A bio-based antibacterial facial mask and its preparation method

Abstract

The present invention discloses a bio-based antibacterial facial mask and a preparation method thereof, relating to the technical field of facial masks. When preparing the bio-based antibacterial facial mask of the present invention, first, chitosan is grafted with gallic acid to obtain modified chitosan. Secondly, magnesium porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin, and 2,5-diaminobenzenesulfonic acid are reacted to prepare functionalized polyimide, and then reacted with thionyl chloride to obtain modified polyimide. Finally, the modified chitosan, hyaluronic acid, and gelatin are mixed and prepared into a functional film through an electrospinning process, and the modified polyimide and ethylenediamine are mixed and electrospun onto the functional film to obtain the bio-based antibacterial facial mask. The bio-based antibacterial facial mask prepared by the present invention has good moisturizing property, antibacterial property, and antioxidant property.

Description

Technical Field

[0001] The present invention relates to the technical field of facial masks, and specifically to a bio-based antibacterial facial mask and a preparation method thereof. Background Art

[0002] Facial masks are a category of skin care products and a carrier for beauty care products. They are applied on the face to achieve beauty functions such as moisturizing, whitening, anti-aging, and balancing oil. There are many types of facial masks on the market. According to the usage method, they can be mainly divided into two categories, namely smear-type and patch-type. The smear-type facial mask is evenly applied on the face and washed off after a period of application, which is relatively troublesome to use; while the patch-type facial mask is convenient to use and easy to carry. It is usually composed of a non-woven fabric substrate and liquid active ingredients, and mainly uses spunlace non-woven fabric as the substrate.

[0003] In the process of the rapid development of the facial mask market, adding natural and mild bio-based materials has become a major focus. Bio-based facial masks with bio-based materials as the main components have the advantages of being natural, safe, mild, having good moisturizing and moisturizing effects, repairing the skin, and reducing skin sensitivity. In daily life, our facial skin is easily exposed to various bacteria, dirt, and pollutants. These harmful substances breed and multiply on the skin surface. Antibacterial facial masks can effectively inhibit the reproduction of facial bacteria and prevent the occurrence of bacterial infections and inflammations. As the main component for the facial mask to exert its efficacy, due to the insufficient water absorption and water retention of the membrane cloth, the essence is prone to dripping and cannot be fully and effectively absorbed by the skin. Therefore, a natural, mild facial mask with good moisturizing and antibacterial properties is needed. Summary of the Invention

[0004] The purpose of the present invention is to provide a bio-based antibacterial facial mask and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions:

[0006] A bio-based antibacterial facial mask, which is prepared by first mixing modified chitosan, hyaluronic acid, and gelatin and preparing a functional membrane through an electrospinning process, and then spinning modified polyimide and ethylenediamine on the functional membrane through an electrospinning process.

[0007] Preferably, the modified chitosan is obtained by grafting gallic acid onto chitosan.

[0008] Preferably, the modified polyimide is a functionalized polyimide obtained by reacting magnesium-based porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin, and 2,5-diaminobenzenesulfonic acid, and then reacting with thionyl chloride.

[0009] A preparation method of a bio-based antibacterial facial mask, comprising the following preparation steps:

[0010] (1) Weigh chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide according to the mass ratio of 1:(3.0 - 3.2):(0.18 - 0.2):(0.1 - 0.13); mix chitosan and 70 wt% ethanol according to the mass ratio of 1:(200 - 300) to obtain a chitosan dispersion. At 0 °C, mix gallic acid and 70 wt% ethanol according to the mass ratio of 1:(20 - 30), then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide and mix for 50 - 60 min to obtain a gallic acid solution. Drop the gallic acid solution into the chitosan dispersion at a dropping rate of 1 mL / min, stir at 0 °C for 30 min, raise the temperature to room temperature and continue the reaction for 24 h. After the reaction is completed, centrifuge to obtain the lower-layer precipitate, wash it with ethanol, and obtain modified chitosan through freeze-drying;

