CN120983303A - Stable skincare compositions based on polyglycerol ester and sucrose ester complex systems - Google Patents

Abstract

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

Description

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

Technical Field

The invention relates to the technical field of cosmetic preparations, in particular to a stable skin care composition based on a polyglycerol ester and sucrose ester compound system.

Background

At present, the cosmetic industry has increasingly higher requirements on an emulsifying system, and not only is stable in formula and excellent in skin feel, but also raw materials are naturally derived and are green and safe. The polyglycerol ester emulsifier has good emulsifying property and electrolyte resistance, but when the polyglycerol ester emulsifier is used alone, the polyglycerol ester emulsifier often brings sticky and thick skin feel, and the aim of modern consumers for refreshing skin feel is difficult to be met. Sucrose ester emulsifying agent is derived from natural sucrose and vegetable fatty acid, has fresh skin feel, good skin-friendly property and good moisturizing property, but has relatively weak emulsifying capacity, insufficient stability support for complex formula system and easy layering or paste destruction phenomenon under high-temperature or low-temperature environment. In the prior art, although two types of emulsifying agents are simply compounded, due to insufficient compatibility and synergistic effect of molecular structures, ideal balance among stability, skin feel and efficacy is difficult to achieve, and particularly, the requirement of efficient permeation of active ingredients is difficult to meet.

With the improvement of the requirements of consumers on the safety and the environmental friendliness of cosmetics, the development of an emulsifying system based on renewable raw materials, which is completely independent of polyethylene glycol structures, has become an important development trend. There is a need in the marketplace for new formulation technologies that can maintain the safety of natural materials, as well as provide the stability of synthetic emulsifiers. Existing emulsifying systems based on natural materials often require the addition of large amounts of co-emulsifiers or stabilizers, which not only increase the complexity of the formulation, but can also present a potential irritation risk. Therefore, how to break through the performance limitation of the raw materials while maintaining the natural properties of the raw materials through the innovative design of the molecular structure becomes a key difficulty in the technical development of the field.

Aiming at the technical bottleneck, the invention starts from the design of a molecular structure, and fundamentally improves the compatibility and the synergy of polyglycerol ester and sucrose ester by developing three modified compounds with brand new structures. The modified compounds not only keep the natural characteristics of the original raw materials, but also remarkably improve the interfacial adsorption capacity and microscopic order of an emulsifying system through molecular hybridization, functional group modification and carrier structure innovation. The invention aims to provide a stable skin care composition with excellent comprehensive performance, which has excellent stability, refreshing skin feel and active ingredient permeation promoting functions while maintaining the advantages of all natural raw materials, and effectively solves the multiple contradictions in the prior art that the composition is difficult to consider.

Disclosure of Invention

The invention aims to provide a stable skin care composition based on a polyglycerol ester and sucrose ester compound system, which solves the technical problems of insufficient stability, sticky skin feel and low active ingredient permeability of the existing polyglycerol ester and sucrose ester compound system.

The invention realizes the above purpose through the following technical scheme:

the stable skin care composition based on the polyglycerol ester and sucrose ester compound system comprises the following raw materials in parts by weight:

20-80 parts by weight of polyglycerol esters;

10-40 parts by weight of sucrose esters;

5-30 parts by weight of cyclodextrin-polyglycerol sucrose hybrid ester;

3-20 parts by weight of silanized polysucrose ester;

5-30 parts by weight of a nanostructured lipid-sucrose polyglycerol carrier;

30-100 parts by weight of caprylic/capric triglyceride;

10-50 parts of jojoba seed oil;

5-20 parts by weight of phytosterol;

10-40 parts by weight of squalene;

200-800 parts of deionized water;

20-60 parts of trehalose;

30-80 parts by weight of 1, 3-butanediol;

1-10 parts by weight of quercetin;

1-5 parts by weight of vitamin E acetate;

0.5-3 parts by weight of sodium hyaluronate;

1-5 parts by weight of xanthan gum;

0.5-3 parts by weight of gellan gum;

2-6 parts by weight of p-hydroxyacetophenone;

1-3 parts by weight of ethylhexyl glycerol;

The preparation method of the cyclodextrin-polyglycerol sucrose hybrid ester comprises the steps of A1, dissolving beta-cyclodextrin in anhydrous dimethyl sulfoxide under the protection of nitrogen, stirring until the beta-cyclodextrin is completely dissolved, then adding polyglycerol-3 and sucrose monostearate, heating a reaction system to 80-85 ℃, adding p-toluenesulfonic acid and molecular sieve 4A for reaction, cooling the mixture to room temperature after the reaction is finished, adding saturated sodium bicarbonate solution, precipitating with deionized water, and finally purifying by column chromatography.

