Collagen microsphere ergothioneine compound, multifunctional efficient broad-spectrum sunscreen composition containing collagen microsphere ergothioneine compound and preparation method of multifunctional efficient broad-spectrum sunscreen composition

Abstract

The invention discloses a collagen microsphere ergothioneine compound, a multifunctional efficient broad-spectrum sunscreen composition containing the collagen microsphere ergothioneine compound and a preparation method, the collagen microsphere ergothioneine compound comprises III-type recombinant human collagen microspheres and ergothioneine, the mass ratio of the III-type recombinant human collagen microspheres to the ergothioneine is (0.5-2): (5-20); the compound further comprises Ectoine, and the content of the Ectoine is 15-140 times that of the III type recombinant human collagen microspheres. Through the use of the collagen microsphere ergothioneine compound, the light stability of the ergothioneine can be protected, quick and efficient permeation can be realized by carrying the ergothioneine by utilizing the extremely high permeability of the III type recombinant human collagen microspheres, and the bioavailability of the ergothioneine and the stability of the ergothioneine in a formula system of the sunscreen composition are improved; meanwhile, the sunscreen composition integrates multiple functions of high-power sunscreen, anti-inflammatory repair, blue light resistance and the like, and has very good market prospects and economic values.

Description

Technical Field

[0001] The invention belongs to the field of biotechnology, and particularly relates to a collagen microsphere ergothioneine complex and a multifunctional, high-efficiency, broad-spectrum sunscreen composition containing the complex and a preparation method thereof. Background Art

[0002] Sunscreen cosmetics refer to cosmetics that contain sunscreen agents that can block or absorb ultraviolet rays to prevent the skin from getting tanned or sunburned. Traditional sunscreen agents commonly used in sunscreen cosmetics are divided into two categories: one is ultraviolet absorbers, which are organic compounds such as ketones; the other is ultraviolet shielding agents, i.e. physical sunscreen agents. Both types of sunscreen agents can cause skin irritation, skin allergies, and clogged skin pores, which have become common problems in current sunscreen cosmetics. Moreover, most of the sunscreen cosmetics currently on the market have a single effect and cannot have the functions of being suitable for sensitive skin, high-power sun protection, anti-inflammatory repair, anti-blue light, refreshing skin feel, easy to apply, and fast film formation.

[0003] Ergothioneine (EGT) is a natural sulfur-containing amino acid with significant antioxidant effects. Its antioxidant effect is 6,000 times higher than that of vitamin E and 20 times that of coenzyme Q10. It is also the only known antioxidant that can enter both mitochondria and cell nuclei at the same time. Studies have shown that EGT can promote cell health and longevity by scavenging free radicals and protecting intracellular DNA from oxidative damage. For example, Chinese invention patent application document CN115252440A discloses a natural sunscreen composition, sunscreen cream, and its preparation method and application, and discloses that ergothioneine can scavenging new free radicals generated by skin irradiated by external ultraviolet rays. In addition, EGT also has anti-inflammatory effects, can inhibit peroxynitrite-mediated amino acid oxidation, and has a certain therapeutic effect on inflammation. A large number of studies at home and abroad have confirmed that ergothioneine has excellent effects in sun protection, whitening, anti-aging, radiation protection, and reducing glycation.

[0004] However, since ergothioneine cannot be synthesized in the human body, it can only be taken in from the outside. On the one hand, EGT itself cannot penetrate the plasma membrane, and its absorption is limited to the expression of its receptor / transporter. The receptor / transporter of EGT is OCTN1, which is a receptor / transporter of various endogenous and exogenous molecules. In addition to EGT, it also participates in the transport of substances such as acetylcholine and carnitine, so the bioavailability of ergothioneine absorbed by the OCTN1 protein transport in the skin is limited. On the other hand, EGT has poor light stability, and long-term ultraviolet irradiation will cause its structure to change, affecting its biological activity; and, the suitable pH range of EGT is narrow, which is easily affected by the environmental pH value, and EGT is also easy to interact with some material components such as oxidants and other active ingredients, thereby affecting its antioxidant and anti-inflammatory effects; especially in cosmetics, EGT is in a dissolved state, which is more susceptible to external factors. Therefore, ergothioneine cannot play its excellent effect in cosmetic compositions. For example, the Chinese invention patent CN113952282A applied for by Guangzhou Huanya Cosmetics Technology Co., Ltd. discloses a composition with whitening and sunscreen effects, its preparation method and application, in which ergothioneine is used in combination with 4-butylresorcinol, paeonol, tetrahydromethylpyrimidine carboxylic acid and Artemia extract as a skin protectant. However, the whitening and brightening effect is mainly achieved by 4-butylresorcinol, and the other components only play a synergistic role. This also indirectly proves that the sunscreen and whitening effect of ergothioneine is limited in the sunscreen composition.

[0005] Therefore, how to increase the transdermal absorption of ergothioneine, improve the bioavailability of ergothioneine, and make it play a good sunscreen and whitening effect, to reduce the amount of sunscreen, solve the problems of skin irritation, allergy, pore clogging, etc. in sunscreen cosmetics, and obtain a sunscreen composition with multiple functions such as high sunscreen, anti-inflammatory repair, and anti-blue light for sensitive skin, which is still a problem worth exploring. Summary of the invention

[0006] In view of the above-mentioned existing problems, and in order to achieve the above-mentioned purpose, the present invention provides a collagen microsphere ergothioneine complex and a multifunctional, efficient, broad-spectrum sunscreen composition and preparation method containing the complex, ergothioneine is compounded with type III recombinant human collagen microspheres developed by the applicant in the early stage, and ergothioneine is wrapped in the cavity of type III recombinant human collagen microspheres, which can not only protect the photostability of ergothioneine, but also use the extremely high permeability of type III recombinant human collagen microspheres to carry ergothioneine to achieve rapid and efficient penetration, thereby improving the bioavailability of ergothioneine. The specific technical scheme is as follows: First, one of the purposes of the present invention is to provide a collagen microsphere ergothioneine complex, in which the mass ratio of type III recombinant human collagen microspheres to ergothioneine is 0.5-2:5-20.

[0007] As a preferred technical solution, ectoine can also be added to the aforementioned collagen microsphere ergothioneine complex, and its content is 15 to 140 times the mass of type III recombinant human protein microspheres.

[0008] As a further preferred technical solution, the aforementioned collagen microsphere ergothioneine complex is composed of type III recombinant human collagen microspheres, ergothioneine, ectoine and deionized water in a mass ratio of 0.5-2:5-20:30-70:40-150.

[0009] Secondly, the second object of the present invention is to provide a sunscreen composition containing the aforementioned collagen microsphere ergothioneine complex, and the sunscreen composition is composed of the following components by 100 parts by total weight: 0.01 to 5 parts of the aforementioned collagen microsphere ergothioneine complex, 10 to 25 parts of a composite sunscreen, 20 to 60 parts of an auxiliary material, and the balance being deionized water.

