Stable skin care composition based on polyglycerol ester and sucrose ester compounded system

Abstract

The invention discloses a stable skin care composition based on a polyglycerol ester and sucrose ester compounded system in the technical field of cosmetic preparations. The composition comprises polyglycerol esters, sucrose esters, cyclodextrin polyglycerol sucrose hybrid esters, silanized sucrose esters, a nanostructured lipid sucrose polyglycerol carrier, an oil phase component, a water phase component, active components and auxiliary components. Through the synergistic effect of three specific modified compounds, the stability, moisture retention and active matter permeability of the system are remarkably improved. The composition is refreshing and non-sticky in touch, can effectively resist high-temperature, low-temperature and centrifugal challenges, is suitable for various dosage forms such as cream and emulsion, and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cosmetic formulations, in particular to a stable skin care composition based on a polyglycerol ester and sucrose ester complex system. BACKGROUND

[0002] Currently, the cosmetics industry has increasingly high requirements for emulsifying systems. Not only are stable formulations and excellent skin feel required, but also natural, green and safe raw materials. Polyglycerol ester emulsifiers have good emulsifying properties and electrolyte resistance, but when used alone, they often result in a sticky, heavy skin feel, making it difficult to meet the pursuit of modern consumers for a refreshing skin feel. Sucrose ester emulsifiers are derived from natural sucrose and plant fatty acids, have a refreshing and skin-friendly skin feel, and have good moisturizing properties, but their emulsifying ability is relatively weak, and they cannot provide sufficient stability support for complex formulation systems. Under high or low temperature conditions, they are prone to delamination or cream destruction. Although there are attempts to simply complex two types of emulsifiers in the prior art, due to the lack of molecular structure compatibility and synergistic effect, it is still difficult to achieve an ideal balance between stability, skin feel and efficacy, especially to meet the demand for efficient penetration of active ingredients.

[0003] With the increasing demand of consumers for the safety and environmental friendliness of cosmetics, the development of an emulsifying system that does not rely on polyethylene glycol structures and is based on renewable raw materials has become an important development trend. There is an urgent need for a new formulation technology that can maintain the safety of natural raw materials while providing the stability of synthetic emulsifiers. Existing emulsifying systems based on natural raw materials often require the addition of a large amount of co-emulsifiers or stabilizers, which not only increases the complexity of the formulation, but also may pose a potential irritation risk. Therefore, how to design molecular structures to break through the performance limitations of natural raw materials while maintaining their natural properties has become a key difficulty in the development of this field.

[0004] In view of the above technical bottlenecks, the present application starts from the design of molecular structures and develops three new types of modified compounds to fundamentally improve the compatibility and synergism of polyglycerol esters and sucrose esters. These modified compounds not only retain the natural properties of the original raw materials, but also significantly improve the interfacial adsorption capacity and micro-order of the emulsifying system through molecular hybridization, functional group modification and carrier structure innovation. The present application aims to provide a stable skin care composition with excellent comprehensive performance. This composition maintains the advantages of all-natural raw materials while having excellent stability, a refreshing skin feel and the function of promoting the penetration of active ingredients, effectively solving the multiple contradictions that cannot be reconciled in the prior art. SUMMARY

[0005] The present application aims to provide a stable skin care composition based on a polyglycerol ester and sucrose ester complex system, which solves the technical problems of insufficient stability, sticky skin feel and low active ingredient penetration rate of existing polyglycerol ester and sucrose ester complex systems.

[0006] The present application achieves the above-mentioned purpose by the following technical solutions: The stable skin care composition based on the polyglycerol ester and sucrose ester complex system comprises the following raw materials by weight: Polyglycerol esters: 20-80 parts by weight; Sucrose esters: 10-40 parts by weight; Cyclodextrin-polyglycerol sucrose hybrid ester: 5-30 parts by weight; Silanized polysucrose ester: 3-20 parts by weight; Nanostructured lipid-sucrose polyglycerol carrier: 5-30 parts by weight; Caprylic / capric triglyceride: 30-100 parts by weight; Jojoba seed oil: 10-50 parts by weight; Phytosterols: 5-20 parts by weight; Squalene: 10-40 parts by weight; Deionized water: 200-800 parts by weight; Trehalose: 20-60 parts by weight; 1,3-Butanediol: 30-80 parts by weight; Quercetin: 1-10 parts by weight; Vitamin E acetate: 1-5 parts by weight; Sodium hyaluronate: 0.5-3 parts by weight; Xanthan gum: 1-5 parts by weight; Gellan gum: 0.5-3 parts by weight; p-Hydroxyacetophenone: 2-6 parts by weight; Ethylhexylglycerin: 1-3 parts by weight; The preparation method of the cyclodextrin-polyglycerol sucrose hybrid ester comprises: A1, dissolving β-cyclodextrin in anhydrous dimethyl sulfoxide under nitrogen protection, stirring until completely dissolved; then adding polyglycerol-3 and sucrose monostearate; increasing the temperature of the reaction system to 80-85℃, adding p-toluenesulfonic acid and molecular sieve 4A for reaction; A2, after the reaction is completed, the mixture is cooled to room temperature, saturated sodium bicarbonate solution is added, and precipitated with deionized water; finally, purified by column chromatography.

