Oleogel composition with network structure as well as preparation method and application of oleogel composition

Abstract

The invention relates to an oil gel composition with a network structure as well as a preparation method and application thereof, and belongs to the technical field of cosmetics. According to the invention, the full-transparent oleogel composition with the network structure is obtained by selecting a specific component proportion and matching the specific components, and the oleogel composition can be used as a cosmetic raw material of a transparent system. In the oil gel composition disclosed by the invention, the active matter can enhance the network structure of the oil-dispersed polymer raw material, and the peony seed fermented oil is matched to enhance the space structure of the network structure, so that the active matter insoluble in water and oil can be applied to a transparent system; when the oleogel composition is applied to a transparent system, not only can the use amount of polymer raw materials of the transparent system be reduced, but also the oxidative rancidity of vegetable fat can be reduced, and the shelf life can be prolonged.

Description

Technical Field

[0001] This invention relates to the field of cosmetic technology, and in particular to an oleogel composition with a network structure, its preparation method, and its application. Background Technology

[0002] Peony callus extract is an active ingredient extracted from peony callus tissue. It includes various active components such as flavonoids, phenolic acids, terpenes, and tannins, primarily flavonoids, phenolic acids, and terpenes. These components possess soothing, anti-aging, and repairing effects, making them suitable for cosmetic applications. However, the active ingredients in peony callus extract are oil-insoluble and water-insoluble molecules, meaning they are neither completely water-soluble nor completely oil-soluble. Although these active molecules possess multiple hydrophilic and lipophilic groups, their strong hydrophobic framework prevents them from being effectively solubilized by water molecules (water-insoluble). Simultaneously, the hydrophilic groups (hydroxyl groups, etc.) disrupt compatibility with non-polar oil phases (oil-insoluble). Furthermore, intermolecular aggregation through hydrophobic interactions and hydrogen bonds further hinders their molecular-level dispersion in water or oil, ultimately resulting in their "water-insoluble, oil-insoluble" characteristics. How to perfectly apply these water-insoluble and oil-insoluble active ingredients to transparent systems (transparent oil systems and transparent aqueous systems) remains a challenging problem.

[0003] For water-insoluble and oil-insoluble active ingredients, there are currently two main approaches to applying them to transparent systems. The first is formulation improvement, which currently involves introducing excess solubilizers into the product system. The amphiphilic nature of solubilizers can potentially disrupt the structure of biological interfaces (such as skin and mucous membranes), and this disruptive effect is amplified with excessive use. The second approach focuses on improving the solubility of raw materials. Most current improvements in raw material solubility concentrate on encapsulating the raw material, such as using cyclodextrins to encapsulate the raw material or preparing it into liposomes. Dextrins are polysaccharides, and for water-insoluble and oil-insoluble substances with large molecular weights and expansive structures (water / oil doubly insoluble substances), a high proportion of cyclodextrin is required. However, a high proportion of cyclodextrin can make the stickiness more pronounced. Water / oil doubly insoluble substances (such as ginsenosides) typically have large molecular weights (triterpenoid skeleton + sugar chain, molecular weight can reach 800-1200 Da) and irregular structures (rigid ring + branched sugar). Due to steric hindrance, they are prone to incomplete entry into the cyclodextrin cavity, or only partial insertion, or even failure to form stable inclusion complexes. Furthermore, the polar groups of these substances (such as hydroxyl groups in the sugar chain) may form hydrogen bonds with the hydroxyl groups in the outer cavity of the cyclodextrin, further hindering the entry of guest molecules into the inner cavity and reducing the inclusion rate (often below 50%). Moreover, the inclusion of cyclodextrin with guest molecules mainly relies on hydrophobic interactions and van der Waals forces, which are relatively weak (the binding constant is usually 10). 2 ~10 4In complex environments (such as high humidity, high temperature, pH fluctuations, or the presence of other competing molecules), inclusion complexes are prone to dissociation, releasing unincluded guest molecules. These molecules are themselves water / oil insoluble and will re-aggregate and precipitate, leading to decreased system stability (such as solution turbidity and layering). Liposomes, on the other hand, firstly, the amphiphilic imbalance (hydrophobic framework + hydrophilic groups) of water / oil insoluble substances makes it difficult for them to stably embed into the liposome structure: they cannot dissolve in the aqueous phase inside the liposome like hydrophilic substances, nor can they integrate into the phospholipid bilayer like hydrophobic substances (due to the repulsion between polar groups and the hydrophobic tails of phospholipids). Ultimately, only a small amount may adsorb on the liposome surface, or be squeezed out during preparation due to interfacial tension, resulting in an encapsulation rate typically below 30%. Furthermore, leakage during storage is easily caused by vesicle fusion and loosening of the phospholipid layer, further reducing the effective loading capacity. Moreover, the stability of liposomes is affected by factors such as phospholipid oxidation and vesicle aggregation / fusion, resulting in poor stability and difficult storage. Therefore, whether it is cyclodextrin inclusion or liposome preparation, it can only improve the stability of the substance in the solvent through "carrier-assisted dispersion", and cannot completely solve the "fundamental dissolution problem" of water / oil doubly insoluble substances. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide an oleogel composition with a network structure suitable for transparent systems, as well as its preparation method and application.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] In a first aspect, the present invention provides an oleogel composition having a network structure, comprising the following components in weight percentage: 4% to 10% oil-dispersible polymer raw material, 0.05% to 0.1% active ingredient, 40% to 60% peony seed fermented oil, and the balance being synthetic oil; wherein the active ingredient is a water-insoluble and oil-insoluble active ingredient; and the oil-dispersible polymer raw material is a polymeric substance capable of dispersing oil.

