An anti-allergic mask for improving a respiratory microenvironment and a method of manufacturing the same

Abstract

The application belongs to the field of medical care products, and particularly relates to an anti-allergy mask for improving respiratory microenvironment and a preparation method thereof. In the application, the outer layer of a traditional N95 mask is replaced by a super-hydrophilic N-TiO2 loaded chitosan fiber membrane (N-TiO2@CS), which can instantly absorb moisture and intercept and photocatalytically degrade pollen allergens, and the porous structure of the membrane guarantees low resistance and air permeability; the inner layer is a sodium alginate hydrophilic modified polypropylene (PP) melt-blown cloth which continuously leads out the exhaled moisture to keep dry. The design significantly improves the air permeability and moisture absorption of the mask while maintaining high-efficiency filtration.

Description

Technical Field

[0001] This invention pertains to medical and health care products, specifically relating to an anti-allergy mask that improves the respiratory microenvironment and its preparation method. Background Technology

[0002] Face masks are a tool for daily protection. The core filter material of commercially available medical protective masks and N95 masks is mostly polypropylene (PP) meltblown fabric. It achieves electrostatic adsorption and filtration of particulate matter and bacteria by increasing the number of non-woven fabric layers or increasing the density of non-woven fabric. Although these masks have a certain ability to block particulate matter and bacteria, their dense structure results in poor breathability and moisture absorption.

[0003] Many masks on the market today often cause stuffiness and discomfort when worn for extended periods due to high breathing resistance and the accumulation of moisture and sweat inside, reducing people's willingness to wear them. More importantly, traditional masks generally lack active antibacterial capabilities and cannot effectively kill or remove bacteria attached to the mask surface; at the same time, they can only physically block some pollen particles and do not have the ability to kill pollen allergens. This makes the protective effect of masks limited in environments with high pollen concentrations, and they cannot fundamentally prevent hay fever. Summary of the Invention

[0004] In view of this, the present invention discloses an anti-allergy mask that improves the respiratory microenvironment and a method for preparing the same.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: The first objective of this invention is to provide an anti-allergy mask that improves the respiratory microenvironment, using non-woven fabric as the outer and inner layers of the anti-allergy mask body, and N-TiO2@CS fiber membrane and sodium alginate-modified polypropylene meltblown non-woven fabric as the middle layer of the anti-allergy mask body.

[0006] The second objective of this invention is to provide a method for preparing an anti-allergy mask that improves the respiratory microenvironment as described above. This method involves replacing the outer layer of the two PP meltblown fabric layers in an N95 mask with an N-TiO2@CS fiber membrane, and modifying the inner PP meltblown fabric layer with sodium alginate. This achieves the filtration and degradation of pollen and improves the breathability and moisture absorption of the N95 mask.

[0007] Specifically, the preparation method of the above-mentioned novel anti-allergy mask includes the following steps: ① Mix titanium source and anhydrous ethanol at a volume ratio of 1:4 at room temperature and stir to obtain solution A; mix concentrated nitric acid, anhydrous ethanol and ammonia at a volume ratio of 1:5:5 at room temperature and stir to obtain solution B; ② Solution B is added dropwise to solution A and mixed at room temperature. After aging, a white sol is obtained. The sol is dried, and a nitrogen source is added and ground into a white powder. The molar ratio of the nitrogen source to the titanium source is (1:50) to (1:200). The nitrogen source is selected from one or more combinations of urea, triethylamine, and ammonia. The titanium source is selected from one or more combinations of tetrabutyl titanate, isopropyl titanate, and titanium tetrachloride. ③ Place the white powder in a muffle furnace and calcine it at a heating rate of 2~5℃ to 400℃ for 3h to obtain light yellow N-TiO2 powder; ④ Dissolve N-TiO2 powder in anhydrous ethanol at a material-to-liquid ratio of 0.005~0.04 g / mL, add 1%~5% polyvinylpyrrolidone dispersant, and then sonicate to obtain a uniform mixture. Immerse the mixture in a chitosan fiber membrane and sonicate. The dispersant is a high molecular weight surfactant, such as, but not limited to, one or more combinations of polyvinylpyrrolidone, polyethylene glycol, sodium dodecylbenzenesulfonate, and hexadecyltrimethylammonium bromide. ⑤ Remove the chitosan fiber membrane, fix N-TiO2 with 0.5%~2.0% crosslinking agent, and dry to obtain N-TiO2@CS fiber membrane. The crosslinking agent is a non-toxic, natural biological crosslinking agent that can react with the amino groups on the chitosan molecular chain, such as genipin or tannic acid. ⑥ Dissolve sodium alginate in deionized water at a material-to-liquid ratio of 0.005 g / mL, and heat in a water bath to dissolve it, thus obtaining a sodium alginate colloidal solution; immerse PP meltblown nonwoven fabric in the sodium alginate colloidal solution, repeat the immersion 3 times, take it out and dry it to obtain sodium alginate modified polypropylene meltblown nonwoven fabric. ⑦ The outer and inner layers of the mask body are made of non-woven fabric, and the middle layer is made of N-TiO2@CS fiber membrane and polypropylene PP meltblown non-woven fabric modified with sodium alginate. The outer non-woven fabric layer, the middle layer and the inner non-woven fabric layer are composited together to form the mask body. A plastic nose bridge strip is installed on the upper side of the mask body as a nose clip, and ear loops are installed on the left and right sides of the mask body to obtain the mask.