[0010] As a preferred technical solution, in the aforementioned sunscreen composition, the composite sunscreen includes a water-soluble sunscreen and an oil-soluble sunscreen; wherein: the water-soluble sunscreen is phenylbenzimidazole sulfonic acid and methylene bis-benzotriazolyl tetramethylbutylphenol; the oil-soluble sunscreen is polysilicone-15, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylamine hydroxybenzoyl hexyl benzoate, and titanium dioxide.

[0011] As a further preferred technical solution, in the aforementioned sunscreen composition, the mass ratio of phenylbenzimidazole sulfonic acid, methylene bis-benzotriazolyl tetramethylbutylphenol, polysilicone-15, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylamine hydroxybenzoyl hexyl benzoate, and titanium dioxide in the composite sunscreen is: 3-8:1-6:2-8:0.5-5:0.5-5:2-9:0.05-3.

[0012] As a preferred technical solution, in the aforementioned sunscreen composition, the auxiliary materials are composed of a chelating agent, an emollient, an emulsifier, a thickener, a pH regulator, a moisturizer, an antioxidant and a skin feel regulator; Chelating agent 0.01-0.3%, emollient 5-20%, emulsifier 1-9%, thickener 0.05-3%, pH adjuster 0.5-2%, humectant 3-15%, antioxidant 0.01-1.2, skin feel regulator 1-4%.

[0013] As a preferred technical solution, in the aforementioned sunscreen composition, the chelating agent is any one of EDTA-2Na and EDTA-4Na; the emollient is one or more of dibutyl adipate, diisopropyl adipate, diisopropyl sebacate, isononyl isononanoate, dioctyl carbonate, C12-15 alcohol benzoate, octyl polymethicone, butyloctanol salicylate, C12-13 alcohol lactate, polydimethylsiloxane, and isopropyl lauroyl sarcosinate; the emulsifier includes a water-soluble emulsifier and an oil-soluble emulsifier, wherein: the water-soluble emulsifier is potassium cetyl phosphate, and the oil-soluble emulsifier is ceteareth-21, ceteareth-30, cetearyl alcohol, glyceryl stearate, PEG-100 stearate. , arachidyl alcohol, behenyl alcohol, arachidyl glucoside, sodium stearoyl glutamate, cetyl alcohol, and stearyl alcohol; the thickener is one or more of xanthan gum, acrylic acid (esters) / C10-30 alkyl acrylate crosspolymer, polyacrylate crosspolymer-6, hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer; the pH adjuster is one or more of aminomethyl propanol, triethanolamine, sodium citrate, and arginine; the moisturizer is one or more of butylene glycol, 1,2-hexanediol, ethylhexylglycerin, 1,3-propylene glycol, allantoin, trehalose, betaine, biosaccharide gum, sodium polyglutamate, and sodium hyaluronate; the antioxidant is p-hydroxyacetophenone, and the skin feel regulator is spherical porous silica with a particle size of less than 20 μm.

[0014] Again, the third object of the present invention is to provide a method for preparing the aforementioned sunscreen composition, comprising the following process steps: S1: Preparation of collagen microspheres and ergothioneine complex Add type III recombinant human protein microspheres, ergothioneine, and ectoine into deionized water in order, and stir to prepare a collagen microsphere ergothioneine complex for later use; S2: Preparation of oil phase mixture Add the emollient, oil-soluble sunscreen, oil-soluble emulsifier and skin feel regulator into the oil phase pot, heat to 75-85°C, stir and disperse evenly at a stirring speed of 150-300 r / min to obtain an oil phase mixture; S3: Preparation of aqueous phase mixture Add water-soluble emulsifier, moisturizer, thickener, chelating agent and deionized water into the water phase pot, start stirring at a speed of 50-120 r / min, heat to 75-85°C, disperse evenly, and obtain a water phase mixture; S4: Emulsification and homogenization The oil phase mixture prepared in step S2 and the water phase mixture prepared in step S3 are simultaneously pumped into an emulsifying pot, homogenized at 7000-8000 r / min for 1-5 min, stirred evenly at a stirring speed of 35-110 r / min, and cooled to 60-70° C. under stirring to obtain an emulsified mixture; S5: Secondary homogenization Add an antioxidant to the emulsified mixture obtained in step S4, stir evenly at 35-110 r / min, briefly homogenize at a low speed of 1500-2800 r / min for 1-5 min, continue stirring and cool to 40° C. to obtain a homogenous mixture; S6: Three-time homogenization The water-soluble sunscreen is pre-dissolved in advance with a pH regulator and part of deionized water, and the pre-dissolved pH regulator and water-soluble sunscreen are added to the homogeneous mixture obtained in step S5, and the mixture is briefly homogenized at a low speed of 1500 to 2800 r / min, and the stirring is continued to obtain a homogeneous mixture; S7: Add collagen microspheres ergothioneine complex The collagen microsphere ergothioneine complex prepared in step S1 is added to the homogeneous mixture obtained in step S6, stirred evenly at 35-110 r / min, and removed from the pot to obtain a sunscreen composition containing the collagen microsphere ergothioneine complex.

[0015] As a preferred technical solution, in step S1, the preparation of the collagen microsphere ergothioneine complex specifically includes the following sub-steps: S1-1: Add type III recombinant human protein microspheres into deionized water and stir to completely dissolve them to form a microsphere collagen solution; S1-2: adding ergothioneine into the microsphere collagen solution obtained in step S1-1 in 2 to 4 times, stirring at 250 to 400 r / min for 10 to 20 min at room temperature to construct a protein microsphere ergothioneine complex; S1-3: Add ectoine to the protein microsphere ergothioneine complex obtained in step S1-2, control the stirring speed at 150-300 r / min, and stir at a high speed until all dissolved to obtain the protein microsphere ergothioneine complex.

[0016] The innovative features and beneficial effects of the present invention are as follows: 1) The collagen microsphere ergothioneine complex of the present invention uses type III recombinant human collagen microspheres, which are a collagen raw material with a completely new structure developed by the applicant of the present invention in the early stage. The traditional linear structure of recombinant collagen is changed by self-cyclization to change the original linear spatial structure of collagen, presenting a spherical structure with a hollow center, and adding 6 hydrophilic amino acid groups, which not only retains the complete triple helix structure of type III recombinant human collagen, but also increases its external hydrophilic solubility, so that it has a very high skin penetration rate. Ergothioneine is compounded with type III recombinant human collagen microspheres. The lipophilic cavity of type III recombinant human collagen microspheres can bind to the non-polar groups of ergothioneine, and the external structure of the protein microspheres can bind to the polar groups of ergothioneine to form hydrogen bonds, thereby encapsulating ergothioneine in the cavity of type III recombinant human collagen microspheres. This can not only protect the photostability of ergothioneine, but also utilize the extremely high permeability of type III recombinant human collagen microspheres to carry ergothioneine for rapid and efficient penetration, thereby improving the bioavailability of ergothioneine.