[0007] This invention obtains a fully transparent oleogel composition with a network structure by selecting specific component ratios and combining them according to specific requirements. The oleogel composition has a melting point of 60–80°C and the following hardness: at room temperature (25°C), penetration is 50–150 (0.1 mm); at 33°C (body temperature simulation), penetration is 200–400 (0.1 mm) (softens and melts upon touch); at 5–50°C, penetration is 80–200 (0.1 mm) (heat resistant and does not deform when shaken).

[0008] The oleogel composition of the present invention forms a uniform three-dimensional network structure (the gelling agent molecules are arranged in an orderly manner without coarse crystals or particles). The oleogel itself can maintain high transparency (the light transmittance is usually ≥90%). When mixed with transparent cosmetic systems (such as transparent serums, transparent gels, transparent lipsticks, transparent sunscreen sticks, etc.), it will not introduce turbidity, milkiness or precipitation, and can maintain the clear and bright appearance of the product, satisfying consumers' visual demand for "transparent texture". It can be used as a raw material for transparent cosmetic systems.

[0009] The oleogel composition of this invention has a stable network structure that efficiently carries active ingredients. The three-dimensional network structure can encapsulate oil-soluble or water-insoluble active ingredients through hydrophobic interactions and van der Waals forces, preventing the active ingredients from precipitating (such as crystallization or stratification) due to temperature fluctuations or concentration changes during storage. This solves the problem of "poor stability of active ingredients" in transparent systems (traditional transparent systems lack a stable carrier, and the active ingredients are prone to turbidity due to changes in solubility).

[0010] The oleogel composition of this invention exhibits excellent physical stability and resistance to environmental interference. The network structure locks in oil phase molecules, significantly improving the system's resistance to high and low temperatures: it is less prone to liquefaction and loss at high temperatures (40–50°C) (due to its higher melting point and the network structure hindering oil phase flow); it does not crystallize or separate at low temperatures (-5–0°C) (the network structure restricts the orderly aggregation of oil molecules, preventing crystallization and turbidity caused by low temperatures); and it does not separate or coarsen during long-term storage (3–6 months), maintaining a transparent appearance and uniform texture, thus reducing the risk of product shelf-life failure.

[0011] The oil-dispersed polymer raw materials in the oleogel composition of this invention have a high dissolution temperature. Dissolving them in plant oils such as peony seed fermentation oil easily accelerates the oxidation and deterioration of the plant oil; therefore, synthetic oils are introduced. The addition of synthetic oils significantly lowers the dissolution temperature of the oil-dispersed polymer raw materials. Synthetic oils (such as caprylic / capric triglycerides) have better intermolecular force matching; their molecular chain structure is regular and their polarity is controllable, enabling them to form more efficient interactions with the polymer raw materials. This allows polymers that originally required high temperatures (e.g., above 100°C) to dissolve to be fully dissolved at 70–80°C, reducing thermal damage to sensitive components (such as active ingredients and plant oils) in the system and significantly improving the oxidative stability of the system. Compared to vegetable oils such as peony seed fermentation oil (rich in unsaturated fatty acids, easily oxidized by high temperatures, light, or oxygen, resulting in rancidity, discoloration, and loss of active ingredients), synthetic oils are mostly saturated structures or contain stable functional groups (such as silicon-oxygen bonds), exhibiting strong antioxidant capabilities. Furthermore, they can reduce the concentration of unsaturated fatty acids in vegetable oils through a "dilution effect," decreasing the probability of oxidation and extending the shelf life of the oil gel (typically from 3-6 months to over 12 months). Secondly, they optimize the physical stability of the oil gel. The viscosity, melting point, and compatibility with polymers of synthetic oils can be precisely controlled. Their addition regulates the overall rheological properties of the oil phase, preventing abnormal viscosity changes (such as thickening or stratification) caused by vegetable oil oxidation. Simultaneously, they enhance the uniformity of the oil gel network structure, ensuring the stability of oil droplet morphology under room temperature and heat-resistant conditions, and reducing hardness fluctuations caused by oxidation. Finally, they reduce production costs and process complexity. The oxidative stability of synthetic oils eliminates the need for the addition of large amounts of antioxidants (such as BHT and vitamin E) during production, storage, and transportation, reducing raw material costs and formulation complexity. At the same time, their lower melting temperature reduces energy consumption during production, shortens high-temperature stirring time, and improves production efficiency.

[0012] As a preferred embodiment of the oleogel composition of the present invention, the oil-dispersible polymeric raw material includes at least one of hydrogenated castor oil / sebacic acid copolymer, castor oil copolymer, dextrin ester, hydrogenated C6-20 polyolefin, or HDI / trimethylolhexyl lactone crosslinking polymer.

[0013] As a preferred embodiment of the oleogel composition of the present invention, the dextrin ester includes at least one of dextrin palmitate, dextrin myristate, dextrin palmitate / ethylhexanoate, and stearic acid inulin.

[0014] In a preferred embodiment of the oleogel composition of the present invention, the oil-dispersible polymer raw material is a castor oil copolymer.

[0015] As a preferred embodiment of the oleogel composition of the present invention, the castor oil copolymer includes at least one of castor oil-based epoxy resin (RCO-EP), polyurethane acrylate (PUA), or castor oil-based polyurethane elastomer (RCO-PU).

