Composite sunscreen composition with excellent film-forming property and sunscreen stability and preparation method thereof

Abstract

The invention discloses a composite sunscreen composition with excellent film-forming property and sunscreen stability as well as a preparation method and application thereof, and belongs to the technical field of daily chemicals. The composite sunscreen composition is prepared from inulin lauryl carbamate, bis (lauramide glutamine) lysine sodium, hydroxypropyl trimethyl ammonium chloride hyaluronic acid, an ammonium acryloyldimethyl taurate / VP copolymer, a sunscreen agent, basic grease, and cosmetically acceptable auxiliary materials and a solvent, the sunscreen emulsion prepared on the basis of the composition can quickly form a stable, light, thin and breathable sunscreen film on the surface of skin, solves the problems that a sunscreen agent in a traditional sunscreen product is non-uniform in agglomeration and dispersion, a formed film is rigid and airtight, the sunscreen effect is easy to lose due to sweating / friction, the skin feeling is poor and the like, and has the advantages of high sunscreen stability, excellent water resistance and good skin feeling; the method can be widely applied to preparation of skin care products with a sunscreen effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of daily chemicals, and particularly relates to a composite sunscreen composition with excellent film-forming property and sunscreen stability and a preparation method thereof. BACKGROUND

[0002] In recent years, with the increasing harm of ultraviolet radiation to human skin, sunscreen products have become an important part of daily skin care. Currently, commercially available sunscreen products rely on physical sunscreen agents (such as titanium dioxide and zinc oxide) or chemical sunscreen agents (such as avobenzone and octocrylene) to achieve the blocking of ultraviolet rays. However, these sunscreen ingredients are prone to agglomeration in the formula, uneven distribution, resulting in local weak points in the sunscreen film, reducing the actual sunscreen effect, and easily falling off in the case of sweating, water or friction, poor durability.

[0003] In the prior art, film-forming agents are often added to enhance the adhesion and water resistance of sunscreen ingredients, but traditional film-forming agents such as polyvinyl alcohol and polyacrylate often have problems such as rigid film formation, poor air permeability, and easy sensitization. On the other hand, natural source film-forming agents such as polysaccharide substances have higher safety, but their film-forming strength, water resistance and compatibility with sunscreen agents are often not ideal.

[0004] Therefore, it is of important practical application value to develop a composite composition that can synergistically enhance the dispersibility, film-forming property, durability and comfort of sunscreen agents. SUMMARY

[0005] The present application aims to overcome the technical defects of uneven dispersion of sunscreen agents, poor film-forming property, poor skin feel and safety to be improved in the prior art sunscreen compositions, and provides a composite sunscreen composition with excellent film-forming property and sunscreen stability, as well as a preparation method and application thereof.

[0006] The sunscreen composition can quickly form a stable, light and breathable sunscreen film on the skin surface through scientific compounding of key active ingredients, effectively solving the problem of sunscreen agent agglomeration, improving the durability and stability of sunscreen effect, and simultaneously having excellent skin feel and high safety.

[0007] To achieve the above-mentioned purpose, the present application discloses the following technical solutions: In a first aspect, the present application provides a composite sunscreen composition, which contains inositol lauryl carbamate, di (lauramide glutamine) sodium lysine, hydroxypropyltrimonium chloride hyaluronic acid and acryloyldimethyl ammonium taurate / VP copolymer, sunscreen agents, base oil, and cosmetically acceptable adjuvants and solvents.

[0008] Preferably, the composition contains in mass percentage 0.05-0.15% of inulin lauryl carbamate, 0.05-0.3% of sodium di(lauroylmido glutamine) lysine, 0.01-0.08% of hydroxypropyltrimonium hydroxypropyl bivalent metal salt, and 0.1-0.4% of acryloyldimethyltaurine ammonium / VP copolymer.

[0009] Further preferably, the sunscreen agent is at least one of a chemical sunscreen agent, a physical sunscreen agent, and a plant sunscreen agent.

