A multi-protective emulsion and its preparation process

Abstract

The present invention provides a multi-protection emulsion and its preparation process, which relates to the technical field of cosmetics and has an IPC classification number belonging to A61K. The multi-protection emulsion of the present invention comprises nano-titanium dioxide composite particles, plant extracts, excipients and solvents; the plant extracts are composed of artemisia argyi extract, lithospermum erythrorhizon extract, angelica polymorpha extract and coix seed extract. Among them, the nano-titanium dioxide composite particles are made by wrapping nano-titanium dioxide with quaternary ammonium salt of chitosan, which improves the dispersion performance of nano-titanium dioxide and alleviates the irritation to the skin; the plant extracts have multiple functions such as multi-level ultraviolet protection, anti-inflammatory, soothing, moisturizing, whitening and anti-pigmentation deposition. The nano-titanium dioxide composite particles and the plant extracts of the present invention have a synergistic effect when compounded, achieving a sunscreen effect by combining multiple aspects of physics, chemistry and biology. The test results show that the multi-protection emulsion of the present invention has good stability, antioxidant performance and excellent sunscreen effect.

Description

Technical Field

[0001] The present invention relates to the technical field of cosmetics, and its IPC classification number belongs to A61K. Specifically, it relates to a multi-protection type emulsion and its preparation process. Background Art

[0002] In today's cosmetics market, emulsions, as a key category for daily skin care, are deeply loved and widely used by consumers. Emulsions can form a thin protective film on the skin surface, which can not only effectively moisturize the skin, prevent water loss, but also provide necessary nutrients for the skin to maintain the healthy state of the skin. However, with the increasing diversification and refinement of consumers' demands for skin care effects, traditional emulsions have gradually revealed many deficiencies in terms of protective functions.

[0003] From the perspective of protecting against ultraviolet rays, long-term exposure to ultraviolet rays (UV) in solar radiation is one of the main causes of skin photoaging, sunburn, and even skin cancer. Although traditional emulsions have certain moisturizing and nourishing effects, their ability to protect against ultraviolet rays is very limited. Most emulsions do not add sufficient and effective sunscreen ingredients. Even if some emulsions contain sunscreen agents, their protection bands are often not comprehensive enough to resist the damage of both long-wave ultraviolet rays (UVA) and medium-wave ultraviolet rays (UVB) at the same time. This makes it impossible for users to obtain sufficient ultraviolet protection when outdoors only relying on traditional emulsions, and the skin is prone to problems such as sunburn, sunburn, and photoaging.

[0004] In response to oxidative stress inside the skin, the skin's own metabolic process and external environmental factors (such as ultraviolet rays, pollution, stress, etc.) will cause the skin to produce excessive free radicals. Excessive free radicals will attack lipids, proteins, and DNA in skin cells, leading to cell damage and aging. Traditional emulsions have deficiencies in the types and dosages of added antioxidant ingredients, and cannot effectively scavenge free radicals in a timely manner, making it difficult to meet the skin's demand for antioxidant protection, and the skin gradually shows aging signs such as wrinkles, sagging, and dullness.

[0005] In view of the deficiencies of traditional emulsions in multiple protection functions such as ultraviolet protection and antioxidant, developing an emulsion and its preparation process that can provide comprehensive and efficient multiple protection for the skin has become an urgent problem to be solved in the cosmetics field. This is not only the key to meeting the growing skin care needs of consumers, but also an important direction to promote the technological innovation and development of the cosmetics industry. Summary of the Invention

[0006] The purpose of the present invention is to provide a multi-protection type emulsion and its preparation process. The emulsion provided by the present invention not only has excellent sunscreen effects, but also has the functions of antioxidant, soothing the skin, and preventing skin photo-damage.

[0007] To achieve the above-mentioned invention object, the present invention provides the following technical solutions:

[0008] The present invention provides a multi-protection type emulsion, which is composed of the following components in parts by weight, based on 100 parts by weight: 5-10 parts of nano-titanium dioxide composite particles, 6-13 parts of plant extracts, 3-8 parts of humectants, 2-6 parts of emollients, 2-6 parts of film-forming agents, 1-5 parts of emulsifiers, 0.1-2 parts of preservatives, and the solvent makes up 100 parts; the plant extracts are composed of Artemisia argyi extract, Lithospermum erythrorhizon extract, Angelica polymorpha Maxim. extract, and Coix seed extract according to the weight ratio of (1-4):(4-10):(3-8):(7-13).

[0009] Preferably, the preparation method of the nano-titanium dioxide composite particles includes: mixing chitosan quaternary ammonium salt with water to obtain a chitosan quaternary ammonium salt solution; mixing nano-titanium dioxide with water, performing ultrasonic treatment to obtain a nano-titanium dioxide dispersion liquid, adding it to the chitosan quaternary ammonium salt solution, and then mixing and crosslinking and curing with a sodium tripolyphosphate solution, centrifuging and washing, and freeze-drying the precipitate to obtain nano-titanium dioxide composite particles.

[0010] More preferably, the concentration of the nano-titanium dioxide dispersion liquid is 1-2 mg / mL, the concentration of the chitosan quaternary ammonium salt solution is 5-10 g / mL, the concentration of the sodium tripolyphosphate solution is 0.5-1.5 g / mL, and the volume ratio of the nano-titanium dioxide dispersion liquid, the chitosan quaternary ammonium salt solution, and the sodium tripolyphosphate solution is 1-3:1-3:2-5.

[0011] More preferably, the temperature of the crosslinking and curing is 25-30 °C, and the time is 3-5 h.

[0012] Preferably, the Artemisia argyi extract and the Lithospermum erythrorhizon extract are obtained by ultrasonic extraction with ethanol.

[0013] Preferably, the Angelica polymorpha Maxim. extract is obtained by enzymatic hydrolysis with β-glucanase and ficin.

[0014] Preferably, the Coix seed extract is obtained by anaerobic fermentation with Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC 6180.