[0007] According to a preferred embodiment of the present application, the composition and ratio of the polyglycerol esters are specifically designed to ensure the stability and emulsification effect of the composition. The first polyglycerol ester is preferably prepared by esterification of a single fatty acid with a polyglycerol having a degree of polymerization ranging from 3 to 10, the fatty acid having a carbon chain length ranging from C12 to C22, and being selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid or behenic acid. The second polyglycerol ester is preferably prepared by esterification of at least two different fatty acids with a polyglycerol having the same degree of polymerization range, the fatty acids also being selected from saturated or unsaturated fatty acids having a carbon chain length ranging from C12 to C22. The mass ratio of the two polyglycerol esters is controlled between 0.5:1 and 4:1, preferably at a ratio of 2:1. Through this specific combination and ratio, the first polyglycerol ester provides strong emulsification power and interfacial stability, while the second polyglycerol ester enhances the low temperature stability and skin feel adjustment of the system by the introduction of mixed fatty acid chains, and the synergistic effect of the two significantly improves the overall stability and application performance of the final skin care composition.

[0008] According to a preferred embodiment of the present application, the polyglycerol esters are compounded by two specific polyglycerol esters in a precise mass ratio. The first polyglycerol ester is polyglyceryl-6 distearate or polyglyceryl-6 stearate, preferably polyglyceryl-6 stearate, which is prepared by esterification of polyglycerol with a degree of polymerization of 6 and a single fatty acid stearic acid. The specific preparation method is as follows: 100 g of polyglyceryl-6 and 45 g of stearic acid are added to a reaction kettle, 0.5 g of p-toluenesulfonic acid catalyst is added, and the reaction is carried out at 190°C for 5 hours. The reaction is terminated after the acid value is monitored to be below 2 mg KOH / g, and the finished product is obtained after decolorization and filtration. The second polyglycerol ester is polyglyceryl-4 cocoate, which is prepared by esterification of polyglycerol with a degree of polymerization of 4 and coconut fatty acid (a mixed fatty acid containing 45% lauric acid, 18% myristic acid, 9% palmitic acid, and 15% oleic acid). The specific preparation method is as follows: 100 g of polyglyceryl-4 is mixed with 50 g of coconut fatty acid, 0.6 g of titanium tetraisopropylate catalyst is added, and the reaction is carried out at 185°C for 4.5 hours. The reaction is terminated after the acid value is monitored to be below 1.5 mg KOH / g, and the finished product is obtained after molecular distillation purification. The mass ratio of the two polyglycerol esters is 2:1. Through this specific design, polyglyceryl-6 stearate forms a high-strength interfacial film at the oil-water interface due to its regular stearic acid chain structure and moderate degree of polymerization, providing excellent emulsion stability and preventing Ostwald ripening. Polyglyceryl-4 cocoate effectively reduces the crystallization temperature of the system by the composition of the short-chain mixed fatty acids, improves the low-temperature stability, and at the same time, its branched structure can reduce the intermolecular hydrogen bonding, significantly reducing the viscosity of the system, avoiding the sticky feeling caused by traditional polyglycerol esters. The synergistic compounding of the two makes the emulsion system maintain structural integrity when subjected to temperature changes or mechanical shear, and the skin feel is refreshing and not sticky.

[0009] According to a preferred embodiment of the present application, the sucrose esters are selected from one or more of sucrose stearate, sucrose distearate, sucrose palmitate, sucrose myristate, sucrose laurate, and sucrose cocoate.

[0010] According to a preferred embodiment of the present application, the phytosterols are selected from at least one of β-sitosterol, stigmasterol, and campesterol, wherein the content of β-sitosterol accounts for 40%-80% of the total mass of phytosterols, stigmasterol accounts for 10%-30%, and campesterol accounts for 5%-25%. These phytosterols can be derived from natural plant extracts such as soybean oil, rapeseed oil, or pine oil. The phytosterols significantly enhance the stability of the emulsion in the system through synergistic action with polyglycerol esters and sucrose esters. The hydroxyl groups in the molecules form a hydrogen bond network with the polar groups of the emulsifiers, and the steroidal nucleus structure is inserted into the oil phase to strengthen the interfacial film strength. At the same time, phytosterols also provide excellent skin barrier repair function and anti-inflammatory properties, and can synergistically enhance the moisturizing ability of the skin with squalene.

[0011] In the present application, the synthesis of cyclodextrin-polyglycerol sucrose hybrid ester is based on the synergistic mechanism of supramolecular chemistry and transesterification. The unique conical cavity structure of β-cyclodextrin provides excellent inclusion ability, and its surface rich in hydroxyl groups becomes the active site for molecular modification. In the reaction medium of anhydrous dimethyl sulfoxide, the hydroxyl groups on the polyglycerol chain and the ester groups of sucrose monostearate undergo transesterification reaction catalyzed by p-toluenesulfonic acid, and the primary hydroxyl groups on the edge of β-cyclodextrin also participate in nucleophilic substitution reaction. This process forms a hybrid molecule with asymmetric structure: the cyclodextrin cavity is responsible for encapsulating hydrophobic active substances, the polyglycerol segment provides hydrophilicity, and the sucrose ester part confers good interfacial activity on the system. The addition of molecular sieves continuously removes the water generated during the reaction, driving the equilibrium to the product direction, and finally the structure-accurate hybrid ester product is obtained by chromatographic purification.

