Soothing and repairing mask and preparation method thereof

Abstract

The invention discloses a soothing and repairing mask and a preparation method thereof, and belongs to the technical field of cosmetics. Chlorosulfonic acid and chitosan are mixed, stirred and reacted to obtain sulfonated chitosan; mixing the sulfonated chitosan, zinc sulfate and a sodium tripolyphosphate solution, stirring and reacting to obtain complexed chitosan; mixing the complexed chitosan, silk fibroin and laccase, stirring and reacting to obtain a modified chitosan complex; mixing and stirring the modified chitosan complex, the modified pullulan polysaccharide compound and sodium alginate to obtain a soothing and repairing compound; hydroxyethyl cellulose, xanthan gum, glycerin, 1, 3-propylene glycol, allantoin, disodium ethylene diamine tetraacetate, a repairing and relieving compound, a centella asiatica extract, panthenol, sodium hyaluronate, vitamin E acetate, ceramide 3B, 1, 2-hexanediol, caprylyl glycol, ethylhexylglycerin and deionized water are mixed and stirred, and mask essence is obtained; cleaning and dehydrating the mask base cloth, and soaking the mask base cloth into the mask essence to obtain the soothing and repairing mask.

Description

Technical Field

[0001] This invention relates to the field of cosmetic technology, specifically to a soothing and repairing facial mask and its preparation method. Background Technology

[0002] In the field of skincare, soothing and repairing masks are gaining increasing attention, especially for sensitive skin, skin with a damaged barrier, or skin inflamed. An ideal soothing and repairing mask should possess multiple benefits: firstly, it should effectively replenish skin lipids (such as ceramides and cholesterol) to rebuild the skin barrier; secondly, it should contain active ingredients with anti-inflammatory and calming effects (such as Centella asiatica extract, bisabolol, and panthenol) to alleviate irritation and promote tissue repair. Furthermore, the transdermal absorption efficiency of the ingredients and the stability of the formulation system are also key factors affecting the actual effectiveness.

[0003] Patent CN108969453A discloses a facial mask containing natural plant ingredients such as Poria cocos, Paeonia lactiflora, Bletilla striata, pearl powder, honey, and peach or rose petals. This solution emphasizes improving dullness, pigmentation, acne, pimples, and acne scars through purely natural ingredients, and claims to have anti-aging and skin-brightening effects. However, this technology primarily focuses on whitening and anti-aging. While the herbal formula used has some nourishing effects, it lacks a clear design for repairing the skin barrier structure and considers the regulatory mechanisms of inflammatory factors, thus limiting its soothing and repairing effects on acutely sensitive or severely damaged skin barriers.

[0004] Patent CN109276502A discloses a water-retaining facial mask that uses a variety of naturally derived ingredients, including Rosa damascena flower water, chamomile flower water, Melaleuca alternifolia leaf water, unsaponifiables from olive oil, wild soybean seed extract, and hydrolyzed collagen, aiming to provide a gentle, moisturizing skincare experience that avoids chemical irritation. This approach emphasizes the safety and natural properties of the raw materials, which can alleviate skin discomfort caused by chemical additives to some extent. However, its core function remains focused on hydration and moisturizing, without systematically integrating barrier lipid replenishment and targeted anti-inflammatory ingredients, nor addressing mechanisms for promoting stratum corneum repair or regulating skin microecological balance. Therefore, its comprehensive repair efficacy is insufficient when addressing symptoms such as persistent redness, stinging, or peeling associated with barrier dysfunction.

[0005] While some existing facial mask products attempt to achieve certain soothing or nourishing effects through combinations of natural ingredients, there are still problems such as imprecise ingredient selection, single mechanism of action, and limited transdermal delivery efficiency in terms of synergistically achieving skin barrier structure reconstruction, inflammatory response suppression, and long-lasting soothing. Summary of the Invention

[0006] This invention provides a soothing and repairing facial mask and its preparation method. By constructing a dual delivery system of modified chitosan complex and modified pullulan polysaccharide complex, and synergistically combining active ingredients such as ceramide, centella asiatica extract, panthenol and dipotassium glycyrrhizate, it solves the problem of insufficient barrier repair speed and depth of single ingredients, and enhances the anti-inflammatory and soothing effects while improving the efficiency of skin barrier repair.

[0007] Specifically, the technical solution of the present invention includes the following:

[0008] A method for preparing a soothing and repairing facial mask, the method comprising the following steps:

[0009] Chlorosulfonic acid and chitosan were mixed and stirred to produce sulfonated chitosan;

[0010] Complexed chitosan was obtained by mixing and stirring sulfonated chitosan, zinc sulfate and sodium tripolyphosphate solution.

[0011] Modified chitosan complex was obtained by mixing and stirring chitosan, silk fibroin and laccase.

[0012] A soothing and repairing complex was obtained by mixing and stirring modified chitosan complex, modified pullulan polysaccharide complex and sodium alginate;

[0013] Hydroxyethylcellulose, xanthan gum, glycerin, 1,3-propanediol, allantoin, disodium EDTA, repair and soothing complex, centella asiatica extract, panthenol, sodium hyaluronate, vitamin E acetate, ceramide 3B, 1,2-hexanediol, caprylyl glycol, ethylhexylglycerin and deionized water are mixed and stirred, then homogenized and filtered to obtain the mask essence.

[0014] After the mask base fabric is cleaned and dehydrated, it is soaked in the mask essence. After soaking, it is folded, packaged, replenished with essence, and heat-sealed to obtain a soothing and repairing mask.

[0015] Furthermore, the weight ratio of chlorosulfonic acid to chitosan is 4~5:1~2.

[0016] Furthermore, the conditions for the mixing and stirring reaction of chlorosulfonic acid and chitosan include a reaction temperature of 60-70°C and a reaction time of 5-6 hours. The reaction of chlorosulfonic acid with chitosan introduces sulfonic acid groups into its backbone to obtain sulfonated chitosan, which can enhance the water solubility and biocompatibility of chitosan. At the same time, the sulfonic acid groups themselves have certain moisturizing and mild anti-inflammatory properties.

