Pickering emulsion with ultraviolet synergistic absorption performance as well as preparation method and application of Pickering emulsion

Abstract

The invention provides Pickering emulsion with ultraviolet synergistic absorption performance as well as a preparation method and application of the Pickering emulsion. The organic sun-screening agent is wrapped by adopting a specific method, and the obtained mesoporous silicon composite material can still remarkably improve the light stability of the organic sun-screening agent and the dispersity of the organic sun-screening agent in a sun-screening product under the condition that a surfactant is not adopted, so that efficient and lasting sun screening is realized, and the mesoporous silicon composite material is very suitable for preparing the sun-screening product. Besides, the mesoporous silicon composite material is further dispersed in a specific Pickering emulsion, and it is found that the mesoporous silicon composite material can further enhance the ultraviolet absorption effect of the mesoporous silicon composite material, indicating that the Pickering emulsion has ultraviolet synergistic absorption performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of cosmetics, and more specifically, relates to a Pickering emulsion with UV synergistic absorption performance, a preparation method and application thereof. Background Art

[0002] With the destruction of the ozone layer, the harm of ultraviolet rays to humans is becoming increasingly serious. Long-term exposure to ultraviolet rays may cause health problems such as sunburn, photoaging and cataracts, and even increase the risk of skin cancer such as melanoma. Therefore, it is very necessary to protect against the sun in daily life. The most common way is to use sunscreen products.

[0003] Organic sunscreens can effectively absorb ultraviolet radiation and convert it into heat or other forms of radiation, so they are often used to prepare sunscreen products. However, there are two major problems with organic sunscreens: (1) they are photo-instable and easily photodegrade under long-term exposure to ultraviolet light, making it difficult to provide long-term sun protection; (2) they often have poor dispersibility in sunscreen products and are prone to agglomeration, resulting in poor sunscreen performance. To solve these two problems, existing sunscreen products often require the addition of surfactants, but the long-term use of surfactants can easily cause skin problems such as impaired barrier function, irritation, allergies and dryness, and the discharge of wastewater containing surfactants can also cause a certain degree of environmental pollution. Summary of the invention

[0004] In view of the deficiencies of the prior art, the present invention aims to provide a mesoporous silica composite material, which can significantly improve the photostability of the organic sunscreen and its dispersibility in sunscreen products without using a surfactant by encapsulating the organic sunscreen in a specific method, thereby achieving efficient and long-lasting sun protection.

[0005] The first object of the present invention is to provide a mesoporous silicon composite material.

[0006] The second object of the present invention is to provide the use of the above-mentioned mesoporous silica composite material in the preparation of sunscreen products.

[0007] The third object of the present invention is to provide a Pickering emulsion stabilized by a mesoporous silica composite material.

[0008] The fourth object of the present invention is to provide a method for preparing the Pickering emulsion.

[0009] The fifth object of the present invention is to provide the use of the above-mentioned mesoporous silica composite material or the above-mentioned Pickering emulsion as and / or in the preparation of cosmetics.

[0010] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0011] The present invention provides a mesoporous silicon composite material, which is prepared by the following method:

[0012] S1. Adding an organic sunscreen agent to an organic solvent and mixing to obtain an organic sunscreen agent solution;

[0013] S2. The hexadecyl trimethyl ammonium bromide is added to an organic solvent, and then added to water, and mixed to obtain a hexadecyl trimethyl ammonium bromide solution;

[0014] S3. The organic sunscreen solution is mixed with the cetyl trimethyl ammonium bromide solution to obtain an organic sunscreen - cetyl trimethyl ammonium bromide mixed solution;

[0015] S4. Add ethyl orthosilicate and mix well, then add aqueous ammonia, and after the reaction is complete, separate the solid and liquid to obtain;

[0016] Wherein, in the hexadecyltrimethylammonium bromide solution described in S2, the concentration of hexadecyltrimethylammonium bromide is 3.8-4.2 mg / mL; S1 and S2 do not limit the execution order.

[0017] The mesoporous silica composite material of the present invention wraps the organic sunscreen agent by a specific method, and can significantly improve the photostability of the organic sunscreen agent and its dispersibility in sunscreen products without using a surfactant, thereby achieving efficient and long-lasting sun protection, and is very suitable for preparing sunscreen products.

[0018] The term “S1 and S2 are not limited in execution order” means that S1 can be executed first and then S2, or S2 can be executed first and then S1, or S1 and S2 can be executed at the same time.

[0019] Preferably, the organic sunscreen agent in S1 is one or more of avobenzone, ethylhexyl methoxycinnamate, ethylhexyl triazone, p-methoxycinnamate, camphor derivatives, benzotriazole UV absorbers and oricrene.

[0020] Preferably, the organic solvent in S1 is one or more of ethanol, methanol, isopropanol, propylene glycol, and n-butanol.

[0021] Preferably, in the organic sunscreen solution described in S1, the concentration of the organic sunscreen is ≥8 mg / mL.

[0022] More preferably, the concentration of the organic sunscreen is 8 to 20 mg / mL.

[0023] Preferably, the mixing in S1 is achieved by ultrasound, such as ultrasound at 30-70 Hz and 300-700 W for 10-60 min.

[0024] Preferably, the organic solvent in S2 is one or more of ethanol, methanol, isopropanol, propylene glycol, and n-butanol.

[0025] Preferably, the volume ratio of the organic solvent to water in S2 is 1:4.8-5.2.

[0026] Preferably, the mixing in S2 is achieved by ultrasound, such as ultrasound at 30-70 Hz and 300-700 W for 10-60 min.

