mass ratio of the supported core, film-forming wall material solution, and interface modifier was 10:75:2. The porous inorganic carrier was mesoporous silica. The antibacterial and deodorizing factor solution was nano-silver solution. The solute in the film-forming wall material solution was chitosan. The interface modifier was silane coupling agent KH-560.

[0046] Example 4:

[0047] This embodiment provides a composite antibacterial and odor-reducing sanitary napkin and its preparation method. In-situ crosslinking technology is used to strengthen the bonding force of the substrate. The method includes the following steps: mixing a hydrophilic spacer-modified polymer, a core-shell structured antibacterial and odor-reducing complex, a crosslinking agent, and a solvent; adding a catalyst and stirring; ultrasonically dispersing; and allowing to stand for degassing to obtain a composite functional finishing liquid. Under conditions of room temperature and relative humidity below 60%, the composite functional finishing liquid is applied to the surface of the sanitary napkin fiber substrate by spraying to form a uniform liquid thin layer. The sanitary napkin fiber substrate with the applied liquid thin layer is placed in an oven and dried using a gradient temperature increase method: first, pre-drying at 52°C for 18 minutes, then heating to 92°C for 6 minutes to cure, resulting in a composite antibacterial and odor-reducing sanitary napkin. When dealing with heavy tidal surges, the hydrophilic spacer arms on the surface of the sanitary napkin can quickly guide the liquid to seep down, reducing surface residue, while the odor-reducing factors within the core-shell structure rapidly neutralize odor molecules.

[0048] The mass ratio of the hydrophilic spacer arm modified polymer, the core-shell structured antibacterial and deodorizing complex, the crosslinking agent, the solvent, and the catalyst is 21:12:5:105:1.2; the solvent is anhydrous ethanol; the catalyst is sodium dihydrogen phosphate; and the crosslinking agent is glutaraldehyde.

[0049] The preparation of the hydrophilic spacer arm modified polymer includes the following steps: mixing a hydrophilic long-chain monomer, an active graft monomer, and deionized water, stirring, adding an initiator under a nitrogen atmosphere, and refluxing for 7 hours. After the reaction, adding a precipitant selected from diethyl ether or acetone, allowing to stand, filtering, washing, and drying to obtain the hydrophilic spacer arm modified polymer; the mass ratio of the hydrophilic long-chain monomer, active graft monomer, deionized water, initiator, and precipitant is 35:9:175:0.25:90; the hydrophilic long-chain monomer is polyethylene glycol methacrylate; and the active graft monomer is methacrylic acid.

[0050] The preparation of the core-shell structured antibacterial and deodorizing complex includes the following steps: Step 1: A porous inorganic carrier is added to an antibacterial and deodorizing factor solution. Vacuum impregnation is performed at a vacuum degree of -0.095 MPa for 2.5 hours. The mixture is then centrifuged and dried to obtain a supported core. Step 2: The supported core is dispersed in a film-forming wall material solution containing deionized water. The mixture was sheared at high speed for 15 minutes, an interface modifier was added, and the reaction was carried out at 58℃ for 3.5 hours. After filtration, washing, and drying, a core-shell structured antibacterial and deodorizing complex was obtained. The mass ratio of the porous inorganic carrier to the antibacterial and deodorizing factor solution was 9:70. The mass ratio of the supported core, film-forming wall material solution, and interface modifier was 11:85:2.5. The porous inorganic carrier was nano-zeolite. The antibacterial and deodorizing factor solution was nano-silver solution. The solute in the film-forming wall material solution was sodium alginate. The interface modifier was silane coupling agent KH-570.

[0051] Embodiment 5:

[0052] The embodiment provides a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof, realizes nanometer thin layer assembly of a functional material on a fiber surface, and comprises the following steps: mixing a hydrophilic spacer arm modified polymer, a core-shell structure antibacterial and odor-reducing compound, a crosslinking agent and a solvent, stirring, adding a catalyst, ultrasonic dispersion, standing and defoaming to obtain a composite functional finishing liquid; under the condition of room temperature and relative humidity of air being less than 60%, the composite functional finishing liquid is applied on the surface of a fiber base material of the sanitary napkin in a spraying mode to form a uniform liquid thin layer; the fiber base material of the sanitary napkin to which the liquid thin layer is applied is placed into an oven, and gradient temperature rising drying is performed, specifically, pre-drying is performed at 55 DEG C for 15 minutes, then the temperature is increased to 95 DEG C for curing for 5 minutes, and a composite antibacterial and odor-reducing sanitary napkin is obtained; in a summer environment with high temperature and high humidity, the sanitary napkin avoids plugging of fiber pores by the functional layer due to excellent interfacial compatibility, and realizes the synergy of antibacterial and odor-reducing and air permeation and heat dissipation;

[0053] The mass ratio of the hydrophilic spacer arm modified polymer, the core-shell structure antibacterial and odor-reducing compound, the crosslinking agent, the solvent and the catalyst is 24:15:6:120:1.5; the solvent is deionized water; the catalyst is sodium bicarbonate; and the crosslinking agent is citric acid.

