阅读说明：本技术 一种多功能口罩及其制备方法 (Multifunctional mask and preparation method thereof ) 是由 霍晓楠 毛萃 孟凡锦 李焕焕 曹青福 史记 于 2020-06-04 设计创作，主要内容包括：本发明提供了一种多功能口罩及其制备方法。多功能口罩主体部分由经过静电纺丝制备的含有抑菌微胶囊的抑菌纳米纤维层、含有调温微胶囊的调温纳米纤维层、含有抑菌微胶囊与护肤微胶囊的护肤抑菌纳米纤维层相互叠加构成,其中护肤抑菌纳米纤维层位于紧贴面部的最内层。其制备方法有机结合微胶囊技术与静电纺丝技术,充分协调这两种技术的优势,采用该制备方法所制得的口罩在保持良好防护功能的同时,亦具有良好的抑菌能力、调温能力与护肤能力,使用安全,用途广泛。(The invention provides a multifunctional mask and a preparation method thereof. The multifunctional mask main body part is formed by mutually overlapping a bacteriostatic nanofiber layer containing bacteriostatic microcapsules, a temperature-regulating nanofiber layer containing temperature-regulating microcapsules and a skin-protecting bacteriostatic nanofiber layer containing the bacteriostatic microcapsules and skin-protecting microcapsules, wherein the skin-protecting bacteriostatic nanofiber layer is positioned at the innermost layer tightly attached to the face. The preparation method organically combines the microcapsule technology and the electrostatic spinning technology, fully coordinates the advantages of the two technologies, and the mask prepared by the preparation method has good bacteriostatic ability, temperature-regulating ability and skin-care ability while keeping good protection function, and is safe to use and wide in application.)

1. A preparation method of a multifunctional mask is characterized by comprising the following steps:

(1) preparing a bacteriostatic microcapsule dispersion liquid: adding 1-80 parts of bacteriostatic agent into 1-100 parts of dispersing agent, and stirring at a high speed of 5-90 ℃ for 3-120 min to form a microcapsule core material; dissolving 2-160 parts of antibacterial microcapsule wall material in a dispersing agent at 10-90 ℃, and uniformly stirring; dissolving 0.2-50 parts of surfactant in distilled water at 10-90 ℃, and uniformly stirring; mixing and stirring the three solutions uniformly, and carrying out shearing emulsification for 2-120 min at a shearing rate of 100-30000 rmp; homogenizing the sheared and emulsified mixed solution for 2-60 min at high pressure by a high-pressure homogenizer of 10-70 Mpa, transferring the mixed solution into a flask, reacting for 1-24 h at the temperature of 5-90 ℃, adjusting the pH value of the solution, and performing ultrasonic dispersion to prepare an antibacterial microcapsule dispersion liquid with an antibacterial function;

(2) preparing a temperature-regulating microcapsule dispersion liquid: dissolving 2-240 parts of temperature-adjusting microcapsule wall material in a dispersing agent at 10-90 ℃, and uniformly stirring; adding 0.2-50 parts of surfactant and 1-80 parts of phase change material into the mixture, and then stirring the mixture at a high speed for 3-120 min at the temperature of 5-90 ℃; uniformly mixing and stirring the solution, and carrying out shearing emulsification for 2-120 min at a shearing rate of 100-30000 rmp; transferring the emulsion after shearing and emulsification into a flask, reacting for 1-24 h at 5-190 ℃, adjusting the pH value of the solution, and performing ultrasonic dispersion to prepare a phase-change microcapsule dispersion liquid with a temperature adjusting function;

(3) preparing a skin care microcapsule dispersion liquid: dissolving 2-240 parts of the skin-care microcapsule wall material in a dispersing agent at 10-90 ℃, and uniformly stirring; adding 0.2-50 parts of surfactant and 1-80 parts of skin care material into the mixture, and stirring at a high speed for 3-120 min at the temperature of 5-90 ℃; uniformly mixing and stirring the solution, and carrying out shearing emulsification for 2-120 min at a shearing rate of 100-30000 rmp; and (3) homogenizing the sheared and emulsified mixed solution for 3-90 min at high pressure by a high-pressure homogenizer of 20-70 Mpa. Transferring the emulsion after shearing and emulsification into a flask, reacting for 1-24 h at 5-190 ℃, adjusting the pH value of the solution, and performing ultrasonic dispersion to prepare a skin care microcapsule dispersion liquid with a skin care function;