[0015] Preferably, the humectant is one or more of glycerol polyether-26, methylpropanediol, and 1,2-pentanediol; the emollient is one or more of polyglyceryl-3 ricinoleate, glyceryl tri(ethylhexanoate), and dicaprylyl carbonate; the emulsifier is one or more of sodium cetostearyl sulfate, polyglyceryl-4 oleate, and laureth-4; the film-forming agent is one or more of trimethylsiloxysilicate, PEG / PPG-18 / 18 dimethicone, and PEG-8 laurate; the preservative is one or more of caprylyl glycol, phenoxyethanol, and ethylhexylglycerin; and the solvent is water.

[0016] The present invention also provides a method for preparing the above-mentioned multi-protection type emulsion, which includes: mixing and heating the emollient and the emulsifier to dissolve, then adding the film-forming agent to obtain an oil phase; mixing and heating the humectant and the solvent, then adding the plant extract to obtain an aqueous phase; mixing the oil phase and the aqueous phase, and adding the nano-titanium dioxide composite particles and the preservative to obtain the multi-protection type emulsion.

[0017] The present invention also provides the application of the above-mentioned multi-protection type emulsion in the preparation of sunscreen products.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The present invention provides a multi-protection type emulsion, which includes: nano-titanium dioxide composite particles, plant extracts, humectants, emollients, film-forming agents, emulsifiers, preservatives, and solvents; the plant extracts are composed of Artemisia argyi leaf extract, Lithospermum erythrorhizon extract, Angelica polymorpha Maxim. extract, and Coix seed extract. Among them, the nano-titanium dioxide composite particles are made by wrapping nano-titanium dioxide with chitosan quaternary ammonium salt, which improves the dispersion performance and alleviates the irritation of titanium dioxide to the skin; the plant extracts have multiple functions such as multi-level ultraviolet protection, anti-inflammatory, soothing, moisturizing, whitening, and anti-pigmentation deposition. The nano-titanium dioxide composite particles and the plant extracts of the present invention have a synergistic effect, and achieve a sunscreen effect by combining multiple aspects of physics, chemistry, and biology. The test results show that the multi-protection type emulsion of the present invention has good stability, antioxidant performance, and excellent sunscreen effect. Detailed implementation mode

[0020] The present invention provides a multi-protection type emulsion, which is composed of the following components in parts by weight. Based on 100 parts by weight: 5-10 parts of nano-titanium dioxide composite particles, 6-13 parts of plant extracts, 3-8 parts of humectants, 2-6 parts of emollients, 2-6 parts of film-forming agents, 1-5 parts of emulsifiers, 0.1-2 parts of preservatives, and the solvent makes up 100 parts; the plant extracts are composed of Artemisia argyi leaf extract, Lithospermum erythrorhizon extract, Angelica polymorpha Maxim. extract, and Coix seed extract in a weight ratio of (1-4):(4-10):(3-8):(7-13).

[0021] The preparation method of the nano-titanium dioxide composite particles described in the present invention preferably includes: mixing chitosan quaternary ammonium salt with water to obtain a chitosan quaternary ammonium salt solution; mixing nano-titanium dioxide with water, subjecting to ultrasonic treatment to obtain a nano-titanium dioxide dispersion liquid, adding it to the chitosan quaternary ammonium salt solution, and then mixing and crosslinking and curing with a sodium tripolyphosphate solution, centrifuging and washing, and freeze-drying the precipitate to obtain the nano-titanium dioxide composite particles.

[0022] The particle size of the nano-titanium dioxide described in the present invention is 30-80 nm. The concentration of the nano-titanium dioxide dispersion liquid is preferably 1-2 mg / mL, more preferably 1.5 mg / mL. The chitosan quaternary ammonium salt is preferably hydroxypropyl trimethyl ammonium chloride chitosan (HACC, molecular weight 100,000, purchased from Shanxi Lanyuan Technology Co., Ltd., product number LYSW-0703-023). The concentration of the chitosan quaternary ammonium salt solution is preferably 5-10 g / mL, more preferably 8 g / mL. The concentration of the sodium tripolyphosphate solution is preferably 0.5-1.5 g / mL, more preferably 1 g / mL. The volume ratio of the nano-titanium dioxide dispersion liquid, the chitosan quaternary ammonium salt solution and the sodium tripolyphosphate solution is preferably 1-3:1-3:2-5, more preferably 2:2:4. The temperature of the crosslinking and curing is preferably 25-30 °C, more preferably 27 °C, and the time is preferably 3-5 h, more preferably 4 h. In the present invention, nano-titanium dioxide is wrapped by chitosan quaternary ammonium salt. On the one hand, it makes titanium dioxide have excellent dispersion performance. On the other hand, it can reduce problems such as the irritation of titanium dioxide to the skin, skin flushing, and acne.

[0023] The artemisia argyi extract and the lithospermum erythrorhizon extract described in the present invention are preferably obtained by ethanol ultrasonic extraction. The preparation method of the artemisia argyi extract preferably includes: pulverizing artemisia argyi and sieving it through a 400-500 mesh sieve, adding 5-8 weights of 60%-70% (v / v) ethanol solution, ultrasonically extracting for 30-40 min under the conditions of 50-60 °C and 150-250 W, filtering, concentrating under reduced pressure to 1 / 5-1 / 3 of the volume of the filtrate, and freeze-drying under vacuum to obtain the artemisia argyi extract. The preparation method of the lithospermum erythrorhizon extract preferably includes: pulverizing lithospermum erythrorhizon and sieving it through a 400-500 mesh sieve, adding 8-12 weights of 70-80% (v / v) ethanol solution, ultrasonically extracting for 20-30 min under the conditions of 40-50 °C and 100-200 W, filtering, concentrating under reduced pressure to 1 / 5-1 / 3 of the volume of the filtrate, and freeze-drying under vacuum to obtain the lithospermum erythrorhizon extract. The artemisia argyi extract prepared by the method of the present invention is rich in flavonoids, phenolic acids and volatile oils, and has antioxidant and anti-inflammatory effects. It can neutralize free radicals induced by ultraviolet rays and reduce skin inflammatory reactions. The lithospermum erythrorhizon extract prepared by the preparation method of the present invention contains naphthoquinone compounds such as shikonin, has anti-inflammatory and antibacterial functions, and can absorb UVA. As a natural ultraviolet absorber, it can assist in sun protection and repair light damage at the same time.