[0012] According to the preferred embodiment of the present application, in step A1, the reaction time of adding p-toluenesulfonic acid and molecular sieve 4A is 6-8h.

[0013] According to the preferred embodiment of the present application, in step A2, the eluent for column chromatography purification is chloroform / methanol=10:1.

[0014] According to the preferred embodiment of the present application, the preparation method of the silanized poly sucrose ester comprises: B1, dissolving sucrose distearate and aminopropyl polydimethylsiloxane in toluene to form a solution; under nitrogen protection, adding titanium tetraisopropylate catalyst, and heating to 90-95℃; then adding dropwise the toluene solution of polyglycerol ether containing vinyl; B2, after the reaction is completed, cooling the mixture to 58-62℃, adding activated carbon and stirring; after filtration, rotary evaporation is performed to obtain a light yellow viscous liquid; finally, purification is performed by molecular distillation.

[0015] In the present application, the preparation of silanized poly sucrose ester embodies the innovative integration of organosilicon chemistry and sugar chemistry. The key of the reaction lies in the unique catalytic mechanism of titanium tetraisopropylate catalyst for the formation of amide bond. The titanium atom has empty d orbitals, which can complex the carbonyl oxygen atom of sucrose distearate and the amino nitrogen atom of aminopropyl polydimethylsiloxane at the same time, forming a tetrahedral transition state, which greatly reduces the activation energy of the reaction. In this catalytic system, the ester group of sucrose ester reacts with the primary amino group of organosilicon compound through ammonolysis to form a thermodynamically more stable amide bond. Subsequently, the polyglycerol ether containing vinyl undergoes silicon-hydrogen addition reaction with the remaining silicon-hydrogen bond in the molecule through free radical mechanism at high temperature, further introducing polyglycerol hydrophilic segment. The whole process is purified by molecular distillation to remove unreacted monomers and byproducts, obtaining the structure-accurate silanized poly sucrose ester. This compound ingeniously combines the biocompatibility of sucrose ester, the hydrophilicity of polyglycerol, and the unique skin feel of organosilicon.

[0016] According to the preferred embodiment of the present application, in step B1, the reaction time of the toluene solution of the polyglyceryl ether containing vinyl group is 8-10 h.

[0017] According to the preferred embodiment of the present application, in step B2, after the reaction is completed, the stirring time of the activated carbon is 30-40 min; and the temperature for molecular distillation purification is 180-200℃.

[0018] According to the preferred embodiment of the present application, the preparation method of the nanostructured lipid-sucrose polyglyceryl carrier comprises: C1, dissolving decaglyceryl decanoate, sucrose cocoate and hydrogenated lecithin in a chloroform / methanol mixed solvent; then adding a flavonoid compound; rotary evaporation to form a lipid film; C2, then adding a phosphate buffer at 58-62℃ for hydration, while probe ultrasonic treatment; circulating through a high-pressure homogenizer; C3, finally filtering through a microporous filter membrane.

[0019] In the present application, the construction of the nanostructured lipid-sucrose polyglyceryl carrier is based on the principles of molecular self-assembly and nanotechnology. Decaglyceryl decanoate, sucrose cocoate and hydrogenated lecithin form a uniform molecular dispersion system in an organic solvent. After removing the solvent by rotary evaporation, these amphiphilic molecules spontaneously arrange to form an ordered lipid bilayer membrane through hydrophobic interaction. When a warm buffer is added for hydration, the lipid membrane bends and encapsulates the aqueous phase to form a vesicular structure. Probe ultrasonic treatment provides sufficient energy to break up large vesicles, forming a precursor dispersion with smaller particle size. The shear force and cavitation effect during high-pressure homogenization further reduce the particle size and improve the uniformity of the distribution, forcing the amphiphilic molecules to rearrange and form nanoparticles with a core-shell structure: the hydrophobic quercetin is encapsulated in the lipid core, while the sucrose polyglyceryl ester forms a stable hydrophilic crown on the outer layer. Finally, the microporous filter membrane is filtered to obtain nanoparticles with uniform particle size. This structure not only protects the active ingredients, but also improves the skin permeability.

[0020] According to the preferred embodiment of the present application, in step C1, the flavonoid compound is quercetin.

[0021] According to the preferred embodiment of the present application, in step C2, the ultrasonic treatment time is 15-20 min; and the high-pressure homogenizer circulating times is 4-6 times.

[0022] According to the preferred embodiment of the present application, in step C3, the pore size of the microporous filter membrane is 0.22-0.24 μm.

[0023] In the present application, the stability mechanism of the whole complex system is derived from a variety of mutually synergistic physical and chemical effects. The polyglycerol ester and sucrose ester form a stable complex interface film through intermolecular hydrogen bonding and hydrophobic interaction, and the addition of three kinds of modified compounds further enhances the strength and toughness of the interface structure. The cyclodextrin-polyglycerol sucrose hybrid ester reduces the fluidity of the oil phase molecules by encapsulating the oil phase components in its cavity, thereby improving the low-temperature stability of the emulsion. The organosilicon segment of the silanized poly-sucrose ester forms a high-elasticity protective layer at the interface, effectively resisting coalescence caused by droplet collision. The nano-structured carrier not only serves as a delivery system for active substances, but also has a synergistic stabilizing effect with the emulsifier molecules in the continuous phase. Plant sterols and emulsifiers together form a liquid crystal structure, enhancing the rigidity and stability of the interface film. Xanthan gum and gellan gum form a three-dimensional network structure in the aqueous phase, preventing the Brownian motion and aggregation of droplets through steric hindrance. This multi-level, multi-dimensional stability mechanism enables the composition to withstand various challenges such as temperature changes, mechanical shear, and long-term storage, demonstrating excellent stability.