[0017] Furthermore, the concentration of the sodium tripolyphosphate solution is 1 wt%.

[0018] Furthermore, the weight ratio of the sulfonated chitosan, zinc sulfate, and sodium tripolyphosphate solution is 6~8:0.24~0.26:15~20.

[0019] Furthermore, the conditions for the mixing and stirring reaction of sulfonated chitosan, zinc sulfate, and sodium tripolyphosphate solution include a reaction temperature of 35-45°C and a reaction time of 2-3 hours. Under acidic conditions, sulfonated chitosan binds with zinc sulfate through ionic interactions and coordination bonds. The introduction of zinc ions endows the material with good antibacterial, anti-inflammatory, and epithelial repair-promoting abilities.

[0020] Furthermore, the weight ratio of the complexed chitosan, silk fibroin and laccase is 10:1~2:0.04~0.06.

[0021] Furthermore, the conditions for the mixed stirring reaction of complexed chitosan, silk fibroin and laccase include a reaction temperature of 40-50℃ and a reaction time of 4-6h. The laccase catalyzes the oxidative cross-linking of tyrosine residues in silk fibroin with chitosan chains to form a stable three-dimensional network structure, which improves the mechanical stability and film-forming properties of the material, and also introduces the inherent moisturizing, repairing and cell affinity properties of silk fibroin.

[0022] Furthermore, the preparation method of the modified pullulan polysaccharide complex includes the following steps:

[0023] Pullulan and sodium periodate were mixed and stirred to produce aldehyde-modified pullulan.

[0024] Dopamine hydrochloride was dispersed in Tris-HCl buffer at pH 8.5 and stirred to obtain a polydopamine dispersion. Polyethyleneimine was then added and the reaction was continued to obtain grafted microspheres.

[0025] Aldehyde-modified pullulan and grafted microspheres were mixed and stirred to obtain composite microspheres;

[0026] Dipotassium glycyrrhizate and composite microspheres were mixed and reacted to obtain a loaded microsphere dispersion. Then, methoxy polyethylene glycol succinate N-hydroxysuccinimide was added and stirred to obtain a modified pullulan polysaccharide complex.

[0027] Furthermore, the weight ratio of pullulan to sodium periodate is 5:4 to 4.5.

[0028] Furthermore, the conditions for the mixed stirring reaction of pullulan and sodium periodate include a reaction temperature of 25°C and a reaction time of 6-8 hours; sodium periodate oxidizes the vicinal diol structure of pullulan to generate an active aldehyde group, thus obtaining aldehyde-modified pullulan.

[0029] Furthermore, the weight ratio of dopamine hydrochloride to polyethyleneimine is 2~3:3~3.5.

[0030] Furthermore, the conditions for the reaction of the dopamine hydrochloride dispersion in a Tris-HCl buffer solution at pH 8.5 include a reaction temperature of 25°C and a reaction time of 24-28 h.

[0031] Furthermore, the conditions for adding polyethyleneimine and continuing the stirring reaction include a reaction time of 8-10 hours; through the self-polymerization of dopamine hydrochloride and grafting with polyethyleneimine, grafted microspheres with strong adhesion and abundant amino groups are formed.

[0032] Furthermore, the weight ratio of the aldehyde-modified pullulan polysaccharide to the grafted microspheres is 3~5:0.2~0.4.

[0033] Furthermore, the conditions for the mixing and stirring reaction of the aldehyde-modified pullulan and the grafted microspheres include a reaction temperature of 25°C, a reaction pH of 6.0~6.3, and a reaction time of 12~14h. The grafted microspheres covalently bind to the aldehyde-modified pullulan through a Schiff base reaction between the aldehyde and amino groups, forming composite microspheres that combine the film-forming and biodegradable properties of pullulan with the strong adhesion and high loading capacity of the grafted microspheres.

[0034] Furthermore, the weight ratio of dipotassium glycyrrhizate, composite microspheres, and methoxy polyethylene glycol succinate N-hydroxysuccinimide is 0.2~0.3:0.8~1.0:0.2~0.4.

[0035] Furthermore, the conditions for the mixed reaction of dipotassium glycyrrhizate and composite microspheres include ultrasonic dispersion at 100W for 10 minutes, followed by standing at 4°C for 24-36 hours.

[0036] Furthermore, the conditions for adding methoxy polyethylene glycol succinate N-hydroxysuccinimide to the stirring reaction include a reaction temperature of 25°C and a reaction time of 8-10 h; the anti-inflammatory active ingredient dipotassium glycyrrhizate is loaded into the network structure of the composite microspheres, and then the surface of the microspheres is modified with methoxy polyethylene glycol succinate N-hydroxysuccinimide, which improves its hydrophilicity, dispersion stability, and permeability and retention on the skin surface.

[0037] Furthermore, the weight ratio of the modified chitosan complex, the modified pullulan polysaccharide complex, and sodium alginate is 0.8~1.2:0.2~0.3:0.08~0.1.

[0038] Furthermore, the conditions for mixing and stirring the modified chitosan complex, the modified pullulan polysaccharide complex, and sodium alginate include a temperature of 25°C and a time of 8-12 hours.

[0039] Further, the weight ratio of the hydroxyethyl cellulose, xanthan gum, glycerin, 1,3-propanediol, allantoin, disodium EDTA, repair and soothing complex, Centella asiatica extract, panthenol, sodium hyaluronate, vitamin E acetate, ceramide 3B, 1,2-hexanediol, caprylyl glycol, and ethylhexylglycerin is 7.6~8.4:1.9~2.1:28.5~31.5:9.5~10.5:0.475~0.525:0.095~0.105:47.5~63.0:4.75~5.25:4.75~5.25:0.95~1.05:0.475~0.525:0.475~0.525:2.85~3.15:0.95~1.05:0.475~0.525.

[0040] Furthermore, the homogenization conditions include a rotation speed of 5000 r / min and a time of 5 min.

[0041] Furthermore, the filtration conditions include filtration using a 0.45 μm filter membrane.

[0042] Furthermore, the mask base fabric is a seaweed fiber mask base fabric.