[0017] 2) The collagen microsphere ergothioneine complex of the present invention also contains ectoine, which has a "preferential repulsion" effect on water molecules, combines with the surrounding water molecules to form "ectoine hydroelectric complexes", and these hydroelectric complexes form a protective and stable hydration shell around the type III recombinant human collagen microspheres, further stably encapsulating and locking the ergothioneine in the collagen microspheres, further improving the binding effect of ergothioneine and collagen microspheres, and at the same time improving the physical and chemical stability of ergothioneine and collagen microspheres, ensuring that ergothioneine is protected from environmental pressures such as high temperature, ultraviolet radiation, etc., and is better used in various types of cosmetic products such as sunscreen.

[0018] 3) The sunscreen composition of the present invention greatly replaces the dosage of traditional sunscreens by adding collagen microsphere ergothioneine complex, solves the problems of skin irritation, allergy and pore clogging caused by sunscreens, and can still achieve high-power sunscreen effect; and the collagen microspheres in the collagen microsphere ergothioneine complex can directly supplement collagen in the deep layer of the skin, and Ecdoin has excellent anti-inflammatory properties. The two are combined with ergothioneine as components of the sunscreen composition, which further improves the anti-inflammatory repair effect of the sunscreen composition. In addition, the addition of collagen microsphere ergothioneine complex makes the sunscreen composition refreshing, easy to apply, and fast film formation, which greatly improves the consumer's experience.

[0019] 4) The sunscreen composition of the present invention adopts a compound of a water-soluble sunscreen and an oil-soluble sunscreen to reduce the amount of the oil-soluble sunscreen, so that the skin feel of the sunscreen composition is more refreshing, wherein the water-soluble sunscreen is selected from phenylbenzimidazole sulfonic acid and methylene bis-benzotriazolyl tetramethylbutylphenol; the oil-soluble sunscreen is selected from polysilicone-15, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylamine hydroxybenzoyl hexyl benzoate and titanium dioxide. This compound of sunscreen is not only a compound of a water-soluble sunscreen and an oil-soluble sunscreen, but also a compound of a physical sunscreen and a chemical sunscreen, thereby avoiding the sunscreen loophole caused by the use of a single type of sunscreen; in addition, the skin feel regulator is selected from spherical porous silica with a particle size of less than 20 μm to absorb oil and bring a more refreshing skin feel and a better use experience. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a schematic diagram of the structure of the collagen microsphere ergothioneine complex of the present invention; Figure 2 This is a standard curve diagram of the antioxidant activity of samples detected by the DPPH method of the present invention; Figure 3 Red zone comparison pictures taken by dermoscopy for human test subjects 1-8 of the sunscreen composition of the present invention; Figure 4 Red zone comparison pictures taken by dermoscopy for 9-16 human test subjects of the sunscreen composition of the present invention; Figure 5 Red zone comparison pictures taken by dermoscopy for 17-20 human test subjects of the sunscreen composition of the present invention. DETAILED DESCRIPTION

[0021] The invention aims at increasing the transdermal absorption amount of ergothioneine, improving the bioavailability of ergothioneine, making it play a good sunscreen effect, reducing the amount of sunscreen, solving the problems of skin irritation, allergy, pore blockage and the like in sunscreen cosmetics, obtaining a sunscreen composition which can be used for sensitive skin and has multiple functions such as high sunscreen, anti-inflammatory repair, anti-blue light and the like, and proposes a collagen microsphere ergothioneine complex and a multifunctional, high-efficiency and broad-spectrum sunscreen composition containing the complex and a preparation method thereof.

[0022] In order to make the purpose, technical solution and advantages of the present invention more clear, the technical solution of the present invention will be clearly and completely described below in conjunction with embodiments.

[0023] Example 1 This embodiment is to prepare a collagen microsphere ergothioneine complex, which is as follows: First, take 1 part of type III recombinant human protein microspheres, 10 parts of ergothioneine, 50 parts of ectoine, and 150 parts of deionized water by weight. The production steps are as follows: 1): Add type III recombinant human protein microspheres into deionized water and stir to completely dissolve them to form a microsphere collagen solution; 2): Add thioneine into the microsphere collagen solution obtained in step 1) in 2 to 4 portions, stir at 250r / min for 10min at room temperature to construct a protein microsphere thioneine complex, the structure of which is shown in the figure below: Figure 1 As shown; 3): Add ectoine to the protein microsphere ergothioneine complex obtained in step 2), control the stirring speed at 150r / min, and stir until it is completely dissolved to obtain the protein microsphere ergothioneine complex, which is set aside.

[0024] Example 2 This embodiment is to prepare a multifunctional, high-efficiency, broad-spectrum sunscreen composition, which is specifically as follows: Take 2.11 parts of the collagen microsphere ergothioneine complex prepared in Example 1, 10 parts of emollient, 11 parts of oil-soluble sunscreen, 3 parts of oil-soluble emulsifier, 2 parts of skin feel regulator, 1 part of water-soluble emulsifier, 8 parts of moisturizer, 0.15 parts of thickener, 0.1 parts of chelating agent, 0.5 parts of antioxidant, 1.2 parts of pH adjuster, 4 parts of water-soluble sunscreen, and 56.94 parts of deionized water by weight.

[0025] Wherein: the emollient is dibutyl adipate; in addition to dibutyl adipate, one or more of diisopropyl adipate, diisopropyl sebacate, isononyl isononanoate, dioctyl carbonate, C12-15 alcohol benzoate, octyl polymethicone, butyloctanol salicylate, C12-13 alcohol lactate, polydimethylsiloxane, and isopropyl lauroyl sarcosinate can also be used; Oil-soluble sunscreens are polysilicone-15, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylamino hydroxybenzoyl hexyl benzoate, and titanium dioxide; The oil-soluble emulsifier is glyceryl stearate and PEG-100 stearate; in addition to glyceryl stearate and PEG-100 stearate, at least one of ceteareth-30, cetearyl alcohol, ceteareth-21, arachidyl alcohol, behenyl alcohol, arachidyl glucoside, sodium stearoyl glutamate, cetyl alcohol, and stearyl alcohol can also be used; The skin feel regulator is a spherical porous silica with a particle size of less than 20 μm, which is used to absorb oil, bringing a more refreshing skin feel and a better use experience; The water-soluble emulsifier is potassium cetyl phosphate; The moisturizers are butylene glycol, 1,2-hexanediol, and ethylhexylglycerin; in addition, one or more of 1,3-propylene glycol, allantoin, trehalose, betaine, biosaccharide gum, sodium polyglutamate, and sodium hyaluronate can also be selected.

[0026] The antioxidant is p-hydroxyacetophenone; The thickener is xanthan gum; in addition to xanthan gum, one or more of acrylic acid (esters) / C10-30 alkyl acrylate crosspolymer, polyacrylate crosspolymer-6, and hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer can also be selected.

[0027] The chelating agent may be EDTA-2Na or EDTA-4Na.

[0028] The pH regulator is aminomethyl propanol. In addition to aminomethyl propanol, one or more of triethanolamine, sodium citrate or arginine can also be selected.

