Preparation and application of a red camellia oil gel bead composition for stabilizing cosmetic active ingredients

Abstract

This invention relates to the preparation and application of a camellia oil bead composition for stabilizing cosmetic active ingredients, belonging to the field of cosmetic technology. The invention unexpectedly discovered that a specific ratio of polyphenols and flavonoids can improve the hardness of oil beads. Polyphenols and flavonoids are rich in phenolic hydroxyl groups, which, at a specific ratio, can form a dense hydrogen bond and π-π stacked composite film at the oil-water interface, enhancing the mechanical strength and shear resistance of the interfacial film and significantly improving the hardness of the oil beads. Based on this, the invention optimizes the extraction process to prepare a water-soluble camellia flower and leaf extract with a specific polyphenol to flavonoid ratio, improving the hardness of the oil beads and thus enhancing the stability of the cosmetic active ingredients. Furthermore, the preparation process of the camellia oil bead composition is optimized by using anionic surfactants to treat the oil beads, enriching and locking the endogenous ionizable lipids within the oil beads at the interface, generating a continuous electrostatic repulsion effect that can prevent bead aggregation and merging for a long time, maintaining stable dispersion of the system.

Description

Technical Field

[0001] This invention belongs to the field of cosmetic technology and relates to the preparation and application of a red camellia oil gel bead composition that stabilizes cosmetic active ingredients. Background Technology

[0002] The stability of cosmetic ingredients is a core foundation for ensuring product efficacy, safety, and shelf life, directly determining whether active ingredients can maintain their effective structure and activity throughout the entire lifecycle of production, storage, transportation, and use. Currently, the mainstream technologies for improving the stability of cosmetic ingredients include: 1. Molecular modification and compounding coordination technologies, such as the formulation of sodium ascorbate phosphate from vitamin C, and the modification of vitamin C into VC-IP; 2. Formulation system stabilization technologies, such as nanoemulsification and multiple emulsification technologies; 3. Nanoencapsulation and carrier technologies, such as liposome technology, molecular inclusion technology, microencapsulation technology, and oil droplet encapsulation technology. The first method has specific requirements for the active substances and a narrower application range. The second method, which disperses components containing active substances into tiny droplets through high-energy input, often struggles to precisely control droplet size, resulting in uneven and uncontrollable particle size distribution in the prepared emulsion. This not only results in poor batch repeatability but also easily leads to problems such as product separation, demulsification, or sedimentation, seriously affecting product quality and long-term storage. To maintain the stability of traditional emulsions, a high amount of chemical emulsifiers is usually required. Some traditional synthetic emulsifiers may pose a risk of skin irritation and also have problems such as low biodegradability and significant environmental risks. The third type has a stable encapsulation structure, which has a significant effect on improving the stability of active ingredients, the release of active ingredients, and enhancing penetration. The simpler encapsulation structure can reduce skin irritation and has become the mainstream solution. However, how to maintain the stability of the encapsulation structure has always been a challenge.

[0003] Patent CN117122539A discloses a method for preparing camellia oil beads, but does not further study the impact of process and formulation on the firmness and dispersibility of the oil beads. Patent CN 119523847A uses dextrin palmitate and long-chain fatty alcohol as excipients and curing agents for oil beads, but does not conduct relevant firmness tests, and such ingredients can give the oil beads a greasy, heavy, and unpleasant skin feel. Patent CN119074569A discloses an oil bead composed of oil-soluble active ingredients, castor oil / IPDI copolymer and / or hydrogenated castor oil / sebacic acid copolymer, and oils. It mentions the protective effect on the active ingredients, but the oils are common base oils in cosmetics, and their protective effect is limited. It also only mentions increasing the viscosity of the aqueous phase with acrylate copolymers and xanthan gum to suspend the oil beads and thus ensure their stability, without changing the firmness of the oil beads themselves, which limits its application range. Chinese patent application CN 122056817A improves system stability by adding relevant nonionic polyglycerol fatty acid esters to the formulation to adjust the interfacial tension between oil droplets and the aqueous phase, but this changes the component ratio inside the oil droplets, thus limiting its application range.

[0004] Therefore, improving the firmness of oil beads and preventing their aggregation or sedimentation, thereby enhancing the stability of cosmetic ingredients, is a pressing technical problem that needs to be solved in this field. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a method for preparing and applying a stable composition of camellia oil beads containing active cosmetic ingredients. This invention unexpectedly discovered that a specific ratio of polyphenols and flavonoids can improve the hardness of the oil beads. Specifically, polyphenols and flavonoids are rich in phenolic hydroxyl groups, which, at a specific ratio, can form a dense hydrogen bond and π-π stacked composite film at the oil-water interface, enhancing the mechanical strength and shear resistance of the interfacial film, reducing breakage caused by external impact, and significantly improving the hardness of the oil beads. Based on this, this invention optimizes the extraction process to prepare a water-soluble camellia flower and leaf extract with a specific polyphenol to flavonoid ratio, and controls the amount of the water-soluble camellia flower and leaf extract to improve the hardness of the oil beads, thereby extending the shelf life of the oil beads and improving the stability of the active cosmetic ingredients. Furthermore, the present invention optimizes the preparation process of the camellia oil bead composition by using anionic surfactants to treat the oil beads, thereby introducing and enriching the endogenous ionizable lipids of the oil beads and locking them at the interface, so that the surface of the beads forms a stable charged surface layer, which can generate a continuous electrostatic repulsion effect, counteract van der Waals attraction, and prevent the beads from aggregating and merging for a long time, thus maintaining the stable dispersion of the system.