[0010] More preferably, the chemical sunscreen agent is at least one of an oil-soluble chemical sunscreen agent and a water-soluble chemical sunscreen agent.

[0011] Preferably, the auxiliary material is at least one of a skin conditioning agent, a pH adjusting agent, a moisturizing agent, a chelating agent, and a preservative. The solvent is water.

[0012] In a second aspect, the present application provides a sunscreen cream having excellent film-forming property and sunscreen stability, the sunscreen cream containing the composite sunscreen composition of the first aspect.

[0013] Preferably, the sunscreen cream is composed of 1-9% of isoamyl p-methoxycinnamate, 1-8% of octocrylene, 1-8% of bis-ethylhexyloxyphenol methoxyphenyl triazine, 0.05-0.15% of inulin lauryl carbamate, 0.05-0.3% of sodium di(lauroylmido glutamine) lysine, 0.01-0.08% of hydroxypropyltrimonium hydroxypropyl bivalent metal salt, 0.1-0.4% of acryloyldimethyltaurine ammonium / VP copolymer, 1-10% of glycerol, 1-10% of diisopropyl sebacate, 1-15% of dicaprylyl carbonate, 0.01-0.5% of p-hydroxyacetophenone, 0.001-1% of a pH adjusting agent, and the balance of deionized water.

[0014] In a third aspect, the present application provides a preparation method of the sunscreen cream of the second aspect, the preparation method comprising the following steps: Step 1. Heating sodium di(lauroylmido glutamine) lysine, hydroxypropyltrimonium hydroxypropyl bivalent metal salt, glycerol, and deionized water to 75-80°C, stirring to dissolve and mix uniformly to obtain phase A; Step 2. Heating isoamyl p-methoxycinnamate, octocrylene, bis-ethylhexyloxyphenol methoxyphenyl triazine, diisopropyl sebacate, and dicaprylyl carbonate to 75-80°C, stirring to mix uniformly to obtain phase B; Step 3. Adding phase B to phase A under homogenizing stirring, maintaining emulsification for 5-10 min to obtain a mixed solution AB; Step 4. The mixed solution AB is cooled to 45-50 DEG C, and the inulin lauryl carbamate and acryloyl dimethyl ammonium taurate / VP copolymer are added, stirred until uniform, and then cooled to 35-40 DEG C. The p-hydroxyacetophenone is added, and the pH is adjusted to 6.5 + / - 0.2 with an appropriate amount of pH adjuster. The product is filtered to obtain the sunscreen cream.

[0015] In a fourth aspect, the present application provides use of the composite sunscreen composition of the first aspect in the preparation of a skin care product with sunscreen efficacy.

[0016] In the present application, The scientific combination of inulin lauryl carbamate, sodium di(lauramide glutamine) lysine, hydroxypropyl trimethyl ammonium chloride hyaluronic acid and acryloyl dimethyl ammonium taurate / VP copolymer solves the problem of sunscreen agglomeration, improves dispersion uniformity, and the synergistic effect of the four can effectively disperse plant sunscreen, chemical sunscreen or physical sunscreen, avoid uneven dispersion caused by sunscreen agglomeration, ensure uniform distribution of sunscreen ingredients in the system, and thus ensure the stability of sunscreen effect and reduce the risk of skin irritation caused by high local ingredient concentration. Optimize film forming performance, and consider stability, lightness and breathability: Inulin lauryl carbamate, as a natural source film forming agent, can form a dense and breathable flexible film layer, avoiding the heavy feeling of traditional synthetic film forming agents. Acryloyl dimethyl ammonium taurate / VP copolymer further optimizes the flexibility and uniformity of the film layer, ensuring the coverage integrity of the sunscreen film on the skin surface and achieving broad-spectrum blocking of UVA / UVB. The combination of the two makes the sunscreen film have stable film forming property, light texture and good breathability, and improves the use skin feel. Enhance the durability and water resistance of the sunscreen film: Sodium di(lauramide glutamine) lysine can enhance the binding force of the sunscreen film and the stratum corneum, reducing the shedding of the sunscreen film due to skin activity. The moisturizing film formed by hydroxypropyl trimethyl ammonium chloride hyaluronic acid not only improves the moisturizing feeling of the skin, but also enhances the adhesion of the sunscreen, reducing the loss of sunscreen ingredients caused by sweating or friction. The combination of the two significantly improves the durability and water resistance of the sunscreen film, achieving long-term sunscreen.