[0016] As a preferred embodiment of the oleogel composition of the present invention, the castor oil-based polyurethane elastomer (RCO-PU) includes at least one of castor oil / IPDI copolymer or castor oil / MDI copolymer (MDI: diphenylmethane diisocyanate).

[0017] In a preferred embodiment of the oleogel composition of the present invention, the castor oil copolymer is a castor oil / IPDI copolymer.

[0018] As a preferred embodiment of the oleogel composition of the present invention, the active ingredient includes at least one of peony callus extract or rare ginsenoside RG3.

[0019] The peony callus extract of this invention is prepared according to the preparation method of peony callus extract described in publication number CN117815148A. The specific preparation steps are as follows:

[0020] (1) Fresh peony callus tissue was freeze-dried to obtain freeze-dried peony callus tissue;

[0021] (2) Take freeze-dried peony callus and grind it into powder to obtain peony callus powder;

[0022] (3) Take the peony callus powder and organic extract, mix them together, and then perform ultrasonic extraction. Filter to obtain peony callus extract.

[0023] (4) Remove the solvent from the peony callus extract to obtain the peony callus extract;

[0024] The organic extract is ethanol;

[0025] In step (3), the ratio of peony callus powder to organic extract is 1:10-20.

[0026] As a preferred embodiment of the oleogel composition of the present invention, the synthetic oil includes at least one of caprylic / capric triglyceride, diisostearate malate, triheptyl alcohol, or polyglycerol-2-triisostearate.

[0027] As a preferred embodiment of the oleogel composition of the present invention, the oleogel composition comprises the following components in weight percentage: 6% oil-dispersed polymer raw material, 0.1% active ingredient, 50% peony seed fermented oil, and the balance being synthetic oil.

[0028] The peony seed fermented oil of this invention can be commercially available or homemade.

[0029] The method for preparing the peony seed fermented oil includes the following steps:

[0030] (1) Activate and culture Lactobacillus plantarum to logarithmic growth, then inoculate it into MRS liquid medium to OD. 600 The concentration was 0.6–1.0, resulting in a fermentation suspension.

[0031] (2) Peony seed powder with a particle size of 15-25 mesh was extracted using supercritical CO2 fluid at an extraction pressure of 28-32 mPa, an extraction temperature of 37-43℃, a carbon dioxide flow rate of 25 kg / h, a separation temperature of 30-40℃, and a separation pressure of 10.5-11.5 MPa to obtain peony seed oil.

[0032] (3) Add water to peony seed powder with a particle size of 100-120 mesh, adjust the pH value to 5.0-5.5, sterilize, and obtain a fermentation medium with a peony seed powder mass percentage of 8%-12%. Inoculate the fermentation medium with a volume percentage of 8%-12% of the fermentation bacteria suspension obtained in step (1), and add a volume percentage of 8%-12% of the peony seed oil obtained in step (2). Incubate at 35-37℃ to obtain the fermented product.

[0033] (4) The fermented product obtained in step (3) is filtered using a ceramic membrane, the filtrate is centrifuged, and the upper oil layer is taken and filtered. The filtrate obtained is peony seed fermented oil.

[0034] More specifically, the method for preparing the peony seed fermented oil includes the following steps:

[0035] (1) Activate and culture Lactobacillus plantarum to logarithmic growth, then inoculate it into MRS liquid medium to OD. 600 The concentration was 0.6–1.0, resulting in a fermentation suspension.

[0036] (2) The peony seeds were dried and pulverized at a constant temperature of 57-59℃ to obtain powder with a particle size of 15-25 mesh; the obtained powder was extracted using supercritical CO2 fluid at an extraction pressure of 28-32 mPa, an extraction temperature of 37-43℃, a carbon dioxide flow rate of 25 kg / h, a separation temperature of 30-40℃, and a separation pressure of 10.5-11.5 MPa to obtain peony seed oil.

[0037] (3) Dry and pulverize peony seeds at a constant temperature of 57-59℃ to obtain peony seed powder with a particle size of 100-120 mesh. Add water to the obtained peony seed powder and adjust the pH value to 5.0-5.5. Sterilize to obtain a fermentation medium with a mass percentage of 8%-12% of peony seed powder. Inoculate the obtained fermentation medium with a volume percentage of 8%-12% of the fermentation bacteria suspension obtained in step (1) and add a volume percentage of 8%-12% of the peony seed oil obtained in step (2). Culture at a constant temperature of 35-37℃ and 180r / min for 19h to obtain fermentation product.

[0038] (4) The fermented product obtained in step (3) is filtered using a ceramic membrane with a pore size of 50 nm, a membrane differential of 0.10 to 0.2 MPa, and a membrane surface flow rate of 3.5 to 4.5 m / s. The filtrate is centrifuged at 4990 to 5010 r / min, and the upper oil layer is filtered. The filtrate obtained is peony seed fermented oil.

[0039] Secondly, the present invention provides a method for preparing the above-mentioned oleogel composition, comprising the following steps:

[0040] S1. Mix the oil-dispersed polymer raw material with the synthetic oil, heat until completely dissolved, adjust the temperature to 83-87℃, add the active ingredient, and homogenize under high pressure with microjet to obtain a uniform viscous liquid.

[0041] S2. Cool the viscous liquid from step S1 to 70-80°C, add peony seed fermentation oil, maintain a constant temperature of 70-80°C, mix until the liquid is completely transparent, and cool to room temperature to obtain the oleogel composition.