[0054] The hydrophilic spacer arm modified polymer is prepared by the following steps: mixing a hydrophilic long-chain monomer, an active grafting monomer and deionized water, stirring, adding an initiator in a nitrogen atmosphere, performing reflux reaction for 8 hours, adding a precipitating agent selected from diethyl ether or acetone after the reaction is completed, standing, suction filtration, washing and drying to obtain the hydrophilic spacer arm modified polymer; the mass ratio of the hydrophilic long-chain monomer, the active grafting monomer, the deionized water, the initiator and the precipitating agent is 40:10:200:0.3:100; the hydrophilic long-chain monomer is polyethylene glycol methacrylate; and the active grafting monomer is acrylic acid.

[0055] The core-shell structure antibacterial and odor-reducing compound is prepared by the following steps: step 1, adding a porous inorganic carrier into an antibacterial and odor-reducing factor solution, performing vacuum impregnation with a vacuum degree of-0.1 MPa, impregnating for 2 hours, centrifuging and drying to obtain a supported inner core; and step 2, dispersing the supported inner core in a film-forming wall material solution containing 1%-5% (by volume) acetic acid, performing vacuum filtration, drying and calcining to obtain the core-shell structure antibacterial and odor-reducing compound. The film-forming wall material solution contains 1%-5% (by volume) acetic acid. The solution of the porous inorganic carrier and the antibacterial and odor-removing factor solution were mixed at a mass ratio of 10:80, and the solution of the loaded inner core, the film-forming wall material, and the interface modifier were mixed at a mass ratio of 12:100:3. The porous inorganic carrier was mesoporous silica. The antibacterial and odor-removing factor solution was a plant polyphenol extract. The solute in the film-forming wall material solution was chitosan. The interface modifier was silane coupling agent KH-560.

[0056] In Examples 1-5 and Comparative Examples 1-2, polyethylene glycol methacrylate (PEGMA) was from Shanghai Aladdin Biochemical Technology Co., Ltd., with an average molecular weight Mn = 360 and CAS number: 25736-21-8; acrylic acid was from Sinopharm Chemical Reagent Co., Ltd., with an analytical purity and CAS number: 79-10-7; methacrylic acid was from Shanghai Maikelin Biotechnology Co., Ltd., with a purity of 99% and CAS number: 79-41-4; mesoporous silica was from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd., with an average pore size of 7-10 nm and a specific surface area of >500 m² / g; nano-zeolite was from the Catalyst Factory of Nankai University, with a model number of NKF-5 and a particle size of 50-100 nm; nano-silver solution was from Shanghai Huzheng Nanometer Technology Co., Ltd., with a model number of Ag-S02 and a silver content of 2000 ppm; plant polyphenol extract (tea polyphenol) was from Xi'an Lvsen Biotechnology Co., Ltd., with a total polyphenol content of ≥98% and CAS number: 84650-60-2; chitosan was from Zhejiang Jinshell Pharmaceutical Co., Ltd., with a degree of deacetylation of ≥95% and CAS number: 9012-76-4; sodium alginate was from Qingdao Mingyue Seaweed Group Co., Ltd., with a viscosity of 200-500 mpa.s and CAS number: 9005-38-3; silane coupling agents KH-560 (glycidyl ether oxypropyl trimethoxysilane) and KH-570 (methacryloyloxypropyl trimethoxysilane) were both from Nanjing Kent Chemical Co., Ltd., with a purity of ≥98%; ordinary acrylic resin was from Wanhua Chemical Group Co., Ltd., with a model number of WA-2041; the initiator was ammonium persulfate (APS), with a purity of 98%; the precipitant was analytical pure diethyl ether or acetone; glacial acetic acid was from [a specific manufacturer, such as Sinopharm Chemical Reagent Co., Ltd.], with an analytical purity; citric acid, glutaraldehyde, sodium dihydrogen phosphate, sodium hypophosphite, and solvents were all commercially available analytical pure products.