[0027] Preferably, the volume ratio of the organic sunscreen solution to the cetyltrimethylammonium bromide solution in S3 is 1:3-8.

[0028] Preferably, the mixing in S3 is achieved by stirring, such as stirring at 350-450 rpm for 0.8-1.2 h.

[0029] Preferably, the concentration of the ammonia water in S4 is 23wt% to 27wt%.

[0030] Preferably, the volume ratio of the organic sunscreen-cetyltrimethylammonium bromide mixed solution, tetraethyl orthosilicate and ammonia water is 10-30:0.1-2:0.1-2.

[0031] Preferably, the reaction time in S4 is 2.5 to 3.5 hours.

[0032] Preferably, the reaction in S4 is also stirred, such as stirring at 900-1100 rpm.

[0033] Preferably, the solid-liquid separation in S4 is centrifugation.

[0034] Preferably, after the solid-liquid separation in S4, post-treatment is further performed, such as washing and drying in sequence.

[0035] More preferably, the washing is washing with water and then with an organic solvent.

[0036] More preferably, the organic solvent is one or more of ethanol, methanol, isopropanol, propylene glycol, and n-butanol.

[0037] More preferably, the drying is performed at 40 to 50° C. for 12 to 36 hours.

[0038] The above-mentioned mesoporous silica composite material uses a specific method to wrap the organic sunscreen agent, and can significantly improve the photostability of the organic sunscreen agent and its dispersibility in sunscreen products without using a surfactant, thereby achieving efficient and long-lasting sun protection, and is very suitable for preparing sunscreen products. Therefore, the application of the above-mentioned mesoporous silica composite material in the preparation of sunscreen products should also be within the protection scope of the present invention.

[0039] In addition, the mesoporous silica composite material of the present invention also has good emulsification properties, can smoothly form a Pickering emulsion without adding a surfactant, and can disperse the organic sunscreen at the oil-water interface of the Pickering emulsion, thereby improving the sunscreen performance of the Pickering emulsion. Therefore, the present invention also provides a Pickering emulsion stabilized by a mesoporous silica composite material, comprising the following components in parts by weight: 0.005 to 0.05 parts of the above-mentioned mesoporous silica composite material, 1 to 10 parts of a moisturizer, 20 to 50 parts of an emollient, 1 to 5 parts of a film former, and 44 to 74 parts of water; wherein the moisturizer is two or three of macadamia seed oil, butanediol, and sodium hyaluronate.

[0040] The present invention compounds a mesoporous silica composite material prepared by a specific method and encapsulating an organic sunscreen with a specific moisturizer and other ingredients, and the obtained Pickering emulsion not only has better stability and sunscreen effect, but also can significantly improve the ultraviolet absorption performance of the organic sunscreen. In addition, compared with the Pickering emulsion prepared by moisturizers with other ingredients or other materials containing organic sunscreens, the Pickering emulsion of the present invention has better sunscreen performance.

[0041] Preferably, the mass ratio of macadamia seed oil, butylene glycol and sodium hyaluronate is (2-5):(2-5):(1-3); or the mass ratio of macadamia seed oil and butylene glycol is (2-5):(2-5); or the mass ratio of macadamia seed oil and sodium hyaluronate is (2-5):(1-3); or the mass ratio of butylene glycol and sodium hyaluronate is (2-5):(1-3).

[0042] Preferably, the emollient is one or more of caprylic / capric triglyceride, squalane and cyclopentasiloxane.

[0043] Preferably, the film former is one or both of trimethylsiloxysilicate and polyvinyl alcohol.

[0044] Preferably, it also contains 0.05 to 1 part of preservative.

[0045] More preferably, the preservative is one or both of p-hydroxyacetophenone and ethylhexylglycerin.

[0046] Optionally, the mass fraction of the mesoporous silicon composite material is 0.005, 0.01, 0.02, 0.03, 0.04, and 0.05 parts; the mass fraction of the moisturizer is 1, 3, 5, 7, 9, and 10 parts; the mass fraction of the emollient is 20, 25, 30, 35, 40, 45, and 50 parts; the mass fraction of the film-forming agent is 1, 2, 3, 4, and 5 parts; the mass fraction of the preservative is 0.05, 0.1, 0.3, 0.5, 0.7, 0.9, and 1 part; and the mass fraction of water is 44, 48, 52, 56, 58, 62, 66, 70, and 74 parts.

[0047] Based on this, the present invention also provides a method for preparing the above Pickering emulsion, comprising the following steps:

[0048] S1. mixing the mesoporous silica composite material, the humectant and water to obtain an aqueous phase;

[0049] S2. mixing the emollient and the film-forming agent to obtain an oil phase;

[0050] S3. Add the oil phase into the water phase and homogenize.

[0051] Preferably, a preservative is also added to S1.

[0052] More preferably, the preservative is one or both of p-hydroxyacetophenone and ethylhexylglycerin.

[0053] Preferably, the homogenization in S3 is carried out at 6000-10000 rpm for 2-5 min.

[0054] The above mesoporous silica composite material and Pickering emulsion both have good stability and sunscreen effect, and can achieve efficient and long-lasting sunscreen. Therefore, the use of the above mesoporous silica composite material or the above Pickering emulsion as and / or in the preparation of cosmetics should be within the protection scope of the present invention.

[0055] Preferably, the cosmetic is one of lotion, cream, liquid foundation and spray.

