CN108367177B - High internal phase emulsion compositions for improving the SPF and rheology of the compositions - Google Patents

Abstract

The present invention relates to sunscreen cosmetic compositions, in particular sunscreen cosmetic compositions in the form of oil-in-water-in-oil (O/W/O) multiple emulsions having an external oil phase, a high internal aqueous phase dispersed in the external oil phase and an internal oil phase dispersed in the high internal aqueous phase, comprising: (a) at least one surfactant having an HLB of less than 13; (b) at least one oil; (c) at least one UV filter; and (d) water; wherein the high internal aqueous phase is present in an amount of 60 wt% or more based on the total weight of the composition and the internal oil phase has a droplet size of less than 200 nanometers.

Description

High internal phase emulsion compositions for improving the SPF and rheology of the compositions

Technical Field

The present invention relates to cosmetic compositions for keratin materials such as the skin, in particular in the form of oil-in-water-in-oil (O/W/O) multiple emulsions.

Background

Emulsion compositions are commonly used in the cosmetic and dermatological fields because they are pleasant to use due to the refreshing feel that the aqueous phase can provide. The emulsions may be in the form of oil-in-water emulsions (O/W emulsions), water-in-oil emulsions (W/O emulsions), water-in-oil-in-water multiple emulsions (W/O/W emulsions), and oil-in-water-in-oil multiple emulsions (O/W/O emulsions). To date, some prior art documents disclose compositions in the form of multiple emulsions.

For example, US-A-5,814,321 discloses A water-in-oil-in-water oil adjuvant vaccine comprising A water-in-oil adjuvant phase comprising from 30 to 90% by weight of an oil phase A), from 0.5 to 30% by weight of an emulsifier B comprising A non-ionic surfactant which is A partial ester derived from A polyol having at least 3 hydroxyl groups and A fatty acid, and A hydroxy fatty acid triglyceride C) wherein the hydroxyl groups of the fatty acid are polyoxyethylenated with from 20 to 60 oxyethylene units, E) from 0.01 to 10% by weight of an amino acid or salt thereof and from 0.01 to 10% by weight of A non-reducing sugar or sugar alcohol having at least 5 hydroxyl groups in the molecule and from 5 to 65% by weight of an aqueous phase D) which contains A biologically acceptable and effective amount of an antigen; and an external aqueous phase F) comprising from 0.2 to 20% by weight of an emulsifier comprising a nonionic surfactant.

High internal water phase W/O emulsions comprising large amounts of water are also known in the cosmetic and dermatological field.

For example, US-A-2003/0064046 discloses A high internal water phase water-in-oil emulsion cosmetic composition comprising (A) one or more crosslinkable polyether-modified silicones having A specific structure in an amount of 0.1 to 10.0% by weight and (B) one or more polyether-modified silicones having A specific structure, and having an aqueous phase component content of at least 50% by weight.

Further, JP-A-2010-132620 discloses ｃA water-in-oil type emulsion cosmetic which contains the following components (A), (B), (C) and (D) and satisfies the following requirements (1) and (2). The components are as follows: (A) one or two or more selected from the group consisting of glycerol monooleate, glycerol monoisostearate and polyoxyethylene glycerol monostearate; (B) an aqueous component; (C) an oily component; and (D) a powder. The method comprises the following steps: (1) an internal water ratio obtained by dividing the sum of the masses of the aqueous components of component (B) by the sum of the masses of the aqueous components of component (a) and component (B) and the oily components of component (C) is at least 50%; (2) for component (a), the purity of glycerol monooleate is at least 90 mass% of the total amount of glycerol monooleate, glycerol dioleate and glycerol trioleate; the purity of the glyceryl monoisostearate is at least 90 mass% of the total amount of the glyceryl monoisostearate, the glyceryl diisostearate and the glyceryl triisostearate; and the purity of the polyoxyethylene glyceryl monostearate is at least 90 mass% of the total amount of the polyoxyethylene glyceryl monostearate, the polyoxyethylene glyceryl distearate and the polyoxyethylene glyceryl tristearate.

These emulsion compositions are often used in the sunscreen cosmetics of keratin materials such as the skin. For sunscreen products, good UV protection is a key function.

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide O/W/O multiple emulsion compositions, preferably cosmetic sunscreen O/W/O multiple emulsion compositions, for keratin materials such as the skin, which have improved UV protection.

The above object of the present invention can be achieved by a composition in the form of an oil-in-water-in-oil multiple emulsion (O/W/O type emulsion) having an external oil phase, a high internal aqueous phase in the external oil phase and an internal oil phase dispersed in the high internal aqueous phase in the form of microdroplets, said composition comprising:

(a) at least one surfactant having an HLB of less than 13;

(b) at least one oil;

(c) at least one UV filter; and

(d) the amount of water is controlled by the amount of water,

wherein the amount of the high internal aqueous phase is 60 wt% or more of the total weight of the composition and the size of the droplets of the internal oil phase is less than 200 nanometers.

The droplets of the internal oil phase may have a size of less than 150 nm, preferably less than 120 nm.

The amount of the high internal aqueous phase may be from 60 to 99 wt%, preferably from 70 to 95 wt%, more preferably from 80 to 90 wt% of the total weight of the composition.

The HLB value of the (a) surfactant may be less than 12, preferably less than 10.

The viscosity of the composition may be from 1 to 500 Pa ∙ s, preferably from 10 to 400 Pa ∙ s, more preferably from 50 to 350 Pa ∙ s, still more preferably from 100 to 300 Pa ∙ s at 25 ℃.

The amount of the internal oil phase may be from 0.5 to 15 wt%, preferably from 1 to 10 wt%, more preferably from 2 to 5 wt% of the total weight of the composition.

The oil (b) in the inner oil phase may be selected from ester oils such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglycerides such as decyl octyl glyceride, sarcosinates such as isopropyl lauroyl sarcosinate, hydrocarbon oils such as isohexadecane, and mineral oils such as paraffin.

The (a) surfactant may be selected from nonionic surfactants which are monoesters of polyhydric alcohols and fatty acids containing 8 to 24 carbon atoms, wherein the polyhydric alcohols are preferably selected from glycerol, sorbitan and diglycerol and the fatty acids are preferably selected from esters of isolauric acid and oleic acid, in particular polyglycerol-2 laurate, glycerol laurate, sorbitan oleate and glycerol oleate, and silicone surfactants which are preferably polyether-modified polydimethylsiloxanes, such as PEG/PPG-18/18 polydimethylsiloxane, and polyether and alkyl-modified polydimethylsiloxane crosspolymers, such as PEG-15/lauryl polydimethylsiloxane crosspolymer; and an anionic surfactant which is a polyoxyethylene alkyl ether carboxylic acid such as polyoxyethylene (3) to (17) lauryl ether carboxylic acids.

The amount of the (a) surfactant may be 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the total weight of the composition.

The amount of the external oil phase may be from 1 to 40 wt%, preferably from 2 to 30 wt%, more preferably from 5 to 20 wt% of the total weight of the composition.

The oil (b) in the external oil phase may be selected from ester oils such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglycerides such as decyl octyl glyceride, sarcosinates such as isopropyl lauroyl sarcosinate, hydrocarbon oils such as isohexadecane, mineral oils such as paraffin, and silicone oils.

The composition may comprise less than 10 wt%, preferably less than 5 wt% of water-soluble solvent relative to the total weight of the composition.

The (c) UV filter may include hydrophilic and hydrophobic UV filters, and the amount of the (c) UV filter may be 1 to 40 wt%, preferably 2 to 30 wt%, more preferably 5 to 20 wt% of the total weight of the composition.

The invention also relates to a cosmetic process for keratin materials such as the skin, comprising the following steps: the composition according to the invention is applied to the keratin materials.

The invention also relates to a method for protecting keratinous materials from ultraviolet radiation comprising applying to the keratinous materials a composition according to the invention.

Brief Description of Drawings

FIG. 1 shows an example of a schematic view of an O/W/O emulsion of the present invention.

Best mode for carrying out the invention

After diligent research, the present inventors have found that the incorporation of a nanoscale oil phase into the aqueous phase in sunscreen O/W/O emulsion compositions surprisingly improves UV protection.

Furthermore, the present inventors have found that the use of a nanoscale oil phase in an O/W/O emulsion improves its stability.

Thus, the cosmetic composition according to the invention, preferably for keratin materials, preferably the skin, is an O/W/O emulsion having an external oil phase, a high internal aqueous phase in the external oil phase and an internal oil phase dispersed in the high internal aqueous phase, comprising:

(a) at least one surfactant having an HLB of less than 13;

(b) at least one oil;

(c) at least one UV filter; and

(d) the amount of water is controlled by the amount of water,

wherein the high internal aqueous phase is present in an amount of 60 wt% or more based on the total weight of the composition and the internal oil phase has a size of less than 200 nanometers.

The compositions according to the invention may exhibit improved UV protection.

The compositions according to the invention are described in detail below.