[0011] (2) Mix magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol according to the mass ratio of 1:(0.5 - 0.7):(1.1 - 1.2):(20 - 30), heat to 50 - 60 °C under nitrogen protection and react for 4 - 5 h. Then add isoquinoline which is 10 times the mass of magnesium-based porphyrin, raise the temperature to 190 °C and react for 10 - 12 h. After the reaction is completed, add methanol which is 10 - 12 times the volume of m-cresol and cool to 5 °C, filter and wash with pure water 3 - 4 times, and dry at 70 - 80 °C for 12 h to obtain functionalized polyimide;

[0012] (3) Mix functionalized polyimide, thionyl chloride, and N,N-dimethylformamide according to the mass ratio of 1:(0.8 - 1.0):(20 - 30), raise the temperature to 30 - 40 °C and react for 3 - 4 h. After the reaction is completed, add ethyl acetate which is 3 - 4 times the volume of N,N-dimethylformamide, filter and wash with pure water 3 - 4 times, and dry at 70 - 80 °C for 12 h to obtain modified polyimide;

[0013] (4) Weigh modified chitosan, hyaluronic acid, and gelatin according to the mass ratio of 1:(0.5 - 0.7):(10 - 12). Mix modified chitosan and 70 wt% acetic acid solution according to the mass ratio of 1:(25 - 30) to obtain a chitosan solution. Mix hyaluronic acid and pure water according to the mass ratio of 1:(10 - 15) to obtain a hyaluronic acid solution. Mix gelatin and hexafluoroisopropanol according to the mass ratio of 1:(3 - 4) to obtain a gelatin solution. Mix the chitosan solution, hyaluronic acid solution, and gelatin solution and carry out electrospinning through an electrospinning process to obtain a functional membrane;

[0014] (5) Mix modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol at a mass ratio of 1:(1.1 - 1.5):(1.1 - 1.2):(8 - 10) at 40 - 50 °C for 3 - 5 min, then continue to spin-coat onto the functional membrane through the electrospinning process. After the spinning is completed, peel off the electrospun membrane and vacuum-dry it at room temperature for 5 - 6 h to obtain the bio-based antibacterial facial mask.

[0015] As an optimization, the degree of deacetylation of the chitosan described in step (1) is ≥90%.

[0016] As an optimization, the preparation method of the magnesium-based porphyrin described in step (2) is as follows: Under nitrogen protection, mix 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride, and chloroform at a mass ratio of 1:(8 - 10):(30 - 40), react at room temperature for 2 - 3 h. After the reaction is completed, add pure water with a volume 2 - 3 times that of chloroform, extract with chloroform, retain the lower-layer organic solution, and obtain the magnesium-based porphyrin by rotary evaporation and drying of the organic solution.

[0017] As an optimization, the molecular weight of the hyaluronic acid described in step (4) is 1×105 Da.

[0018] As an optimization, the electrospinning process parameters described in step (4) are: the voltage is 20 kV, the feeding speed is 3 mL / h, the receiving distance is 17 cm, the rotation speed of the receiving roller is 220 r / min, the diameter of the receiving roller is 7.5 cm, the length is 25 cm, and a layer of silicone oil paper is wrapped on the receiving roller; the areal density of the functional membrane is 1.2 mg / cm 2 .

[0019] As an optimization, the electrospinning process parameters described in step (5) are: the electrospinning voltage is 12 kV, the feeding speed is 2 mL / h, the receiving distance is 10 cm, the rotation speed of the receiving roller is 220 r / min, and the spinning time is 24 min.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] When preparing the bio-based antibacterial facial mask of the present invention, first, graft gallic acid onto chitosan to obtain modified chitosan. Secondly, react magnesium-based porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin, and 2,5-diaminobenzenesulfonic acid to prepare functionalized polyimide, and then react with thionyl chloride to obtain modified polyimide; finally, mix modified chitosan, hyaluronic acid, and gelatin and prepare a functional membrane through the electrospinning process, and spin the modified polyimide and ethylenediamine onto the functional membrane through the electrospinning process to obtain the bio-based antibacterial facial mask.

