Emulsion and preparation method therefor

Abstract

An emulsion and a preparation method therefor. The emulsion comprises an emulsifier, glycerol, oil-phase active matter, pentaerythrityl tetraethylhexanoate, and water; the emulsifier is lipopeptide; the weight percentages of the lipopeptide and the glycerol are not less than 3%; the weight ratio of the oil-phase active matter to the pentaerythrityl tetraethylhexanoate is 1:(3-13); the ratio of the sum of the weight of the lipopeptide and the glycerol to the sum of the weight of the oil-phase active matter and the pentaerythrityl tetraethylhexanoate is 1:(3-10); and the ratio of the sum of the weight of the lipopeptide, the glycerol, the oil-phase active matter, and the pentaerythrityl tetraethylhexanoate to the weight of the water is 1:(1-4). In the emulsion, sodium surfactin is used in combination with the glycerol and the pentaerythrityl tetraethylhexanoate, so that the diffusion of the oil-phase active matter at an emulsion interface can be effectively inhibited, the oxidative degradation of the oil-phase active matter is reduced, and the effective action time of the oil-phase active matter in the emulsion is greatly prolonged.

Description

Emulsion and preparation method thereof

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on August 21, 2023, with application number 202311056263.X and invention name “A kind of emulsion and its preparation method”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present application belongs to the technical field of daily chemical industry, and specifically relates to an emulsion and a preparation method thereof. Background Art

[0003] The stabilization of oil-phase active ingredients has long been a research hotspot in cosmetics development. Long-chain conjugated molecules such as retinol, phenolic molecules such as equol, and polyhydroxy alcohols such as ascorbic acid palmitate are susceptible to degradation, discoloration, and deterioration due to light and heat in everyday environments, posing significant challenges to their application in cosmetics. Current strategies for stabilizing oil-phase active ingredients in cosmetics primarily focus on the self-assembly of various surfactants to form inclusion bodies such as liposomes, aqueous gels, microemulsions, and emulsions. These structures, through a tight surfactant interfacial membrane, inhibit the consumption of oil-phase active ingredients by oxidants, thereby stabilizing the active ingredients.

[0004] Lipopeptides are secondary metabolites (usually a mixture) produced during microbial fermentation. They are a type of biosurfactant typically composed of β-amino or β-hydroxy fatty acids (lipophilic groups) and peptide chains or peptide rings (hydrophilic groups). Subtilis lipopeptide sodium is a lipopeptide biosurfactant, also known as surfactant, produced by fermentation of Bacillus subtilis strains. The hydrophilic group of its molecule is composed of a cyclic peptide. The cyclic peptide composed of 7 amino acids has abundant hydrogen bond acceptors and donors. It is a bio-based anionic surfactant. Lipopeptides have advantages such as being green and safe, and are a hot topic in current surfactant research. Currently, lipopeptides have been used in the preparation of daily chemical products such as emulsions and gels. However, in the prior art, there are few studies on the use of lipopeptides to protect oil-phase active ingredients from rapid degradation over time. In addition, the protective effect of lipopeptides on oil-phase active ingredients is also related to other co-ingredients, and the influencing factors are relatively complex. Therefore, it is necessary to provide a product that uses lipopeptides to provide good antioxidant protection for oil-phase active ingredients and solve the problems of complex preparation processes and poor versatility commonly found in various inclusions in the prior art.

[0005] Summary of the Invention

[0006] To address the above-mentioned problems, an emulsion and a preparation method thereof are provided. The emulsion provided herein utilizes sodium subtilisin in combination with glycerol and pentaerythritol tetra(ethylhexanoate) to prepare an emulsion containing an oil-phase active substance. The addition of sodium subtilisin can effectively inhibit the diffusion of the oil-phase active substance at the emulsion interface, thereby reducing the oxidative degradation of the oil-phase active substance and extending the effective action time of the oil-phase active substance in the emulsion. The preparation process is simple, thereby solving the common problems of complex preparation process and poor versatility in the prior art for treating the easy degradation of oil-phase active substances.

