Hyaluronic acid moisturizing and repairing composition and preparation method thereof

Abstract

The invention discloses a hyaluronic acid moisturizing and repairing composition and a preparation method thereof, belongs to the field of cosmetics, and specially meets the requirement of dry skin. The composition consists of a core moisturizing component, an auxiliary functional component and the balance of purified water, the core moisturizing component comprises hyaluronic acid components with oligomeric, low, medium and high molecular weights and sodium hyaluronate cross-linked polymer microbeads with gradient particle sizes; the auxiliary functional components comprise bionic liposome, a nonionic emulsifier, polyol, a natural penetration enhancer, a retardant and a preservative. The gradient microbeads and HA with different molecular weights achieve all-around water replenishing and locking from the surface layer to the deep layer of the skin, the bionic lipidosome promotes component permeation and repairs the skin barrier, the composition is good in stability, mild and free of irritation, the problems that the deep layer of the dry skin is dry, water is continuously deficient, and the barrier is fragile can be effectively solved, and the composition has wide cosmetic application prospects.

Description

Technical Field

[0001] This invention relates to the field of cosmetics, and more specifically to a hyaluronic acid moisturizing and repairing composition and its preparation method. Background Technology

[0002] Hyaluronic acid is a naturally occurring polysaccharide molecule widely found in human and animal tissues, playing a particularly important physiological role in skin tissue. Its hydrating ability helps the skin retain sufficient moisture, ensuring its smoothness and softness. However, the amount of hyaluronic acid in the body gradually decreases with age. Therefore, hyaluronic acid is widely used in the fields of beauty and skin management, using exogenous hyaluronic acid to improve the skin's moisture balance and delay the skin aging process.

[0003] Patent CN112957277A discloses a multi-component hyaluronic acid nanocomposition, its preparation method, and its cosmetic applications. The composition contains four different molecular weight hyaluronic acids (oligomeric, low, medium, and high molecular weight), combined with oils, emulsifiers, polyols, penetration enhancers, barrier agents, and water. It is prepared through an oil-water phase process, including mixing, emulsification, micronization, and high-pressure homogenization. Its advantages include targeted delivery of hyaluronic acid, improved stability and transdermal absorption, and extended duration of action of the active ingredients.

[0004] However, the HA-type cosmetics in this patent have obvious limitations when applied to dry skin: on the one hand, dry skin has less sebum secretion and a weaker skin barrier function, making it easier for moisture to be lost through the epidermis. The long-term water-locking ability of ordinary HA moisturizing systems is insufficient, making it difficult to solve the problem of deep dryness and continuous dehydration; on the other hand, the active ingredients in traditional HA compositions do not have strong skin targeting, and cannot achieve comprehensive and layered moisturizing and repair from the skin surface to the deep layers.

[0005] Therefore, it is crucial to develop a hyaluronic acid moisturizing and repairing composition that is better suited to dry skin. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention discloses a hyaluronic acid moisturizing and repairing composition and its preparation method, which has long-lasting water-locking ability and can solve the problem of deep dryness and continuous dehydration of dry skin, achieving comprehensive and multi-layered moisturizing and repairing effects.

[0007] Specifically, the present invention provides a hyaluronic acid moisturizing and repairing composition, comprising the following components by weight percentage:

[0008] By weight percentage, it includes 3.3%-15.3% core moisturizing components, 12.3%-40% auxiliary functional components, and the remainder purified water;

[0009] The core moisturizing component consists of 2.2%-12.2% hyaluronic acid components and 1.1%-3.1% graded particle size sodium hyaluronate cross-linked polymer microbeads;

[0010] The hyaluronic acid components include: 0.1%-10% oligomeric hyaluronic acid with a molecular weight <1WDa, 0.1%-10% low molecular weight hyaluronic acid with a molecular weight of 1WDa-50WDa, 0.01%-1% medium molecular weight hyaluronic acid with a molecular weight of 50WDa-200WDa, and 0.01%-1% high molecular weight hyaluronic acid with a molecular weight >200WDa;

[0011] The gradient particle size sodium hyaluronate cross-linked polymer microspheres comprise: 0.3%-1% of 3-10μm small particle size microspheres, 0.4%-1.1% of 15-25μm medium particle size microspheres, and 0.4%-1% of 30μm-50μm large particle size microspheres;

[0012] The auxiliary functional components include: 1%-8% biomimetic liposomes, 1%-12% emulsifier, 10%-30% polyol, 0.1%-5% penetration enhancer, 0.1%-5% inhibitor, and 0.1%-1% preservative.