[0024] The Angelica polymorpha Maxim. extract of the present invention is preferably obtained by enzymatic hydrolysis with β-glucanase and ficin. The preparation method of the Angelica polymorpha Maxim. extract preferably includes: drying and pulverizing the Angelica polymorpha Maxim. stems, passing through a 500-600 mesh sieve, mixing with 10-15 times the weight of water, adding β-glucanase and ficin, and performing enzymatic hydrolysis at 50-55 °C and a pH value of 5.5-6.5 for 60-90 min, inactivating the enzyme, filtering, concentrating under reduced pressure to 1 / 5-1 / 3 of the volume of the filtrate, and freeze-drying under vacuum to obtain the Angelica polymorpha Maxim. extract. The enzyme activity of the β-glucanase is preferably 20,000-50,000 U / g, more preferably 30,000 U / g, and the addition amount is preferably 3%-8% of the weight of the Angelica polymorpha Maxim. stems, more preferably 5%; the enzyme activity of the ficin is preferably 10,000-30,000 U / g, more preferably 20,000 U / g, and the addition amount is preferably 2%-5% of the weight of the Angelica polymorpha Maxim. stems, more preferably 3%. The Angelica polymorpha Maxim. extract obtained by the enzymatic hydrolysis method of the present invention contains polysaccharides, small molecule peptides and amino acids, has antioxidant, enhanced moisturizing and skin barrier functions, can relieve dryness and sensitivity after sun exposure, and soothe the irritation caused by ultraviolet rays.

[0025] The Coix seed extract of the present invention is preferably obtained by anaerobic fermentation with Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC6180. The preparation method of the Coix seed extract preferably includes: pulverizing Coix seeds, passing through a 100-200 mesh sieve, adding 15-25 times the weight of water, inoculating Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC 6180, and performing anaerobic fermentation at 35-40 °C and a pH value of 5.5-6.5 for 24-36 h, sterilizing, filtering, concentrating under reduced pressure to 1 / 5-1 / 3 of the volume of the filtrate, and freeze-drying to obtain the Coix seed extract. The Bacillus velezensis NKY1 is purchased from the China Center for Type Culture Collection, with the preservation number CCTCC NO:M 2021848, disclosed in CN114058532A, the viable count is preferably 1×10⁹-2×10⁹ CFU / g, more preferably 1.5×10⁹ CFU / g, and the addition amount is preferably 5‰-8‰ of the weight of the Coix seeds, more preferably 6‰; the Bifidobacterium adolescentis CICC 6180 is purchased from the China Center for Industrial Culture Collection Management, the viable count is preferably 5×10⁸-1×10⁹ CFU / g, more preferably 8×10⁸ CFU / g, and the addition amount is preferably 3‰-5‰ of the weight of the Coix seeds, more preferably 4‰. The Coix seed extract obtained by the fermentation method of the present invention is rich in organic acids, polypeptides and polysaccharides, has enhanced antioxidant, whitening and anti-inflammatory effects, inhibits melanin production, prevents sunburn and has a soothing effect.

[0026] The plant extract of the present invention has multiple functions such as multi-level ultraviolet protection, anti-inflammatory, soothing, moisturizing, whitening, and anti-pigmentation deposition. Multi-level ultraviolet protection: The extract of purple gromwell root can absorb UVA, complement with the physical sunscreen of nano-titanium dioxide composite particles, broaden the protection spectrum, and the extracts of Artemisia argyi, Angelica polymorpha Maxim., and Coix seed have antioxidant effects, which can reduce photoaging damage; Anti-inflammatory + Soothing: The extracts of Artemisia argyi and purple gromwell root can reduce phototoxic reactions such as erythema and swelling, and the moisturizing and barrier repair effects of the extract of Angelica polymorpha Maxim. can reduce the release of inflammatory factors and relieve post-sun sensitivity; Moisturizing: The extracts of Angelica polymorpha Maxim. and Coix seed form a water-locking network, maintain the water hydration degree of the stratum corneum, and resist the barrier damage caused by ultraviolet rays; Whitening + Anti-pigmentation deposition: The extract of Coix seed can inhibit the activity of tyrosinase, reduce melanin synthesis, and the extracts of Artemisia argyi and purple gromwell root block the pigmentation induced by oxidative stress and prevent post-sun dark spots.

[0027] The nano-titanium dioxide composite particles of the present invention and the plant extract have a synergistic effect in compounding, achieving a sunscreen effect from three aspects of physics, chemistry, and biology. The nano-titanium dioxide composite particles can reflect / scatter UVB (290 - 320 nm) and short-wave UVA (320 - 350 nm), providing an immediate physical barrier, reducing the direct penetration of ultraviolet rays, and reducing acute phototoxic reactions such as erythema and burning; The extract of purple gromwell root selectively absorbs long-wave UVA (340 - 400 nm), makes up for the protection gap of titanium dioxide against long-wave UVA, and forms a complementary spectral coverage; The anti-inflammatory components in the extracts of Artemisia argyi and purple gromwell root can relieve post-sun inflammation; The extracts of Artemisia argyi, Angelica polymorpha Maxim., and Coix seed all have antioxidant effects, which can reduce photoaging damage; The extracts of Angelica polymorpha Maxim. and Coix seed promote the proliferation and barrier repair of keratinocytes, accelerate the recovery of the post-sun epidermis, and reduce desquamation and sensitivity.