(4) preparing a bacteriostatic nanofiber layer: mixing the antibacterial microcapsule dispersion liquid prepared in the step (1) with spinning stock solution according to a certain proportion, and carrying out high-speed shearing emulsification, filtration and vacuum defoaming on the mixture, and then carrying out electrostatic spinning on the mixture to obtain an antibacterial nanofiber layer containing antibacterial microcapsules;

(5) preparing a temperature-adjusting nanofiber layer: mixing the temperature-regulating microcapsule dispersion liquid prepared in the step (2) with spinning stock solution according to a certain proportion, and performing high-speed shearing emulsification, filtration and vacuum defoaming, and then performing electrostatic spinning to obtain a temperature-regulating nanofiber layer containing temperature-regulating microcapsules;

(6) preparing a skin-care bacteriostatic nanofiber layer: mixing the antibacterial microcapsule dispersion liquid prepared in the step (1), the skin care microcapsule dispersion liquid prepared in the step (3) and a spinning stock solution according to a certain proportion, and performing high-speed shearing emulsification, filtration and vacuum defoaming, and then performing electrostatic spinning to obtain a skin care antibacterial nanofiber layer containing antibacterial microcapsules and skin care microcapsules;

(7) carrying out multi-layer compounding and combination on the bacteriostatic nanofiber layer, the temperature-adjusting nanofiber layer and the skin-protecting bacteriostatic nanofiber layer prepared in the steps (4), (5) and (6) to prepare the mask main body, wherein the skin-protecting bacteriostatic nanofiber layer is positioned on the innermost layer contacting the skin;

(8) and (4) carrying out 3D cutting on the mask main body prepared in the step (7) according to the prior art, and connecting a mask belt and a nose clip.

2. The method of claim 1, wherein: the capsule wall material of the antibacterial microcapsule is at least one of chitosan, chitosan ammonium chloride, carboxymethyl chitosan, nano cellulose, methyl vitamin, hydroxymethyl cellulose, sodium carboxymethyl cellulose, cellulose nitrate, maltodextrin, cyclodextrin, corn syrup, starch, sucrose, lactose, pectin, sodium alginate, carrageenan, arabic gum, gelatin, soybean protein, hemoglobin, casein, whey protein, beeswax, paraffin, grease, liposome, polyurea, polyamide, polystyrene, amino resin, urea-formaldehyde resin, phenolic resin, epoxy resin, polyurethane, polyacrylate and polyvinyl alcohol.

3. The method of claim 1, wherein: the antibacterial microcapsule core material is at least one of nano silver, nano zinc, chlorhexidine gluconate, xanthorrhizol, ethyl vanillin, acylaniline, hinokitiol, imidazole, sorbic acid, vanillin, thiazoles, isothiazolinone derivatives, biguanidine, dodecyl ethoxy sulfobetaine and tetradecyl methyl dihydroxy ethyl ammonium bromide.

4. The method of claim 1, wherein: the capsule wall material of the temperature-regulating microcapsule is at least one of urea-formaldehyde resin, phenolic resin, melamine formaldehyde resin, methyl etherified melamine formaldehyde resin, butyl etherified melamine formaldehyde resin, polyurethane and prepolymer thereof, polymethyl methacrylate, chitosan, sodium alginate, cellulose acetate, gelatin and acacia.

5. The method of claim 1, wherein: the temperature-regulating microcapsule core material is at least one of paraffin, carboxylic acid, carboxylic ester, polyalcohol, n-alkyl alcohol, sugar alcohol and polyether.

6. The method of claim 1, wherein: the capsule wall material of the skin-care microcapsule is at least one of chitosan, chitosan ammonium chloride, carboxymethyl chitosan, nano cellulose, polyvinyl alcohol, starch, maltodextrin, gelatin, Arabic gum, soybean protein and collagen.

7. The method of claim 1, wherein: the skin-care microcapsule core material is at least one of essential oil, vitamins, amino acids and proteins.