[0043] Furthermore, the soaking conditions include soaking at 25°C for 35 minutes, with a soaking ratio of 1:22~25 (m). 干面膜基布 :m 面膜精华液 ).

[0044] Furthermore, the heat sealing conditions include a temperature of 185°C, a pressure of 0.35 MPa, and a time of 2.5 s.

[0045] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0046] (1) The modified chitosan complex in this invention mainly targets the reconstruction of the physical barrier. It enhances skin affinity through sulfonation modification, provides basic antibacterial and anti-inflammatory activity by complexing zinc ions, and forms a stable three-dimensional moisturizing and repairing network by cross-linking silk fibroin with laccase. This material can quickly form a breathable protective film on the skin surface, immediately reducing transepidermal water loss and resisting external stimuli, effectively solving the problems of slow onset and single target of traditional repair ingredients. However, its anti-inflammatory mechanism mainly relies on zinc ions, and its inhibition depth and persistence on complex inflammatory pathways are still limited. To this end, a specially designed modified pullulan polysaccharide complex provides a precise solution. This complex uses aldehyde-modified pullulan polysaccharide as the backbone and combines polydopamine-polyethyleneimine grafted microspheres through Schiff base reaction to construct a delivery system with strong adhesion and high loading capacity. The system is further loaded with dipotassium glycyrrhizate and modified with polyethylene glycol, which significantly improves the penetration efficiency and retention capacity into the deep layers of the skin. Its mechanism of action is as follows: by utilizing the adhesive properties of microspheres to anchor them to the stratum corneum, it slowly releases dipotassium glycyrrhizate, a potent anti-inflammatory component, to achieve multi-pathway and deep-level inflammation suppression and immune regulation, thereby directly making up for the shortcomings of chitosan complexes in long-term deep soothing.

[0047] (2) The soothing and repairing mask prepared by this invention, by combining the above-mentioned synergistic system with an optimized formula and carrier, comprehensively achieves rapid repair, deep anti-inflammation, and long-term stabilization. At the application level, the minerals and polysaccharides rich in the seaweed fiber mask base fabric, combined with the film-forming properties of the modified chitosan complex in the essence, jointly enhance the immediate moisturizing and barrier simulation functions. At the same time, the modified pullulan polysaccharide complex in the essence, as an intelligent delivery carrier, efficiently penetrates the stratum corneum, delivering the dipotassium glycyrrhizate it carries, along with the soothing ingredients such as Centella asiatica extract and panthenol added to the formula, to the target site, synergistically inhibiting key inflammatory factors and relieving discomfort such as redness and stinging. Classic barrier components such as ceramides, sodium hyaluronate, and vitamin E are better stabilized and utilized in the affinity environment constructed by the material, jointly replenishing intercellular lipids and enhancing the skin's own moisturizing and defense capabilities. Detailed Implementation

[0048] The technical solution of the present invention will be clearly and completely described below through embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be prepared by known methods.

[0050] Chitosan (90% deacetylation) was purchased from Qingdao Lizhong Chitosan Company.

[0051] Laccase (enzyme activity 1072 U / mL) was purchased from Novozymes (China) Biotechnology Co., Ltd.

[0052] Polyethyleneimine (PEI, Mw=1800Da) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0053] Example 1

[0054] A method for preparing a soothing and repairing facial mask includes the following steps:

[0055] Four parts by weight of chlorosulfonic acid were dispersed in 15 parts by weight of N,N-dimethylformamide. The dispersion was carried out at 0°C and stirred at 200 r / min for 10 min to obtain a sulfonating agent. The temperature was raised to 25°C, and one part by weight of chitosan was added. The temperature was raised to 60°C and stirred at 200 r / min for 5 h under a nitrogen atmosphere. After the reaction was completed, 500 parts by weight of anhydrous ethanol was added to the reaction mixture and stirred for 20 min. The precipitate was collected by filtration and dispersed in deionized water. The precipitate was dialyzed with a 14000 Da dialysis bag for 72 h. After concentration under reduced pressure at 50°C, the sulfonated chitosan was obtained by freeze drying.

[0056] Six parts by weight of sulfonated chitosan and 0.24 parts by weight of zinc sulfate were dispersed in 100 parts by weight of deionized water. The pH was adjusted to 4.0, and the mixture was heated to 35°C and stirred at 400 r / min for 1.5 h for adsorption. Then, 15 parts by weight of 1 wt% sodium tripolyphosphate solution were added dropwise to the above reaction system at a rate of 0.001 mL / s. After the addition was completed, the reaction was stirred for another 2 h. After the reaction was completed, the mixture was centrifuged at 12000 r / min for 20 min, the precipitate was collected, washed three times with distilled water, resuspended in deionized water, dialyzed with a 14000 Da dialysis bag for 72 h, concentrated under reduced pressure at 50°C, and then freeze-dried to obtain complexed chitosan.

[0057] 10 parts by weight of complexed chitosan and 1 part by weight of silk fibroin were dispersed in 100 parts by weight of pH 6.5 phosphate buffer. After stirring and mixing at 220 r / min for 10 min, 0.04 parts by weight of laccase were added, the temperature was raised to 40℃, and the reaction was continued to be stirred for 4 h in an oxygen atmosphere. After the reaction was completed, the mixture was centrifuged at 5000 r / min for 10 min, washed three times each with deionized water, 70 wt% ethanol, and deionized water, and then vacuum dried at 40℃ for 12 h to obtain the modified chitosan complex.

[0058] Five parts by weight of pullulan were dispersed in 50 parts by weight of deionized water and stirred at 300 r / min for 30 min. The mixture was then heated to 50 °C and stirred for 1.5 h. After cooling to 25 °C, a polysaccharide solution was obtained. Four parts by weight of sodium periodate were dispersed in 40 parts by weight of deionized water to obtain a sodium periodate solution. Under light-protected conditions, the sodium periodate solution was added dropwise to the polysaccharide solution at a rate of 2 mL / min and the reaction was continued for 6 h. After the reaction was completed, 0.2 parts by weight of ethylene glycol was added and the mixture was stirred for 30 min. The filtrate was collected by filtration through a 0.45 μm filter membrane and dialyzed in deionized water for 72 h using a dialysis bag with a molecular weight cutoff of 3500 Da. The filtrate was then freeze-dried to obtain aldehyde-modified pullulan.