[0056] The present invention has the following beneficial effects:

[0057] 1. The mesoporous silica composite material of the present invention wraps the organic sunscreen agent by a specific method, and can significantly improve the photostability of the organic sunscreen agent and its dispersibility in sunscreen products without using a surfactant, thereby achieving efficient and long-lasting sun protection, and is very suitable for preparing sunscreen products.

[0058] 2. The mesoporous silica composite material of the present invention has good emulsifying properties and can smoothly form a Pickering emulsion without adding a surfactant, and can disperse the organic sunscreen at the oil-water interface of the Pickering emulsion, thereby improving the sunscreen performance of the Pickering emulsion.

[0059] 3. The present invention compounds a mesoporous silica composite material prepared by a specific method and coated with an organic sunscreen with a specific moisturizer and other ingredients, and the obtained Pickering emulsion not only has better stability and sunscreen effect, but also can significantly improve the ultraviolet absorption effect of the mesoporous silica composite material, indicating that the Pickering emulsion of the present invention has ultraviolet synergistic absorption performance. In addition, compared with the Pickering emulsion prepared by moisturizers with other ingredients or other materials containing organic sunscreens, the Pickering emulsion of the present invention has better sunscreen performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 The results of measuring the subcutaneous accumulation of the organic sunscreen in the AB@MPS-hydrogel obtained in Example 1 are shown.

[0061] Figure 2 These are the results of measuring the subcutaneous accumulation of the organic sunscreen in the OMC@MPS-hydrogel obtained in Example 2.

[0062] Figure 3 The results of determination of subcutaneous accumulation of organic sunscreen in T150@MPS-hydrogel obtained in Example 3 are shown.

[0063] Figure 4 This is the change result of the ultraviolet absorption properties of avobenzone dispersion.

[0064] Figure 5 The results of the changes in the ultraviolet absorption properties of the AB@MPS composite material dispersion.

[0065] Figure 6 This is the change result of the ultraviolet absorption property of ethylhexyl methoxycinnamate dispersion.

[0066] Figure 7 This is the change result of ultraviolet absorption properties of OMC@MPS composite dispersion.

[0067] Figure 8 This is the change result of the ultraviolet absorption performance of ethylhexyl triazone dispersion.

[0068] Fig. 9 The results of the changes in the ultraviolet absorption properties of the T150@MPS composite material dispersion are shown.

[0069] Fig.10 Photograph of Pickering Emulsion 1.

[0070] Fig.11 Optical microscopy image of Pickering emulsion 1.

[0071] Fig.12 Confocal microscopy image of a fluorescent Pickering emulsion.

[0072] Fig.13 The change of Pickering emulsion droplet size.

[0073] Fig.14 This is the UV-visible absorption spectrum of AB in different dispersion forms.

[0074] Fig.15 UV-visible absorption spectra of OMC and T150 in different dispersion forms. DETAILED DESCRIPTION

[0075] The present invention is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0076] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0077] Example 1 Preparation of mesoporous silicon composite material

[0078] S1. Avobenzone (AB) was added to anhydrous ethanol and subjected to ultrasonic homogenization at 50 Hz and 500 W for 30 min to obtain an organic sunscreen solution with a concentration of 8 mg / mL;

[0079] S2. cetyltrimethylammonium bromide was added to anhydrous ethanol, and then deionized water was added (so that the volume ratio of anhydrous ethanol to deionized water was 1:5), and ultrasonic homogenization was performed at 50 Hz and 500 W for 30 min to obtain a cetyltrimethylammonium bromide solution with a concentration of 4 mg / mL;

[0080] S3. The organic sunscreen solution and the cetyl trimethyl ammonium bromide solution were mixed in a volume ratio of 1:4 and stirred at 400 rpm for 1 h to obtain a uniformly dispersed organic sunscreen-cetyl trimethyl ammonium bromide mixed solution;

[0081] S4. Add tetraethyl orthosilicate and mix well, then add 25wt% ammonia water (so that the volume ratio of organic sunscreen agent-cetyltrimethylammonium bromide mixed solution, tetraethyl orthosilicate and ammonia water is 15:1:0.2), stir the reaction at 1000rpm for 3h, collect the solid by centrifugation, wash it with deionized water and ethanol for 3 times respectively, and dry it in an oven at 42°C for 24h to obtain the mesoporous silica composite material (AB@MPS composite material).

[0082] Example 2 Preparation of mesoporous silicon composite material

[0083] S1. Ethylhexyl methoxycinnamate (OMC) was added to anhydrous ethanol and subjected to ultrasonic homogenization at 30 Hz and 700 W for 60 min to obtain an organic sunscreen solution with a concentration of 8 mg / mL;

[0084] S2. Add hexadecyltrimethylammonium bromide to anhydrous ethanol, then add deionized water (so that the volume ratio of anhydrous ethanol to deionized water is 1:4.8), and perform ultrasonic homogenization at 30 Hz and 700 W for 60 min to obtain a hexadecyltrimethylammonium bromide solution with a concentration of 3.8 mg / mL;

[0085] S3. The organic sunscreen solution and the cetyl trimethyl ammonium bromide solution were mixed in a volume ratio of 1:3 and stirred at 350 rpm for 1.2 h to obtain a uniformly dispersed organic sunscreen-cetyl trimethyl ammonium bromide mixed solution;

[0086] S4. Add tetraethyl orthosilicate and mix well, then add 27wt% ammonia water (so that the volume ratio of organic sunscreen agent-cetyltrimethylammonium bromide mixed solution, tetraethyl orthosilicate and ammonia water is 10:0.1:0.1), stir the reaction at 900rpm for 3.5h, collect the solid by centrifugation, wash it twice with deionized water and ethanol respectively, and dry it in an oven at 50°C for 12h to obtain the mesoporous silica composite material (OMC@MPS composite material).

