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CN108354864B - A kind of preparation method of emulsion with whitening and moisturizing effect - Google Patents

A kind of preparation method of emulsion with whitening and moisturizing effect Download PDF

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CN108354864B
CN108354864B CN201810293810.9A CN201810293810A CN108354864B CN 108354864 B CN108354864 B CN 108354864B CN 201810293810 A CN201810293810 A CN 201810293810A CN 108354864 B CN108354864 B CN 108354864B
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emulsion
oil phase
weighing
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CN108354864A (en
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邵平
牛犇
蒋丽刚
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Zhejiang University of Technology ZJUT
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
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    • A61K8/675Vitamin B3 or vitamin B3 active, e.g. nicotinamide, nicotinic acid, nicotinyl aldehyde
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    • AHUMAN NECESSITIES
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/02Preparations for care of the skin for chemically bleaching or whitening the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
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Abstract

The invention provides a preparation method of an emulsion with whitening and moisturizing effects, which comprises the following steps: (1) weighing hydrogenated soybean oil, and heating to 75-85 ℃ to obtain a liquid oil phase I; (2) weighing arbutin, ascorbyl glucoside and nicotinamide in proportion, and mixing the three substances to obtain a composite whitening active substance; (3) adding the composite whitening active substance into the liquid oil phase I according to a certain proportion, and uniformly mixing to obtain a liquid oil phase II; (4) weighing the algal polysaccharide enzymolysis product, phospholipid and distilled water according to a proportion, heating to 75-85 ℃, and uniformly mixing to obtain a liquid water phase; (5) weighing the liquid oil phase II, the liquid water phase and the tea polyphenol according to the proportion, mixing and stirring uniformly to obtain a mixed solution, and homogenizing the mixed solution at high pressure to obtain the nano emulsion; and cooling the obtained nano emulsion to room temperature, and adding a proper amount of preservative to obtain the emulsion with the whitening and moisturizing effects. The emulsion prepared by the invention has whitening and moisturizing effects and good stability.

Description

一种具有美白保湿功效的乳液的制备方法A kind of preparation method of emulsion with whitening and moisturizing effect

(一)技术领域(1) Technical field

本发明属于化妆品技术领域,具体涉及一种具有美白保湿功效的乳液的制备方法。The invention belongs to the technical field of cosmetics, and in particular relates to a preparation method of an emulsion with whitening and moisturizing effects.

(二)技术背景(2) Technical background

美白一直以来都被人们所热切关注,美白护肤品也一直被广大女性推崇和追求。人体的肤色差异通常取决于表皮黑色素的含量与分布、真皮胶原纤维结构以及角质层的厚度与含水量等因素。Whitening has always been paid close attention by people, and whitening skin care products have always been respected and pursued by the majority of women. Differences in human skin color usually depend on factors such as the content and distribution of epidermal melanin, the structure of dermal collagen fibers, and the thickness and water content of the stratum corneum.

目前,市面上大部分美白类的护肤产品都普遍存在美白机理单一的问题:产品仅针对黑色素的形成与转移机制,从抑制酪氨酸酶活性、还原已经生成的黑色素以及抑制黑色素的转移这三步来进行美白配方设计,无法实现全效美白。并且产品稳定性差,由于美白剂易被氧化失活,或在光照下被分解,若直接添加到配方中,则易导致产品变色、变味,甚至出现膏体分层、变粗等问题。At present, most whitening skin care products on the market generally have the problem of a single whitening mechanism: the products are only aimed at the formation and transfer mechanism of melanin, from inhibiting tyrosinase activity, reducing the generated melanin and inhibiting the transfer of melanin. Step by step to carry out whitening formula design, can not achieve full effect whitening. And the product stability is poor, because the whitening agent is easily oxidized and deactivated, or decomposed under the light, if it is directly added to the formula, it will easily lead to the product discoloration, odor, and even problems such as stratification and thickening of the paste.

专利CN 107374988 A公开了一种具有美白功效的非离子型囊泡的制备方法。该加工方法以传统美白剂、羟基苯氧基丙酸、根皮素、羟基酪醇、珠丝毛蓝耳草根提取物与多元醇为美白成分,以甘油油酸酯柠檬酸酯、鲸蜡硬脂基葡糖苷、聚甘油-3甲基葡糖二硬脂酸酯为非离子表面活性剂预混剂,经过均质得到一种具有美白功效的非离子型囊泡。但是该方法都是利用非离子表面活性剂,无法将所有的活性成分有效包裹。Patent CN 107374988 A discloses a preparation method of nonionic vesicles with whitening effect. The processing method uses traditional whitening agent, hydroxyphenoxypropionic acid, phloretin, hydroxytyrosol, extract of Rhizoma chinensis root and polyhydric alcohol as whitening components, and uses glycerol oleate citric acid ester, spermaceti hard Aliphatic glucoside and polyglycerol-3 methyl glucodistearate are nonionic surfactant premixes, and after homogenization, a nonionic vesicle with whitening effect is obtained. However, this method uses non-ionic surfactants and cannot effectively encapsulate all the active ingredients.

专利CN 103690380 A公开了一种制备具有固相内核的美白纳米粒乳液的方法,该方法以丹皮酚、雏菊花提取物、黑茶镳子种子油、苦杏仁酸为美白剂,以甘油硬脂酸酯、鲸蜡硬脂醚-20、鲸蜡硬脂醚-12为乳化剂,经过均质、降温,得具有固相内核的美白纳米粒乳液。该方法制备出的乳液由于是固核,因此,在使用的时候会有颗粒感,给人以一种活性成分没有完全溶解的感觉。Patent CN 103690380 A discloses a method for preparing a whitening nanoparticle emulsion with a solid-phase core. The method uses paeonol, daisy flower extract, black tea seed oil, and mandelic acid as whitening agents, and glycerin hard Fatty acid ester, cetearyl ether-20 and cetearyl ether-12 are emulsifiers, and after homogenization and cooling, a whitening nanoparticle emulsion with a solid core is obtained. Since the emulsion prepared by this method is a solid core, it will have a grainy feeling when used, giving a feeling that the active ingredient is not completely dissolved.