[0059] Two parts by weight of dopamine hydrochloride were dispersed in 300 parts by weight of pH 8.5 Tris-HCl buffer solution. The mixture was stirred at 400 rpm in the dark at 25 °C for 24 h under a nitrogen atmosphere to obtain a polydopamine dispersion. Three parts by weight of polyethyleneimine were added, and the mixture was stirred in the dark for another 8 h. After the reaction was completed, the supernatant was collected by centrifugation at 5000 rpm for 10 min to remove large aggregates. The supernatant was then centrifuged at 15000 rpm for 30 min to collect the precipitate. The precipitate was washed three times each with pH 8.5 Tris-HCl buffer solution and deionized water. After ultrafiltration with a polyethersulfone membrane with a molecular weight cutoff of 100 kDa, the grafted microspheres were obtained by freeze drying.

[0060] Three parts by weight of aldehyde-modified pullulan polysaccharide were dispersed in 50 parts by weight of phosphate buffer at pH 6.0. After stirring at 200 r / min for 50 min at 25 °C, 0.2 parts by weight of grafted microspheres were added, the pH was adjusted to 6.0, and the mixture was stirred at 250 r / min in the dark for 12 h. After dialyzing in deionized water for 72 h using a dialysis bag with a molecular weight cutoff of 5000 Da, the composite microspheres were obtained by gel chromatography and freeze drying.

[0061] 0.2 parts by weight of dipotassium glycyrrhizate were dispersed in 50 parts by weight of deionized water and sonicated at 100W for 5 min. 0.8 parts by weight of composite microspheres were added and sonicated at 100W for 10 min. The mixture was then allowed to stand at 4℃ for 24 h to obtain a loaded microsphere dispersion. 0.2 parts by weight of methoxy polyethylene glycol succinate N-hydroxysuccinimide (Mw=5000) were dispersed in 10 parts by weight of pH 7.4 PBS buffer and added dropwise to the loaded microsphere dispersion at a rate of 0.5 mL / min. The mixture was stirred at 100 r / min in the dark at 25℃ for 8 h. After the reaction was completed, the mixture was centrifuged at 15000 r / min for 30 min, the precipitate was collected, washed three times with pH 7.4 PBS buffer, and then dialyzed and freeze-dried to obtain the modified pullulan polysaccharide complex.

[0062] 1.0 parts by weight of modified chitosan complex and 0.2 parts by weight of modified pullulan polysaccharide complex were dispersed in 30 parts by weight of deionized water, and 0.08 parts by weight of sodium alginate were added. After stirring at 20 r / min for 8 h at 25 °C, the mixture was filtered through a 0.22 μm filter membrane to obtain the repair and soothing complex.

[0063] 7.6 parts by weight of hydroxyethyl cellulose and 1.9 parts by weight of xanthan gum were dispersed in 500 parts by weight of deionized water. The mixture was heated to 75°C and stirred at 600 rpm for 20 minutes. After cooling to 35°C, 28.5 parts by weight of glycerin, 9.5 parts by weight of 1,3-propanediol, 0.475 parts by weight of allantoin, and 0.095 parts by weight of disodium EDTA were added. The mixture was stirred and dispersed for another 20 minutes. After cooling to 30°C, 47.5 parts by weight of a repair and soothing complex were added, followed by 4.75 parts by weight of Centella asiatica extract, 4.75 parts by weight of... Add panthenol, 0.95 parts by weight of sodium hyaluronate, 0.475 parts by weight of vitamin E acetate and 0.475 parts by weight of ceramide 3B, and continue stirring for 10 min. Add 2.85 parts by weight of 1,2-hexanediol, 0.95 parts by weight of caprylyl glycol and 0.475 parts by weight of ethylhexylglycerin to the system after premixing, stir for 20 min, then adjust the pH to 5.5 with lactic acid, add deionized water to a total weight of 1000 parts by weight, homogenize at 5000 r / min for 5 min, degas under vacuum and filter through a 0.45 μm filter membrane to obtain the mask essence.

[0064] The seaweed fiber mask base fabric was soaked and washed twice with ultrapure water and centrifuged to remove water. It was then immersed in a 25°C mask essence for 35 minutes, with an immersion ratio of 1:22 (m³). 干面膜基布 :m 面膜精华液 After being removed, the masks are centrifuged and drained, and the total weight of each mask (mask base cloth + mask essence) is controlled to be 45g. After being folded, they are placed into aluminum foil composite film bags, each bag is replenished with 2.375 parts by weight of mask essence, and then heat-sealed at 185℃ and 0.35MPa for 2.5s. After cooling, they are packaged to obtain soothing and repairing masks.

[0065] Example 2

[0066] A method for preparing a soothing and repairing facial mask includes the following steps:

[0067] Five parts by weight of chlorosulfonic acid were dispersed in 18 parts by weight of N,N-dimethylformamide. The dispersion was carried out at 0°C and stirred at 200 r / min for 10 min to obtain a sulfonating agent. The temperature was raised to 25°C, and 1.5 parts by weight of chitosan were added. The temperature was raised to 65°C, and the reaction was carried out at 200 r / min for 5.5 h under a nitrogen atmosphere. After the reaction was completed, 500 parts by weight of anhydrous ethanol was added to the reaction mixture and stirred for 20 min. The precipitate was collected by filtration and dispersed in deionized water. The precipitate was dialyzed with a 14000 Da dialysis bag for 72 h. After concentration under reduced pressure at 50°C, the sulfonated chitosan was obtained by freeze drying.

[0068] 7 parts by weight of sulfonated chitosan and 0.25 parts by weight of zinc sulfate were dispersed in 100 parts by weight of deionized water. The pH was adjusted to 4.8, and the mixture was heated to 40°C and stirred at 400 r / min for 2.0 h for adsorption. Then, 18 parts by weight of 1 wt% sodium tripolyphosphate solution was added dropwise to the above reaction system at a rate of 0.001 mL / s. After the addition was completed, the reaction was stirred for another 2.5 h. After the reaction was completed, the mixture was centrifuged at 12000 r / min for 20 min, the precipitate was collected, washed three times with distilled water, resuspended in deionized water, dialyzed with a 14000 Da dialysis bag for 72 h, concentrated under reduced pressure at 50°C, and then freeze-dried to obtain complexed chitosan.