[0008] It should be noted that this invention features an innovative design for the core filter layer of the N95 mask, employing a functionally complementary dual-layer structure. One layer is a sodium alginate-modified PP meltblown fabric, whose excellent hydrophilicity allows for rapid wicking of exhaled moisture, significantly improving dryness during wear. Its dense fiber network also enables highly efficient physical interception of larger particles, such as juniper pollen (approximately 23 μm in diameter), making it suitable for functional wear in cases of pollen allergies. The other layer is an N-TiO2@CS fiber membrane. This layer utilizes the moisture wicked from the inner layer to undergo a photocatalytic reaction under visible light, generating highly oxidizing hydroxyl radicals, which then catalytically degrade the intercepted pollen and bacteria in situ. This design creates a synergistic microenvironment where the inner layer provides moisture and the outer layer catalyzes self-cleaning, giving the mask a durable and proactive self-cleaning capability.

[0009] This invention conducted multiple performance tests on the novel mask filter layer: it can block 100% of juniper pollen and inactivate 96% of pollen cells within 4 hours; the photocatalytic elimination rate against Escherichia coli and Staphylococcus aureus both exceed 99%. Simultaneously, its double-layer filter layer possesses excellent air permeability (452 ​​mm / s) and moisture permeability (5281.979 g / m²). 2 (day), far exceeding N95 masks (165mm / s, 2416.96g / m²). 2 ·day).

[0010] Compared with the prior art, the beneficial effects of the present invention are: This invention discloses a novel face mask specifically designed for preventing pollen allergies, combining highly effective protection with excellent comfort. It not only efficiently filters airborne pollen through physical barriers but also utilizes advanced photocatalytic technology to actively degrade pollen allergens, achieving dual protection from "interception" to "inactivation." While providing robust protection, the mask's optimized double-layer filter structure significantly enhances breathability and moisture absorption. Its breathability far exceeds that of conventional protective masks, and it quickly wicks away moisture, keeping the face dry for extended periods. This design successfully addresses the common problem of stuffiness in high-protection masks, significantly improving comfort during prolonged wear and truly achieving a balance between protection and comfort. Attached Figure Description

[0011] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, 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 embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0012] Figure 1 This is a structural diagram of the anti-allergy mask for improving the respiratory microenvironment according to the present invention.

[0013] Figure 2 This is a photograph of the N-TiO2@CS fiber membrane prepared in Example 3 of the present invention.

[0014] Figure 3 This is a scanning electron microscope image of the N-TiO2@CS fiber membrane prepared in Example 3 of the present invention.

[0015] Figure 4 Photos of PP meltblown fabric and PP meltblown fabric coated with sodium alginate.

[0016] Figure 5 This is a scanning electron microscope image of the sodium alginate-coated PP meltblown fabric prepared in Example 5 of the present invention.

[0017] Figure 6 Line graphs showing the contact angles of PP meltblown fabric, sodium alginate-coated PP meltblown fabric, and N-TiO2@CS fiber membrane.

[0018] Figure 7 A comparison chart showing the pollen filtration efficiency of ordinary medical protective masks, N95 masks, and the self-cleaning pollen mask of this invention.

[0019] Figure 8 Line graphs showing pollen survival rates after photocatalytic experiments of N-TiO2@CS fiber membranes with different N-TiO2 loadings under light and dark conditions.

[0020] Figure 9 A bar chart showing the air permeability of a new type of allergy-resistant mask compared to ordinary medical masks and N95 masks.