[0057] Comparative Example 1:

[0058] ​​​The comparative example provides a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof, which is different from example 3 in that a common acrylic resin binder is used instead of a hydrophilic spacer arm modified polymer, including the following steps: mixing a common acrylic resin, a core-shell structure antibacterial and odor-removing compound, a crosslinking agent and a solvent, adding a catalyst and stirring, ultrasonic dispersion, standing and defoaming to obtain a finishing liquid; the subsequent spraying and gradient temperature drying steps are the same as those of example 3; due to the lack of a spacer arm structure constructed by a hydrophilic long-chain monomer, the rigid hydrophobic film layer formed by the common resin hinders the rapid infiltration of liquid when the sanitary napkin prepared in this comparative example contacts menstrual blood, resulting in a sticky surface feeling for the user during the menstrual period, and due to the lack of the buffering of the flexible spacer layer, the functional coating is prone to micro-cracks and falls off when the substrate deforms, affecting the long-acting antibacterial performance;

[0059] The mass ratio of the common acrylic resin, the core-shell structure antibacterial and odor-removing compound, the crosslinking agent, the solvent and the catalyst is 18:10:4:90:1.0.

[0060] Comparative example 2:

[0061] The comparative example provides a composite antibacterial and odor-reducing sanitary napkin and a preparation method thereof, which is different from example 3 in that a core-shell structure antibacterial and odor-removing compound is not used, but an equal amount of an antibacterial and odor-removing factor is directly added, including the following steps: mixing a hydrophilic spacer arm modified polymer, a nano-silver solution, a crosslinking agent and a solvent, adding a catalyst and stirring, ultrasonic dispersion, standing and defoaming to obtain a finishing liquid; the subsequent spraying and gradient temperature drying steps are the same as those of example 3; due to the lack of the protection of the porous inorganic carrier and the slow-release effect of the film-forming wall material, the odor control of the sanitary napkin prepared in this comparative example is acceptable at the beginning of opening, but after contacting with a humid environment, the active factor is released too quickly, resulting in a rapid decay of the antibacterial and odor-removing effect in a short period of time, which cannot meet the protection requirements during the replacement interval of the entire menstrual period, and direct contact with high concentration may irritate sensitive skin;

[0062] The mass ratio of the hydrophilic spacer arm modified polymer, the nano-silver solution, the crosslinking agent, the solvent and the catalyst is 18:10:4:90:1.0.

[0063] The composite antibacterial and odor-reducing sanitary napkins prepared in comparative examples 1-2 and example 1-5 are subjected to corresponding tests, and the test results are as follows:

[0064] (1) Liquid infiltration and reverse osmosis performance test

[0065] The sanitary napkins prepared in Examples 1-5 and Comparative Examples 1-2 were tested for penetration speed and reverse penetration amount using standard synthetic menstrual blood according to the GB / T8939-2018 "Sanitary Napkin (Panty Liner)" standard; the test samples were fixed on an inclined plane, 5 ml of synthetic menstrual blood was injected, and the time required for complete penetration was recorded; then a certain pressure was applied on the surface of the sample, and the mass of the back-penetrated liquid was measured; each group of samples was repeatedly measured 5 times, and the average value was recorded, and the test results are shown in Table 1;

[0066] Table 1

[0067]

[0068] As can be seen from Table 1, the composite antibacterial and odor-reducing sanitary napkins prepared in Examples 1-5 all exhibit extremely fast penetration speed (<3.5s) and extremely low reverse penetration amount, which are significantly better than Comparative Example 1;

[0069] Among them, the penetration performance of Example 4 is the best, which is due to the optimized formula ratio of the functional layer to realize the nano-thin layer assembly on the surface of the fiber, and the pore structure of the substrate is maximally reserved;

[0070] Hydrophilic difference: the penetration time of Comparative Example 1 is as long as 15.68 seconds, and the reverse penetration is serious; this is because Comparative Example 1 uses ordinary acrylic resin adhesive, which forms a rigid hydrophobic film layer on the surface of the fiber after curing; this hydrophobic barrier hinders the rapid conduction of liquid to the absorbent core layer, causing the liquid to stay on the surface layer, not only increasing the reverse penetration amount, but also making the user feel hot and humid; in contrast, Examples 1-5 introduce a hydrophilic spacer arm modified polymer, which is polymerized from polyethylene glycol methacrylate and active grafting monomers; the polymer introduces long-chain hydrophilic groups through molecular structure design, and constructs a three-dimensional hydrophilic network on the surface of the fiber; when the liquid contacts the surface of the sanitary napkin, the hydrophilic spacer arm can quickly capture water molecules and guide them to penetrate downward, thereby breaking the hydrophobic barrier caused by the traditional chemical adhesive and realizing zero-resistance liquid transmission;