[0029] The water-soluble sunscreens are phenylbenzimidazole sulfonic acid and methylene bis-benzotriazolyl tetramethylbutylphenol.

[0030] In this embodiment, the mass ratio of the components of the water-soluble sunscreen and the oil-soluble sunscreen is: phenylbenzimidazole sulfonic acid: methylene bis-benzotriazolyl tetramethylbutylphenol: polysilicone-15: bis-ethylhexyloxyphenol methoxyphenyl triazine: ethylhexyl triazone: diethylamine hydroxybenzoyl hexyl benzoate: titanium dioxide = 2.5:1.5:3.5:1.5:2:3:1.

[0031] The preparation method of the sunscreen composition of this embodiment comprises the following process steps: (1) Add the emollient, oil-soluble sunscreen, oil-soluble emulsifier, and skin feel regulator into the oil phase pot, heat to 80°C, and stir at 200 r / min to disperse evenly to obtain an oil phase mixture; (2) Add water-soluble emulsifier, humectant, thickener, chelating agent and deionized water into the water phase pot, heat to 80°C, start stirring at 80r / min to disperse evenly, and obtain a water phase mixture; (3) The prepared oil phase mixture and the prepared water phase mixture are simultaneously pumped into an emulsifier, homogenized at 8000 r / min for 3 min, stirred evenly at 50 r / min, cooled to 65°C by stirring, an antioxidant is added, stirred evenly, and homogenized at 2000 r / min for 3 min to obtain an emulsified mixture; (4) Continue stirring and cool down to 40°C. Pre-dissolve the water-soluble sunscreen with a pH adjuster and part of deionized water. Add the pre-dissolved pH adjuster and water-soluble sunscreen to the emulsified mixture. Stir evenly at 50 r / min. Homogenize at a low speed of 2000 r / min for 3 min to obtain a homogeneous mixture. (5) Add the collagen microsphere ergothioneine complex prepared in Example 1 to the homogenized mixture, stir evenly at 50 r / min, and remove from the pan to obtain a sunscreen composition containing the collagen microsphere ergothioneine complex.

[0032] Example 3 The present embodiment is to investigate the influence of the amount of type III humanized collagen microspheres and ectoine on the photostability and absorption effect of ergothioneine in the collagen microsphere ergothioneine complex. The present embodiment is carried out based on Example 1, and the preparation method of the collagen microsphere ergothioneine complex for investigation is consistent with Example 1, except that the amount of type III humanized collagen microspheres and ectoine in the collagen microsphere ergothioneine complex used. In the formula containing only ergothioneine, ergothioneine is dissolved in deionized water. In the present embodiment, the mass fractions of type III humanized collagen and ectoine contained in the collagen microsphere ergothioneine complex for investigation are as shown in Table 1.

[0033] Table 1. Mass fraction of each component in collagen microsphere ergothioneine complex

[0034] This example tests the effects of type III humanized collagen microspheres and ectoine on the protection and absorption effects of ergothioneine through photostability experiments and transdermal experiments. The specific experiments are as follows: Experiment 1: Ergothioneine photostability test In this experiment, the collagen microsphere ergothioneine complex prepared by the above formula 1-10 was used as a sample, and the ergothioneine content in the sample was determined. The degradation of the collagen microsphere ergothioneine complex during use was simulated by light conditions (1000 Lux) to test the photoprotective effect of the collagen microsphere ergothioneine complex of the present invention on ergothioneine. The experimental method is as follows: (1) The collagen microsphere ergothioneine complex sample prepared by formula 1-10 was placed in a transparent plastic bottle and placed in a light incubator at 25° C. for 20 days with a light cycle of 24:0 (light / dark).

[0035] (2) The content of ergothioneine in the collagen microsphere ergothioneine complex composition was determined by high performance liquid chromatography. The conditions were as follows: chromatographic column: Hypersil ODS ℃ 18 column (250 mm × 4.6 mm, particle size 5 μm); column temperature: 30 ° C; mobile phase: acetonitrile-water (3:97); flow rate: 1.0 mL / min; detection wavelength: 254 nm; injection volume: 20 μL. The results are shown in Table 2.

[0036] Table 2. Ergothioneine concentration and retention rate of collagen microsphere ergothioneine complex

[0037] From the experimental results in Table 2, it can be seen that in formula 10 without using type III humanized collagen microspheres and ectoine, the retention rate of ergothioneine is 74%, and in formula 1 (Example 2) using only ectoine without using type III humanized collagen microspheres, the retention rate of ergothioneine is also 74%. In formula 5 using only type III humanized collagen microspheres without ectoine, the retention rate of ergothioneine is 85%, indicating that ectoine has no protective effect on ergothioneine, while type III humanized collagen microspheres can significantly improve ergothioneine. The photostability of thionine; when type III humanized collagen microspheres and ectoine are used in combination, the protective effect of ergothioneine is further improved than that of type III humanized collagen microspheres alone, and when the mass ratio of type III recombinant human collagen microspheres: ergothioneine: ectoine: deionized water = 1:10:50:150, the retention rate of ergothioneine is more than 95%. It can be seen that type III humanized collagen and ectoine in the collagen microsphere ergothioneine complex of the present invention can effectively protect ergothioneine and improve its photostability.

[0038] Experiment 2: Ergothioneine transdermal test This transdermal absorption test method is carried out with reference to GB / T 27818-2011 In vitro test method for skin absorption of chemicals.

[0039] This experiment is based on the suckling pig skin-Franz cell diffusion pool equipment. The suckling pig back skin is used as the basis. The collagen microsphere ergothioneine complex prepared by the above formula 1-10 is used as a sample to carry out a Franz diffusion cell permeability experiment to investigate the transdermal ability of ergothioneine in the collagen microsphere ergothioneine complex to the isolated pig back skin.

[0040] The specific experiment is: each sample is placed in the skin sample pool of the Franz cell diffusion cell device respectively, and after 24 hours, the ergothioneine concentration of the subcutaneous receiving pool of the Franz cell diffusion cell device is measured by HPLC, and the results are shown in Table 3.

[0041] Table 3. Results of transdermal testing of ergothioneine in collagen microsphere ergothioneine complex

[0042] It can be seen from the transdermal absorption experimental results in Table 3 that in Formula 10 which does not use type III humanized collagen microspheres and ectoine and in Formula 1 which only uses ectoine but does not use type III humanized collagen microspheres, the subcutaneous acceptance concentration of ergothioneine is below 40 PPM, and the transdermal rate is very low. In the formulas using type III humanized collagen microspheres, the subcutaneous absorption concentration of ergothioneine was greatly increased. Among them, in formula 5 using type III humanized collagen microspheres alone, the subcutaneous absorption concentration of ergothioneine was 132.55 PPM, which was more than 3.5 times that of the formula without protein microspheres, indicating that type III humanized collagen microspheres can improve the transdermal absorption effect of ergothioneine. In the formula using type III humanized collagen microspheres and ectoine at the same time, the subcutaneous absorption concentration of ergothioneine was further improved; and when the dosage of type III humanized collagen microspheres and ergothioneine remained unchanged, the transdermal concentration of ergothioneine increased with the increase of ectoine dosage. Analysis shows that this is because ectoine can block more ergothioneine in the cavity of type III humanized collagen microspheres, thereby increasing the transdermal rate.