[0007] According to one aspect of the present application, there is provided an emulsion comprising an emulsifier, glycerin, an oil phase active substance, pentaerythritol tetra(ethylhexanoate) and water;

[0008] The emulsifier is a lipopeptide;

[0009] The weight percentage of the lipopeptide and glycerol is not less than 3%;

[0010] The weight ratio of the oil phase active substance to pentaerythritol tetra(ethylhexanoate) is 1:3-13;

[0011] The ratio of the sum of the weight of the lipopeptide and glycerol to the sum of the weight of the oil phase active substance and pentaerythritol tetra(ethylhexanoate) is 1:3-10;

[0012] The ratio of the sum of the weight of the lipopeptide, glycerol, oil phase active substance and pentaerythritol tetra(ethylhexanoate) to the weight of water is 1:1-4.

[0013] Furthermore, the weight percentage of the lipopeptide and glycerol is selected from 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% and any percentage therebetween.

[0014] Furthermore, the weight ratio of the oil phase active substance to pentaerythritol tetra(ethylhexanoate) is selected from 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12 and any value therebetween.

[0015] Furthermore, the ratio of the sum of the weight of the lipopeptide and glycerol to the sum of the weight of the oil phase active ingredients and pentaerythritol tetra(ethylhexanoate) is selected from 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 and any value therebetween.

[0016] Furthermore, the weight ratio of the sum of the weights of the lipopeptide, glycerol, oil phase active ingredients and pentaerythritol tetra(ethylhexanoate) to the weight of water is selected from 1:1.5, 1:2, 1:2.5, 1:3 or 1:3.5 and any value therebetween.

[0017] The emulsion provided herein utilizes the aforementioned components in specific proportions to form a microemulsion gel, which in turn forms an oil-in-water emulsion during dilution. This emulsion offers the advantages of small particle size and high stability. Due to the large hydrophilic head groups of the lipopeptides, hydrogen bonds can form between the cyclic peptides to hinder the diffusion of oxidizing species from the aqueous phase into the oil phase, thereby protecting and stabilizing the active ingredients in the oil phase and inhibiting their oxidative deterioration and degradation.

[0018] Optionally, the weight percentage of the lipopeptide and glycerol is not less than 5%, and further optionally 5% to 12%; and / or,

[0019] The weight ratio of the oil phase active substance to pentaerythritol tetra(ethylhexanoate) is 1:5-11.

[0020] Optionally, the lipopeptide comprises any one or more of sodium subtilisin, iturin, feninterferon, fengyuansuan, daptomycin, polymyxin, bacillus antibiotic L, phosphatidylserine, and bacillus antibiotic D.

[0021] Optionally, the oil phase active ingredient comprises one or more of retinol, retinyl acetate, retinyl propionate, retinyl palmitate, bakuchiol, equol, nervonic acid, ascorbyl palmitate, ascorbyl tetrapalmitate, and phenylethylresorcinol.

[0022] According to another aspect of the present application, a method for preparing any of the above-mentioned emulsions is provided, the method comprising the following steps:

[0023] 1) Dissolve the lipopeptide in glycerol, heat and stir to obtain solution A;

[0024] 2) dissolving the oil phase active substance in pentaerythritol tetra(ethylhexanoate) and stirring to obtain solution B;

[0025] 3) Adding solution A to solution B in a constant temperature water bath with stirring to obtain an oleogel;

[0026] 4) adding the aqueous phase to the oil gel under stirring conditions and mixing them thoroughly to obtain the lipopeptide-containing emulsion.

[0027] Optionally, the lipopeptide in step 1) comprises any one or more of sodium subtilisin, iturin, feninterferon, fengyuansuan, daptomycin, polymyxin, bacillus antibiotic L, phosphatidylserine, and bacillus antibiotic D.

[0028] Optionally, the temperature of heating and stirring in step 1) is 75-85°C.

[0029] Optionally, the temperature of the constant temperature water bath in step 3) is 45-55°C.

[0030] Optionally, the stirring speed in step 3) is not less than 600 rpm.

[0031] Optionally, the stirring temperature in step 4) is 20-30°C. After the oil gel is formed, since solutions A and B are already uniformly mixed during the stirring and dilution process in step 4), slight heating or room temperature conditions are sufficient. Room temperature is preferred, as room temperature is more conducive to the preservation of the oil phase active ingredients.

[0032] Optionally, in step 3), solution B is slowly added to solution A in batches; further, solution B is added only after each addition of solution B is fully emulsified.

[0033] According to the last aspect of the present application, there is provided a use of any of the above-mentioned emulsions in cosmetics.

[0034] The beneficial effects of this application include but are not limited to:

[0035] 1. The emulsion according to the present application has the advantages of small particle size and high stability, and will not break after high-temperature storage, hot and cold cycles, shear tests, etc.

