Multi-protection type emulsion and preparation process thereof

Abstract

The invention provides a multi-protection type emulsion and a preparation process thereof, relates to the technical field of cosmetics, and belongs to A61K in IPC classification number. The multi-protection type emulsion comprises nano titanium dioxide composite particles, a plant extract, an auxiliary material and a solvent, the plant extract consists of a folium artemisiae argyi extract, a radix arnebiae extract, an angelica sinensis extract and a coix seed extract. Wherein the nano titanium dioxide composite particles are prepared by wrapping nano titanium dioxide with chitosan quaternary ammonium salt, so that the dispersing performance of the nano titanium dioxide is improved, and the irritation to the skin is relieved; the plant extract has multiple effects of multi-layer ultraviolet protection, anti-inflammation, soothing, moisturizing, whitening and anti-pigmentation. The nano titanium dioxide composite particles and the plant extract have a compound synergistic effect, and the sunscreen effect is achieved by combining multiple aspects of physics, chemistry and biology. Test results show that the multi-protection type emulsion disclosed by the invention has good stability, oxidation resistance 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. The present invention particularly relates to a multi-protective emulsion and a preparation process thereof. Background Art

[0002] In today's cosmetics market, lotions are a key category for daily skin care and are deeply loved and widely used by consumers. Lotions can form a thin protective film on the skin surface, which can not only effectively moisturize the skin and prevent moisture loss, but also provide the skin with necessary nutrients to maintain the skin's health. However, as consumers' demands for skin care effects become increasingly diversified and refined, traditional lotions have gradually exposed many deficiencies in terms of protective functions.

[0003] From the perspective of UV protection, 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 lotions have certain moisturizing and nourishing effects, their ability to protect against UV rays is very limited. Most lotions fail to add enough effective sunscreen ingredients. Even if some lotions contain sunscreens, their protection bands are often not comprehensive enough to simultaneously protect against long-wave ultraviolet rays (UVA) and medium-wave ultraviolet rays (UVB). This means that when users are outdoors, they cannot get sufficient UV protection by relying solely on traditional lotions, and their skin is prone to tanning, sunburn, and sun aging.

[0004] In terms of dealing with internal oxidative stress in 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 too many free radicals. Excessive free radicals will attack the lipids, proteins and DNA in skin cells, causing cell damage and aging. Traditional lotions are insufficient in the types and dosages of antioxidant ingredients added, and are unable to effectively remove free radicals in a timely manner, making it difficult to meet the skin's needs for antioxidant protection, causing the skin to gradually show signs of aging such as wrinkles, sagging, and dullness.

[0005] Given the lack of multiple protective functions of traditional emulsions such as UV protection and anti-oxidation, 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 consumers' growing skin care needs, but also an important direction to promote technological innovation and development in the cosmetics industry. Summary of the invention

[0006] The purpose of the present invention is to provide a multi-protective emulsion and a preparation process thereof. The emulsion provided by the present invention not only has an excellent sunscreen effect, but also has the effects of anti-oxidation, soothing the skin and preventing skin photodamage.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The invention provides a multi-protective 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 moisturizers, 2-6 parts of emollients, 2-6 parts of film formers, 1-5 parts of emulsifiers, 0.1-2 parts of preservatives and 100 parts of solvents; the plant extracts are composed of wormwood leaf extract, lithospermum root extract, celery extract and coix seed extract in a weight ratio of (1-4):(4-10):(3-8):(7-13).

[0008] Preferably, the preparation method of the nano titanium dioxide composite particles comprises: mixing chitosan quaternary ammonium salt with water to obtain a chitosan quaternary ammonium salt solution; mixing nano titanium dioxide with water, ultrasonically treating to obtain a nano titanium dioxide dispersion, adding the dispersion to the chitosan quaternary ammonium salt solution, and then mixing with a sodium tripolyphosphate solution for cross-linking and curing, centrifugation washing, and freeze-drying the precipitate to obtain nano titanium dioxide composite particles.

[0009] More preferably, the concentration of the nano-titanium dioxide dispersion 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, the chitosan quaternary ammonium salt solution and the sodium tripolyphosphate solution is 1-3:1-3:2-5.

[0010] More preferably, the cross-linking curing temperature is 25-30° C. and the time is 3-5 hours.

[0011] Preferably, the Artemisia argyi extract and Lithospermum officinale root extract are obtained by ethanol ultrasonic extraction.

[0012] Preferably, the celery extract is obtained by enzymolysis with β-glucanase and ficin.

[0013] Preferably, the coix seed extract is obtained by anaerobic fermentation of Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC 6180.

[0014] Preferably, the moisturizer is one or more of glyceryl polyether-26, methyl propanediol and 1,2-pentanediol; the emollient is one or more of polyglyceryl-3 ricinoleate, triethylhexanoin and dicaprylyl carbonate; the emulsifier is one or more of sodium cetearyl sulfate, polyglyceryl-4 oleate and laureth-4; the film-forming agent is one or more of trimethylsiloxysilicate, PEG / PPG-18 / 18 polydimethylsiloxane and PEG-8 laurate; the preservative is one or more of caprylyl glycol, phenoxyethanol and ethylhexylglycerin; and the solvent is water.