[0028] The moisturizer described in the present invention is preferably one or more of glycerol polyether-26, methylpropanediol, and 1,2-pentanediol; the emollient is preferably one or more of polyglyceryl-3 ricinoleate, glyceryl tri(ethylhexanoate), and dicaprylyl carbonate; the emulsifier is preferably one or more of sodium cetostearyl sulfate, polyglyceryl-4 oleate, and laureth-4; the film-forming agent is preferably one or more of trimethylsilyloxy silicate, PEG / PPG-18 / 18 dimethicone, and PEG-8 laurate; the preservative is preferably one or more of caprylyl glycol, phenoxyethanol, and ethylhexylglycerin; the solvent is preferably water.

[0029] The present invention also provides a method for preparing the above-mentioned multi-protection emulsion, which includes: mixing and heating an emollient and an emulsifier to dissolve them, then adding a film-forming agent to obtain an oil phase; mixing and heating a humectant and a solvent, then adding a plant extract to obtain an aqueous phase; mixing the oil phase and the aqueous phase, and adding nano-titanium dioxide composite particles and a preservative to obtain the multi-protection emulsion.

[0030] The usage method of the multi-protection emulsion of the present invention is as follows: Clean the facial skin, and after basic skin care, take an appropriate amount of this product and apply it to the exposed parts such as the face, neck, arms, and legs in the sun, gently massage until evenly distributed, and use it 30 minutes before going out daily.

[0031] The present invention also provides the application of the above-mentioned multi-protection emulsion in the preparation of sunscreen products.

[0032] In the present invention, unless otherwise specified, all raw material components are commercially available products well-known to those skilled in the art.

[0033] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without creative efforts shall fall within the protection scope of the present invention.

[0034] In the following embodiments, unless otherwise specified, all are conventional methods.

[0035] In the following embodiments, the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0036] Hydroxypropyltrimethylammonium chloride chitosan (HACC), with a molecular weight of 100,000, was purchased from Shanxi Lanyuan Technology Co., Ltd., and the product number is LYSW-0703-023;

[0037] Chitosan was purchased from Xi'an Tianhe Pharmaceutical Co., Ltd., and the product number is TH-DERER;

[0038] PEG / PPG-18 / 18 polydimethylsiloxane was purchased from Hubei Langbowan Biopharmaceutical Co., Ltd., and the model is 2024;

[0039] Bacillus velezensis NKY1 was purchased from China Center for Type Culture Collection, and the preservation number is CCTCC NO: M2021848;

[0040] Bifidobacterium adolescentis CICC 6180 and Bifidobacterium longum CICC6212 were purchased from China National Center for Industrial Culture Collection Management;

[0041] Bacillus subtilis XDK06 was purchased from the Guangdong Provincial Culture Collection Center of Microorganisms, with the preservation number GDMCC No: 61260, and is disclosed in the patent CN112458017A.

[0042] Example 1

[0043] Multi-protective emulsion

[0044] (1) Preparation of nano-titanium dioxide composite particles

[0045] Mix HACC with deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 8 g / mL; add nano-titanium dioxide to deionized water and perform ultrasonic treatment at 200 W for 30 min to obtain a nano-titanium dioxide dispersion with a concentration of 1.5 mg / mL; after dropping the nano-titanium dioxide dispersion into the chitosan quaternary ammonium salt solution, add a 1 g / mL sodium polyphosphate solution, adjust the pH value to 5.8, crosslink and cure at 800 rpm for 4 h, centrifuge the reaction solution at 9000 rpm for 18 min, wash the precipitate with deionized water, and vacuum freeze-dry until the water content is 4% to obtain nano-titanium dioxide composite particles;

[0046] Among them, the volume ratio of the nano-titanium dioxide dispersion, the chitosan quaternary ammonium salt solution, and the sodium tripolyphosphate solution is 2:2:4;

[0047] (2) Preparation of plant extracts

[0048] Dry and crush Artemisia argyi leaves through a 450-mesh sieve, add 6 times the weight of a 65% (v / v) ethanol solution, perform ultrasonic extraction at 55 °C and 200 W for 35 min, then filter, concentrate under reduced pressure to 1 / 4 of the original volume of the filtrate, and vacuum freeze-dry until the water content is 3% to obtain the Artemisia argyi extract;

[0049] Dry and crush Lithospermum erythrorhizon roots through a 450-mesh sieve, add 10 times the weight of a 75% (v / v) ethanol solution, perform ultrasonic extraction at 45 °C and 150 W for 25 min, then filter, concentrate under reduced pressure to 1 / 4 of the original volume of the filtrate, and vacuum freeze-dry until the water content is 4% to obtain the Lithospermum erythrorhizon root extract;

[0050] Dry and crush the stems of Angelica polymorpha Maxim., mix with 13 times the weight of deionized water, add β-glucanase and ficin, enzymatically hydrolyze at 52 °C and pH 6 for 70 min, inactivate the enzyme, filter, concentrate under reduced pressure to 1 / 4 of the original volume of the filtrate, and vacuum freeze-dry until the water content is 5% to obtain the Angelica polymorpha Maxim. extract; among them, the enzyme activity of β-glucanase is 30,000 U / g, and the addition amount is 5% of the weight of the Angelica polymorpha Maxim. stems, and the enzyme activity of ficin is 20,000 U / g, and the addition amount is 3% of the weight of the Angelica polymorpha Maxim. stems;

[0051] Dry Coix seeds, crush them and sieve through a 150-mesh sieve. Add water with a weight 20 times that of the Coix seeds. Inoculate with Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC6180, and anaerobically ferment at 37 °C and pH 6 for 30 h. Sterilize, filter, and concentrate under reduced pressure to 1 / 4 of the filtrate volume, and then vacuum freeze-dry to a water content of 4% to obtain the Coix seed extract. Among them, the viable count of Bacillus velezensis NKY1 is 1.5 billion CFU / g, and the inoculation amount is 6‰ of the weight of Coix seeds; the viable count of Bifidobacterium adolescentis CICC6180 is 800 million CFU / g, and the inoculation amount is 4‰ of the weight of Coix seeds.