(三)发明内容(3) Contents of the invention

本发明所要解决的技术问题是提供一种具有美白保湿功效且稳定性良好的乳液的制备方法。The technical problem to be solved by the present invention is to provide a preparation method of an emulsion with whitening and moisturizing effect and good stability.

下面对本发明的技术方案进行具体说明:The technical scheme of the present invention is specifically described below:

本发明提供了一种具有美白保湿功效的乳液的制备方法,包括如下步骤:The invention provides a preparation method of an emulsion with whitening and moisturizing effect, comprising the following steps:

(1)称量氢化大豆油,加热至75-85℃,得到液态油相I;(1) Weighing hydrogenated soybean oil, heating to 75-85 ° C to obtain liquid oil phase I;

(2)按质量比为2-4∶3-6∶1的比例称取熊果苷、抗坏血酸葡糖苷、烟酰胺,将上述三种物质混合,获得复合美白活性物;(2) weigh arbutin, ascorbic acid glucoside, nicotinamide in a ratio of 2-4: 3-6: 1 by mass ratio, and mix the above-mentioned three substances to obtain a composite whitening active substance;

(3)将所述复合美白活性物加入步骤(1)所得的液态油相I中,混合均匀,得到液态油相II;其中复合美白活性物与液态油相I的质量比为0.15~0.30∶1;(3) adding the composite whitening active substance to the liquid oil phase I obtained in step (1), and mixing uniformly to obtain a liquid oil phase II; wherein the mass ratio of the composite whitening active substance to the liquid oil phase I is 0.15 to 0.30: 1;

(4)按质量比为0.08~0.2:0.05~0.1∶1的比例称取海藻多糖酶解产物、磷脂和蒸馏水,加热至75~85℃,混合均匀得到液态水相;(4) Weigh seaweed polysaccharide enzymolysis product, phospholipid and distilled water in a ratio of 0.08~0.2:0.05~0.1:1 by mass, heat to 75~85°C, and mix well to obtain a liquid water phase;

(5)按质量比为15~25∶120~150:1称取步骤(3)所得液态油相II、步骤(4)所得液态水相和茶多酚,混合搅拌均匀得混合液,将混合液在高压均质机中进行高压均质得到纳米乳液,保证高压均质机出口段混合液温度不超过90℃;将所得纳米乳液冷却至室温,添加适量防腐剂,得具有美白保湿功效的乳液。(5) weigh the liquid oil phase II obtained in step (3), the liquid water phase obtained in step (4), and tea polyphenols in a mass ratio of 15 to 25: 120 to 150: 1, mix and stir to obtain a mixed solution, and mix The liquid is subjected to high-pressure homogenization in a high-pressure homogenizer to obtain a nanoemulsion, ensuring that the temperature of the mixed solution at the outlet of the high-pressure homogenizer does not exceed 90 °C; the obtained nanoemulsion is cooled to room temperature, and an appropriate amount of preservative is added to obtain an emulsion with whitening and moisturizing effects. .

本发明中,所述海藻多糖酶解产物通过以下方法制备:海藻经水提醇沉得到海藻多糖,海藻多糖经葡聚糖酶酶解得到海藻多糖酶解产物。具体操作步骤如下:In the present invention, the enzymatic hydrolysis product of seaweed polysaccharide is prepared by the following method: seaweed polysaccharide is obtained by water extraction and alcohol precipitation, and seaweed polysaccharide is obtained by enzymatic hydrolysis of seaweed polysaccharide by glucanase. The specific operation steps are as follows:

(a)海藻多糖提取方法:将海藻洗净,烘干,粉碎,得到藻粉;取藻粉,加体积分数为95%的乙醇溶液浸泡脱脂,静置过夜;取脱脂后的藻粉,按1kg:8~12L(优选1kg:10L)料液比加入蒸馏水,80~100℃(优选95℃)水浴1~3h(优选2h),热水提取结束冷却静置0.5~1.5h(优选1h),冷冻离心,取上清液即多糖粗提液旋转蒸发浓缩至一定体积,加入乙醇溶液(优选体积分数为95%的乙醇溶液)至最终乙醇体积分数为30%,静置过夜;样液冷冻离心,取沉淀,加入适量蒸馏水将沉淀完全溶解,减压蒸发并将残留酒精完全蒸发,浓缩,冷冻干燥得海藻多糖;(a) Extraction method of seaweed polysaccharide: wash seaweed, dry, pulverize to obtain algal powder; take algal powder, add 95% ethanol solution to soak and degrease, and let stand overnight; take degreased algal powder, press 1kg:8~12L (preferably 1kg:10L), add distilled water in the ratio of material to liquid, 80~100℃ (preferably 95℃) water bath for 1~3h (preferably 2h), after hot water extraction, cool and let stand for 0.5~1.5h (preferably 1h) , freeze and centrifuge, take the supernatant, i.e. the crude polysaccharide extract, and concentrate it to a certain volume by rotary evaporation, add ethanol solution (preferably ethanol solution with a volume fraction of 95%) until the final ethanol volume fraction is 30%, and let stand overnight; the sample solution is frozen Centrifuge, take the precipitate, add an appropriate amount of distilled water to completely dissolve the precipitate, evaporate under reduced pressure and completely evaporate the residual alcohol, concentrate, and freeze-dry to obtain the seaweed polysaccharide;