[0013] The emulsifier is selected from one or more of polyglycerol-6 laurate, polyglycerol-10 isostearate, and lauryl ether-9. These emulsifiers are all nonionic emulsifiers with extremely low irritation, avoiding the skin stinging and redness problems that may be caused by anionic emulsifiers, and meeting the tolerance needs of dry and sensitive skin.

[0014] The polyols are selected from one or more of glycerin, butylene glycol, and 1,3-propanediol. All of these polyols are natural moisturizing factors that can bind to moisture in the air through hydrogen bonds, forming a temporary moisturizing film on the skin surface. This complements the "layered moisturizing" effect of the core components, alleviating the immediate dryness of dry skin. Simultaneously, the polyols possess certain hygroscopic and thickening properties, reducing the evaporation rate of water in the system, minimizing structural shrinkage of the gradient microspheres due to moisture loss, and extending the shelf life and stability of the composition.

[0015] The penetration enhancer is selected from one or both of cinnamyl alcohol and menthol. All of the above penetration enhancers are of natural origin and are far less irritating than chemically synthesized penetration enhancers. In addition, menthol has a cooling and soothing effect, which can relieve the tightness and discomfort of dry skin.

[0016] The inhibitor is selected from one or both of 1,4-cyclohexanediol and 1,2-hexanediol. The inhibitor provides both water-locking and gentle protection, making it suitable for the moisture retention needs of dry skin.

[0017] One or both of phenoxyethanol and methylparaben are selected as preservatives. Phenoxyethanol is a mild preservative with far less irritation than formaldehyde-releasing preservatives. Methylparaben has a broad antibacterial spectrum and low concentration dependence, thus avoiding further damage to the skin barrier due to preservative irritation.

[0018] The biomimetic liposome is a mixture of one or more of phosphatidylcholine, cholesterol, and phytosterols in a mass ratio of 1-3:0.5-1:0.2-0.8. Its structure is similar to that of skin cell membrane, and it has good compatibility. It can encapsulate active ingredients, promote the penetration of ingredients into the deep layers of the skin, reduce the loss of active ingredients, and enhance the stability of the composition.

[0019] Gradient-size sodium hyaluronate cross-linked polymer microbeads are cross-linked polymers of sodium hyaluronate and 1,4-butanediol diglycidyl ether. The sodium hyaluronate is selected with a molecular weight of 50-200 WDa, and the amount of 1,4-butanediol diglycidyl ether is 4%-6% of the mass of sodium hyaluronate.

[0020] Specifically, the preparation method of gradient particle size sodium hyaluronate cross-linked polymer microbeads is as follows: (1) Pre-cross-linking: Sodium hyaluronate and cross-linking agent are mixed evenly in an alkaline solution and allowed to stand at 1-4℃ for 10-12h; wherein the alkaline solution is a 1%wt sodium hydroxide solution and the mass volume concentration of sodium hyaluronate in the alkaline solution is 20%;

[0021] (2) Repeated cross-linking: The pre-cross-linking reaction solution is allowed to stand at 60-70℃ for 15-20 min, and then placed at 1-4℃ for 2-3 h. This cross-linking step is repeated 3-5 times to obtain cross-linked hyaluronic acid gel blocks.

[0022] (3) Gradient classification: The gel block was dialyzed to remove the unreacted crosslinking agent, and after crushing, classification precipitation, sieving and freeze drying, microbeads with particle sizes of 3μm-10μm, 15μm-25μm and 30μm-50μm were obtained respectively.