[0042] In the preparation method of the oleogel composition of this invention, the complete dissolution and swelling of the oily polymer will exceed 100°C. Adding the active ingredient at such a high temperature will affect its activity. Therefore, the system temperature needs to be reduced to about 85°C (83-87°C) before adding the active ingredient. Multiple treatments using a microfluidic high-pressure homogenizer are performed to form co-hydrogen bonds between the active ingredient and the polymer raw materials. Multiple treatments can gradually refine the dispersed particle size of the oil-phase polymer, reduce interfacial resistance, and make it easier for the hydroxyl-containing active ingredient to penetrate to the polymer surface or inter-chain spaces. This increases the probability of collisions between hydroxyl groups and polar groups in the polymer, causing the polymer chains to partially extend and expose previously encapsulated polar groups (such as hidden hydroxyl or carbonyl groups), providing more sites for hydrogen bond formation.

[0043] Microfluidic treatment promotes co-hydrogen bonding. Multiple treatments can gradually refine the dispersed particle size of oil-phase polymers, reduce interfacial resistance, and make it easier for hydroxyl-containing active substances to penetrate to the polymer surface or inter-chain spaces, increasing the probability of collision between hydroxyl groups and polar polymer groups and improving contact efficiency. High-pressure shearing may cause local stretching of polymer chains, exposing previously encapsulated polar groups (such as hidden hydroxyl or carbonyl groups), providing more sites for hydrogen bond formation and promoting conformational exposure. Mechanical forces can temporarily weaken existing weak intermolecular interactions (such as hydrogen bonds or hydrophobic interactions within the polymer), freeing up energy space for the formation of cross-substance hydrogen bonds (co-hydrogen bonds) and lowering the energy barrier.

[0044] Thirdly, the present invention provides the application of the above-mentioned oleogel composition in the preparation of cosmetics.

[0045] Fourthly, the present invention provides a cosmetic comprising the above-described oil gel composition.

[0046] Fifthly, the present invention provides a toner comprising the above-described oil gel composition.

[0047] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0048] In the oleogel composition of the present invention, the active ingredient can enhance the network structure of the oil-dispersible polymer raw material. Combined with peony seed fermented oil, the spatial structure of the network structure is enhanced, thereby enabling the application of water-insoluble and oil-insoluble active ingredients in transparent systems. When the oleogel composition is used in transparent systems, it can not only reduce the amount of polymer raw material used in transparent systems, but also reduce the oxidative rancidity of vegetable oils and extend the shelf life. Attached Figure Description

[0049] Figure 1 This is a schematic diagram of the structure of the oleogel composition of the present invention, wherein gray represents carbon atoms, blue represents hydrogen atoms, and red represents oxygen atoms;

[0050] Figure 2 The states of toner 1 and control toner 3 in test example 2 of this invention after being stored at 60°C for 18 days are shown. A represents toner 1 and B represents control toner 3.

[0051] Figure 3 These are fluorescence images of the blank control group, positive control group, and toner 1 in test example 3 of this invention. Detailed Implementation

[0052] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0053] Unless otherwise specified, all other materials and reagents used in the examples are commercially available.

[0054] Peony callus extract, prepared in-house, was prepared according to the preparation method of peony callus extract described in publication number CN117815148A. The specific preparation steps are as follows:

[0055] (1) Fresh peony callus tissue was freeze-dried to obtain freeze-dried peony callus tissue;

[0056] (2) Take freeze-dried peony callus and grind it into powder to obtain peony callus powder;

[0057] (3) Take the peony callus powder and organic extract, mix them together, and then perform ultrasonic extraction. Filter to obtain peony callus extract.

[0058] (4) Remove the solvent from the peony callus extract to obtain the peony callus extract;

[0059] The organic extract is ethanol;

[0060] In step (3), the ratio of peony callus powder to organic extract is 1:10-20.

[0061] Rare ginsenoside RG3 was purchased from Sanyi Technology (Guangzhou) Co., Ltd.

[0062] MRS liquid culture medium: 10g beef extract, 5g yeast powder, 5g glucose, 10g peptone, 2g diammonium hydrogen citrate, 2g dipotassium hydrogen phosphate, 0.05g manganese sulfate monohydrate, 5g anhydrous sodium acetate, and 0.2g magnesium sulfate heptahydrate, 1mL Tween-80, 1L distilled water, pH 6.8, sterilized at 121℃ for 20min.

[0063] Fish embryo culture medium: Prepared by dissolving 2940mg anhydrous calcium chloride, 1233mg magnesium sulfate heptahydrate, 630mg sodium bicarbonate, and 55mg potassium chloride in 10L of water. The pH value is 6.5-8.5. All chemicals are of analytical grade.

[0064] Cellular Reactive Oxygen Species Assay Kit (H2DCFDA), purchased from Thermo Fisher Scientific (Invitrogen). TM ).

[0065] Peony seed fermented oil can be prepared at home using the following method:

[0066] (1) Activate and culture Lactobacillus plantarum to logarithmic growth, then inoculate it into MRS liquid medium until the medium reaches OD. 600 The concentration was 0.6–1.0, resulting in a fermentation suspension.

