A stable multiple emulsion composition
Patent Information
- Application Number
- EP2024884979
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-11-02
- Filing Date
- 2024-11-01
- Publication Date
- 2026-09-09
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Figure PCTCN2024129398-FTAPPB-I100001 
Figure PCTCN2024129398-FTAPPB-I100002 
Figure PCTCN2024129398-FTAPPB-I100003
Abstract
Description
A Stable Multiple Emulsion CompositionTECHNICAL FIELD
[0001] The present invention relates to a multiple emulsion composition. The multiple emulsion can provide improved stability and personal care beneficial effects.BACKGROUND OF THE INVENTION
[0002] An emulsion is a dispersed fluidic state of two or more liquids that are normally immiscible. Common emulsion examples are oil-in-water (O / W) and water-in-oil (W / O) emulsions. Multiple emulsions are formed with more than two fluids, or more than two fluids arranged in a more complex manner than a typical two-fluid emulsion. For example, a multiple emulsion could be oil-in-water-in-oil (O / W / O) , or water-in-oil-in-water (W / O / W) . Multiple emulsions are of particular interests because of current and potential applications in fields such as pharmaceutical delivery, paints, inks and coatings, food and beverage, chemical separations, and personal care.
[0003] Multiple emulsion is a novel emulsion technology with unique structure of “three-phase and two-membrane” , which could potentially bring excellent benefits to cosmetic formulations because it combines the advantages of both oil-in-water (O / W) and water-in-oil (W / O) emulsions, including long lasting moisturizing power and refreshing skin feel, protecting and stabilizing both hydrophilic and hydrophobic active substances, improving the release of active substances on skin and enhancing skin delivery. In addition, multiple emulsion exhibits transformative texture due to the special water-in-oil-in-water structure and brings unique skin sensory to consumers which cannot be achieved by traditional single emulsions. However, a big challenge to make stable multiple emulsions is its excessive surface free energy causing its thermodynamical instability.
[0004] This invention is related to a multiple emulsion comprising, at least one water-in-oil emulsifier, at least one oil-in-water emulsifier and at least one oil component. In particular, the multiple emulsion is water-in-oil-in-water emulsion. The present invention is also related to a method for preparing a stable multiple emulsion, which could be applied in cosmetic industry.SUMMARY
[0005] The present invention is related to a multiple emulsion comprising, at least one water-in-oil emulsifier, at least one oil-in-water emulsifier and at least one oil component, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, esters or diesters of polyethylene glycol (PEG) , linear or branched silicone emulsifiers and a mixture thereof; wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters, monoesters or diesters of sulfosuccinate and a mixture thereof. In particular, the multiple emulsion is water-in-oil-in-water emulsion.
[0006] The present invention is also related to a method for preparing a stable water-in-oil-in-water emulsion, comprising i) preparing a water-in-oil emulsion which comprises a step of mixing an oil phase comprising at least one water-in-oil emulsifier and at least one oil component with the first aqueous phase, and ii) mixing the water-in-oil emulsion obtained in the step (i) with the second aqueous phase comprising at least one oil-in-water emulsifier to obtain a stable water-in-oil-in-water emulsion, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, esters or diesters of polyethylene glycol, linear or branched silicone emulsifiers; wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters and monoesters or diesters of sulfosuccinate.Detailed Description of the Invention
[0007] Before explaining at least one embodiment of the presently disclosed and / or claimed inventive concept (s) in detail, it is to be understood that the presently disclosed and / or claimed inventive concept (s) is not limited in its application to the details of construction and the arrangement of the components or steps or methodologies set forth in the following description. The presently disclosed and / or claimed inventive concept (s) is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.
[0008] Unless otherwise defined herein, technical terms used in connection with the presently disclosed and / or claimed inventive concept (s) shall have the meanings that are commonly understood by those of ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.
[0009] All of the compositions and / or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of the presently disclosed and / or claimed inventive concept (s) have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations may be applied to the compositions and / or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the presently disclosed and / or claimed inventive concept (s) . All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the presently disclosed and / or claimed inventive concept (s) .
[0010] As utilized in accordance with the present disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.
[0011] Throughout the description, including the claims, the term "comprising one" or “comprising a" should be understood as being synonymous with the term "comprising at least one" , unless otherwise specified, and "between" should be understood as being inclusive of the limits.
[0012] The terms “a” , “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
[0013] The term “and / or” includes the meanings “and” , “or” and also all the other possible combinations of the elements connected to this term.
[0014] As used herein, “HLB” refers to the hydrophilic lipophilic balance or hydrophile-lipophile balance of a surfactant and is a measure of the hydrophilic or lipophilic nature of a surfactant.
[0015] The present invention is related to a multiple emulsion comprising, at least one water-in-oil emulsifier, at least one oil-in-water emulsifier and at least one oil component, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, esters or diesters of polyethylene glycol (PEG) , linear or branched silicone emulsifiers and a mixture thereof; wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters, monoesters or diesters of sulfosuccinate and a mixture thereof. In particular, the multiple emulsion is water-in-oil-in-water emulsion.
[0016] Water-in-Oil Emulsifiers
[0017] Water-in-oil emulsifiers have a hydrophilic-lipophilic balance (HLB) value less than 10, preferably, water-in-oil emulsifiers have an HLB value of 6 or less. According to any one embodiment of the present invention, suitable water-in-oil emulsifiers include polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, monoesters or diesters of polyethylene glycol, linear or branched silicone emulsifiers.