[0006] The objective of this invention can be achieved through the following methods: In a first aspect, the present invention provides a camellia oil gel bead composition, the camellia oil gel bead composition comprising camellia oil gel beads and a camellia extract dispersion in a mass ratio of 1-4:1-10; wherein, the camellia oil gel beads comprise: 5-35 parts of oil-soluble camellia extract, 1-10 parts of cosmetic active ingredients, 50-85 parts of synthetic oil, and 5-15 parts of oil-phase thickener; the camellia extract dispersion comprises: 1-10 parts of water-soluble camellia flower and leaf extract, 1-5 parts of water-phase thickener, and 70-97 parts of water, wherein the mass ratio of polyphenols to flavonoids in the water-soluble camellia flower and leaf extract is 1-3:2-4.

[0007] As one embodiment of the present invention, the preparation method of the oil-soluble camellia extract, referring to Chinese patent application CN109157454A, includes the following steps: A1. After crushing and sieving the red camellia seeds, mix them with an anti-coagulant, add activated clay, perform supercritical extraction, and then perform two-stage separation. A2. The initial extract obtained in step A1 is purified to obtain the supercritical extract of red camellia seed. A3. Mix red camellia flowers and red camellia leaves, crush and sieve them, then perform supercritical extraction, followed by two-stage separation. A4. The initial extract obtained in step A3 is purified and filtered to obtain the supercritical extract of red camellia leaves and red camellia leaf residue. A5. Add enzyme preparation and alcohol solvent to the red camellia flower leaf residue obtained by the method described in step A4 and stir to react, to obtain the enzymatic hydrolysis alcohol extract of red camellia flower leaf residue; A6. After coarsely filtering the enzymatic hydrolysis alcohol extract of red camellia flower leaf residue, the filtrate is concentrated under vacuum to obtain an extract. A7. The extract is reconstituted and then refined to obtain the red camellia flower and leaf residue extract. A8. Mix the supercritical extract of red camellia seeds, the supercritical extract of red camellia flowers and leaves, and the extract of red camellia flower and leaf residue to obtain the oil-soluble red camellia composite extract.

[0008] In one embodiment of the present invention, in step A1, the extraction pressure of the supercritical extraction is 15-30 MPa.

[0009] As one embodiment of the present invention, in step A3, the red camellia flower and leaves include red camellia flowers and red camellia leaves in a mass ratio of 1:1-4.

[0010] In one embodiment of the present invention, in step A5, the enzyme preparation comprises: pectinase at a weight of 0.1-0.5‰ of the camellia flower and leaf residue, cellulase at a weight of 1-5‰ of the camellia flower and leaf residue, and amylase at a weight of 1-5‰ of the camellia flower and leaf residue; the amount of solvent added is 15-20 times the weight of the camellia flower and leaf residue; the conditions for the stirring reaction are: reaction temperature 40-50℃, reaction time 30-60 min, and stirring speed 100-200 rpm / min.

[0011] In one embodiment of the present invention, in step A6, the temperature of vacuum concentration is 50-55°C, and the concentration is carried out to 1 / 12 to 1 / 16 of the volume of the filtrate.

[0012] As one embodiment of the present invention, in step A7, the components used for resolution are anhydrous ethanol and hydrogenated castor oil; the mass percentage of each component in the solution obtained by resolution is as follows: extract 1-5%, anhydrous ethanol 50-70%, hydrogenated castor oil 50-70%; the refining process includes ceramic membrane filtration and ultrafiltration membrane filtration.

[0013] As one embodiment of the present invention, the cosmetic active ingredient is selected from one or more of coenzyme Q10, retinol and its derivatives, hexylresorcinol, paeonol, α-arbutin, nicotinamide, Dalbergia odorifera bark extract, tocopheryl acetate, glycyrrhizin, bioactive enzymes, and acids; wherein the bioactive enzyme is selected from at least one of papain and bromelain, the acid is selected from at least one of mandelic acid and salicylic acid, and the retinol derivative includes hydroxypinazone retinate.

[0014] As one embodiment of the present invention, the synthetic oil is selected from one or more of caprylic / capric triglyceride, coconut oil alcohol-caprylic / capric ester, triglyceride (ethylhexanoate), squalane, and isononyl isononanoate. Preferably, it is triglyceride (ethylhexanoate), or a mixture of triglyceride (ethylhexanoate) and caprylic / capric triglyceride in a mass ratio of 10:1.