According to a preferred embodiment of the invention, the composition and the proportions of the polyglycerol esters are specifically designed to ensure stability and emulsifying effect of the composition. The first polyglycerides are preferably prepared by esterification of a single fatty acid having a carbon chain length ranging from C12 to C22 and selected from one of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid or behenic acid with a polyglyceride having a degree of polymerization of 3 to 10. The second polyglycerol esters are preferably prepared by esterification of at least two different fatty acids, likewise selected from saturated or unsaturated fatty acids having a carbon chain length of from C12 to C22, with polyglycerols of the same degree of polymerization. The mass ratio of the two polyglycerol esters is controlled between 0.5:1 and 4:1, preferably 2:1. Through the specific combination and the specific proportion, the first polyglycerol ester provides stronger emulsifying force and interface stability, while the second polyglycerol ester enhances the low-temperature stability and skin feel regulating effect of the system through the introduction of the mixed fatty acid chain, and the synergistic effect of the first polyglycerol ester and the second polyglycerol ester obviously improves the overall stability and application performance of the final skin care composition.

According to the preferred embodiment of the invention, the polyglycerol esters are compounded by two polyglycerol esters with specific structures according to the precise mass ratio. The first polyglyceryl ester is polyglyceryl-6 distearate or polyglyceryl-6-stearate, preferably polyglyceryl-6-stearate, wherein the polyglyceryl-6-stearate is prepared by esterification reaction of polyglyceryl with the polymerization degree of 6 and single fatty acid stearic acid, and the specific preparation method comprises the steps of adding 100g of polyglyceryl-6 and 45g of stearic acid into a reaction kettle, adding 0.5g of p-toluenesulfonic acid catalyst, reacting for 5 hours at 190 ℃, monitoring that the acid value is reduced to below 2mg KOH/g, stopping the reaction, decoloring and filtering to obtain the finished product. The second polyglyceryl ester is polyglyceryl-4-cocoate, which is prepared by esterification reaction of polyglyceryl with polymerization degree of 4 and coco fatty acid (mixed fatty acid containing 45% of lauric acid, 18% of myristic acid, 9% of palmitic acid and 15% of oleic acid), and is prepared by mixing 100g of polyglyceryl-4 with 50g of coco fatty acid, adding 0.6g of tetraisopropyl titanate catalyst, reacting for 4.5 hours at 185 ℃, monitoring the acid value to be lower than 1.5mg KOH/g, stopping the reaction, and purifying by molecular distillation. The mass ratio of the two polyglycerol esters is 2:1. Through the specific design, the polyglycerol-6-stearate forms a high-strength interfacial film on an oil-water interface by virtue of a regular stearic acid chain structure and a moderate polymerization degree, provides excellent emulsion stability and prevents Ostwald ripening, and the polyglycerol-4-cocoanut oleate effectively reduces the crystallization temperature of a system and improves the low-temperature stability by virtue of the composition of short-chain mixed fatty acid, meanwhile, the branching structure of the polyglycerol-4-cocoanut oleate can reduce intermolecular hydrogen bonding, obviously reduces the viscosity of the system and avoids sticky feel caused by the traditional polyglycerol ester. The synergistic combination of the two can ensure that the emulsion system can still keep the structural integrity when the emulsion system is subjected to temperature change or mechanical shearing, and the skin feel is fresh and not sticky.

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

According to a preferred embodiment of the present invention, the phytosterol is at least one selected from the group consisting of beta-sitosterol, stigmasterol and campesterol, wherein the beta-sitosterol content is 40% -80% of the total mass of the phytosterol, stigmasterol is 10% -30% and campesterol is 5% -25%. The phytosterols may be derived from natural plant extracts such as soybean oil, canola oil or pine oil. The stability of the emulsion is obviously enhanced by the synergistic effect of the plant sterols and the polyglycerol ester and the sucrose ester in the system, the hydroxyl in the molecule and the polar group of the emulsifier form a hydrogen bond network, and the steroid nucleus structure is inserted into the oil phase to strengthen the strength of the interfacial film. At the same time, the phytosterol also provides excellent skin barrier repair function and anti-inflammatory property, and can synergistically enhance the moisturizing capability of skin with squalene.

In the invention, the synthesis of cyclodextrin-polyglycerol sucrose hybrid ester is based on the synergistic mechanism of supermolecular chemistry and transesterification reaction. The unique tapered cavity structure of the beta-cyclodextrin molecule provides excellent inclusion capacity for the beta-cyclodextrin molecule, and the hydroxyl groups on the surface of the beta-cyclodextrin molecule become active sites for molecular modification. In the reaction medium of anhydrous dimethyl sulfoxide, through the catalysis of p-toluenesulfonic acid, the hydroxyl on the polyglycerol chain and the ester group of sucrose monostearate are subjected to transesterification, and meanwhile, the primary hydroxyl at the edge of beta-cyclodextrin also participates in nucleophilic substitution reaction. This process forms hybrid molecules with asymmetric structures, cyclodextrin cavities are responsible for encapsulating hydrophobic active substances, polyglycerol segments provide hydrophilicity, and sucrose ester moieties give the system good interfacial activity. The addition of molecular sieves continuously removes the moisture generated by the reaction, pushes the equilibrium to move towards the direction of the product, and finally obtains the hybridization ester product with precise structure through chromatographic purification.