[0018] Linear and / or branched silicone emulsifiers
[0019] Bis-Butyldimethicone Polyglyceryl-3; Bis-PEG / PPG-14 / 14 Dimethicone; Bis-butyldimethicone Polyglyceryl-3; Bis-isobutyl PEG / PPG-10 / 7 Dimethicone copolymer; Bis-PEG / PPG-18 / 6 Dimethicone; Bis-PEG / PPG-20 / 20 Dimethicone; Bis-PEG / PPG-16 / 16 PEG / PPG-16 / 16 Dimethicone; Bis (PPG-7 Undeceneth-21-Dimethicone; Cetyl Dimethicone PEG-7 Acetate; Cetyl PEG- 8 Dimethicone; Cetyl PEG / PPG-15 / 16 Butyl Ether Dimethicone; Cetyl PEG / PPG-15 / 15 Butyl Ether Dimethicone; Cetyl PEG / PPG-7 / 3 Dimethicone; Cetyl PEG / PPG-10 / 1 Dimethicone; Dimethicone PEG-15 Acetate; Dimethicone PEG-7 Cocoate; Dimethicone PEG-7 Phosphate; Dimethicone PEG-IO Phosphate; Dimethicone PEG / PPG-7 / 4 Phosphate; Dimethicone PEG / PPG-12 / 4 Phosphate; Dimethicone PEG-7 Undecylenate; Lauryl Dimethicone PEG-IO Phosphate; Isopolyglyceryl-3 Dimethicone; Isopolyglyceryl-3 Dimethiconol; Isostearyl Carboxyldecyl PEG-8 Dimethicone; Lauryl Methicone PEG-10 Phosphate; Lauryl PEG-8 Dimethicone; Lauryl PEG-10 Methyl Ether Dimethicone; Lauryl PEG / PPG-18 / 18 Methicone; PEG-6 Methyl Ether Dimethicone; PEG-7 Methyl Ether Dimethicone; PEG-9 Methyl Ether Dimethicone; PEG-10 Methyl Ether Dimethicone; PEG-11 Methyl Ether Dimethicone; PEG-11 Methyl Ether Dimethicone; PEG-32 Methyl Ether Dimethicone; PEG-PEG / PPG-28 / 21 Acetate Dimethicone; PEG / PPG-22 / 22 Butyl Ether Dimethicone; PEG / PPG-23 / 23 Butyl Ether Dimethicone; PEG / PPG-24 / 18 Butyl Ether Dimethicone; PEG / PPG-3 / 10 Dimethicone; PEG / PPG-4 / 12 Dimethicone; PEG / PPG-6 / 11 Dimethicone; PEG / PPG-8 / 14 Dimethicone; PEG / PPG-12 / 16 Dimethicone; PEG / PPG-12 / 18 Dimethicone; PEG / PPG-14 / 4 Dimethicone; PEG / PPG-15 / 5 Dimethicone; PEG / PPG-15 / 15 Dimethicone; PEG / PPG-16 / 2 Dimethicone; PEG / PPG-16 / 8 Dimethicone; PEG / PPG-17 / 18 Dimethicone; PEG / PPG-18 / 12 Dimethicone; PEG / PPG-19 / 19 Dimethicone; PEG / PPG-20 / 6 Dimethicone; PEG / PPG-20 / 15 Dimethicone; PEG / PPG-20 / 20 Dimethicone; PEG / PPG-20 / 29 Dimethicone; PEG / PPG-22 / 23 Dimethicone; PEG / PPG-22 / 24 Dimethicone; PEG / PPG-25 / 25 Dimethicone; PEG / PPG-27 / 27 Dimethicone; PEG / PPG-30 / 10 Dimethicone; PEG / PPG-10 / 3 Oleyl Ether Dimethicone; PEG-8 trisiloxane; Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone; PPG-12 Butyl Ether Dimethicone; Silicone Quaternium-17; TEA-Dimethicone PEG-7 Phosphate; and mixtures thereof. Preferably, the most suitable silicone emulsifier for the present invention is Cetyl PEG / PPG-10 / 1 Dimethicone.
[0020] Polyglyceryl fatty acid ester comprising 2 to 6 glycerol units
[0021] One of the suitable water-in-oil emulsifiers for the present invention includes polyglyceryl fatty acid ester comprising 2 to 6 glycerol units. Exemplary water-in-oil emulsifiers include polyglyceryl laurate having 2 to 6 glycerol units, polyglyceryl mono / dioleate / trioleate having 2 to 6 glycerol units, polyglyceryl stearate having 2 to 6 glycerol units, polyglyceryl isostearate having 2 to 6 glycerol units, polyglyceryl distearate / diisostearate having 2 to 6 glycerol units, polyglyceryl polyhydroxystearate having 2 to 6 glycerol units, polyglyceryl dipolyhydroxystearate having 2 to 6 glycerol units and polyglyceryl polyricinoleate having 2 to 6 glycerol units. Particularly preferred water-in-oil emulsifiers include polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-2-diisostearate, polyglyceryl-2-polyhydroxystearate and polyglyceryl-6 polyricinoleate.
[0022] Polyglyceryl polyricinoleate
[0023] The term “Polyglyceryl polyricinoleate” is meant in the sense of the invention an ester resulting from the esterification of one or more polyglycerols with at least one polyricinoleic acid.
[0024] A polyglyceryl polyricinoleate surfactant suitable for the invention can be a total or partial ester. Within the meaning of the invention, the term “partial ester” is intended to denote a compound in which all the –OH groups of the polyglycerol units have not been esterified with polyricinoleic acid, in other words, a polyglyceryl polyricinoleate comprising at least one a free-OH group on the polyglycerolated chain. Suitable polyglycerol polyricinoleate for the present invention may include polyglyceryl-3 polyricinoleate, polyglyceryl-5 polyricinoleate, polyglyceryl-6 polyricinoleate, and more particularly, is chosen from polyglyceryl-3 polyricinoleate and polyglyceryl-6 polyricinoleate, and mixtures thereof, and even more preferentially polyglyceryl-6 polyricinoleate.
[0025] (Mono) Esters or Diesters of polyethylene glycol
[0026] Preferred suitable water-in-oil emulsifiers are esters or diesters of polyethylene glycol (PEG) , such as, for example, PEG-30 dipolyhydroxystearate, PEG-4 dilaurate, PEG-8 dioleate, PEG-40 sorbitan peroleate, PEG-7 glyceryl cocoate, PEG-25 hydrogenated castor oil, PEG-7 olive, PEG-8 oleate, PEG-8 laurate. Preferably, PEG-30 dipolyhydroxystearate is one of the most suitable water-in-oil emulsifier for the present invention.