[0015] The present invention also provides a method for preparing the above-mentioned multi-protective emulsion, comprising: mixing an emollient and an emulsifier, heating and dissolving them, and then adding a film-forming agent to obtain an oil phase; mixing a humectant and a solvent, heating them, and then adding a plant extract to obtain an aqueous phase; mixing the oil phase with the aqueous phase, adding nano-titanium dioxide composite particles and a preservative to obtain the multi-protective emulsion.

[0016] The present invention also provides the use of the multi-protective emulsion in preparing sunscreen products.

[0017] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a multi-protective emulsion comprising: nano titanium dioxide composite particles, plant extracts, moisturizers, emollients, film formers, emulsifiers, preservatives and solvents; the plant extracts are composed of wormwood extracts, lithospermum root extracts, celery extracts and coix seed extracts. The nano titanium dioxide composite particles are made of chitosan quaternary ammonium salts encapsulating nano titanium dioxide, which improves the dispersion performance and alleviates the irritation of titanium dioxide to the skin; the plant extracts have multiple functions of multi-level ultraviolet protection, anti-inflammatory, soothing, moisturizing, whitening and anti-pigmentation. The nano titanium dioxide composite particles of the present invention have a compound synergistic effect with the plant extracts, and the sunscreen effect is achieved by combining multiple aspects of physics, chemistry and biology. The test results show that the multi-protective emulsion of the present invention has good stability, antioxidant properties and excellent sunscreen effect. DETAILED DESCRIPTION

[0018] The invention provides a multi-protective 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 moisturizers, 2-6 parts of emollients, 2-6 parts of film formers, 1-5 parts of emulsifiers, 0.1-2 parts of preservatives and 100 parts of solvents; the plant extracts are composed of wormwood leaf extract, lithospermum root extract, celery extract and coix seed extract in a weight ratio of (1-4):(4-10):(3-8):(7-13).

[0019] The preparation method of the nano titanium dioxide composite particles of the present invention preferably comprises: mixing chitosan quaternary ammonium salt with water to obtain a chitosan quaternary ammonium salt solution; mixing nano titanium dioxide with water, ultrasonically treating to obtain a nano titanium dioxide dispersion, adding the dispersion to the chitosan quaternary ammonium salt solution, and then mixing with a sodium tripolyphosphate solution for cross-linking and curing, centrifugation washing, and freeze-drying the precipitate to obtain nano titanium dioxide composite particles.

[0020] The particle size of the nano titanium dioxide of the present invention is 30-80nm, the concentration of the nano titanium dioxide dispersion is preferably 1-2mg / mL, more preferably 1.5mg / mL, the chitosan quaternary ammonium salt is preferably hydroxypropyltrimethylammonium chloride chitosan (HACC, molecular weight 100,000, purchased from Shanxi Lanyuan Technology Co., Ltd., item number LYSW-0703-023), the concentration of the chitosan quaternary ammonium salt solution is preferably 5-10g / mL, more preferably 8g / mL, the concentration of the sodium tripolyphosphate solution is preferably 0.5-1.5g / mL, more preferably 1g / mL, the volume ratio of the nano titanium dioxide dispersion, 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 cross-linking curing is preferably 25-30°C, more preferably 27°C, and the time is preferably 3-5h, more preferably 4h. The present invention encapsulates nano titanium dioxide by chitosan quaternary ammonium salt, which not only makes titanium dioxide have excellent dispersibility, but also reduces the irritation of titanium dioxide to the skin, skin redness, acne and other problems.

[0021] The wormwood leaf extract and the lithospermum root extract of the present invention are preferably obtained by ethanol ultrasonic extraction. The preparation method of the wormwood leaf extract preferably includes: crushing the wormwood leaf through a 400-500 mesh sieve, adding 5-8 weight 60%-70% (v / v) ethanol solution, ultrasonic extraction at 50-60°C, 150-250W for 30-40min, filtering, concentrating under reduced pressure to 1 / 5-1 / 3 of the volume of the filtrate, and vacuum freeze drying to obtain the wormwood leaf extract. The preparation method of the lithospermum root extract preferably includes: crushing the lithospermum root through a 400-500 mesh sieve, adding 8-12 weight 70-80% (v / v) ethanol solution, ultrasonic extraction at 40-50°C, 100-200W for 20-30min, filtering, concentrating under reduced pressure to 1 / 5-1 / 3 of the volume of the filtrate, and vacuum freeze drying to obtain the lithospermum root extract. The wormwood leaf extract prepared by the method of the present invention is rich in flavonoids, phenolic acids and volatile oils, has antioxidant and anti-inflammatory effects, can neutralize ultraviolet-induced free radicals, and alleviate skin inflammatory reactions; the lithospermum root extract obtained by the preparation method of the present invention contains naphthoquinone compounds such as shikonin, has anti-inflammatory and antibacterial functions, and can absorb UVA, serving as a natural ultraviolet absorber, to assist in sun protection and repair light damage at the same time.