[0052] Mix the Artemisia argyi extract, Lithospermum erythrorhizon extract, Angelica polymorpha var. sinensis extract and Coix seed extract according to a weight ratio of 3:5:4:10 to obtain the plant extract.

[0053] (3)Preparation of the multi-protection emulsion

[0054] Weigh 7 parts by weight of nano-titanium dioxide composite particles, 8 parts by weight of plant extract, 4 parts by weight of glycerol polyether-26, 3 parts by weight of glyceryl tri(ethylhexanoate), 3 parts by weight of trimethylsiloxysilicate, 2 parts by weight of cetylstearyl sulfate, 1 part by weight of caprylyl glycol, and make up to 100 parts by weight with deionized water.

[0055] Mix glyceryl tri(ethylhexanoate) and cetylstearyl sulfate, heat and dissolve at 75 °C and 500 rpm, then add trimethylsiloxysilicate, and continue to stir at 500 rpm for 10 min to obtain the oil phase. Mix glycerol polyether-26 and 62 parts by weight of deionized water, stir at 75 °C and 2500 rpm for 20 min, cool to 40 °C and then add the plant extract to obtain the water phase. Mix the oil phase and the water phase, stir at 3000 rpm for 10 min, add the dispersion of nano-titanium dioxide composite particles (mix nano-titanium dioxide composite particles with 10 parts by weight of deionized water and ultrasonically treat at 200 W for 30 min to obtain the dispersion) and caprylyl glycol, stir at 5000 rpm for 15 min, adjust the pH value to 5.8, and perform vacuum degassing and sterilization to obtain the multi-protection emulsion.

[0056] Example 2

[0057] Multi-protection emulsion

[0058] (1)Preparation of nano-titanium dioxide composite particles

[0059] Mix HACC with deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 5 g / mL; add nano-titanium dioxide to deionized water, and perform ultrasonic treatment at 150 W for 45 min to obtain a nano-titanium dioxide dispersion with a concentration of 1 mg / mL; after dropping the nano-titanium dioxide dispersion into the chitosan quaternary ammonium salt solution, add a 0.5 g / mL sodium polyphosphate solution, adjust the pH value to 5.5, crosslink and cure at 700 rpm for 5 h, centrifuge the reaction solution at 8000 rpm for 15 min, wash the precipitate with deionized water, and vacuum freeze-dry until the water content is 3% to obtain nano-titanium dioxide composite particles;

[0060] Among them, the volume ratio of the nano-titanium dioxide dispersion, the chitosan quaternary ammonium salt solution, and the sodium tripolyphosphate solution is 3:3:5;

[0061] (2)Preparation of plant extracts

[0062] Dry and crush mugwort leaves through a 400-mesh sieve, add 5 times the weight of 60% (v / v) ethanol solution, perform ultrasonic extraction at 50 °C and 150 W for 40 min, then filter, concentrate under reduced pressure to 1 / 5 of the original volume of the filtrate, and vacuum freeze-dry until the water content is 2% to obtain the mugwort leaf extract;

[0063] Dry and crush purple gromwell roots through a 400-mesh sieve, add 8 times the weight of 70% (v / v) ethanol solution, perform ultrasonic extraction at 40 °C and 100 W for 30 min, then filter, concentrate under reduced pressure to 1 / 5 of the original volume of the filtrate, and vacuum freeze-dry until the water content is 4% to obtain the purple gromwell root extract;

[0064] Dry and crush the stems of Angelica polymorpha Maxim. var. sutchuenensis (Franch.) Yuan et Shan through a 500-mesh sieve, mix with 10 times the weight of deionized water, add β-glucanase and ficin, enzymatically hydrolyze at 50 °C and pH 5.5 for 90 min, inactivate the enzyme, filter, concentrate under reduced pressure to 1 / 5 of the original volume of the filtrate, and vacuum freeze-dry until the water content is 1% to obtain the Angelica polymorpha Maxim. var. sutchuenensis (Franch.) Yuan et Shan extract; among them, the enzyme activity of β-glucanase is 20,000 U / g, and the addition amount is 8% of the weight of the stems of Angelica polymorpha Maxim. var. sutchuenensis (Franch.) Yuan et Shan, the enzyme activity of ficin is 10,000 U / g, and the addition amount is 5% of the weight of the stems of Angelica polymorpha Maxim. var. sutchuenensis (Franch.) Yuan et Shan;

[0065] Dry and crush coix seeds through a 100-mesh sieve, add 15 times the weight of water, inoculate Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC6180, anaerobically ferment at 35 °C and pH 5.5 for 36 h, sterilize, filter, concentrate under reduced pressure to 1 / 5 of the original volume of the filtrate, and vacuum freeze-dry until the water content is 2% to obtain the coix seed extract; among them, the viable count of Bacillus velezensis NKY1 is 1 billion CFU / g, and the inoculation amount is 8‰ of the weight of coix seeds, the viable count of Bifidobacterium adolescentis CICC6180 is 500 million CFU / g, and the inoculation amount is 5‰ of the weight of coix seeds;

[0066] Mix the Artemisia argyi leaf extract, Lithospermum erythrorhizon extract, Angelica polymorpha Maxim. extract and Coix seed extract in a weight ratio of 1:4:3:7 to obtain a plant extract;

[0067] (3)Preparation of the multi-protection emulsion

[0068] Weigh 5 parts by weight of nano-titanium dioxide composite particles, 11 parts by weight of plant extract, 3 parts by weight of methyl propylene glycol, 4 parts by weight of dicaprylyl carbonate, 2 parts by weight of PEG / PPG-18 / 18 dimethicone, 4 parts by weight of laureth-4, 0.1 part by weight of phenoxyethanol and make up to 100 parts by weight with deionized water;