[0036] 2. The emulsion of the present application can effectively protect the oil phase active ingredients from oxidative degradation, inhibit the degradation and discoloration of oil phase active ingredients such as retinol propionate, and significantly improve the retention rate of the oil phase active ingredients in the emulsion over time.

[0037] 3. The emulsion according to the present application has the characteristics of simple preparation process and low equipment requirements, which makes the production cost low and easy to operate. The preparation of the emulsion does not require the use of complex equipment such as high-pressure homogenization. An emulsion with excellent oil phase active ingredient antioxidant properties can be prepared by simple stirring and mixing.

[0038] 4. The emulsion according to the present application has the characteristics of simple ingredients, mild raw materials and low irritation, which is in line with the trend of green and safe raw materials in the daily chemical industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0040] FIG1 is a schematic diagram of the molecular structure of sodium subtilisin;

[0041] FIG2 is a schematic diagram of the photographic results of the oil phase gels of Examples 1 to 3 of the present application (labeled numbers 1, 2, and 3 in the figure correspond to Examples 1, 2, and 3, respectively);

[0042] FIG3 is a schematic diagram of the emulsion photograph results of Examples 1 to 3 of the present application (labels 1 and 2 in the figure correspond to Examples 1 and 2, respectively);

[0043] FIG4 is a schematic diagram of the stability results of Example 1 and Comparative Example 2 of the present application (in the figure, numbers 1 and D2 correspond to Example 1 and Comparative Example 2, respectively);

[0044] FIG5 is a schematic diagram of the stability results of Example 2 and Comparative Example 4 of the present application (in the figure, reference numbers 2 and D4 correspond to Example 2 and Comparative Example 4, respectively);

[0045] FIG6 is a schematic diagram of the photographic results of Comparative Examples 1 and 3 of the present application (labels D1 and D3 in the figure correspond to Comparative Example 1 and Comparative Example 3, respectively);

[0046] FIG7 is a schematic diagram of the photographic results of Comparative Example 7 of the present application (label D7 in the figure corresponds to Comparative Example 7);

[0047] FIG8 is a schematic diagram of the stability results of Example 9 of the present application (reference number 9 in the figure corresponds to Example 9);

[0048] FIG9 is a schematic diagram of the stability results of comparative example 9 of the present application (label D9 in the figure corresponds to comparative example 9). DETAILED DESCRIPTION

[0049] The present invention is described in detail below with reference to the examples, but the present invention is not limited to these examples. Unless otherwise specified, the raw materials and catalysts in the examples of the present invention were purchased from commercial sources.

[0050] As shown in Figure 1, a schematic diagram of the molecular structure of sodium subtilisin. In the prior art, sodium subtilisin has been reported to be used as an emulsifier in the preparation of daily necessities such as gels or emulsions. The addition of sodium subtilisin in the prior art mainly acts as an emulsifier to form a stable emulsion from a mixed liquid of two or more immiscible components. In the present application, the inventors discovered that the addition of sodium subtilisin, in combination with glycerol and pentaerythritol tetra(ethylhexanoate), to an emulsion containing an oil-phase active substance can effectively inhibit the diffusion of the oil-phase active substance at the emulsion interface, thereby reducing the oxidative degradation of the oil-phase active substance and extending the effective action time of the oil-phase active substance in the emulsion.

[0051] The inventors further experimentally discovered that the protective effect of sodium subtilisin on inhibiting the oxidation of oil-phase active ingredients is closely related to the selection of components with which it is combined and the addition ratio of the corresponding components. For example, the use of oleic acid and GTCC, which are commonly used in the preparation of emulsions, does not achieve a good synergistic effect and may even prevent the formation of an emulsion, thus limiting their compatibility with sodium subtilisin.

[0052] In the present application, the inventors have explored the effects of ingredients suitable for combination with sodium subtilisin and the addition ratio based on the application of sodium subtilisin to improve the retention rate of oil-phase active substances over time, and obtained an emulsion solution that can significantly improve the retention rate of oil-phase active substances over time, thereby greatly improving the preservation effect of oil-phase active substances. The present application solution is further illustrated below through specific examples, comparative examples, and test examples.

[0053] Example 1

[0054] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0055] It is prepared according to the following method:

[0056] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 15g of retinol propionate in 75g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase containing the active ingredient (B);

[0057] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0058] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0059] 160 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0060] The photographic results of the oil phase gel prepared in Example 1 are shown in the picture labeled 1 in FIG2 , and the photographic results of the emulsion are shown in the picture labeled 1 in FIG3 .