[0022] The celery extract of the present invention is preferably obtained by enzymolysis with β-glucanase and ficin. The preparation method of the celery extract preferably includes: drying and crushing the celery stem through a 500-600 mesh sieve, mixing with 10-15 weight of water, adding β-glucanase and ficin, enzymolysis for 60-90 minutes at 50-55°C and pH 5.5-6.5, inactivating the enzyme, filtering, concentrating under reduced pressure to 1 / 5-1 / 3 of the volume of the filtrate, and vacuum freeze drying to obtain the celery extract. The β-glucanase activity 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 celery stem, more preferably 5%, and the ficin activity 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 celery stem, more preferably 3%. The celery extract obtained by the enzymatic hydrolysis method of the present invention contains polysaccharides, small molecule peptides and amino acids, has the functions of anti-oxidation, enhancing moisturizing and skin barrier, relieving dryness and sensitivity after sun exposure, and soothing the stimulation caused by ultraviolet rays.

[0023] The coix seed extract of the present invention is preferably obtained by anaerobic fermentation of Bacillus Velez NKY1 and Bifidobacterium adolescentis CICC6180. The preparation method of the coix seed extract preferably comprises: crushing coix seeds through a 100-200 mesh sieve, adding 15-25 times the weight of water, inoculating Bacillus Velez NKY1 and Bifidobacterium adolescentis CICC 6180, anaerobic fermentation at 35-40°C and pH 5.5-6.5 for 24-36 hours, 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 Velez Bacillus NKY1 was purchased from the China Center for Type Culture Collection, with a collection number of CCTCC NO: M 2021848, disclosed in CN114058532A, and the bacterial activity is preferably 1 billion to 2 billion CFU / g, more preferably 1.5 billion CFU / g, and the addition amount is preferably 5‰ to 8‰ of the weight of the coix seeds, more preferably 6‰; the adolescent Bifidobacterium CICC 6180 was purchased from the China Industrial Microbiological Culture Collection Management Center, with a bacterial activity of 500 million to 1 billion CFU / g, more preferably 800 million CFU / g, and the addition amount is preferably 3‰ to 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.

[0024] The plant extract of the present invention has multiple functions of multi-level ultraviolet protection, anti-inflammatory, soothing, moisturizing, whitening, and anti-pigmentation. Multi-level ultraviolet protection: Lithospermum officinale root extract can absorb UVA, complement with nano titanium dioxide composite particle physical sunscreen, broaden the protection spectrum, wormwood leaf extract, celery extract and coix seed extract have antioxidant effects, and can reduce photoaging damage; anti-inflammatory + soothing: wormwood leaf extract and lithospermum officinale root extract reduce phototoxic reactions such as erythema and swelling, and the moisturizing and barrier repair effects of celery extract can reduce the release of inflammatory factors and relieve post-sun sensitivity; moisturizing: celery extract and coix seed extract form a water-locking network to maintain the hydration of the stratum corneum and resist barrier damage caused by ultraviolet rays; whitening + anti-pigmentation: coix seed extract can inhibit tyrosinase activity and reduce melanin synthesis, wormwood leaf extract and lithospermum officinale root extract block oxidative stress-induced pigmentation and prevent post-sun dark spots.

[0025] The nano titanium dioxide composite particles of the present invention have a compound synergistic effect with the plant extract, and achieve sun protection effects from three aspects: physical, chemical and biological. The nano titanium dioxide composite particles can reflect / scatter UVB (290-320 nm) and short-wave UVA (320-350 nm), provide an immediate physical barrier, reduce direct ultraviolet penetration, and reduce acute phototoxic reactions such as erythema and burning; the lithospermum root extract selectively absorbs long-wave UVA (340-400 nm), making up for the protection gap of titanium dioxide against long-wave UVA, forming a complementary spectrum coverage; the anti-inflammatory components in the wormwood leaf extract and the lithospermum root extract can relieve post-sun inflammation; the wormwood leaf extract, the celery extract and the coix seed extract all have antioxidant effects and can reduce photoaging damage; the celery extract and the coix seed extract promote the proliferation of keratinocytes and barrier repair, accelerate the recovery of the epidermis after sun exposure, and reduce desquamation and sensitivity.

[0026] The moisturizer of the present invention is preferably one or more of glyceryl polyether-26, methyl propanediol and 1,2-pentanediol; the emollient is preferably one or more of polyglyceryl-3 ricinoleate, triethylhexanoin and dicaprylyl carbonate; the emulsifier is preferably one or more of sodium cetearyl sulfate, polyglyceryl-4 oleate and laureth-4; the film-forming agent is preferably one or more of trimethylsiloxysilicate, PEG / PPG-18 / 18 polydimethylsiloxane and PEG-8 laurate; the preservative is preferably one or more of caprylyl glycol, phenoxyethanol and ethylhexylglycerin; the solvent is preferably water.

[0027] The present invention also provides a method for preparing the above-mentioned multi-protective emulsion, comprising: mixing an emollient and an emulsifier, heating and dissolving them, and then adding a film-forming agent to obtain an oil phase; mixing a humectant and a solvent, heating them, and then adding a plant extract to obtain an aqueous phase; mixing the oil phase with the aqueous phase, adding nano-titanium dioxide composite particles and a preservative to obtain the multi-protective emulsion.