[0022] First, chitosan is grafted with gallic acid to obtain modified chitosan. Chitosan has excellent biocompatibility, biodegradability, and antibacterial activity, which can endow the facial mask with good moisturizing and antibacterial properties. As one of the abundant plant secondary metabolites in nature, gallic acid has excellent biological activities such as good antioxidant and antibacterial properties. Grafting gallic acid onto chitosan can endow the facial mask with good antioxidant properties;

[0023] Secondly, magnesium porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin, and 2,5-diaminobenzenesulfonic acid are reacted to prepare functionalized polyimide. The magnesium ions in magnesium porphyrin can increase the content of hyaluronic acid in the skin by promoting the expression of hyaluronic acid synthase, thereby effectively maintaining the moisture and elasticity of the skin and making the skin more moist and smooth; the functionalized polyimide is then reacted with thionyl chloride to convert the sulfonic acid functional group on the functionalized polyimide into sulfonyl chloride;

[0024] Finally, the modified chitosan, hyaluronic acid, and gelatin are mixed and prepared into a functional film by electrospinning process. The modified polyimide and ethylenediamine are mixed and electrospun onto the functional film to prepare a bio-based antibacterial facial mask. The sulfonyl chloride functional group contained in the side chain of the modified polyimide reacts with ethylenediamine to generate a sulfonamide structure with antibacterial properties, which can not only further improve the antibacterial performance of the facial mask but also form a certain degree of crosslinked network when the modified polyimide is electrospun into a film, enhancing the mechanical properties of the modified polyimide. The modified polyimide can be used as the base layer of the functional film to improve the convenience of using the functional film. Secondly, the functional film with good hydrophilicity is used as the inner functional layer, and the polyimide with certain hydrophobic properties is used as the outer hydrophobic layer, which can also achieve the unidirectional moisture conduction of the facial mask; the carboxylic acid functional group on hyaluronic acid has good complexing ability with metal ions and can complex with the magnesium ions in the polyimide, enabling the functional layer and the polyimide layer to be more tightly combined. Specific embodiments

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0026] The degree of deacetylation of chitosan used in the following examples and comparative examples is ≥90%; the molecular weight of hyaluronic acid is 1×10 5 Da.

[0027] Example 1:

[0028] A preparation method of a bio-based antibacterial facial mask, the preparation method of the bio-based antibacterial facial mask comprising the following preparation steps:

[0029] (1) Weigh chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide according to a mass ratio of 1:3.0:0.18:0.1; mix chitosan and 70 wt% ethanol according to a mass ratio of 1:200 to obtain a chitosan dispersion. At 0 °C, mix gallic acid and 70 wt% ethanol according to a mass ratio of 1:20, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide and mix for 60 min to obtain a gallic acid solution. Drop the gallic acid solution into the chitosan dispersion at a dropping rate of 1 mL / min, stir at 0 °C for 30 min, raise the temperature to room temperature and continue the reaction for 24 h. After the reaction is completed, centrifuge to obtain the lower-layer precipitate, wash it with ethanol, and obtain modified chitosan by freeze-drying;

[0030] (2) Under nitrogen protection, mix 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride, and chloroform according to a mass ratio of 1:8:30, react at room temperature for 3 h. After the reaction is completed, add pure water twice the volume of chloroform, extract with chloroform, and retain the lower-layer organic solution. The organic solution is obtained by rotary evaporation and drying to obtain magnesium-based porphyrin; mix magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol according to a mass ratio of 1:0.5:1.1:20, heat to 60 °C under nitrogen protection and react for 5 h, then add isoquinoline 10 times the mass of magnesium-based porphyrin, raise the temperature to 190 °C and react for 12 h. After the reaction is completed, add methanol 12 times the volume of m-cresol and cool to 5 °C, filter and wash with pure water 4 times, and dry at 80 °C for 12 h to obtain functionalized polyimide;