[0087] Example 3 Preparation of mesoporous silicon composite material

[0088] S1. Ethylhexyl triazone (T150) was added to anhydrous ethanol and homogenized by ultrasound at 70 Hz and 300 W for 10 min to obtain an organic sunscreen solution with a concentration of 20 mg / mL;

[0089] S2. cetyltrimethylammonium bromide was added to anhydrous ethanol, and then deionized water was added (so that the volume ratio of anhydrous ethanol to deionized water was 1:5.2), and ultrasonic homogenization was performed at 70 Hz and 300 W for 10 min to obtain a cetyltrimethylammonium bromide solution with a concentration of 4.2 mg / mL;

[0090] S3. The organic sunscreen solution and the cetyl trimethyl ammonium bromide solution were mixed in a volume ratio of 1:8 and stirred at 450 rpm for 0.8 h to obtain a uniformly dispersed organic sunscreen-cetyl trimethyl ammonium bromide mixed solution;

[0091] S4. Add tetraethyl orthosilicate and mix well, then add 23wt% ammonia water (so that the volume ratio of organic sunscreen agent-cetyltrimethylammonium bromide mixed solution, tetraethyl orthosilicate and ammonia water is 30:2:2), stir the reaction at 1100rpm for 2.5h, collect the solid by centrifugation, wash it with deionized water and ethanol for 3 times respectively, and dry it in an oven at 40°C for 36h to obtain the mesoporous silica composite material (T150@MPS composite material).

[0092] Comparative Example 1 Preparation of Mesoporous Silicon Composite Material

[0093] The same as Example 1, except that avobenzone is not added, that is, S1 is not performed, and the organic sunscreen solution in S3 is replaced by an equal volume of anhydrous ethanol.

[0094] Comparative Example 2 Preparation of Mesoporous Silicon Composite Material

[0095] The same as Example 1, except that, in S4, 25 wt % ammonia water is first added, and then ethyl orthosilicate is added, that is, S4 is specifically:

[0096] S4. Add 25wt% ammonia water, then add tetraethyl orthosilicate and mix well (make the volume ratio of organic sunscreen agent-cetyltrimethylammonium bromide mixed solution, tetraethyl orthosilicate and ammonia water to be 15:1:0.2), stir the reaction at 1000rpm for 3h, collect the solid by centrifugation, wash it with deionized water and ethanol for 3 times respectively, and dry it in an oven at 42°C for 24h to obtain the mesoporous silica composite material.

[0097] Experimental Example 1 Physical and Chemical Properties of Mesoporous Silica Composite Materials

[0098] 1. Determination of subcutaneous accumulation

[0099] The mesoporous silica composite materials obtained in Examples 1 to 3 and the corresponding organic sunscreen agents (ensuring that the masses of the organic sunscreen agents contained in the two are consistent) were added to carbomer hydrogel (0.60 wt % carbomer C491, 0.42 wt % arginine, and 98.98 wt % deionized water were homogenized in a magnetic stirrer at 800 rpm for 5 h) (so that the content of the organic sunscreen agent in the carbomer hydrogel is 0.0938 wt %) to obtain mesoporous silica composite material-hydrogel and organic sunscreen agent-hydrogel (4 parallel samples were set for each, and the results were averaged).

[0100] The cellulose membrane was soaked in pure water for 1 h before being placed between the donor chamber and the receptor chamber of a transdermal diffusion cell (the receptor chamber had a capacity of 24 mL, and the receptor phase was a phosphate buffer solution with a pH of 7.4 containing 2% (v / v) Tween 20, and was stirred continuously at 37°C and 350 rpm). The surface temperature of the cellulose membrane was maintained at 35°C. The effective permeation area of ​​the cellulose membrane (the area of ​​the cellulose membrane covered by the contact surface between the donor chamber and the receptor chamber, 4.90 cm) was then 2 ) was evenly applied with 500 mg of mesoporous silica composite material-hydrogel and organic sunscreen-hydrogel, and then 1 mL of receptor phase was taken out at 0, 1, 2, 3, 4, 5, 6, and 24 h respectively (each time it was replenished with an equal volume of receptor phase), the absorbance of the taken out receptor phase at 356 nm was measured by ultraviolet spectrophotometer, and then the concentration of organic sunscreen in the receptor phase was determined according to the standard curve of the corresponding organic sunscreen to characterize the subcutaneous accumulation.

[0101] The results are as follows Figures 1 to 3 As shown, it can be seen that the subcutaneous accumulation of organic sunscreens in the AB@MPS-hydrogel obtained in Example 1, the OMC@MPS-hydrogel obtained in Example 2, and the T150@MPS-hydrogel obtained in Example 3 is significantly lower than that of the corresponding organic sunscreen-hydrogels, which are safer for the skin, indicating that the mesoporous silica composite material of the present invention has higher safety.

[0102] 2. Light stability test

[0103] The mesoporous silica composite materials obtained in Examples 1 to 3 and the corresponding organic sunscreens (ensuring that the mass of the organic sunscreens contained in the two are consistent) are dispersed in anhydrous ethanol, and then the absorbances of the two at 356 nm are adjusted to be consistent by dilution to obtain sample dispersions. The sample dispersions are placed under simulated sunlight at 35° C., and the absorbances of the sample dispersions at 280 to 400 nm are measured by an ultraviolet spectrophotometer at 0, 1, 2, 3, 4, and 5 hours.