[ composition ]

The composition according to the invention is in the form of an O/W/O emulsion having an external oil phase, a high internal aqueous phase in the external oil phase and an internal oil phase dispersed in the high internal aqueous phase. The outer oil phase forms a continuous oil phase. The high internal aqueous phase is in an amount of 60% by weight or more of the total weight of the composition. The inner oil phase forms nano-scale droplets less than 200 nanometers in size. The composition comprises (a) at least one surfactant having an HLB of less than 13, (b) at least one oil, (c) at least one UV filter; and (d) water.

The compositions according to the invention are preferably cosmetic compositions for keratin materials, such as the skin, in particular cosmetic sunscreen compositions.

The compositions according to the invention may exhibit improved UV protection. Furthermore, the composition according to the invention may have good stability even if it does not comprise any thickener or only comprises traces of thickener.

First, the O/W/O structure of the composition according to the present invention is explained below.

(external oil phase)

The external oil phase in the O/W/O emulsion of the present invention is a continuous oil phase and comprises (b) at least one oil. In addition to the (b) oil, the external oil phase may also contain other hydrophobic/oil-soluble ingredients, such as hydrophobic UV filters and oil-soluble cosmetic active ingredients.

The amount of the external oil phase is not limited, but is generally 1 to 40% by weight, preferably 2 to 30% by weight, more preferably 5 to 20% by weight, based on the total weight of the composition.

(high internal Water phase)

The high internal aqueous phase in the O/W/O emulsion of the invention comprises (d) water and other hydrophilic/water-soluble ingredients, such as hydrophilic UV filters, cosmetically acceptable hydrophilic organic solvents (water-soluble solvents), thickeners and neutralizing agents.

The high internal aqueous phase provides a High Internal Phase Emulsion (HIPE). Due to the high amount of aqueous phase, in general, the droplet shape of the aqueous phase becomes polyhedral. Furthermore, the high amount of aqueous phase may comprise a high amount of water, which may thus provide the composition according to the invention with a refreshing feel when it is applied to the skin.

The high internal aqueous phase forms micron-sized droplets. The size of the internal aqueous phase may be 1 micron or greater, preferably less than 20 microns, more preferably less than 10 microns. The size of the aqueous droplets can be measured using, for example, a particle size analyzer (Vasco, Cordoun Technologies).

The amount of the high internal aqueous phase is 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more based on the total weight of the composition. The upper limit of the amount of the high internal aqueous phase is not limited, but is generally less than 99% by weight, preferably less than 95% by weight, more preferably less than 90% by weight, of the total weight of the composition.

(internal oil phase)

The inner oil phase in the O/W/O emulsion of the present invention forms droplets dispersed in the high inner water phase and comprises (b) at least one oil. In addition to the (b) oil, the inner oil phase may also comprise other hydrophobic/oil-soluble ingredients, such as hydrophobic UV filters and oil-soluble cosmetic active ingredients.

The inner oil phase forms nano-scale droplets. The droplets of the inner oil phase have a size of less than 200 nm, preferably less than 150 nm, more preferably less than 120 nm. In general, the droplets of the internal oil phase have a size of more than 1 nm, preferably more than 5 nm, more preferably more than 10 nm. The size of the droplets of the oil phase is a number average particle size and can be measured using, for example, a particle size analyzer (Vasco, Cordoun Technologies).

The amount of the internal oil phase is not limited, but is generally 0.5 to 15% by weight, preferably 1 to 10% by weight, more preferably 2 to 5% by weight, based on the total weight of the composition.

Surprisingly, the inventors found that nanoscale internal oil droplets in such an O/W/O emulsion can improve the UV protection effect of the composition according to the invention.

Furthermore, the inventors have found that the nanoscale internal oil droplets in the O/W/O emulsion can improve the stability of the composition, as it can provide the composition with viscosity. Thus, the composition according to the invention is stable even if it comprises substantially no thickener or only trace thickeners.

In one embodiment of the invention, the composition according to the invention is substantially free of thickeners, preferably comprises less than 5% by weight, more preferably less than 1% by weight of thickeners, relative to the total weight of the composition.

The viscosity of the composition according to the present invention is not particularly limited. The viscosity can be measured at 25 ℃ using a rheometer, such as a DHR2 rheometer (TA instrument) with parallel plate geometry. The viscosity of the composition excluding any thickener may preferably be, for example, from 1 to 500 Pa ∙ s, preferably from 10 to 400 Pa ∙ s, more preferably from 50 to 350 Pa ∙ s, still more preferably from 100 to 300 Pa ∙ s at 25 ℃ and from 0.01 to 10001/s. Furthermore, the composition may have newtonian properties.

The stability of the composition according to the invention can also be characterized by its high yield stress value. Yield stress, as used herein, refers to the maximum stress up to which the material retains its structure. Beyond this stress, the material tends to flow or destabilize. In other words, high yield stress contributes to improved stability. The high yield stress value can be calculated, for example, from a shear rate vs. stress curve measured at 25 ℃ using a rheometer, such as a DHR2 rheometer (TA instrument) with parallel plate geometry. The yield stress value of the O/W/O multiple emulsion according to the invention may preferably be greater than 30 Pa, preferably greater than 50 Pa, more preferably greater than 70 Pa, for example at 25 ℃ and from 0.01 to 10001/s.

FIG. 1 shows an example of a schematic of an O/W/O emulsion of the present invention. This figure is for reference only and does not limit the scope of the invention. As shown in fig. 1, the emulsion of the present invention has a multiple architecture, the outer oil phase forming the continuous oil phase in the emulsion, the high inner water phase forming polyhedral droplets in the outer oil phase, and the inner oil phase forming nanoscale droplets dispersed in the high inner water phase.

Next, the components of the composition according to the present invention are explained below.

(a) Surface active agent

The composition according to the invention comprises (a) at least one surfactant having an HLB (hydrophilic lipophilic balance) of less than 13. Two or more (a) surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used.

The term HLB ("hydrophilic-lipophilic balance") is well known to those skilled in the art and refers to the hydrophilic-lipophilic balance of a surfactant. The HLB or hydrophile-lipophile balance of the surfactant or surfactants used in accordance with the invention is a publicationJ. HLB according to Griffin as defined in Soc, cosm, chem, 1954 (Vol 5), page 249-256, or by Experimental and as author F.Publication by Puisieux and M. Seiller, entitled Galenica 5 Les sys mes dispers systems]Volume I-Agents de surfaces et mechanics [ Surface Agents and mechanisms ]]Section IV-notes de HLB et de HLB critique [ notes of HLB and of critical HLB]Page 153-194 paragraph 1.1.2. D determination de HLB par voie exp ementational [ Experimental determination of HLB]HLB as determined as described in page 164-180.

Preferably, the (a) surfactant used in the composition has an HLB value of less than 12, more preferably less than 10. If two or more surfactants are used, the HLB value can be determined by a weighted average of the HLB values of all the surfactants.

Calculation of the HLB value is preferably considered. The calculated HLB is defined as the following factor:

calculated HLB = 20 × molar mass of hydrophilic moiety/total molar mass

The lipophilic portion of the surfactant is preferably composed of carbon and hydrogen atoms or silicon and hydrogen atoms.

The surfactant used in the composition according to the invention may be selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. (a) The surfactant is preferably selected from the group consisting of nonionic surfactants and anionic surfactants.

Nonionic surfactant

The nonionic Surfactants are compounds known per se (see, for example, "Handbook of Surfactants", M.R. Porter, Blackie & Son published (Glasgow and London), 1991, page 116-.

Thus, (a) the surfactant may for example be selected from the group consisting of alcohols, α -diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerinated and having at least one fatty chain comprising for example from 8 to 30 carbon atoms, the number of oxyethylene or oxypropylene groups may be from 2 to 50 and the number of glycerinated groups may be from 1 to 30.

(a) The surfactant may preferably be selected from mono-oxyalkylene, polyoxyalkylenated, mono-glycerated or polyglycerated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units or combinations thereof, preferably oxyethylene units.

Examples of mono-or poly-oxyalkylene nonionic surfactants which may be mentioned include:

(C) mono-or poly-oxyalkylenated₈-C₂₄) An alkyl phenol, a phenol derivative,

saturated or unsaturated, linear or branched, mono-or polyoxyalkylenated C₈-C₃₀The alcohol is added into the mixture of the alcohol,

saturated or unsaturated, linear or branched, mono-or polyoxyalkylenated C₈-C₃₀The acid amide,

saturated or unsaturated, linear or branched C₈-C₃₀Esters of an acid and a polyalkylene glycol,

saturated or unsaturated, linear or branched C₈-C₃₀Mono-or polyoxyalkylene esters of acids and sorbitol,

saturated or unsaturated, mono-or polyoxyalkylenated vegetable oils,

especially condensates of ethylene oxide and/or propylene oxide, alone or in mixtures.

The surfactant preferably contains from 1 to 100, most preferably from 2 to 50, moles of oxyethylene and/or oxypropylene. Advantageously, the nonionic surfactant does not contain any oxypropylene units.