[0031] (3) Mix functionalized polyimide, thionyl chloride, and N,N-dimethylformamide according to a mass ratio of 1:0.8:20, raise the temperature to 40 °C and react for 4 h. After the reaction is completed, add ethyl acetate 4 times the volume of N,N-dimethylformamide, filter and wash with pure water 4 times, and dry at 80 °C for 12 h to obtain modified polyimide;

[0032] (4) Weigh modified chitosan, hyaluronic acid, and gelatin according to a mass ratio of 1:0.5:10. Mix modified chitosan and 70 wt% acetic acid solution at a mass ratio of 1:25 to obtain a chitosan solution. Mix hyaluronic acid and pure water at a mass ratio of 1:10 to obtain a hyaluronic acid solution. Mix gelatin and hexafluoroisopropanol at a mass ratio of 1:3 to obtain a gelatin solution. Mix the modified chitosan solution, hyaluronic acid solution, and gelatin solution and perform electrospinning through an electrospinning process to obtain a functional membrane. The electrospinning process parameters are as follows: voltage is 20 kV, the feeding speed is 3 mL / h, the receiving distance is 17 cm, the rotation speed of the receiving roller is 220 r / min, the diameter of the receiving roller is 7.5 cm, the length is 25 cm, and a layer of siliconized paper is wrapped on the receiving roller. The areal density of the functional membrane is 1.2 mg / cm 2 ;

[0033] (5) Mix modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol at a mass ratio of 1:1.1:1.1:8 at 50 °C for 5 min, and then continue electrospinning onto the functional membrane through an electrospinning process. After the electrospinning is completed, remove the electrospinning membrane and vacuum dry it at room temperature for 6 h to obtain a bio-based antibacterial facial mask. The electrospinning voltage is 12 kV, the feeding speed is 2 mL / h, the receiving distance is 10 cm, the rotation speed of the receiving roller is 220 r / min, and the electrospinning time is 24 min.

[0034] Example 2:

[0035] A preparation method of a bio-based antibacterial facial mask, the preparation method of the bio-based antibacterial facial mask includes the following preparation steps:

[0036] (1) Weigh chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide according to a mass ratio of 1:3.1:0.19:0.12. Mix chitosan and 70 wt% ethanol at a mass ratio of 1:250 to obtain a chitosan dispersion. At 0 °C, mix gallic acid and 70 wt% ethanol at a mass ratio of 1:25, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide and mix for 55 min to obtain a gallic acid solution. Drop the gallic acid solution into the chitosan dispersion at a dropping speed of 1 mL / min, stir at 0 °C for 30 min, raise the temperature to room temperature and continue the reaction for 24 h. After the reaction is completed, centrifuge to take the lower layer precipitate, wash it with ethanol, and obtain modified chitosan through freeze-drying;

[0037] (2) Under nitrogen protection, 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride, and chloroform were mixed at a mass ratio of 1:9:35 and reacted at room temperature for 2.5 h. After the reaction, pure water 2.5 times the volume of chloroform was added, and extraction was carried out with chloroform. The lower-layer organic solution was retained, and the organic solution was obtained as magnesium-based porphyrin after rotary evaporation and drying; magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol were mixed at a mass ratio of 1:0.6:1.15:25 and heated to 55 °C under nitrogen protection for 4.5 h. Then, isoquinoline 10 times the mass of magnesium-based porphyrin was added, and the temperature was raised to 190 °C for 11 h. After the reaction, methanol 11 times the volume of m-cresol was added and the temperature was lowered to 5 °C. It was filtered and washed with pure water 3 times, and dried at 75 °C for 12 h to obtain functionalized polyimide;

[0038] (3) Functionalized polyimide, thionyl chloride, and N,N-dimethylformamide were mixed at a mass ratio of 1:0.9:25 and heated to 35 °C for 3.5 h. After the reaction, ethyl acetate 3 times the volume of N,N-dimethylformamide was added, and it was filtered and washed with pure water 3 times, and dried at 75 °C for 12 h to obtain modified polyimide;