(b)海藻多糖酶解方法:取海藻多糖,用蒸馏水配置质量浓度2~7%(优选5%)海藻多糖溶液,而后加入质量为海藻多糖质量2~5%(优选3.5%)的葡聚糖酶,在pH=4.8、温度48℃的条件下进行反应1~3h(优选2h),静置冷却,减压蒸发浓缩至一定浓度待用;选取孔径大小为500Da规格的透析袋,装入浓缩液流水透析12~36h(优选24h),静置过夜;重复多次,并将透析液减压浓缩,冷冻干燥,得海藻多糖酶解产物。(b) Enzymatic hydrolysis method of seaweed polysaccharide: take seaweed polysaccharide, prepare a solution of seaweed polysaccharide with a mass concentration of 2-7% (preferably 5%) with distilled water, and then add dextran having a mass of 2-5% (preferably 3.5%) of seaweed polysaccharide mass Carbohydrase, react for 1-3h (preferably 2h) under the conditions of pH=4.8 and temperature 48°C, stand to cool, evaporate under reduced pressure and concentrate to a certain concentration for later use; select a dialysis bag with a pore size of 500Da, put it in The concentrated liquid is dialyzed under running water for 12-36 h (preferably 24 h), and left to stand overnight; repeated several times, the dialysate is concentrated under reduced pressure, and freeze-dried to obtain the enzymatic hydrolysis product of seaweed polysaccharide.

本发明步骤(5)中,防腐剂可选择本领域常用的防腐剂,如苯甲醇、咪唑烷基脲、尼泊金甲酯等,本发明优选以苯甲醇、咪唑烷基脲、尼泊金甲酯的混合物作为防腐剂,防腐剂的加入质量为纳米乳液质量的0.3~0.4%,最优选以0.2%苯甲醇、0.1%咪唑烷基脲和0.05%尼泊金甲酯作为防腐剂。In step (5) of the present invention, the preservatives can be selected from commonly used preservatives in the field, such as benzyl alcohol, imidazolidinyl urea, methylparaben, etc. In the present invention, preferably benzyl alcohol, imidazolidinyl urea, paraben The mixture of methyl esters is used as a preservative, and the added mass of the preservative is 0.3-0.4% of the mass of the nanoemulsion, and the most preferably 0.2% benzyl alcohol, 0.1% imidazolidinyl urea and 0.05% methylparaben are used as the preservative.

本发明步骤(5)中,高压均质条件为:在70~150MPa压力、75~90℃温度条件下,通过高压均质机循环均质5~15次,在高压均质机出口使用冷却装置,保证高压均质机出口段混合液温度不超过90℃,均质完成后得纳米乳液。In step (5) of the present invention, the high-pressure homogenization conditions are: under the conditions of 70-150MPa pressure and 75-90°C temperature, circulating homogenization through the high-pressure homogenizer for 5-15 times, and using a cooling device at the outlet of the high-pressure homogenizer , to ensure that the temperature of the mixed liquid at the outlet of the high-pressure homogenizer does not exceed 90 °C, and the nanoemulsion is obtained after the homogenization is completed.

本发明的优点和产生的有益效果:The advantages of the present invention and the beneficial effects produced:

(1)本发明将海藻多糖经酶解处理后与磷脂混合,形成复配乳化剂,复配乳化剂具有较好的乳化性和保湿性。(1) In the present invention, seaweed polysaccharide is mixed with phospholipid after enzymolysis treatment to form a compound emulsifier, and the compound emulsifier has better emulsifying and moisturizing properties.

具体而言,海藻多糖具有优良的胶体特性,并且还具有一定的保湿性。海藻多糖经葡聚糖酶酶解处理后,糖苷键的断裂使多糖分子量变小,溶液黏度变小,并且还能暴露出海藻多糖的疏水区域及活性位点,使得海藻多糖的乳化活性及抗氧化活性都有所提高。磷脂是一种天然的两性乳化剂,具有良好的保湿能力和乳化能力,并且形成的乳液具有较好的稳定性。将海藻多糖酶解产物与磷脂混合,得到复配型乳化剂,形成的乳液,不仅有大分子多糖作为界面稳定剂,还有小分子磷脂分布在大分子之间,能有效的降低表面活化能。海藻多糖酶解产物上的亲水基团与磷脂的亲水基团结构不同,能稳定不同的活性成分,将两者复配使用,产生乳化优势互补以及良好的保湿效果。Specifically, seaweed polysaccharide has excellent colloidal properties and also has certain moisturizing properties. After the seaweed polysaccharide is hydrolyzed by glucanase, the cleavage of the glycosidic bond reduces the molecular weight of the polysaccharide and the viscosity of the solution, and also exposes the hydrophobic region and active site of the seaweed polysaccharide, which makes the emulsifying activity and resistance of the seaweed polysaccharide more effective. The oxidative activity was improved. Phospholipid is a natural amphoteric emulsifier with good moisturizing and emulsifying ability, and the formed emulsion has good stability. The enzymatic hydrolysis product of seaweed polysaccharide is mixed with phospholipids to obtain a compound emulsifier. The formed emulsion not only has macromolecular polysaccharides as interface stabilizers, but also small molecular phospholipids are distributed among the macromolecules, which can effectively reduce the surface activation energy. . The hydrophilic group on the hydrolyzed product of seaweed polysaccharide is different from the hydrophilic group of phospholipid, which can stabilize different active ingredients. The combination of the two can produce complementary emulsifying advantages and good moisturizing effect.