[0069] 10 parts by weight of complexed chitosan and 1.5 parts by weight of silk fibroin were dispersed in 100 parts by weight of pH 6.5 phosphate buffer. After stirring and mixing at 220 r / min for 10 min, 0.05 parts by weight of laccase were added, the temperature was raised to 45℃, and the reaction was continued to be stirred for 5 h in an oxygen atmosphere. After the reaction was completed, the mixture was centrifuged at 5000 r / min for 10 min, washed three times each with deionized water, 70 wt% ethanol, and deionized water, and then vacuum dried at 40℃ for 12 h to obtain the modified chitosan complex.

[0070] The preparation of the modified pullulan polysaccharide complex was consistent with that in Example 1;

[0071] 1.1 parts by weight of modified chitosan complex and 0.22 parts by weight of modified pullulan polysaccharide complex were dispersed in 30 parts by weight of deionized water, and 0.09 parts by weight of sodium alginate were added. After stirring at 20 r / min for 10 h at 25 °C, the mixture was filtered through a 0.22 μm filter membrane to obtain the repair and soothing complex.

[0072] Subsequent operations are consistent with those in Example 1.

[0073] Example 3

[0074] A method for preparing a soothing and repairing facial mask includes the following steps:

[0075] The preparation method of the modified chitosan complex is consistent with that in Example 2;

[0076] Five parts by weight of pullulan were dispersed in 50 parts by weight of deionized water and stirred at 300 r / min for 30 min. The mixture was then heated to 50 °C and stirred for 1.5 h. After cooling to 25 °C, a polysaccharide solution was obtained. Four and five parts by weight of sodium periodate were dispersed in 40 parts by weight of deionized water to obtain a sodium periodate solution. Under light-protected conditions, the sodium periodate solution was added dropwise to the polysaccharide solution at a rate of 2 mL / min and the reaction was continued for 8 h. After the reaction was completed, 0.2 parts by weight of ethylene glycol were added and the mixture was stirred for 30 min. The filtrate was collected by filtration through a 0.45 μm filter membrane and dialyzed in deionized water for 72 h using a dialysis bag with a molecular weight cutoff of 3500 Da. The filtrate was then freeze-dried to obtain aldehyde-modified pullulan.

[0077] Three parts by weight of dopamine hydrochloride were dispersed in 300 parts by weight of pH 8.5 Tris-HCl buffer solution. The mixture was stirred at 400 rpm in the dark at 25 °C for 28 h under a nitrogen atmosphere to obtain a polydopamine dispersion. Three and five parts by weight of polyethyleneimine were added, and the mixture was stirred in the dark for another 10 h. After the reaction was completed, the supernatant was collected by centrifugation at 5000 rpm for 10 min to remove large aggregates. The supernatant was then centrifuged at 15000 rpm for 30 min to collect the precipitate. The precipitate was washed three times each with pH 8.5 Tris-HCl buffer solution and deionized water. After ultrafiltration with a polyethersulfone membrane with a molecular weight cutoff of 100 kDa, the grafted microspheres were obtained by freeze drying.

[0078] Five parts by weight of aldehyde-modified pullulan polysaccharide were dispersed in 50 parts by weight of phosphate buffer at pH 6.0. After stirring at 200 r / min for 50 min at 25 °C, 0.4 parts by weight of grafted microspheres were added, the pH was adjusted to 6.3, and the mixture was stirred at 250 r / min in the dark for 14 h. After dialyzing in deionized water for 72 h using a dialysis bag with a molecular weight cutoff of 5000 Da, the composite microspheres were obtained by gel chromatography and freeze drying.

[0079] 0.3 parts by weight of dipotassium glycyrrhizate were dispersed in 50 parts by weight of deionized water and sonicated at 100W for 5 min. 1.0 part by weight of composite microspheres were added and sonicated at 100W for 10 min. The mixture was then allowed to stand at 4℃ for 36 h to obtain a loaded microsphere dispersion. 0.4 parts by weight of methoxy polyethylene glycol succinate N-hydroxysuccinimide (Mw=5000) were dispersed in 10 parts by weight of pH 7.4 PBS buffer and added dropwise to the loaded microsphere dispersion at a rate of 0.5 mL / min. The mixture was stirred at 100 r / min in the dark at 25℃ for 10 h. After the reaction, the mixture was centrifuged at 15000 r / min for 30 min, the precipitate was collected, washed three times with pH 7.4 PBS buffer, and then dialyzed and freeze-dried to obtain the modified pullulan polysaccharide complex.

[0080] 1.0 parts by weight of modified chitosan complex and 0.25 parts by weight of modified pullulan polysaccharide complex were dispersed in 30 parts by weight of deionized water, and 0.1 parts by weight of sodium alginate were added. After stirring at 20 r / min for 12 h at 25 °C, the mixture was filtered through a 0.22 μm filter membrane to obtain the repair and soothing complex.

[0081] Subsequent operations are consistent with those in Example 1.

[0082] Example 4

[0083] A method for preparing a soothing and repairing facial mask includes the following steps:

[0084] The preparation method of the modified chitosan complex is consistent with that in Example 2;

[0085] The preparation method of the modified pullulan polysaccharide complex is consistent with that in Example 3;

[0086] 0.9 parts by weight of modified chitosan complex and 0.28 parts by weight of modified pullulan polysaccharide complex were dispersed in 30 parts by weight of deionized water, and 0.09 parts by weight of sodium alginate were added. After stirring at 20 r / min for 10 h at 25 °C, the mixture was filtered through a 0.22 μm filter membrane to obtain the repair and soothing complex.

[0087] Subsequent operations are consistent with those in Example 1.