[0039] (4) Modified chitosan, hyaluronic acid, and gelatin were weighed at a mass ratio of 1:0.6:11. A chitosan solution was obtained by mixing modified chitosan and 70 wt% acetic acid solution at a mass ratio of 1:27. A hyaluronic acid solution was obtained by mixing hyaluronic acid and pure water at a mass ratio of 1:12. A gelatin solution was obtained by mixing gelatin and hexafluoroisopropanol at a mass ratio of 1:3.5. The modified chitosan solution, hyaluronic acid solution, and gelatin solution were mixed and electrospun to obtain a functional membrane; The electrospinning process parameters were a voltage of 20 kV, a feeding speed of 3 mL / h, a receiving distance of 17 cm, a rotation speed of the receiving roller of 220 r / min, a diameter of the receiving roller of 7.5 cm, a length of 25 cm, and a layer of silicone oil paper wrapped on the receiving roller; The areal density of the functional membrane was 1.2 mg / cm 2 ;

[0040] (5) Modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol were mixed at a mass ratio of 1:1.3:1.15:9 at 45 °C for 4 min, and then electrospun onto the functional membrane. After electrospinning, the electrospun membrane was peeled off and vacuum dried at room temperature for 5.5 h to obtain a bio-based antibacterial facial mask; The electrospinning voltage was 12 kV, the feeding speed was 2 mL / h, the receiving distance was 10 cm, the rotation speed of the receiving roller was 220 r / min, and the electrospinning time was 24 min.

[0041] Example 3:

[0042] A preparation method of a bio-based antibacterial facial mask, the preparation method of the bio-based antibacterial facial mask comprising the following preparation steps:

[0043] (1) Weigh chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide according to a mass ratio of 1:3.2:0.2:0.13; mix chitosan and 70 wt% ethanol according to a mass ratio of 1:300 to obtain a chitosan dispersion. At 0 °C, mix gallic acid and 70 wt% ethanol according to a mass ratio of 1:30, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide and mix for 50 min to obtain a gallic acid solution. Drop the gallic acid solution into the chitosan dispersion at a dropping rate of 1 mL / min, stir at 0 °C for 30 min, raise the temperature to room temperature and continue to react for 24 h. After the reaction is completed, centrifuge to obtain the lower-layer precipitate, wash it with ethanol, and obtain modified chitosan by freeze-drying;

[0044] (2) Under nitrogen protection, mix 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride, and chloroform according to a mass ratio of 1:10:40, react at room temperature for 2 h. After the reaction is completed, add pure water with a volume 3 times that of chloroform, extract with chloroform, and retain the lower-layer organic solution. The organic solution is obtained by rotary evaporation and drying to obtain magnesium-based porphyrin; mix magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol according to a mass ratio of 1:0.7:1.2:30, heat to 50 °C under nitrogen protection and react for 4 h, then add isoquinoline with a mass 10 times that of magnesium-based porphyrin, raise the temperature to 190 °C and react for 10 h. After the reaction is completed, add methanol with a volume 12 times that of m-cresol and cool to 5 °C, filter and wash 3 times with pure water, and dry at 70 °C for 12 h to obtain functionalized polyimide;

[0045] (3) Mix functionalized polyimide, thionyl chloride, and N,N-dimethylformamide according to a mass ratio of 1:1.0:30, raise the temperature to 30 °C and react for 3 h. After the reaction is completed, add ethyl acetate with a volume 4 times that of N,N-dimethylformamide, filter and wash 3 times with pure water, and dry at 70 °C for 12 h to obtain modified polyimide;