(2)本发明将熊果苷、抗坏血酸葡糖苷、烟酰胺按照一定的比例混合作为油相,具有美白作用。(2) In the present invention, arbutin, ascorbic acid glucoside and nicotinamide are mixed in a certain proportion as an oil phase, which has a whitening effect.

具体而言,熊果苷是源于绿色植物的天然活性物质,它能迅速渗入肌肤,在不影响细胞增殖浓度的同时,能有效地抑制皮肤中的酪氨酸酶的活性,阻断黑色素的形成,通过自身与酪氨酶直接结合,加速黑色素的分解与排泄,从而减少皮肤色素沉积,祛除色斑和雀斑,而且对黑色素细胞不产生毒害性、刺激性、致敏性等副作用,同时还有杀菌、消炎的作用。还原型谷胱甘肽是一种含γ-酰胺键和巯基的三肽,由谷氨酸、半胱氨酸及甘氨酸组成,具有抗氧化作用和整合解毒作用,生物体中以还原型谷胱甘肽居多,其能够纠正乙酰胆碱、胆碱酯酶的不平衡,起到抗过敏作用,还可防止皮肤老化及色素沉着,减少黑色素的形成,并使皮肤产生光泽。烟酰胺是维生素B3的一种衍生物,参与黑素的转运过程并能加快黑素细胞中黑素小体的运动速率,抑制已经形成的黑色素向表皮角质细胞转运,从而使得皮肤中黑色素减少。三者分别从抑制酪氨酸酶的活性、还原黑色素形成过程中各中间体、抑制已经形成的黑色素向表皮角质细胞转运三种不同的机制来达到美白效果。Specifically, arbutin is a natural active substance derived from green plants. It can quickly penetrate into the skin. It can effectively inhibit the activity of tyrosinase in the skin without affecting the concentration of cell proliferation and block the production of melanin. Formation, through its direct combination with tyrosinase, accelerates the decomposition and excretion of melanin, thereby reducing skin pigmentation, removing pigmentation and freckles, and does not produce toxic, irritating, sensitizing and other side effects to melanocytes, and also It has bactericidal and anti-inflammatory effects. Reduced glutathione is a tripeptide containing γ-amide bond and sulfhydryl group. It is composed of glutamic acid, cysteine and glycine. It has antioxidant effects and integrated detoxification. Most of them are glycerides, which can correct the imbalance of acetylcholine and cholinesterase, play an anti-allergic effect, prevent skin aging and pigmentation, reduce the formation of melanin, and make the skin shiny. Niacinamide is a derivative of vitamin B3, which participates in the process of melanin transport and can accelerate the movement rate of melanosomes in melanocytes, inhibit the transport of formed melanin to epidermal keratinocytes, thereby reducing melanin in the skin. The three have three different mechanisms to achieve the whitening effect from inhibiting the activity of tyrosinase, reducing the intermediates in the process of melanin formation, and inhibiting the transport of the formed melanin to the epidermal keratinocytes.

(3)本发明将茶多酚添加到乳液中,不仅能增加乳液的美白作用,还能起到稳定乳液的作用。(3) In the present invention, adding tea polyphenols into the emulsion can not only increase the whitening effect of the emulsion, but also play a role in stabilizing the emulsion.

具体而言,从化妆品角度而言,除了从上述三种机制上来达到美白效果,目前,内皮素拮抗剂也是一种新的美白策略。茶多酚是一种内皮素拮抗剂,它的作用机理不同于酪氨酸酶活性的抑制,是通过抑制内皮素对黑色素细胞增殖的调控来达到美白祛斑效果的。在茶多酚的作用下,内皮素不能与黑皮素细胞上的受点联结,因此不会再有额外的黑色素形成。另外,茶多酚可以通过氢键、静电相互作用等与海藻多糖酶解产物相互作用,茶多酚的加入可以改变海藻多糖酶解产物的二级结构,进而提高海藻多糖酶解产物的乳化性能。Specifically, from a cosmetic point of view, in addition to achieving the whitening effect from the above three mechanisms, currently, endothelin antagonists are also a new whitening strategy. Tea polyphenol is an endothelin antagonist. Its mechanism of action is different from the inhibition of tyrosinase activity. It achieves the effect of whitening and freckle removal by inhibiting the regulation of endothelin on the proliferation of melanocytes. Under the action of tea polyphenols, endothelin cannot connect with receptors on melanocortin cells, so no additional melanin will be formed. In addition, tea polyphenols can interact with seaweed polysaccharide hydrolysis products through hydrogen bonding, electrostatic interaction, etc. The addition of tea polyphenols can change the secondary structure of seaweed polysaccharide hydrolysis products, thereby improving the emulsifying properties of seaweed polysaccharide hydrolysis products. .

(四)具体实施方法(4) Specific implementation methods

下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:The present invention is further described below in conjunction with specific embodiment, but the protection scope of the present invention is not limited to this:

实施例1:海藻多糖酶解产物的制备Example 1: Preparation of seaweed polysaccharide enzymatic hydrolysis product