[0017] The present application has the following advantages: 1. The composite sunscreen composition provided by the present application can efficiently solve the problem of uneven dispersion of sunscreen agglomeration, make the SPF value of the sunscreen cream stable at 48.9-50.8, the human body SPF value reach 30.2-36.1, and have a higher SPF retention rate under high temperature storage, while reducing the skin irritation caused by high local concentration of sunscreen, improving the stability and safety of sunscreen.

[0018] 2. The sunscreen cream provided by the present application can form a stable, light, thin and breathable sunscreen film, has UVA / UVB broad-spectrum blocking effect and excellent skin feel, and the sensory comprehensive score is 4.3-4.5, solving the problems of traditional sunscreen products such as film forming rigidity, skin stuffiness and stickiness. DETAILED DESCRIPTION

[0019] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in combination with specific examples. Those skilled in the art should understand that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0020] Unless otherwise specified, the test methods used in the examples and comparative examples are conventional methods; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels; the percentages mentioned in the examples and comparative examples, unless otherwise specified, are mass percentages.

[0021] Preparation of the sunscreen cream

[0022] The raw materials were accurately weighed according to the mass percentages in Tables 1 and 2; Step 1. Components two (sodium lauroylmethyl glutamate), hydroxypropyltrimonium chloride hyaluronate, glycerol and deionized water were heated to 75-80°C, stirred and dissolved to mix uniformly to obtain phase A; Step 2. Components sunscreen agent (isopentyl p-methoxycinnamate, octocrylene, bis-ethylhexyl oxyphenol methoxyphenyl triazine), diisopropyl sebacate and dicaprylyl carbonate were heated to 75-80°C, stirred and mixed uniformly to obtain phase B; Step 3. Phase B was added to phase A under homogenizing stirring, and emulsification was maintained for 5-10 min to obtain a mixed solution AB; Step 4. The mixed solution AB was cooled to 45-50°C, and chitosan lauryl carbamate and acryloyldimethyltaurine ammonium / VP copolymer were added and slowly stirred until uniform; Step 5. Cooling to 38°C, adding p-hydroxyacetophenone, adjusting the pH to 6.5±0.2 with an appropriate amount of pH adjuster, and filtering the product to obtain the sunscreen cream.

[0023] Table 1. Mass percentages of raw materials of the sunscreen cream of the examples Raw Material Name Example 1 Example 2 Example 3 Isoamyl p-methoxycinnamate 6 6 6 Octocrylene 5 5 5 Bis-ethylhexyloxyphenol methoxyphenyl triazine 2 2 2 Chicory powder lauryl carbamate 0.08 0.1 0.12 Sodium di(lauroamidoglutamate) lysine 0.3 0.07 0.05 Hydroxypropyltrimonium hydrolyzed hyaluronic acid 0.01 0.05 0.08 Acryloyldimethyltauramide / VP copolymer 0.4 0.2 0.1 Glycerin 2 2 2 Diisopropyl sebacate 5 5 5 Dicaprylyl carbonate 7 7 7 p-Hydroxyacetophenone 0.1 0.1 0.1 pH Adjuster q.s. q.s. q.s. Deionized Water q.s. 100 q.s. 100 q.s. 100