[0067] (2) After drying the peony seeds at a constant temperature of 58℃ for 24 hours, crush and pulverize them and then sieve them (the crushing particle size is 15-25 mesh, preferably 20 mesh). Use supercritical CO2 fluid to extract peony seed oil, wherein the extraction pressure is set to 28-32 mPa, the extraction temperature is set to 37-43℃, the carbon dioxide flow rate is 25 kg / h, the separation temperature is set to 30-40℃, and the separation pressure is set to 10.5-11.5 MPa to obtain peony seed oil;

[0068] (3) After drying the peony seeds at 58℃ for 24 hours, crush and pulverize them and sieve them through 20, 40, 60, 80 and 100 mesh sieves respectively, a total of 5 mesh sieves. Weigh 10g of peony seed powder, add 90g of water to prepare a culture medium with a peony seed powder mass concentration of 10%, adjust the pH value to 5.0~5.5, sterilize at 120℃ for 30min, then inoculate with 10% by volume of the fermentation bacteria suspension obtained in step (1), add 10% by volume of the peony seed oil obtained in step (2) as the substrate oil, and ferment in a constant temperature shaking incubator at 180r / min at a temperature of 36±1℃ for 19h to obtain the fermentation product;

[0069] (4) The fermentation product obtained in step (3) is filtered using a ceramic membrane device to remove bacteria and impurities. A ceramic membrane with a pore size of 50 nm is selected, the membrane differential is set to 0.15 ± 0.05 MPa, and the membrane surface flow rate is controlled at 4 ± 0.5 m / s. The filtrate is collected. The filtered filtrate is centrifuged at 5000 ± 10 r / min, and the upper oil layer is retained. The filtrate obtained by vacuum filtration is peony seed fermentation oil. Using a 50 nm pore size ceramic membrane, 99.9% of bacterial fragments (particle size > 0.1 μm) can be retained under a pressure differential of 0.15 MPa, while retaining a high content of small molecule active substances (such as tocotrienols), and the filtrate has high clarity.

[0070] In the preparation method described above: 10% peony seed powder (by mass) is compounded with supercritical peony seed oil to form a "solid-liquid two-phase fermentation system," which promotes the adsorption of microorganisms on the surface of oil droplets. Supercritical peony oil serves as the base oil for fermentation, preserving active ingredients more completely and meeting the metabolic needs of microorganisms. The pH is controlled at 5.0–5.5 and the temperature at 36±1℃. Under these conditions, the β-glucosidase activity of *Lactobacillus plantarum* is high, which can efficiently hydrolyze phenolic glycosides in peony seeds. Combined with centrifugation at 5000 r / min and a negative pressure of 0.08 MPa, the water content in the oil can be reduced to an extremely low level, improving the purity, clarity, and stability of the fermented peony oil.

[0071] Examples 1-10 and Comparative Examples 1-7

[0072] This invention utilizes the intermolecular forces between a polymeric raw material with a network structure (such as castor oil / IPDI copolymer) and a water-insoluble and oil-insoluble active ingredient, combined with peony fermentation oil to enhance its spatial structure, to form a transparent oleogel composition with a network structure. A schematic diagram of the oleogel composition is shown below. Figure 1 As shown, gray represents carbon atoms, blue represents hydrogen atoms, and red represents oxygen atoms.

[0073] The oleogel composition of the present invention comprises the following components in weight percentages: 4%–10% oil-dispersible polymer raw material, 0.05%–0.1% active ingredient, 40%–60% peony seed fermented oil, and the balance being synthetic oil; wherein the oil-dispersible polymer raw material includes one or more of hydrogenated castor oil / sebacic acid copolymer, castor oil copolymer, dextrin palmitate, dextrin myristate, dextrin palmitate / ethylhexanoate, stearic acid inulin and other dextrin esters, hydrogenated C6-20 polyolefin, or HDI / trimethylolhexyl lactone crosslinking polymer; wherein the castor oil copolymer includes castor oil-based epoxy resin (RCO-EP), polyurethane acrylate (PUA), or castor oil-based polyurethane elastomer (RCO-PU); and the castor oil-based polyurethane elastomer (RCO-PU) includes castor oil / IPDI copolymer or castor oil / MDI copolymer (MDI: diphenylmethane diisocyanate). The synthetic oils include caprylic / capric triglyceride, diisostearate malate, triheptyl alcohol, or polyglycerol-2 triisostearate.

[0074] The composition and content of the oleogel compositions of Examples 1-10 and the compositions of Comparative Examples 1-7 are shown in Tables 1-1 and 1-2 below.

[0075] Table 1-1

[0076]

[0077] Table 1-2

[0078]

[0079] The preparation methods of the compositions of Examples 1-10 and Comparative Examples 1-7 include the following steps:

[0080] S1. Add the oil-dispersed polymer raw material to the synthetic oil and stir and heat (to close to 100°C) until completely dissolved. Quickly add the active ingredient and control the temperature at 83-87°C. Process the mixture 5 times with a microfluidic high-pressure homogenizer to obtain a homogeneous viscous liquid.

[0081] S2. Place the liquid obtained in step S1 in a water bath at 70-80°C and stir for 30 minutes. Add peony seed fermentation oil (or refined peony seed oil), stir quickly and evenly, then quickly (for as short a time as possible, no more than 30 seconds) raise the temperature to 90°C, maintain a constant temperature of 70-80°C, and stir until the liquid is completely transparent. Then cool directly to room temperature to obtain the oil gel composition / composition.

[0082] Application examples

[0083] An example of the application of the oleogel composition of the present invention is to prepare a toner by combining the oleogel composition with excipients. The components of toners 1-2 and comparative toners 1-4 are shown in Table 2 below.

[0084] Table 2

[0085]

[0086] The preparation methods of toners 1-2 and comparative toners 1-4 are as follows: carbomer is dispersed in water until it is uniform and free of particles. Then, it is placed in a water bath at 75°C and heated with stirring until it reaches 75°C. Next, the oily active ingredients that have been dissolved into a liquid state are added, and stirring is started until oil droplets are formed. Stirring is continued while cooling. When the temperature drops below 40°C, preservatives and neutralizing agent sodium hydroxide are added and stirred evenly to obtain an aqueous solution with suspended oil droplets, which is the toner.