[0043] Example 4 This example is to investigate the effect of the dosage of type III humanized collagen microspheres on the stability of ergothioneine in a sunscreen composition.

[0044] In this example, the stability of the multifunctional, efficient and broad-spectrum sunscreen composition of the collagen microsphere ergothioneine complex of the present invention is evaluated by examining the changes in pH, color and centrifugal test of the composition after the sunscreen compositions with different pH values ​​are stored for different periods of time under the conditions of the investigation, as well as the changes in the concentration of ergothioneine therein.

[0045] This example is investigated on the basis of Example 2. In the formula of the sunscreen composition used for investigation, except that the amount of type III humanized collagen and the amount of pH regulator are different from those in Example 2, the preparation methods of each sunscreen composition are consistent with those in Example 2. Similarly, the preparation method of the collagen microsphere ergothioneine complex in each sunscreen composition is the same as that in Example 1, and the formula of the complex not containing type III humanized collagen microspheres discards the corresponding steps, and the rest of the preparation process is the same as that in Example 1; in this embodiment, the amount of type III humanized collagen microspheres and the amount of pH regulator in the sunscreen composition used for investigation are shown in Table 4, and the unit is %.

[0046] Table 4. Amounts of collagen microsphere ergothioneine complex and pH regulator in each sunscreen composition

[0047] The sunscreen composition prepared by the formula in Table 4 of this experiment is a sample. The stability of ergothioneine in the sunscreen composition is evaluated by examining the pH, color, and centrifugal test of each sunscreen composition as an indicator, and the protective effect of type III recombinant humanized collagen microspheres on ergothioneine is evaluated by examining the concentration of ergothioneine in each sunscreen composition. Among them, the pH determination method is to dilute it with 1:10 (experimental water), heat it at 40°C and stir it evenly, and then keep it warm to 25°C for determination. The color is directly observed by the naked eye. The centrifugal test is to inject the composition into the centrifuge tube 2 / 3 height, add a stopper, keep it warm at 38°C for 1h, take it out after centrifugation at 2000r / min for 30min, and observe the stratification. The method for determining the content of ergothioneine is consistent with that in Example 3, and the sample is stored at room temperature (about 25°C) in the warehouse for conventional storage. The test results are shown in Table 5.

[0048] Table 5. Stability test results of various sunscreen compositions

[0049] From the results of the stability test in Table 5, all the sunscreen composition samples in the present embodiment have good stability, and no discoloration or centrifugal stratification occurs after being stored at room temperature for 6 months; from the concentration results of ergothioneine in formulas 11, 12, 13, 16, and 17 in the table after being stored at room temperature for 6 months, the use of type III recombinant humanized collagen microspheres to construct a complex can effectively improve the stability of ergothioneine, and as the amount of type III recombinant humanized collagen microspheres increases, the stability of ergothioneine in the sunscreen composition shows an increasing trend, wherein when the ratio of type III recombinant humanized collagen microspheres, ergothioneine, and idene in the complex is 1:10:50, the stability of ergothioneine in the sunscreen composition has been significantly improved; the concentration results of formulas 13, 14, and 15 ergothioneine after being stored at room temperature for 6 months show that the use of type III recombinant humanized collagen microspheres to construct a complex can effectively improve the stability of ergothioneine under weak acid, neutral, and weak base conditions.

[0050] Example 5 This example is to investigate the synergistic anti-inflammatory effect of the combined use of type III humanized collagen microspheres and ectoine.

[0051] The present embodiment is also investigated on the basis of Example 1. The preparation method of the collagen microsphere ergothioneine complex in each collagen microsphere ergothioneine complex is the same as that in Example 1. The formula of the complex not containing type III humanized collagen is omitted, and the remaining preparation processes are the same as those in Example 1. In the present embodiment, the amount of type III humanized collagen and the amount of ectoine in the collagen microsphere ergothioneine complex used for investigation are shown in Tables 1 and 6.

[0052] Table 6. Mass fraction of each component in collagen microsphere ergothioneine complex

[0053] The anti-inflammatory experiment of this embodiment is as follows: The anti-inflammatory activity was investigated by establishing an inflammatory cell model by intervening mouse mononuclear macrophages (RAW264.7) with lipopolysaccharide (LPS). The main reagents included: mouse mononuclear macrophages (Shanghai Yaji Biotechnology Co., Ltd.), DMEM high glucose medium (Bio-Channel), fetal bovine serum (FBS, Bio-Channel), penicillin-streptomycin solution (Bio-Channel), pancreatic enzyme (Bio-Channel), lipopolysaccharide (LPS, Beijing Solebold Technology Co., Ltd.), dexamethasone (Shanghai Yuanye Biotechnology Co., Ltd.), interleukin-6 (IL-6) detection kit (Shanghai Bioengineering Co., Ltd.). The main instruments included: cell culture incubator (Thermo Fisher Scientific Co., Ltd.), ultra-clean biological workbench (Suzhou Purification Equipment Co., Ltd.), low-speed centrifuge (Hunan Xiangyi Centrifuge Instrument Co., Ltd.), inverted microscope (Shanghai Optical Instrument Factory No. 1), and enzyme-linked immunosorbent assay (Thermo Fisher Scientific Co., Ltd.). Other reagents or instruments used below without indicating the manufacturer are all conventional products that can be purchased commercially unless otherwise specified.

[0054] Sample: The collagen microsphere ergothioneine complex shown in Table 1 was dissolved in 10% FBS DMEM culture medium to obtain the experimental sample.

[0055] Experimental method: 96-well plates were used for cell inoculation, 200 μL / well, 4×10 4 cells / well, incubate for 24h, discard the culture medium, start induction and administration. Add the culture medium of the test sample and LPS to the test wells, add the cell culture medium containing LPS (2μg / ml) to the negative control wells, add the culture medium containing the positive control (dexamethasone 100μg / ml) and LPS to the positive control wells, and add the cell culture medium in the blank / solvent control wells, 200μL per well, incubate for 24h. After LPS stimulation, collect the cell culture supernatant and perform ELISA detection according to the instructions of the ELISA kit.

[0056] Result analysis: The readings were based on the negative control group, and the relative content of IL-6 was expressed as a percentage, which was set as 100%. The absolute value of the relative content of IL-6 in the experimental group minus the relative content of IL-6 in the negative control group was taken as the IL-6 inhibition rate. Among them, the synergistic effect of the combination was determined using the Golden formula:

[0057] Among them, Q<0.55 is obvious antagonism, Q=0.55-0.85 is antagonism, Q=0.85-1.15 is additive, and Q>1.15 is synergistic.

[0058] The specific test results of each formulation are shown in Table 7.