[0024] Table 2. Mass percentages of raw materials of the sunscreen cream of the comparative examples Raw Material Name Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Isoamyl p-methoxycinnamate 6 6 6 6 6 6 Octocrylene 5 5 5 5 5 5 Bis-ethylhexyloxyphenol methoxyphenyl triazine 2 2 2 2 2 2 Chicory powder lauryl carbamate 0.17 / 0.1 0.1 / 0.1 Hydrogenated lecithin / / / / 0.1 / Sodium di(lauroamidoglutamate) lysine / 0.17 0.07 0.07 0.07 0.07 Hydroxypropyltrimonium hydrolyzed hyaluronic acid 0.05 0.05 / 0.25 0.05 / Acryloyldimethyltauramide / VP copolymer 0.2 0.2 0.25 / 0.2 0.2 Hyaluronic acid / / / / / 0.05 Glycerin 2 2 2 2 2 2 Diisopropyl sebacate 5 5 5 5 5 5 Dicaprylyl carbonate 7 7 7 7 7 7 p-Hydroxyacetophenone 0.1 0.1 0.1 0.1 0.1 0.1 pH Adjuster q.s. q.s. q.s. q.s. q.s. q.s. Deionized Water q.s. 100 q.s. 100 q.s. 100 q.s. 100 q.s. 100 q.s. 100

[0025] Note: " / " in the table means no addition.

[0026] Performance test

[0027] 1 In vitro SPF determination Take 0.0276±0.0003g of each sample prepared in Example 1-3 and Comparative Example 1-6, and evenly apply the sample on a PMMA plate (5cm x 5cm). Use a finger wearing a disposable glove to evenly spread the sample within the specified time. Allow the sample to air dry for 30 minutes in a constant temperature and humidity environment in the dark. Test the SPF value of the sample using a UV-2000s. Test 3 plates for each sample, and 5 different points on each plate. Take the average value.

[0028] 2 Water resistance test After immersing the PMMA plate coated with the sample in a constant temperature water bath at 25±0.5℃ for 40 minutes with stirring at 20r / min, remove the plate and allow it to air dry in a constant temperature and humidity environment in the dark. Test the SPF value again.

[0029] 3 Centrifugal stability test Centrifuge the sunscreen lotion samples prepared in Example 1-3 and Comparative Example 1-6 at 3000rpm for 30 minutes. Observe whether there is oil separation, layering, precipitation, turbidity, etc. If not, it is qualified.

[0030] 4 Long-term SPF retention rate test Store the sunscreen lotion samples prepared in Example 1-3 and Comparative Example 1-6 at 50℃ for 30 days, and test their SPF values. Calculate the long-term SPF retention rate according to the formula "retention rate = SPF value after 30 days / initial SPF value x 100%".

[0031] 5 Sensory test Select 15 volunteers aged 25-55, half male and half female, with skin types including dry, oily, and mixed. Use the sunscreen lotions prepared in Example 1-3 and Comparative Example 1-6, and score them from four dimensions: spreadability, greasiness, film formation speed, and residue. Each dimension is scored from 1 to 5, with higher scores indicating better sensory performance. Take the average of the sum of the average scores of each dimension divided by 4, and then take the average of 20 volunteers. This is the sensory score.

[0032] 6 Human SPF determination SPF measures the protective ability of sunscreen products against UVB (medium wave ultraviolet light), and is calculated as the ratio of the time required for the skin to produce minimal erythema after using sunscreen products to that without using them.

[0033] Select healthy Asian subjects for testing, predict the minimum erythema dose MED of the subjects' skin. In the back of the subjects, respectively ① no application, ② uniform application of 2 mg SPF standard (prepared according to the “Cosmetic Safety Technical Specifications 2015” SPF standard), ③ uniform application of 2 mg of Example 1-3 in the designated area, stand for 20 minutes to form a film. After 24 hours, record the MED values of the three cases respectively.

[0034] SPF = MED protection / MED unprotect (take the average value of all subjects).

[0035] The results of the above test items are shown in Tables 3 and 4.