[0087] Test Example 1

[0088] Using the oleogel compositions of Examples 1-10 and the compositions of Comparative Examples 1-7 as samples, the melting point, hardness, state, stability and transparency of the samples were measured.

[0089] Melting point: Using the capillary method, the sample is placed in a glass capillary tube with an inner diameter of 1-2 mm, so that the sample height is about 2-3 mm. The capillary tube is fixed to a thermometer with a rubber band and placed in a heating bath (such as a silicone oil bath). The temperature is slowly increased (1-2℃ / min), and the temperature at which the sample completely melts is observed. This temperature is the melting point.

[0090] Hardness: determined using a texture analyzer (Rheotech Fudoh Eheo meter, RTC-3005D).

[0091] Status and transparency are determined visually.

[0092] Stability: The prepared composition was placed in an environment of 25°C, and after 1 day, the composition was visually inspected for any oil seepage.

[0093] The results of the measurements of melting point, hardness, state, stability, and transparency are shown in Table 3 below.

[0094] Table 3

[0095]

[0096] Table 3 shows that the oleogel compositions of Examples 1-10 are completely transparent gels with melting points of 67-80℃ and hardness of 70-87N. No oil seepage was observed after one day at 25℃, indicating good short-term stability and suitable compatibility. As the proportion of oil-dispersible polymer raw materials increases, the melting point and hardness of the compositions also increase, demonstrating that the oil-dispersible polymer raw materials are the core component of the oleogel.

[0097] The oleogel composition of this invention achieves a balance between stability, transparency, and protection against heat-sensitive substances through its melting point and hardness. A melting point of 67–80°C ensures that the activity of the active ingredients remains unaffected; a hardness of 70–87 N results in a soft, easy-to-apply paste, enhancing the user experience.

[0098] Comparative Examples 2-4 had excessively high melting points (≥90℃). Although they were gels, their transparency decreased (slightly hazy / semi-hazy). Furthermore, the high melting point increased processing temperature, exacerbating the degradation risk of heat-sensitive active ingredients (such as peony callus or ginsenosides). They also had a poor skin feel, were difficult to melt upon contact with the skin, and produced a "waxy" texture. Comparative Example 6 had an excessively low melting point (30℃), resulting in a sauce-like consistency, oil seepage, and poor stability.

[0099] Based on the results of Example 2 and Comparative Examples 1 and 2, it can be seen that the content of oil-dispersed polymer raw materials cannot be too high or too low, and must be within the range of the examples. If it is too low, an oil gel cannot be obtained, and if it is too high, the melting point and hardness of the oil gel will be too high. A high melting point will increase the processing temperature and exacerbate the degradation risk of heat-sensitive active ingredients (such as peony callus or ginsenosides). If the hardness is too high, the prepared paste will be too hard, with high friction when applied, and a sticky feel on the skin, which does not meet the requirement of "lightweight and easy to spread" in cosmetics.

[0100] Based on the results of Example 2 and Comparative Example 3, the addition of active ingredients helps lower the melting point of the composition and also reduces the hardness of the oleogel. A lower melting point allows for a lower processing temperature (≤80℃), protecting the heat-sensitive active ingredients. A low melting point results in immediate melting upon contact with the skin (close to body temperature of 37℃), leading to a smoother feel. Reduced hardness makes the prepared ointment soft and easy to apply, improving the user experience. This also demonstrates that a fully transparent oleogel cannot be obtained without active ingredients.

[0101] According to the results of Example 2 and Comparative Example 4, the addition of peony seed fermented oil can lower the melting point of the entire system and increase the hardness of the oleogel, as the polar components strengthen the gel network; without peony seed fermented oil, the composition cannot obtain a fully transparent oleogel.

[0102] Based on the results of Example 2 and Comparative Example 5, it is evident that the peony seed fermented oil in the composition of this invention is an irreplaceable component. Replacing it with other peony seed oils will not yield a fully transparent oil gel, and the stability of the oil gel will decrease. This is because there are compatibility issues between oil-dispersible polymers and vegetable oils; not just any vegetable oil can be used. Peony seed fermented oil improves stability and has better compatibility with oil-dispersible polymers.

[0103] Based on the results of Example 2 and Comparative Example 6, it can be seen that the content of the active ingredient cannot be too high. If it exceeds the range of the examples, a fully transparent oleogel cannot be obtained, and the stability of the oleogel will be reduced.

[0104] Based on the results of Example 2 and Comparative Example 7, it is evident that the addition of the active ingredient can reduce the amount of oil-dispersible polymer raw material required, thereby helping to lower the melting point of the composition and also reducing the hardness of the oleogel. This also indicates that a fully transparent oleogel cannot be obtained without the active ingredient.

[0105] This invention achieves an oleogel with "low melting point, moderate hardness, high transparency, and stable state" through the synergistic ratio of components (polymer + active ingredient + specific plant oil). Its core advantage should be interpreted from the perspective of "functional synergy" (rather than simply the addition of hardness).

[0106] The core function of "oil-dispersed polymer raw material (polymer)" is thickening. Comparing Example 2 (polymer 6%) and Comparative Example 2 (polymer 15%), both contain "active ingredient 0.1% + oil phase (peony fermented oil + synthetic oil)". However, the amount of polymer used in Example 2 is only 40% of that in Comparative Example 2 (6% vs 15%), yet it also forms a gel. Moreover, Example 2 is "fully transparent". This demonstrates the synergistic effect of "active ingredient + oil phase (peony fermented oil)" and "polymer", which reduces the amount of thickener used while maintaining the gel structure.