[0088] Example 5

[0089] A method for preparing a soothing and repairing facial mask includes the following steps:

[0090] Five parts by weight of chlorosulfonic acid were dispersed in 20 parts by weight of N,N-dimethylformamide. The dispersion was carried out at 0°C and stirred at 200 r / min for 10 min to obtain a sulfonating agent. The temperature was raised to 25°C, and two parts by weight of chitosan were added. The temperature was raised to 70°C and stirred at 200 r / min for 6 h under a nitrogen atmosphere. After the reaction was completed, 500 parts by weight of anhydrous ethanol was added to the reaction mixture and stirred for 20 min. The precipitate was collected by filtration and dispersed in deionized water. The precipitate was dialyzed with a 14000 Da dialysis bag for 72 h. After concentration under reduced pressure at 50°C, the sulfonated chitosan was obtained by freeze drying.

[0091] Eight parts by weight of sulfonated chitosan and 0.26 parts by weight of zinc sulfate were dispersed in 100 parts by weight of deionized water. The pH was adjusted to 5.2, and the mixture was heated to 45°C and stirred at 400 r / min for 2.5 h for adsorption. Then, 20 parts by weight of 1 wt% sodium tripolyphosphate solution were added dropwise to the above reaction system at a rate of 0.001 mL / s. After the addition was completed, the reaction was stirred for another 3 h. After the reaction was completed, the mixture was centrifuged at 12000 r / min for 20 min, the precipitate was collected, washed three times with distilled water, resuspended in deionized water, dialyzed with a 14000 Da dialysis bag for 72 h, concentrated under reduced pressure at 50°C, and then freeze-dried to obtain complexed chitosan.

[0092] 10 parts by weight of complexed chitosan and 2 parts by weight of silk fibroin were dispersed in 100 parts by weight of pH 6.5 phosphate buffer. After stirring and mixing at 220 r / min for 15 min, 0.06 parts by weight of laccase were added, the temperature was raised to 50℃, and the reaction was continued to be stirred for 6 h in an oxygen atmosphere. After the reaction was completed, the mixture was centrifuged at 5000 r / min for 10 min, washed three times each with deionized water, 70 wt% ethanol, and deionized water, and then vacuum dried at 40℃ for 12 h to obtain the modified chitosan complex.

[0093] Five parts by weight of pullulan were dispersed in 50 parts by weight of deionized water and stirred at 300 r / min for 30 min. The mixture was then heated to 50 °C and stirred for 1.5 h. After cooling to 25 °C, a polysaccharide solution was obtained. Four and five parts by weight of sodium periodate were dispersed in 40 parts by weight of deionized water to obtain a sodium periodate solution. Under light-protected conditions, the sodium periodate solution was added dropwise to the polysaccharide solution at a rate of 2 mL / min and the reaction was continued for 8 h. After the reaction was completed, 0.2 parts by weight of ethylene glycol were added and the mixture was stirred for 30 min. The filtrate was collected by filtration through a 0.45 μm filter membrane and dialyzed in deionized water for 72 h using a dialysis bag with a molecular weight cutoff of 3500 Da. The filtrate was then freeze-dried to obtain aldehyde-modified pullulan.

[0094] Three parts by weight of dopamine hydrochloride were dispersed in 300 parts by weight of pH 8.5 Tris-HCl buffer. The mixture was stirred at 400 rpm in the dark at 25 °C for 28 h under a nitrogen atmosphere. Then, 3.5 parts by weight of polyethyleneimine were added, and the mixture was stirred in the dark for another 10 h. After the reaction was completed, the supernatant was collected by centrifugation at 5000 rpm for 10 min to remove large aggregates. The supernatant was then centrifuged at 15000 rpm for 30 min to collect the precipitate. The precipitate was washed three times each with pH 8.5 Tris-HCl buffer and deionized water. After ultrafiltration with a polyethersulfone membrane with a molecular weight cutoff of 100 kDa, the grafted microspheres were obtained by freeze drying.

[0095] Five parts by weight of aldehyde-modified pullulan polysaccharide were dispersed in 50 parts by weight of phosphate buffer at pH 6.0. After stirring at 200 r / min for 50 min at 25 °C, 0.4 parts by weight of grafted microspheres were added, the pH was adjusted to 6.3, and the mixture was stirred at 250 r / min in the dark for 14 h. After dialyzing in deionized water for 72 h using a dialysis bag with a molecular weight cutoff of 5000 Da, the composite microspheres were obtained by gel chromatography and freeze drying.

[0096] 0.3 parts by weight of dipotassium glycyrrhizate were dispersed in 50 parts by weight of deionized water and sonicated at 100W for 5 min. 1.0 part by weight of composite microspheres were added and sonicated at 100W for 10 min. The mixture was then allowed to stand at 4℃ for 36 h to obtain a loaded microsphere dispersion. 0.4 parts by weight of methoxy polyethylene glycol succinate N-hydroxysuccinimide (Mw=5000) were dispersed in 10 parts by weight of pH 7.4 PBS buffer and added dropwise to the loaded microsphere dispersion at a rate of 0.5 mL / min. The mixture was stirred at 100 r / min in the dark at 25℃ for 10 h. After the reaction, the mixture was centrifuged at 15000 r / min for 30 min, the precipitate was collected, washed three times with pH 7.4 PBS buffer, and then dialyzed and freeze-dried to obtain the modified pullulan polysaccharide complex.

[0097] 0.8 parts by weight of modified chitosan complex and 0.3 parts by weight of modified pullulan polysaccharide complex were dispersed in 30 parts by weight of deionized water, and 0.1 parts by weight of sodium alginate were added. After stirring at 20 r / min for 12 h at 25 °C, the mixture was filtered through a 0.22 μm filter membrane to obtain the repair and soothing complex.

[0098] Subsequent operations are consistent with those in Example 1.

[0099] Comparative Example 1

[0100] A method for preparing a soothing and repairing facial mask includes the following steps:

[0101] Replace 0.06 parts by weight of laccase in Example 5 with 0.1 parts by weight of glutaraldehyde, and keep all other operations the same as in Example 5.

[0102] Comparative Example 2

[0103] A method for preparing a soothing and repairing facial mask includes the following steps:

[0104] Remove zinc sulfate and sodium tripolyphosphate from Example 5, and then react 10 parts by weight of sulfonated chitosan with 2 parts by weight of silk fibroin. Other operations are the same as in Example 5.