[0027] In some preferred embodiments of the present invention, the water-in-oil emulsifier is monoesters or diesters of polyethylene glycol, polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, or a combination of monoesters or diesters of polyethylene glycol and polyglyceryl fatty acid comprising 2 to 6 glycerol units.
[0028] Preferably, the water-in-oil emulsifier is PEG-30 dipolyhydroxystearate, polyglyceryl polyhydroxystearate having 2 to 6 glycerol units, polyglyceryl dipolyhydroxystearate having 2 to 6 glycerol units, polyglyceryl polyricinoleate having 2 to 6 glycerol units, polyglyceryl distearate / diisostearate having 2 to 6 glycerol units or their mixture. Still preferably, the water-in-oil emulsifier is PEG-30 dipolyhydroxystearate, polyglyceryl-2 dipolyhydroxystearate, polyglyceryl polyricinoleate (for example polyglyceryl-6-polyricinoleate) or a mixture thereof. Still more preferably, the water-in-oil emulsifier is PEG-30 dipolyhydroxystearate or a combination of PEG-30 dipolyhydroxystearate and polyglyceryl-2 dipolyhydroxystearate.
[0029] Oil-in-Water Emulsifiers
[0030] Oil-in-water emulsifiers have a hydrophilic-lipophilic balance (HLB) value greater than or equal to 10. Preferably the oil-in-water emulsifiers suitable for the present invention have an HLB value greater than 10.
[0031] The oil-in-water emulsifier suitable for the present invention is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters and monoester or diester of sulfosuccinate.
[0032] Polyoxyethylene sorbitan fatty acid esters
[0033] Suitable polyoxyethylene sorbitan fatty acid esters include Polysorbate 20, Polysorbate 80, Polysorbate 60, and Polysorbate 85.
[0034] Alkyl Glucoside
[0035] Alkyl glucosides are those containing an alkyl group comprising from 6 to 30 carbon atoms and preferably 8 to 18 carbon atoms and containing a hydrophilic (glucoside) group preferably comprising from 1.2 to 3 saccharide units. Examples that may be suitable for the present invention include, caprylyl / capryl glucoside, laurylglucoside, cocoglucoside, cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol.
[0036] In a preferred embodiment, cetostearyl (cetearyl) glucoside is the most preferred to be used for the present invention.
[0037] N-acyl amino acid emulsifiers
[0038] The N-acyl amino acid emulsifier to be used in the present invention is N-long-chain acyl amino acids or their salts. The long-chain acryl group constitutes the N-long chain acyl acidic amino acid, a linear or branched acyl group having 6 to 20 carbon atoms, and the hydrocarbon chain may be either saturated or unsaturated. When the acyl group is unsaturated, two or more unsaturated bonds may be contained, and the unsaturated bonds may be either conjugated or not conjugated. Examples of the acyl group include, for example, acyl groups that can be derived from caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, linolic acid, linoleic acid, oleic acid, isostearic acid, 2-ethylhexanioic acid, coconut oil fatty acid, tallow fatty acid, hydrogenated tallow fatty acid and the like. Among them, acyl groups having 8 to 18 carbon atoms, or 10 to 16 carbon atoms are more preferred, and examples thereof include capryloyl group, caprinoyl group, lauroyl group, myristyl group, palmitoyl group, stearoyl group, coconut oil fatty acid acyl group (cocoyl group) , hydrogenated tallow fatty acid acyl group, palm kernel oil fatty acid acyl group and the like. In the specification, a mixed acyl group means a mixture of acyl groups with different lengths of chains. Examples of the acidic amino acids constituting the long-chain acyl acidic amino acids include taurine, sarcosine, glycine, serine, alanine, lysine, arginine, proline, threonine, valine, isoleucine, histidine, phenylalanine, preferably glutamic acid, sarcosine and taurine, among them, glutamic acid and taurine are preferred in the present invention. Types of salts of the N-long chain acyl acidic amino acids are not particularly limited. Examples of the salts include sodium salt, magnesium salt, potassium salt, ammonium salt, diethanolamine salt, triethanolamine salt, arginine salt, lysine salt and the like.
[0039] Examples of the N-long-chain acyl acidic amino acids and salts thereof include N-long chain acyl-glutamic acids and salts thereof such as N-cocoyl glutamic acids and salts thereof, N-lauroylglutamic acid and salts thereof, N-stearoylglutamic acid and salts thereof, N-myristoylglutamic acid and salts thereof, N-palmitoylglutamic acid and salts thereof and N-oleoylglutamic acid and salts thereof; N-long chain acyl taurine and salts thereof such as N-cocoyl taurine and salts the thereof, N-stearoyl taurine and salts thereof, N-myristoyl taurine and salts thereof, N-palmitoyl taurine and salts thereof and N-oleoyl taurine and salts thereof and N-lauroyl taurine or salts thereof; N-long chain acyl sarcosine and salts thereof such as N-cocoyl sarcocine and salts the thereof, N-stearoyl sarcosine and salts thereof and N-lauroyl sarcosine or salts thereof and the like. Among them, particularly preferred examples include N-cocoyl glutamic acids and salts thereof and N-lauroylglutamic acid and salts thereof. Among them, particularly preferred examples include N-stearoyl glutamic acids and salts thereof and N-lauroylglutamic acid and salts thereof. Two or more kinds of N-long chain acyl acidic amino acids or salts thereof may be used in combination. The most preferred example is monosodium salt of N-stearoyl glutamic acid (sodium stearoyl glutamate) and N-cocoyl glutamic acid (sodium cocoyl glutamate) .
[0040] Polyglycerol-10 fatty acid esters
[0041] Suitable oil-in-water emulsifier can also include polyglycerol-10 fatty acid esters, for example Polyglyceryl -10 oleate, Polyglyceryl -10 dioleate, Polyglyceryl -10 isostearate, Polyglyceryl -10 trilaurate, Polyglyceryl -10 myristate, Polyglyceryl -10 dimyristate, Polyglyceryl -10 stearate, Polyglyceryl -10 distearate. Preferred polyglyceryl fatty acid ester is polyglyceryl-10 stearate and polyglyceryl-10 oleate.