[0104] The results of the changes in the ultraviolet absorption properties of avobenzone dispersion are as follows Figure 4 As shown in Figure 2, the UV absorption performance of the AB@MPS composite dispersion changes as shown in Figure 2. Figure 5 As shown in the figure, the UV absorption performance change of ethylhexyl methoxycinnamate dispersion is as follows Figure 6 As shown in Figure 2, the UV absorption performance of the OMC@MPS composite dispersion changes as shown in Figure 2. Figure 7 As shown, the UV absorption performance change results of ethylhexyl triazone dispersion are as follows Figure 8 As shown in Figure 2, the UV absorption performance of the T150@MPS composite dispersion changes as shown in Figure 2. Fig. 9 It can be seen that after 5 hours of simulated sunlight illumination, the absorbance of the mesoporous silicon composite material of the present invention has no significant change, indicating that the mesoporous silicon composite material of the present invention has high light stability and can make the sunscreen effect more lasting.

[0105] Experimental Example 2 Effect of different concentrations of hexadecyltrimethylammonium bromide solution on the emulsification properties of mesoporous silica composites

[0106] 1. Preparation method of mesoporous silicon composite material

[0107] S1. Avobenzone (AB) was added to anhydrous ethanol and subjected to ultrasonic homogenization at 50 Hz and 500 W for 30 min to obtain an organic sunscreen solution with a concentration of 8 mg / mL;

[0108] S2. cetyltrimethylammonium bromide was added to anhydrous ethanol, and then deionized water was added (so that the volume ratio of anhydrous ethanol to deionized water was 1:5), and after ultrasonic homogenization at 50 Hz and 500 W for 30 min, cetyltrimethylammonium bromide solutions with concentrations of 0.67, 1.33, 2.67, 3.33, 3.80, 4.00, 4.20, and 4.67 mg / mL were obtained, respectively;

[0109] S3. The organic sunscreen solution and the cetyl trimethyl ammonium bromide solution were mixed in a volume ratio of 1:4 and stirred at 400 rpm for 1 h to obtain a uniformly dispersed organic sunscreen-cetyl trimethyl ammonium bromide mixed solution;

[0110] S4. Add tetraethyl orthosilicate and mix well, then add 25wt% ammonia water (so that the volume ratio of organic sunscreen agent-cetyltrimethylammonium bromide mixed solution, tetraethyl orthosilicate and ammonia water is 15:1:0.2), stir the reaction at 1000rpm for 3h, collect the solid by centrifugation, wash it with deionized water and ethanol for 3 times respectively, and dry it in an oven at 42°C for 24h to obtain the mesoporous silica composite material (AB@MPS composite material).

[0111] 2. Determination method of three-phase contact angle of mesoporous silica composites

[0112] The AB@MPS composite materials prepared above were added to n-hexane (the amount of n-hexane was sufficient to make the AB@MPS composite materials uniformly dispersed), and ultrasonicated at 50 Hz and 500 W for 10 min to obtain a dispersion. The dispersion was aspirated and dripped onto a glass sheet, dried at 37 ° C, and the dripping and drying operations were repeated until a dense layer of AB@MPS composite materials was evenly covered on the glass sheet. The glass sheet was then transferred to a cuvette, caprylic / capric triglyceride was added to the cuvette (so that the glass sheet was completely covered), and 3 μL of ultrapure water was aspirated and slowly dripped onto the glass sheet. After the droplets were stable, the droplets were photographed and the three-phase contact angles at 5 different positions on each glass sheet were calculated using the image processing software Image J, and the average value was taken.

[0113] 3. Results of the three-phase contact angle measurement of mesoporous silica composites

[0114] The measurement results are shown in Table 1.

[0115] Table 1

[0116] Hexadecyltrimethylammonium bromide solution concentration Three-phase contact angle 0.67mg / mL 12.1° 1.33mg / mL 29.5° 2.67mg / mL 60.5° 3.33mg / mL 72.8° 3.80mg / mL 80.4° 4.00mg / mL 90.7° 4.20mg / mL 105.3° 4.67mg / mL 127.6°

[0117] It can be seen that when the concentration of hexadecyltrimethylammonium bromide is 3.8-4.2 mg / mL, the three-phase contact angle of the mesoporous silica composite material is 90°±10°, indicating that it can form a stable Pickering emulsion. And when the concentration of hexadecyltrimethylammonium bromide is 4 mg / mL, the three-phase contact angle of the mesoporous silica composite material is 90.7°, which has good amphiphilicity, can be more balanced in adsorption at the oil-water interface, and can form a more stable Pickering emulsion. Therefore, the mesoporous silica composite material of the present invention has better emulsification properties and can still smoothly form a Pickering emulsion without adding a surfactant.

[0118] Application Example 1 Pickering emulsion stabilized by mesoporous silica composites

[0119] 1. Preparation of Pickering emulsion

[0120] (1) Preparation of Pickering Emulsion 1

[0121] S1. Mix 0.02 parts by mass of the mesoporous silica composite material obtained in Example 1, 1 part by mass of a humectant, 0.05 parts by mass of p-hydroxyacetophenone and 55 parts by mass of deionized water to obtain an aqueous phase;

[0122] S2. 40 parts by mass of caprylic / capric triglyceride and 1 part by mass of trimethylsiloxysilicate were mixed to obtain an oil phase;

[0123] S3. The oil phase was added to the aqueous phase and homogenized at 8000 rpm for 3 min to obtain the Pickering emulsion;

[0124] Among them, the moisturizer described in S1 is macadamia seed oil, butylene glycol and sodium hyaluronate in a mass ratio of 3.5:3.5:2.