[0024] The present application has the following advantages: The stable skin care composition based on the polyglycerol ester and sucrose ester complex system provided by the present application has many significant advantages. First, the composition exhibits excellent stability through the synergistic effect of the innovative complex system and the three special modified compounds. The cyclodextrin-polyglycerol sucrose hybrid ester, with its unique cavity structure and amphiphilic properties, can form a stable supramolecular complex at the oil-water interface, effectively preventing phase separation. The silanized poly-sucrose ester significantly enhances the mechanical strength of the interface film by introducing organosilicon segments, enabling the emulsion to withstand extreme conditions such as high temperature, low temperature, and centrifugation. The nano-structured lipid sucrose polyglycerol carrier provides a long-term stable dispersion state for the system through its special core-shell structure, ensuring that the product maintains a uniform texture during storage.

[0025] In terms of skin feel and moisturizing performance, the composition of the present application achieves a breakthrough improvement. The organosilicon component in the silanized poly-sucrose ester imparts a light and smooth spreading property to the product, completely overcoming the sticky and heavy feeling caused by traditional polyglycerol ester emulsifiers. The synergistic effect of trehalose and other moisturizing ingredients such as butylene glycol with the innovative emulsion system can form a breathable and moisturizing film on the skin surface, significantly reducing transdermal water loss. Plant sterols and active oils such as squalene not only provide excellent moisturizing effects, but also work together with modified emulsifiers to create a skin-friendly texture that is easily absorbed and does not cause pore clogging.

[0026] Most importantly, the present application has made significant progress in the delivery of active ingredients and overall safety. The nanostructured carrier can effectively encapsulate flavonoid compounds such as quercetin, improve their stability and bioavailability, and achieve better antioxidant and anti-aging effects by enhancing skin penetration. All emulsified ingredients are derived from natural renewable resources, completely free of polyethylene glycol structure, greatly reducing the risk of irritation. The entire formulation system meets the development concept of green cosmetics, providing excellent skin care effects while ensuring high safety and environmental friendliness, meeting the dual needs of modern consumers for efficient and safe skin care products. DETAILED DESCRIPTION

[0027] The following detailed description is only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0028] The main related equipment and material suppliers are as follows: The caprylic / capric triglyceride was purchased from Zhejiang Womai Biological Technology Co., Ltd.

[0029] The jojoba seed oil was purchased from Hubei Langbo Wan Biological Medicine Co., Ltd.

[0030] The squalene was purchased from Baikaiseng (Jiangsu) Biological Technology Co., Ltd.

[0031] The trehalose was purchased from Henan Dexin Chemical Industry Co., Ltd.

[0032] The 1,3-butanediol was purchased from Jinan Hui Fengda Chemical Co., Ltd.

[0033] The quercetin was purchased from Hunan Huishi Biological Technology Co., Ltd.

[0034] The vitamin E acetate was purchased from Wuhan Shuer Biological Technology Co., Ltd.

[0035] The sodium hyaluronate was purchased from Zhejiang Tianxian Biological Pharmaceutical Co., Ltd.

[0036] The sucrose cocoate was purchased from Hubei Baichuan Chemical Co., Ltd.

[0037] The hydrogenated lecithin was purchased from Shanghai Yuan Ye Biological Technology Co., Ltd.

[0038] The xanthan gum was purchased from Hebei Xinhai Biological Chemical Co., Ltd.

[0039] The gellan gum was purchased from Jiangsu Zhongxuan Biological Technology Co., Ltd.

[0040] The p-hydroxyacetophenone was purchased from Huzhou Jiajie Biological Technology Co., Ltd.

[0041] The ethylhexyl glycerin is purchased from Shanghai Youhe Biotechnology Co., Ltd.

[0042] The beta-cyclodextrin is purchased from Zibo Qianhui Biotechnology Co., Ltd.

[0043] The polyglyceryl-3 is purchased from Henan Haiston Biotechnology Co., Ltd.

[0044] The sucrose monostearate is purchased from Guangxi Xianggui Biotechnology Co., Ltd.

[0045] The p-toluenesulfonic acid is purchased from Tianjin Kemio Chemical Reagent Co., Ltd.

[0046] The molecular sieve 4A is purchased from Shanghai Hengye Molecular Sieve Co., Ltd.

[0047] The sucrose distearate is purchased from Fujian KeHong Bioengineering Co., Ltd.

[0048] The amino propyl polydimethyl siloxane is purchased from Guangzhou Tianci High-tech Materials Co., Ltd.

[0049] The titanium acid tetraisopropyl ester is purchased from Yantai Jiumu Chemical Co., Ltd.

[0050] The vinyl-containing polyglyceryl ether is purchased from Liaoning Kelong Fine Chemical Co., Ltd.

[0051] The decaglycerol decanoate is purchased from Henan Zhengtong Chemical Co., Ltd.

[0052] The chloroform is purchased from China National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0053] The phosphate buffer is purchased from Shanghai Yuan Ye Biotechnology Co., Ltd.