[0042] Monoesters or diesters of sulfosuccinate
[0043] Suitable oil-in-water emulsifiers can include monoesters or diesters of sulfosuccinate. Exemplary sulfosuccinates include ammonium lauryl sulfosuccinates, diammonium lauryl sulfosuccinates, dioctyl sodium sulfosuccinate, disodium cetearyl sulfosuccinate, disodium cocamido sulfosuccinates, disodium coco-glucoside sulfosuccinate, disodium dimethicone copolyol sulfosuccinate, disodium hydrogenated cottonseed glyceride sulfosuccinate, disodium isostearyl sulfosuccinate, disodium laureth sulfosuccinate and the like.
[0044] In some preferred embodiments of the present invention, the oil-in-water emulsifiers are N-acyl amino acid emulsifier, polyglyceryl-10 fatty acid esters, monoester or diesters of sulfosuccinate, or their mixtures. Preferably the oil-in-water emulsifier is selected from the group consisting of sodium stearoyl glutamate, sodium cocoyl glutamate, polyglyceryl-10 stearate, polyglyceryl-10 oleate, disodium cetearyl sulfosuccinate and their mixture. More preferably the oil-in-water emulsifier is selected from the group consisting of sodium stearoyl glutamate, disodium cetearyl sulfosuccinate and their mixture.
[0045] According to any one embodiment of the present invention, the present invention is related to a multiple emulsion comprising at least one water-in-oil emulsifier, at least one oil-in-water emulsifier and at least one oil component, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, monoesters or diesters of polyethylene glycol (PEG) , linear or branched silicone emulsifiers and a mixture thereof; wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters, monoesters or diesters of sulfosuccinate and a mixture thereof. In particular, the multiple emulsion is water-in-oil-in-water emulsion. Preferably, in some embodiments of the present invention, the multiple emulsion comprises a water-in-oil emulsifier selected from the group consisting of monoesters or diesters of polyethylene glycol, polyglyceryl fatty acid ester comprising 2 to 6 glycerol units and a combination thereof; and an oil-in-water emulsifier selected from the group consisting of N-acyl amino acidic emulsifier, polyglyceryl-10 fatty acid esters, monoesters or diesters of sulfosuccinate and their mixture. Preferably, the multiple emulsion comprises a water-in-oil emulsifier selected from the group consisting of PEG-30 dipolyhydroxystearate, polyglyceryl polyhydroxystearate having 2 to 6 glycerol units, polyglyceryl dipolyhydroxystearate having 2 to 6 glycerol units, polyglyceryl distearate / diisostearate having 2 to 6 glycerol units, polyglyceryl polyricinoleate having 2 to 6 glycerol units and their mixture. More preferably, the multiple emulsion comprises a water-in-oil emulsifier selected from the group consisting of PEG-30 dipolyhydroxystearate, polyglyceryl-2 dipolyhydroxystearate, polyglyceryl-6 polyricinoleate and a combination thereof. Particularly, the multiple emulsion of the present invention also comprises an oil-in-water emulsifier selected from the group consisting of sodium stearoyl glutamate, sodium cocoyl glutamate, polyglyceryl-10 stearate, polyglyceryl-10 oleate, disodium cetearyl sulfosuccinate and their mixtures. Still more preferably, in some embodiment of the present invention, the multiple emulsion comprises a water-in-oil emulsifier selected from the group consisting of PEG-30 dipolyhydroxystearate and a combination of PEG-30 dipolyhydroxystearate and polyglyceryl-2-dipolyhydroxysterate, an oil-in-water emulsifier selected from the group consisting of sodium stearoyl glutamate, disodium cetearyl sulfosuccinate and their mixture.
[0046] In some preferred embodiments, the water-in-oil emulsifier is present in an amount of 0.2 to 10%, preferably 0.3%to 8%, more preferably 0.3%to 6%based on the total weight of the multiple emulsion; preferably the oil component is present in an amount of 0.5%to 20%, preferably 0.5%to 15%based on the total weight of the multiple emulsion; preferably the oil-in-water emulsifier is present in an amount of 0.2%to 6.0%, preferably 0.4%to 4.0%, more preferably 0.4%to 3.0%based on the total weight of the multiple emulsion.
[0047] Oil component
[0048] Any conventional used oil components are suitable for the present invention. The oil component / emollient may be selected from the group consisting of oils of animal or plant origin, synthetic glycerides, fatty esters, fatty alcohols and aliphatic hydrocarbons. These materials may be volatile or non-volatile. Suitable oil may be selected from aliphatic hydrocarbons, plant oils, fatty alcohols, esters of fatty alcohols and / or fatty acids other than animal or plant oils and synthetic glycerides, or mixtures thereof. Particularly suitable oil may be selected from the group consisting of plant oils, esters of fatty alcohols, and mixtures thereof.
[0049] Suitable plant oils for use in the cosmetic composition of the present invention may nonexclusively include linseed oil, camellia oil, sunflower oil, apricot oil, hazelnut oil, vegetable squalane oil, sasanqua oil, grapeseed oil, peanut oil, coconut oil, palm kernel oil, soybean oil, macadamia nut oil, avocado oil, safflower oil, sweet almond oil, apricot oil, corn oil, jojoba oil, olive oil, sesame oil, palm oil, eucalyptus oil, rosemary oil, lavender oil, pine oil, thyme oil, mint oil, cardamom oil, orange-blossom oil, bran oil, rice oil, rapeseed oil, castor oil, and mixtures thereof.
[0050] Suitable animal oils for use in the cosmetic composition of the present invention may nonexclusively include squalene, perhydrosqualene, squalane and mixtures thereof.
[0051] Suitable fatty alcohols may be C10-C26 alcohols, preferably monoalcohols.