[0069] Mix dicaprylyl carbonate and laureth-4, heat and dissolve at 70 °C and 400 rpm, then add PEG / PPG-18 / 18 dimethicone, and continue to stir at 400 rpm for 15 min to obtain an oil phase; Mix methyl propylene glycol and 60.9 parts by weight of deionized water, stir at 70 °C and 2300 rpm for 25 min, cool to 35 °C and then add the plant extract to obtain an aqueous phase; Mix the oil phase and the aqueous phase, stir at 2500 rpm for 15 min, add the dispersion of nano-titanium dioxide composite particles (mix nano-titanium dioxide composite particles with 10 parts by weight of deionized water and ultrasonically treat for 40 min under 100 W to obtain a dispersion) and phenoxyethanol, stir at 4500 rpm for 20 min, adjust the pH value to 5.5, carry out vacuum degassing and sterilization to obtain the multi-protection emulsion.

[0070] Example 3

[0071] Multi-protection emulsion

[0072] (1)Preparation of nano-titanium dioxide composite particles

[0073] Mix HACC with deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 10 g / mL; Add nano-titanium dioxide to deionized water and ultrasonically treat at 250 W for 20 min to obtain a nano-titanium dioxide dispersion with a concentration of 2 mg / mL; After dropping the nano-titanium dioxide dispersion into the chitosan quaternary ammonium salt solution, add a 1.5 g / mL sodium polyphosphate solution, adjust the pH value to 6, crosslink and cure at 900 rpm for 2 h, centrifuge the reaction solution at 10000 rpm for 15 min, wash the precipitate with deionized water, and vacuum freeze-dry until the water content is 2% to obtain nano-titanium dioxide composite particles;

[0074] Among them, the volume ratio of the nano-titanium dioxide dispersion, the chitosan quaternary ammonium salt solution and the sodium tripolyphosphate solution is 1:1:2;

[0075] (2)Preparation of plant extracts

[0076] Dry and crush Artemisia argyi leaves, sieve them through a 500-mesh sieve, add an ethanol solution with 8 times the weight and a concentration of 70% (v / v), perform ultrasonic extraction for 30 min at 60 °C and 250 W, then filter, concentrate under reduced pressure to 1 / 3 of the filtrate volume, and vacuum freeze-dry until the water content is 5% to obtain the Artemisia argyi extract;

[0077] Dry and crush Lithospermum erythrorhizon roots, sieve them through a 500-mesh sieve, add an ethanol solution with 12 times the weight and a concentration of 80% (v / v), perform ultrasonic extraction for 20 min at 50 °C and 200 W, then filter, concentrate under reduced pressure to 1 / 3 of the filtrate volume, and vacuum freeze-dry until the water content is 3% to obtain the Lithospermum erythrorhizon root extract;

[0078] Dry and crush Angelica polymorpha Maxim. stems, sieve them through a 600-mesh sieve, mix with 15 times the weight of deionized water, add β-glucanase and ficin, enzymatically hydrolyze at 55 °C and pH 6.5 for 60 min, inactivate the enzyme, filter, concentrate under reduced pressure to 1 / 3 of the filtrate volume, and vacuum freeze-dry until the water content is 2% to obtain the Angelica polymorpha Maxim. extract; wherein the enzyme activity of β-glucanase is 50,000 U / g, and the addition amount is 3% of the weight of Angelica polymorpha Maxim. stems, and the enzyme activity of ficin is 30,000 U / g, and the addition amount is 2% of the weight of Angelica polymorpha Maxim. stems;

[0079] Dry and crush Coix lacryma-jobi L. seeds, sieve them through a 200-mesh sieve, add 25 times the weight of water, inoculate Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC6180, perform anaerobic fermentation at 40 °C and pH 6.5 for 24 h, sterilize, filter, concentrate under reduced pressure to 1 / 3 of the filtrate volume, and vacuum freeze-dry until the water content is 3% to obtain the Coix lacryma-jobi L. seed extract; wherein the viable count of Bacillus velezensis NKY1 is 2 billion CFU / g, and the inoculation amount is 5‰ of the weight of Coix lacryma-jobi L. seeds, and the viable count of Bifidobacterium adolescentis CICC6180 is 1 billion CFU / g, and the inoculation amount is 3‰ of the weight of Coix lacryma-jobi L. seeds;

[0080] Mix the Artemisia argyi extract, Lithospermum erythrorhizon root extract, Angelica polymorpha Maxim. extract and Coix lacryma-jobi L. seed extract according to a weight ratio of 4:10:8:12 to obtain the plant extract;

[0081] (3)Preparation of multi-protection emulsion

[0082] 10 parts of nano-titanium dioxide composite particles, 6 parts of plant extract, 4 parts of 1,2-pentanediol, 2 parts of polyglyceryl-3 ricinoleate, 3 parts of PEG-8 laurate, 2 parts of polyglyceryl-4 oleate, 1 part of ethylhexylglycerin, and the solvent is made up to 100 parts;

[0083] Mix polyglyceryl-3 ricinoleate and polyglyceryl-4 oleate, heat and dissolve them at 80 °C under the condition of 550 rpm, add PEG-8 laurate, and continue to stir for 8 min under the condition of 550 rpm to obtain the oil phase; mix 1,2-pentanediol and 57 parts by weight of deionized water, stir at 80 °C under the condition of 2800 rpm for 18 min, cool down to 45 °C and then add the plant extract to obtain the water phase; mix the oil phase and the water phase, stir at 3500 rpm for 8 min, add the dispersion of nano-titanium dioxide composite particles (mix nano-titanium dioxide composite particles with 15 parts by weight of deionized water, and ultrasonically treat for 30 min under the condition of 250 W to obtain the dispersion) and ethylhexylglycerin, stir at 55000 rpm for 13 min, adjust the pH value to 6, and perform vacuum degassing and sterilization to obtain the multi-protective emulsion.