[0046] (4) Weigh modified chitosan, hyaluronic acid, and gelatin according to a mass ratio of 1:0.7:12. Mix modified chitosan and 70wt% acetic acid solution at a mass ratio of 1:30 to obtain a chitosan solution. Mix hyaluronic acid and pure water at a mass ratio of 1:15 to obtain a hyaluronic acid solution. Mix gelatin and hexafluoroisopropanol at a mass ratio of 1:4 to obtain a gelatin solution. Mix the modified chitosan solution, hyaluronic acid solution, and gelatin solution and perform electrospinning through an electrospinning process to obtain a functional membrane; the electrospinning process parameters are a voltage of 20 kV, a feeding speed of 3 mL / h, a receiving distance of 17 cm, the rotational speed of the receiving roller is 220 r / min, the diameter of the receiving roller is 7.5 cm, the length is 25 cm, and a layer of siliconized paper is wrapped on the receiving roller; the areal density of the functional membrane is 1.2 mg / cm 2 ;

[0047] (5) Mix modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol at a mass ratio of 1:1.5:1.2:10 at 40 °C for 3 min, and then continue electrospinning onto the functional membrane through an electrospinning process. After electrospinning, remove the electrospinning membrane and vacuum dry it at room temperature for 5 h to obtain a bio-based antibacterial facial mask; the electrospinning voltage is 12 kV, the feeding speed is 2 mL / h, the receiving distance is 10 cm, the rotational speed of the receiving roller is 220 r / min, and the electrospinning time is 24 min.

[0048] Comparative Example 1:

[0049] The difference between the preparation method of the bio-based antibacterial facial mask in Comparative Example 1 and that in Example 2 is that step (2) is modified as follows: Mix 5,15-(aminophenyl)-10,20-phenylporphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol at a mass ratio of 1:0.6:1.15:25, heat to 55 °C under nitrogen protection and react for 4.5 h, then add isoquinoline 10 times the mass of magnesium-based porphyrin, raise the temperature to 190 °C and react for 11 h. After the reaction, add methanol 11 times the volume of m-cresol and cool to 5 °C, filter and wash with pure water 3 times, and dry at 75 °C for 12 h to obtain functionalized polyimide.

[0050] Comparative Example 2:

[0051] The difference between the preparation method of the bio-based antibacterial facial mask in Comparative Example 2 and that in Example 2 is that step (5) is modified as follows: Mix modified polyimide and hexafluoroisopropanol at a mass ratio of 1:9 at 45 °C for 4 min, and then continue electrospinning onto the functional membrane through an electrospinning process. After electrospinning, remove the electrospinning membrane and vacuum dry it at room temperature for 5.5 h to obtain a bio-based antibacterial facial mask; the electrospinning voltage is 12 kV, the feeding speed is 2 mL / h, the receiving distance is 10 cm, the rotational speed of the receiving roller is 220 r / min, and the electrospinning time is 24 min.

[0052] Comparative Example 3:

[0053] The preparation method of the bio-based antibacterial facial mask in Comparative Example 3 is different from that in Example 2 in that step (1) is not included, and step (4) is modified as follows: Weigh hyaluronic acid and gelatin according to a mass ratio of 0.6:11. Mix hyaluronic acid and pure water according to a mass ratio of 1:12 to obtain a hyaluronic acid solution. Mix gelatin and hexafluoroisopropanol according to a mass ratio of 1:3.5 to obtain a gelatin solution. Mix the hyaluronic acid solution and the gelatin solution and perform electrospinning to obtain a functional membrane; the electrospinning process parameters are as follows: the voltage is 20 kV, the feeding speed is 3 mL / h, the receiving distance is 17 cm, the rotation speed of the receiving roller is 220 r / min, the diameter of the receiving roller is 7.5 cm, the length is 25 cm, and a layer of siliconized paper is wrapped on the receiving roller; the areal density of the functional membrane is 1.2 mg / cm 2 .

[0054] Test Example 1:

[0055] Testing of mechanical properties:

[0056] Testing method: Using a fiber strength and elongation tester, cut the facial masks prepared in the examples and comparative examples into rectangular samples with a size of 5 mm × 30 mm. During the experiment, set the stretching speed of the instrument to 20 mm / min and the upper and lower clamping distance to 20 mm, and test the breaking strength of the samples. The results are shown in Table 1.