[0052] Suitable fatty esters or esters of fatty alcohols for use in the cosmetic composition of the present invention may include fatty acid polyglycerides for example diglyceride, triglycerides, preferably triglyceryl esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids with a chain length of from 6 to 24, in particular 6 to 18 carbon atoms more preferably triethylhexanoin and caprylic capric triglyceride, dialkyl carbonate such as dioctyl carbonate and dicaprylyl carbonate, diisopropyl sebacate, ethyl laurate, butyl laurate, hexyl laurate, isohexyl laurate, isopropyl laurate, methyl myristate, ethyl myristate, butyl myristate, isobutyl myristate, isopropyl myritate, 2-octyldodecyl myristate, 2-ethylhexyl monococoate (or octyl monococoate) , ethyl palmitate, isopropyl palmitate, isobutyl palmitate, 2-ethylhexyl palmitate (or octyl palmitate) , butyl stearate, isopropyl stearate, isobutyl stearate, isocetyl stearate, isosteary isostearate, isopropyl isostearate, 2-ethylhexyl stearate (or octyl stearate) , decyl oleate, isononyl isononanoate, tridecyl neopentanoate, isocetyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate and isoarachidyl neopentanoate, and mixtures thereof.
[0053] In an embodiment, the suitable oils may be commercially available, for example as GTEH, GTEH-SD, 318 RC, CC, PS6, C24 RC, ININ, SN-1 SD, and ULTIMATE from BASF. All commercially available (from BASF) and cosmetically acceptable oils or mixtures thereof are suitable for use in the compositions of the present invention.
[0054] In the present invention, some waxes can be also used in the oil phase. Suitable waxes may include, waxes of natural origin, for instance beeswax, lanolin wax, Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax, Japan wax and sumach wax, montan wax, orange wax, lemon wax, ozokerite, and hydrogenated oils such as hydrogenated jojoba oil; waxes of synthetic origin, such as microcrystalline waxes, paraffin wax, polyethylene waxes, which is derived from the polymerization of ethylene; the waxes obtained by Fischer-Tropsch synthesis (Fischer-Tropsch waxes) and waxy copolymers, and also esters thereof; fatty acids or esters obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains, preferably C16 to C18 chains; silicone waxes; fluoro waxes; or a mixture thereof. Suitable waxes can be also solid linear ester derived from C6-C30 fatty acid, examples include stearyl stearate, tetradecyl tetradecanoate (INCI name: myristyl myristate) , cetyl myristate, stearyl myristate, myristyl palmitate, stearyl palmitate, myristyl stearate, cetyl stearate, stearyl stearate and cetyl palmitate, and mixtures thereof.
[0055] The multiple emulsion of the present invention, comprises at least one water-in-oil emulsifier, at least one oil-in-water emulsifier and at least one oil component, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, monoesters or diesters of polyethylene glycol (PEG) , and linear or branched silicone emulsifiers; wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters, monoesters or diesters of sulfosuccinate and a mixture thereof. In particular, the multiple emulsion is water-in-oil-in-water emulsion. Still preferably, in some embodiments of the present invention, the multiple emulsion comprises a water-in-oil emulsifier selected from the group consisting of monoesters or diesters of polyethylene glycol, polyglyceryl fatty acid ester comprising 2 to 6 glycerol units and a combination thereof; and an oil-in-water emulsifier selected from the group consisting of N-acyl amino acidic emulsifier, polyglyceryl-10 fatty acid esters, monoesters or diesters of sulfosuccinate and their mixture. preferably the water-in-oil emulsifier is present in an amount of 0.2 to 10%, preferably 0.3%to 8%, more preferably 0.3%to 6%based on the total weight of the multiple emulsion; preferably the oil component is present in an amount of 0.5%to 20%, preferably 0.5%to 15%based on the total weight of the multiple emulsion; preferably the oil-in-water emulsifier is present in an amount of 0.2%to 6.0%, preferably 0.4%to 4.0%, more preferably 0.4%to 3.0%based on the total weight of the multiple emulsion.
[0056] The multiple emulsion of the present invention may be used in any suitable personal care or cosmetic formulations. In an embodiment of the presently claimed invention. In a preferred embodiment, the personal care and / or cosmetic composition may further comprise additional nonionic, anionic emulsifiers.
[0057] In an embodiment of the present invention, the personal care and / or cosmetic composition further comprises at least one auxiliary agent selected form the group consisting of anti-wrinkle active agents, anti-acne active agents, emulsifiers, antioxidants, emollients, self-tanning active agents, skin lightening agents, sunscreen agents, UV absorbing agents, thickening agents, humectants, abrasives, absorbents, fragrances, buffering agents, opacifying agents, colorants, preservatives, fillers, pH adjusting agents and solvents.
[0058] In some embodiments of the present invention, the active agents are selected from the group consisting of anti-wrinkle agents like retinol, hyaluronic acid, ceramides, niacinamide, vitamin E, alpha hydroxy acids, anti -acne agents like clindamycin, benzamycin, benzoyl peroxide, and isotretinoin. In some embodiments of the present invention, the skin lightening agents are selected from the group consisting of tretinoin, hydroquinone, resorcinol, arbutin, kojic acid, azelaic acid, vitamin C, glutathione and alpha hydroxy acids.
[0059] In some embodiments of the present invention, the personal care and / or cosmetic composition may further comprise at least one thickening agent. The thickening agents can be selected from the group consisting of polymer thickening agents include non-ionic thickening agents and anionic thickening agents, or mixtures thereof. Suitable non-ionic thickening agents include polyacrylamide polymers, crosslinked poly (N-vinylpyrrolidones) , polysaccharides, natural or synthetic gums or polysaccharides, polyvinylpyrrolidone, and polyvinylalcohol. Suitable anionic thickening agents include polyacrylate, acrylic acid / ethyl acrylate copolymers, carboxyvinyl polymers and crosslinked copolymers of alkyl vinyl ethers and maleic anhydride.