[0023] This invention also discloses a method for preparing a hyaluronic acid moisturizing and repairing composition, comprising the following steps:

[0024] (1) Preparation of aqueous phase: Oligomeric hyaluronic acid, low molecular weight hyaluronic acid, medium molecular weight hyaluronic acid, high molecular weight hyaluronic acid, and gradient particle size sodium hyaluronate cross-linked polymer microbeads are mixed with purified water and stirred and dissolved in a water bath at 45-60℃. The stirring rate is 500-800r / min, and the mixture is kept at the temperature for 10-20min to ensure uniform dispersion of the microbeads, thus obtaining the aqueous phase;

[0025] (2) Preparation of oil phase: Biomimetic liposomes, emulsifiers and penetration enhancers are mixed and dissolved by stirring in a water bath at 45-60℃ at a stirring rate of 300-500 r / min to obtain the oil phase;

[0026] (3) Mixing and emulsification: Under stirring conditions (speed 600-800r / min), the oil phase is added to the aqueous phase at a rate of 3-8 drops / second. After the addition is completed, stirring is continued for 15-20min to obtain the first mixture;

[0027] (4) Optimization and adjustment: Add polyol, inhibitor and preservative to the first mixture, keep at 45-60℃, stir at 500-700r / min, mix for 10-15min to obtain the second mixture;

[0028] (5) Shear emulsification: The second mixture is subjected to high-speed shear emulsification at a shearing speed of 8000-12000 r / min and a shearing time of 4-6 min to obtain a dispersion;

[0029] (6) High pressure homogenization treatment: The dispersion is subjected to high pressure homogenization treatment at a pressure of 800-1000 bar, 4-5 cycles, and the temperature is maintained at 50-60℃. After cooling to room temperature, the moisturizing and repairing composition is obtained.

[0030] The present invention also provides the application of the above-mentioned hyaluronic acid moisturizing and repairing composition in the preparation of moisturizing and repairing cosmetics for dry skin.

[0031] This invention constructs a comprehensive moisturizing and repairing system from the surface to the deep layers of the skin by preparing gradient-size sodium hyaluronate cross-linked polymer microbeads, combined with biomimetic liposomes and four different molecular weight HAs. Small-diameter microbeads, carried by oligomeric hyaluronic acid, penetrate to the superficial dermis for swelling and hydration; medium-diameter microbeads build a moisturizing barrier in the epidermis; and large-diameter microbeads form an immediate water-locking film on the skin surface. These microbeads, in conjunction with the transdermal penetration and barrier repair effects of the biomimetic liposomes, significantly enhance the long-lasting moisturizing effect and skin barrier repair capacity of dry skin. This composition exhibits good stability, is gentle and non-irritating, and is specifically tailored to the needs of dry skin, showing broad prospects for cosmetic applications. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention are further described below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely for the purpose of helping to understand the technical content and effects of this invention and should not be considered as limitations on this invention.

[0033] I. Preparation of gradient particle size sodium hyaluronate cross-linked polymer microspheres: Preparation Examples 1-3 yielded sodium hyaluronate cross-linked polymer microspheres with small, medium, and large particle sizes, respectively.

[0034] Preparation Example 1 (Small-diameter microbeads)

[0035] Pre-crosslinking: Take sodium hyaluronate with a molecular weight of 100 WDa, add 1% wt sodium hydroxide solution to prepare a sodium hyaluronate solution with a mass-volume concentration of 20%, and then add 5% by mass of 1,4-butanediol diglycidyl ether as a crosslinking agent. After stirring evenly, place it in an environment of 2℃ and let it stand for 11 hours to complete the pre-crosslinking.

[0036] Repeated crosslinking: The pre-crosslinking reaction solution was transferred to a 65°C water bath and allowed to stand for 20 min. Then it was quickly placed in a 2°C environment and allowed to stand for 3 h. This crosslinking step of "65°C heat preservation - 2°C refrigeration" was repeated 4 times to obtain crosslinked hyaluronic acid gel blocks.