According to a preferred embodiment of the invention, in step A1, p-toluene sulfonic acid is added and the reaction time of molecular sieve 4A is from 6 to 8 hours.

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

According to the preferred embodiment of the invention, the preparation method of the silanized polysucrose ester comprises the steps of B1, dissolving sucrose distearate and aminopropyl polydimethylsiloxane into toluene to form a solution, adding a tetraisopropyl titanate catalyst under the protection of nitrogen, heating to 90-95 ℃, then dropwise adding a toluene solution containing vinyl polyglycerol ether for reaction, B2, cooling the mixture to 58-62 ℃ after the reaction is completed, adding active carbon for stirring, filtering, performing rotary evaporation to obtain light yellow viscous liquid, and finally purifying by molecular distillation.

In the invention, the preparation of the silanized polysucrose ester represents innovative fusion of organosilicon chemistry and saccharide. The key to this reaction is the unique catalytic mechanism of tetraisopropyl titanate catalyst to amide bond formation. The titanium atom has an empty d orbit, can simultaneously complex the carbonyl oxygen atom of the sucrose distearate and the amino nitrogen atom of the aminopropyl polydimethylsiloxane to form a tetrahedral transition state, and greatly reduces the reaction activation energy. In this catalytic system, the ester group of sucrose ester undergoes ammonolysis with the primary amino group of the organosilicon compound to form a thermodynamically more stable amide bond. Then, the polyglycerin ether containing vinyl groups undergoes hydrosilylation reaction with the residual silicon-hydrogen bonds in the molecules at high temperature through a free radical mechanism, and a polyglycerin hydrophilic chain segment is further introduced. The whole process is purified by molecular distillation to remove unreacted monomers and byproducts, thus obtaining the silanized polysucrose ester with definite structure. The compound smartly combines the biocompatibility of sucrose ester, the hydrophilicity of polyglycerol and the unique skin feel of organic silicon.

According to a preferred embodiment of the present invention, in step B1, the toluene solution of the vinyl-containing polyglyceryl ether is added dropwise for a reaction time of 8 to 10 hours.

According to a preferred embodiment of the present invention, in step B2, after the completion of the reaction, activated carbon is added and stirred for 30 to 40 minutes, and the temperature for molecular distillation purification is 180 to 200 ℃.

According to a preferred embodiment of the present invention, the method for preparing the nanostructured lipid-sucrose polyglycerol carrier comprises:

C1, dissolving decaglycerol decastearate, sucrose cocoate and hydrogenated lecithin in a chloroform/methanol mixed solvent, then adding flavonoid compounds, and performing rotary evaporation to form a lipid film;

Adding 58-62 ℃ phosphate buffer solution for hydration, and simultaneously carrying out ultrasonic treatment on the probe;

and C3, finally filtering through a microporous filter membrane.

In the invention, the construction of the nanostructured lipid-sucrose polyglycerol carrier is based on the principles of molecular self-assembly and nanotechnology. The decaglycerol decastearate, the sucrose cocoate and the hydrogenated lecithin form a uniform molecular dispersion system in an organic solvent, and after the solvent is removed by rotary evaporation, the amphiphilic molecules spontaneously align through hydrophobic interaction to form an ordered lipid bilayer membrane. Upon hydration with the addition of warm buffer, the lipid membrane flexes and encapsulates the aqueous phase, forming a vesicle structure. The probe sonication provides sufficient energy to break up the large vesicles to form a precursor dispersion of smaller particle size. The shearing force and cavitation effect during high pressure homogenization further reduce particle size and improve distribution uniformity, forcing the amphiphilic molecules to rearrange to form nanoparticles with core-shell structure, hydrophobic quercetin is encapsulated in lipid core, and sucrose polyglycerol ester forms stable hydrophilic crown on outer layer. Finally, the nano-carrier with uniform particle size is obtained through filtration of the microporous filter membrane, and the structure not only protects active ingredients, but also improves skin permeability.

According to a preferred embodiment of the present invention, in step C1, the flavonoid compound is quercetin.

According to a preferred embodiment of the invention, in step C2, the time of the ultrasonic treatment is 15-20min and the number of cycles of the high-pressure homogenizer is 4-6.

According to a preferred embodiment of the invention, in step C3, the pore size of the microporous filter membrane is 0.22-0.24. Mu.m.

In the invention, the stabilizing mechanism of the whole compound system is derived from a plurality of mutually synergistic physicochemical effects. The polyglycerol ester and sucrose ester form a stable composite interface film through intermolecular hydrogen bond and hydrophobic interaction, and the strength and toughness of the interface structure are further enhanced by adding three modifying compounds. The cyclodextrin-polyglycerol sucrose hybrid ester contains oil phase components through the cavity, so that the fluidity of oil phase molecules is reduced, and the low-temperature stability of emulsion is improved. The organosilicon chain segments of the silanized polysucrose ester are arranged at the interface to form a high-elasticity protective layer, so that coalescence caused by collision of liquid drops is effectively resisted. The nanostructured carrier not only serves as a delivery system for the active substance, but also the sucrose polyglycerol ester on the surface thereof has a synergistic stabilizing effect with the emulsifier molecules in the continuous phase. The phytosterol and the emulsifier form a liquid crystal structure together, so that the rigidity and stability of the interfacial film are enhanced. The xanthan gum and the gellan gum form a three-dimensional network structure in the water phase, and the Brownian movement and aggregation of liquid drops are prevented through the steric hindrance effect. This multi-layered, multi-dimensional stabilization mechanism enables the composition to resist various challenges presented by temperature changes, mechanical shear, and long-term storage, exhibiting excellent stability.