[0015] In one embodiment of the present invention, the oil-phase thickener is selected from one or more of castor oil / IPDI copolymer, hydrogenated castor oil / sebacic acid copolymer, HDI / trimethylolcaprolactone crosslinking polymer, and hydrogenated C6-20 polyolefin. Preferably, it is castor oil / IPDI copolymer, or a mixture of castor oil / IPDI copolymer, HDI / trimethylolcaprolactone crosslinking polymer, and hydrogenated C6-20 polyolefin in a mass ratio of 30:1:5.

[0016] As one embodiment of the present invention, the aqueous thickener is selected from at least one of carbomer, acrylate / C10-30 alkanol acrylate crosspolymer, and xanthan gum.

[0017] As one embodiment of the present invention, the preparation method of the water-soluble camellia flower and leaf extract, referring to Chinese patent application CN115252489A, includes the following steps: B1. Mix the red camellia tea powder and red camellia flower powder evenly, and perform supercritical CO2 extraction. After the extraction is completed, take out the red camellia flower powder. B2. Add an alcohol solution to the red camellia leaf powder obtained by extraction in step B1, and then sonicate. B3. After ultrasonic treatment, cellulase was added to the solution for extraction, and the solution was filtered to obtain crude extract of red camellia flower and leaf. B4. The filtrate obtained from step B3 by ultrafiltration membrane filtration is then purified by adsorption with macroporous resin to obtain the water-soluble camellia flower and leaf extract.

[0018] This invention optimizes the extraction process to maintain the mass ratio of polyphenols to flavonoids in the water-soluble camellia flower and leaf extract within a specific range. Polyphenols and flavonoids synergistically strengthen the bead shell structure through hydrogen bonding, π-π stacking, and interfacial crosslinking. Within this specific range, stable synergy between interfacial adsorption, crosslinking, and membrane strength is maintained. When the ratio is 1:1, the interfacial composite membrane achieves the optimal balance of density, rigidity, and toughness, resulting in the best hardness. If the ratio is too low (too few polyphenols), insufficient interfacial crosslinking leads to a softer membrane structure and insufficient mechanical strength; if the ratio is too high (too many polyphenols), excessive crosslinking can cause shell embrittlement, making it prone to breakage under external force.

[0019] Furthermore, this invention preferably uses a water-soluble camellia flower and leaf extract within a specific range. If the amount is too low, the interfacial coating is incomplete, resulting in a weak membrane structure and insufficient strength; if the amount is too high, excessive accumulation at the interface will disrupt the membrane's uniformity, causing internal stress, embrittlement, or softening of the shell layer, thus reducing mechanical strength and fracture resistance. Therefore, only within a suitable range can the optimal balance between interfacial stability and structural strength be achieved.

[0020] In one embodiment of the present invention, in step B1, the mass ratio of red mountain tea powder to red mountain camellia flower powder is 10:1-1:10; in the supercritical CO2 extraction, the extraction pressure is 10MPa-30MPa, the extraction temperature is 35℃-50℃, and the extraction time is 30min-2h.

[0021] In one embodiment of the present invention, in step B2, the alcohol solution is an aqueous solution of ethanol with an ethanol content of 10%-90%, and the amount of the aqueous solution of ethanol is 10-20 times the mass of the red camellia flower leaf powder; the temperature of the ultrasonic treatment is controlled below 40°C, the ultrasonic time is 10-60 min, and the ultrasonic power is 500W-3000W.

[0022] In one embodiment of the present invention, in step B3, the cellulase extraction temperature is controlled at 40℃-70℃, and the extraction is carried out by stirring for 1h-4h; the amount of cellulase used is 0.2-2% of the mass of the red camellia flower and leaf powder.

[0023] In one embodiment of the present invention, in step B4, the molecular weight cutoff of the ultrafiltration membrane is 500-3500.

[0024] In one embodiment of the present invention, step B4, the adsorption purification includes the following steps: B4.1. Pass 0.5-3 BV of camellia flower and leaf extract through a macroporous resin adsorption column at a rate of 0.5-3 BV / h; BV refers to the bed volume of the macroporous resin. B4.2. Rinse the macroporous resin adsorption column with water at a rate of 1-3 BV / h until the effluent is colorless. B4.3. Elute the macroporous resin column with a 2-5 BV ethanol solution at a flow rate of 0.5-3 BV / h. The ethanol content in the ethanol solution should be 30%-90%. Recover the eluent and concentrate it to 1 / 4-1 / 10 of its mass. B4.4 Add a mixture of water and polyol, which is 1-2 times its mass, to the concentrate. The polyol in the mixture is 0.1%-65% by mass, and the remainder is water; then filter.