1、海藻多糖提取方法:将海藻洗净,控水,置于烘箱内60℃烘干,粉碎。取1kg藻粉,加2L 95%乙醇溶液浸泡脱脂,静置过夜。取脱脂后的藻粉,按1kg:10L料液比加入蒸馏水,95℃水浴2h。热水提取结束冷却静置1h,冷冻离心10min(转速10000rpm,温度4℃)。取上清液即多糖粗提液旋转蒸发浓缩至2L,加入95%乙醇溶液至最终乙醇体积分数为30%,静置过夜。样液冷冻离心10min(转速10000rpm,温度4℃),取沉淀,加入少量蒸馏水将沉淀完全溶解,减压蒸发并将残留酒精完全蒸发,并浓缩至20mL,经冷冻干燥得海藻多糖。1. Extraction method of seaweed polysaccharide: Wash the seaweed, control the water, dry in an oven at 60°C, and pulverize. Take 1kg of algal powder, add 2L of 95% ethanol solution to soak and degrease, and let stand overnight. Take the degreased algal powder, add distilled water at a ratio of 1kg:10L of material to liquid, and take a water bath at 95°C for 2h. After the hot water extraction was completed, it was left to cool and stand for 1 h, and then refrigerated and centrifuged for 10 min (rotation speed 10000 rpm, temperature 4 °C). The supernatant, ie the crude polysaccharide extract, was concentrated to 2 L by rotary evaporation, and 95% ethanol solution was added until the final ethanol volume fraction was 30%, and left standing overnight. The sample solution was refrigerated and centrifuged for 10 min (rotation speed 10000 rpm, temperature 4 °C), the precipitate was taken, a small amount of distilled water was added to completely dissolve the precipitate, evaporated under reduced pressure and the residual alcohol was completely evaporated, and concentrated to 20 mL, and freeze-dried to obtain seaweed polysaccharide.

2、海藻多糖酶解方法:取海藻多糖,用蒸馏水配置5%海藻多糖溶液,而后加入质量为海藻多糖质量3.5%的葡聚糖酶(购自宁夏夏盛实业集团有限公司),在pH=4.8、温度48℃的条件下进行反应2h,静置冷却,减压蒸发浓缩至4%待用。选取孔径大小为500Da规格的透析袋,装入可溶性固形物4%的20mL酶解反应液分别流水透析24h,静置过夜。重复多次,并将透析液减压浓缩至10mL,冷冻干燥,得海藻多糖酶解产物。2. Enzymatic hydrolysis method of seaweed polysaccharide: take seaweed polysaccharide, prepare 5% seaweed polysaccharide solution with distilled water, and then add glucanase (purchased from Ningxia Xiasheng Industrial Group Co., Ltd.) with a mass of 3.5% of seaweed polysaccharide mass, at pH= 4.8. The reaction was carried out under the condition of temperature of 48°C for 2h, left to cool, evaporated under reduced pressure and concentrated to 4% for use. A dialysis bag with a pore size of 500 Da was selected, and 20 mL of the enzymatic hydrolysis reaction solution containing 4% soluble solids was put into running water for dialysis for 24 hours, and left to stand overnight. Repeated for several times, the dialysate was concentrated under reduced pressure to 10 mL, and freeze-dried to obtain an enzymatic hydrolysis product of seaweed polysaccharide.

实施例2:Example 2:

(1)称量氢化大豆油(购自武汉市合中生化制造有限公司)20g,加热至85℃,得到液态油相I;(1) 20 g of hydrogenated soybean oil (purchased from Wuhan Hezhong Biochemical Manufacturing Co., Ltd.) was weighed, heated to 85° C. to obtain liquid oil phase I;

(2)按质量比为4∶6∶1的比例称取熊果苷(购自西安绿天生物技术有限公司)4g、抗坏血酸葡糖苷(购自西安万方生物科技有限公司)6g、烟酰胺(购自河南大唐化工有限公司)1g,将上述三种物质混合,获得复合美白活性物;(2) 4g of arbutin (purchased from Xi'an Lutian Biotechnology Co., Ltd.), 6g of ascorbyl glucoside (purchased from Xi'an Wanfang Biotechnology Co., Ltd.), nicotinamide were weighed in a ratio of 4:6:1 by mass (purchased from Henan Datang Chemical Co., Ltd.) 1g, the above-mentioned three kinds of substances are mixed to obtain a composite whitening active substance;

(3)按质量比复合美白活性物∶液体油相I=0.30∶1称取复合美白活性物6g加入步骤(1)所得的液态油相I中,混合均匀,得到液态油相II;(3) composite whitening active substance by mass ratio: liquid oil phase I=0.30: 1, take by weighing composite whitening active substance 6g and add in the liquid oil phase I of step (1) gained, mix homogeneously, obtain liquid oil phase II;

(4)按质量比为0.2:0.1∶1的比例称取海藻多糖酶解产物30g、磷脂15g和蒸馏水150g,加热至75~85℃,混合均匀得到液态水相;(4) weigh 30g of seaweed polysaccharide enzymolysis product, 15g of phospholipids and 150g of distilled water in a ratio of 0.2:0.1:1 by mass, heat to 75-85°C, and mix to obtain a liquid water phase;

(5)按质量比为25∶150:1称取步骤(3)所得液态油相II 25g、步骤(4)所得液态水相150g和茶多酚1g,将所述液态油相II、液态水相和茶多酚混合搅拌均匀得混合液,将混合液在150MPa压力、90℃温度条件下,通过高压均质机循环均质5次,在高压均质机出口使用冷却装置,保证高压均质机出口段混合液温度不超过90℃,均质完成后得纳米乳液;将所得纳米乳液冷却至室温,以乳液质量为100%计,添加0.2%苯甲醇、0.1%咪唑烷基脲、0.05%尼泊金甲酯作为防腐剂,得具有美白保湿功效的乳液。(5) weigh 25 g of liquid oil phase II obtained in step (3), 150 g of liquid water phase obtained in step (4) and 1 g of tea polyphenols in a mass ratio of 25: 150: 1, and weigh the liquid oil phase II, liquid water The phase and tea polyphenols are mixed and stirred evenly to obtain a mixed liquid. The mixed liquid is circulated and homogenized for 5 times through a high-pressure homogenizer under the conditions of 150MPa pressure and 90 °C temperature, and a cooling device is used at the outlet of the high-pressure homogenizer to ensure high-pressure homogenization. The temperature of the mixed liquid at the outlet of the machine does not exceed 90 °C, and the nanoemulsion is obtained after the homogenization is completed; the obtained nanoemulsion is cooled to room temperature, and 0.2% benzyl alcohol, 0.1% imidazolidinyl urea, 0.05% benzyl alcohol, 0.1% imidazolidinyl urea, 0.05% are added based on the emulsion quality as 100%. Methylparaben is used as a preservative to obtain a whitening and moisturizing lotion.