[0057] Table 1

[0058]

[0059] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the bio-based antibacterial facial mask prepared by the present invention has good mechanical properties.

[0060] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that a functional membrane is prepared by mixing modified chitosan, hyaluronic acid, and gelatin through an electrospinning process, and a bio-based antibacterial facial mask is prepared by electrospinning a mixture of modified polyimide and ethylenediamine onto the functional membrane. The sulfonyl chloride functional groups contained in the side chain of the modified polyimide form a certain degree of crosslinked network during the electrospinning and film-forming process of the modified polyimide by reacting with ethylenediamine, enhancing the mechanical properties of the modified polyimide.

[0061] Test Example 2:

[0062] Testing of antibacterial properties:

[0063] Testing method: Refer to Standard GB / T20944.2 to test the antibacterial properties of the bio-based antibacterial facial masks prepared in the examples and comparative examples. The results are shown in Table 2.

[0064] Table 2

[0065]

[0066] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 2, it can be found that the bio-based antibacterial mask prepared by the present invention has good antibacterial properties.

[0067] By comparison, the antibacterial rates of Examples 1-3 are greater than that of Comparative Example 2, indicating that a functional film is prepared by electrospinning a mixture of modified chitosan, hyaluronic acid, and gelatin, and a bio-based antibacterial mask is prepared by electrospinning a mixture of modified polyimide and ethylenediamine on the functional film. The sulfonyl chloride functional group contained in the side chain of the modified polyimide reacts with ethylenediamine to generate a sulfonamide structure with antibacterial properties, which can further improve the antibacterial performance of the mask.

[0068] Test Example 3:

[0069] Test of moisturizing performance:

[0070] Test method: First, weigh a glass slide and record it as M0; then cut the masks prepared in the examples and comparative examples into 2.5 cm x 2.5 cm sizes and place them on the glass slide and weigh them together, record it as M1; then moisten the mask with 20 mL of water and wipe off the water on the places other than the mask on the glass slide with a dry paper towel, and weigh it at this time and record it as M2; after waiting for 20 min, weigh the glass slide with the wet mask again and record it as M3. This experiment is carried out under the conditions of a temperature of 25 °C and a relative humidity of 30%, and is used to calculate the water retention rate N of the mask, N = (M3 - M0) / (M1 - M0) * 100%. The results are shown in Table 3.

[0071] Table 3

[0072]

[0073] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 3, it can be found that the bio-based antibacterial mask prepared by the present invention has good moisturizing properties.

[0074] The water retention rates of Examples 1-3 are greater than that of Comparative Example 3, indicating that modified chitosan is obtained by grafting gallic acid onto chitosan. Chitosan has excellent biocompatibility, biodegradability, and antibacterial activity, which can endow the mask with good moisturizing properties.

[0075] It is obvious to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, in any respect, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description. Thus, all changes that fall within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention. Any reference signs in the claims should not be construed as limiting the claim concerned.