[0028] The method of using the multi-protective emulsion of the present invention is: after washing the facial skin and performing basic skin care, take an appropriate amount of the product and apply it to the face, neck, arms, legs and other parts exposed to the sun, gently massage until evenly distributed, and use it 30 minutes before going out daily.

[0029] The present invention also provides the use of the multi-protective emulsion in preparing sunscreen products.

[0030] In the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0031] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] In the following embodiments, unless otherwise specified, all of them are conventional methods.

[0033] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0034] Hydroxypropyltrimethylammonium chloride chitosan (HACC), molecular weight 100,000, purchased from Shanxi Lanyuan Technology Co., Ltd., catalog number LYSW-0703-023; Chitosan was purchased from Xi'an Tianhe Pharmaceutical Co., Ltd., product number TH-DERER; PEG / PPG-18 / 18 polydimethylsiloxane, purchased from Hubei Langbowan Biopharmaceutical Co., Ltd., model 2024; Bacillus velez NKY1 was purchased from China Center for Type Culture Collection with the collection number CCTCC NO:M2021848; Bifidobacterium adolescentis CICC 6180 and Bifidobacterium longum CICC6212 were purchased from China Industrial Microbiological Culture Collection Center; Bacillus subtilis XDK06 was purchased from Guangdong Microbiological Culture Collection Center with a collection number of GDMCC No: 61260, which is disclosed in patent CN112458017A.

[0035] Example 1 Multi-protective lotion (1) Preparation of nano-titanium dioxide composite particles The HACC was mixed with deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 8 g / mL; nano-titanium dioxide was added to the deionized water, and ultrasonic treatment was performed at 200 W for 30 min to obtain a nano-titanium dioxide dispersion with a concentration of 1.5 mg / mL; the nano-titanium dioxide dispersion was added dropwise to the chitosan quaternary ammonium salt solution, and then 1 g / mL sodium polyphosphate solution was added, the pH value was adjusted to 5.8, and cross-linking and curing was performed at 800 rpm for 4 h. The reaction solution was centrifuged at 9000 rpm for 18 min, the precipitate was washed with deionized water, and vacuum freeze-dried to a water content of 4% to obtain nano-titanium dioxide composite particles; The volume ratio of nano-titanium dioxide dispersion, chitosan quaternary ammonium salt solution and sodium tripolyphosphate solution is 2:2:4; (2) Preparation of plant extracts The wormwood leaf is dried and crushed through a 450-mesh sieve, and 6 times the weight of a 65% (v / v) ethanol solution is added, and ultrasonic extraction is performed at 55°C and 200W for 35 minutes, followed by filtration, concentration under reduced pressure to 1 / 4 of the volume of the filtrate, and vacuum freeze-drying to a water content of 3% to obtain the wormwood leaf extract; The lithospermum root is dried and crushed through a 450-mesh sieve, and 10 times the weight of a 75% (v / v) ethanol solution is added, and ultrasonic extraction is performed at 45° C. and 150 W for 25 min, followed by filtration, concentration under reduced pressure to 1 / 4 of the volume of the filtrate, and vacuum freeze-drying to a water content of 4% to obtain the lithospermum root extract; The stems of the celery are dried, crushed and passed through a 550-mesh sieve, mixed with 13 times the weight of deionized water, and then β-glucanase and ficin are added. The mixture is enzymolyzed at 52°C and pH 6 for 70 minutes, the enzymes are inactivated, filtered, concentrated under reduced pressure to 1 / 4 of the volume of the filtrate, and vacuum freeze-dried to a water content of 5% to obtain the celery extract; wherein the β-glucanase activity is 30,000 U / g, and the addition amount is 5% of the weight of the celery stems; the ficin activity is 20,000 U / g, and the addition amount is 3% of the weight of the celery stems; The coix seeds are dried and crushed through a 150-mesh sieve, 20 times the weight of water is added, Bacillus Velez NKY1 and Bifidobacterium adolescentis CICC6180 are inoculated, anaerobically fermented at 37°C and pH 6 for 30 hours, sterilized, filtered, concentrated under reduced pressure to 1 / 4 of the volume of the filtrate, and vacuum freeze-dried to a water content of 4% to obtain the coix seed extract; wherein the bacterial activity of Bacillus Velez NKY1 is 1.5 billion CFU / g, and the inoculation amount is 6‰ of the weight of the coix seeds, and the bacterial activity of Bifidobacterium adolescentis CICC6180 is 800 million CFU / g, and the inoculation amount is 4‰ of the weight of the coix seeds; Mixing wormwood leaf extract, lithospermum officinale root extract, celery extract and coix seed extract in a weight ratio of 3:5:4:10 to obtain a plant extract; (3) Preparation of multi-protective emulsion Weigh 7 parts by weight of nano titanium dioxide composite particles, 8 parts by weight of plant extract, 4 parts by weight of glyceryl polyether-26, 3 parts by weight of glyceryl tri(ethylhexanoate), 3 parts by weight of trimethylsiloxysilicate, 2 parts by weight of sodium cetearyl sulfate, and 1 part by weight of caprylyl glycol, and make up to 100 parts by weight with deionized water; Glyceryl tri(ethylhexanoate) ester and sodium cetearyl sulfate are mixed, heated and dissolved at 75°C and 500rpm, trimethylsiloxysilicate is added, and stirring is continued at 500rpm for 10min to obtain an oil phase; glyceryl polyether-26 and 62 parts by weight of deionized water are mixed, stirred at 75°C and 2500rpm for 20min, and plant extracts are added after cooling to 40°C to obtain an aqueous phase; the oil phase and the aqueous phase are mixed, stirred at 3000rpm for 10min, a dispersion of nano-titanium dioxide composite particles (nano-titanium dioxide composite particles are mixed with 10 parts by weight of deionized water, and ultrasonically treated at 200W for 30min to obtain a dispersion) and caprylyl glycol are added, and the mixture is stirred at 5000rpm for 15min, the pH value is adjusted to 5.8, vacuum degassed and sterilized to obtain the multi-protective emulsion.