[0025] Secondly, the present invention provides a method for preparing the aforementioned camellia oil granule composition, comprising the following steps: S1. Preparation of Camellia Oil Solution: S1.1 Add oil phase thickener to synthetic fat and stir to obtain oil phase 1; S1.2 After cooling the oil phase 1, add the oil-soluble red camellia extract and stir to obtain the oil phase 2; S1.3 Add cosmetic active ingredients to oil phase 2 and stir to obtain red camellia oil phase, which is the red camellia oil solution; S2. Preparation of red camellia extract dispersion: S2.1 Add an aqueous thickener to water and stir to obtain aqueous phase 1; S2.2 After cooling the aqueous phase 1, add the water-soluble red camellia flower and leaf extract and stir to obtain a red camellia extract dispersion; S3, Aqueous Phase Preparation: An anionic surfactant, polyvinyl alcohol, and water are mixed to obtain an aqueous phase; Preparation of S4, Red Camellia Oil Beads Composition: Camellia oil solution was introduced into a microfluidic inner phase channel, and aqueous phase was introduced into a microfluidic outer phase channel. The flowing camellia oil solution was sheared, and after washing and filtration to remove the aqueous phase, camellia oil beads were obtained. Camellia oil beads were then uniformly mixed with camellia extract dispersion to obtain camellia oil bead composition.

[0026] In one embodiment of the present invention, in step S1.1, the stirring temperature is 110-120℃, the stirring speed is 600-650rpm, and the stirring time is 60-80min.

[0027] In one embodiment of the present invention, in step S1.2, the temperature is lowered to 75-85°C.

[0028] In one embodiment of the present invention, in step S1.2, the stirring speed is 300-350 rpm and the time is 20-25 min.

[0029] In one embodiment of the present invention, in step S1.3, the stirring speed is 200-300 rpm and the time is 3-5 min.

[0030] In one embodiment of the present invention, in step S2.1, the stirring temperature is 90-100℃, the stirring speed is 800-900rpm, and the stirring time is 100-120min.

[0031] In one embodiment of the present invention, in step S2.2, the temperature is lowered to 15-25°C.

[0032] In one embodiment of the present invention, in step S2.2, the stirring speed is 200-300 rpm and the time is 10-20 min.

[0033] In one embodiment of the present invention, in step S3, the aqueous phase comprises the following raw materials by mass fraction: 2%-20% anionic surfactant, 2-8% polyvinyl alcohol, and 75%-93% water. Preferably, the mass fraction of the anionic surfactant is 2%-10%.

[0034] Furthermore, the anionic surfactant is selected from one or more of sodium lauryl ether sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, sodium α-alkenyl sulfonate, sodium / potassium cocoyl glycinate, sodium lauroyl glutamate, sodium cocoyl sarcosinate, sodium methyl lauroyl taurate, sodium cocoyl malic acid, sodium lauroyl lactylate, and disodium dilauryl sulfosuccinate.

[0035] As one embodiment of the present invention, in step S4, the temperature at which the camellia oil solution is introduced into the microfluidic inner phase channel is 75-90°C, and the temperature at which the camellia extract dispersion is introduced into the microfluidic outer phase channel is 18-35°C.

[0036] In one embodiment of the present invention, in step S4, the flow rate ratio of the aqueous phase to the camellia oil solution is 15-30:1, and the diameter of the camellia oil droplets after shearing is 0.3-1.5 mm.

[0037] Thirdly, the present invention provides the application of the aforementioned camellia oil bead composition in the preparation of formulations for improving the stability of active ingredients in cosmetics.

[0038] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention unexpectedly discovered that a specific ratio of polyphenols to flavonoids can improve the hardness of oil beads. Specifically, polyphenols and flavonoids significantly enhance the hardness of oil beads through synergistic effects of interface strengthening, cross-linking protection, and antioxidant properties. Both are rich in phenolic hydroxyl groups, which can form dense hydrogen bonds and π-π stacked composite films at the oil-water interface, enhancing the mechanical strength and shear resistance of the interfacial film and reducing breakage caused by external impacts. Simultaneously, polyphenols can undergo oxidative cross-linking with the shell polymer, and flavonoids can form non-covalent complexes with polysaccharides / proteins, further improving the film's density and hardness. Furthermore, both synergistically scavenge free radicals, chelate metal ions, inhibit the oxidative degradation of the shell material, and prevent membrane embrittlement and breakage, comprehensively improving the structural stability and robustness of oil beads from both short-term impact resistance and long-term anti-aging perspectives. Based on this, this invention optimizes the extraction process to prepare a water-soluble camellia flower and leaf extract with a specific polyphenol to flavonoid ratio, and controls the amount of the water-soluble camellia flower and leaf extract to improve the hardness of the oil beads, thereby extending the shelf life of the oil beads and the stability of the active ingredients in cosmetics.

[0039] 2. This invention discovers that fatty acids and antioxidants in oil-soluble camellia extract can effectively protect the activity of cosmetic active ingredients. Furthermore, the hardness and release rate of the beads can be controlled by the oil phase thickener, and the active ingredients can be physically isolated and chemically stabilized in the microenvironment within the oil beads, thereby improving the stability and shelf life of cosmetic active ingredients.

[0040] 3. This invention uses a method of encapsulating active ingredients in red camellia oil beads and using red camellia extract dispersion to improve the firmness of the oil beads, which solves the problem that active ingredients in cosmetics are easily deactivated and precipitated by the external environment, and achieves the effect of extending the shelf life of active ingredients.