[0061] Example 2

[0062] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerol; phase B comprises the following raw materials in parts by weight: 15 g of bakuchiol and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0063] It is prepared according to the following method:

[0064] 1 g of sodium subtilisin was dissolved in 20 g of glycerol, heated and stirred at 80°C for 20 min to obtain a clear and stable phase D (A); 15 g of bakuchiol was dissolved in 75 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase containing the active ingredient (B);

[0065] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0066] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0067] 160 g of aqueous phase (C) was added to the oleogel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oleogel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing bakuchiol.

[0068] The photographic results of the oil phase gel prepared in Example 2 are shown in the picture labeled 2 in FIG2 , and the photographic results of the emulsion are shown in the picture labeled 2 in FIG3 .

[0069] Example 3

[0070] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerol; phase B comprises the following raw materials in parts by weight: 15 g of ascorbyl tetrapalmitate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0071] It is prepared according to the following method:

[0072] 1 g of sodium subtilisin was dissolved in 20 g of glycerol, heated at 80°C with stirring for 20 min to obtain a clear and stable phase D (A); 15 g of ascorbyl tetrapalmitate was dissolved in 75 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient;

[0073] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0074] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0075] 160 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing ascorbyl tetrapalmitate.

[0076] The photograph of the oil phase gel prepared in Example 3 is shown in Figure 2 as number 3.

[0077] Example 4

[0078] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 111 g of water.

[0079] It is prepared according to the following method:

[0080] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 15g of retinol propionate in 75g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase containing the active ingredient (B);

[0081] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0082] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0083] 111 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0084] Example 5

[0085] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 444 g of water.

[0086] It is prepared according to the following method:

[0087] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 15g of retinol propionate in 75g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase containing the active ingredient (B);

[0088] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0089] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0090] 444 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0091] Example 6

[0092] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 10 g of retinol propionate and 80 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0093] It is prepared according to the following method:

[0094] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 10g of retinol propionate in 80g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase containing the active ingredient (B);

[0095] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0096] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0097] 160 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0098] Example 7

[0099] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 0.45 g of sodium subtilisin and 8.55 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0100] It is prepared according to the following method:

[0101] 0.45 g of sodium subtilisin was dissolved in 8.55 g of glycerol, and the mixture was heated at 80°C with stirring for 20 min to obtain a clear and stable phase D (A). 15 g of retinol propionate was dissolved in 75 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient.

[0102] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0103] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm, ensuring that each addition of the oil phase is completely emulsified and dissolved before further addition of the oil phase to obtain an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, and finally, an oil gel containing the active ingredient is obtained;

[0104] 160 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0105] Example 8

[0106] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1.5 g of sodium subtilisin and 28.5 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 200 g of water.

[0107] It is prepared according to the following method:

[0108] 1.5 g of sodium subtilisin was dissolved in 28.5 g of glycerol, and the mixture was heated at 80° C. and stirred for 20 min to obtain a clear and stable phase D (A). 15 g of retinol propionate was dissolved in 75 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient.

[0109] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0110] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm, ensuring that each addition of the oil phase is completely emulsified and dissolved before further addition of the oil phase to obtain an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, and finally, an oil gel containing the active ingredient is obtained;

[0111] 200 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0112] Example 9

[0113] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 0.75 g of sodium subtilisin and 6.75 g of glycerol; phase B comprises the following raw materials in parts by weight: 2 g of phenylethylresorcinol and 20.5 g of pentaerythritol tetra(ethylhexanoate); and phase C is 70 g of water.

[0114] It is prepared according to the following method:

[0115] 0.75 g of sodium subtilisin was dissolved in 6.75 g of glycerol, and the mixture was heated at 80° C. with stirring for 20 min to obtain a clear and stable phase D (A). 2 g of phenylethyl resorcinol was dissolved in 20.5 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient.

[0116] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0117] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm, ensuring that each addition of the oil phase is completely emulsified and dissolved before further addition of the oil phase to obtain an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, and finally, an oil gel containing the active ingredient is obtained;

[0118] 70 g of aqueous phase (C) was added to the oleogel while stirring at 500 rpm. The mixture was stirred for 10 minutes until the oleogel was completely dissolved, yielding an oil-in-water (O / W) emulsion containing phenylethylresorcinol. The stability results are shown in Figure 8, labeled 9.