[0036] Example 2 Multi-protective lotion (1) Preparation of nano-titanium dioxide composite particles The HACC was mixed with deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 5 g / mL; nano-titanium dioxide was added to the deionized water, and ultrasonic treatment was performed at 150W for 45 minutes to obtain a nano-titanium dioxide dispersion with a concentration of 1 mg / mL; the nano-titanium dioxide dispersion was added dropwise to the chitosan quaternary ammonium salt solution, and then 0.5 g / mL sodium polyphosphate solution was added, the pH value was adjusted to 5.5, and cross-linked and cured at 700 rpm for 5 hours, the reaction solution was centrifuged at 8000 rpm for 15 minutes, the precipitate was washed with deionized water, and vacuum freeze-dried to a water content of 3%, to obtain nano-titanium dioxide composite particles; The volume ratio of nano-titanium dioxide dispersion, chitosan quaternary ammonium salt solution and sodium tripolyphosphate solution is 3:3:5; (2) Preparation of plant extracts The wormwood leaf is dried and crushed through a 400-mesh sieve, 5 times the weight of a 60% (v / v) ethanol solution is added, ultrasonic extraction is performed at 50°C and 150W for 40 minutes, and then filtered, concentrated under reduced pressure to 1 / 5 of the volume of the filtrate, and vacuum freeze-dried to a water content of 2% to obtain the wormwood leaf extract; The lithospermum root was dried and crushed through a 400-mesh sieve, 8 times the weight of a 70% (v / v) ethanol solution was added, and ultrasonic extraction was performed at 40° C. and 100 W for 30 min, followed by filtration, concentration under reduced pressure to 1 / 5 of the volume of the filtrate, and vacuum freeze-drying to a water content of 4% to obtain the lithospermum root extract; The stems of the celery are dried, crushed and passed through a 500-mesh sieve, mixed with 10 times the weight of deionized water, and then β-glucanase and ficin are added. The mixture is enzymolyzed at 50°C and pH 5.5 for 90 minutes, the enzymes are inactivated, filtered, concentrated under reduced pressure to 1 / 5 of the volume of the filtrate, and vacuum freeze-dried to a water content of 1% to obtain the celery extract; wherein the β-glucanase activity is 20,000 U / g, and the addition amount is 8% of the weight of the celery stems; the ficin activity is 10,000 U / g, and the addition amount is 5% of the weight of the celery stems; The coix seeds are dried and crushed through a 100-mesh sieve, 15 times the weight of water is added, Bacillus Velez NKY1 and Bifidobacterium adolescentis CICC6180 are inoculated, anaerobically fermented at 35°C and pH 5.5 for 36 hours, sterilized, filtered, concentrated under reduced pressure to 1 / 5 of the volume of the filtrate, and vacuum freeze-dried to a water content of 2% to obtain the coix seed extract; wherein the bacterial activity of Bacillus Velez NKY1 is 1 billion CFU / g, and the inoculation amount is 8‰ of the weight of the coix seeds, and the bacterial activity of Bifidobacterium adolescentis CICC6180 is 500 million CFU / g, and the inoculation amount is 5‰ of the weight of the coix seeds; Mixing the wormwood leaf extract, the lithospermum root extract, the celery extract and the coix seed extract in a weight ratio of 1:4:3:7 to obtain a plant extract; (3) Preparation of multi-protective emulsion Weigh 5 parts by weight of nano titanium dioxide composite particles, 11 parts by weight of plant extract, 3 parts by weight of methylpropanediol, 4 parts by weight of dicaprylyl carbonate, 2 parts by weight of PEG / PPG-18 / 18 polydimethylsiloxane, 4 parts by weight of laureth-4, 0.1 parts by weight of phenoxyethanol and make up to 100 parts by weight with deionized water; Dicaprylyl carbonate and laureth-4 are mixed, heated and dissolved at 70°C and 400rpm, PEG / PPG-18 / 18 polydimethylsiloxane is added, and stirring is continued at 400rpm for 15min to obtain an oil phase; methylpropanediol and 60.9 parts by weight of deionized water are mixed, stirred at 70°C and 2300rpm for 25min, and plant extracts are added after cooling to 35°C to obtain an aqueous phase; the oil phase and the aqueous phase are mixed, stirred at 2500rpm for 15min, a dispersion of nano-titanium dioxide composite particles (nano-titanium dioxide composite particles are mixed with 10 parts by weight of deionized water, and ultrasonically treated at 100W for 40min to obtain a dispersion) and phenoxyethanol are added, and the mixture is stirred at 4500rpm for 20min, the pH value is adjusted to 5.5, vacuum degassed and sterilized to obtain the multi-protective emulsion.