[0125] (2) Preparation of Pickering Emulsion 2

[0126] S1. Mix 0.005 parts by mass of the mesoporous silica composite material obtained in Example 1, 1 part by mass of a humectant, 0.05 parts by mass of p-hydroxyacetophenone and 44 parts by mass of deionized water to obtain an aqueous phase;

[0127] S2. Mix 20 parts by mass of caprylic / capric triglyceride and 1 part by mass of trimethylsiloxysilicate to obtain an oil phase;

[0128] S3. The oil phase was added to the aqueous phase and homogenized at 6000 rpm for 5 min to obtain the Pickering emulsion;

[0129] Among them, the moisturizer described in S1 is macadamia seed oil, butylene glycol and sodium hyaluronate in a mass ratio of 2:2:1.

[0130] (3) Preparation of Pickering Emulsion 3

[0131] S1. Mix 0.05 parts by mass of the mesoporous silica composite material obtained in Example 1, 10 parts by mass of a humectant, 1 part by mass of p-hydroxyacetophenone and 74 parts by mass of deionized water to obtain an aqueous phase;

[0132] S2. Mix 50 parts by mass of caprylic / capric triglyceride and 5 parts by mass of trimethylsiloxysilicate to obtain an oil phase;

[0133] S3. The oil phase was added to the aqueous phase and homogenized and emulsified at 10000 rpm for 2 min using a homogenizer to obtain the Pickering emulsion;

[0134] Among them, the moisturizer described in S1 is macadamia seed oil, butylene glycol and sodium hyaluronate in a mass ratio of 5:5:3.

[0135] (4) Preparation of Pickering Emulsion 4

[0136] Same as Pickering Lotion 1, except that caprylic / capric triglyceride is replaced with squalane.

[0137] (5) Preparation of Comparative Pickering Emulsion 1

[0138] Same as Pickering Lotion 1, except that the moisturizer is replaced with an equal amount of macadamia seed oil.

[0139] (6) Preparation of Comparative Pickering Emulsion 2

[0140] Same as Pickering Lotion 1, except that the moisturizer is replaced with an equal amount of butylene glycol.

[0141] (7) Preparation of Comparative Pickering Emulsion 3

[0142] Same as Pickering Lotion 1, except that the moisturizer is replaced with an equal amount of sodium hyaluronate.

[0143] (8) Preparation of Comparative Pickering Emulsion 4

[0144] The same as Pickering emulsion 1, except that the mesoporous silica composite material is replaced with an equal mass of a common emulsified sunscreen, wherein the preparation method of the common emulsified sunscreen is as follows:

[0145] 0.0005 parts by mass of avobenzone was added to 0.02 parts by mass of Tween 20, and the mixture was homogenized and emulsified at 8000 rpm for 3 minutes.

[0146] (9) Preparation of Comparative Pickering Emulsion 5

[0147] Same as Pickering emulsion 1, except that the mesoporous silica composite material is replaced with an equal mass of Tween 20.

[0148] (10) Preparation of Comparative Pickering Emulsion 6

[0149] The same as Pickering emulsion 1, except that the mesoporous silica composite material obtained in Example 1 is replaced by the mesoporous silica composite material obtained in Comparative Example 1.

[0150] (11) Preparation of Comparative Pickering Emulsion 7

[0151] The same as Pickering emulsion 1, except that the mesoporous silica composite material obtained in Example 1 is replaced by the mesoporous silica composite material obtained in Comparative Example 2.

[0152] 2. Macro Image

[0153] Pickering Lotion 1 photo Fig.10 As shown, Pickering emulsion 1 is in the form of a white emulsion, which is uniform and not stratified. This indicates that the mesoporous silica composite material of the present invention has better emulsification properties and can still form a Pickering emulsion smoothly without adding a surfactant.

[0154] 3. Optical microscope observation

[0155] The Pickering emulsion 1 was observed under an optical microscope. Fig.11 As shown, it can be seen that the emulsion layer is dense and the emulsion droplets are uniform in size, indicating that the mesoporous silica composite material of the present invention has better emulsification performance and can still form a Pickering emulsion smoothly without adding a surfactant.

[0156] 4. Confocal Microscope Observation

[0157] (1) Preparation of fluorescent Pickering emulsion

[0158] S1. FITC fluorescent dye and avobenzone were mixed at a mass ratio of 1:4 to obtain AB+FITC, which was then used to replace avobenzone in S1 of Example 1, and then the (AB+FITC)@MPS composite material was prepared according to the method of Example 1;

[0159] S2. Mix 0.02 parts by mass of (AB + FITC) @ MPS composite material, 1 part by mass of humectant, 0.05 parts by mass of p-hydroxyacetophenone and 55 parts by mass of deionized water to obtain an aqueous phase;

[0160] S3. Nile red was added to caprylic acid / capric acid triglyceride (so that the concentration of Nile red was 1 μg / mL), and the caprylic acid / capric acid triglyceride was uniformly dyed at 600 rpm for 10 min, and then 40 parts by mass of the dyed caprylic acid / capric acid triglyceride and 1 part by mass of trimethylsiloxysilicate were mixed to obtain an oil phase;

[0161] S4. The oil phase was added to the aqueous phase and homogenized at 8000 rpm for 3 min to obtain the fluorescent Pickering emulsion;

[0162] Among them, the moisturizer described in S2 is macadamia seed oil, butylene glycol and sodium hyaluronate in a mass ratio of 3.5:3.5:2.