According to one embodiment of the invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty alcohols (polyethylene glycol ethers of fatty alcohols) and polyoxyethylenated fatty esters (polyethylene glycol esters of fatty acids).

Mention may be made of polyoxyethylenated fatty alcohols (or C)₈-C₃₀Alcohols) include adducts of ethylene oxide with lauryl alcohol, especially those containing from 7 to 50 oxyethylene units, more especially those containing from 6 to 12 oxyethylene units (CTFA name laureth-7 to laureth-12); adducts of ethylene oxide with behenyl alcohol, especially those containing from 5 to 50 oxyethylene units (CTFA name beheneth-5 to beheneth-50); adducts of ethylene oxide with cetostearyl alcohol (mixtures of cetostearyl and stearyl alcohols), especially those containing from 7 to 30 oxyethylene units (CTFA name ceteareth-7 to ceteareth-30); adducts of ethylene oxide with cetyl alcohol, especially those containing from 7 to 30 oxyethylene units (CTFA name ceteth-7 to ceteth-30); adducts of ethylene oxide with stearyl alcohol, especially those containing from 7 to 30 oxyethylene units (CTFA name steareth-7 to steareth-30); adducts of ethylene oxide with isostearyl alcohols, especially those containing from 8 to 50 oxyethylene units (CTFA name isosteareth-8 to isosteareth-50); and mixtures thereof.

As examples of mono-or polyglycerolated nonionic surfactants, preference is given to using mono-or polyglycerolated C₈-C₄₀An alcohol.

In particular, mono-or polyglycerolated C₈-C₄₀The alcohol corresponds to the formula:

RO-[CH₂-CH(CH₂OH)-O]_m-H or RO- [ CH (CH)₂OH)-CH₂O]_m-H

Wherein R represents a linear or branched C₈-C₄₀Preferably C₈-C₃₀Alkyl or alkenyl, and m represents 1 to 30, preferably 1.5 toA value of 10.

As examples of compounds suitable for use in the context of the present invention, mention may be made of lauryl alcohol containing 4 moles of glycerol (INCI name: polyglyceryl-4 lauryl ether), lauryl alcohol containing 2 moles of glycerol (INCI name: polyglyceryl-2 lauryl ether), lauryl alcohol containing 1.5 moles of glycerol, oleyl alcohol containing 4 moles of glycerol (INCI name: polyglyceryl-4 oleyl ether), oleyl alcohol containing 2 moles of glycerol (INCI name: polyglyceryl-2 oleyl ether), cetearyl alcohol containing 2 moles of glycerol, cetearyl alcohol containing 6 moles of glycerol, oleyl alcohol cetyl alcohol containing 6 moles of glycerol, and stearyl alcohol containing 6 moles of glycerol.

The alcohol may represent a mixture of alcohols, just as the value of m represents a statistical value, which means that several polyglycerolated fatty alcohols may coexist in the form of a mixture in commercial products.

Among the mono-or polyglycerolated alcohols, C containing 1 mol of glycerol is preferably used₈/C₁₀Alcohol, C containing 1 mol of glycerin₁₀/C₁₂Alcohol and C containing 1.5 moles of Glycerol₁₂An alcohol.

Mono-or polyglycerolated C₈-C₄₀The fatty esters may conform to the formula:

R’O-[CH₂-CH(CH₂OR’’’)-O]_m-R ' ' or R ' O- [ CH (CH)₂OR’’’)-CH₂O]_m-R’’

Wherein R ', R' 'and R' '' each independently represent a hydrogen atom or a linear or branched C₈-C₄₀Preferably C₈-C₃₀An alkyl-CO-or alkenyl-CO-group, with the proviso that at least one of R ', R' 'and R' '' is not a hydrogen atom and m represents a number from 1 to 30, preferably from 1.5 to 10.

Examples of polyoxyethylenated fatty esters which may be mentioned include the adducts of ethylene oxide with esters of lauric, palmitic, stearic or behenic acid and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (CTFA name: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA name: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA name: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate (palmitostearate); PEG-9 to PEG-50 behenate (CTFA name: PEG-9 to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG-100 stearate); and mixtures thereof.

According to one embodiment of the invention, the nonionic surfactant may be chosen from esters of polyhydric alcohols with fatty acids having a saturated or unsaturated chain containing, for example, from 8 to 24 carbon atoms, preferably from 12 to 22 carbon atoms, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, more preferably from 10 to 100, oxyalkylene units, such as one or more C₈-C₂₄Preferably C₁₂-C₂₂Mono-or polyglycerol esters of fatty acids and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, more preferably from 10 to 100, oxyalkylene units; one or more C₈-C₂₄Preferably C₁₂-C₂₂Sorbitol esters of fatty acids and polyoxyalkylene derivatives thereof, preferably containing from 10 to 200, more preferably from 10 to 100 oxyalkylene units; one or more C₈-C₂₄Preferably C₁₂-C₂₂Sugar (sucrose, maltose, glucose, fructose, sorbitol, sorbitan and/or alkyl sugar (alkyl sugar)) esters of fatty acids and polyoxyalkylene derivatives thereof, preferably containing from 10 to 200, more preferably from 10 to 100, oxyalkylene units; ethers of fatty alcohols; sugar and one or more C₈-C₂₄Preferably C₁₂-C₂₂Ethers of fatty alcohols; and mixtures thereof.

As glycerides of fatty acids, mention may be made of glycerol laurate (mono-, di-and/or trilaurates), in particular glycerol monolaurate (CTFA name: glycerol laurate, sold by Taiyo Kagaku), glycerol stearate (glycerol mono-, di-and/or tristearate) (CTFA name: glycerol stearate), glycerol monooleate (CTFA name: glycerol oleate, sold by Taiyo Kagaku) or glycerol ricinoleate and mixtures thereof, as polyoxyalkylenated derivatives thereof there may be mentioned mono-, di-or triesters of fatty acids with polyoxyalkylenated glycerols (mono-, di-or triesters of fatty acids with polyalkylene glycol ethers of glycerol), preferably polyoxyethylenated glycerol stearates (mono =, di-and/or tristearates), such as PEG-20 glycerol stearate (mono-, di-and/or tristearate), Di-and/or tristearate).

Mixtures of these surfactants may also be used, for example the products sold by Uniqema under the name ARLACEL 165 containing glyceryl stearate and PEG-100 stearate, and the products sold by Goldschmidt under the name TEGIN containing glyceryl stearate (glyceryl monostearate and glyceryl distearate) and potassium stearate (CTFA name: glyceryl stearate SE).

As the polyglycerol ester of (a) fatty acids, there may be mentioned products containing 2 to 10 glycerol units, such as polyglycerol monolaurate, in particular diglycerol monolaurate (CTFA name: polyglycerol-2 laurate sold by Taiyo Kagaku), oleate, myristate, caprylate or stearate comprising 2 to 10 glycerol units, polyglycerol mono (iso) stearate comprising 2 to 10 glycerol units, polyglycerol dioleate comprising 2 to 10 glycerol units, polyglycerol dilaurate comprising 2 to 10 glycerol units, polyglycerol dimyristate comprising 2 to 10 glycerol units, polyglycerol trimyristate comprising 2 to 10 glycerol units, polyglycerol trioleate comprising 2 to 10 glycerol units and polyglycerol tricaprylate comprising 2 to 10 glycerol units.

C₈-C₂₄The sorbitan esters of fatty acids and their polyoxyalkylene derivatives may be selected from sorbitan palmitate, sorbitan isostearate, sorbitan oleate, sorbitan stearate, sorbitan sesquioleate, sorbitan laurate, sorbitan caprylate and sorbitan trioleate, and esters of fatty acids and alkoxylated sorbitan containing, for example, 20 to 100 EO, such as sorbitan monooleate (CTFA name: sorbitan oleate, sold by Croda), sorbitan monostearate sold by ICI under the name Span 60 (CTFA name: sorbitan stearate), sorbitan sold by ICI under the name Span 40Anhydride monopalmitate (CTFA name: sorbitan palmitate) and sorbitan tristearate 20 EO (CTFA name: polysorbate 65) sold by ICI corporation under the name Tween 65, polyethylene sorbitan trioleate (polysorbate 85) or compounds sold by Uniqema under the name Tween 20 or Tween 60.

As esters of fatty acids and glucose or alkylglucose, mention may be made of glucose palmitate, alkylglucose sesquistearate, such as methyl glucose sesquistearate, alkylglucose palmitate, such as methyl glucose palmitate or ethylglucose palmitate, fatty esters of methyl glucoside, diesters of methyl glucoside and oleic acid (CTFA name: methyl glucose dioleate), mixed esters of methyl glucoside and oleic acid/hydroxystearic acid mixtures (CTFA name: methyl glucose dioleate/hydroxystearate), esters of methyl glucoside and isostearic acid (CTFA name: methyl glucose isostearate), esters of methyl glucoside and lauric acid (CTFA name: methyl glucose laurate), mixtures of monoesters and diesters of methyl glucoside and isostearic acid (CTFA name: methyl glucose sesquiisostearate), Mixtures of mono-and diesters of methylglucoside and stearic acid (CTFA name: methylglucose sesquistearate), in particular the product sold by AMERCHOL under the name Glucate SS, and mixtures thereof.