[0071] Although Comparative Example 2 does not use hydrophobic resin, its penetration speed is close to that of the examples, but the fixing force of its functional layer is weak, and due to the lack of spacer arm buffer, the distribution of liquid at the micro interface is not as uniform as that of the examples;

[0072] (2) Long-acting antibacterial and odor-removing performance test

[0073] According to GB15979-2002 "Hygienic Standard for Disposable Hygienic Products", the bacteriostatic performance of Examples 1-5 and Comparative Examples 1-2 was tested, and Staphylococcus aureus and Escherichia coli were selected as the bacteria, and the bacteriostatic rate was measured at 1 hour and 24 hours after inoculation, respectively; at the same time, the odor removal efficiency of the sample on standard ammonia gas of a certain concentration was tested by gas chromatography to simulate the control ability on menstrual odor; the test results are shown in Table 2.

[0074] Table 2

[0075]

[0076] As can be seen from Table 2, Examples 1-5 maintained a bacteriostatic rate close to 100% and excellent odor removal effect for a long time, verifying the effectiveness of the core-shell structure microcapsule technology;

[0077] Slow-release mechanism: Comparative Example 2 has a high bacteriostatic rate within 1 hour, but it significantly decreases to 75.41% after 24 hours, and the odor removal efficiency is also the lowest; this is because Comparative Example 2 does not use a core-shell structure antibacterial and odor removal composite, but directly adds a nano-silver solution; this direct addition method causes uncontrolled rapid ion precipitation or loss with liquid migration of the active factor in the initial contact with the humid environment, although the initial activity is high, but the consumption is extremely fast, which cannot meet the long-acting protection needs during the entire menstrual replacement interval, and the high concentration release may stimulate the skin;

[0078] Examples 1-5 of the present application use a core-shell structure antibacterial and odor removal composite, i.e., a porous inorganic carrier such as mesoporous silica or nano-zeolite is used as the inner core to load antibacterial factors, and a chitosan or sodium alginate film-forming wall material is used for external wrapping; this special microstructure plays a role in intelligent slow release: the wall material is closed when dry to prevent factor oxidation or volatilization; after absorbing moisture, it swells moderately and slowly releases the nano-silver or plant polyphenol loaded inside; this mechanism ensures that the antibacterial and odor removal functions are continuously and smoothly output within 24 hours, avoiding the decay of efficacy;

[0079] The bacteriostatic rate and odor removal rate of Comparative Example 1 are lower than those of the examples, because the ordinary acrylic resin used in Comparative Example 1 wraps part of the functional particles, hindering the effective contact of active sites with bacteria or odor molecules;

[0080] (3) Function layer bonding strength (rubbing resistance) test

[0081] In order to evaluate the adhesion stability of the functional material on the fiber substrate, the friction environment during human movement is simulated; the sample surface is tested by dry friction and wet friction using a rubbing color fastness instrument, the rubbing head is wrapped with white cotton cloth, the weight is 200g, and the reciprocating friction is 50 times; after the test, the retention rate of the antibacterial and odor-removing compound on the sample surface is measured, which is calculated by trace element quantitative analysis or active ingredient tracking by inductively coupled plasma mass spectrometry, and the 24h antibacterial rate retention value of the sample after rubbing is retested; the test results are shown in Table 3;

[0082] Table 3

[0083]

[0084] As can be seen from the data in Table 3, the functional layer retention rate of Examples 1-5 is still as high as 96% or more after experiencing severe friction, and the antibacterial performance is almost unchanged; the performance of Comparative Examples 1 and 2 has significantly declined, especially Comparative Example 2, the antibacterial rate after rubbing is only 52.1%;

[0085] Comparative Example 2 lacks a bonding system, and the functional particles are only physically attached to the surface of the fiber, which is easy to fall off; although Comparative Example 1 uses a resin bond, the film layer formed by the ordinary resin is relatively brittle, and the interfacial compatibility with the substrate is poor, which is easy to produce micro-cracks and cause the coating to peel off when the substrate is deformed;

[0086] Examples 1-5 solve this problem through hydrophilic spacer arm modified polymer and in-situ crosslinking technology;

[0087] The hydrophilic long-chain spacer arm acts as a molecular bridge between inorganic functional materials and organic fiber substrates, improving the interfacial compatibility;

[0088] The spacer arm structure has a certain flexibility, which can buffer the shear force generated by friction like a spring, preventing the functional layer from brittle cracking and falling off when the substrate is deformed;

[0089] Under the action of crosslinking agent and catalyst, a firm chemical crosslinking network is formed between the polymer, core-shell compound and the fiber substrate; this chemical anchoring effect ensures that the functional layer remains stable even in large quantities of tides or in the scene of intense movement, achieving the process goal of high activity and firm combination.