实施例3:Example 3:

(1)称量氢化大豆油(购自武汉市合中生化制造有限公司)15g,加热至85℃,得到液态油相I;(1) 15 g of hydrogenated soybean oil (purchased from Wuhan Hezhong Biochemical Manufacturing Co., Ltd.) was weighed, heated to 85° C. to obtain liquid oil phase I;

(2)按质量比为2∶3∶1的比例称取熊果苷(购自西安绿天生物技术有限公司)1g、抗坏血酸葡糖苷(购自西安万方生物科技有限公司)1.5g、烟酰胺(购自河南大唐化工有限公司)0.5g,将上述三种物质混合,获得复合美白活性物;(2) 1 g of arbutin (purchased from Xi'an Lvtian Biotechnology Co., Ltd.), 1.5 g of ascorbyl glucoside (purchased from Xi'an Wanfang Biotechnology Co., Ltd.), Amide (purchased from Henan Datang Chemical Co., Ltd.) 0.5g, the above three substances were mixed to obtain a composite whitening active substance;

(3)按质量比复合美白活性物∶液体油相I=0.15∶1称取复合美白活性物2.25g加入步骤(1)所得的液态油相I中,混合均匀,得到液态油相II;(3) by mass ratio composite whitening active substance: liquid oil phase I=0.15: 1 take by weighing composite whitening active substance 2.25g and add in the liquid oil phase I of step (1) gained, mix homogeneously, obtain liquid oil phase II;

(4)按质量比为0.08:0.05∶1的比例称取海藻多糖酶解产物12g、磷脂7.5g和蒸馏水150g,加热至75~85℃,混合均匀得到液态水相;(4) weigh 12g of seaweed polysaccharide enzymolysis product, 7.5g of phospholipid and 150g of distilled water in a ratio of 0.08:0.05:1 by mass, heat to 75~85°C, and mix to obtain a liquid water phase;

(5)按质量比为15∶120:1称取步骤(3)所得液态油相II 15g、步骤(4)所得液态水相120g和茶多酚1g,将所述液态油相II、液态水相和茶多酚混合搅拌均匀得混合液,将混合液在150MPa压力、90℃温度条件下,通过高压均质机循环均质5次,在高压均质机出口使用冷却装置,保证高压均质机出口段混合液温度不超过90℃,均质完成后得纳米乳液;将所得纳米乳液冷却至室温,以乳液质量为100%计,添加0.2%苯甲醇、0.1%咪唑烷基脲、0.05%尼泊金甲酯作为防腐剂,得具有美白保湿功效的乳液。(5) weigh 15 g of liquid oil phase II obtained in step (3), 120 g of liquid water phase obtained in step (4) and 1 g of tea polyphenols in a mass ratio of 15: 120: 1, and weigh the liquid oil phase II, liquid water The phase and tea polyphenols are mixed and stirred evenly to obtain a mixed liquid. The mixed liquid is circulated and homogenized for 5 times through a high-pressure homogenizer under the conditions of 150MPa pressure and 90 °C temperature, and a cooling device is used at the outlet of the high-pressure homogenizer to ensure high-pressure homogenization. The temperature of the mixed liquid at the outlet of the machine does not exceed 90 °C, and the nanoemulsion is obtained after the homogenization is completed; the obtained nanoemulsion is cooled to room temperature, and 0.2% benzyl alcohol, 0.1% imidazolidinyl urea, 0.05% benzyl alcohol, 0.1% imidazolidinyl urea, 0.05% are added based on the emulsion quality as 100%. Methylparaben is used as a preservative to obtain a whitening and moisturizing lotion.

实施例4:Example 4:

(1)称量氢化大豆油(购自武汉市合中生化制造有限公司)20g,加热至85℃,得到液态油相I(1) 20 g of hydrogenated soybean oil (purchased from Wuhan Hezhong Biochemical Manufacturing Co., Ltd.) was weighed, heated to 85° C. to obtain liquid oil phase I

(2)按质量比为2∶6∶1的比例称取熊果苷(购自西安绿天生物技术有限公司)1.6g、抗坏血酸葡糖苷(购自西安万方生物科技有限公司)4.8g、烟酰胺(购自河南大唐化工有限公司)0.8g,将上述三种物质混合,获得复合美白活性物;(2) 1.6 g of arbutin (purchased from Xi'an Lutian Biotechnology Co., Ltd.), 4.8 g of ascorbic acid glucoside (purchased from Xi'an Wanfang Biotechnology Co., Ltd.), Niacinamide (purchased from Henan Datang Chemical Co., Ltd.) 0.8g, the above three substances were mixed to obtain a composite whitening active substance;

(3)按质量比复合美白活性物∶液体油相I=0.2∶1称取复合美白活性物4g加入步骤(1)所得的液态油相I中,混合均匀,得到液态油相II;(3) by mass ratio composite whitening active substance: liquid oil phase I=0.2: 1 take by weighing composite whitening active substance 4g and add in the liquid oil phase I of step (1) gained, mix homogeneously, obtain liquid oil phase II;