[0059] Table 7. Anti-inflammatory test results of various sunscreen compositions

[0060] From the results in Table 7, it can be seen that both the use of ectoine alone (Formula 1) and the use of type III humanized collagen microspheres alone (Formula 5) have anti-inflammatory effects; when ectoine and type III humanized collagen microspheres are used in combination, they both show a synergistic effect, and the synergistic effect is best when the mass ratio of type III humanized collagen microspheres to ectoine is 1:50.

[0061] Example 6 This example is to investigate the performance of the collagen microsphere ergothioneine complex of the present invention, including anti-inflammatory repair, anti-aging, anti-blue light, etc. The specifics are as follows: 1. Anti-inflammatory repair This experiment uses the collagen microsphere ergothioneine complex prepared in Example 1 as the basis for investigation, and the specific experiment is as follows: In this example, the expression changes of inflammatory cytokines in human fibroblasts were detected by ELISA kit to evaluate the anti-inflammatory and repair effects of the collagen microsphere ergothioneine complex of the present invention. Specifically, the logarithmic phase cells were washed with PBS, collected by trypsin digestion, centrifuged at 1000 rpm for 5 min, the supernatant was removed, and an appropriate amount of culture medium was added to make it a single cell suspension; the cells were counted and the cell density was adjusted to 1×10 5 / mL, 2mL / well inoculated in a 6-well plate, 3 replicates per group; the collagen microsphere ergothioneine complex prepared in Example 1 was diluted with culture medium; 37°C, 5% CO2 constant temperature culture, after the cells adhered to the wall, the diluted complex was added, a blank group (normal cell group) and a negative control group (LPS-induced model group) were set up, and they were placed in an incubator together. After culturing for 24 hours, the supernatant was discarded, the cells were washed twice with PBS buffer, and the cells were collected by trypsin digestion. The cell fluid was transferred into a 1.5mL tube, centrifuged at 1000rpm for 5min, the supernatant was removed, the PBS buffer was washed twice, the cell pellet was collected, and the supernatant was discarded. The expression changes of IL-1α, IL-6, IL-10, and TNF-α in human skin fibroblasts were detected by ELISA kit. The results are shown in Table 8.

[0062] Table 8. Test results of collagen microsphere ergothioneine complex repair experiment

[0063] It can be seen from the results in Table 8 that the collagen microsphere ergothioneine complex of the present invention can significantly inhibit the production of cytokines IL-1α, IL-6 and TNF-α, and promote the production of IL-10 (anti-inflammatory factor), showing a good repair effect.

[0064] 2. Anti-aging experiment This experiment also uses the collagen microsphere ergothioneine complex prepared in Example 1 as the basis for investigation.

[0065] In this experiment, different concentrations of collagen microsphere ergothioneine complex were added to human skin fibroblasts, and the total human collagen detection kit was used to detect the content of collagen in the cell fluid. The specific experiment is as follows: Digest and collect cells in logarithmic growth phase, resuspend the cells, and adjust the cell density to 5×10 4 cells / ml, added to the corresponding position of the 96-well plate, 100μl / well, the edge wells were filled with sterile PBS, and then placed in an incubator for culture. After incubation for 24h, the culture medium containing the collagen microsphere ergothioneine complex sample of the corresponding concentration was added to the corresponding position of the 96-well plate, and 3 parallels were set for each experimental group and placed in an incubator for culture. The experimental group without any sample was used as the control group. At 16h, 24h and 48h after the sample was added, each group of cell culture fluid was taken, centrifuged at 3000rpm for 10min, the supernatant was taken, stored at -20°C, and then the content of collagen in each group was detected using a human total collagen detection kit. The results are shown in Table 9.

[0066] Table 9. Collagen content of collagen microspheres and ergothioneine complex on HSF cells at different time points (pg / ml)

[0067] From the results in the above table, it can be seen that the collagen microsphere ergothioneine complex has a significant promoting effect on the collagen synthesis of human skin fibroblasts in the concentration range of 0.105%~0.211%, and the strongest effect is at 24h.

[0068] 3. Anti-blue light experiment This experiment uses the sunscreen composition prepared in Implementation 1 as the basis for investigation, and uses purified water as the control experimental sample.

[0069] This example uses CellTiter96 (MTS) to evaluate the protective effect of the multifunctional, high-efficiency, broad-spectrum sunscreen composition of the present invention against blue light damage. This example uses human epidermal keratinocytes and human dermal fibroblasts to conduct experiments to detect the survival rate and proliferation rate of the two cells. The test method is as follows: Accurately weigh 0.5 g of the collagen microsphere ergothioneine complex prepared in Implementation 1 and a solution dissolved in dimethyl sulfoxide with purified water to form an experimental sample solution, wherein the mass concentration of the sample in the solution is 0.5%.

[0070] The two cells were cultured in a 96-well plate, with the same number of cells in each well. A flat-bottom sterilized plate containing sample solution and purified water was used to cover the wells containing the two cells, and LED blue light was irradiated for 9 hours at a distance of 30 cm from the culture dish, with LED parameters of 476 nm and 1900 lux.

[0071] Finally, the cell viability was determined by MTS, and the average of three measurements was taken. The test results are shown in Table 10.

[0072] Table 10. Results of the blue light experiment of collagen microspheres and ergothioneine complex

[0073] As shown in Table 10 results, compared to the comparison purified water not adding protein microsphere thioneine complex, in the collagen microsphere thioneine complex experimental group prepared by implementation 1 of the present invention, human epidermal keratinocyte activity is as high as 98.1, and human dermal fibroblast activity is 99.6, which increases by 63.2% and 37.6% respectively, and the effect is very obvious, indicating that the collagen microsphere thioneine complex has a significant anti-blue light effect.

[0074] Example 7 This example is to examine the multifunctional and highly effective sunscreen composition of the present invention, including anti-oxidation, moisturizing, and usage evaluation.

[0075] 1. Antioxidant Experiment This experiment also uses the sunscreen composition prepared in Example 2 as the basis for investigation, and uses the comparative sunscreen composition 1, the collagen microsphere ergothioneine complex prepared in Example 1, and formulas 23, 24, and 25 in Table 11 as control experimental samples.

[0076] In the sunscreen composition formulas used for investigation in Table 11, except that the amount of type III humanized collagen and the amount of pH regulator are different from those in Example 2, the preparation methods of each sunscreen composition are consistent with those in Example 2. Similarly, the preparation method of the collagen microsphere ergothioneine complex in each sunscreen composition is the same as that in Example 1, and in the formula containing only ergothioneine, ergothioneine is dissolved in deionized water.

[0077] Table 11. Amount of each component of type III recombinant human collagen microspheres in each sunscreen composition

[0078] The specific experiments are as follows: This embodiment evaluates the antioxidant effect of the multifunctional, high-efficiency, broad-spectrum sunscreen composition of the present invention by detecting the antioxidant activity of the sample by the DPPH method. DPPH is a stable free radical, and its ethanol solution is purple, with a maximum absorption peak of 516nm in the visible light region. When a free radical scavenger is added to the DPPH solution, the solution color becomes lighter, the absorbance value becomes smaller, and the degree of absorbance reduction is linearly related to the degree of free radical scavenging. Therefore, it can be used to detect the scavenging of free radicals, thereby evaluating the antioxidant capacity of a substance, and its capacity is represented by the scavenging rate. The greater the scavenging rate, the stronger the antioxidant capacity.