[0037] Gradient grading: The gel block was placed in a dialysis bag and dialyzed with purified water for 72 hours to remove unreacted crosslinking agents and impurities. The dialyzed gel block was then crushed, graded and precipitated, sieved, and freeze-dried to obtain small-particle-size sodium hyaluronate crosslinked polymer microbeads with a particle size of 3-10 μm.

[0038] Preparation Example 2 (Medium-sized microbeads)

[0039] The same steps as in Preparation Example 1 were followed, except that medium-sized microspheres with a particle size of 15-25 μm were obtained through different sieving processes.

[0040] Preparation Example 3 (Large-size microbeads)

[0041] The same steps as in Preparation Example 1 were followed, except that different sieving methods were used to obtain large-diameter microspheres with a particle size of 30-50 μm.

[0042] Examples 1-3 and Comparative Examples 1-3 were prepared using the following steps.

[0043] (1) Preparation of aqueous phase: Weigh oligo hyaluronic acid, low molecular weight hyaluronic acid, medium molecular weight hyaluronic acid, high molecular weight hyaluronic acid and microbeads of three particle sizes according to the ratio, mix with purified water, place in a 50℃ water bath, stir and dissolve at a rate of 600r / min, keep warm for 15min to ensure uniform dispersion of microbeads, and obtain aqueous phase.

[0044] (2) Preparation of oil phase: Weigh biomimetic liposomes, emulsifiers and penetration enhancers, place them in a 50℃ water bath, and stir at a rate of 400r / min to dissolve them to obtain the oil phase.

[0045] (3) Mixing and emulsification: Under stirring conditions of 600 r / min, the oil phase is slowly added to the aqueous phase at a rate of 5 drops / second. After the addition is completed, stirring is continued for 18 min to obtain the first mixture.

[0046] (4) Optimization and adjustment: Add polyol, inhibitor and preservative to the first mixture, maintain the temperature at 50°C, and stir at a rate of 600r / min for 12min to obtain the second mixture.

[0047] (5) Shear emulsification: The second mixture is subjected to high-speed shear emulsification at a speed of 10,000 r / min and a shearing time of 5 min to obtain a dispersion.

[0048] (6) High pressure homogenization treatment: The dispersion is subjected to high pressure homogenization treatment at 900 bar for 4 cycles, while maintaining the temperature at 55°C. After cooling to room temperature, the hyaluronic acid moisturizing and repairing composition is obtained.

[0049] The specific raw material ratios for Examples 1-3 are shown in Tables 1-3 below (all ratios are by mass percentage).

[0050] Table 1

[0051]

[0052] Table 2

[0053]

[0054] Table 3

[0055]

[0056] The only difference between Comparative Example 1 and Example 1 is that it does not contain sodium hyaluronate cross-linked polymer microbeads, and the proportion of purified water in the remaining component is increased accordingly.

[0057] The only difference between Comparative Example 2 and Example 1 is that 1.1% of medium-sized microbeads (15-25 μm) were used instead of gradient microbeads, while the other conditions remained the same.

[0058] The only difference between Comparative Example 3 and Example 1 is that it does not contain biomimetic liposomes and is replaced with olive oil.

[0059] The following performance tests were performed on Examples 1-3 and Comparative Examples 1-3.

[0060] (1) Long-lasting moisturizing effect: Using a Corneometer CM825 skin moisture meter, 30 volunteers with dry skin (aged 25-45 years, stratum corneum moisture content <30AU) were randomly divided into 6 groups (5 people in each group). The subjects sat quietly for 30 minutes in a constant temperature and humidity environment (temperature 20℃±2℃, relative humidity 50%±10%). After cleaning the inner side of the forearm, the composition samples of Examples 1-3 and Comparative Examples 1-3 were applied at a dosage of (2.0±0.1) mg / cm². The skin moisture content (%) was measured before application and at 0.5h, 6h, 12h, 24h and 48h after application using a CM825 skin moisture meter from CK GmbH, Germany. Each measurement was performed in parallel 5 times and the average value was taken. The test results are shown in Table 4.