[0090] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting, although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present application.

Claims

1. A method for preparing a composite antibacterial and odor-reducing sanitary napkin, characterized in that, Includes the following steps: A hydrophilic spacer-arm modified polymer, a core-shell structured antibacterial and deodorizing complex, a crosslinking agent and a solvent are mixed, a catalyst is added and stirred, ultrasonically dispersed, and allowed to stand to degas, to obtain a composite functional finishing liquid; Under conditions of room temperature and relative humidity below 60%, the composite functional finishing liquid is applied to the surface of the sanitary napkin fiber substrate by spraying to form a uniform liquid thin layer. The sanitary napkin fiber substrate with a liquid thin layer applied is placed in an oven, dried and cured by gradient temperature increase to obtain a composite antibacterial and odor-reducing sanitary napkin; The preparation of the hydrophilic spacer arm modified polymer includes the following steps: The hydrophilic long-chain monomer, the active grafted monomer and deionized water are mixed and stirred. Initiator is added under nitrogen atmosphere and refluxed for 4-8 hours. After the reaction is completed, a precipitant selected from diethyl ether or acetone is added, the mixture is allowed to stand, filtered, washed and dried to obtain the hydrophilic spacer arm modified polymer. The preparation of the core-shell structured antibacterial and deodorizing complex includes the following steps: Step 1: Add the porous inorganic carrier to the antibacterial and deodorizing factor solution, vacuum impregnate, centrifuge, and dry to obtain the loaded core; Step 2: Disperse the supported core in a film-forming wall material solution containing 1%-2% acetic acid by volume, perform high-speed shearing, add an interface modifier, react and keep warm for 2-4 hours; filter, wash, and dry to obtain a core-shell structured antibacterial and deodorizing complex.

2. The method for preparing a composite antibacterial and odor-reducing sanitary napkin according to claim 1, characterized in that, The mass ratio of the hydrophilic spacer arm modified polymer, the core-shell structured antibacterial and deodorizing compound, the crosslinking agent, the solvent and the catalyst is (12-24):(5-15):(2-6):(60-120):(0.5-1.5).

3. The composite antibacterial and odor-reducing sanitary napkin and its preparation method according to claim 1, characterized in that, The solvent is any one of deionized water, anhydrous ethanol, or acetic acid solution with a volume fraction of 1%-2%; the catalyst is sodium dihydrogen phosphate or sodium hypophosphite; and the crosslinking agent is any one of citric acid or glutaraldehyde.

4. The method for preparing a composite antibacterial and odor-reducing sanitary napkin according to claim 1, characterized in that, The gradient temperature drying process involves first pre-drying at 45-55℃ for 15-30 minutes, then gradually increasing the temperature to... Curing time is 3-8 minutes.

5. The method for preparing a composite antibacterial and odor-reducing sanitary napkin according to claim 1, characterized in that, The mass ratio of hydrophilic long-chain monomer, active grafted monomer, deionized water, initiator and precipitant is (20-40):(5-10):(100-200):(0.1-0.3):(50-100).

6. The method for preparing a composite antibacterial and odor-reducing sanitary napkin according to claim 1, characterized in that, The hydrophilic long-chain monomer is polyethylene glycol methacrylate; the active graft monomer is either acrylic acid or methacrylic acid.

7. The method for preparing a composite antibacterial and odor-reducing sanitary napkin according to claim 1, characterized in that, The mass ratio of the porous inorganic carrier to the antibacterial and deodorizing agent solution is (5-10):(40-80); the vacuum degree of vacuum impregnation is -0.08MPa to -0.1MPa, and the impregnation time is 2-4 hours.

8. The method for preparing a composite antibacterial and odor-reducing sanitary napkin according to claim 1, characterized in that, The porous inorganic carrier is either mesoporous silica or nano-zeolite; the antibacterial and deodorizing factor solution is nano-silver solution or plant polyphenol extract.

9. The method for preparing a composite antibacterial and odor-reducing sanitary napkin according to claim 1, characterized in that, The mass ratio of the supported core, film-forming wall material solution, and interface modifier is (8-12):(50-100):(1-3); the solute in the film-forming wall material solution is chitosan or sodium alginate; the interface modifier is... Glycidyl etheroxypropyltrimethoxysilane or Methacryloxypropyltrimethoxysilane; in use When processing methacryloyloxypropyltrimethoxysilane, an initiator with a mass fraction of 0.1%-0.5% needs to be added to the reaction system to initiate the double bond polymerization grafting.

10. A composite antibacterial and odor-reducing sanitary napkin, characterized in that, It is prepared by the preparation method according to any one of claims 1-10.

Images