As ethoxylated ethers of fatty acids and of glucose or of alkylglucose, mention may be made, for example, of ethoxylated ethers of fatty acids and of methylglucose, in particular of polyethylene glycol ethers of the diesters of methylglucose and of stearic acid containing about 20 moles of oxyethylene (CTFA name: PEG-20 methylglucose distearate), such as the one sold under the name Glucam E-20 distearate by AMERCHOL, of polyethylene glycol ethers of the mixture of monoesters and diesters of methylglucose and of stearic acid containing about 20 moles of oxyethylene (CTFA name: PEG-20 methylglucose sesquistearate), in particular of AMERCHOL sold under the name Glucamate SSE-20 and of GOLDSCHMIDT sold under the name Grillose PSE-20, and mixtures thereof.

As sucrose esters, mention may be made, for example, of sucrose palmitostearate, sucrose stearate and sucrose monolaurate.

As sugar ethers, use may be made of alkyl polyglucosides, for example sugars and C may be mentioned in particular_8-C₂₄Ethers of fatty alcohols including decyl glucosides such as the product sold by Kao Chemicals under the name MYDOL 10, the product sold by Henkel under the name PLANTAREN 2000 and the product sold by Seppic under the name ORAMIX NS 10, octyl/decyl glucosides such as the product sold by Seppic under the name ORAMIX CG 110 or by BASF under the name lutensgd ol 70, lauryl glucosides such as the products sold by Henkel under the names PLANTAREN 1200N and PLANTACARE 1200, coco glucosides such as the product sold by Henkel under the name PLANTACARE 818/UP, cetostearyl glucosides such as the product sold by Seppic under the name MONTANOV 68, Goldschmidt under the name TEGO-CARE CG90 and Henkel under the name EMULGADE KE 2 (possibly mixed with cetostearyl alcohol), arachidyl glucosides such as the mixture of eicosyl glucoside and behenyl glucoside sold under the name tagov 202 and behenyl glucoside such as the mixture of cetostearyl glucosides 33082, ethyl glucosides such as the mixture of cetostearyl glucosides 33082 and behenyl glucosides such as cetostearyl glucosides under the form 35/65, and mixtures thereof.

Mixtures of glycerides of alkoxylated vegetable oils, such as mixtures of ethoxylated (200 EO) palm oil (palm) and coconut oil (copra) (7 EO) glycerides, may also be mentioned.

The nonionic surfactants according to the invention preferably contain alkenyl groups or branched C₁₂-C₂₂Acyl chains, such as oleyl or isostearyl. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

According to one embodiment of the invention, the nonionic surfactant may be chosen from copolymers of ethylene oxide and propylene oxide, in particular copolymers of formula:

HO(C₂H₄O)_a(C₃H₆O)_b(C₂H₄O)_cH

wherein a, b and c are integers such that a + c is from 2 to 100 and b is from 14 to 60, and mixtures thereof.

In particular, among these nonionic surfactants, monoesters of polyhydric alcohols and fatty acids are preferably used in the present invention. As the polyhydric alcohol, glycerin, sorbitan and diglycerin are particularly preferable, and as the fatty acid, lauric acid and oleic acid are particularly preferable. The most preferred esters are polyglycerol-2 laurate, glycerol laurate, sorbitan oleate and glycerol oleate.

According to one embodiment of the invention, the nonionic surfactant may be chosen from copolymers of ethylene oxide and propylene oxide, in particular copolymers of formula:

HO(C₂H₄O)_a(C₃H₆O)_b(C₂H₄O)_cH

wherein a, b and c are integers such that a + c is from 2 to 100 and b is from 14 to 60, and mixtures thereof.

According to one embodiment of the invention, the nonionic surfactant may be selected from silicone surfactants. Mention may be made, without being limitative, of those disclosed in documents US-A-5364633 and US-A-5411744.

The silicone surfactant may preferably be a compound of formula (I):

wherein:

R₁、R₂and R₃Independently of one another represent C₁-C₆Alkyl or a radical- (CH)₂)_x-(OCH₂CH₂)_y-(OCH₂CH₂CH₂)_z-OR₄At least one radical R₁、R₂Or R₃Is not an alkyl group; r₄Is hydrogen, alkyl or acyl;

a is an integer from 0 to 200;

b is an integer of 0 to 50; provided that A and B are not equal to 0 at the same time;

x is an integer from 1 to 6;

y is an integer from 1 to 30;

z is an integer from 0 to 5.

According to a preferred embodiment of the invention, in the compound of formula (I), alkyl is methyl, x is an integer from 2 to 6 and y is an integer from 4 to 30.

As examples of silicone surfactants of formula (I), mention may be made of compounds of formula (II):

wherein A is an integer from 20 to 105, B is an integer from 2 to 10 and y is an integer from 10 to 20.

As examples of silicone surfactants of formula (I), mention may also be made of compounds of formula (III):

H-(OCH₂CH₂)_y-(CH₂)₃-[(CH₃)₂SiO]_A’-(CH₂)₃-(OCH₂CH₂)_y-OH (III)

wherein A' and y are integers from 10 to 20.

Useful compounds of the invention are those sold by Dow Corning under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667. Compounds DC 5329, DC 7439-146 and DC 2-5695 are wherein A is 22, B is 2 and y is 12, respectively; a is 103, B is 10 and y is 12; a is 27, B is 3 and y is 12. Compound Q4-3667 is a compound of formula (III) wherein a is 15 and y is 13.

In particular, the silicone surfactant may comprise alkyl dimethicone copolyols, especially those having an alkyl group containing from 10 to 22 carbon atoms and having from 2 to 50 oxyethylene groups and from 2 to 50 oxypropylene groups, such as Cetyl dimethicone copolyol (INCI name: CetylPEG/PPG-10/1 dimethicone), such as the product sold under the name Abil EM-90 by the company Goldschmidt; lauryl dimethicone copolyol (INCI name: Lauryl PEG/PPG-18/18 Methicone) and a mixture of about 91% Lauryl dimethicone copolyol and about 9% isostearyl alcohol such as that sold by Dow Corning corporation under the name DOW CORNING 5200 FORMULATION AID; dimethicone copolyols, especially those having from 2 to 50 oxyethylene groups and from 2 to 50 oxypropylene groups, are polyether modified linear or branched polysiloxane polymers, for example a dimethicone copolyol having 18 oxyethylene groups and 18 oxypropylene groups (PEG/PPG-18/18 dimethicone sold by Shinetsu Chemical), such as that sold under the name DC-3225C or DC2-5225C by the company Dow Corning, having 18 oxyethylene groups and 18 oxypropylene groups, a mixture of cyclopentadimethylsiloxane (cyclopentasiloxane) and water (PPG 10/88/2) (INCI name: cyclopentadimethylsiloxane/PEG-18/18 dimethicone), or a mixture having 14 oxyethylene groups and 14 oxypropylene groups (PEG/PPG-14/14 dimethicone), in particular, for example, a mixture of dimethicone copolyol having 14 oxyethylene groups and 14 oxypropylene groups and cyclopentadimethicone (85/15) sold by Goldschmidt corporation under the name Abil EM-97 (INCI name: Bis-PEG/PPG-14/14 dimethicone/cyclopentadimethicone).

The silicone surfactant may also include cross-linked silicone elastomers such as polyether substituted or unsubstituted dimethicone/copolyol crosspolymers, dimethicone and dimethicone/PEG-10/15 crosspolymers, substituted or unsubstituted dimethicone/polyglycerin crosspolymers, dimethicone and dimethicone/polyglycerin-3 crosspolymers. Such suitable emulsifying crosslinked silicone elastomers are sold or manufactured, for example, under the names "KSG-210" (polyether modified dimethicone crosspolymer, INCI named dimethicone (and) dimethicone/PEG-10/15 crosspolymer) and "KSG-710" (polyglycerine modified dimethicone crosspolymer, INCI named dimethicone (and) dimethicone/polyglycerine-3 crosspolymer), both available from ShinEtsu Silicones of America, inc. Among the polyether-modified cross-linked silicone elastomers, polyether and alkyl chain-modified cross-linked silicone elastomers such as PEG-10/lauryldimethicone crosspolymer and PEG-15/lauryldimethicone crosspolymer sold under the names "KSG-310", "KSG-320", "KSG-330" or "KSG-340" by Shinetsu Chemical are preferably used in the present invention. In polyether and alkyl chain modified cross-linked silicone elastomers, the polyether units may be from 2 to 50, preferably from 5 to 20, and the alkyl chain includes from 8 to 24, preferably from 12 to 22 carbon atoms.