8. The method of claim 1, wherein: the solute in the spinning solution is at least one of cellulose acetate, cellulose polymer, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, nitrocellulose, nano-cellulose, polyacrylonitrile, polyurethane, polystyrene, nylon 6, nylon 66, silk fibroin, fibrinogen, zein, soybean protein isolate, wheat protein, whey protein, gelatin, chitosan, dextran, hyaluronic acid, sodium alginate, soybean polysaccharide, pectin, xanthan gum, carrageenan and polyvinyl alcohol.

9. The method of claim 1, wherein: the mass ratio of the microcapsule dispersion liquid to the spinning solution is 1: 9-7: 3.

10. The method of claim 1, wherein: the electrostatic spinning process parameters are as follows: the voltage is 10 KV-40 KV, the flow rate is 0.1 mL/h-10 mL/h, the receiving distance is 5 cm-30 cm, and the rotating speed of the receiving hub is 10 rpm-1000 rpm.

11. A multifunctional mask is characterized in that: the main body part is formed by mutually overlapping a bacteriostatic nanofiber layer containing bacteriostatic microcapsules, a temperature-regulating nanofiber layer containing temperature-regulating microcapsules and a skin-protecting bacteriostatic nanofiber layer containing the bacteriostatic microcapsules and skin-protecting microcapsules, wherein the skin-protecting bacteriostatic nanofiber layer is positioned at the innermost layer tightly attached to the face.

Technical Field

The invention relates to the field of sanitary protective articles, in particular to a multifunctional mask with functions of temperature regulation, bacteriostasis and skin care and a preparation method thereof.

Background

The rapid development of industrial civilization has caused more and more environmental problems, such as global warming and air quality deterioration. Due to global warming, plateau glaciers and polar glaciers are unfrozen, and many frozen ancient viruses and microorganisms are gradually released, and along with the gradual decline of air quality, the viruses and microorganisms can cause a plurality of epidemic diseases, which is a great threat to human beings on the earth.

With the increase of human safety awareness, people usually wear a mask to protect themselves in order to cope with the increasingly poor air quality and epidemic diseases. The existing masks in the market are full of various types of masks, and the types of the masks can be divided into a disposable half mask, a replaceable half mask and a full mask according to the national standard definition. However, each mask has many defects, and many disposable masks have insufficient protection capability and cause great waste of material resources by using a disposable usage method. The filtering efficiency of the masks KN90 and KN95 specified in the national standard needs to be respectively more than 90.0% and 95.0%, the requirement ensures effective interception of haze pollutants, but for most filter materials, the higher the filtering efficiency is, the larger the breathing resistance is, the more uncomfortable breathing of a wearer is, and the more serious the breathing uncomfortable breathing of the wearer is, and the skin problem is caused after the mask is used for a long time. At present, most masks do not have the temperature regulation capability, the bacteriostasis capability and the skin care capability, so that the mask has great theoretical significance and application value for endowing the traditional masks with the functions of temperature regulation, bacteriostasis and skin care.

The electrostatic spinning is to charge the high molecular solution or melt, place the charged solution or melt in a high-voltage electric field between a spinning nozzle and a receiving screen, overcome the surface tension of the high molecular solution or melt through electrostatic attraction, so that the spinning solution becomes a charged jet flow, moves in the electric field, and finally gathers on a metal reticular receiving screen to become a non-woven fabric-shaped fiber felt, and the high molecular solution or melt is solidified due to the evaporation of a solvent or the cooling of the melt, so that the nano-fiber non-woven fabric is formed. The filtering membrane prepared by the electrostatic spinning nano-fiber has the advantages of small diameter (generally dozens to hundreds of nanometers), high specific surface area, high filtering efficiency, low air resistance and the like. Compared with the conventional fiber filtering membrane, the filtering efficiency of the nanofiber filtering membrane with the same mass can be improved by 70%. The density of the traditional filtering membrane is reported to be 39g/m²The density of the PEO filtering membrane prepared by the electrostatic spinning technology can reach 3g/m²Can filter particles with the size of about 100 nm. In addition, it is shown that the smaller the diameter of the nanofiber, the higher the filtration efficiency, and the diameter distribution of the fiber is closely related to the filtration efficiency of the membrane. Moreover, most of the existing PM2.5 masks adopt electret melt-blown cloth to prepare an efficient filter layer, and adopt a corona discharge mode to enable the common melt-blown cloth to carry charges so as to improve the trapping and filtering of particles, and the electret effect is reduced along with the enrichment of the particles and the change of temperatureObviously, the protective capability of the mask is reduced sharply. The non-woven fabric prepared by electrostatic spinning has certain static electricity and good charge stability, so that an additional electret effect is not needed, and the operation is simple, convenient and fast.