[0079] 1) DPPH standard curve: Weigh 22.5 mg of DPPH standard accurately, dissolve it in anhydrous ethanol, place it in a 50 mL brown volumetric flask, adjust to volume, and shake well to obtain a 0.45 g / L DPPH standard stock solution (about 1.14×10-3 mol / L). Store it in a refrigerator away from light for later use (prepare it for immediate use). Accurately transfer 0, 1, 2, 3, 4, and 5 mL of the stock solution to a 10 mL volumetric flask, and adjust to volume with anhydrous ethanol. Measure the absorbance values ​​(A) at the maximum absorption wavelength of 516 nm, and draw a standard curve, such as Figure 2 shown.

[0080] 2) Preparation of sample solution: The sunscreen composition prepared in Example 2, the comparative sunscreen composition 1, the protein microsphere ergothioneine complex prepared in Example 1, and the sunscreen compositions prepared in formulas 23, 24, and 25 of this embodiment were completely dissolved in deionized water, and prepared into sample solutions with final concentrations of 5, 10, 20, 30, 40, and 50 mg / mL (i.e., a concentration of 0.5% to 5%), respectively, for standby testing.

[0081] Take 3.00 mL of each sample solution and 1.00 mL of DPPH solution (the stock solution was diluted 10 times with ethanol before use, and the working concentration was 1.14×10- 4 mol / L), added to the same test tube, shaken, left to stand, and reacted for 30 min in the dark, then the A value was measured at 516 nm, and the corresponding mixed solution without sample was used as a blank control. The results are shown in Table 12.

[0082] Table 12. Antioxidant test results of various sunscreen compositions

[0083] Result analysis: The results show that compared with the comparative sunscreen composition 1, the sunscreen composition sample prepared in Example 2 has a significant antioxidant effect, and is comparable to the antioxidant effect of the collagen microsphere ergothioneine complex, indicating that other ingredients in the sunscreen composition have no significant effect on the antioxidant effect of the complex, reflecting good compatibility. According to the results of Formula 23, Formula 24 and Formula 25, it can be seen that ectoine plays a necessary additive role in the antioxidant effect of the complex.

[0084] 3. Moisturizing experiment This experiment also uses the sunscreen composition prepared in Implementation 2 as the basis for investigation, and uses the comparative sunscreen composition 1 as the control experimental sample.

[0085] This example evaluates the moisturizing degree of the multifunctional, high-efficiency, broad-spectrum sunscreen composition of the present invention by monitoring the moisture content of human skin. The specific experiment is as follows: 30 subjects were selected to have a specific test area on the inner side of their forearms (3cm*3cm). After the area was cleaned, the subjects were required to sit quietly in a constant temperature and humidity room for 30 minutes. The skin moisture basal value of the subjects was measured using a skin moisture tester. The subjects applied the designated test sample (0.05g) to the test area for 3 seconds and then started timing. The timing lasted for 15 minutes. After the timing was over, the test area was gently wiped with absorbent paper to wipe off excess sample and water, and the skin moisture content of the subjects was measured using a skin moisture tester. The test results were recorded and data analysis was performed. The results are shown in Table 13.

[0086] Table 13. Moisturizing test results of various sunscreen compositions

[0087] The results in Table 13 show that the skin moisture content (15 minutes) of the sunscreen composition prepared in Implementation 2 and the comparative sunscreen composition 1 was measured after application, and the significant P value was less than 0.001, and the statistical difference was extremely significant; among them, the sunscreen composition prepared in Implementation 2 had an improvement rate of 88.01% on skin moisturizing, while the improvement rate of the comparative sunscreen composition 1 was only 18.52%. It can be seen that the moisturizing effect of the sunscreen composition with the addition of the microsphere collagen composition can be significantly improved.

[0088] 5. Sun protection index test This experiment also uses the sunscreen composition prepared in Implementation 2 as the basis for investigation, and uses the comparative sunscreen composition 1 as the control experimental sample.

[0089] This experiment tested the SPF value and PA value of the sunscreen composition prepared in Implementation 2 and the comparison sunscreen composition 1 according to the "Sunscreen Cosmetics Safety Technical Specification 2015 Edition" "Sunscreen Cosmetics Sun Protection Index (SPF Value) Test Method" and "Sunscreen Cosmetics Long-wave Ultraviolet Protection Index (PFA Value) Test Method" and the test results retained the integer part. The specific test results are shown in Table 14.

[0090] Table 14. Test results of sun protection index of various sunscreen compositions

[0091] As shown in Table 14, compared with the comparison sunscreen composition 1 to which the protein microsphere ergothioneine complex is not added, the sunscreen composition prepared by Embodiment 2 of the present invention has a high-efficiency sunscreen effect, indicating that the protein microsphere ergothioneine complex has a significant effect on improving the sunscreen value of the sunscreen composition.

[0092] VII: Human testing and evaluation of sunscreen compositions In this example, the sunscreen composition prepared in Example 2 was provided to 20 volunteers aged 20-50 years old. All 20 volunteers used the "West China Questionnaire" compiled by dermatologists from West China Hospital of Sichuan University to self-test their skin sensitivity. The results showed that they were mild to severe sensitive. Before use and 3 days after use, the red area on the face of the subjects was photographed with a Reveal dermatoscope to compare the improvement effect of the red area, and the product's moisturizing, soothing, mild and non-irritating, sensitive skin applicability and skin feel were evaluated using a Likert 5-point satisfaction questionnaire. The comparison of the red area photographed by the dermatoscope is shown in the attached figure. Figures 3 to 5 The subjective evaluation results of the subjects are shown in Table 15.

[0093] Table 15. Subjective evaluation results of the subjects

[0094] It can be seen that the subjects were generally satisfied with the effects of the products of the present invention, and the satisfaction with soothing sensitive skin and improving fine lines after use, which had lower scores, also reached 95%, indicating that the products of the present invention have indeed achieved multiple effects such as supplementing collagen, reducing the formation of wrinkles, making the skin feel refreshing and non-greasy, easy to apply, and forming a film quickly, with significant effects.

[0095] In summary, the sunscreen composition prepared by the present invention has safety, no stimulation, high sun protection index, and has multifunctional effects such as moisturizing, anti-inflammatory, anti-aging, repairing, anti-blue light, and sensitive skin applicability. Among them, the protein microsphere ergothioneine complex prepared by the present invention can not only be used for sunscreen compositions, but also can be used for the preparation of other cosmetics such as creams, emulsions, essences, etc., and has a wide range of applications.