(4)按质量比为0.08:0.1∶1的比例称取海藻多糖酶解产物12g、磷脂15g和蒸馏水150g,加热至75~85℃,混合均匀得到液态水相;(4) weigh 12g of seaweed polysaccharide enzymolysis product, 15g of phospholipids and 150g of distilled water in a ratio of 0.08:0.1:1 by mass, heat to 75~85°C, and mix to obtain a liquid water phase;

(5)按质量比为25∶140:1称取步骤(3)所得液态油相II 25g、步骤(4)所得液态水相140g和茶多酚1g,将所述液态油相II、液态水相和茶多酚混合搅拌均匀得混合液,将混合液在150MPa压力、90℃温度条件下,通过高压均质机循环均质5次,在高压均质机出口使用冷却装置,保证高压均质机出口段混合液温度不超过90℃,均质完成后得纳米乳液;将所得纳米乳液冷却至室温,以乳液质量为100%计,添加0.2%苯甲醇、0.1%咪唑烷基脲、0.05%尼泊金甲酯作为防腐剂,得具有美白保湿功效的乳液。(5) weigh 25 g of liquid oil phase II obtained in step (3), 140 g of liquid water phase obtained in step (4) and 1 g of tea polyphenols in a mass ratio of 25: 140: 1, and weigh the liquid oil phase II, liquid water The phase and tea polyphenols are mixed and stirred evenly to obtain a mixed liquid. The mixed liquid is circulated and homogenized for 5 times through a high-pressure homogenizer under the conditions of 150MPa pressure and 90 °C temperature, and a cooling device is used at the outlet of the high-pressure homogenizer to ensure high-pressure homogenization. The temperature of the mixed liquid at the outlet of the machine does not exceed 90 °C, and the nanoemulsion is obtained after the homogenization is completed; the obtained nanoemulsion is cooled to room temperature, and 0.2% benzyl alcohol, 0.1% imidazolidinyl urea, 0.05% benzyl alcohol, 0.1% imidazolidinyl urea, 0.05% are added based on the emulsion quality as 100%. Methylparaben is used as a preservative to obtain a whitening and moisturizing lotion.

实施例5:乳液性能测试:Example 5: Emulsion performance test:

(1)酪氨酸酶抑制率测定实验方法:(1) Experimental method for determination of tyrosinase inhibition rate:

加入样品体系:配制pH=6.8的磷酸缓冲液(PBS);浓度为200U/mL的酪氨酸酶磷酸缓冲溶液(在冰水浴中操作、保存);浓度为2.5mmol/L的L-酪氨酸缓冲溶液;取1.5mL L-酪氨酸缓冲溶液,1.5mLPBS溶液,1mL上述实施例制备的具有美白保湿功效的乳液,混合,于37℃水浴中保温10min,加入1mL酪氨酸酶磷酸缓冲溶液,反应10min,在475nm处测定吸光值。Add sample system: prepare pH=6.8 phosphate buffer solution (PBS); 200U/mL tyrosinase phosphate buffer solution (operated and stored in ice-water bath); 2.5mmol/L L-tyrosine Acid buffer solution; take 1.5 mL of L-tyrosine buffer solution, 1.5 mL of PBS solution, and 1 mL of the emulsion with whitening and moisturizing effect prepared in the above example, mix them, and keep them in a 37°C water bath for 10 min, and add 1 mL of tyrosinase phosphate buffer. The solution was reacted for 10 min, and the absorbance was measured at 475 nm.

未加样品体系:配制pH=6.8的磷酸缓冲液(PBS);浓度为200U/mL的酪氨酸酶磷酸缓冲溶液(在冰水浴中操作、保存);浓度为2.5mmol/L的L-酪氨酸缓冲溶液;取1.5mL L-酪氨酸缓冲溶液,1.5mLPBS溶液,1mL去离子水,混合,于37℃水浴中保温10min,加入1mL酪氨酸酶磷酸缓冲溶液,反应10min,在475nm处测定吸光值。System without sample added: Phosphate buffer solution (PBS) with pH=6.8; tyrosinase phosphate buffer solution with concentration of 200U/mL (operated and stored in ice-water bath); L-phenol with concentration of 2.5mmol/L acid buffer solution; take 1.5mL L-tyrosine buffer solution, 1.5mL PBS solution, 1mL deionized water, mix, incubate in 37°C water bath for 10min, add 1mL tyrosinase phosphate buffer solution, react for 10min, at 475nm Absorbance value was measured.

按下式计算酪氨酸酶的抑制率:The inhibition rate of tyrosinase was calculated as follows:

抑制率=(A-B)/A×100%Inhibition rate=(A-B)/A×100%

其中A为未加样品体系的吸光度值,B为加入样品后体系的吸光度值。Among them, A is the absorbance value of the system without adding the sample, and B is the absorbance value of the system after adding the sample.

测试结果见表1。The test results are shown in Table 1.