[0037] Example 3 Multi-protective lotion (1) Preparation of nano-titanium dioxide composite particles The HACC was mixed with deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 10 g / mL; nano-titanium dioxide was added to the deionized water, and ultrasonic treatment was performed at 250 W for 20 min to obtain a nano-titanium dioxide dispersion with a concentration of 2 mg / mL; the nano-titanium dioxide dispersion was added dropwise to the chitosan quaternary ammonium salt solution, and then 1.5 g / mL sodium polyphosphate solution was added, the pH value was adjusted to 6, and cross-linked and cured at 900 rpm for 2 h, the reaction solution was centrifuged at 10000 rpm for 15 min, the precipitate was washed with deionized water, and vacuum freeze-dried to a water content of 2% to obtain nano-titanium dioxide composite particles; The volume ratio of nano-titanium dioxide dispersion, chitosan quaternary ammonium salt solution and sodium tripolyphosphate solution is 1:1:2; (2) Preparation of plant extracts The wormwood leaf is dried and crushed through a 500-mesh sieve, 8 times the weight of a 70% (v / v) ethanol solution is added, ultrasonic extraction is performed at 60°C and 250W for 30 minutes, and then filtered, concentrated under reduced pressure to 1 / 3 of the volume of the filtrate, and vacuum freeze-dried to a water content of 5% to obtain the wormwood leaf extract; The lithospermum root was dried and crushed through a 500-mesh sieve, and 12 times the weight of an 80% (v / v) ethanol solution was added, and ultrasonic extraction was performed at 50° C. and 200 W for 20 min, followed by filtration, concentration under reduced pressure to 1 / 3 of the volume of the filtrate, and vacuum freeze-drying to a water content of 3% to obtain the lithospermum root extract; The stems of the celery are dried, crushed and passed through a 600-mesh sieve, mixed with 15 times the weight of deionized water, and then β-glucanase and ficin are added. The mixture is enzymolyzed at 55°C and pH 6.5 for 60 minutes, the enzymes are inactivated, filtered, concentrated under reduced pressure to 1 / 3 of the volume of the filtrate, and vacuum freeze-dried to a water content of 2% to obtain the celery extract; wherein the β-glucanase activity is 50,000 U / g, and the addition amount is 3% of the weight of the stems of the celery; and the ficin activity is 30,000 U / g, and the addition amount is 2% of the weight of the stems of the celery; The coix seeds are dried and crushed through a 200-mesh sieve, 25 times the weight of water is added, Bacillus Velez NKY1 and Bifidobacterium adolescentis CICC6180 are inoculated, anaerobically fermented at 40°C and pH 6.5 for 24 hours, sterilized, filtered, concentrated under reduced pressure to 1 / 3 of the volume of the filtrate, and vacuum freeze-dried to a water content of 3% to obtain the coix seed extract; wherein the bacterial activity of Bacillus Velez NKY1 is 2 billion CFU / g, and the inoculation amount is 5‰ of the weight of the coix seeds, and the bacterial activity of Bifidobacterium adolescentis CICC6180 is 1 billion CFU / g, and the inoculation amount is 3‰ of the weight of the coix seeds; Mixing the wormwood leaf extract, the lithospermum root extract, the celery extract and the coix seed extract in a weight ratio of 4:10:8:12 to obtain a plant extract; (3) Preparation of multi-protective emulsion 10 parts of nano titanium dioxide composite particles, 6 parts of plant extracts, 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 100 parts of solvent; Polyglycerol-3 ricinoleate and polyglycerol-4 oleate are mixed, heated and dissolved at 80°C and 550rpm, PEG-8 laurate is added, and stirring is continued at 550rpm for 8min to obtain an oil phase; 1,2-pentanediol and 57 parts by weight of deionized water are mixed, stirred at 80°C and 2800rpm for 18min, and plant extracts are added after cooling to 45°C to obtain an aqueous phase; the oil phase and the aqueous phase are mixed, stirred at 3500 rpm for 8min, a dispersion of nano-titanium dioxide composite particles (nano-titanium dioxide composite particles are mixed with 15 parts by weight of deionized water, and ultrasonically treated at 250W for 30min to obtain a dispersion) and ethylhexylglycerol are added, and the mixture is stirred at 55000 rpm for 13min, the pH value is adjusted to 6, vacuum degassing and sterilization are performed to obtain the multi-protective emulsion.

[0038] Comparative Example 1 The difference from Example 1 is that the chitosan quaternary ammonium salt in step (1) is replaced by chitosan, and "mixing HACC with deionized water to obtain a chitosan quaternary ammonium salt solution with a concentration of 8 g / mL" is replaced by "mixing chitosan with 1% (v / v) acetic acid solution to obtain a chitosan solution with a concentration of 8 g / mL".