[0119] Comparative Example 1

[0120] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinyl propionate and 75 g of oleic acid; and phase C is 160 g of water.

[0121] It is prepared according to the following method:

[0122] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 15g of retinol propionate in 75g of liquid oil phase oleic acid to obtain an oil phase containing the active ingredient (B);

[0123] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0124] In a constant temperature water bath at 50°C, the oil phase (B) was slowly added to the D phase (A) while stirring at 600 rpm. It was found that the two phases were not miscible or emulsified, as shown in Figure 6, D1.

[0125] Comparative Example 2

[0126] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinyl propionate and 75 g of GTCC; and phase C is 160 g of water.

[0127] It is prepared according to the following method:

[0128] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 15g of retinol propionate in 75g of the liquid oil phase GTCC to obtain an oil phase containing the active ingredient (B);

[0129] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0130] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0131] 160 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0132] The results are shown in Figure 4, D2, which shows that the emulsion is unstable during storage and can cause problems such as precipitation and discoloration.

[0133] Comparative Example 3

[0134] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of butylene glycol; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0135] It is prepared according to the following method:

[0136] 1 g of sodium subtilisin was dissolved in 20 g of butanediol and heated at 80°C with stirring for 20 min. No clear and stable phase D (A) could be obtained. 15 g of bakuchiol was dissolved in 75 g of the liquid oil phase pentaerythritol tetraethylhexanoate to obtain the oil phase (B) containing the active ingredient.

[0137] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0138] When the oil phase (B) was slowly added to the D phase (A) under a constant temperature water bath at 50°C and stirred at 600 rpm, no oil phase gel was formed, as shown in Figure D3 in Figure 6.

[0139] Comparative Example 4

[0140] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerol; phase B comprises the following raw materials in parts by weight: 15 g of bakuchiol and 75 g of GTCC; and phase C is 160 g of water.

[0141] It is prepared according to the following method:

[0142] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 15g of bakuchiol in 75g of liquid GTCC to obtain an oil phase containing the active ingredient (B);

[0143] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0144] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0145] 160 g of aqueous phase (C) was added to the oleogel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oleogel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing bakuchiol.

[0146] The results are shown in D4 in Figure 5, which show that the emulsion is unstable during storage and may cause problems such as precipitation and discoloration.

[0147] Comparative Example 5

[0148] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 100 g of water.

[0149] It is prepared according to the following method:

[0150] Dissolve 1g of sodium subtilisin in 20g of glycerol, heat and stir at 80°C for 20min to obtain a clear and stable phase D (A); dissolve 15g of retinol propionate in 75g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase containing the active ingredient (B);

[0151] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0152] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0153] When 100 g of aqueous phase (C) was added to the oil gel under stirring at 500 rpm and stirred for 10 min, the oil gel could not be completely dissolved, and a highly viscous and opaque mixture was obtained, which did not fall into the category of an emulsion.

[0154] Comparative Example 6

[0155] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 0.5 g of sodium subtilisin and 20.5 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0156] It is prepared according to the following method:

[0157] 0.5 g of sodium subtilisin was dissolved in 20.5 g of glycerol, and the mixture was heated at 80° C. and stirred for 20 min to obtain a clear and stable phase D (A). 15 g of retinol propionate was dissolved in 75 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient.

[0158] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0159] In a constant temperature water bath at 50°C, the oil phase (B) was slowly added while stirring phase D (A) at 600 rpm. It was found that the oil phase could not be completely emulsified or dissolved in phase D, and there was always free oil phase present, indicating that the ratio of lipopeptide and glycerol was too low to form an oil phase gel, resulting in the inability to form an emulsion.

[0160] Comparative Example 7

[0161] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 0.4 g of sodium subtilisin and 8 g of glycerin; phase B comprises the following raw materials in parts by weight: 15 g of retinol propionate and 75 g of pentaerythritol tetra(ethylhexanoate); and phase C is 138 g of water.

[0162] It is prepared according to the following method:

[0163] 0.4 g of sodium subtilisin was dissolved in 8 g of glycerol, and the mixture was heated at 80° C. and stirred for 20 min to obtain a clear and stable phase D (A). 15 g of retinol propionate was dissolved in 75 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient.

[0164] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0165] In a constant temperature water bath at 50°C, the oil phase (B) was slowly added to the D phase (A) while stirring at 600 rpm. It was found that the oil phase could not be completely emulsified or dissolved in the D phase, and there was always free oil phase present. This indicates that the A:B ratio is too low to form an oil phase gel, and therefore no emulsion can be formed. The result is shown in Figure D7 in Figure 7.