[0041] 4. This invention also optimizes the preparation process of the camellia oil bead composition by using anionic surfactants to treat the oil beads before washing them away. This process enriches and locks the endogenous ionizable lipids of the oil beads at the interface, allowing the bead surface to form a stable charged surface layer. This generates a continuous electrostatic repulsion effect, counteracting van der Waals forces and preventing bead aggregation and coalescence for a long period, thus maintaining stable dispersion of the system. Attached Figure Description

[0042] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings: Figure 1 The results are from simulated transport tests of the compositions in Examples 1-8 and Comparative Examples 3-4. Figure 2 The results of simulated transport tests on the composition samples of Example 2 and Comparative Example 5 are shown. Figure 3 The results are from simulated transport tests of the composition samples in Comparative Examples 6-9. Detailed Implementation

[0043] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. The following examples are implemented under the premise of the technical solution of the present invention, providing detailed implementation methods and specific operating procedures, which will help those skilled in the art to further understand the present invention. It should be noted that the scope of protection of the present invention is not limited to the following embodiments; any adjustments and improvements made under the concept of the present invention are all within the scope of protection of the present invention.

[0044] Raw materials used in the embodiments and comparative examples of this invention: The oil-soluble red camellia extract was prepared according to Example 1 in patent application CN109157454A; The water-soluble camellia flower and leaf extract 1 was prepared according to Example 1 in patent application CN115252489A; wherein the polyphenol content was 3195.5 ppm and the flavonoid content was 4344.1 ppm; Water-soluble red camellia flower and leaf extract 2 refers to the red camellia flower extract in Example 1 of patent application CN117122539A; wherein the polyphenol content is 1027.8ppm and the flavonoid content is 6287.5ppm.

[0045] The synthetic oil is: triglyceride (ethylhexanoate); The oil phase thickener is: castor oil / IPDI copolymer; The aqueous thickener is carbomer. Examples 1-8 Examples 1-8 describe the preparation of camellia oil beads according to the raw materials and parts by weight in Table 1, specifically including the following steps: S1. Preparation of Camellia Oil Solution: S1.1 Add oil phase thickener to synthetic grease and stir (120℃, 650rpm, 80min) to obtain oil phase 1; S1.2 Cool oil phase 1 to 85℃, add oil-soluble red camellia extract, and stir (350 rpm, 25 min) to obtain oil phase 2; S1.3 Add the cosmetic active ingredients to the oil phase 2 and stir (300 rpm, 5 min) to obtain the red camellia oil phase, which is the red camellia oil solution. S2. Preparation of red camellia extract dispersion: S2.1 Add an aqueous thickener to water and stir (100℃, 900rpm, 120min) to obtain aqueous phase 1; S2.2 Cool the aqueous phase 1 to 25°C, add the water-soluble red camellia flower and leaf extract, and stir (300 rpm, 20 min) to obtain a red camellia extract dispersion; S3, Aqueous Phase Preparation: An anionic surfactant (sodium lauryl sulfate), polyvinyl alcohol, and water are mixed to obtain an aqueous phase; wherein the aqueous phase comprises: 10% sodium lauryl sulfate, 5% polyvinyl alcohol, and 85% water.

[0046] Preparation of S4, Red Camellia Oil Beads Composition: A 90°C camellia oil solution was introduced into a microfluidic inner phase channel, while an aqueous phase was introduced into a microfluidic outer phase channel. The flowing camellia oil solution was sheared (flow rate ratio 30:1), and after washing and filtration to remove the aqueous phase, camellia oil beads were obtained. The camellia oil beads were then uniformly mixed with a 25°C camellia extract dispersion to obtain a camellia oil bead composition. The mass ratio of the camellia oil beads to the camellia extract dispersion was 1:1.

[0047] Table 1

[0048] Comparative Examples 1-5 Comparative Examples 1-5 were prepared according to the raw materials and weight parts in Table 2, and with reference to the preparation methods in the examples, to obtain camellia oil granule composition samples.

[0049] Table 2

[0050] Comparative Example 6 The raw materials and weight parts of the comparative example red camellia oil beads composition are the same as those in Example 2. The main difference in the preparation method is that the shearing operation in steps S3 and S4 is omitted. Specifically: S1. Preparation of Camellia Oil Solution: S1.1 Add oil phase thickener to synthetic grease and stir (120℃, 650rpm, 80min) to obtain oil phase 1; S1.2 Cool oil phase 1 to 85℃, add oil-soluble red camellia extract, and stir (350 rpm, 25 min) to obtain oil phase 2; S1.3 Add the cosmetic active ingredients to the oil phase 2 and stir (300 rpm, 5 min) to obtain the red camellia oil phase, which is the red camellia oil solution. S2. Preparation of red camellia extract dispersion: S2.1 Add an aqueous thickener to water and stir (100℃, 900rpm, 120min) to obtain aqueous phase 1; S2.2 Cool the aqueous phase 1 to 25°C, add the water-soluble red camellia flower and leaf extract, and stir (300 rpm, 20 min) to obtain a red camellia extract dispersion; Preparation of S3 and Camellia Oil Beads: A 90°C camellia oil solution was passed through a microfluidic internal phase channel, and after washing and filtration to remove the aqueous phase, camellia oil beads were obtained. The camellia oil beads were then uniformly mixed with a 25°C camellia extract dispersion to obtain a camellia oil bead composition. The mass ratio of the camellia oil beads to the camellia extract dispersion was 1:1.