The capsule is a tiny 'container' with a core-shell structure, is used for protecting or controlling release of capsule core substances, shielding odor and the like, realizes permanent solidification of the capsule core substances, and facilitates use, storage and transportation of the capsule core substances. The particle size can be classified into: nano capsules with the particle size of less than 1 mu m, microcapsules with the particle size of 1-1000 mu m and macrocapsules with the particle size of more than 1 mm. The composite material has wide application in the fields of aerospace, construction, environmental protection, textile and clothing, medical and health, electronic device cooling, military camouflage and the like.

In recent years, many patents have been made on the improvement of antibacterial ability of masks. The Chinese patent CN201610444058.4 takes the prepared Fe3+, N codoped titanium dioxide and biomass high polymer micro/nano fiber microporous membrane as a mask base material, and prepares the mask which can effectively block PM2.5 and has the effects of resisting bacteria and efficiently treating organic pollutants. Chinese patent CN201610012431.9 adopts nano silver particles as an antibacterial layer, and adopts an electro-spraying method to spray nano silver ions onto the spunbonded fabric of the non-woven fabric layer, so that the mask has a certain antibacterial ability, but the nano silver ion antibacterial agent is only attached to the surface of the mask, and does not form a chemical bond, and the combination is relatively unstable, and on the other hand, the nano silver ions have certain migration toxicity, which is not beneficial to human health in the using process. JP2016056481A discloses that organic acid cyanoacrylate polymer particles are added to the surface or inside of a fiber to provide the fiber with antibacterial ability, but the cyano group in the cyanoacrylate polymer has a certain toxicity, and the acrylic group has a certain peculiar smell to exert a certain influence on the human body. Japanese patent JP5885917B2 discloses that metal phthalocyanine and metal ammonia complex are loaded on the fiber, so that the fiber has certain antibacterial performance. The above patent methods are only used for preparing a mask having a single bacteriostatic function, and a mask having a bacteriostatic function, a temperature-regulating function and a skin-care function and a preparation method thereof are rarely reported.

Disclosure of Invention

In order to solve the above mentioned problems, the invention provides a mask having the functions of bacteriostasis, temperature adjustment and skin care and a preparation method thereof, aiming at the defects of the prior art. The preparation method organically combines the electrostatic spinning technology and the microcapsule technology, and the prepared product is light, thin and soft, has excellent antibacterial performance, stable temperature regulation performance and remarkable skin care function. The mask prepared by the preparation method has good heat storage and temperature regulation functions and skin care capability while keeping good bacteriostatic ability, is light and comfortable to wear, greatly reduces respiratory resistance, has excellent filtering performance, and has great application value and wide market prospect.

The invention discloses a multifunctional mask which comprises the following specific steps:

(1) preparing a bacteriostatic microcapsule dispersion liquid: adding 1-80 parts of bacteriostatic agent into 1-100 parts of dispersing agent, and stirring at a high speed of 5-90 ℃ for 3-120 min to form a microcapsule core material; dissolving 2-160 parts of antibacterial microcapsule wall material in a dispersing agent at 10-90 ℃, and uniformly stirring; dissolving 0.2-50 parts of surfactant in distilled water at 10-90 ℃, and uniformly stirring; mixing and stirring the three solutions uniformly, and carrying out shearing emulsification for 2-120 min at a shearing rate of 100-30000 rmp; and (3) homogenizing the sheared and emulsified mixed solution for 2-60 min at high pressure by a high-pressure homogenizer of 10-70 Mpa, transferring the mixed solution into a flask, reacting for 1-24 h at the temperature of 5-90 ℃, adjusting the pH value of the solution, and performing ultrasonic dispersion to prepare the antibacterial microcapsule dispersion liquid with the antibacterial function.