[0061] Table 4

[0062]

[0063] Based on the skin hydration test data in Table 4, the moisturizing effects of Examples 1-3 were significantly better than those of Comparative Examples 1-3, exhibiting a clear synergistic effect. The hydration content of Comparative Example 1 (without microbeads) was significantly lower than that of Example 1 at the same time point after application. Comparative Example 2 (single medium-sized microbeads) had a hydration content of 18.3% after 48 hours, only reaching 53.5% of Example 1. This indicates that the synergistic effect of gradient-sized microbeads can significantly prolong the moisturizing effect, while single-sized microbeads or the absence of microbeads cannot achieve this effect. Comparative Example 3 (using olive oil instead of biomimetic liposomes) had a hydration content of 10.2% after 48 hours, only 29.8% of Example 1, and the hydration content at each time point was lower than that of Examples 1-3. This suggests that biomimetic liposomes, due to their similar structure to skin cell membranes, can effectively encapsulate HA components to penetrate deeper into the skin, reducing the loss of active ingredients. Ordinary oils such as olive oil cannot achieve this transdermal penetration effect, causing moisturizing ingredients to remain only on the surface and be easily lost.

[0064] (2) Barrier repair capacity: The TEWL values ​​of the volunteers were measured before and after 28 days of continuous use using the samples using a Tewameter TM300 transepidermal water loss meter. The skin barrier repair effect was evaluated, and the test results are shown in Table 5.

[0065] Table 5

[0066]

[0067] According to the TEWL (transepidermal water loss) test results in Table 5, the TEWL values ​​after 28 days of continuous use in Examples 1-3 were 12.8, 11.5, and 13.2 g / ( The difference is much smaller than that in comparative examples 1-3. This indicates that gradient-sized microbeads can build a physical moisturizing barrier on the skin surface, reducing moisture loss, while biomimetic liposomes can repair the skin cell membrane structure and enhance barrier function. The two work synergistically to achieve the dual effect of "physical barrier + biological repair", and no single component or alternative component can achieve the same repair efficiency.

[0068] (3) Mildness test: Human skin patch test was conducted according to GB / T 16886.10 standard. Skin irritation reaction was observed at 24h and 48h, and the positive rate was calculated. The positive rate was 0% in all tests. In addition, 42 healthy rabbits were randomly divided into 7 groups of 6 rabbits each. The sample was applied to the hairless skin on the back of the rabbits 3 times a day for 7 consecutive days, and the skin congestion and swelling were observed. After the samples in Examples 1-3 and Comparative Examples 1-3 were applied, the rabbit skin did not show congestion or swelling, indicating that the composition of the present invention is mild and non-irritating, has high safety, and is suitable for use on dry and sensitive skin.

[0069] Therefore, this invention addresses the core pain points of dry skin through its core formula design, and is gentle and non-irritating, thus possessing good application value.

[0070] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A hyaluronic acid moisturizing and repairing composition, characterized in that, By weight percentage, it includes 3.3%-15.3% core moisturizing components, 12.3%-40% auxiliary functional components, and the remainder purified water; The core moisturizing component consists of 2.2%-12.2% hyaluronic acid components and 1.1%-3.1% graded particle size sodium hyaluronate cross-linked polymer microbeads; The hyaluronic acid components include: 0.1%-10% oligomeric hyaluronic acid with a molecular weight <1WDa, 0.1%-10% low molecular weight hyaluronic acid with a molecular weight of 1WDa-50WDa, 0.01%-1% medium molecular weight hyaluronic acid with a molecular weight of 50WDa-200WDa, and 0.01%-1% high molecular weight hyaluronic acid with a molecular weight >200WDa; The gradient particle size sodium hyaluronate cross-linked polymer microspheres comprise: 0.3%-1% of 3-10μm small particle size microspheres, 0.4%-1.1% of 15-25μm medium particle size microspheres, and 0.4%-1% of 30μm-50μm large particle size microspheres; The auxiliary functional components include: 1%-8% biomimetic liposomes, 1%-12% emulsifier, 10%-30% polyol, 0.1%-5% penetration enhancer, 0.1%-5% inhibitor, and 0.1%-1% preservative.