[0163] (2) Observation of fluorescent Pickering emulsion

[0164] The fluorescent Pickering emulsion was observed using a confocal microscope. Fig.12It can be seen that the Pickering emulsion of the present invention is an oil-in-water type, and avobenzone is dispersed at the oil-water interface of the Pickering emulsion, indicating that the mesoporous silica composite material of the present invention effectively improves the dispersibility of the organic sunscreen in the Pickering emulsion.

[0165] 5. Storage stability test

[0166] The Pickering emulsion 1 was stored in an environment with a temperature of 25° C. and a humidity of 50 wt %. At 0, 30, 60, 120, 180, and 240 days, the changes in the droplet size of the Pickering emulsion were observed using an optical microscope and statistically analyzed using Image J software.

[0167] The results are as follows Fig.13 It can be seen that the particle size of Pickering emulsion 1 within 240 days does not exceed 160 μm, indicating that the Pickering emulsion of the present invention has better stability.

[0168] 6. Sunscreen performance test

[0169] (1) UVA protection performance test method

[0170] Pickering emulsions 1-4 and comparative Pickering emulsions 1-7 (three parallel samples were set up respectively, and the results were averaged) were mixed at 1.86 mg / cm 2 The amount was applied on a high-transmittance quartz glass slide and irradiated with UVA (320-400nm) and UVB (290-320nm) for 8 hours. The UVA / UVB ratio of the sample is calculated to evaluate the protective effect of the sample against UVA band ultraviolet rays. In the formula, A(λ) is the average absorbance of each wavelength (measured by UV spectrophotometer), and dλ is the measurement interval of the wavelength (in this test, the measurement is performed once every 1nm wavelength interval, so dλ is 1).

[0171] (2) SPF value determination method

[0172] Pickering emulsions 1-4 and comparative Pickering emulsions 1-7 (three parallel samples were set up respectively, and the results were averaged) were mixed at 2 mg / cm 2 The dosage was applied on a high-transmittance quartz glass slide and irradiated with a UV light with a wavelength range of 290 to 320 nm for 8 hours. The SPF value of the sample is calculated. In the formula, CF is the correction factor (=10), EE(λ)×I(λ) is a constant as shown in Table 2, and Abs(λ) is the absorbance of the sample (measured by UV spectrophotometer).

[0173] Table 2

[0174]

[0175]

[0176] (3) Sunscreen performance test results

[0177] The results are shown in Table 3.

[0178] Table 3

[0179] UVA / UVB Ratio SPF value Pickering Lotion 1 10.37 26.8 Pickering Lotion 2 9.17 25.7 Pickering Lotion 3 11.41 27.8 Pickering Lotion 4 10.06 27.0 Compare Pickering Lotion 1 6.76 18.4 Compare Pickering Lotion 2 7.03 19.1 Compare Pickering Lotion 3 6.32 15.4 Compare Pickering Lotion 4 3.67 14.3 Compare Pickering Lotion 5 0.51 0.3 Compare Pickering Lotion 6 1.33 1.1 Compare Pickering Lotion 7 6.43 17.6

[0180] It can be seen that in terms of the overall level of UVA / UVB ratio and SPF value, Pickering Emulsions 1 to 4 are significantly better than the comparative Pickering Emulsions 1 to 7, indicating that the Pickering emulsion obtained by compounding the mesoporous silica composite material prepared by a specific method and encapsulating an organic sunscreen with specific moisturizers and other ingredients in the present invention has better sun protection performance, and compared with the Pickering emulsion prepared by using moisturizers with other ingredients or other materials containing organic sunscreens, the sun protection performance of the Pickering emulsion of the present invention is more excellent.

[0181] VII. Test of UV absorption performance of organic sunscreens in different dispersion forms

[0182] 1. Test of UV absorption performance of avobenzone in different dispersion forms

[0183] (1) Experimental groups

[0184] ①: AB@MPS Pickering emulsion: same as Pickering emulsion 1.

[0185] ②: Pure water dispersion of AB@MPS: 0.02 parts by weight of the AB@MPS composite material obtained in Example 1 was dispersed in 98 parts by weight of deionized water.

[0186] ③: Surfactant-stabilized Pickering emulsion:

[0187] S1. 0.0004 parts by mass of avobenzone, 2 parts by mass of Tween 20, 1 part by mass of a humectant, 0.05 parts by mass of p-hydroxyacetophenone and 55 parts by mass of deionized water were mixed to obtain an aqueous phase;

[0188] S2. 40 parts by mass of caprylic / capric triglyceride and 1 part by mass of trimethylsiloxysilicate were mixed to obtain an oil phase;

[0189] S3. The oil phase was added to the aqueous phase and homogenized and emulsified at 8000 rpm for 3 min using a homogenizer to obtain a Pickering emulsion stabilized by the surfactant;

[0190] Among them, the moisturizer described in S1 is macadamia seed oil, butylene glycol and sodium hyaluronate in a mass ratio of 3.5:3.5:2.

[0191] (2) Ultraviolet absorption performance test

[0192] Disperse ① to ③ in RO water to make the final concentration of AB 0.04wt%, and place them in a 96-well plate. Use an ELISA reader to test the absorbance in the wavelength range of 290-400nm. The measured UV-visible absorption spectrum is shown in the figure below: Fig.14 It can be seen that the absorbance of ① is higher than that of ② to ③, that is, the Pickering emulsion of the present invention can further enhance the ultraviolet absorption effect of the mesoporous silica composite material, indicating that it has a synergistic ultraviolet absorption performance.