[0060] In some embodiments of present invention, the thickening agents are selected from the group consisting of polysaccharides including cellulose, carboxymethyl hydroxyethylcellulose, cellulose acetate propionate carboxylate, hydroxyethylcellulose, hydroxyethyl ethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, methyl hydroxyethylcellulose, microcrystalline cellulose, sodium cellulose sulfate, and mixtures thereof, natural gums like acacia, agar, alginic acid, ammonium alginate, amylopectin, calcium alginate, calcium carrageenan, carnitine, carrageenan, dextrin, gelatin, gellan gum, guar gum, guar hydroxypropyltrimonium chloride, hectorite, hyaluronic acid, hydrated silica, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, kelp, locust bean gum, natto gum, potassium alginate, potassium carrageenan, propylene glycol alginate, sclerotium gum, sodium carboxymethyl dextran, sodium carrageenan, tragacanth gum, xanthan gum, and mixtures thereof, preferably the thickening agent is selected from the group consisting of xanthan gum, succinoglycan, gellan gum, pectin, alginates, starches, guars, acrylates, acrylate copolymers, carbomers and associative thickeners. According to any one embodiment of the present invention, the thickening agent is present in an amount in the range of 0.1 %to 5 %by weight, based on the total weight of the personal care and / or cosmetic composition.
[0061] In some embodiments of the present invention, the humectants are selected from the group consisting sodium 2-pyrrolidone-5-carboxylate (NaPCA) , guanidine, glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium) , lactic acid and lactate salts (e.g. ammonium and quaternary alkyl ammonium) , aloe vera in any of its variety of forms (e.g., aloe vera gel) , hyaluronic acid and derivatives thereof (e.g., salt derivatives such as sodium hyaluronate) , lactamide monoethanolamine, acetamide monoethanolamine, urea, panthenol and derivatives thereof, and mixtures thereof.
[0062] In some embodiments of the present invention, the buffering agents are selected from the group consisting of lactic acid, lactates, gluconic acid, glucono-delta-lactone, sodium gluconate and potassium gluconate, trisodium citrate, tripotassium citrate, sodium lactate, potassium lactate triethanolamine and sodium hydroxide.
[0063] In some embodiments of the present invention, the solvents are selected from the group consisting of polyhydric alcohol include glycerin, diglycerin, triglycerin, polyglycerin, polypropylene glycol, polyethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, glucose, maltose, sucrose, lactose, xylitose, xylitol, sorbitol, mannitol, maltitol, malbit, panthenol, pentaerythritol, and hyaluronic acid and its salts, water, ethanol and isopropanol. In some embodiments of the present invention, the solvents are selected from the group consisting of glycerin, water and ethanol.
[0064] According to any one of the invention embodiments, the personal care and / or cosmetic composition further comprises a carrier, or a mixture of such carriers, which are suitable for application to the skin and / or hair. Suitable carriers for use in topical compositions include water, C1-C6 alcohols, lower alkyl acetate and mixtures thereof. In some embodiments, the carriers can also contain a wide variety of additional materials such as acetone, hydrocarbons such as isobutane, hexane, decene, halogenated hydrocarbons and volatile silicones such as cyclomethicone. In one embodiment, water is present in the topical composition in an amount in the range of 5 %to 80 %by weight, based on the total weight of the composition.
[0065] The present invention is also related to a method for preparing a stable water-in-oil-in-water emulsion, comprising i) preparing a water-in-oil emulsion which comprises a step of mixing an oil phase comprising at least one water-in-oil emulsifier and at least one oil component with the first aqueous phase, and ii) mixing the water-in-oil emulsion obtained in step (i) with the second aqueous phase comprising at least one oil-in-water emulsifier, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, (mono) esters or diesters of polyethylene glycol, linear or branched silicone emulsifiers; wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters and monoesters or diester of sulfosuccinate. In some preferred embodiments, the step (ii) of mixing the water-in-oil emulsion obtained in the step (i) with the second aqueous phase further comprises a step of homogenization, wherein the homogenizing speed is between 3000 to 6000 rpm.
[0066] In abovementioned method, still preferably, the water-in-oil emulsifier is monoesters or diesters of polyethylene glycol, polyglyceryl fatty acid ester having 2 to 6 glycerol units or a mixture thereof, more preferably, the water-in-oil emulsifier is PEG-30 dipolyhydroxystearate, polyglyceryl-2 dipolyhydroxystearate, polyglyceryl-6 polyricinoleate or a mixture thereof, still more preferably, the water-in-oil emulsifier is PEG-30 dipolyhydroxystearate, or a combination of PEG-30 dipolyhydroxystearate and polyglyceryl-2 dipolyhydroxystearate. More preferably, the oil-in-water emulsifier is selected from the group consisting of N-acyl amino acid emulsifier, polyglyceryl-10 fatty acid esters, monoester or diesters of sulfosuccinate and their mixtures. More preferably, the oil-in-water emulsifier is selected from the group consisting of sodium stearoyl glutamate, sodium cocoyl glutamate, polyglyceryl-10 stearate, polyglyceryl-10 oleate, disodium cetearyl sulfosuccinate and a mixture thereof. Still more preferably the oil-in-water emulsifier is sodium stearoyl glutamate, sodium cocoyl glutamate, disodium cetearyl sulfosuccinate or their mixture.
[0067] EXAMPLES
[0068] The present invention is now further illustrated by reference to the following examples, however, the examples are used for the purpose of explanation and not intended to limit the scopes of the present invention.
[0069] RAW MATERIALS
[0070] The industrial products used in the examples are listed in the table below and are used as received.
[0071] Table 1. Industrial products used in the examples.
[0072] Propylene glycol, magnesium sulfate heptahydrate, glycerin, mineral oil (10#) , and triethanolamine are obtained as chemical reagents and are used as received.
[0073] PREPARATION METHODS
[0074] Manufacturing process
[0075] Unless specified otherwise, the formulations containing water-in-oil-in-water (W / O / W) structure were manufactured in the same way as described below.
[0076] 1. Prepare phase O: Mix each composition in phase O. Heat the mixture up to around 50-60℃. Stir phase O until it is uniform.