(2) Preparing a temperature-regulating microcapsule dispersion liquid: dissolving 2-240 parts of temperature-adjusting microcapsule wall material in a dispersing agent at 10-90 ℃, and uniformly stirring; adding 0.2-50 parts of surfactant and 1-80 parts of phase change material into the mixture, and then stirring the mixture at a high speed for 3-120 min at the temperature of 5-90 ℃; uniformly mixing and stirring the solution, and carrying out shearing emulsification for 2-120 min at a shearing rate of 100-30000 rmp; and then transferring the emulsion after shearing and emulsification into a flask to react for 1-24 h at the temperature of 5-190 ℃, adjusting the pH value of the solution, and performing ultrasonic dispersion to prepare the phase-change microcapsule dispersion liquid with the temperature adjusting function.

(3) Preparing a skin care microcapsule dispersion liquid: dissolving 2-240 parts of the skin-care microcapsule wall material in a dispersing agent at 10-90 ℃, and uniformly stirring; adding 0.2-50 parts of surfactant and 1-80 parts of skin care material into the mixture, and stirring at a high speed for 3-120 min at the temperature of 5-90 ℃; uniformly mixing and stirring the solution, and carrying out shearing emulsification for 2-120 min at a shearing rate of 100-30000 rmp; and (3) homogenizing the sheared and emulsified mixed solution for 3-90 min at high pressure by a high-pressure homogenizer of 20-70 Mpa. And then transferring the emulsion after shearing and emulsification into a flask to react for 1-24 h at the temperature of 5-190 ℃, adjusting the pH value of the solution, and performing ultrasonic dispersion to prepare the skin-care microcapsule dispersion liquid with the skin-care function.

(4) Preparation of the antibacterial layer: and (2) mixing the antibacterial microcapsule dispersion liquid prepared in the step (1) with spinning stock solution according to a certain proportion, and carrying out high-speed shearing emulsification, filtration and vacuum defoaming on the mixture, and then carrying out electrostatic spinning on the mixture to obtain the antibacterial nanofiber layer containing the antibacterial microcapsules.

(5) Preparing a temperature adjusting layer: and (3) mixing the temperature-regulating microcapsule dispersion liquid prepared in the step (2) with spinning stock solution according to a certain proportion, and performing high-speed shearing emulsification, filtration and vacuum defoaming, and then performing electrostatic spinning to obtain the temperature-regulating nanofiber layer containing the temperature-regulating microcapsules.

(6) Preparing a skin-care antibacterial layer: and (3) mixing the antibacterial microcapsule dispersion liquid prepared in the step (1), the skin care microcapsule dispersion liquid prepared in the step (3) and the spinning stock solution according to a certain proportion, and carrying out high-speed shearing emulsification, filtration and vacuum defoaming on the mixture, and then carrying out electrostatic spinning on the mixture to obtain the skin care antibacterial nanofiber layer containing the antibacterial microcapsules and the skin care microcapsules.

(7) And (3) carrying out multi-layer compounding and combination on the bacteriostatic nanofiber layer, the temperature-adjusting nanofiber layer and the skin-protecting bacteriostatic nanofiber layer prepared in the steps (4), (5) and (6) to prepare the mask main body, wherein the skin-protecting bacteriostatic nanofiber layer is positioned on the innermost layer contacting with the skin.

(8) And (4) carrying out 3D cutting on the mask main body prepared in the step (7) according to the prior art, and connecting a mask belt and a nose clip.

The capsule wall material of the antibacterial microcapsule is at least one of chitosan, chitosan ammonium chloride, carboxymethyl chitosan, nano cellulose, methyl vitamin, hydroxymethyl cellulose, sodium carboxymethyl cellulose, cellulose nitrate, maltodextrin, cyclodextrin, corn syrup, starch, sucrose, lactose, pectin, sodium alginate, carrageenan, arabic gum, gelatin, soybean protein, hemoglobin, casein, whey protein, beeswax, paraffin, grease, liposome, polyurea, polyamide, polystyrene, amino resin, urea-formaldehyde resin, phenolic resin, epoxy resin, polyurethane, polyacrylate and polyvinyl alcohol.