[0021] Figure 10 A bar chart showing the moisture permeability of a new type of allergy-resistant mask compared to ordinary medical masks and N95 masks. Detailed Implementation

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0023] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0024] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0025] In the description of this invention, it should be understood that the terms "middle", "upper", "lower", "rise", "fall", "vertical", "surface", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0026] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0027] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0028] This invention discloses a method for preparing an anti-allergy mask that improves the respiratory microenvironment. By replacing the outer layer of the two PP meltblown fabrics in an N95 mask with an N-TiO2@CS fiber membrane and modifying the inner PP meltblown fabric with sodium alginate, the method achieves the filtration and degradation of pollen and improves the breathability and moisture absorption of the N95 mask.

[0029] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.

[0030] Example 1 ① Take tetrabutyl titanate as the titanium source, mix it with anhydrous ethanol at a volume ratio of 1:4 at room temperature and stir to obtain solution A; take concentrated nitric acid, anhydrous ethanol and ammonia water at a volume ratio of 1:5:5 at room temperature and stir to obtain solution B; ② Solution B is added dropwise to solution A and mixed at room temperature. After aging, a white sol is obtained. The sol is dried, and urea is added as a nitrogen source and ground into a white powder. The molar ratio of the nitrogen source to the titanium source is (1:50). ③ The white powder was placed in a muffle furnace and calcined at 400°C for 3 hours at a heating rate of 3°C to obtain a light yellow N-TiO2 powder; ④ Dissolve N-TiO2 powder in anhydrous ethanol at a material-to-liquid ratio of 0.005 g / mL, add 1% polyvinylpyrrolidone dispersant by mass, and then sonicate to obtain a uniform mixture. Immerse the mixture in a chitosan fiber membrane and sonicate. ⑤ Remove the chitosan fiber membrane, fix N-TiO2 with 0.5% genipin crosslinking agent by mass, and dry to obtain N-TiO2@CS-#1 fiber membrane.

[0031] Example 2 ① Take tetrabutyl titanate as the titanium source, mix it with anhydrous ethanol at a volume ratio of 1:4 at room temperature and stir to obtain solution A; take concentrated nitric acid, anhydrous ethanol and ammonia water at a volume ratio of 1:5:5 at room temperature and stir to obtain solution B; ② Solution B is added dropwise to solution A and mixed at room temperature. After aging, a white sol is obtained. The sol is dried, and urea is added as a nitrogen source and ground into a white powder. The molar ratio of the nitrogen source to the titanium source is (1:50). ③ The white powder was placed in a muffle furnace and calcined at 400°C for 3 hours at a heating rate of 3°C to obtain a light yellow N-TiO2 powder; ④ Dissolve N-TiO2 powder in anhydrous ethanol at a material-to-liquid ratio of 0.01 g / mL, add 1% polyvinylpyrrolidone dispersant by mass, and then sonicate to obtain a uniform mixture. Immerse the mixture in a chitosan fiber membrane and sonicate. ⑤ Remove the chitosan fiber membrane, fix N-TiO2 with 0.5% genipin crosslinking agent by mass, and dry to obtain N-TiO2@CS-#2 fiber membrane.

[0032] Example 3 ① Take tetrabutyl titanate as the titanium source, mix it with anhydrous ethanol at a volume ratio of 1:4 at room temperature and stir to obtain solution A; take concentrated nitric acid, anhydrous ethanol and ammonia water at a volume ratio of 1:5:5 at room temperature and stir to obtain solution B; ② Solution B is added dropwise to solution A and mixed at room temperature. After aging, a white sol is obtained. The sol is dried, and urea is added as a nitrogen source and ground into a white powder. The molar ratio of the nitrogen source to the titanium source is (1:10). ③ The white powder was placed in a muffle furnace and calcined at 400°C for 3 hours at a heating rate of 3°C to obtain a light yellow N-TiO2 powder; ④ Dissolve N-TiO2 powder in anhydrous ethanol at a material-to-liquid ratio of 0.02 g / mL, add 1% polyvinylpyrrolidone dispersant by mass, and then sonicate to obtain a uniform mixture. Immerse the mixture in a chitosan fiber membrane and sonicate. ⑤ Remove the chitosan fiber membrane, fix N-TiO2 with 0.5% genipin crosslinking agent by mass, and dry to obtain N-TiO2@CS-#3 fiber membrane.