[0084] Comparative Example 1

[0085] The difference from Example 1 is that the quaternary ammonium salt of chitosan in step (1) is replaced by chitosan, and "mix HACC and deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 8 g / mL" is replaced by "mix chitosan with 1% (v / v) acetic acid solution to obtain a chitosan solution with a concentration of 8 g / mL".

[0086] Comparative Example 2

[0087] The difference from Example 1 is that the ethanol solution in the Artemisia argyi extract and Lithospermum erythrorhizon extract in step (2) is replaced by deionized water.

[0088] Comparative Example 3

[0089] The difference from Example 1 is that the preparation method of the Coix seed extract in step (2) is as follows: dry and crush Coix seeds through a 150-mesh sieve, add 20 times the weight of water, inoculate Bacillus subtilis XDK06 and Bifidobacterium longum CICC6212, anaerobically ferment at 37 °C and pH 6 for 30 h, sterilize, filter, concentrate under reduced pressure to 1 / 4 of the volume of the filtrate, and vacuum freeze-dry to a water content of 4% to obtain the Coix seed extract; among them, the viable count of Bacillus subtilis XDK06 is 1.5 billion CFU / g, the inoculation amount is 6‰ of the weight of Coix seeds, the viable count of Bifidobacterium longum CICC6212 is 800 million CFU / g, and the inoculation amount is 4‰ of the weight of Coix seeds.

[0090] Comparative Example 4

[0091] The difference from Example 1 is that in step (3), "7 parts by weight of nano-titanium dioxide composite particles and 8 parts by weight of plant extract" is replaced by 15 parts by weight of nano-titanium dioxide composite particles.

[0092] Comparative Example 5

[0093] The difference from Example 1 is that in step (3), "7 parts by weight of nano-titanium dioxide composite particles and 8 parts by weight of plant extract" is replaced with 15 parts by weight of plant extract.

[0094] Test Example 1

[0095] Stability experiment

[0096] The stability of the multi-protection emulsion of Examples 1-3 and Comparative Examples 1-5 was detected and measured respectively by the following methods:

[0097] (1) Centrifugation: Centrifuge at 3000 rpm for 30 min and observe whether there is stratification.

[0098] (2) High temperature: Keep 50 g of the multi-protection emulsion at a constant temperature of 48 °C for 20 d, then restore to room temperature and keep it for more than 8 h, and observe whether there is stratification, precipitation of solids or other non-uniform phenomena in the multi-protection emulsion.

[0099] (3) Low temperature: Keep 50 g of the multi-protection emulsion frozen at -25 °C for 20 d, then restore to room temperature and keep it for more than 8 h, and observe whether there is stratification, precipitation of solids or other non-uniform phenomena in the skin care lotion.

[0100] (4) High and low temperature alternation: Keep 50 g of the multi-protection emulsion at 48 °C and -25 °C for 20 d with 24 h hot and cold alternating cycles, then restore to room temperature and keep it for more than 8 h, and observe whether there is stratification, precipitation of solids or other non-uniform phenomena in the skin care lotion.

[0101] If there is no stratification, precipitation of solids or other non-uniform phenomena in the multi-protection emulsion, the stability test passes; otherwise, the stability test fails.

[0102] The experimental results show that the multi-protection emulsions prepared in Examples 1-3, Comparative Examples 2-3 and Comparative Example 5 did not show stratification after the above methods and passed the stability test.

[0103] Comparative Examples 1 and 4 only passed the first stability test, and the other tests failed, indicating that coating titanium dioxide by the method of the present invention and adjusting the dosage of nano-titanium dioxide composite particles can improve the stability of the multi-protection emulsion.

[0104] Test Example 2

[0105] Antioxidant property

[0106] The antioxidant properties of the multi-protection emulsions of Examples 1-3 and Comparative Examples 1-5 were respectively detected in terms of DPPH radical scavenging ability, hydroxyl radical scavenging ability and superoxide radical scavenging ability.

[0107] The DPPH free radical scavenging ability and hydroxyl free radical scavenging ability were detected by spectrophotometry, and the superoxide free radical scavenging ability was detected by the pyrogallol method.

[0108] Each experiment was repeated 3 times, and the specific results of the DPPH free radical scavenging rate, hydroxyl free radical scavenging rate, and superoxide free radical scavenging rate of different multi-protective emulsions are shown in Table 1.

[0109] Table 1 Antioxidant properties of different multi-protective emulsions

[0110]

[0111] It can be seen from the data in Table 1 that the multi-protective emulsions of Examples 1-3 and Comparative Example 5 have stronger antioxidant ability than those of Comparative Examples 1-4. By comparing the data of Example 1 and Comparative Example 1, it can be seen that using quaternary ammonium salt of chitosan to coat nano-titanium dioxide has stronger antioxidant ability than using chitosan. By comparing the data of Example 1 and Comparative Examples 2-3, it can be seen that using different extraction solvents and different microorganisms can affect the antioxidant ability of the multi-protective emulsion, and the multi-protective emulsion prepared by the method of the present invention has stronger antioxidant ability. By comparing the data of Example 1 and Comparative Examples 2-3, it can be seen that the compound of plant extract and nano-titanium dioxide composite particles has stronger antioxidant performance, which can improve the resistance of the skin and increase the self-repair ability of the skin.

[0112] Test Example 3

[0113] Sun protection performance

[0114] The sun protection factor (SPF) represents the ability of the product to defend against medium-wave ultraviolet rays with specific values, and it is a protection index for evaluating the ability of sun protection cosmetics to protect the skin from sunburn erythema / sunburn. The long-wave ultraviolet protection index (PFA) is used to measure and reflect the indication value of the UVA protection effect of sun protection cosmetics, and it reflects the protection ability of sun protection products against long-wave ultraviolet rays (UVA).

[0115] The SPF values and PFA values of the multi-protective emulsions of Example 1 and Comparative Examples 1-5 were measured respectively, and the specific results are shown in Table 2.