[0054] Example 1 A stable skin care composition based on a polyglycerol ester and sucrose ester complex system, the raw material composition is as follows: polyglycerol esters 50g, sucrose esters 25g, cyclodextrin-polyglyceryl sucrose hybrid ester 18g, silanized polysucrose ester 12g, nanostructured lipid-sucrose polyglycerol carrier 18g, caprylic / capric triglyceride 65g, jojoba seed oil 30g, phytosterols 12g, squalene 25g, deionized water 500g, trehalose 40g, 1,3-butanediol 55g, quercetin 5g, vitamin E acetate 3g, sodium hyaluronate 1.5g, xanthan gum 3g, gellan gum 1.5g, p-hydroxyacetophenone 4g, ethylhexylglycerin 2g. The preparation method of cyclodextrin-polyglyceryl sucrose hybrid ester includes: β-cyclodextrin 20g is dissolved in 200ml anhydrous dimethyl sulfoxide under nitrogen protection, mechanical stirring for 30 minutes to completely dissolve to form a transparent solution; then add polyglycerol-3 15g and sucrose stearate 10g, continue to stir for 20 minutes to fully mix; the temperature of the reaction system is raised to 83℃ at a rate of 2℃ per minute, add p-toluenesulfonic acid 2g and molecular sieve 4A 5g, maintain 83℃ for 7 hours, the whole process is carried out in nitrogen atmosphere; after the reaction is completed, the mixture is cooled to room temperature at a rate of 10℃ per hour, add 100ml saturated sodium bicarbonate solution to neutralize the acid, and precipitate the product with 500ml deionized water; after standing for 2 hours, the precipitate is collected by filtration, and finally purified by silica gel column chromatography, the eluent is a mixture of chloroform and methanol at a volume ratio of 10 to 1, the target fraction is collected and rotary evaporated to remove the solvent to obtain white solid product. The preparation method of silanized polysucrose ester includes: sucrose distearate 15g and aminopropyl polydimethylsiloxane 8g are dissolved in 100ml anhydrous toluene, magnetic stirring for 30 minutes to form a homogeneous solution; under nitrogen protection, add titanium tetraisopropylate catalyst 0.5g, and raise the temperature to 93℃ at a rate of 1.5℃ per minute; then slowly drop 50ml of toluene solution of vinyl-containing polyglyceryl ether 10g using a constant pressure dropping funnel, control the dropping speed to 1 drop per second, after dropping is completed, maintain 93℃ for 9 hours; after the reaction is completed, the mixture is cooled to 60℃ at a rate of 15℃ per hour, add 3g of activated carbon for decolorization, mechanical stirring for 35 minutes; remove the activated carbon by filtering through a Buchner funnel, and rotary evaporate the filtrate at 60℃ to remove the toluene solvent to obtain a pale yellow viscous liquid; finally, molecular distillation purification is carried out under vacuum degree 0.1Pa, the distillation temperature is 190℃, and the main fraction is collected to obtain the target product.The preparation method of the nanostructured lipid-sucrose polyglycerol carrier includes: dissolving 10g of decaglycerol decastearate, 5g of sucrose cocoate, and 3g of hydrogenated lecithin in 100ml of a solvent containing chloroform and methanol in a 2:1 ratio, and stirring in a 40℃ water bath for 20 minutes until completely dissolved; then adding 2g of quercetin and continuing to stir for 10 minutes to ensure uniform dispersion; removing the organic solvent by rotary evaporation in a 50℃ water bath to form a uniform lipid film; then adding 100ml of phosphate buffer at 60℃ for hydration, during which the emulsion is ultrasonically treated with a probe sonicator at 500W power for 18 minutes, with a 2-second sonication interval of 1 second; the resulting emulsion is homogenized five times under 800 bar pressure using a high-pressure homogenizer; finally, it is filtered and sterilized through a microporous membrane with a 0.23μm pore size to obtain the nanostructured lipid carrier. The preparation method of the stable skin care composition includes: first, heating 500g of deionized water to 75℃, then sequentially adding 40g of trehalose, 55g of 1,3-butanediol, 1.5g of sodium hyaluronate, 3g of xanthan gum, and 1.5g of gellan gum, and stirring at 2000rpm for 15 minutes using a high-speed homogenizer until completely dissolved and homogeneous, obtaining an aqueous phase for later use; separately, preparing 50g of polyglycerol esters, 25g of sucrose esters, 18g of cyclodextrin-polyglycerol-sucrose hybrid esters, 12g of silanized polysucrose esters, 18g of nanostructured lipid-sucrose polyglycerol carriers, 65g of caprylic / capric triglycerides, 30g of jojoba seed oil, 12g of phytosterols, and keratin... 25g of squalene and 3g of vitamin E acetate were mixed and heated to 75°C. The mixture was then stirred at 500 rpm for 20 minutes with a magnetic stirrer until completely dissolved and homogeneous, yielding the oil phase. The oil phase was then slowly added to the aqueous phase at a constant temperature of 75°C, and homogenized and emulsified at 10,000 rpm for 5 minutes using a high-shear emulsifier. The mixture was then cooled to 45°C at a rate of 2°C per minute, and 5g of quercetin, 4g of p-hydroxyacetophenone, and 2g of ethylhexylglycerin were added. The mixture was then slowly stirred at 200 rpm for 30 minutes with a paddle stirrer until completely dissolved. Finally, the mixture was cooled to 30°C at a rate of 1.5°C per minute and discharged to obtain the final skincare composition product.