[0051] Comparative Example 7 The raw materials and weight parts of the comparative example red camellia oil granule composition are the same as those in Example 2. The main difference in the preparation method is that the mass fraction of sodium lauryl sulfate in the aqueous phase of step S3 is adjusted to 1%.

[0052] Comparative Example 8 The raw materials and weight parts of the comparative example red camellia oil granule composition are the same as those in Example 2. The main difference in the preparation method is that the mass fraction of sodium lauryl sulfate in the aqueous phase of step S3 is adjusted to 25%.

[0053] Comparative Example 9 The raw materials and weight parts of the comparative example red camellia oil beads composition are the same as those in Example 2. The main difference in the preparation method is that sodium lauryl sulfate in the aqueous phase of step S3 is replaced with a cationic surfactant (hexadecyltrimethylammonium chloride).

[0054] Comparative Example 10 The raw materials and weight parts of the comparative example camellia oil beads composition are the same as those in Example 2. The main difference in the preparation method is that the camellia oil phase is homogeneously added to the camellia extract dispersion to form an emulsion, and the camellia oil beads composition is not formed by microfluidics.

[0055] Test Example 1: Hardness Test of Red Camellia Oil Beads 1. Test method: Simulated transportation 1.1 Sample Preparation: Prepare a transparent essence base material, mix the camellia oil granule composition and transparent base material in a 1:1 ratio, and fill it into 120mL finished product bottles. Conduct a simulated transportation test with 6 bottles per box. Observe the sample status every 2 hours.

[0056] 1.2 Equipment parameters: Model of simulated transportation equipment - HD-A521 (Haida International Equipment Co., Ltd.), amplitude 210rpm.

[0057] 2. Judgment Criteria: Pass: Camellia oil beads are intact, the material is transparent and clear, and the oil beads are homogeneously dispersed in the system without aggregation or adhesion. Fail: Camellia oil beads are broken, the material is noticeably cloudy, the oil beads are not homogeneously dispersed in the system, and the oil beads aggregate or adhere. The simulated 8-hour transportation test passed and met the internal control standards for finished products.

[0058] 3. Experimental conclusions: Table 3. Simulated transport test results in serum for Examples 1-8 and Comparative Examples 3-9 (0-14h)

[0059] The results are shown in Table 3. The camellia oil bead essence water (Examples 1-8) provided by this invention exhibited excellent stability under simulated transportation conditions: all sample examples remained in a qualified state during the simulated transportation period of 0h to 8h, with no breakage of the camellia oil beads, and the material was transparent and clear, meeting the internal control standards for finished products (qualified after 8h of simulated transportation). Extending the simulated transportation time to 10h, all sample examples still maintained a qualified state, with no bead breakage or turbidity observed. Further extending to 12h-14h, only some sample examples showed non-compliance (bead breakage, turbidity), with Examples 2 and 7 remaining qualified after 14h of simulated transportation, demonstrating optimal transportation stability.

[0060] Comparative examples 3 to 9 all failed to meet the 8-hour internal control standard. Comparative examples 3 and 9 failed after 2 hours, comparative example 4 failed after 4 hours, and comparative examples 5 to 8 all failed after 6 hours, indicating a significant deterioration in stability.

[0061] In summary, Examples 1-8 provided by this invention exhibit excellent anti-crack stability and material clarification in a simulated transportation environment, indicating that the oil beads have good hardness that meets marketable standards, effectively ensuring product quality during transportation, and are far superior to the comparative samples.

[0062] Depend on Figure 1 It can be seen that the materials in Examples 2 and 7 remained transparent and clear with no condensation breakage after 14 hours, making them the samples with the best stability. The remaining examples (1, 3, 4, 5, 6, 8) showed a small number of condensation breakages and slight turbidity after 14 hours, but were still significantly better than the comparative samples overall. The materials in Comparative Examples 3 and 4 showed condensation breakage, obvious turbidity, and unevenness, which contrasted sharply with the sample of the examples.

[0063] Depend on Figure 2It can be seen that, in Comparative Example 5, the material showed signs of oil bead rupture, obvious turbidity, and unevenness after 14 hours.

[0064] Depend on Figure 3 It can be seen that in Comparative Examples 6-8, the oil beads agglomerated, adhered, and were unevenly dispersed after 14 hours. In Comparative Example 9, the oil beads ruptured and the material became significantly turbid after 14 hours, indicating that using cationic surfactants to shear the oil beads would reduce their firmness.

[0065] Test Example 2: Active Ingredient Retention Rate Test Sample preparation: Take samples from Examples 1-5 and Comparative Examples 1-10, place them in light-proof bottles, and place them under RT, 48℃, and light conditions. Take samples at 0, 3, and 15 days to test the content of coenzyme Q10 in the samples.

[0066] Test method: Samples under each condition were placed in a centrifuge at 20,000 rpm for 15 minutes. The upper oil phase was collected, and the coenzyme Q10 content was determined by high-performance liquid chromatography (HPLC), and the retention rate was calculated.