Anionic surfactants

The anionic surfactant may be chosen in particular from phosphates and alkyl phosphate salts, carboxylates, sulfosuccinates, amino acid derivatives, alkyl sulfates, alkyl ether sulfates, sulfonates, isethionates, taurates, polyoxyethylene alkyl ether carboxylic acids, alkyl sulfoacetates, polypeptides and mixtures thereof.

1) As phosphates and alkyl Phosphate salts there may be mentioned, for example, monoalkyl phosphates and dialkyl phosphates, such as dodecyl monophosphate sold under the name MAP 20 by Kao Chemicals, the potassium salt of dodecyl Phosphate, a mixture of mono-and diesters (predominantly diesters) sold under the name Craflol AP-31 by Cognis, a mixture of octyl Phosphate mono-and diesters sold under the name Craflol AP-20 by Cognis, a mixture of ethoxylated (7 mol EO) 2-butyl octyl Phosphate mono-and diesters sold under the name Isofol 127 EO-Phosphoester by Condea, mono (C. RTM. EO) sold under the name Arlatone MAP 230K-40 and Arlatone MAP 230T-60 by Uniqema₁₂-C₁₃) Potassium or triethanolamine salts of alkyl phosphate esters, potassium dodecyl phosphate sold by Rhodia Chimie as Dermalcare MAP XC-99/09 @, and potassium cetyl phosphate sold by Uniqema as Arlatone MAP 160K.

2) As the carboxylate, there may be mentioned:

acylaminoether carboxylates (AEC), sodium laurylaminoether carboxylates sold under the name Akypo Foam 30 by Kao Chemicals (3 EO);

salts of polyoxyethylenated carboxylic acids, for example sodium oxyethylenated (6 EO) dodecylether carboxylic acid sold under the name Akypo Soft 45 NV by Kao Chemicals (65/25/10C)₁₂-C₁₄-C₁₆)、Biologia E Tecnologia polyethylene oxide and carboxymethylated fatty acids from olive oil sold under the name Olivem 400 or sodium oxyethylated (6 EO) tridecyl ether carboxylate sold under the name Nikkol ECTD-6 NEX of Nikkol; and

-having C neutralized with an organic or inorganic base, such as potassium hydroxide, sodium hydroxide, triethanolamine, N-methylglucamine, lysine and arginine₆To C₂₂Salts of fatty acids with alkyl chains (soaps).

3) As amino acid derivatives, mention may be made in particular of the alkali metal salts of amino acids, such as:

sarcosinates, such as sodium lauroyl Sarcosinate sold under the name of Ciba under the name of Sarkosyl NL 97 or Seppic under the name Oramix L30, sodium myristoyl Sarcosinate sold under the name of Nikkol Sarcosinate MN or sodium palmitoyl Sarcosinate sold under the name of Nikkol Sarcosinate PN by Nikkol Sarcosinate PN;

alanine salts, such as Sodium N-lauroyl-N-methylaminopropionate sold under the name of Nikkol Sodium Nikkol Alaninate LN30 or Kawaken Sodium T-lauroyl-N-methylaminopropionate sold under the name of Alanone ALE or triethanolamine N-lauroyl-N-methylalanine sold under the name of Kawaken Alanone ALTA;

glutamate such as triethanolamine mono-cocoyl glutamate sold by Ajinomoto under the name Acylglutamate CT-12 @, triethanolamine lauroyl glutamate sold by Ajinomoto under the name Acylglutamate LT-12 @;

-aspartate, such as a mixture of triethanolamine N-lauroyl aspartate and triethanolamine N-myristoyl aspartate sold under the name Asparck by Mitsubishi;

-glycine derivatives (glycinates) such as sodium N-cocoyl glycinate sold by Ajinomoto under the names Amilite GCS-12 and Amilite GCK 12;

citrates, such as the citric acid monoester of oxyethylenated (9 moles) cocool sold by Goldschmidt under the name Witconol EC 1129; and

galacturonate, such as sodium dodecyl D-galactoside uronate sold by Soliance.

4) As the sulfosuccinate, there may be mentionedTo for example oxyethylenated (3 EO) lauryl alcohol (70/30C) sold under the names Setacin 103 Special and Rewopol SB-FA 30K 4 by Witco₁₂/C₁₄) Monosulfosuccinate, Zschimmer Schwarz sold under the name Setacin F specific Paste C₁₂-C₁₄Disodium salt of an alcohol hemisulfosuccinate, disodium oxyethylated (2 EO) oleyl amidosulfosuccinate sold by Cognis under the name of Standapol SH 135, oxyethylated (5 EO) lauramide monosulfosuccinate sold by Sanyo under the name of Lebon A-5000, oxyethylated (10 EO) lauryl citric acid monosulfosuccinate sold by Witco under the name of Rewopol SB CS 50 or ricinoleic acid monoethanolamide monosulfosuccinate sold by Witco under the name of Rewoderm S1333. Polydimethylsiloxane sulfosuccinates such as disodium PEG-12 polydimethylsiloxane sulfosuccinate sold by MacIntyre under the name Mackanate-DC30 may also be used.

5) As the alkyl sulfate, for example, triethanolamine lauryl sulfate (CTFA name: TEA lauryl sulfate), such as the product sold by Huntsman under the name Empicol TL40 FL or by Cognis under the name Texapon T42, which is a 40% aqueous solution. Mention may also be made of ammonium dodecylsulfate (CTFA name: ammonium dodecylsulfate), such as the product sold by Huntsman under the name Empicol AL 30FL, which is a 30% aqueous solution.

6) As the alkyl ether sulfate, for example, sodium lauryl ether sulfate (CTFA name: sodium laureth sulfate), such as those sold by Cognis under the names Texapon N40 and Texapon AOS 225 UP, or ammonium lauryl ether sulfate (CTFA name: ammonium laureth sulfate), such as that sold by Cognis under the name Standapol EA-2.

7) As sulfonates, mention may be made, for example, of alpha-olefin sulfonates such AS Stepan marketed by Bio-Terge AS-40 @, Witco marketed by Witconate AOS Prot g and Sulframine AOS PH 12 @, or Stepan marketed by Bio-Terge AS-40 CG @ (C sodium olefin sulfonate marketed by C @)_14-16) Clariant is sodium sec-olefin sulfonate sold under the name Hostapur SAS 30; or linear alkylaryl sulfonates such as Manro manufactured as Manrosol SXS30, Manrosol SXS40 and polyethylene terephthalate ® polyethylene terephthalate (polyethylene terephthalate) polyethylene terephthalate (PET)Manrosol SXS93 was a commercial sodium xylene sulfonate.

8) As isethionate, mention may be made of acyl isethionates, such as sodium cocoyl isethionate, such as the product sold by Jordan under the name Jordapon CI P.

9) As the taurate, the sodium salt of palm kernel oil methyl taurine sold under the name of Hostapon CT Pat @byClariant can be mentioned; N-acyl-N-methyltaurates, such as sodium N-cocoyl-N-methyltaurate sold under the name of Hostapon LT-SF by Clariant or Nikkol CMT-30-T by Nikkol CMT-30-T, sodium palmitoyl methyltaurate sold under the name of Nikkol PMT by Nikkol, or sodium stearoyl methyltaurate sold under the name of Sunsoft O-30S by Taiyo Kagaku.

10) Mention may be made of polyoxyethylene alkyl ether carboxylic acids, such as the compounds conforming to formula (IV):

RO[CH₂O]_u[(CH₂)_xCH(R’)(CH₂)_y(CH₂)_zO]_v[CH₂CH₂O]_wCH₂COOH (IV)

wherein:

r is a hydrocarbon group containing 6 to 40 carbon atoms;

u, v and w represent, independently of one another, a number from 0 to 60;

x, y and z independently of one another represent a number from 0 to 13;

r' represents hydrogen, alkyl, preferably C₁-C₁₂An alkyl group; and is

The sum of x + y + z is 0 or more.

In formula (IV), R is linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted. As examples of substituents, mention may be made of monovalent functional groups, such as halogen atoms, hydroxyl groups, C₁-C₆Alkoxy, amino, C₁-C₆Alkylamino radical, C₁-C₆Dialkylamino, nitro, carbonyl, acyl, carboxyl, cyano, and the like. Typically, R is a straight or branched chain, acyclic C₆-C₄₀Alkyl or alkenyl or C₁-C₄₀Alkylphenyl, more usually C₈-C₂₄Alkyl or alkenyl or C₄-C₂₀Alkylphenyl, even more usually C₁₀-C₁₈Alkyl or alkenyl or C₆-C₁₆An alkylphenyl group which may be substituted; u, v, w are independently of each other a number typically from 2 to 20, more typically from 3 to 17, most typically from 5 to 15; x, y, z are independently of each other a number typically from 2 to 13, more typically from 1 to 10, most typically from 0 to 8;

the polyoxyethylene alkyl ether carboxylic acid corresponding to formula (IV) may be obtained by alkoxylation of the alcohol ROH with ethylene oxide as the sole alkoxide or with several alkoxides and subsequent oxidation. The values u, v and w each represent the degree of alkoxylation. On the molecular level, the values u, v and w and the overall degree of alkoxylation may be only integers, including 0, while on the macroscopic level they are averages in fractional form. The fatty ether carboxylic acid may comprise polyoxyalkylenated (C)₆-C₃₀) Alkyl ether carboxylic acids and their salts, more particularly polyoxyethylenated (C)₆-C₃₀) Alkyl ether carboxylic acids and their salts; polyalkylene oxide (C)₆-C₃₀) Alkyl aryl ether carboxylic acids and their salts; and polyoxyalkylenation (C)₆-C₃₀) Alkyl amido ether carboxylic acids. The fatty ether carboxylic acid is preferably polyoxyethylene (3) to (17) lauryl ether carboxylic acid.