The invention has the beneficial effects that:

The stable skin care composition based on the polyglycerol ester and sucrose ester compound system provided by the invention has various remarkable beneficial effects. Firstly, the composition exhibits excellent stability through the synergistic effect of the innovative compounding system and three specific modifying compounds. The cyclodextrin polyglycerol sucrose hybrid ester can form a stable supermolecule complex at an oil-water interface by virtue of the unique cavity structure and the unique amphiphilicity of the cyclodextrin polyglycerol sucrose hybrid ester, so that the phase separation phenomenon is effectively prevented. The silanized polysucrose ester obviously enhances the mechanical strength of the interfacial film by introducing the organic silicon chain segment, so that the emulsion can withstand extreme conditions such as high temperature, low temperature, centrifugation and the like. The nanostructured lipid sucrose polyglycerol carrier provides a long-term stable dispersion state for the system through the special core-shell structure, and ensures that the product maintains uniform and consistent texture during storage.

The composition of the present invention achieves a breakthrough improvement in skin feel and moisturization performance. The organosilicon component in the silanized polysucrose ester endows the product with light and smooth spreading characteristics, and completely overcomes the sticky and thick feel brought by the traditional polyglycerol ester emulsifier. The moisturizing components such as trehalose and butanediol and the innovative emulsifying system generate a synergistic effect, so that a breathable moisturizing film can be formed on the surface of the skin, and the percutaneous moisture loss is remarkably reduced. The active grease such as the phytosterol, the squalene and the like not only provides excellent moisturizing effect, but also constructs a texture with extremely strong skin-friendly property together with the modified emulsifier, so that the product is easy to absorb and pores are not blocked.

Most importantly, the present invention provides significant improvements in active ingredient delivery and overall safety. The nanostructured carrier can effectively encapsulate flavonoid compounds such as quercetin, improve the stability and bioavailability of the flavonoid compounds, and realize better antioxidant and anti-aging effects by enhancing the skin penetration capability. All the emulsifying components are derived from natural renewable resources, and the emulsion does not contain polyethylene glycol structure, so that the irritation risk is greatly reduced. The whole formula system accords with the development concept of green cosmetics, ensures high safety and environmental friendliness while providing excellent skin care efficacy, and meets the double requirements of modern consumers on efficient safe skin care products.

Detailed Description

The following detailed description is for further illustration of the application and is not to be construed as limiting the scope of the application, since numerous insubstantial modifications and adaptations of the application will be to those skilled in the art in light of the foregoing disclosure.

The information of domestic suppliers of the main relevant equipment and materials is as follows:

The caprylic/capric triglyceride is purchased from Zhejiang physical and chemical biotechnology limited company.

The jojoba seed oil was purchased from Hubei langevin biomedical limited.

The squalene was purchased from Baikaisheng (Jiangsu) biotechnology limited.

The trehalose was purchased from Henan Dexin chemical industry Co.

The 1, 3-butanediol was purchased from Jinan Toyoda chemical Co., ltd.

The quercetin was purchased from Hunan Hui Rui biotechnology Co.

The vitamin E acetate was purchased from Wuhan's Biotechnology Co.

The sodium hyaluronate was purchased from the company of the biological pharmaceutical company of the Narcissus thunbergii.

The sucrose cocoate was purchased from Hubei ferry chemical Co.

The hydrogenated lecithin was purchased from Shanghai Seiyaka Biotechnology Co.

The xanthan gum is purchased from Hebei Xinhe Biochemical Co.

The gellan gum was purchased from Jiangsu Zhuan biotechnology limited.

The p-hydroxyacetophenone was purchased from the Huzhou Jiajie biosciences Co.

The ethylhexyl glycerol is purchased from Shanghai Biotechnology Inc.

The beta-cyclodextrin is purchased from the company Bohui Biotechnology Co.

The polyglycerol-3 was purchased from Henan Haaston biotechnology Co.

The sucrose monostearate was purchased from Guangxi Hunan and Guangxi Biotechnology Inc.

The p-toluenesulfonic acid was purchased from Tianjin Miou chemical Co.

The molecular sieve 4A was purchased from Shanghai Hengda molecular sieve Co., ltd.

The sucrose distearate was purchased from Fujian macrobioengineering Co.Ltd.

The aminopropyl polydimethylsiloxane was purchased from new materials, inc. of Gangsu high Material, guangzhou.

The tetraisopropyl titanate was purchased from tabacco, nine mesh chemical Co., ltd.