[0033] Example 4 ① Take tetrabutyl titanate as the titanium source, mix it with anhydrous ethanol at a volume ratio of 1:4 at room temperature and stir to obtain solution A; take concentrated nitric acid, anhydrous ethanol and ammonia water at a volume ratio of 1:5:5 at room temperature and stir to obtain solution B; ② Solution B is added dropwise to solution A and mixed at room temperature. After aging, a white sol is obtained. The sol is dried, and urea is added as a nitrogen source and ground into a white powder. The molar ratio of the nitrogen source to the titanium source is (1:50). ③ The white powder was placed in a muffle furnace and calcined at 400°C for 3 hours at a heating rate of 3°C to obtain a light yellow N-TiO2 powder; ④ Dissolve N-TiO2 powder in anhydrous ethanol at a material-to-liquid ratio of 0.04 g / mL, add 1% polyvinylpyrrolidone dispersant by mass, and then sonicate to obtain a uniform mixture. Immerse the mixture in a chitosan fiber membrane and sonicate. ⑤ Remove the chitosan fiber membrane, fix N-TiO2 with 0.5% genipin crosslinking agent by mass, and dry to obtain N-TiO2@CS-#4 fiber membrane.

[0034] Example 5 Sodium alginate was dissolved in deionized water at a ratio of 0.005 g / mL and heated in a water bath to obtain a sodium alginate colloidal solution. PP meltblown nonwoven fabric was immersed in the sodium alginate colloidal solution and repeatedly immersed 3 times. After being removed and dried, sodium alginate-modified polypropylene meltblown nonwoven fabric was obtained.

[0035] Example 6 The outer and inner layers of the mask body are made of non-woven fabric, and the middle layer is made of N-TiO2@CS-#3 fiber membrane and sodium alginate modified PP meltblown fabric. The outer non-woven fabric layer, the middle layer and the inner non-woven fabric layer are combined together to form the mask body. A plastic nose bridge strip is installed on the upper side of the mask body as a nose clip, and ear loops are installed on the left and right sides of the mask body to obtain the mask.

[0036] To further demonstrate the beneficial effects of the present invention and to better understand it, the following experimental examples and comparative examples further illustrate the technical features disclosed in the present invention, but should not be construed as limiting the present invention. Other improvements made by those skilled in the art based on the above-described invention, without inventive effort, are also considered to fall within the protection scope of the present invention.

[0037] Comparative Example 1 Ordinary medical protective masks consist of three layers: inner and outer non-woven fabric and a middle layer of polypropylene meltblown fabric. N95 masks consist of four layers: inner and outer non-woven fabric and two middle layers of polypropylene meltblown fabric. They are based on ordinary medical protective masks and improve protective performance by adding an intermediate filter layer.

[0038] This invention compares the pollen-blocking performance and comfort of traditional N95 masks and ordinary medical protective masks. Because polypropylene meltblown fabric is a highly hydrophobic, dense fiber membrane, its breathability and moisture permeability are insufficient. This invention's anti-allergy mask is an improvement on the N95 mask, replacing only the middle layer. The outermost layer of the middle layer is replaced with an N-TiO2@CS fiber membrane, which can instantly absorb moisture and intercept and photocatalytically degrade pollen allergens. Its porous structure ensures low-resistance breathability. The innermost layer of the middle layer is sodium alginate-modified polypropylene meltblown fabric. Through the hydrophilic modification of sodium alginate, it continuously wicks away exhaled moisture to keep the user dry. The wicked moisture is transferred to the N-TiO2@CS fiber membrane, which also provides water-based raw materials for photocatalysis to generate highly oxidizing hydroxyl radicals, thus degrading the intercepted pollen in situ.

[0039] Test Example 1: Performance against chemical powder This experiment used an experimental setup constructed according to GB / T29864—2013 "Test Methods for Pollen Repellency of Textiles - Airflow Method", with a concentration of 0.06 g / m³. 3 0.12g / m 3 0.18g / m 3 0.24g / m 3 0.30g / m 3 Medical protective masks, N95 masks, and anti-allergy masks prepared based on Example 5 were tested at five concentrations. The test results showed that the medical protective mask could intercept about 96% of pollen, and the anti-allergy mask of the present invention could achieve the same 100% pollen interception performance as the N95 mask.