[0036] Table 3 Test results of each group Group In vitro SPF value SFP value after water immersion Centrifugal stability Retention rate / % Sensory score Example 1 49.5 45.2 Pass 95.2 4.5 Example 2 50.8 46.1 Pass 96.0 4.4 Example 3 48.9 44.5 Pass 94.8 4.3 Comparative Example 1 46.0 35.8 Pass 85.1 3.8 Comparative Example 2 45.2 34.0 Pass 83.5 3.6 Comparative Example 3 47.1 36.2 Slightly delaminated 84.3 3.9 Comparative Example 4 46.8 35.0 Pass 82.7 3.7 Comparative Example 5 44.5 32.5 Oil phase separation 80.2 3.5 Comparative Example 6 45.5 33.1 Pass 81.5 3.4

[0037] Table 4 Test results of human SPF value Group SPF value Example 1 33.6 Example 2 36.1 Example 3 30.2

[0038] Results analysis: According to the results in Table 3, Examples 1-3 show high and stable initial SPF values and excellent water resistance, with SPF values remaining above 44 after water immersion and SPF loss rates less than 12%, which is due to the synergistic compounding of the four key ingredients: chitosan lauryl carbamate can form a dense and continuous flexible film, effectively fixing sunscreen, di (lauramide glutamine) lysine sodium enhances the adhesion of the film to the interface, significantly improves the water washing resistance, acryloyl dimethyl ammonium glycolate / VP copolymer optimizes the uniformity and flexibility of the film layer, ensures the consistency of UV blocking effect, and hyd roxypropyl trimethyl ammonium chloride hyaluronic acid further enhances the adhesion and durability of sunscreen through cationic properties and moisturizing effect.

[0039] The initial SPF value and the water-resistant SPF value of Comparative Examples 1-6 are significantly lower than those of the Examples. The water resistance of Comparative Example 1 is significantly reduced after the absence of sodium di(lauramidoglutamine) lysine, indicating that this ingredient is essential for enhancing the adhesion of the film layer and the water washing resistance; the film forming compactness is insufficient in Comparative Example 2 after the absence of chitosan lauryl carbamate, resulting in poor sunscreen fixation, and the initial SPF and water-resistant SPF are both low; the moisturizing property and affinity of the film layer are reduced in Comparative Example 3 after the absence of hydroxypropyltrimonium hyaluronate, resulting in poor water resistance and durability, and a slight delamination, indicating that the stability of the system is affected; the film uniformity and flexibility are insufficient in Comparative Example 4 after the absence of acryloyldimethyltaurine ammonium / VP copolymer, resulting in uneven distribution of sunscreen, and a decrease in the SPF value and water resistance. The performance is the worst in Comparative Example 5 after the use of hydrogenated lecithin to replace chitosan lauryl carbamate, because the traditional emulsifier cannot form an effective continuous film in a specific system, resulting in serious oil phase separation. The sunscreen adhesion and durability are significantly reduced in Comparative Example 6 after the use of ordinary hyaluronic acid to replace hydroxypropyltrimonium hyaluronate, because of the lack of cationic properties and film forming auxiliary functions.

[0040] In terms of stability, Examples 1-3 are all qualified, indicating that the system is emulsified stably and has good compatibility. Comparative Examples 3 and 5 have a slight delamination and oil phase separation, respectively, proving that the four ingredients are indispensable, otherwise the overall stability of the system will be affected. In terms of thermal stability, the retention rates of Examples 1-3 are all higher than 94%, indicating that the composition of the application has excellent thermal storage stability, and the sunscreen is not prone to degradation or agglomeration. The retention rates of Comparative Examples 1-6 decrease relative to Example 2, further confirming the role of the compounded system in maintaining the long-term stability of the sunscreen.

[0041] The sensory scores of Examples 1-3 are all higher than 4.3 points, and the volunteers generally feedback that the film is formed quickly, the skin feels light and thin, is not greasy, and has no residual feeling, indicating that the composition of the application has excellent skin feel while improving the performance. The sensory scores of Comparative Examples are generally low, especially the scores of Comparative Examples 5 and 6 are the lowest, again indicating that the absence or replacement of any key ingredient will have a negative impact on the use experience of the final product.