The vinyl-containing polyglyceryl ether was purchased from Liaoning Colon fine chemical Co., ltd.

The decaglycerol decastearate was purchased from Henan, inc.

The chloroform was purchased from national pharmaceutical group chemical company, ltd.

The phosphate buffer was purchased from Shanghai source leaf Biotechnology Inc.

Example 1A stable skin care composition based on a polyglycerol ester and sucrose ester complex system comprises the following raw materials of 50g of polyglycerol ester, 25g of sucrose ester, 18g of cyclodextrin-polyglycerol sucrose hybrid ester, 12g of silanized polysucrose ester, 18g of nanostructured lipid-sucrose polyglycerol carrier, 65g of caprylic/capric triglyceride, 30g of jojoba seed oil, 12g of phytosterol, 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 ethylhexyl glycerol. The preparation method of the cyclodextrin-polyglycerol sucrose hybrid ester comprises the steps of dissolving 20g of beta-cyclodextrin in 200ml of anhydrous dimethyl sulfoxide under the protection of nitrogen, mechanically stirring for 30 minutes until the beta-cyclodextrin is completely dissolved to form a transparent solution, then adding 15g of polyglycerol-3 and 10g of sucrose monostearate, continuously stirring for 20 minutes to fully mix the materials, raising the temperature of a reaction system to 83 ℃ at a rate of 2 ℃ per minute, adding 2g of p-toluenesulfonic acid and 5g of molecular sieve 4A, maintaining the reaction at 83 ℃ for 7 hours, cooling the mixture to the room temperature at the rate of 10 ℃ per hour after the reaction is finished, adding 100ml of saturated sodium bicarbonate solution for neutralization acidity, precipitating a precipitation product by 500ml of deionized water, standing for 2 hours, filtering and collecting the precipitate, finally purifying by silica gel column chromatography, mixing chloroform and methanol according to a volume ratio of 10 to 1, collecting a target fraction, and rotationally evaporating to remove the solvent to obtain a white solid product. The preparation method of the silanized polysucrose ester comprises the steps of dissolving 15g of sucrose distearate and 8g of aminopropyl polydimethylsiloxane in 100ml of anhydrous toluene, magnetically stirring for 30 minutes to form a homogeneous solution, adding 0.5g of tetraisopropyl titanate catalyst under the protection of nitrogen, heating to 93 ℃ at the rate of 1.5 ℃ per minute, slowly dropwise adding 50ml of toluene solution containing 10g of vinyl polyglycerol ether by using a constant pressure dropping funnel, controlling the dropwise acceleration to be 1 drop per second, maintaining 93 ℃ for reaction for 9 hours after the dropwise addition, cooling the mixture to 60 ℃ at the rate of 15 ℃ per hour after the completion of the reaction, adding 3g of activated carbon for decoloring, mechanically stirring for 35 minutes, filtering by using a Buchner funnel to remove the activated carbon, rotationally evaporating the filtrate at 60 ℃ to remove the toluene solvent to obtain a viscous liquid, finally carrying out molecular distillation purification under the condition of 0.1Pa, keeping the dropwise distillation temperature to 190 ℃, and collecting main fractions to obtain the target product. the preparation method of the nanostructured lipid-sucrose polyglycerol carrier comprises the steps of mixing 10g of decaglycerol decastearate, 5g of sucrose cocoate and 3g of hydrogenated lecithin are dissolved in 100ml of a solvent in which chloroform and methanol are mixed according to a ratio of 2 to 1, water bath is carried out at 40 ℃ for 20 minutes until the mixture is completely dissolved, then 2g of quercetin is added, stirring is continued for 10 minutes to uniformly disperse the mixture, organic solvent is removed by rotary evaporation under the condition of 50 ℃ water bath to form a uniform lipid film, then 100ml of phosphate buffer solution at 60 ℃ is added for hydration, a probe ultrasonic instrument is used for ultrasonic treatment at 500W power for 18 minutes in the hydration process, ultrasonic operation is carried out for 2 seconds intermittently for 1 second, the obtained emulsion is circularly treated for 5 times under 800bar pressure by a high-pressure homogenizer, and finally filtration sterilization is carried out by a microporous filter membrane with a pore diameter of 0.23 mu m to obtain the nanostructured lipid carrier. The preparation method of the stable skin care composition comprises heating 500g deionized water to 75deg.C, sequentially adding trehalose 40g, 1, 3-butanediol 55g, sodium hyaluronate 1.5g, xanthan gum 3g and gellan gum 1.5g, stirring at 2000rpm with a high speed homogenizer for 15 min to completely dissolve uniformly to obtain water phase, adding polyglycerides 50g, sucrose esters 25g, cyclodextrin-polyglyceride sucrose hybrid ester 18g, silanized polysucrose ester 12g, nanostructured lipid-sucrose polyglyceride carrier 18g, caprylic/capric triglyceride 65g, jojoba seed oil 30g, and, Mixing 12g of phytosterol, 25g of squalene and 3g of vitamin E acetate, heating to 75 ℃, stirring for 20 minutes at 500rpm by magnetic stirring until the mixture is completely dissolved uniformly to obtain an oil phase, slowly adding the oil phase into an aqueous phase at a constant temperature of 75 ℃, homogenizing and emulsifying for 5 minutes at 10000rpm by a high-shear emulsifying machine, then adding 5g of quercetin, 4g of p-hydroxyacetophenone and 2g of ethylhexyl glycerin when the temperature is reduced to 45 ℃ at a rate of 2 ℃ per minute, slowly stirring for 30 minutes at 200rpm by a paddle stirrer until the mixture is completely dissolved, and finally continuously cooling to 30 ℃ at a rate of 1.5 ℃ per minute for discharging to obtain the final skin care composition product.