[0166] Comparative Example 8

[0167] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 1 g of sodium subtilisin and 20 g of glycerin; phase B comprises the following raw materials in parts by weight: 30 g of retinol propionate and 60 g of pentaerythritol tetra(ethylhexanoate); and phase C is 160 g of water.

[0168] It is prepared according to the following method:

[0169] 1 g of sodium subtilisin was dissolved in 20 g of glycerol, and the mixture was heated at 80°C with stirring for 20 min to obtain a clear and stable phase D (A). 30 g of retinol propionate was dissolved in 60 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient.

[0170] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0171] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm to ensure that each addition of the oil phase is completely emulsified and dissolved. Further addition of the oil phase will yield an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, ultimately yielding an oil gel containing the active ingredient.

[0172] 160 g of aqueous phase (C) was added to the oil gel while stirring at 500 rpm, and the mixture was stirred for 10 min until the oil gel was completely dissolved, thereby obtaining an oil-in-water (o / w) emulsion containing retinyl propionate.

[0173] Comparative Example 9

[0174] An emulsion comprises a phase A, a phase B and a phase C, wherein phase A comprises the following raw materials in parts by weight: 0.4 g of sodium subtilisin and 7.1 g of glycerol; phase B comprises the following raw materials in parts by weight: 2 g of phenylethylresorcinol and 28 g of pentaerythritol tetra(ethylhexanoate); and phase C is 62.5 g of water.

[0175] It is prepared according to the following method:

[0176] 0.4 g of sodium subtilisin was dissolved in 7.1 g of glycerol, and the mixture was heated at 80° C. and stirred for 20 min to obtain a clear and stable phase D (A). 2 g of phenylethyl resorcinol was dissolved in 28 g of the liquid oil phase pentaerythritol tetra(ethylhexanoate) to obtain an oil phase (B) containing the active ingredient.

[0177] Heat phase D (A) and oil phase (B) in a water bath at 50°C;

[0178] In a constant temperature water bath at 50°C, slowly add the oil phase (B) to the D phase (A) while stirring at 600 rpm, ensuring that each addition of the oil phase is completely emulsified and dissolved before further addition of the oil phase to obtain an oil gel containing the active ingredient. As the oil phase content increases, the viscosity of the system gradually increases, and finally, an oil gel containing the active ingredient is obtained;

[0179] While stirring the oleogel at 500 rpm, 62.5 g of aqueous phase (C) was added and stirred for 10 minutes until the oleogel was completely dissolved. This yielded an oil-in-water (O / W) emulsion containing phenylethylresorcinol. The stability results are shown in Figure 9, D9.

[0180] Test Example 1

[0181] Determination of the degradation rate of active ingredients: The degradation rate of active ingredients such as retinol propionate, bakuchiol, and phenylethyl resorcinol was determined by high-performance liquid chromatography-ultraviolet detection. Specifically, Examples 1 to 9, Comparative Example 2, Comparative Example 4, and Comparative Example 8 prepared were placed in a 50°C constant temperature oven. Every 7 days, 15 days, and 28 days, the emulsion was dissolved with methanol, and the degradation rate was determined by high-performance liquid chromatography. The specific high-performance liquid chromatography conditions are as follows: the chromatographic column uses a C18 reverse phase chromatographic column (250*4.6mm, 5um), the mobile phase composition is 98vol% methanol, 2vol% water, the mobile phase flow rate is 1ml / min, the detection wavelength is 325nm, and the external standard method is used for quantitative detection.

[0182] Among them, Table 1 shows the component proportions of the emulsions of Examples 1 to 9 and Comparative Examples 1 to 9, and Table 2 shows the results of the active substance degradation rate determination experiment in Test Example 1.

[0183] Table 1 Proportion of components in emulsion

[0184] Table 2 Results of active substance degradation rate determination experiment

[0185] According to the results in Table 2, the emulsions of the present application examples have a higher retention rate over time than those of comparative examples 2 and 4. Compared with GTCC, the oil phase component pentaerythritol tetra(ethylhexanoate) in the present application solution has a better compatibility with other ingredients and can still maintain a high retention rate after 28 days, while comparative examples 2 and 4 have already experienced precipitation problems after 28 days.