[0042] In summary, the sunscreen synergistic film forming system provided by the application, which is compounded from chitosan lauryl carbamate, sodium di(lauramidoglutamine) lysine, hydroxypropyltrimonium hyaluronate and acryloyldimethyltaurine ammonium / VP copolymer, has significantly better effects than those of the Comparative Examples in terms of sunscreen performance, water resistance, stability and skin feel. The data of the Comparative Examples prove that the absence of any ingredient will result in a decrease in performance. The composition is suitable for the development of high-end sunscreen and pre-makeup products, and has good industrialization prospects.

[0043] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that the technical solutions described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalent ones. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A composite sunscreen composition, characterized in that, The composition contains inulin lauryl carbamate, sodium di(lauramide-glutamine)lysine, hydroxypropyltrimethylammonium chloride hyaluronic acid and ammonium acryloyldimethyltaurate / VP copolymer, sunscreen, base oil, and cosmetic-acceptable excipients and solvents.

2. The composite sunscreen composition according to claim 1, characterized in that, The composition contains, by weight percentage, 0.05-0.15% inulin lauryl carbamate, 0.05-0.3% sodium di(lauramide-glutamine)lysine, 0.01-0.08% hydroxypropyltrimethylammonium chloride hyaluronic acid, and 0.1-0.4% ammonium acryloyldimethyl taurate / VP copolymer.

3. The composite sunscreen composition according to claim 2, characterized in that, The sunscreen agent is at least one of chemical sunscreen agents, physical sunscreen agents, and plant-based sunscreen agents.

4. The composite sunscreen composition according to claim 3, characterized in that, The chemical sunscreen agent is at least one of oil-soluble chemical sunscreen agents and water-soluble chemical sunscreen agents.

5. The composite sunscreen composition according to claim 1, characterized in that, The excipients are at least one of the following: skin conditioning agents, pH adjusters, moisturizers, chelating agents, and preservatives. The solvent is water.

6. A sunscreen lotion with excellent film-forming properties and sun protection stability, characterized in that, The sunscreen lotion contains the composite sunscreen composition according to any one of claims 1-5.

7. The sunscreen lotion according to claim 6, characterized in that, By weight percentage, the sunscreen lotion comprises 1-9% isoamyl p-methoxycinnamate, 1-8% octocrylene, 1-8% bis-ethylhexyloxyphenol methoxyphenyl triazine, 0.05-0.15% inulin lauryl carbamate, 0.05-0.3% sodium bis(lauramide-glutamine)lysine, 0.01-0.08% hydroxypropyltrimethylammonium chloride hyaluronic acid, 0.1-0.4% ammonium acryloyldimethyl taurate / VP copolymer, 1-10% glycerin, 1-10% diisopropyl sebacate, 1-15% dioctyl carbonate, 0.01-0.5% p-hydroxyacetophenone, 0.001-1% pH adjuster, and the balance being deionized water.

8. The method for preparing sunscreen lotion according to claim 7, characterized in that, The preparation method includes the following steps: Step 1. Heat sodium di(lauramide-glutamine)lysine, hydroxypropyltrimethylammonium chloride, hyaluronic acid, glycerol, and deionized water to 75-80℃ and stir to dissolve and mix evenly to obtain phase A; Step 2. Heat isoamyl p-methoxycinnamate, octocrylene, bis-ethylhexyloxyphenol methoxyphenyl triazine, diisopropyl sebacate and dioctyl carbonate to 75-80℃ and stir until homogeneous to obtain phase B; Step 3. Add phase B to phase A under homogenous stirring, maintain emulsification for 5-10 minutes, and obtain a mixed solution AB; Step 4. Cool the mixed solution AB to 45-50℃, add inulin lauryl carbamate and ammonium acryloyl dimethyl taurate / VP copolymer, stir until uniform, then cool to 35-40℃, add p-hydroxyacetophenone, adjust the pH to 6.5±0.2 with an appropriate amount of pH adjuster, filter and discharge to obtain the sunscreen lotion.

9. The use of the composite sunscreen composition according to any one of claims 1-5 in the preparation of skin care products with sunscreen function.