Example 2 the specific embodiment is the same as example 1, except that the stable skin care composition based on the polyglycerol ester and sucrose ester complex system comprises the following raw materials of 20g of polyglycerol ester, 10g of sucrose ester, 5g of cyclodextrin-polyglycerol sucrose hybrid ester, 3g of silanized polysucrose ester, 5g of nano structured lipid-sucrose polyglycerol carrier, 30g of caprylic/capric triglyceride, 10g of jojoba seed oil, 5g of phytosterol, 10g of squalene, 200g of deionized water, 20g of trehalose, 30g of 1, 3-butanediol, 1g of quercetin, 1g of vitamin E acetate, 0.5g of sodium hyaluronate, 1g of xanthan gum, 0.5g of gellan gum, 2g of p-hydroxyacetophenone and 1g of ethylhexyl glycerol. The preparation method of the cyclodextrin-polyglycerol sucrose hybrid ester comprises the steps of dissolving 15g of beta-cyclodextrin in 150ml of anhydrous dimethyl sulfoxide, adding 3g of polyglycerol and 5g of sucrose monostearate, heating to 80 ℃, adding 1g of p-toluenesulfonic acid and 3g of molecular sieve for reaction for 6 hours, cooling, neutralizing and precipitating, and eluting with chloroform methanol 10 to 1 for column chromatography. The preparation method of the silanized polysucrose ester comprises the steps of dissolving 10g of sucrose distearate and 5g of aminopropyl polydimethylsiloxane in toluene, adding 0.3g of tetraisopropyl titanate catalyst, heating to 90 ℃, dropwise adding 5g of toluene solution containing vinyl polyglycerol ether, reacting for 8 hours, cooling to 58 ℃, adding 2g of active carbon, stirring for 30 minutes, filtering, evaporating, and purifying by molecular distillation at 180 ℃. The preparation method of the nanostructured lipid-sucrose polyglycerol carrier comprises the steps of dissolving 5g of decaglycerol decastearate, 2g of sucrose cocoate and 1g of hydrogenated lecithin, adding 0.5g of quercetin, adding 58 ℃ phosphate buffer solution for hydration after spin evaporation to form a film, carrying out ultrasonic treatment for 15 minutes, homogenizing for 4 times under high pressure, and filtering with a 0.22 mu m filter membrane. The preparation method of the stable skin care composition comprises heating water phase and oil phase to 70deg.C respectively, mixing, homogenizing, cooling to 40deg.C, adding antiseptic, cooling to 28deg.C, and discharging.

Example 3 the specific embodiment is the same as example 1, except that the stable skin care composition based on the polyglycerol ester and sucrose ester complex system comprises the following raw materials of 80g of polyglycerol ester, 40g of sucrose ester, 30g of cyclodextrin-polyglycerol sucrose hybrid ester, 20g of silanized polysucrose ester, 30g of nano structured lipid-sucrose polyglycerol carrier, 100g of caprylic/capric triglyceride, 50g of jojoba seed oil, 20g of phytosterol, 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 ethylhexyl glycerol. The preparation method of the cyclodextrin-polyglycerol sucrose hybrid ester comprises the steps of dissolving 25g of beta-cyclodextrin in 250ml of anhydrous dimethyl sulfoxide, adding 15g of polyglycerol-3 and sucrose monostearate, heating to 85 ℃, adding 3g of p-toluenesulfonic acid and 8g of molecular sieve for reaction for 8 hours, cooling, neutralizing and precipitating, and eluting with chloroform methanol 10 to 1 for column chromatography. The preparation method of the silanized polysucrose ester comprises the steps of dissolving 20g of sucrose distearate and 10g of aminopropyl polydimethylsiloxane in toluene, adding 0.8g of tetraisopropyl titanate catalyst, heating to 95 ℃, dropwise adding 15g of toluene solution containing vinyl polyglycerol ether, reacting for 10 hours, cooling to 62 ℃, adding 5g of active carbon, stirring for 40 minutes, filtering, evaporating, and purifying by molecular distillation at 200 ℃. The preparation method of the nanostructured lipid-sucrose polyglycerol carrier comprises the steps of dissolving 15g of decaglycerol decastearate, 8g of sucrose cocoate and 5g of hydrogenated lecithin, adding 3g of quercetin, adding 62 ℃ phosphate buffer for hydration after spin evaporation to form a film, carrying out ultrasonic treatment for 20 minutes, homogenizing for 6 times under high pressure, and filtering with a 0.24 mu m filter membrane. The preparation method of the stable skin care composition comprises heating water phase and oil phase to 80deg.C respectively, mixing, homogenizing, cooling to 50deg.C, adding antiseptic, cooling to 35deg.C, and discharging.