[0077] 2. Prepare phase W1: Mix the ingredients in W1 phase. Heat the mixture up to around 50-60℃. Stir phase W1 until it is uniform.
[0078] 3. Add phase W1 into phase O slowly under agitating. Then homogenize (5000 rpm, 3 minutes for 200 g sample) . This is the W1 / O emulsion. Set it aside for later use.
[0079] 4. Prepare phase W2: Mix the ingredients in W2 phase. Heat the mixture up to around 50-60℃. Stir phase W2 until it is uniform. Add polymers at last to avoid long time heating.
[0080] 5. Heat the W1 / O emulsion prepared in Step 3 to around 50-60℃. Avoid the long-time heating of the W1 / O emulsion.
[0081] 6. Add the W1 / O emulsion to phase W2 under stirring. Then homogenize (1500 rpm, 3 minutes for 200 g sample) .
[0082] 7. Cool the sample to room temperature.
[0083] EXAMPLE 1
[0084] This example demonstrates the importance of selection of water-in-oil emulsifiers in the formulation.
[0085] The compositions of Formulations 1 to 4 are listed in Table 2.
[0086] The weight ratios of all the ingredients in W1 / O emulsion in below formulations (Formulations 1 to 33) are calculated based on the active matters in the W1 / O emulsion. The weight ratios of the W1 / O emulsion and ingredients in outer aqueous (W2) phase in below formulations (Formulations 1 to 33) are calculated based on the active matters in the formulation.
[0087] TABLE 2: Compositions of Formulations 1 to 4.
[0088] The weight ratios of all the ingredient of Formulations 1 to 4 present in the multiple emulsions are shown in below Table 2-1. The weight ratios of the ingredients used in the Oil phase (O) and the Inner Aqueous phase (W1) are adjusted to the amounts present in the multiple emulsions (W1 / O / W2) .
[0089] Table 2-1
[0090] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0091] Formulation 1-4 all exhibited multiple emulsion structure under optical microscope, indicating that all of these four w / o emulsifiers PEG-30 Dipolyhydroxystearate, Polyglyceryl-2 Dipolyhydroxystearate, Cetyl PEG / PPG-10 / 1 Dimethicone, and Polyglyceryl-6 Polyricinoleate could be used to form multiple emulsion.
[0092] To optimize the dosage of W / O emulsifier in the formulation, formulations in Example 2 were prepared. Here, PEG-30 Dipolyhydroxystearate was selected as the W / O emulsifier.
[0093] EXAMPLE 2
[0094] This example demonstrates the appropriate dosage range of water-in-oil emulsifier in the formulation.
[0095] The compositions of Formulations 5 and 6 are listed in Table 3.
[0096] TABLE 3: Compositions of Formulations 5 and 6.
[0097] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0098] The results showed that multiple emulsion structure was observed for both Formulation 1 and 5.
[0099] Different types of emollient were further evaluated on the formation and stability of the multiple emulsion structure, the formulations in Table 4 were prepared.
[0100] EXAMPLE 3
[0101] This example further demonstrates the emollient compatibility of this W / O / W emulsion formulation structure.
[0102] The compositions of Formulations 7 to 13 are listed in Table 4.
[0103] TABLE 4: Compositions of Formulations 7 to 13
[0104] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0105] Microscope imaging results showed that all the formulations in Table 4 exhibited multiple emulsion structure, indicating that the multiple emulsion structure possesses good compatibility with all the oil components / emollients with various polarity and chemical structures.
[0106] EXAMPLE 4
[0107] This example demonstrates the importance of selection of oil-in-water emulsifiers in the multiple emulsion formulations.
[0108] The compositions of Formulations 14 to 20 are listed in Table 5.
[0109] TABLE 5: Compositions of Formulations 14 to 20.
[0110] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0111] Formulation 1, 14, 15, 18 could all exhibit multiple emulsion structure under optical microscope, indicating that all of these O / W emulsifiers (Polysorbate 80, Disodium Cetearyl Sulfosuccinate, Sodium Stearoyl Glutamate, and Polyglyceryl-10 stearate) could be used to form multiple emulsion. In addition, the microscope image of formulation 19 and 20 exhibited multiple emulsion structure as well, giving the insight that the O / W emulsifier pair (Polyglyceryl-10 Oleate paired with Cetearyl Glucoside) was also able to form multiple emulsion structure. By comparison, the microscope image of formulation 16 and 17 exhibited non-spherical morphology, indicating these combinations cannot stabilize the inner W / O emulsion well.
[0112] To further optimize the dosage of O / W emulsifier in the formulation, formulations in Example 5 were prepared. Here, the inventors select Sodium Stearoyl Glutamate as the O / W emulsifier.
[0113] EXAMPLE 5
[0114] This example demonstrates the appropriate dosage range of oil-in-water emulsifier in the formulation.
[0115] The compositions of Formulations 21 and 22 are listed in Table 6.
[0116] TABLE 6: Compositions of Formulations 21 and 22.
[0117] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0118] The results showed that all of the formulations 15, 21, and 22 exhibited multiple emulsion structure and passed the 3-month stability test. Thus, the dosage of Sodium Stearoyl Glutamate is recommended to lie in the range between 0.4 to 1.0%.
[0119] EXAMPLE 6
[0120] This example demonstrates the polymer compatibility in the formulation.
[0121] The compositions of Formulations 23 and 24 are listed in Table 7.
[0122] Table 7: Compositions of Formulations 23 and 24
[0123] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0124] The results showed that all of the formulations 15, 23, and 24 exhibited multiple emulsion structure and passed the 3-month stability test, indicating that the multiple emulsion structure possesses good compatibility with various polymers.
[0125] EXAMPLE 7
[0126] This example demonstrates the appropriate range of W1 / O content in the formulation.
[0127] The compositions of Formulations 25 and 26 are listed in Table 8.
[0128] Table 8: Compositions of Formulations 25 and 26
[0129] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0130] The results showed that all of the Formulations 15, 25, and 26 exhibited multiple emulsion structure and passed the 3-month stability test, indicating that the W1 / O content in the formulation could range between 20%and 60%.