[0105] Comparative Example 3

[0106] A method for preparing a soothing and repairing facial mask includes the following steps:

[0107] In Example 5, 5 parts by weight of pullulan were replaced with 5 parts by weight of sodium hyaluronate (Mw=50000Da). In subsequent steps, all “aldehyde-modified pullulan” were replaced with “aldehyde-modified hyaluronic acid”. Other operations were the same as in Example 5.

[0108] Comparative Example 4

[0109] A method for preparing a soothing and repairing facial mask includes the following steps:

[0110] Polydopamine microspheres were obtained by removing polyethyleneimine from Example 5. 0.4 parts by weight of grafted microspheres were replaced with 0.4 parts by weight of polydopamine microspheres, and other operations were the same as in Example 5.

[0111] Comparative Example 5

[0112] A method for preparing a soothing and repairing facial mask includes the following steps:

[0113] Replace 60.0 parts by weight of the repair and soothing complex in Example 5 with 1.0 parts by weight of chitosan, 0.3 parts by weight of pullulan, and 0.3 parts by weight of dipotassium glycyrrhizate, while keeping all other operations the same as in Example 5.

[0114] Comparative Example 6

[0115] A method for preparing a soothing and repairing facial mask includes the following steps:

[0116] The methoxy polyethylene glycol succinate N-hydroxysuccinimide in Example 5 was removed, and all other operations remained the same as in Example 5.

[0117] Performance testing

[0118] The properties of the soothing and repairing masks prepared in Examples 1-5 and Comparative Examples 1-6 were tested using the following methods:

[0119] In vitro skin barrier repair model test: using ex vivo pig skin, the change rate of transepidermal water loss (TEWL) before and after sample treatment (measured 2 h after treatment), and the immediate increase and retention rate of stratum corneum moisture content (measured by Cornemometer) after 4 h were measured.

[0120] In vitro anti-inflammatory activity assay: A lipopolysaccharide (LPS)-induced RAW 264.7 macrophage inflammation model was used. The levels of tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) in the cell supernatant were measured. The inhibition rate of the sample on the release of inflammatory factors was calculated.

[0121] Transdermal permeation and retention assay of active ingredient: A Franz diffusion cell and isolated porcine skin were used, with dipotassium glycyrrhizate as a tracer. The amount that permeated through the skin (permeation) and the amount that remained in the skin (retention) were measured over 6 hours.

[0122] Product stability test: The finished mask was placed in an accelerated stability test chamber at 40℃ and 75% relative humidity. Samples were taken at 0, 1, 2 and 3 months to observe the properties of the essence and to test the retention rate of the main active ingredients (such as dipotassium glycyrrhizate and ceramide).

[0123] The test results are shown in Table 1.

[0124] TEWL reduction rate (%) Moisture retention rate over 4 hours (%) TNF-α inhibition rate (%) IL-6 inhibition rate (%) <![CDATA[Dipotassium Glycyrrhizinate Skin Retention Amount (μg / cm 2 )]]> 3-month active ingredient retention rate (%) Example 1 18.5 35.2 45.1 48.3 1.85 92.1 Example 2 25.3 42.7 47.8 50.5 1.92 93.5 Example 3 24.8 43.5 58.9 62.1 2.45 94 Example 4 28.9 50.1 65.4 68.9 3.1 95.8 Example 5 32.7 55.8 72.5 75.2 3.88 96.5 Comparative Example 1 26.5 41.2 68.9 70.1 3.2 90.3 Comparative Example 2 20.1 38.9 35.2 33.8 3.65 96 Comparative Example 3 15.8 30.5 60.3 63.5 1.95 88.7 Comparative Example 4 30.1 52.3 48.7 51.2 1.02 95.2 Comparative Example 5 10.5 20.8 40.5 43.2 0.45 82.4 Comparative Example 6 29.8 53.1 70.8 73.5 1.58 96.1

[0125] According to the test results in Table 1, it can be observed that the soothing and repairing masks prepared in Examples 1-5 of the present invention have good skin barrier repair and anti-inflammatory soothing properties, while the performance of the soothing and repairing masks prepared in Comparative Examples 1-6 is reduced.

[0126] The performance degradation in Comparative Example 1 may be due to the replacement of the mild enzymatic crosslinking of laccase with the aggressive chemical crosslinking of glutaraldehyde. This could lead to an overly dense or brittle material network structure, reduced flexibility and biocompatibility, and potentially introduce the risk of irritation from residual crosslinking agents.

[0127] The performance degradation in Comparative Example 2 may be due to the omission of the zinc ion complexation step. This causes the material to lose the core activities provided by zinc ions, such as immediate antibacterial, anti-inflammatory, and wound-healing promotion, retaining only the basic physical barrier function, resulting in a severe deficiency in the product's ability to intervene rapidly in the early stages of inflammation.

[0128] The performance degradation in Comparative Example 3 may be due to the use of sodium hyaluronate instead of pullulan as the reaction backbone. Differences in molecular conformation, chain rigidity, and post-oxidation activity between the two polysaccharides may cause uncontrollable changes in the structural stability, mechanical properties, and skin adhesion behavior of the formed aldehyde products and their subsequent assemblies, thereby affecting the reliability of the entire delivery system.

[0129] The performance degradation in Comparative Example 4 may be due to the use of ungrafted polyethyleneimine (PEI) ordinary polydopamine microspheres. This results in a lack of high-density amino groups introduced by PEI on the microsphere surface, which not only reduces the covalent bonding strength with aldehyde-modified polysaccharides but also significantly weakens the loading capacity and binding force of dipotassium glycyrrhizate, ultimately leading to a decrease in sustained-release efficiency and anti-inflammatory effect.

[0130] The performance degradation in Comparative Example 5 may be due to the direct physical mixing of ordinary raw materials, completely abandoning the comprehensive design of chemical modification, structural assembly, and synergistic delivery. The components cannot achieve synergy in terms of time, space, and level of action, resulting in poor penetration, short-lived efficacy, and unpleasant skin feel, with overall performance reverting to the level of traditional formulations.