[0067] Table 4. Retention rate of active ingredients in Examples 1-5 and Comparative Examples 1-10 (%) ± SD

[0068] The results are shown in Table 4. Examples 1-5 of the camellia oil granule compositions of this invention exhibited excellent activity stability under ambient temperature (RT), high temperature (48℃), and light conditions. The retention rates at 3 days and 7 days were significantly higher than those of the comparative samples, with Example 2 showing the best stability. Comparative samples 1-10 showed faster degradation and lower retention rates of the active ingredients under the same conditions, especially Comparative Sample 10, which exhibited the worst stability.

[0069] In terms of short-term stability (3 days): Examples 1-5 of this invention showed significantly higher retention rates of active ingredients than Comparative Examples 1-10 under normal temperature, 48°C, and light irradiation conditions. Example 2 showed the best performance, with retention rates of 93.28±0.36% (RT), 87.61±1.77% (48°C), and 86.32±1.54% (light irradiation) under various 3-day conditions, respectively. Comparative Example 10 showed the worst performance, with retention rates of only 44.75±4.28% (RT), 35.20±3.73% (48°C), and 48°C (light irradiation) under various 3-day conditions. ℃), 38.28±4.21% (light); In terms of long-term stability (15d): the retention rate of active ingredients in Examples 1-5 decreased gradually and remained at a high level. Example 2 still performed best, with retention rates of 88.84±1.32% (RT), 82.63±1.25% (48℃), and 83.17±0.97% (light) under various conditions at 15d. The active ingredients in Comparative Examples 1-10 degraded significantly, and the retention rate decreased sharply. The retention rate of Comparative Example 5 was less than 25% under various conditions at 15d.

[0070] In summary, based on the results of the simulated transportation, this composition can achieve continuous dispersion of oil beads by optimizing the preparation process of the camellia oil beads composition and combining the oil-soluble camellia extract and the water-soluble camellia flower and leaf extracts. At the same time, it provides multiple effects such as providing a good preservation solvent for the active ingredients and providing good hardness for the oil beads. The technical solution of this invention can effectively improve the activity retention rate of the active ingredients and significantly delay their degradation under normal temperature, high temperature and light conditions.

[0071] Test Example 3: Appearance Stability Test Test method: Refer to T / GDCQMA 002-2023 "Standard for Stability Testing of Cosmetics". High temperature test: Take 25 ml of each of the camellia oil beads composition described in Examples 1-8 and Comparative Examples 1-9 and place them in a sealed container. After storing at high temperature (48℃±2℃) for 3 months, observe the appearance and state of each composition. The results are shown in Table 3. Low temperature test: Take 25 ml of each of the compositions described in Examples 1-8 and Comparative Examples 1-9 and place them in a sealed container. After storing at low temperature (5℃±2℃) for 3 months, observe the appearance and state of each composition. The results are shown in Table 5.

[0072] Light exposure experiment: Take 25 ml of each of the compositions described in Examples 1-8 and Comparative Examples 1-9 and place them in a sealed container. After storage under light conditions (D65 light source) for 3 months, observe the appearance and state of each composition. The results are shown in Table 3.

[0073] Table 5

[0074] As shown in Table 5 above, after 90 days to 3 months of storage under normal temperature, high temperature (48℃±2℃), low temperature (5℃±2℃) and light conditions, the appearance of Examples 1-8 was completely consistent with the initial state (0d). The transparent red camellia oil beads were uniformly suspended, without cracks, turbidity, discoloration, layering, or odor, demonstrating excellent long-term storage stability.

[0075] After being stored under the same conditions, Comparative Examples 1-9 all exhibited varying degrees of stability degradation: Comparative Examples 1-2 only showed turbidity and discoloration; Comparative Examples 3-4 further showed stratification; Comparative Example 5 was also accompanied by obvious precipitation; Comparative Examples 6-8 showed obvious agglomeration and adhesion of oil beads; and Comparative Example 9 was also accompanied by the rupture of oil beads. The overall stability of the above comparative examples was significantly worse than that of the example samples.

[0076] In summary, the camellia oil bead composition of the present invention exhibits excellent long-term storage stability under various extreme environments, effectively maintaining the structural integrity and product appearance uniformity of the camellia oil beads, which is significantly better than the comparative sample, providing a reliable guarantee for extending the product's shelf life.

[0077] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A composition of red camellia oil beads, characterized in that, The camellia oil gel composition comprises camellia oil gels and a camellia extract dispersion in a mass ratio of 1-4:1-10; wherein, the camellia oil gels comprise: 5-35 parts of oil-soluble camellia extract, 1-10 parts of cosmetic active ingredients, 50-85 parts of synthetic oil, and 5-15 parts of oil phase thickener; the camellia extract dispersion comprises: 1-10 parts of water-soluble camellia flower and leaf extract, 1-5 parts of water phase thickener, and 70-97 parts of water, wherein the mass ratio of polyphenols to flavonoids in the water-soluble camellia flower and leaf extract is 1-3:2-4.