[0055] Example 2 is implemented in the same way as Example 1, except that it is a stable skin care composition based on a polyglycerol ester and sucrose ester compound system. The raw material composition is as follows: 20g polyglycerol ester, 10g sucrose ester, 5g cyclodextrin-polyglycerol-sucrose hybrid ester, 3g silanized polysucrose ester, 5g nanostructured lipid-sucrose polyglycerol carrier, 30g caprylic / capric triglyceride, 10g jojoba seed oil, 5g phytosterols, 10g squalene, 200g deionized water, 20g trehalose, 30g 1,3-butanediol, 1g quercetin, 1g vitamin E acetate, 0.5g sodium hyaluronate, 1g xanthan gum, 0.5g gellan gum, 2g p-hydroxyacetophenone, and 1g ethylhexylglycerin. The preparation method of cyclodextrin-polyglycerol sucrose hybrid ester includes: dissolving 15g of β-cyclodextrin in 150ml of anhydrous dimethyl sulfoxide, adding 10g of polyglycerol-3 and 5g of sucrose monostearate; raising the temperature to 80℃, adding 1g of p-toluenesulfonic acid and 3g of molecular sieve 4A, and reacting for 6 hours; after cooling, neutralizing the precipitate, and purifying by column chromatography with elution using chloroform-methanol at a ratio of 10:1. The preparation method of silanized polysucrose ester includes: dissolving 10g of sucrose distearate and 5g of aminopropyl polydimethylsiloxane in toluene, adding 0.3g of tetraisopropyl titanate catalyst, and raising the temperature to 90℃; adding dropwise a toluene solution containing 5g of vinyl polyglycerol ether, and reacting for 8 hours; cooling to 58℃, adding 2g of activated carbon, and stirring for 30 minutes; filtration and evaporation followed by molecular distillation purification at 180℃. The preparation method of the nanostructured lipid-sucrose polyglycerol carrier includes: dissolving 5g of decaglycerol decastearate, 2g of sucrose cocoate, and 1g of hydrogenated lecithin, adding 0.5g of quercetin; rotary evaporating to form a film, then hydrating with 58℃ phosphate buffer, and sonicating for 15 minutes; homogenizing under high pressure four times, and filtering through a 0.22μm filter membrane. The preparation method of the stable skincare composition includes: heating the aqueous and oil phases separately to 70℃, mixing and homogenizing, cooling to 40℃, adding preservatives, and further cooling to 28℃ before discharging.

[0056] Example 3 is implemented in the same way as Example 1, except that it is a stable skin care composition based on a polyglycerol ester and sucrose ester compound system. The raw material composition is as follows: 80g of polyglycerol esters, 40g of sucrose esters, 30g of cyclodextrin-polyglycerol-sucrose hybrid ester, 20g of silanized polysucrose ester, 30g of nanostructured lipid-sucrose polyglycerol carrier, 100g of caprylic / capric triglyceride, 50g of jojoba seed oil, 20g of phytosterols, 40g of squalene, 800g of deionized water, 60g of trehalose, 80g of 1,3-butanediol, 10g of quercetin, 5g of vitamin E acetate, 3g of sodium hyaluronate, 5g of xanthan gum, 3g of gellan gum, 6g of p-hydroxyacetophenone, and 3g of ethylhexylglycerin. The preparation method of cyclodextrin-polyglycerol sucrose hybrid ester includes: dissolving 25g of β-cyclodextrin in 250ml of anhydrous dimethyl sulfoxide, adding 20g of polyglycerol-3 and 15g of sucrose monostearate; raising the temperature to 85℃, adding 3g of p-toluenesulfonic acid and 8g of molecular sieve 4A, and reacting for 8 hours; after cooling, neutralizing the precipitate, and purifying by column chromatography with elution using chloroform-methanol at a ratio of 10:1. The preparation method of silanized polysucrose ester includes: dissolving 20g of sucrose distearate and 10g of aminopropyl polydimethylsiloxane in toluene, adding 0.8g of tetraisopropyl titanate catalyst, and raising the temperature to 95℃; adding dropwise a toluene solution containing 15g of vinyl polyglycerol ether, and reacting for 10 hours; cooling to 62℃, adding 5g of activated carbon, and stirring for 40 minutes; filtration and evaporation followed by molecular distillation purification at 200℃. The preparation method of the nanostructured lipid-sucrose polyglycerol carrier includes: dissolving 15g of decaglycerol decastearate, 8g of sucrose cocoate, and 5g of hydrogenated lecithin, and adding 3g of quercetin; rotary evaporating to form a film, then hydrating with phosphate buffer at 62℃, and sonicating for 20 minutes; homogenizing under high pressure 6 times, and filtering through a 0.24μm filter membrane. The preparation method of the stable skincare composition includes: heating the aqueous and oil phases separately to 80℃, mixing and homogenizing, cooling to 50℃, adding preservatives, and further cooling to 35℃ before discharging.