2. The hyaluronic acid moisturizing and repairing composition according to claim 1, characterized in that, The emulsifier is selected from one or more of polyglycerol-6 lauryl ester, polyglycerol-10 isostearate, and lauryl ether-9.

3. The hyaluronic acid moisturizing and repairing composition according to claim 1, characterized in that, The polyol is selected from one or more of glycerol, butanediol, and 1,3-propanediol.

4. The hyaluronic acid moisturizing and repairing composition according to claim 1, characterized in that, The penetration enhancer is selected from one or two of cinnamyl alcohol and menthol; the retardant is selected from one or two of 1,4-cyclohexanediol and 1,2-hexanediol; and the preservative is selected from one or two of phenoxyethanol and methylparaben.

5. The hyaluronic acid moisturizing and repairing composition according to claim 1, characterized in that, The biomimetic liposome is a mixture of phosphatidylcholine, cholesterol, and phytosterols in a mass ratio of 1-3:0.5-1:0.2-0.

8.

6. The hyaluronic acid moisturizing and repairing composition according to claim 1, characterized in that, The gradient particle size sodium hyaluronate cross-linked polymer microbeads are cross-linked polymers of sodium hyaluronate and 1,4-butanediol diglycidyl ether, wherein the molecular weight of sodium hyaluronate is 50-200 WDa, and the amount of 1,4-butanediol diglycidyl ether is 4%-6% of the mass of sodium hyaluronate.

7. The hyaluronic acid moisturizing and repairing composition according to claim 6, characterized in that, The preparation of gradient-size sodium hyaluronate cross-linked polymer microspheres includes the following steps: (1) Pre-crosslinking: Sodium hyaluronate and crosslinking agent are mixed evenly in 1%wt sodium hydroxide solution. The mass volume concentration of sodium hyaluronate in alkaline solution is 20%. Let stand at 1-4℃ for 10-12h. (2) Repeated cross-linking: The pre-cross-linking reaction solution is allowed to stand at 60-70℃ for 15-20 min, and then placed at 1-4℃ for 2-3 h. This cross-linking step is repeated 3-5 times to obtain cross-linked hyaluronic acid gel blocks. (3) Gradient classification: The gel block was dialyzed to remove the unreacted crosslinking agent, and after crushing, classification precipitation, sieving and freeze drying, microbeads with particle sizes of 3μm-10μm, 15μm-25μm and 30μm-50μm were obtained respectively.

8. A method for preparing the hyaluronic acid moisturizing and repairing composition according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Preparation of aqueous phase: Hyaluronic acid components, gradient particle size sodium hyaluronate cross-linked polymer microbeads and purified water are mixed and dissolved by stirring at a rate of 500-800 r / min under a water bath at 45-60℃, and kept at the temperature for 10-20 min to obtain aqueous phase; (2) Preparation of oil phase: Biomimetic liposomes, emulsifiers and penetration enhancers are mixed and dissolved by stirring at a rate of 300-500 r / min under water bath conditions of 45-60℃ to obtain oil phase; (3) Mixing and emulsification: Under stirring conditions of 600-800 r / min, the oil phase is added to the aqueous phase at a rate of 3-8 drops / second. After the addition is completed, stirring is continued for 15-20 min to obtain the first mixture; (4) Optimization and adjustment: Add polyol, inhibitor and preservative to the first mixture, keep at 45-60℃, stir at 500-700r / min for 10-15min to obtain the second mixture; (5) Shear emulsification: The second mixture is subjected to high-speed shear emulsification at a shearing speed of 8000-12000 r / min and a shearing time of 4-6 min to obtain a dispersion; (6) High pressure homogenization treatment: The dispersion is subjected to high pressure homogenization treatment at a pressure of 800-1000 bar, 4-5 cycles, and the temperature is maintained at 50-60℃. After cooling to room temperature, the moisturizing and repairing composition is obtained.

9. The use of the hyaluronic acid moisturizing and repairing composition according to any one of claims 1-7 in the preparation of moisturizing and repairing cosmetics for dry skin.

Images