Suitable polyoxyethylene alkyl ether carboxylic acids include, but are not limited to, the following representatives mentioned by their INCI names: butyl phenol polyether (Butoxynol) -5 to 19 carboxylic acids, octanol polyether-4 to 25 carboxylic acids, coconut oil polyether-7 carboxylic acids, C_9-15Alkyl polyether (Pareth) -6 to 8 carboxylic acid, decyl alcohol polyether-7 carboxylic acid, lauryl alcohol polyether-3 to 17 carboxylic acid, such as lauryl alcohol polyether-5 carboxylic acid, PPG-6-lauryl alcohol polyether-6 carboxylic acid, PPG-8-stearyl alcohol polyether-7 carboxylic acid, myristyl alcohol polyether-3 to 5 carboxylic acid, nonoxynol-5 to 10 carboxylic acid, Octeth-3 carboxylic acid, Octoxynol-20 (Octoxynol-20) carboxylic acid, oleyl alcohol polyether-3 to 10 carboxylic acid, PPG-3-caprylyl alcohol polyether-2 carboxylic acid, cetyl alcohol polyether-13 carboxylic acid, decyl alcohol polyether-2 carboxylic acid, hexyl alcohol polyether-4 carboxylic acid, isostearyl alcohol polyether-6 to 11 carboxylic acid, Trudeech-3 to 12 carboxylic acid, tridecyl alcohol polyether-3 to 19 carboxylic acid, and mixtures thereof, Undecapeth-5-carboxylic acidAnd mixtures thereof.

The surfactant (a) used in the composition according to the invention may preferably be chosen from nonionic surfactants which are monoesters of polyhydric alcohols and fatty acids containing 8 to 24 carbon atoms, wherein said polyhydric alcohols are preferably chosen from glycerol, sorbitan and diglycerol and said fatty acids are preferably chosen from isolauric acid and oleic acid, in particular esters of polyglyceryl-2 laurate, glycerol laurate, sorbitan oleate and glycerol oleate, and silicone surfactants which are preferably polyether-modified polydimethylsiloxanes, such as PEG/PPG-18/18 polydimethylsiloxane, and polyether and alkyl-modified polydimethylsiloxane crosspolymers, such as PEG-15/lauryl polydimethylsiloxane crosspolymers; and an anionic surfactant which is a polyoxyethylene alkyl ether carboxylic acid such as polyoxyethylene (3) to (17) lauryl ether carboxylic acids.

Representative examples of the surfactant used in the present invention and HLB values are shown below.

Name of surfactant	HLB
		PEG/PPG-18/18 polydimethylsiloxane	< 9
Polyglycerol-2 laurate	8.5
		PEG-15/lauryl dimethicone crosspolymer	< 8
Lauric acid glyceride	5.3
		Sorbitan oleate	4.3
Oleic acid glyceride	2.8
		Laureth-5-carboxylic acid	9.5

(a) The amount of the surfactant in the composition according to the present invention is not limited, and may be 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the total weight of the composition.

(b) Oil

The composition according to the invention comprises (b) at least one oil. Two or more (b) oils may be used in combination. Thus, a single type of oil or a combination of different types of oil may be used. In the present invention, (b) oil may be included in the outer oil phase and the inner oil phase.

The expression "oil" as used herein means a fatty compound or substance which is in the form of a liquid or paste (non-solid) at room temperature (25 ℃) and atmospheric pressure (760 mmHg). These oils may be volatile or non-volatile, preferably non-volatile.

(b) The oil may be a non-polar oil, such as hydrocarbon oil, silicone oil, or the like; polar oils, such as vegetable or animal oils and ester or ether oils; or mixtures thereof.

The hydrocarbon oil may be selected from:

-linear or branched, optionally cyclic C₆-C₁₆A lower alkane. Examples which may be mentioned include hexane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isododecane and isodecane; and

straight-chain or branched hydrocarbons having more than 16 carbon atoms, such as liquid paraffin, liquid petrolatum, polydecene and hydrogenated polyisobutene, such as Parleam @, or squalane.

As preferred examples of hydrocarbon oils, there may be mentioned, for example, straight-chain or branched-chain hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalene, and the like; hydrogenated polyisobutenes, isoeicosane and decene/butene copolymers; and mixtures thereof.

As examples of the silicone oil, there may be mentioned, for example, linear organopolysiloxanes such as dimethylpolysiloxanes, methylphenylpolysiloxanes, methylhydropolysiloxanes, and the like; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.

The silicone oil is preferably chosen from liquid polydialkylsiloxanes, in particular liquid Polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aromatic group.

These silicone oils may also be organically modified. The organomodified silicones which can be used according to the invention are silicone oils as defined above and which comprise in their structure one or more organofunctional groups linked via a hydrocarbon-based group.

The organopolysiloxanes are defined in more detail in Walter Noll' sChemistry and Technology of Silicones(1968) Academic Press. They may be volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of from 60 ℃ to 260 ℃, more particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7, preferably from 4 to 5, silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular by Union Carbide under the name of Volatile Silicone 7207 or Rhodia under the name of Silibione 70045V 2, Union Carbide under the name of Volatile Silicone 7158, decamethylcyclopentasiloxane sold by Rhodia under the name of Silibione 70045V 5, and dodecamethylcyclopentasiloxane sold by Momentive Performance Materials under the name of Silsoft 1217, and mixtures thereof. Mention may also be made of cyclic copolymers such as dimethylsiloxane/methylalkylsiloxane, for example Silicone Volatile FZ 3109 sold by Union Carbide having the formula:

。

mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetrakis (trimethylsilyl) pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1, 1 '-bis (2,2, 2', 2', 3, 3' -hexatrimethylsilyloxy) neopentane;

(ii) containing 2 to 9 silicon atoms and having a molecular weight of less than or equal to 5X 10 at 25 DEG C^-6Linear volatile polydialkylsiloxanes having a viscosity of m/s. One example is decamethyltetrasiloxane, sold under the name SH 200 by the company Toray Silicone in particular. Silicones belonging to this class are also described in Cosmetics and Toiletries, volume 91, jan. 76, pages 27-32, Todd&Articles published by ByersVolatile Silicone Fluids for CosmeticsIn (1). The viscosity of the silicone was measured at 25 ℃ according to ASTM standard 445, appendix C.

Nonvolatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

Among these polydialkylsiloxanes, the following commercial products may be mentioned without limitation:

sildione series 47 and 70047 sold by Rhodia^®Oil or Mirasil^®Oils, such as oil 70047V 500000;

mirasil sold by Rhodia^®A series of oils;

200 series oils from Dow Corning, e.g. having a viscosity of 60000 mm²DC200 of/s;

viscasil from General Electric^®Oil and some oils from the SF series of General Electric (SF 96, SF 18).

Mention may also be made of dimethiconol (CTFA), known under the name dimethiconol, which contains dimethylsilanol end groups, such as the oils of the series 48 from Rhodia.

Aryl group-containing silicones include polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes. Examples that may be mentioned include products sold under the following names:

-70641 series of Silbaine oil from Rhodia;

rhodorsil 70633 and 763 series of oils from Rhodia;

-oil from Dow Corning 556 Cosmetic Grade Fluid;

silicones from the PK series of Bayer, such as product PK 20;

certain oils from the SF series of General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

As examples of vegetable oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil (sasanqua oil), castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil and mixtures thereof.

As examples of animal oils, mention may be made of, for example, squalene and squalane.

As examples of synthetic oils, mention may be made of alkane oils, such as isododecane and isohexadecane, ester oils, ether oils and artificial triglycerides.

The ester oil is preferably saturated or unsaturated, straight or branched C₁-C₂₆Aliphatic mono-or poly-acids and saturated or unsaturated, linear or branched C₁-C₂₆A liquid ester of an aliphatic mono-or polyol, the ester having a total number of carbon atoms greater than or equal to 10.

Preferably, for esters of monoalcohols, at least one of the alcohols and acids used to form the esters of the present invention is branched.

Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dioctyl carbonate, alkyl myristate, such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

C may also be used₄-C₂₂Di-or tricarboxylic acids and C₁-C₂₂Esters of alcohols and monocarboxylic, dicarboxylic or tricarboxylic acids and non-sugar C₄-C₂₆Esters of dihydric, trihydric, tetrahydroxyl or pentahydric alcohols.