[0057] Comparative Example 1 The specific implementation method is the same as in Example 1, except that a skin care composition is provided, the raw material composition of which is as follows: 50g of polyglycerol esters, 25g of sucrose esters, 12g of silanized polysucrose esters, 18g of nanostructured lipid-sucrose polyglycerol carrier, 65g of caprylic / capric triglycerides, 30g of jojoba seed oil, 12g of phytosterols, 25g of squalene, 500g of deionized water, 40g of trehalose, 55g of 1,3-butanediol, 5g of quercetin, 3g of vitamin E acetate, 1.5g of sodium hyaluronate, 3g of xanthan gum, 1.5g of gellan gum, 4g of p-hydroxyacetophenone, and 2g of ethylhexylglycerin. Cyclodextrin-polyglycerol sucrose hybrid esters are not added during the preparation process.

[0058] Comparative Example 2 The specific implementation method is the same as in Example 1, except that a skin care composition is provided, the raw material composition of which is as follows: 50g of polyglycerol esters, 25g of sucrose esters, 18g of cyclodextrin-polyglycerol-sucrose hybrid ester, 18g of nanostructured lipid-sucrose polyglycerol carrier, 65g of caprylic / capric triglyceride, 30g of jojoba seed oil, 12g of phytosterols, 25g of squalene, 500g of deionized water, 40g of trehalose, 55g of 1,3-butanediol, 5g of quercetin, 3g of vitamin E acetate, 1.5g of sodium hyaluronate, 3g of xanthan gum, 1.5g of gellan gum, 4g of p-hydroxyacetophenone, and 2g of ethylhexylglycerin. No silanized polysucrose esters are added during the preparation process.

[0059] Comparative Example 3 The specific implementation method is the same as in Example 1, except that a skin care composition is provided, the raw material composition of which is as follows: 50g of polyglycerol esters, 25g of sucrose esters, 18g of cyclodextrin-polyglycerol-sucrose hybrid ester, 12g of silanized polysucrose ester, 65g of caprylic / capric triglyceride, 30g of jojoba seed oil, 12g of phytosterols, 25g of squalene, 500g of deionized water, 40g of trehalose, 55g of 1,3-butanediol, 5g of quercetin, 3g of vitamin E acetate, 1.5g of sodium hyaluronate, 3g of xanthan gum, 1.5g of gellan gum, 4g of p-hydroxyacetophenone, and 2g of ethylhexylglycerin. No nanostructured lipid-sucrose polyglycerol carrier is added during the preparation process.

[0060] Performance testing The stable skincare compositions prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance testing according to the following methods: The skincare composition samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were allowed to stand for 24 hours at 25°C and 60% humidity to equilibrate before undergoing various performance tests. Stability testing was performed using a LUMiSizer stability analyzer. 5 mL of sample was placed in a 2 mm thick sample cell and centrifuged at 4000 rpm for 30 minutes at 25°C. Transmittance data was collected every 10 seconds, and the instability index was calculated using software. Particle size and distribution testing was performed using a Malvern Zetasizer NanoZS90 laser particle size analyzer. The sample was diluted 100 times with deionized water and placed in the sample cell. After equilibration at 25°C for 2 minutes, measurements were taken, and the results were repeated three times, with the average value taken. Zeta potential testing was performed using the same instrument with a folded capillary sample cell, and the measurements were taken three times, with the average value taken. Rheological property testing was performed using a Haake MARS 60 rheometer with a 35mm diameter cone-plate system, a 1° cone angle, and a 0.105mm gap. After determining the linear viscoelastic region by amplitude scanning at 25℃, frequency scanning was conducted within the range of 0.1-10Hz. Moisturizing performance testing was performed using a Corneometer CM825 probe. At 22℃ and 50% humidity, a 3×3cm test area was marked on the inner forearm of the volunteer. Initial values ​​were measured after cleaning, and a 2mg / cm² moisturizing agent was evenly applied. 2 The moisture content of the samples was measured at 1 hour, 4 hours, and 8 hours after sample collection. The average value was taken from 6 volunteers in each group. Antioxidant performance was tested using the DPPH free radical scavenging method. 0.1 g of sample was accurately weighed and dissolved in 10 mL of ethanol, and 2 mL of 0.1 mmol / L DPPH ethanol solution was added. After reacting in the dark for 30 minutes, the absorbance was measured at 517 nm, and the scavenging rate was calculated. Skin irritation was tested using the patch test. A Finn Chamber patch applicator was applied to normal skin on the back of the volunteers, and removed after 24 hours of closed contact. Dermatologists scored the irritation at 0.5 hours, 24 hours, and 48 hours according to the International Contact Dermatitis Study Group standards. 30 volunteers were tested in each group.

[0061] Performance test results: Table 1: Performance test results of each embodiment and comparative example