[0116] The methods specified in Chapter 8 of the "Technical Specifications for Cosmetics Safety (2015 Edition)", Test Methods for Human Efficacy Evaluation, 2 Determination Method of Sun Protection Index (SPF Value) of Sun Protection Cosmetics and 4 Determination Method of Long-Wave Ultraviolet Protection Index (PFA Value) of Sun Protection Cosmetics were used to detect the SPF values and PFA values of the multi-protective emulsions of Comparative Example 1 and Comparative Examples 1-5 respectively.

[0117] When detecting the SPF value, 60 female volunteers aged 25 - 45 years old were selected (meeting the selection criteria for subjects in Section 4.2 of Chapter 8 "Determination Method of Sun Protection Factor (SPF Value) of Sunscreen Cosmetics" in the Cosmetics Safety and Technology Specifications). They were evenly divided into 6 groups. There were no significant differences in age and skin condition among the volunteers in each group, and the SPF value could be detected.

[0118] When detecting the PFA value, 60 female volunteers aged 25 - 45 years old were selected (meeting the regulations in Section 4.1 "Selection of Subjects and Test Sites" of Chapter 4 "Determination Method of Long-Wave Ultraviolet Protection Factor (PFA Value) of Sunscreen Cosmetics" in the Cosmetics Safety and Technology Specifications). They were evenly divided into 6 groups. There were no significant differences in age and skin condition among the volunteers in each group, and the PFA value could be detected.

[0119] Table 2 Sun Protection Performance of Different Multi-Protection Emulsions

[0120]

[0121] From the data in Table 2, generally speaking, the SPF value and PFA value of Example 1 are higher than those of Comparative Examples 1 - 5. By comparing the data of Example 1 and Comparative Example 1, it can be seen that compared with using chitosan, chitosan quaternary ammonium salt-coated nano-titanium dioxide can better improve the SPF value and PFA value. By comparing the data of Example 1 and Comparative Examples 2 - 3, it can be seen that the SPF value and PFA value of the multi-protection emulsions obtained by extraction with different solvents and fermentation by different microorganisms are different. By comparing the data of Example 1 and Comparative Examples 4 - 5, it can be seen that the compounding of plant extracts and nano-titanium dioxide composite particles can improve the SPF value and PFA value, has a stronger sun protection effect, reduces the occurrence of sunburn erythema, and can be used for outdoor sun protection.

[0122] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can still be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A multi-protection emulsion, characterized in that, It consists of the following components by weight parts, based on 100 weight parts: 5 - 10 parts of nano-titanium dioxide composite particles, 6 - 13 parts of plant extracts, 3 - 8 parts of humectants, 2 - 6 parts of emollients, 2 - 6 parts of film-forming agents, 1 - 5 parts of emulsifiers, 0.1 - 2 parts of preservatives, and the solvent makes up 100 parts; the plant extracts are composed of artemisia argyi extract, lithospermum erythrorhizon extract, angelica polymorpha maxim extract, and coix seed extract in a weight ratio of (1 - 4):(4 - 10):(3 - 8):(7 - 13). The preparation method of the nano-titanium dioxide composite particles includes: mixing chitosan quaternary ammonium salt with water to obtain a chitosan quaternary ammonium salt solution; mixing nano-titanium dioxide with water, subjecting it to ultrasonic treatment to obtain a nano-titanium dioxide dispersion liquid, adding it to the chitosan quaternary ammonium salt solution, and then mixing and cross-linking and curing with a sodium tripolyphosphate solution, centrifuging and washing, and freeze-drying the precipitate to obtain nano-titanium dioxide composite particles. The artemisia argyi extract and lithospermum erythrorhizon extract are obtained by ethanol ultrasonic extraction. The angelica polymorpha maxim extract is obtained by enzymatic hydrolysis with β-glucanase and ficin. The coix seed extract is obtained by anaerobic fermentation with bacillus velezensis NKY1 and bifidobacterium adolescentis CICC 6180.

2. The multi-protective emulsion according to claim 1, characterized in that The concentration of the nano-titanium dioxide dispersion liquid is 1 - 2 mg / mL, the concentration of the chitosan quaternary ammonium salt solution is 5 - 10 g / mL, the concentration of the sodium tripolyphosphate solution is 0.5 - 1.5 g / mL, and the volume ratio of the nano-titanium dioxide dispersion liquid, chitosan quaternary ammonium salt solution, and sodium tripolyphosphate solution is 1 - 3:1 - 3:2 - 5.

3. The multi-protective emulsion according to claim 1, wherein The temperature of the cross-linking and curing is 25 - 30 °C, and the time is 3 - 5 h.

4. The multi-protective emulsion according to claim 1, characterized in that, The humectant is one or more of polyglycerin ether - 26, methyl propylene glycol, and 1,2 - pentanediol. The emollient is one or more of polyglyceryl - 3 ricinoleate, glyceryl tri(ethylhexanoate), and dicaprylyl carbonate. The emulsifier is one or more of sodium cetostearyl sulfate, polyglyceryl - 4 oleate, and laureth - 4. The film-forming agent is one or more of trimethylsilyloxy silicate, PEG / PPG - 18 / 18 dimethicone, and PEG - 8 laurate. The preservative is one or more of caprylyl glycol, phenoxyethanol, and ethylhexylglycerin. The solvent is water.

5. The preparation method of the multi-protection emulsion according to any one of claims 1-4, characterized in that, It includes: Mixing the emollient and emulsifier, heating and dissolving them, then adding the film-forming agent to obtain an oil phase; mixing the humectant and solvent, heating them, and then adding the plant extract to obtain an aqueous phase; mixing the oil phase and the aqueous phase, adding the nano-titanium dioxide composite particles and the preservative to obtain the multi-protection type emulsion.

6. Use of the multi-protection type emulsion according to any one of claims 1 - 4 in the preparation of a sunscreen product.

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