(2)稳定性试验指标:(2) Stability test index:

a.耐热性。将美白保湿乳液在40℃存放15d后,目测观察发现其与试验前的性状及颜色是否产生明显差异,有无分层、浮油现象,若无明显差异,表明乳液产品耐热性较好。a. Heat resistance. After the whitening and moisturizing lotion was stored at 40°C for 15 days, it was visually observed whether there was a significant difference between the properties and color before the test, whether there was delamination and oil slick.

b.耐寒性。将美白保湿乳液在0℃存放15d后,目测观察发现其与试验前的性状及颜色是否产生明显差异,有无分层、浮油现象,若无明显差异,表明乳液产品耐寒性较好。b. Cold resistance. After the whitening and moisturizing lotion was stored at 0°C for 15 days, it was visually observed whether there was a significant difference between the properties and color before the test, whether there was delamination or oil slick.

c.冷热循环。美白保湿乳液经冷热循环交替实验(40℃放置15天,而后在0℃放置15天,循环处理3次)后,目测观察发现其与试验前的性状及颜色是否产生明显差异,有无分层、浮油现象,若无明显差异,表明乳液产品耐寒性较好。c. Hot and cold cycle. After the whitening and moisturizing lotion was tested by alternating hot and cold cycles (15 days at 40°C, then 15 days at 0°C, and 3 cycles of treatment), it was visually observed whether it was significantly different from the properties and colors before the test. Layer and oil slick phenomenon, if there is no obvious difference, it indicates that the emulsion product has better cold resistance.

测试结果见表1。The test results are shown in Table 1.

(3)保湿性能测试:分别将乳液涂抹在手上15min后,用皮肤水分测试仪(海岳皮肤测试仪)测定30min内皮肤含水量的变化,注意在手部的同样位置进行测定,测定3次,取平均值。未涂抹美白保湿乳液前,经过30min手部同样位置的皮肤水分率基本保持在33.6%。(3) Moisturizing performance test: After smearing the lotion on the hands for 15 minutes, use a skin moisture tester (Haiyue skin tester) to measure the change in skin moisture content within 30 minutes, pay attention to the same position on the hands to measure, and measure 3 times, take the average value. Before applying the whitening and moisturizing lotion, the moisture rate of the skin at the same position on the hand remained basically at 33.6% after 30 minutes.

表1Table 1

Figure BDA0001618257830000101
Figure BDA0001618257830000101

Claims (3)

1. A preparation method of an emulsion with whitening and moisturizing effects comprises the following steps:
(1) weighing hydrogenated soybean oil, and heating to 75-85 ℃ to obtain a liquid oil phase I;
(2) weighing arbutin, ascorbyl glucoside and nicotinamide according to the mass ratio of 2-4: 3-6: 1, and mixing the three substances to obtain a composite whitening active substance;
(3) adding the composite whitening active substance into the liquid oil phase I obtained in the step (1), and uniformly mixing to obtain a liquid oil phase II; wherein the mass ratio of the composite whitening active substance to the liquid oil phase I is 0.15-0.30: 1;
(4) according to the mass ratio of 0.08-0.2: weighing the algal polysaccharide enzymolysis product, phospholipid and distilled water according to the ratio of 0.05-0.1: 1, heating to 75-85 ℃, and uniformly mixing to obtain a liquid water phase;
(5) according to the mass ratio of 15-25: 120-150: 1, weighing the liquid oil phase II obtained in the step (3), the liquid water phase obtained in the step (4) and tea polyphenol, mixing and stirring uniformly to obtain a mixed solution, carrying out high-pressure homogenization on the mixed solution in a high-pressure homogenizer to obtain nano emulsion, and ensuring that the temperature of the mixed solution at an outlet section of the high-pressure homogenizer is not more than 90 ℃; cooling the obtained nano emulsion to room temperature, and adding a proper amount of preservative to obtain the emulsion with whitening and moisturizing effects;
the preparation method of the algal polysaccharide enzymolysis product comprises the following specific operation steps:
(a) the algal polysaccharide extraction method comprises the steps of cleaning algae, drying and crushing to obtain algal powder, soaking and degreasing the algal powder in 95% ethanol solution by volume, standing overnight, adding distilled water into the degreased algal powder according to the material-liquid ratio of 1kg to 8-12L, carrying out water bath at 80-100 ℃ for 1-3 h, cooling and standing for 0.5-1.5 h after hot water extraction is finished, carrying out refrigerated centrifugation, taking supernate, namely polysaccharide crude extract, carrying out rotary evaporation and concentration to a certain volume, adding the ethanol solution until the final ethanol volume fraction is 30%, standing overnight, carrying out refrigerated centrifugation on sample liquid, taking precipitate, adding a proper amount of distilled water to completely dissolve the precipitate, carrying out reduced pressure evaporation, completely evaporating residual ethanol, concentrating, and carrying out freeze drying to obtain algal polysaccharide;
(b) the algal polysaccharide enzymolysis method comprises the following steps: preparing a seaweed polysaccharide solution with the mass concentration of 2-7% by using distilled water, adding glucanase with the mass concentration of 2-5% by mass of the seaweed polysaccharide, reacting for 1-3 h under the conditions that the pH value is 4.8 and the temperature is 48 ℃, standing, cooling, and carrying out reduced pressure evaporation and concentration to a certain concentration for later use; selecting a dialysis bag with the aperture size of 500Da, filling the dialysis bag into concentrated liquid flow for dialysis for 12-36 h, and standing overnight; repeating the steps for multiple times, decompressing and concentrating the dialyzate, and freeze-drying to obtain the algal polysaccharide enzymolysis product.
2. The method of claim 1, wherein: in the step (5), the preservative is a mixture of benzyl alcohol, imidazolidinyl urea and methyl paraben, and the adding mass of the preservative is 0.3-0.4% of the mass of the nano emulsion.
3. The method of claim 1, wherein: in the step (5), the high-pressure homogenizing condition is as follows: and circularly homogenizing for 5-15 times by a high-pressure homogenizer under the conditions of 70-150 MPa pressure and 75-90 ℃, using a cooling device at the outlet of the high-pressure homogenizer to ensure that the temperature of the mixed liquid at the outlet section of the high-pressure homogenizer is not more than 90 ℃, and obtaining the nano emulsion after homogenization.
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