2. The camellia oil beads composition according to claim 1, characterized in that, The active ingredients of the cosmetic are selected from one or more of the following: coenzyme Q10, retinol and its derivatives, hexylresorcinol, paeonol, α-arbutin, nicotinamide, Dalbergia odorifera bark extract, tocopheryl acetate, glycyrrhizin, bioactive enzymes, and acids; wherein the bioactive enzymes are selected from at least one of papain and bromelain, the acids are selected from at least one of mandelic acid and salicylic acid, and the retinol derivatives include hydroxypinazone retinate.

3. The camellia oil beads composition according to claim 1, characterized in that, The synthetic oil is selected from one or more of the following: caprylic / capric triglyceride, coconut oil alcohol-caprylic / capric ester, triglyceride (ethylhexanoate), squalane, and isononyl isononanoate.

4. The camellia oil beads composition according to claim 1, characterized in that, The oil phase thickener is selected from one or more of the following: castor oil / IPDI copolymer, hydrogenated castor oil / sebacic acid copolymer, HDI / trimethylolcaprolactone crosspolymer, and hydrogenated C6-20 polyolefin.

5. The camellia oil bead composition according to claim 1, characterized in that, The aqueous thickener is selected from at least one of carbomer, acrylate / C10-30 alkanol acrylate crosspolymers, and xanthan gum.

6. The camellia oil bead composition according to claim 1, characterized in that, The preparation method of the water-soluble camellia flower and leaf extract includes the following steps: B1. Mix the red camellia tea powder and red camellia flower powder evenly, and perform supercritical CO2 extraction. After the extraction is completed, take out the red camellia flower powder. B2. Add an alcohol solution to the red camellia leaf powder obtained by extraction in step B1, and then sonicate. B3. After ultrasonic treatment, cellulase was added to the solution for extraction, and the solution was filtered to obtain crude extract of red camellia flower and leaf. B4. The filtrate obtained from step B3 by ultrafiltration membrane filtration is then purified by adsorption with macroporous resin to obtain the water-soluble camellia flower and leaf extract.

7. The camellia oil bead composition according to claim 6, characterized in that, It also includes at least one of the following technical features: In step B1, the mass ratio of red mountain tea powder to red mountain camellia flower powder is 10:1-1:10; in the supercritical CO2 extraction, the extraction pressure is 10MPa-30MPa, the extraction temperature is 35℃-50℃, and the extraction time is 30min-2h. In step B2, the alcohol solution is an aqueous solution of ethanol with an ethanol content of 10%-90%, and the amount of the aqueous solution of ethanol is 10-20 times the mass of the red camellia flower leaf powder; the temperature of the ultrasonic treatment is controlled below 40℃, the ultrasonic time is 10min-60min, and the ultrasonic power is 500W-3000W. In step B3, the cellulase extraction temperature is controlled at 40℃-70℃, and the extraction is carried out by stirring for 1h-4h; the amount of cellulase used is 0.2-2% of the mass of the red camellia flower and leaf powder. In step B4, the ultrafiltration membrane has a molecular weight cutoff of 500-3500.

8. A method for preparing the camellia oil bead composition as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Preparation of Camellia Oil Solution: S1.1 Add oil phase thickener to synthetic fat and stir to obtain oil phase 1; S1.2 After cooling the oil phase 1, add the oil-soluble red camellia extract and stir to obtain the oil phase 2; S1.3 Add cosmetic active ingredients to oil phase 2 and stir to obtain red camellia oil phase, which is the red camellia oil solution; S2. Preparation of red camellia extract dispersion: S2.1 Add an aqueous thickener to the water and stir to obtain aqueous phase 1; S2.2 After cooling the aqueous phase 1, add the water-soluble red camellia flower and leaf extract and stir to obtain a red camellia extract dispersion; S3, Aqueous Phase Preparation: An anionic surfactant, polyvinyl alcohol, and water are mixed to obtain an aqueous phase; Preparation of S4, Red Camellia Oil Beads Composition: Camellia oil solution was introduced into a microfluidic inner phase channel, and aqueous phase was introduced into a microfluidic outer phase channel. The flowing camellia oil solution was sheared, and after washing and filtration to remove the aqueous phase, camellia oil beads were obtained. Camellia oil beads were then uniformly mixed with camellia extract dispersion to obtain camellia oil bead composition.

9. The preparation method according to claim 8, characterized in that, In step S3, the aqueous phase comprises the following raw materials by mass fraction: 2%-20% anionic surfactant, 2-8% polyvinyl alcohol, and 75%-93% water; the anionic surfactant is selected from one or more of sodium lauryl ether sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, sodium α-alkenyl sulfonate, sodium / potassium cocoyl glycinate, sodium lauroyl glutamate, sodium cocoyl sarcosinate, sodium methyl lauroyl taurate, sodium cocoyl malic acid, sodium lauroyl lactylate, and disodium dilauryl sulfosuccinate.

10. The use of the camellia oil bead composition as described in any one of claims 1-7 in the preparation of formulations for improving the stability of active ingredients in cosmetics.

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