[0186] In addition, according to the experimental results recorded in Examples 1 to 9, Comparative Examples 1 to 9, and the experimental results in Figures 2 to 9, it can be seen that when the components of the emulsion in the present application are mixed in appropriate proportions, while being able to achieve excellent protection effects on the oil phase active ingredients, the emulsion product can also be successfully prepared and obtained. However, when other components are mixed or the ratios are inappropriate, there are problems such as easy precipitation, failure to form an emulsion, failure to form an oil gel, and large degree of discoloration. Among them, as can be seen from Figure 5, the emulsion of Comparative Example 4 broke after storage, a large amount of retinol propionate precipitated, and the discoloration was severe; as can be seen from Figure 6, the discoloration degree of Comparative Example 3 was large after storage, and in Comparative Example 1, the oil, lipopeptide, and glycerol were mixed without forming an oil gel, but rather a stratification phenomenon; as can be seen from Figure 7, the oil gel in Comparative Example 7 was of poor quality and free oil was present; as can be seen from Figure 9, the emulsion in Comparative Example 9 was obviously stratified, indicating that the emulsion stability was poor.

[0187] The embodiment of the present application, by introducing sodium subtilisin, and preferably selecting glycerin and pentaerythritol tetra(ethylhexanoate) for compatibility with the oil phase active ingredients, and the proportion of the compatibility, enables the embodiment to have an excellent protective effect on the oil phase active ingredients. After 28 days, the retention rate of the oil phase active ingredients can still be maintained at more than 90%, which can effectively reduce the degradation of the oil phase active ingredients.

[0188] The foregoing is merely an embodiment of the present application, and the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application may have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc. made within the technical ideas and principles of the present application should be included in the scope of protection of the present application.

Claims

1. An oil gel, characterized in that The oil gel comprises: (a) at least one lipopeptide; (b) glycerol; (c) pentaerythritol tetra(ethylhexanoate); and (d) at least one oil phase active.

2. The oil gel according to claim 1, characterized in that The weight percentage of the lipopeptide and glycerol is not less than 3%.

3. The oil gel according to claim 1, characterized in that The weight ratio of the oil phase active substance to pentaerythritol tetra(ethylhexanoate) is 1:3-13.

4. The oil gel according to claim 1, characterized in that The ratio of the sum of the weight of the lipopeptide and glycerol to the sum of the weight of the oil phase active substance and pentaerythritol tetra(ethylhexanoate) ester is 1:3-10.

5. The oil gel according to claim 2, characterized in that The weight percentage of the lipopeptide and glycerol is not less than 5%.

6. The oil gel according to claim 5, characterized in that The weight percentage of the lipopeptide and glycerol is 5% to 12%.

7. The oil gel according to claim 3, characterized in that The weight ratio of the oil phase active substance to pentaerythritol tetra(ethylhexanoate) is 1:5-11.

8. The oil gel according to claim 1, characterized in that The lipopeptide comprises any one or more of sodium subtilisin, iturin, feninterferon, fengyuansu, daptomycin, polymyxin, bacillus antibiotic L, levofloxacin, and bacillus antibiotic D.

9. The oil gel according to claim 1, characterized in that The oil phase active substance comprises one or more of retinol, retinyl acetate, retinyl propionate, retinyl palmitate, bakuchiol, equol, nervonic acid, ascorbyl palmitate, ascorbyl tetrapalmitate, and phenethylresorcinol.

10. An emulsion, characterized in that The method comprises water and the oil gel according to any one of claims 1 to 9.

11. The emulsion according to claim 10, characterized in that The ratio of the sum of the weights of the lipopeptide, glycerol, oil phase active substances and pentaerythritol tetra(ethylhexanoate) to the weight of water is 1:1-4.

12. [Corrected 02.09.2024 according to Rule 91] A method for preparing an oil gel according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: 1) Dissolve the lipopeptide in glycerol, heat and stir to obtain solution A; 2) dissolving the oil phase active substance in pentaerythritol tetra(ethylhexanoate) and stirring to obtain solution B; 3) Add solution A to solution B in a constant temperature water bath with stirring to obtain an oil gel.

13. The method for preparing the emulsion according to claim 11 or 12, characterized in that: The method also includes adding a water phase to the oil gel under stirring conditions and fully mixing the two phases to obtain the emulsion containing the lipopeptide.

14. Use of the oil gel according to any one of claims 1 to 9 or the emulsion according to claim 10 or 11 in cosmetics.

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