[0039] Comparative Example 2 The difference from Example 1 is that the ethanol solution in the Artemisia argyi extract and the Lithospermum officinale root extract in step (2) is replaced by deionized water.

[0040] Comparative Example 3 The difference from Example 1 is that the preparation method of the coix seed extract in step (2) is: drying the coix seeds, crushing them through a 150-mesh sieve, adding 20 times the weight of water, inoculating Bacillus subtilis XDK06 and Bifidobacterium longum CICC6212, anaerobically fermenting them at 37°C and pH 6 for 30 hours, sterilizing, filtering, concentrating under reduced pressure to 1 / 4 of the volume of the filtrate, and vacuum freeze-drying to a water content of 4% to obtain the coix seed extract; wherein the bacterial activity of Bacillus subtilis XDK06 is 1.5 billion CFU / g, and the inoculation amount is 6‰ of the weight of the coix seeds, and the bacterial activity of Bifidobacterium longum CICC6212 is 800 million CFU / g, and the inoculation amount is 4‰ of the weight of the coix seeds.

[0041] Comparative Example 4 The difference from Example 1 is that the "7 parts by weight of nano-titanium dioxide composite particles and 8 parts by weight of plant extract" in step (3) is replaced by 15 parts by weight of nano-titanium dioxide composite particles.

[0042] Comparative Example 5 The difference from Example 1 is that the "7 parts by weight of nano-titanium dioxide composite particles and 8 parts by weight of plant extract" in step (3) is replaced by 15 parts by weight of plant extract.

[0043] Test Example 1 Stability test The stability of the multi-protective emulsions of Examples 1-3 and Comparative Examples 1-5 was tested by the following methods: (1) Centrifugation: Centrifuge at 3000 rpm for 30 min and observe whether stratification occurs. (2) High temperature: Keep 50 g of the multi-protective emulsion at 48 °C for 20 days, then return to room temperature for more than 8 hours to observe whether the multi-protective emulsion has stratification, solid precipitation or other inhomogeneity; (3) Low temperature: Freeze 50 g of multi-protective lotion at -25°C for 20 days, then return to room temperature and keep for more than 8 hours to observe whether the lotion has stratification, solid precipitation or other inhomogeneities; (4) High and low temperature alternation: Place 50g of multi-protective lotion in a 24-hour hot and cold cycle at 48℃ and -25℃ for 20 days, then return to room temperature and maintain for more than 8 hours. Observe whether the skin care lotion has stratification, solid precipitation or other uneven phenomena.

[0044] If the multi-protective emulsion has no stratification, solid precipitation or other inhomogeneity, the stability test has passed; otherwise, the stability test has failed.

[0045] The experimental results show that the multi-protective emulsions prepared in Examples 1-3, Comparative Examples 2-3 and Comparative Example 5 did not show stratification after the above method and passed the stability performance test.

[0046] Comparative Examples 1 and 4 only passed the first stability test and failed the other tests, indicating that the stability of the multi-protective emulsion can be improved by encapsulating titanium dioxide using the method of the present invention and adjusting the amount of nano-titanium dioxide composite particles.

[0047] Test Example 2 Antioxidant The antioxidant properties of the multi-protective emulsions of Examples 1-3 and Comparative Examples 1-5 were tested in terms of DPPH free radical scavenging ability, hydroxyl free radical scavenging ability and superoxide free radical scavenging ability.

[0048] 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 pyrogallol method.

[0049] Each experiment was repeated three times. The specific results of DPPH radical scavenging rate, hydroxyl radical scavenging rate and superoxide radical scavenging rate of different multi-protective emulsions are shown in Table 1.

[0050] Table 1 Antioxidant properties of different multi-protective emulsions

[0051] It can be seen from the data in Table 1 that the antioxidant capacity of the multiple protective emulsions of Examples 1-3 and Comparative Example 5 is stronger than that of Comparative Example 1-4. Comparison of the data of Example 1 with Comparative Example 1 shows that the use of chitosan quaternary ammonium salt to wrap nano titanium dioxide has a stronger antioxidant capacity than chitosan. Comparison of the data of Example 1 with Comparative Examples 2-3 shows that the use of different extraction solvents and different microorganisms can affect the antioxidant capacity of the multiple protective emulsion, and the antioxidant capacity of the multiple protective emulsion prepared by the method of the present invention has a stronger antioxidant capacity. Comparison of the data of Example 1 with Comparative Examples 2-3 shows that the compound of plant extracts and nano titanium dioxide composite particles has a stronger antioxidant property, improves the resistance of the skin, and increases the self-repair ability of the skin.

[0052] Test Example 3 Sun protection performance The Sun Protection Factor (SPF) is a specific numerical value that indicates the ability of a product to protect against medium-wave ultraviolet rays. It is a protection index for evaluating the ability of sunscreen cosmetics to protect the skin from sunburn / sunburn. The UVA protection index (PFA) is used to measure and reflect the indicator value of the UVA protection effect of sunscreen cosmetics. It reflects the protection ability of sunscreen products against long-wave ultraviolet rays (UVA).