[0062] As shown in Table 1, the analysis results indicate that Examples 1-3 significantly improved upon Comparative Examples 1-3 in terms of stability, skin feel, and active ingredient efficacy, successfully solving the technical problems of insufficient stability, sticky skin feel, and low active ingredient penetration in existing polyglycerol ester and sucrose ester blends. Specifically, the instability index of Examples 1-3 was less than or equal to 0.15, while that of Comparative Examples 1-3 was as high as 0.38 or higher. This directly demonstrates that the synergistic effect of cyclodextrin-polyglycerol-sucrose hybrid ester, silanized polysucrose ester, and nanostructured lipid-sucrose polyglycerol carrier greatly enhanced the physical stability of the system and effectively inhibited phase separation and particle aggregation. The average particle size of Examples 1-3 was controlled at around 130 nm and was uniformly distributed, while the particle size of Comparative Examples 1-3 all exceeded 215 nm and was widely distributed. This fine nanoscale structure significantly improved the skin feel of the product and avoided the stickiness and heaviness problems caused by excessively large particle size in traditional formulations. In terms of moisturizing performance, the moisturizing rate of Examples 1-3 remained above 21% after 8 hours, far exceeding the 10.2%-12.6% of Comparative Examples 1-3. This is attributed to the efficient encapsulation and sustained release of active ingredients by the nanocarrier, significantly improving the skin penetration and duration of action of active ingredients such as quercetin. Furthermore, the DPPH free radical scavenging rate of Examples 1-3 was as high as approximately 85%, while that of Comparative Examples 1-3 was only about 60-65%, demonstrating that the complete compound system can more effectively protect the active ingredients and exert antioxidant efficacy. Finally, the skin irritation scores of Examples 1-3 were extremely low, all at or below 0.3, far lower than the 0.8-1.1 of Comparative Examples 1-3, indicating that the system has good biocompatibility and mildness. In summary, this invention, through three specifically designed modified compounds, optimizes the system structure at the molecular level, completely solving the three major technical bottlenecks of insufficient stability, sticky skin feel, and low penetration rate of active ingredients.

[0063] The above-described embodiments are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A stable skincare composition based on a polyglycerol ester and sucrose ester compound system, characterized in that, Including the following parts by weight of raw materials: Polyglycerol esters: 20-80 parts by weight; Sucrose esters: 10-40 parts by weight; Cyclodextrin-polyglycerol sucrose hybrid ester: 5-30 parts by weight; Silanized polysucrose ester: 3-20 parts by weight; Nanostructured lipid-sucrose polyglycerol carrier: 5-30 parts by weight; Caprylic / capric triglycerides: 30-100 parts by weight; Jojoba seed oil: 10-50 parts by weight; Phytosterols: 5-20 parts by weight; Squalene: 10-40 parts by weight; Deionized water: 200-800 parts by weight; Trehalose: 20-60 parts by weight; 1,3-Butanediol: 30-80 parts by weight; Quercetin: 1-10 parts by weight; Vitamin E acetate: 1-5 parts by weight; Sodium hyaluronate: 0.5-3 parts by weight; Xanthan gum: 1-5 parts by weight; Gellan gum: 0.5-3 parts by weight; p-Hydroxyacetophenone: 2-6 parts by weight; Ethylhexylglycerin: 1-3 parts by weight; The preparation method of the cyclodextrin-polyglycerol sucrose hybrid ester includes: A1, dissolving β-cyclodextrin in anhydrous dimethyl sulfoxide under nitrogen protection and stirring until completely dissolved; then adding polyglycerol-3 and sucrose monostearate; raising the temperature of the reaction system to 80-85℃, adding p-toluenesulfonic acid and molecular sieve 4A for reaction; A2, after the reaction is completed, cooling the mixture to room temperature, adding saturated sodium bicarbonate solution, and precipitating with deionized water; finally, purifying by column chromatography.

2. The stable skincare composition according to claim 1, characterized in that, In step A1, p-toluenesulfonic acid and molecular sieve 4A are added, and the reaction time is 6-8 hours.

3. The stable skincare composition according to claim 1, characterized in that, In step A2, the eluent for column chromatography purification is chloroform / methanol = 10:

1.

4. The stable skincare composition according to claim 1, characterized in that, The preparation method of the silanized polysucrose ester includes: B1, dissolving sucrose distearate and aminopropyl polydimethylsiloxane in toluene to form a solution; adding tetraisopropyl titanate catalyst under nitrogen protection and heating to 90-95℃; then adding a toluene solution containing vinyl polyglycerol ether dropwise for reaction; B2, after the reaction is completed, cooling the mixture to 58-62℃, adding activated carbon and stirring; filtering and rotary evaporating to obtain a pale yellow viscous liquid; finally purifying by molecular distillation.

5. The stable skincare composition according to claim 4, characterized in that, In step B1, the reaction time for adding the toluene solution containing vinyl polyglycerol ether is 8-10 hours.

6. The stable skincare composition according to claim 4, characterized in that, In step B2, after the reaction is complete, activated carbon is added and the stirring time is 30-40 min; the temperature for molecular distillation purification is 180-200℃.

7. The stable skincare composition according to claim 1, characterized in that, The preparation method of the nanostructured lipid-sucrose polyglycerol carrier includes: C1. Decaglycerol decastearate, sucrose cocoate, and hydrogenated lecithin were dissolved in a chloroform / methanol mixed solvent; then flavonoid compounds were added; and the mixture was rotary evaporated to form a lipid film. C2. Then add phosphate buffer solution at 58-62℃ for hydration, while simultaneously sonicating the probe; circulate through a high-pressure homogenizer. C3. Finally, it is filtered through a microporous membrane.

8. The stable skincare composition according to claim 7, characterized in that, In step C1, the flavonoid compound is quercetin.

9. The stable skincare composition according to claim 7, characterized in that, In step C2, the ultrasonic treatment time is 15-20 minutes; the high-pressure homogenizer cycles are 4-6 times.

10. The stable skincare composition according to claim 7, characterized in that, In step C3, the pore size of the microporous filter membrane is 0.22-0.24 μm.

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