[0131] EXAMPLE 8
[0132] This example demonstrates the manufacturing process of the formulations.
[0133] The compositions and manufacturing process of Formulations 27 to 31 are listed in Table 9.
[0134] Table 9: Compositions and manufacturing process of Formulations 27 to 31
[0135] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 11. Besides, formulation stability was also recorded in Table 13.
[0136] Except for the homogenizing speed and duration of Step 6 in the manufacturing process, other steps are remained the same as the process mentioned above.
[0137] The results showed that formulations 27-30 exhibited multiple emulsion structure and passed the 3-month stability test and the homogenizing speed can be between 3000-6000 rpm and homogenizing duration can be between 3 to 10 min, without compromising the structure and stability of the multiple emulsion.
[0138] EXAMPLE 9
[0139] This example demonstrates the application of the formulation technology.
[0140] The compositions of Formulations 32 and 33 are listed in Table 10.
[0141] Table 10: Compositions of Formulations 32 and 33.
[0142] The micro-structure of each formulation was characterized by an optical microscope of which the results were shown in Table 12. Besides, formulation stability was also recorded in Table 13.
[0143] The results showed that formulations 32 and 33 exhibited multiple emulsion structure and passed the 3-month stability test, indicating that both water-soluble and oil-soluble actives could be encapsulated in the multiple emulsion.
[0144] These application formulations possess multiple structures after 3-month storage at 50℃, 40 ℃ and 25℃, indicating the stable structure of this multiple emulsion.
[0145] Table 12: Micro-structure of Formulation 32 and 33.
[0146] Stability of the samples
[0147] Unless specified otherwise, the stability of the formulations was evaluated by storing each of the formulations at 50℃, 40℃, 25℃, and 5℃ for 12 weeks, respectively, and its stability was rated according to the following criteria.
[0148] The stability test results show that the Formulations 14, 15, 20-30 and 32-33 lead to surprisingly improved stability, all these Formulations passed 3-month stability tests at 5 ℃, 25 ℃, 40 ℃, 50 ℃.
Claims
1.A multiple emulsion composition, comprises at least one water-in-oil emulsifier, at least one oil-in-water emulsifier and at least one oil component;wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid esters comprising 2 to 6 glycerol units, esters or diesters of polyethylene glycol, linear or branched silicone emulsifier and a mixture thereof;wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, alkyl glucoside, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters, monoesters or diesters of sulfosuccinate and a mixture thereof;wherein the multiple emulsion is water-in-oil-in-water emulsion.2.The multiple emulsion according to claim 1, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, ester or diester of polyethylene glycol and a mixture thereof, preferably PEG-30 dipolyhydroxystearate, polyglyceryl polyhydroxystearate having 2 to 6 glycerol units, polyglyceryl dipolyhydroxystearate having 2 to 6 glycerol units, polyglyceryl distearate / diisostearate having 2 to 6 glycerol units, polyglyceryl polyricinoleate having 2 to 6 glycerol units and their mixture;preferably, the water-in-oil emulsifier is selected from the group consisting of PEG-30 dipolyhydroxystearate, polyglyceryl-2 dipolyhydroxystearate, polyglyceryl-6 polyricinoleate and a mixture thereof;more preferably the water-in-oil emulsifier is selected from the group consisting of PEG-30 dipolyhydroxystearate and a combination of PEG-30 dipolyhydroxystearate and polyglyceryl-2 dihydroxystearate.3.The multiple emulsion according to claim 1, wherein the oil-in-water emulsifier is selected from the group consisting of N-acyl amino acid emulsifier, polyglyceryl-10 fatty acid esters, monoesters or diesters of sulfosuccinate and a mixture thereof;preferably the oil-in-water emulsifier is selected from the group consisting of sodium stearoyl glutamate, sodium cocoyl glutamate, polyglyceryl-10 stearate, polyglyceryl-10 oleate, disodium cetearyl sulfosuccinate and a mixture thereof;more preferably, the oil-in-water emulsifier is sodium stearoyl glutamate, disodium cetearyl sulfosuccinate or their mixture.4.The multiple emulsion according to any one of claims 1 to 3, wherein the water-in-oil emulsifier is present in an amount of 0.2%to 10%based on the total weight of the emulsion composition; wherein the oil-in-water emulsifier is present in an amount of 0.2%to 6.0%based on the total weight of the emulsion composition.5.The multiple emulsion according to any one of claims 1 to 4, further comprises one or more auxiliary agents selected form the group consisting of anti-wrinkle active agents, anti-acne active agents, emulsifiers, antioxidants, emollients, self-tanning active agents, skin lightening agents, sunscreen agents, UV absorbing agents, thickening agents, humectants, abrasives, absorbents, fragrances, buffering agents, opacifying agents, colorants, preservatives, fillers, pH adjusting agents and solvents.6.The multiple emulsion according to any one of claims 1 to 5 is used in a personal care or cosmetic formulation.7.A method for preparing a stable water-in-oil-in-water emulsion, comprising i) preparing a water-in-oil emulsion which comprises a step of mixing an oil phase comprising at least one water-in-oil emulsifier and at least one oil component with the first aqueous phase, and ii) mixing the water-in-oil emulsion obtained in step (i) with the second aqueous phase comprising at least one oil-in-water emulsifier, wherein the water-in-oil emulsifier is selected from the group consisting of polyglyceryl fatty acid ester comprising 2 to 6 glycerol units, (mono) esters or diesters of polyethylene glycol, linear or branched silicone emulsifiers; wherein the oil-in-water emulsifier is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, N-acyl amino acid emulsifiers, polyglycerol-10 fatty acid esters and monoesters or diester of sulfosuccinate.8.The method for preparing a stable water-in-oil-in-water emulsion, wherein the step (ii) of mixing the water-in-oil emulsion obtained in the step (i) with the second aqueous phase further comprises a step of homogenization, wherein the homogenizing speed is between 3000 to 6000 rpm.