[0131] The reduced performance of Comparative Example 6 may be due to the omission of the polyethylene glycol (PEG) surface modification step. This reduces the hydrophilicity and colloidal stability of the composite microspheres, and more importantly, severely weakens their ability to penetrate the skin's stratum corneum barrier. As a result, most of the active ingredients remain on the skin surface, failing to achieve effective deep delivery and soothing.

[0132] The embodiments described above provide a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. A method for preparing a soothing and repairing facial mask, characterized in that, The preparation method includes the following steps: Chlorosulfonic acid and chitosan were mixed and stirred to produce sulfonated chitosan; Complexed chitosan was obtained by mixing and stirring sulfonated chitosan, zinc sulfate and sodium tripolyphosphate solution. Modified chitosan complex was obtained by mixing and stirring chitosan, silk fibroin and laccase. A soothing and repairing complex was obtained by mixing and stirring modified chitosan complex, modified pullulan polysaccharide complex and sodium alginate. Hydroxyethylcellulose, xanthan gum, glycerin, 1,3-propanediol, allantoin, disodium EDTA, repair and soothing complex, centella asiatica extract, panthenol, sodium hyaluronate, vitamin E acetate, ceramide 3B, 1,2-hexanediol, caprylyl glycol, ethylhexylglycerin and deionized water are mixed and stirred, then homogenized and filtered to obtain the mask essence. After the mask base fabric is cleaned and dehydrated, it is soaked in the mask essence. After soaking, it is folded, packaged, replenished with essence, and heat-sealed to obtain a soothing and repairing mask.

2. The method for preparing a soothing and repairing facial mask as described in claim 1, characterized in that, The weight ratio of chlorosulfonic acid to chitosan is 4~5:1~2; the conditions for the mixing and stirring reaction of chlorosulfonic acid and chitosan include a reaction temperature of 60~70℃ and a reaction time of 5~6h.

3. The method for preparing a soothing and repairing facial mask as described in claim 1, characterized in that, The concentration of the sodium tripolyphosphate solution is 1 wt%; the weight ratio of the sulfonated chitosan, zinc sulfate, and sodium tripolyphosphate solution is 6~8:0.24~0.26:15~20; the conditions for mixing and stirring the sulfonated chitosan, zinc sulfate, and sodium tripolyphosphate solution include a reaction temperature of 35~45℃ and a reaction time of 2~3h.

4. The method for preparing a soothing and repairing facial mask as described in claim 1, characterized in that, The weight ratio of the complexed chitosan, silk fibroin and laccase is 10:1~2:0.04~0.06; the conditions for the mixed stirring reaction of the complexed chitosan, silk fibroin and laccase include a reaction temperature of 40~50℃ and a reaction time of 4~6h.

5. The method for preparing a soothing and repairing facial mask as described in claim 1, characterized in that, The preparation method of the modified pullulan polysaccharide complex includes the following steps: Pullulan and sodium periodate were mixed and stirred to produce aldehyde-modified pullulan. Dopamine hydrochloride was dispersed in Tris-HCl buffer at pH 8.5 and stirred to obtain a polydopamine dispersion. Polyethyleneimine was then added and the reaction was continued to obtain grafted microspheres. Aldehyde-modified pullulan and grafted microspheres were mixed and stirred to obtain composite microspheres; Dipotassium glycyrrhizate and composite microspheres were mixed and reacted to obtain a loaded microsphere dispersion. Then, methoxy polyethylene glycol succinate N-hydroxysuccinimide was added and stirred to obtain a modified pullulan polysaccharide complex.

6. The method for preparing a soothing and repairing facial mask as described in claim 5, characterized in that, The weight ratio of dopamine hydrochloride to polyethyleneimine is 2~3:3~3.5; further, the conditions for the reaction of dopamine hydrochloride dispersed in Tris-HCl buffer at pH 8.5 include a reaction temperature of 25°C and a reaction time of 24~28h; the conditions for the addition of polyethyleneimine and continued stirring include a reaction time of 8~10h.

7. The method for preparing a soothing and repairing facial mask as described in claim 5, characterized in that, The weight ratio of the aldehyde-modified pullulan to the grafted microspheres is 3~5:0.2~0.4; the conditions for the mixing and stirring reaction of the aldehyde-modified pullulan and the grafted microspheres include a reaction temperature of 25℃, a reaction pH of 6.0~6.3, and a reaction time of 12~14h.

8. The method for preparing a soothing and repairing facial mask as described in claim 5, characterized in that, The weight ratio of dipotassium glycyrrhizate, composite microspheres, and methoxy polyethylene glycol succinate N-hydroxysuccinimide is 0.2~0.3:0.8~1.0:0.2~0.4; the conditions for the mixing reaction of dipotassium glycyrrhizate and composite microspheres include ultrasonic dispersion at 100W for 10 min, followed by standing at 4℃ for 24~36 h; the conditions for the stirring reaction of adding methoxy polyethylene glycol succinate N-hydroxysuccinimide include a reaction temperature of 25℃ and a reaction time of 8~10 h.

9. The method for preparing a soothing and repairing facial mask as described in claim 1, characterized in that, The weight ratio of the modified chitosan complex, the modified pullulan polysaccharide complex, and sodium alginate is 0.8~1.2:0.2~0.3:0.08~0.1; the weight ratio of the hydroxyethyl cellulose, xanthan gum, glycerin, 1,3-propanediol, allantoin, disodium EDTA, repair and soothing complex, Centella asiatica extract, panthenol, sodium hyaluronate, vitamin E acetate, ceramide 3B, 1,2-hexanediol, caprylyl glycol, and ethylhexylglycerin is... 7.6~8.4: 1.9~2.1: 28.5~31.5: 9.5~10.5: 0.475~0.525: 0.095~0.105: 47.5~63.0: 4.75~5.25: 4.75~5.25: 0.95~1.05: 0.475~0.525: 0.475~0.525: 2.85~3.15: 0.95~1.05: 0.475~0.

525.

10. A soothing and repairing facial mask, characterized in that, It is prepared by the preparation method of a soothing and repairing facial mask as described in any one of claims 1 to 9.