Comparative example 1

The specific embodiment of the skin care composition is the same as that of example 1, and the skin care composition comprises 50g of polyglycerol esters, 25g of sucrose esters, 12g of silanized polysucrose esters, 18g of nanostructured lipid-sucrose polyglycerol carriers, 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 ethylhexyl glycerol. During the preparation, cyclodextrin-polyglycerol sucrose hybrid ester is not added.

Comparative example 2

The specific embodiment of the skin care composition is the same as that of example 1, and the skin care composition comprises the following raw materials of 50g of polyglycerol esters, 25g of sucrose esters, 18g of cyclodextrin-polyglycerol sucrose hybrid ester, 18g of nano structured lipid-sucrose polyglycerol carrier, 65g of caprylic/capric triglyceride, 30g of jojoba seed oil, 12g of phytosterol, 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 ethylhexyl glycerol. The silanized polysucrose ester is not added in the preparation process.

Comparative example 3

The specific embodiment of the skin care composition is the same as that of example 1, and the skin care composition comprises 50g of polyglycerol esters, 25g of sucrose esters, 18g of cyclodextrin-polyglycerol sucrose hybrid ester, 12g of silanized polysucrose esters, 65g of caprylic/capric triglyceride, 30g of jojoba seed oil, 12g of phytosterols, 25g of squalene, 500g of deionized water, 40g of trehalose, 1, 3-butanediol 55g, 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 ethylhexyl glycerol. The nanostructured lipid-sucrose polyglycerol carrier is not added in the preparation process.

Performance testing

The stable skin care compositions prepared in examples 1-3 and comparative examples 1-3 above were tested for performance according to the following procedure:

Samples of the skin care compositions prepared in examples 1 to 3 and comparative examples 1 to 3 were equilibrated at 25 ℃ and 60% humidity for 24 hours, and each performance test was performed. Stability test Using LUMiSizer mL of the sample was placed in a 2mm thick cell and centrifuged at 4000rpm for 30 minutes at 25℃with light transmittance data collected every 10 seconds, and the instability index was calculated by software. Particle size and distribution testing using Malvern Zetasizer Nano ZS90,90 laser particle sizer, samples were diluted 100 times with deionized water and placed in a sample cell, equilibrated at 25 ℃ for 2 minutes, and measured, and averaged 3 times repeatedly. The Zeta potential test uses the same instrument and uses a folded capillary sample cell to measure 3 times and average. Rheological property test adopts HAAKE MARS rheometer, using 35mm diameter cone-plate system, cone angle 1 degree, gap 0.105mm, amplitude scanning at 25deg.C to determine linear viscoelastic region, and frequency scanning at 0.1-10 Hz. The moisture retention performance test adopts a Corneometer CM825 probe, a 3X 3CM test area is defined on the inner side of the forearm of a volunteer under the conditions of the temperature of 22 ℃ and the humidity of 50%, an initial value is measured after cleaning, moisture content changes after 1 hour, 4 hours and 8 hours are respectively measured after 2mg/CM ² samples are uniformly smeared, and the average value is obtained for 6 volunteers in each group. The oxidation resistance test adopts a DPPH free radical elimination method, 0.1g of sample is accurately weighed and dissolved in 10mL of ethanol, 2mL of 0.1mmol/L DPPH ethanol solution is added, the absorbance is measured at 517nm wavelength after light-shielding reaction for 30 minutes, and the elimination rate is calculated. Skin irritation test using Patch test, a Finn Chamber plaque tester was applied to the back of volunteers at normal skin, removed after 24 hours of closed contact, and scored by dermatologists at three time points of 0.5 hours, 24 hours, 48 hours according to international contact dermatitis study group criteria, 30 volunteers per group.

Performance test results:

TABLE 1 Performance test results for examples and comparative examples

As can be seen from table 1, the analysis results show that, compared with comparative examples 1-3, examples 1-3 have significantly improved stability, skin feel and active ingredient efficacy, and successfully solve the technical problems of insufficient stability, sticky skin feel and low active ingredient permeability of the existing polyglyceryl ester and sucrose ester compound system. Specifically, examples 1-3 have an instability index less than or equal to 0.15, while comparative examples 1-3 are as high as 0.38 or more, which directly demonstrates that the synergistic effect of the cyclodextrin-polyglycerin sucrose hybrid ester, the silylated polysucrose ester and the nanostructured lipid-sucrose polyglycerol carrier greatly enhances the physical stability of the system, effectively inhibiting phase separation and particle aggregation. The average particle size of examples 1-3 was controlled to be about 130nm and distributed uniformly, while the particle sizes of comparative examples 1-3 were all over 215nm and distributed widely, the nanoscale fine structure significantly improved the skin feel of the product, and the problems of stickiness and heavy weight caused by the oversized particle size of the conventional formulation were avoided. In the aspect of moisture retention, the moisture retention rate of the examples 1-3 after 8 hours is still kept above 21 percent, which is far higher than that of the comparative examples 1-3 by 10.2% -12.6%, which benefits from the efficient entrapment and slow release of the active ingredients by the nano-carrier, and obviously improves the skin permeability and action durability of the functional ingredients such as quercetin. In addition, the DPPH radical scavenging rate of examples 1-3 is as high as about 85%, while comparative examples 1-3 are only about 60-65%, demonstrating that the complete compounded system can more effectively protect the active ingredients and exert antioxidant effect. Finally, examples 1-3 have very low skin irritation scores of 0.3 and below, well below 0.8-1.1 for comparative examples 1-3, indicating good biocompatibility and mildness of the system. In conclusion, the invention optimizes the system structure from the molecular level through three specially designed modified compounds, and thoroughly solves the three technical bottlenecks of insufficient stability, sticky skin feel and low active ingredient permeability.

The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.

Claims (10)

1. The stable skin care composition based on the polyglycerol ester and sucrose ester compound system is characterized by comprising the following raw materials in parts by weight:

20-80 parts by weight of polyglycerol esters;

10-40 parts by weight of sucrose esters;

5-30 parts by weight of cyclodextrin-polyglycerol sucrose hybrid ester;

3-20 parts by weight of silanized polysucrose ester;

5-30 parts by weight of a nanostructured lipid-sucrose polyglycerol carrier;

30-100 parts by weight of caprylic/capric triglyceride;

10-50 parts of jojoba seed oil;

5-20 parts by weight of phytosterol;

10-40 parts by weight of squalene;

200-800 parts of deionized water;

20-60 parts of trehalose;

30-80 parts by weight of 1, 3-butanediol;

1-10 parts by weight of quercetin;

1-5 parts by weight of vitamin E acetate;

0.5-3 parts by weight of sodium hyaluronate;

1-5 parts by weight of xanthan gum;

0.5-3 parts by weight of gellan gum;

2-6 parts by weight of p-hydroxyacetophenone;

1-3 parts by weight of ethylhexyl glycerol;

The preparation method of the cyclodextrin-polyglycerol sucrose hybrid ester comprises the steps of A1, dissolving beta-cyclodextrin in anhydrous dimethyl sulfoxide under the protection of nitrogen, stirring until the beta-cyclodextrin is completely dissolved, then adding polyglycerol-3 and sucrose monostearate, heating a reaction system to 80-85 ℃, adding p-toluenesulfonic acid and molecular sieve 4A for reaction, cooling the mixture to room temperature after the reaction is finished, adding saturated sodium bicarbonate solution, precipitating with deionized water, and finally purifying by column chromatography.

2. The stable skin care composition according to claim 1, wherein in step A1, p-toluene sulfonic acid and molecular sieve 4A are added for a reaction time of 6 to 8 hours.

3. The stable skin care composition according to claim 1, wherein in step A2, the eluent for column chromatography purification is chloroform/methanol=10:1.

4. The stable skin care composition according to claim 1, wherein the preparation method of the silanized polysucrose ester comprises the steps of dissolving sucrose distearate and aminopropyl polydimethylsiloxane in toluene to form a solution, adding a tetraisopropyl titanate catalyst under the protection of nitrogen, heating to 90-95 ℃, then dropwise adding a toluene solution containing vinyl polyglycerol ether for reaction, cooling the mixture to 58-62 ℃ after the reaction is completed, adding active carbon for stirring, filtering, rotationally evaporating to obtain a light yellow viscous liquid, and finally purifying by molecular distillation.

5. The stable skin care composition according to claim 4, wherein in step B1, the toluene solution of the vinyl-containing polyglyceryl ether is added dropwise for a reaction time of 8 to 10 hours.

6. The stable skin care composition according to claim 4, wherein in the step B2, the activated carbon is added for 30 to 40 minutes after the completion of the reaction, and the temperature for molecular distillation purification is 180 to 200 ℃.

7. The stable skin care composition of claim 1, wherein the method of preparing the nanostructured lipid-sucrose polyglycerol carrier comprises:

C1, dissolving decaglycerol decastearate, sucrose cocoate and hydrogenated lecithin in a chloroform/methanol mixed solvent, then adding flavonoid compounds, and performing rotary evaporation to form a lipid film;

Adding 58-62 ℃ phosphate buffer solution for hydration, and simultaneously carrying out ultrasonic treatment on the probe;

and C3, finally filtering through a microporous filter membrane.

8. The stable skin care composition of claim 7, wherein in step C1, the flavonoid compound is quercetin.

9. The stable skin care composition according to claim 7, wherein in step C2, the time of the ultrasonic treatment is 15 to 20 minutes and the number of cycles of the high pressure homogenizer is 4 to 6.

10. The stable skin care composition according to claim 7, wherein in step C3, the pore size of the microporous filter membrane is from 0.22 to 0.24 μm.