The antibacterial microcapsule core material is at least one of nano silver, nano zinc, chlorhexidine gluconate, xanthorrhizol, ethyl vanillin, acylaniline, hinokitiol, imidazole, sorbic acid, vanillin, thiazoles, isothiazolinone derivatives, biguanidine, dodecyl ethoxy sulfobetaine and tetradecyl methyl dihydroxy ethyl ammonium bromide.

The capsule wall material of the temperature-regulating microcapsule is at least one of urea-formaldehyde resin, phenolic resin, melamine formaldehyde resin, methyl etherified melamine formaldehyde resin, butyl etherified melamine formaldehyde resin, polyurethane and prepolymer thereof, polymethyl methacrylate, chitosan, sodium alginate, cellulose acetate, gelatin and acacia.

The temperature-regulating microcapsule core material is at least one of paraffin, carboxylic acid, carboxylic ester, polyalcohol, n-alkyl alcohol, sugar alcohol and polyether.

The surfactant is any one or a mixture of any several of polyvinyl alcohol, polyvinylpyrrolidone, sorbitan oleate, an emulsifier OP10, fatty alcohol-polyoxyethylene ether sodium sulfate, a styrene maleic anhydride copolymer, fatty alcohol-polyoxyethylene ether, Turkey red oil, sodium alkyl benzene sulfonate, sodium dodecyl sulfate, propylene alginate, polyoxyethylene sorbitan monooleate, sodium alkyl sulfate or nekal in any ratio.

The phase transition temperature of the temperature-adjusting microcapsule is 25-40 ℃.

The capsule wall material of the skin-care microcapsule is at least one of chitosan, chitosan ammonium chloride, carboxymethyl chitosan, nano cellulose, polyvinyl alcohol, starch, maltodextrin, gelatin, Arabic gum, soybean protein and collagen.

The skin-care microcapsule core material is at least one of essential oil, vitamins, amino acids and proteins.

The particle size range of the capsule is 2 nm-20 mu m.

The solute in the spinning solution is at least one of cellulose acetate, nano-cellulose, cellulose polymer, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, nitrocellulose, polyacrylonitrile, polyurethane, polystyrene, nylon 6, nylon 66, silk fibroin, fibrinogen, zein, soybean protein isolate, wheat protein, whey protein, gelatin, chitosan, dextran, hyaluronic acid, sodium alginate, soybean polysaccharide, pectin, xanthan gum, carrageenan and polyvinyl alcohol.

The solvent in the spinning solution is at least one of N, N-dimethylformamide, N-dimethylacetamide, acetone, formic acid, acetic acid, ethanol and distilled water.

The mass ratio of the microcapsule dispersion liquid to the spinning solution is 1: 9-7: 3.

The electrostatic spinning process parameters are as follows: the voltage is 10 KV-40 KV, the flow rate is 0.1 mL/h-10 mL/h, the receiving distance is 5 cm-30 cm, and the rotating speed of the receiving hub is 10 rpm-1000 rpm.

The prepared antibacterial nanofiber layer, the temperature-adjusting nanofiber layer and the skin-protecting antibacterial nanofiber layer can be compounded in multiple layers according to actual needs, so that masks with different layers can be prepared in a combined mode, and the mask is suitable for multiple fields. Because the nanofiber layer thickness that electrostatic spinning prepared is thinner, even multilayer nanofiber layer combines to be superimposed and forms the gauze mask together, can not appear great breathing resistance when wearing yet, in addition the thermoregulation effect of phase transition microcapsule in the gauze mask, the temperature in the gauze mask can effectively be controlled, very big reduction the sense of oppressing. In addition, the pore diameter of the nanofiber layer prepared by electrostatic spinning is smaller and about 10 nm-20 microns, most of particulate matters and bacteria and viruses can be prevented and isolated, and the antibacterial microcapsules in the electrostatic spinning can kill the bacteria and viruses intercepted by the antibacterial microcapsules, so that the mask can be repeatedly utilized; the skin care substance in the skin care microcapsule can be gradually released to the facial skin when the mask is worn, so that the effect of moistening the skin is achieved, and the facial skin can still keep healthy even if the mask is worn for a long time.

Drawings

FIG. 1 is an electron micrograph (scanning electron micrograph) of a temperature-regulating nanofiber layer prepared in example 1.

Detailed Description

The methods described herein are further illustrated by the following specific examples, but are not intended to be limiting of the invention.