[0107] Example 2 (6% polymer + 0.1% active ingredient + 50% fermented oil) and Comparative Example 5 (6% polymer + 0.1% active ingredient + 50% refined peony seed oil) used the same amount of polymer and active ingredient, only the oil phase was changed from "fermented oil" to "refined oil". Example 2 was completely transparent and had no oil seepage; Comparative Example 5 was slightly hazy and had surface oil seepage. This shows that the combination of "fermented oil + polymer + active ingredient" achieves synergy in transparency and stability (1+1+1>3), rather than simply the sum of hardness.

[0108] Synergistic effect of active ingredient with polymer and vegetable oil (peony seed fermented oil): In Example 2, the active groups (such as hydroxyl and carboxyl groups) of the active ingredient form hydrogen bonds with the polyurethane bonds (-NH-CO-) of the polymer, and at the same time interact with the polar metabolites of the vegetable oil, synergistically strengthening the network structure, lowering the melting point (easier to melt), increasing hardness (more dense network), and optimizing transparency (more uniform network); while in Comparative Example 3, when the active ingredient is absent, the network of polymer + vegetable oil is maintained only by hydrophobic interaction and van der Waals forces, and the structure is loose (high melting point, low hardness, light scattering leads to micro-haze).

[0109] Test Example 2

[0110] The above-mentioned toners 1-2 and the control toners 1-4 were used as samples for oxidative stability testing.

[0111] 1. DPPH free radical scavenging rate

[0112] Set up tubes T, T0, C, and C0. Add 50.0 μL of sample (5% concentration) and 100.0 μL of water to tubes T and T0 respectively, and mix well. Add 150.0 μL of water to tubes C and C0. Add 50.0 μL of DPPH solution (0.12 mg / mL) to tubes T and C. -1 ), 50.0 μL of ethanol solution (95%, v / v) was added to tubes T0 and C0, mixed well, and incubated at 30°C for 5 min. The absorbance was measured at 517 nm. The DPPH free radical scavenging rate was calculated based on the absorbance. The formula for calculating the DPPH free radical scavenging rate (R) is: R% = (1 - [A] i -A j ] / A c )×100, where A c The absorbance of tube C is A. i A is the absorbance of the T-tube; j This is the absorbance value of tube T0.

[0113] The solvent (water + 95% ethanol) has an extremely low absorbance (close to 0) at 517 nm, which is the absorbance of tube C0 (denoted as A). c0 The absorbance of tube C is negligible (e.g., Ac0 < 0.02). c The actual absorbance is close to the "DPPH pure absorbance value" (i.e., A). c -A c0 ≈A c Therefore, the calculation can be simplified and the calibration of the C0 tube can be omitted.

[0114] 2. Hydroxyl radical scavenging rate

[0115] Set up tubes T, T0, and C. Add 30.0 μL of sample (using water instead of the sample solution in tube C) and 30.0 μL of FeSO4 solution (8.0 mmol·L⁻¹) to each tube sequentially.-1 ), 100.0 μL salicylic acid (3.0 mmol·L -1 ) and 100.0 μL H2O2 (8.8 mmol·L -1 (Use water instead of the sample solution in tube T0), mix well, incubate at 37°C for 10 min, and measure the absorbance at 510 nm. Perform three replicates per tube, and take the average of the three sets. Calculate the hydroxyl radical scavenging rate based on the absorbance value using the following formula:

[0116] Hydroxyl radical scavenging rate (%) = [A0 - (A x -A x0 [) / A0]*100 where A0 is the absorbance of the blank control (tube C), A x To add the absorbance value of the sample (T tube), A x0 The absorbance value is for tube T0 without the addition of colorimetric reagent H2O2.

[0117] 3. Test the peroxide value (POV value).

[0118] Toners 1-2 and control toners 1-4 were stored in a 60℃ oven for 18 days. The POV value of the samples was tested every 3 days to investigate the change in POV value of the toners under accelerated conditions. The method for determining the peroxide value was in accordance with GB5009.227-2023 National Food Safety Standard for Determination of Peroxide Value in Food.

[0119] 4. Shelf life determination

[0120] Shelf life testing refers to the process of determining, through systematic experiments and analysis, the maximum time a product can maintain its expected quality characteristics (safety, sensory acceptability, physicochemical stability, functional properties, etc.) and be suitable for sale and consumption under specified storage conditions (25°C, protected from light, and sealed).

[0121] The shelf life of this invention is predicted using POV (Potential Oxidation Value). Samples are stored at temperatures above room temperature (e.g., 30°C, 37°C, 45°C), and POV is periodically measured and recorded at the time when POV reaches a "threshold" (the upper limit of POV for oils specified in national standards, or the POV value corresponding to sensory changes in the product, such as the appearance of off-odors when POV ≥ 20 meq / kg). A fitted kinetic model is used: assuming that oil oxidation follows a first-order reaction (POV ≥ 20 meq / kg). (t) =POV0·e kt (where k is the rate constant), the POV growth rate at different temperatures is fitted using the Arrhenius formula, and the activation energy E is calculated. a Combined with Vant'Hoff's empirical formula Q 10 The model assumes that the oxidation rate doubles for every 10°C increase in temperature, i.e., Q 10=2). Based on this, the time it takes for POV to reach the threshold at room temperature (25℃) is the shelf life.