[0193] 2. Test of UV absorption performance of ethylhexyl methoxycinnamate in different dispersion forms

[0194] (1) Experimental groups

[0195] ①: OMC@MPS Pickering emulsion: Same as Pickering emulsion 1, except that the AB@MPS composite material obtained in Example 1 is replaced by the OMC@MPS composite material obtained in Example 2.

[0196] ②: Pure water dispersion of OMC@MPS: 0.02 parts by weight of the OMC@MPS composite material obtained in Example 2 was dispersed in 98 parts by weight of deionized water.

[0197] (2) Ultraviolet absorption performance test

[0198] Disperse ① to ② in RO water to make the final concentration of OMC 0.04wt%, and place them in a 96-well plate. Use an ELISA reader to test the absorbance in the wavelength range of 290-400nm. The measured UV-visible absorption spectrum is shown in the figure below. Fig.15 It can be seen that the absorbance of ① is higher than that of ②, that is, the Pickering emulsion of the present invention can further enhance the ultraviolet absorption effect of the mesoporous silica composite material, indicating that it has ultraviolet synergistic absorption performance.

[0199] 3. Test of UV absorption performance of ethylhexyl triazone in different dispersion forms

[0200] (1) Experimental groups

[0201] ①: T150@MPS Pickering emulsion: Same as Pickering emulsion 1, except that the AB@MPS composite material obtained in Example 1 is replaced by the T150@MPS composite material obtained in Example 3.

[0202] ②: Pure water dispersion of T150@MPS: 0.02 parts by weight of the T150@MPS composite material obtained in Example 3 was dispersed in 98 parts by weight of deionized water.

[0203] (2) Ultraviolet absorption performance test

[0204] Disperse ① to ② in RO water to make the final concentration of T150 0.04wt%, and place them in a 96-well plate. Use an ELISA reader to test the absorbance in the wavelength range of 290-400nm. The measured UV-visible absorption spectrum is shown in the figure below: Fig.15 It can be seen that the absorbance of ① is higher than that of ②, that is, the Pickering emulsion of the present invention can further enhance the ultraviolet absorption effect of the mesoporous silica composite material, indicating that it has ultraviolet synergistic absorption performance.

[0205] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A mesoporous silicon composite material, characterized in that: Prepared by the following method: S1. Adding an organic sunscreen agent to an organic solvent and mixing to obtain an organic sunscreen agent solution; S2. The hexadecyl trimethyl ammonium bromide is added to an organic solvent, and then added to water, and mixed to obtain a hexadecyl trimethyl ammonium bromide solution; S3. The organic sunscreen solution is mixed with the cetyl trimethyl ammonium bromide solution to obtain an organic sunscreen - cetyl trimethyl ammonium bromide mixed solution; S4. Add ethyl orthosilicate and mix well, then add aqueous ammonia, and after the reaction is complete, separate the solid and liquid to obtain; Wherein, in the hexadecyltrimethylammonium bromide solution described in S2, the concentration of hexadecyltrimethylammonium bromide is 3.8-4.2 mg / mL; S1 and S2 do not limit the execution order.

2. The mesoporous silicon composite material according to claim 1, characterized in that: In the organic sunscreen solution described in S1, the concentration of the organic sunscreen is ≥8 mg / mL.

3. The mesoporous silicon composite material according to claim 1, characterized in that: The volume ratio of the organic solvent to water in S2 is 1:4.8-5.

2.

4. The mesoporous silicon composite material according to claim 1, characterized in that: S3 The volume ratio of the organic sunscreen solution to the cetyltrimethylammonium bromide solution is 1:3-8.

5. The mesoporous silicon composite material according to claim 1, characterized in that: The volume ratio of the organic sunscreen-cetyltrimethylammonium bromide mixed solution, ethyl orthosilicate and ammonia water is 10-30:0.1-2:0.1-2.

6. Use of the mesoporous silica composite material according to any one of claims 1 to 5 in the preparation of sunscreen products.

7. A Pickering emulsion stabilized by a mesoporous silica composite material, characterized in that: The composition comprises the following components in parts by weight: 0.005 to 0.05 parts of the mesoporous silicon composite material according to any one of claims 1 to 5, 1 to 10 parts of a moisturizer, 20 to 50 parts of an emollient, 1 to 5 parts of a film-forming agent, and 44 to 74 parts of water; Wherein, the moisturizing agent is two or three of macadamia seed oil, butylene glycol and sodium hyaluronate.

8. The Pickering emulsion according to claim 7, characterized in that The mass ratio of macadamia seed oil, butylene glycol and sodium hyaluronate is (2-5):(2-5):(1-3); or the mass ratio of macadamia seed oil and butylene glycol is (2-5):(2-5); or the mass ratio of macadamia seed oil and sodium hyaluronate is (2-5):(1-3); or the mass ratio of butylene glycol and sodium hyaluronate is (2-5):(1-3).

9. The method for preparing the Pickering emulsion according to any one of claims 7 to 8, characterized in that: The steps include: S1. mixing the mesoporous silica composite material, the humectant and water to obtain an aqueous phase; S2. mixing the emollient and the film-forming agent to obtain an oil phase; S3. Add the oil phase into the water phase and homogenize.

10. Use of the mesoporous silica composite material according to any one of claims 1 to 5 or the Pickering emulsion according to any one of claims 7 to 8 as and / or in the preparation of cosmetics.

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