Mention may in particular be made of: sebacic acid diethyl ester; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis (2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis (2-ethylhexyl) adipate; diisooctadecyl adipate; bis (2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisooctadecyl citrate; glycerol trilactate; tricaprylin; trioctyl dodecyl citrate; triolein citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As ester oil, C can be used₆-C₃₀And preferably C₁₂-C₂₂Sugar esters and diesters of fatty acids. To reiterate, the term "saccharide" means an oxygen-containing hydrocarbon-based compound containing several alcohol functions, with or without aldehyde or ketone functions, and comprising at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars which may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose and their derivatives, especially alkyl derivatives, such as methyl derivatives, for example methyl glucose.

The sugar esters of fatty acids may be chosen in particular from the aforementioned sugars and linear or branched, saturated or unsaturated C₆-C₃₀Preferably C₁₂-C₂₂Esters or ester mixtures of fatty acids. If they are unsaturated, these compounds may have from 1 to 3 conjugated or unconjugated carbon-carbon double bonds.

The esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters and polyesters and mixtures thereof.

These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate and arachidonate or mixtures thereof, such as, inter alia, oil palmitate (oleosphite), mixed esters of oil stearate (oleosphite) and palm stearate (palmitostearate), and pentaerythritol tetraacetate.

More particularly, mono-and diesters are used, in particular sucrose, mono-or dioleates of glucose or methylglucose, stearates, behenates, oleyl palmitates, linoleates, linolenates or oleyl stearates.

One example which may be mentioned is the product sold under the name Glucate DO by Amerchol which is methyl glucose dioleate.

As examples of preferred ester oils, mention may be made, for example, of diisopropyl adipate, dioctyl adipate, 2-ethylhexyl caproate, ethyl laurate, cetyl octanoate, octyl dodecyl octanoate, isodecyl pivalate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate/decanoate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dioctyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri (2-ethylhexanoate), pentaerythritol tetra (2-ethylhexanoate), 2-ethylhexyl succinate, ethyl hexanoate, isopropyl myristate, octyl octanoate, isopropyl palmitate, isopropyl myristate, isopropyl oleate, glyceryl tri (2-ethylhexanoate), glyceryl tetra (2-ethylhexanoate), pentaerythritol tetra (2-ethylhexyl succinate, and mixtures thereof, Diethyl sebacate and mixtures thereof.

As examples of artificial triglycerides, mention may be made, for example, of decyl octyl glyceride, trimyristin, tripalmitin, trilinolein, trilaurin, tricaprin, tricaprylin, tri (capric/caprylic) glyceride and tri (capric/caprylic/linolenic) glyceride.

(b) The oil is preferably chosen from non-polar hydrocarbon oils, in particular mineral oils, such as paraffins, which are in liquid form at room temperature.

(b) The oil is also preferably selected from oils having a molecular weight below 600 g/mol.

(b) The oil preferably has a low molecular weight, such as less than 600 g/mol, more preferably less than 500 g/mol, in particular less than 400 g/mol, and is selected from ester or ether oils (C) having one or more short hydrocarbon chains₁-C₁₈E.g. isopropyl myristate, isopropyl palmitate, isononyl isononanoate, dioctyl carbonate, ethylhexyl palmitate, dioctyl ethers, in particular sarcosinates, such as isopropyl lauroyl sarcosinate), hydrocarbon oils having one or more short alkyl chains (C)₁-C₁₈E.g., isododecane, isohexadecane, and squalane) and short alcohol type oils, such as octyldodecanol.

(b) The oil is also preferably selected from hydrocarbon oils, C₄-C₂₂Di-or tricarboxylic acids and C₁-C₂₂Esters of alcohols, and C₄-C₂₂Monocarboxylic, dicarboxylic or tricarboxylic acids and non-sugar C₄-C₂₆Dihydroxy, C₄-C₁₅Esters of trihydric, tetrahydric or pentahydric alcohols, and mixtures thereof.

(b) The oil is also preferably selected from ester oils such as isopropyl myristate, isopropyl palmitate, isononyl isononanoate, dioctyl carbonate, ethylhexyl palmitate, dioctyl ether, especially sarcosinates such as isopropyl lauroyl sarcosinate, artificial triglycerides such as decyl octyl glyceride, and silicone oils.

(b) The amount of oil in the composition according to the present invention is not limited, and may be 1 to 40 wt%, preferably 2 to 30 wt%, more preferably 5 to 20 wt% of the total weight of the composition.

The oil (b) constituting the internal oil phase is preferably selected from ester oils such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglycerides such as decyl octyl glyceride, sarcosinates such as isopropyl lauroyl sarcosinate, hydrocarbon oils such as isohexadecane, mineral oils such as paraffin.

(b) The amount of oil in the inner oil phase of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more.

The oil (b) constituting the external oil phase is preferably selected from ester oils such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, triglycerides such as decyl octyl glyceride, sarcosinates such as isopropyl lauroyl sarcosinate, hydrocarbon oils such as isohexadecane, mineral oils such as paraffin, and silicone oils.

(b) The amount of oil in the outer oil phase of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more.

(c) UV filter

The composition according to the invention comprises (c) at least one UV filter. Two or more UV filters may be used in combination. Thus, a single type of UV filter or a combination of different types of UV filters may be used.

The term "UV" as used herein includes the UV-B region (wavelength 260-320 nm) and the UV-A region (wavelength 320-400 nm). UV filter therefore means any material which has a filtering effect on the wavelengths in the UV-A and/or UV-B region. The compositions according to the invention preferably cover the UV-A and UV-B regions.

In the present invention, the UV filter may be an organic UV filter. Both hydrophilic UV filters and hydrophobic UV filters may be used in the composition according to the invention.

The term "hydrophilic UV filter" as used herein is understood to mean any agent which shields UV radiation and is capable of being completely dissolved in the aqueous phase in the molecular state or of being dispersed in the aqueous phase of an O/W/O emulsion in colloidal form (for example in the form of micelles). Thus, hydrophilic UV filters can be formulated in the internal aqueous phase of the present invention.

The term "hydrophobic UV filter" as used herein is understood to mean any agent which shields UV radiation and is capable of being completely dissolved in the oil phase in the molecular state or of being dispersed in the oil phase of an O/W/O emulsion in colloidal form (for example in the form of micelles). Thus, hydrophobic UV filters may be formulated in the outer and inner oil phases of the present invention.

(hydrophilic UV filters)

The hydrophilic UV filters used in the present invention, alone or in combination, may be active in the UV-A and/or UV-B region, preferably in both the UV-A and UV-B region.

Hydrophilic UV-a filters include, but are not limited to:

benzylidene camphor derivatives, such as p-xylylene dicamphor sulfonic acid manufactured by Chimex under the name "Mexoryl SX",

bis-benzoxazolyl derivatives as described in patents EP 669323 and US 2,463,264, more particularly the compound disodium phenyldibenzoimidazole tetrasulfonate sold under the trade name "Neo Heliopan AP" by Haarmann and Reimer.

Hydrophilic UV-B filters include, but are not limited to:

derivatives of para-aminobenzoic acid (PABA), such as PABA, glycerol para-aminobenzoate and PEG-25 PABA, such as that sold under the name "Uvinul P25" by BASF,

phenylbenzimidazole derivatives, such as phenylbenzimidazole sulfonic acid sold by Merck under the name "Eusolex 232", and disodium phenylbenzimidazole tetrasulfonate sold by Haarmann, Reimer under the name "Neo Heliopan AP",

phenylbenzimidazole sulfonic acids, such as Merck, are sold in particular under the trade name "Eusolex 232",

the concentration of the ferulic acid is controlled by the concentration of the ferulic acid,

the content of the salicylic acid is as follows,

DEA-methoxy cinnamate is used as the base,

benzylidene camphorsulfonic acids, such as are manufactured by Chimex under the name "Mexoryl SL",

camphorbenzammonium methylsulfates, such as Chimex, are manufactured under the name "Mexoryl SO".

Hydrophilic UV-a and UV-B filters include, but are not limited to:

benzophenone-4, such as that sold by BASF under the trade name "Uvinul MS 40", benzophenone-5 and benzophenone-9.

The hydrophilic UV filter is preferably selected from benzylidene camphor derivatives, such as p-xylylene dicamphor sulfonic acid, and phenyl benzimidazole derivatives, such as phenyl benzimidazole sulfonic acid.

The amount of hydrophilic UV filter in the composition may be from 1 to 40 wt%, preferably from 3 to 30 wt%, more preferably from 5 to 20 wt% of the total weight of the composition.

(hydrophobic UV filters)

The hydrophobic filters of the present invention may be formulated in both the external and internal oil phases, or in either the external or internal oil phases.

The hydrophobic UV filters used in the present invention, alone or in combination, may be active in the UV-A and/or UV-B region, preferably both the UV-A and UV-B region.