[0122] 5. Results

[0123] The oxidative stability test results of toners 1-2 and comparative toners 1-4 are shown in Table 4 below.

[0124] Table 4

[0125]

[0126] Table 4 shows that the DPPH free radical scavenging rate of toners 1 and 2 was 88.9%–91.6%, and the hydroxyl free radical scavenging rate was 75.3%–79.1%, indicating good antioxidant properties. After 18 days of storage at 60℃, the POV value changed less, indicating good oxidative stability. The shelf life reached 448 days.

[0127] Based on the results of toner 1 and comparative toners 1-3, it can be seen that the active ingredients and peony seed fermented oil are essential components in the oil gel composition of the present invention. Peony seed fermented oil is also irreplaceable. The absence or substitution of other components will lead to a decrease in the antioxidant properties, oxidative stability, and shelf life of the toner prepared by the oil gel composition.

[0128] Based on the results of toner 1 and comparative toner 4, it can be seen that the oil phase that is not made into an oil gel (only peony seed oil) will lead to reduced stability.

[0129] Test results showed that toners 1-2 exhibited good heat resistance and maintained a uniform oil-water mixture. In contrast, toners 1-4 showed varying degrees of turbidity, with oil droplets dissolving into the water, turning the clear aqueous phase hazy. The states of toner 1 and toner 3 after 18 days of storage at 60℃ were as follows: Figure 2 As shown, A represents toner 1, and B represents comparison toner 3.

[0130] Test Example 3

[0131] ROS removal effect was tested using toners 1 and 2 as samples.

[0132] Blank control group: 24 two-day-old zebrafish embryos were randomly selected and placed into a 96-well plate, with one embryo and 0.2 mL of embryo culture medium in each well.

[0133] Positive control group: 24 two-day-old zebrafish embryos were randomly selected and placed into 96-well plates, with one fish embryo and 0.2 mL of glutathione-containing culture medium per well; the glutathione-containing culture medium was fish embryo culture medium containing 0.1 g / L glutathione.

[0134] Experimental group: 24 two-day-old zebrafish embryos were randomly selected and placed into 96-well plates. Each well contained one fish embryo and 0.2 mL of sample culture medium. The sample culture medium was a fish embryo culture medium containing 5 g / L toner.

[0135] Fish embryos from each group were cultured in a 28℃±1℃ incubator for 24h±1h. They were then transferred to 24-well plates, with each well containing 12 fish embryos and 2mL of reactive oxygen species (ROS) test solution, and placed in a 28℃±1℃ incubator for another 2h±0.2h. H2DCFDA staining was performed using a cell reactive oxygen species analysis kit (H2DCFDA). The fish embryos were placed sideways and photographed under a fluorescence stereomicroscope using standardized parameters. ROS signal intensity was measured, and ROS clearance rate was calculated.

[0136] Test results showed that the ROS scavenging rate of toners 1 and 2 was over 45%. The ROS scavenging rates of the blank control group, positive control group, and toner 1 are shown in Table 5 below. Fluorescence images of the blank control group, positive control group, and toner 1 are shown below. Figure 3 As shown,

[0137] Table 5

[0138] Blank control group Positive control group Toner 1 ROS clearance rate (%) 0 15 47

[0139] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An oleogel composition having a network structure, characterized in that, It is composed of the following components by mass percentage: 4% to 10% oil-dispersible polymer raw material, 0.05% to 0.1% active ingredient, 40% to 60% peony seed fermented oil, and the balance of synthetic oil; the active ingredient is a water-insoluble and oil-insoluble active ingredient; the oil-dispersible polymer raw material is a polymeric substance capable of dispersing oil.

2. The oleogel composition according to claim 1, characterized in that, The oil-dispersible polymeric raw material includes at least one of hydrogenated castor oil / sebacic acid copolymer, castor oil copolymer, dextrin ester, hydrogenated C6-20 polyolefin, or HDI / trimethylolhexyl lactone crosspolymer.

3. The oleogel composition according to claim 2, characterized in that, The dextrin ester includes at least one of dextrin palmitate, dextrin myristate, dextrin palmitate / ethylhexanoate, or stearic acid inulin. And / or, the castor oil copolymer includes at least one of castor oil-based epoxy resin, polyurethane acrylate, or castor oil-based polyurethane elastomer.

4. The oleogel composition according to claim 3, characterized in that, The castor oil-based polyurethane elastomer includes at least one of castor oil / IPDI copolymer or castor oil / MDI copolymer.

5. The oleogel composition according to claim 1, characterized in that, The active ingredient includes at least one of peony callus extract or rare ginsenoside RG3.

6. The oleogel composition according to claim 1, characterized in that, The synthetic oil includes at least one of caprylic / capric triglyceride, diisostearate malate, triheptyl ether or polyglycerol-2-triisostearate.

7. A method for preparing the oleogel composition according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Mix the oil-dispersible polymer raw material with the synthetic oil, heat until completely dissolved, adjust the temperature to 83-87℃, add the active ingredient, and homogenize under high pressure with microjet to obtain a viscous liquid. S2. Cool the viscous liquid from step S1 to 70-80°C, add peony seed fermentation oil, maintain a constant temperature of 70-80°C, mix until the liquid is completely transparent, and cool to room temperature to obtain the oleogel composition.

8. The use of the oleogel composition according to any one of claims 1 to 6 in the preparation of cosmetics.

9. A cosmetic product, characterized in that, The oleogel composition includes any one of claims 1 to 6.

10. A toner, characterized in that, The oleogel composition includes any one of claims 1 to 6.

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