[0053] 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.

[0054] The methods specified in Chapter 8 Human Efficacy Evaluation Test Method 2 Sunscreen Cosmetics Sun Protection Index (SPF Value) Determination Method and 4 Sunscreen Cosmetics Long-wave Ultraviolet Protection Index (PFA Value) Determination Method of "Technical Specifications for Safety of Cosmetics" 2015 Edition were used to test the SPF value and PFA value of Comparative Example 1 and Comparative Examples 1-5 multi-protective emulsions, respectively.

[0055] For the SPF value test, 60 female volunteers aged 25-45 years old were selected (in compliance with 4.2 Subject selection criteria in Chapter 8, 2 Method for Determination of Sun Protection Index (SPF value) of Sunscreen Cosmetics in the Cosmetic Safety Technical Specifications)) and were divided into 6 groups on average. There was no significant difference in age and skin condition among the volunteers in each group, so the SPF value test could be carried out.

[0056] When testing the PFA value, 60 female volunteers aged 25-45 were selected (in compliance with the provisions of 4.1 Selection of subjects and test sites in Chapter 8, 4, Determination of the Long-wave Ultraviolet Protection Index (PFA value) of Sunscreen Cosmetics, Technical Specifications for Safety of Cosmetics), and were evenly divided into 6 groups. There was no significant difference in age and skin condition among the volunteers in each group, so the PFA value could be tested.

[0057] Table 2 Sunscreen performance of different multi-protection emulsions

[0058] It can be seen from the data in Table 2 that, overall, Example 1 has higher SPF and PFA values ​​than Comparative Examples 1-5. Comparison of the data in Example 1 and Comparative Example 1 shows that, compared with chitosan, chitosan quaternary ammonium salt encapsulating nano titanium dioxide can further improve the SPF and PFA values. Comparison of the data in Example 1 and Comparative Examples 2-3 shows that the multiple protective emulsions extracted with different solvents and fermented with different microorganisms have different SPF and PFA values. Comparison of the data in Example 1 and Comparative Examples 4-5 shows that the compounding of plant extracts and nano titanium dioxide composite particles can improve the SPF and PFA values, has a stronger sunscreen effect, reduces the occurrence of sunburn erythema, and can be used for outdoor sunscreen.

[0059] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A multi-protective emulsion, characterized in that: The invention 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 moisturizers, 2-6 parts of emollients, 2-6 parts of film formers, 1-5 parts of emulsifiers, 0.1-2 parts of preservatives and 100 parts of solvents; the plant extracts are composed of wormwood leaf extract, lithospermum root extract, celery extract and coix seed extract in a weight ratio of (1-4):(4-10):(3-8):(7-13).

2. The multi-protective emulsion according to claim 1, characterized in that: The preparation method of nano titanium dioxide composite particles comprises: mixing chitosan quaternary ammonium salt with water to obtain chitosan quaternary ammonium salt solution; mixing nano titanium dioxide with water, ultrasonically treating to obtain nano titanium dioxide dispersion, adding the dispersion to the chitosan quaternary ammonium salt solution, mixing with sodium tripolyphosphate solution for cross-linking and curing, washing by centrifugation, and freeze-drying the precipitate to obtain nano titanium dioxide composite particles.

3. The multi-protective emulsion according to claim 2, characterized in that: The concentration of the nano-titanium dioxide dispersion 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, the chitosan quaternary ammonium salt solution and the sodium tripolyphosphate solution is 1-3:1-3:2-5.

4. The multi-protective emulsion according to claim 2, characterized in that: The cross-linking curing temperature is 25-30°C and the time is 3-5h.

5. The multi-protective emulsion according to claim 1, characterized in that: The wormwood leaf extract and the lithospermum root extract are obtained by ethanol ultrasonic extraction.

6. The multi-protective emulsion according to claim 1, characterized in that: The celery extract is obtained by enzymolysis with beta-glucanase and ficin.

7. The multi-protective emulsion according to claim 1, characterized in that: The coix seed extract is obtained by anaerobic fermentation of Bacillus velezensis NKY1 and Bifidobacterium adolescentis CICC 6180.

8. The multi-protective emulsion according to claim 1, characterized in that: The moisturizing agent is one or more of glyceryl polyether-26, methyl propanediol 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 cetearyl sulfate, polyglyceryl-4 oleate and laureth-4; The film former is one or more of trimethylsiloxysilicate, PEG / PPG-18 / 18 polydimethylsiloxane, and PEG-8 laurate; The preservative is one or more of caprylyl glycol, phenoxyethanol and ethylhexylglycerin; The solvent is water.

9. The method for preparing the multi-protective emulsion according to any one of claims 1 to 8, characterized in that: include: The emollient and the emulsifier are mixed, heated and dissolved, and then a film former is added to obtain an oil phase; the moisturizer and the solvent are mixed, heated and then a plant extract is added to obtain an aqueous phase; the oil phase and the aqueous phase are mixed, and nano titanium dioxide composite particles and a preservative are added to obtain the multi-protective emulsion.

10. Use of the multi-protective emulsion according to any one of claims 1 to 8 in the preparation of sunscreen products.

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