[0096] Finally, it should be noted that: for those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. In addition, it should be understood that although this specification is described in accordance with the implementation mode, it does not contain only one technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in the embodiments can also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A collagen microsphere ergothioneine complex, characterized in that: The invention comprises type III recombinant human collagen microspheres and ergothioneine, wherein the mass ratio of the type III recombinant human collagen microspheres to ergothioneine is 0.5-2:5-20.

2. The collagen microsphere ergothioneine complex according to claim 1, characterized in that: The complex also includes ectoine, the content of which is 15 to 140 times that of type III recombinant human collagen microspheres.

3. The collagen microsphere ergothioneine complex according to claim 2, characterized in that: The complex is composed of type III recombinant human collagen microspheres, ergothioneine, ectoine and deionized water in a mass ratio of 0.5-2:5-20:30-70:40-150.

4. A sunscreen composition containing the collagen microsphere ergothioneine complex described in any one of claims 1-3, characterized in that: Based on 100 parts by total weight, the sunscreen composition comprises the following components: composition: 0.01 to 5 parts of the collagen microsphere ergothioneine complex according to any one of claims 1 to 3, 10-25 parts of composite sunscreen, 20 to 60 parts of auxiliary materials, The balance was deionized water.

5. The sunscreen composition according to claim 4, characterized in that: The composite sunscreen comprises a water-soluble sunscreen and an oil-soluble sunscreen; wherein: The water-soluble sunscreens are phenylbenzimidazole sulfonic acid and methylene bis-benzotriazolyl tetramethylbutylphenol; The oil-soluble sunscreen agents are polysilicone-15, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylamino hydroxybenzoyl hexyl benzoate, and titanium dioxide.

6. The sunscreen composition according to claim 5, characterized in that: The mass ratio of phenylbenzimidazole sulfonic acid, methylene bis-benzotriazolyl tetramethylbutylphenol, polysilicone-15, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylamine hydroxybenzoyl hexyl benzoate and titanium dioxide in the composite sunscreen is: 3-8:1-6:2-8:0.5-5:0.5-5:2-9:0.05-3.

7. The sunscreen composition according to claim 4, characterized in that: The auxiliary materials are composed of chelating agents, emollients, emulsifiers, thickeners, pH regulators, moisturizers, antioxidants and skin feel regulators; Chelating agent 0.01~0.3%, Emollient 5-20%, Emulsifier 1~9%, Thickener 0.05~3%, pH adjuster 0.5~2%, Moisturizer 3-15%, Antioxidant 0.01~1.2, Skin feel regulator 1~4%.

8. The sunscreen composition according to claim 7, characterized in that: The chelating agent is any one of EDTA-2Na and EDTA-4Na; The emollient is one or more of dibutyl adipate, diisopropyl adipate, diisopropyl sebacate, isononyl isononanoate, dioctyl carbonate, C12-15 alcohol benzoate, octyl polymethicone, butyloctanol salicylate, C12-13 alcohol lactate, polydimethylsiloxane, and isopropyl lauroyl sarcosinate; The emulsifier includes a water-soluble emulsifier and an oil-soluble emulsifier; wherein: the water-soluble emulsifier is potassium cetyl phosphate, and the oil-soluble emulsifier is at least one of ceteareth-21, ceteareth-30, cetearyl alcohol, glyceryl stearate, PEG-100 stearate, arachidyl alcohol, behenyl alcohol, arachidyl glucoside, sodium stearoyl glutamate, cetyl alcohol, and stearyl alcohol; The thickener is one or more of xanthan gum, acrylic acid (esters) / C10-30 alkyl acrylate cross-linked polymer, polyacrylate cross-linked polymer-6, hydroxyethyl acrylate / sodium acryloyl dimethyl taurate copolymer; The pH regulator is one or more of aminomethyl propanol, triethanolamine, sodium citrate, and arginine; The moisturizing agent is one or more of 1,2-hexanediol, ethylhexylglycerin, butylene glycol, 1,3-propylene glycol, allantoin, trehalose, betaine, biosaccharide gum, sodium polyglutamate, and sodium hyaluronate; The antioxidant is p-hydroxyacetophenone; The skin feel regulator is spherical porous silica with a particle size of less than 20 μm.

9. A method for preparing the sunscreen composition according to any one of claims 4 to 8, characterized in that: The process steps include: S1: Preparation of collagen microspheres and ergothioneine complex Add type III recombinant human protein microspheres, ergothioneine, and ectoine into deionized water in order, and stir to prepare a collagen microsphere ergothioneine complex for later use; S2: Preparation of oil phase mixture Add the emollient, oil-soluble sunscreen, oil-soluble emulsifier and skin feel regulator into the oil phase pot, heat to 75-85°C, stir and disperse evenly at a stirring speed of 150-300 r / min to obtain an oil phase mixture; S3: Preparation of aqueous phase mixture Add water-soluble emulsifier, moisturizer, thickener, chelating agent and deionized water into the water phase pot, start stirring at a speed of 50-120 r / min, heat to 75-85°C, disperse evenly, and obtain a water phase mixture; S4: Emulsification and homogenization After the oil phase mixture prepared in step S2 is pumped into the emulsification pot, the water phase mixture prepared in step S3 is pumped into the emulsification pot, stirred evenly, homogenized at 7000-8000 high speed, stirred evenly, the stirring speed is 35-110r / min, stirred and cooled to 60-70°C to obtain an emulsified mixture; S5: Secondary homogenization Add an antioxidant to the emulsified mixture obtained in step S4, stir evenly, at a stirring speed of 35 to 110 r / min, briefly homogenize at a low speed of 1500 to 2800 r / min for 1 to 5 min, continue stirring and cool to 40° C. to obtain a homogeneous mixture; S6: Three-time homogenization The water-soluble sunscreen is pre-dissolved in advance with a pH regulator and part of deionized water, and the pre-dissolved pH regulator and water-soluble sunscreen are added to the homogeneous mixture obtained in step S5, and the mixture is homogenized at a low speed of 1500 to 2800 r / min for 1 to 5 minutes, and the stirring is continued to obtain a homogeneous mixture; S7: Add collagen microspheres ergothioneine complex The collagen microsphere ergothioneine complex prepared in step S1 is added to the homogeneous mixture obtained in step S6, stirred evenly at 35-110 r / min, and removed from the pot to obtain a sunscreen composition containing the collagen microsphere ergothioneine complex.

10. The method for preparing the sunscreen composition according to claim 9, characterized in that: In step S1, the preparation of collagen microsphere ergothioneine complex specifically includes the following sub-steps: S1-1: Add type III recombinant human collagen microspheres into deionized water and stir evenly to form a microsphere collagen solution; S1-2: adding ergothioneine into the microsphere collagen solution obtained in step S1-1 in 2 to 4 times, stirring at 250 to 400 r / min for 10 to 20 min at room temperature to construct a protein microsphere ergothioneine complex; S1-3: Add ectoine to the collagen microsphere ergothioneine complex obtained in step S1-2, control the stirring speed at 150-300 r / min, and stir at a high speed until all dissolved to obtain the protein microsphere ergothioneine complex.

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