[0040] Experimental Example 2: Photocatalytic Performance This experiment investigated the optimal N-doping ratio of N-TiO2-loaded chitosan fiber membranes with different N-doping contents prepared in Examples 1, 2, and 3 under simulated sunlight in a photochemical reaction chamber (product model: CEL-LB70, Beijing Zhongjiao Jinyuan Technology Co., Ltd.) and a xenon lamp light source system (product model: CEL-HXF300-S, Beijing Zhongjiao Jinyuan Technology Co., Ltd.). Four types of N-TiO2 nanoparticle-loaded chitosan fiber membranes (N-TiO2@CS-#1, N-TiO2@CS-#2, N-TiO2@CS-#3, and N-TiO2@CS-#4) were prepared in this experiment. Samples were taken every 30 minutes for 4 hours, stained with trypan blue, and pollen viability was observed under an optical microscope. The results showed that under illumination, only 3.53% of the pollen in N-TiO2@CS-#3 survived after 4 hours of photocatalysis. This is because the higher the N-TiO2 content, the easier it is for N-TiO2 nanoparticles to aggregate, resulting in a reduction of active sites.

[0041] Test Example 3: Air permeability and moisture permeability This experiment was conducted according to GB / T 5453 "Determination of Air Permeability of Textile Fabrics" and GB / T 12704.1 "Test Method for Moisture Permeability of Textile Fabrics". The results show that, in terms of air permeability, the anti-allergy mask (452 ​​mm / s) prepared based on Example 5 above has similar air permeability to a medical protective mask (483.6 mm / s), and is approximately 2.7 times that of an N95 mask (165 mm / s). Regarding moisture permeability, the anti-allergy mask of this invention (5281.98 g / m³) exhibits good moisture permeability. 2 (day), far superior to ordinary medical masks (3060.07g / m²). 2 (day), and it is an N95 mask (2416.96g / m²). 2 It is twice as effective as an N95 mask. In short, this invention's anti-allergy mask achieves 100% pollen filtration efficiency, the same as an N95 mask, while its breathability and moisture permeability are more than twice that of an N95 mask.

[0042] 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 method for preparing an anti-allergy mask that improves the respiratory microenvironment, characterized in that, Includes the following steps: ① Mix titanium source and anhydrous ethanol at room temperature and stir to obtain solution A; mix concentrated nitric acid, anhydrous ethanol and ammonia water at room temperature and stir to obtain solution B; ② Add solution B dropwise to solution A and mix at room temperature. After aging, a white sol is obtained. The sol is dried, and a nitrogen source is added and the mixture is ground into a white powder. ③ The white powder was calcined in a muffle furnace to obtain a pale yellow N-TiO2 powder; ④ Dissolve N-TiO2 powder in anhydrous ethanol at a material-to-liquid ratio of 0.005~0.04 g / mL, add 1~5% dispersant by mass, and then sonicate to obtain a uniform mixture. Immerse the mixture in a chitosan fiber membrane and sonicate. ⑤ Remove the chitosan fiber membrane, fix N-TiO2 with a crosslinking agent at a mass ratio of 0.5~2.0%, and dry to obtain N-TiO2@CS fiber membrane; ⑥ Dissolve sodium alginate in deionized water and heat in a water bath to obtain a sodium alginate colloidal solution; immerse PP meltblown nonwoven fabric in the sodium alginate colloidal solution, repeatedly soak, remove and dry to obtain sodium alginate modified polypropylene meltblown nonwoven fabric. ⑦ The outer and inner layers of the mask body are made of non-woven fabric, and the middle layer is made of N-TiO2@CS fiber membrane and polypropylene meltblown non-woven fabric modified with sodium alginate. The outer non-woven fabric layer, the middle layer and the inner non-woven fabric layer are combined together to form the mask body. A plastic nose bridge strip is installed on the upper side of the mask body as a nose clip, and ear loops are installed on the left and right sides of the mask body to obtain the mask. The volume ratio of titanium source to anhydrous ethanol is 1:4, and the volume ratio of concentrated nitric acid, anhydrous ethanol, and ammonia is 1:5:5; the molar ratio of nitrogen source to titanium source is (1:50) to (1:200); the nitrogen source is selected from one or more combinations of urea, triethylamine, and ammonia; the titanium source is selected from one or more combinations of tetrabutyl titanate, isopropyl titanate, and titanium tetrachloride. In step ③, the calcination parameters are: calcining at 400℃ for 3 hours with a heating rate of 2~5℃. The ratio of N-TiO2 powder dissolved in anhydrous ethanol is 0.005~0.04 g / mL; the dispersant is a high molecular weight surfactant, specifically one or more combinations of polyvinylpyrrolidone, polyethylene glycol, sodium dodecylbenzenesulfonate, and hexadecyltrimethylammonium bromide; The crosslinking agent is a non-toxic, natural biological crosslinking agent that can react with the amino groups on the chitosan molecular chain, specifically genipin or tannic acid; The ratio of sodium alginate dissolved in deionized water is 0.005 g / mL.

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