Claims

1. A preparation method of a bio-based antibacterial facial mask, characterized in that, It includes the following preparation steps: (1) Weigh chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide according to the mass ratio of 1:(3.0 - 3.2):(0.18 - 0.2):(0.1 - 0.13); mix chitosan and 70wt% ethanol according to the mass ratio of 1:(200 - 300) to obtain a chitosan dispersion. At 0°C, mix gallic acid and 70wt% ethanol according to the mass ratio of 1:(20 - 30), then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide and mix for 50 - 60 min to obtain a gallic acid solution. Drop the gallic acid solution into the chitosan dispersion at a dropping rate of 1 mL / min, stir at 0°C for 30 min, raise the temperature to room temperature and continue the reaction for 24 h. After the reaction is completed, centrifuge to take the lower-layer precipitate, wash it with ethanol, and obtain modified chitosan through freeze-drying; (2) Mix magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol according to the mass ratio of 1:(0.5 - 0.7):(1.1 - 1.2):(20 - 30), heat to 50 - 60°C under nitrogen protection and react for 4 - 5 h, then add isoquinoline which is 10 times the mass of magnesium-based porphyrin, raise the temperature to 190°C and react for 10 - 12 h. After the reaction is completed, add methanol which is 10 - 12 times the volume of m-cresol and cool to 5°C, filter and wash with pure water 3 - 4 times, and dry at 70 - 80°C for 12 h to obtain functionalized polyimide; (3) Mix functionalized polyimide, thionyl chloride, and N,N-dimethylformamide according to the mass ratio of 1:(0.8 - 1.0):(20 - 30), raise the temperature to 30 - 40°C and react for 3 - 4 h. After the reaction is completed, add ethyl acetate which is 3 - 4 times the volume of N,N-dimethylformamide, filter and wash with pure water 3 - 4 times, and dry at 70 - 80°C for 12 h to obtain modified polyimide; (4) Weigh modified chitosan, hyaluronic acid, and gelatin according to the mass ratio of 1:(0.5 - 0.7):(10 - 12). Mix modified chitosan and 70wt% acetic acid solution according to the mass ratio of 1:(25 - 30) to obtain a chitosan solution, mix hyaluronic acid and pure water according to the mass ratio of 1:(10 - 15) to obtain a hyaluronic acid solution, mix gelatin and hexafluoroisopropanol according to the mass ratio of 1:(3 - 4) to obtain a gelatin solution, and mix the chitosan solution, hyaluronic acid solution, and gelatin solution and carry out electrospinning through an electrospinning process to obtain a functional membrane; (5) Mix modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol according to the mass ratio of 1:(1.1 - 1.5):(1.1 - 1.2):(8 - 10) at 40 - 50°C for 3 - 5 min, then continue electrospinning on the functional membrane through an electrospinning process. After electrospinning is completed, peel off the electrospinning membrane and vacuum dry at room temperature for 5 - 6 h to obtain a bio-based antibacterial facial mask.

2. The preparation method of a bio-based antibacterial facial mask according to claim 1, wherein The deacetylation degree of the chitosan described in step (1) is ≥90%.

3. The preparation method of a bio-based antibacterial facial mask according to claim 1, wherein The preparation method of the magnesium-based porphyrin described in step (2) is as follows: Under nitrogen protection, 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride, and chloroform are mixed in a mass ratio of 1:(8-10):(30-40), and reacted at room temperature for 2-3 h. After the reaction, pure water with a volume 2-3 times that of chloroform is added, and extraction is carried out using chloroform. The lower-layer organic solution is retained, and the organic solution is obtained as the magnesium-based porphyrin through rotary evaporation and drying.

4. The preparation method of a bio-based antibacterial facial mask according to claim 1, characterized in that, The molecular weight of the hyaluronic acid described in step (4) is 1×10 5 Da.

5. The preparation method of a bio-based antibacterial facial mask according to claim 1, characterized in that, The electrospinning process parameters described in step (4) are as follows: the voltage is 20 kV, the feeding speed is 3 mL / h, the receiving distance is 17 cm, the rotational speed of the receiving roller is 220 r / min, the diameter of the receiving roller is 7.5 cm, the length is 25 cm, and a layer of silicon oil paper is wrapped on the receiving roller; the areal density of the functional film is 1.2 mg / cm 2 .

6. The preparation method of a bio-based antibacterial facial mask according to claim 1, characterized in that, The electrospinning process parameters described in step (5) are as follows: the electrospinning voltage is 12 kV, the feeding speed is 2 mL / h, the receiving distance is 10 cm, the rotation speed of the receiving roller is 220 r / min, and the spinning time is 24 min.

7. A bio-based antibacterial facial mask prepared by the preparation method of a bio-based antibacterial facial mask according to any one of claims 1-6.

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