Hydrophobic UV-a filters useful in the present invention may include, but are not limited to, aminobenzophenone compounds, dibenzoylmethane compounds, anthranilic acid compounds, and 4, 4-diarylbutadiene compounds.

As aminobenzophenone compound, mention may be made of n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, a variant of which is diethylaminohydroxybenzoyl hexyl benzoate (DHHB), sold by BASF under the trade name "Uvinul A +".

As the dibenzoylmethane compound, there may be mentioned 4-isopropyldibenzoylmethane sold by Merck under the name "Eusolex 8020", 1- (4-methoxy-1-benzofuran-5-yl) -3-phenylpropane-1, 3-dione sold by Quest under the name "Pongamol", 1- (4- (tert-butyl) phenyl) -3- (2-hydroxyphenyl) propane-1, 3-dione, and butylmethoxydibenzoylmethane sold by Hoffmann-La Roche under the name "Parsol 1789".

As anthranilic acid compound, mention may be made of the menthyl anthranilate sold by Symrise under the name "NEO HELIPAN MA".

As the 4, 4-diarylbutadiene compounds, there may be mentioned 1, 1-dicarboxy (2,2' -dimethylpropyl) -4, 4-diphenylbutadiene and diphenylbutadiene malonates and malononitrile.

The hydrophobic UV-B filter used in the present invention may include, but is not limited to, triazine compounds, p-aminobenzoic acid compounds, salicylic acid compounds, cinnamate compounds, β -diphenylacrylate compounds, benzylidenecamphor compounds, imidazoline compounds, benzylidenemalonate compounds, and mecocyanine compounds.

As triazine compounds, mention may be made of ethylhexyl triazone sold by BASF under the name "UVINUL T-150", diethylhexyl butamidotriazone sold by SIGMA 2V under the name "UVASORB HEB", diethylhexyl butamido triazone sold by SIGMA 2V under the name "UVASORB HEB", dineopentyl 2,4, 6-tris (4 '-aminobenzylidene malonate) -s-triazine, di-isobutyl 2, 4-bis (4' -aminobenzylidene malonate) -6- (4 '-aminobenzoic acid n-butyl ester) -s-triazine, 2, 4-bis (4' -aminobenzoic acid n-butyl ester) -6- (aminopropyl trisiloxane) -s-triazine.

As para-aminobenzoic acid derivatives, mention may be made of para-aminobenzoates (PABAs), such as ethyl PABA (para-aminobenzoate), ethyl dihydroxypropyl para-aminobenzoate and ethylhexyl dimethyl para-aminobenzoate sold under the name "escanol 5972" by ISP.

As salicylic acid compounds, mention may be made of trimethylcyclohexyl salicylate (homosalate) sold by Rona/EM Industries under the name "Eusolex HMS", and ethylhexyl salicylate sold by Symrise under the name "NEO HELIOPAN OS".

As cinnamate compounds, mention may be made of ethylhexyl methoxycinnamate sold under the name "PARSOL MCX" by DSM NUTRITIONAL PRODUCTS, isopropyl ethoxycinnamate, isoamyl methoxycinnamate sold under the name "NEO HELIOPAN E1000" by Symrise, diisopropyl methyl cinnamate, cinoxate and dimethoxycinnamate glyceryl ethylhexanoate.

As β, β -diphenylacrylate compounds, mention may be made of octocrylene sold by BASF under the name "uvinlu N539" and etoricine sold by BASF under the name "UNIVUL N35".

As the benzylidene camphor compounds, there may be mentioned 3-benzylidene camphor sold by CHIMEX under the name "MEXORYL SD", methylbenzylidene camphor sold by MERCK under the name "EUSOLEX 6300", and polyacrylamidomethylbenzylidene camphor sold by CHIMEX under the name "MEXORYL SW".

As the imidazoline compound, ethylhexyl dimethoxybenzylidenedioxoimidazolidinepropionate may be mentioned.

As the benzylidene malonate compounds there may be mentioned polyorganosiloxanes containing benzylidene malonate moieties, such as Polysilicone-15 sold under the name "Parsol SLX" by DSM NUTRITIONAL PRODUCTS, and dipentanyl 4' -methoxybenzylidenemalonate.

Hydrophobic UV-a and UV-B filters useful in the present invention include, but are not limited to:

benzophenone compounds such as benzophenone-1 sold by BASF under the name "UVINUL 400", benzophenone-2 sold by BASF under the name "UNIVUL 500", benzophenone-3 or oxybenzone sold by BASF under the name "UVINUL M40", benzophenone-6 sold by norquay under the name "Helisorb 11", benzophenone-8 sold by American Cyanamid under the name "Spectra-Sorb UV-24", benzophenone-10, benzophenone-11 and benzophenone-12;

benzotriazole compounds, such AS cresoltrazole trisiloxane sold under the name "Silatrizole" by Rhodia Chimie and bumetazole sold under the name "TINOGUARTD AS" by CIBA-GEIGY;

bis-resorcinyl triazines, such as bis-ethylhexyloxyphenylmethoxyphenyl triazine sold under the name "TINOSORB S" by CIBA-GEIGY; and

benzoxazole compounds, such as 2, 4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino ] -6- (2-ethylhexyl) imino-1, 3, 5-triazine sold under the name "Uvasorb K2A" by Sigma 3V.

The hydrophobic UV filter is preferably selected from cinnamate compounds such as ethylhexyl methoxycinnamate, isopropyl ethoxycinnamate, isoamyl methoxycinnamate, diisopropyl methyl cinnamate, cinoxate and dimethoxycinnamate glycerol ethylhexanoate.

The amount of the one or more hydrophobic UV filters in the inner oil phase is not limited but may be from 0.1 to 5 wt%, preferably less than 2 wt%, of the total weight of the composition. The amount of the one or more hydrophobic UV filters in the outer oil phase is not limited, but may be 1 to 15 wt%, preferably less than 5 wt%, of the total weight of the composition.

In general, the amount of (c) one or more UV filters including one or more hydrophilic and hydrophobic UV filters may range from 1 to 40 weight percent, preferably from 2 to 30 weight percent, more preferably from 5 to 20 weight percent of the total weight of the composition.

(d) Water (W)

The composition according to the invention comprises (d) water. (d) Water constitutes the high internal water phase of the present invention.

(d) The amount of water is not limited and may be 40 to 99 wt%, preferably 50 to 95 wt%, more preferably 60 to 90 wt% of the total weight of the composition. (d) The amount of water in the high internal aqueous phase may be greater than 60 wt%, preferably greater than 70 wt%, more preferably greater than 80 wt% of the total weight of the aqueous phase.

(other Components)

The composition according to the invention may also comprise at least one additional ingredient.

The composition according to the invention may comprise at least one thickener. The thickeners used in the compositions according to the invention may include water-soluble polymers, such as high molecular weight crosslinked homopolymers of acrylic acid, and acrylates/acrylates C₁₀-₃₀Alkyl ester crosslinked polymers, such as Carbopol and Pemulen @; anionic acrylate polymers such as Salcare AST and cationic acrylate polymers such as Salcare SC 96; acrylamidopropyl trimethyl ammonium chloride/acrylamide; hydroxyethyl methacrylate polymers, steareth-10 allyl ether/acrylate copolymers; acrylate/behenyl alcohol polyether-25 methacrylate copolymer referred to as Aculyn 28; poly (glycerol methacrylate), acrylate/steareth-20 methacrylate copolymers; bentonite; gums such as alginates, carrageenan, acacia, gum arabic, gum ghatti (gum ghatti), karaya, tragacanth, guar gum; guar hydroxypropyltrimonium chloride, xanthan gum or gellan gum; cellulose derivatives, such as sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxymethylcarboxyethylcellulose, hydroxymethylcarboxypropylcellulose, ethylcellulose, sulfated cellulose, hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, microcrystalline cellulose; agar; pectin; gelatin; starch and its derivatives; chitosan and its derivatives, such as hydroxyethyl chitosan; polyvinyl alcohol, PVM/MA copolymer, PVM/MA decadieneCross-linked polymers, poly (oxyethylene) -based gelling agents, sodium carbomer, and mixtures thereof.

The composition according to the invention is preferably substantially free of thickeners. The composition according to the invention preferably comprises less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight of thickening agent, relative to the total weight of the composition.

The composition according to the invention may comprise at least one cosmetic active ingredient. The term "active ingredient" as used herein refers to an organic compound having any cosmetic or dermatological effect. The active ingredient for the composition is preferably selected from skin whitening ingredients, anti-aging ingredients, antioxidant ingredients and perfumes.

As skin whitening ingredients there may be mentioned, for example, L-ascorbic acid and its derivatives, such as ascorbyl tetraisopalmitate, alkoxysalicylic acid, hydroquinone glycosides and derivatives thereof, tranexamic acid and derivatives thereof, resorcinol or resorcinol derivatives, such as phenylethyl resorcinol, kojic acid and derivatives thereof, ellagic acid and resveratrol. The skin lightening ingredient is preferably selected from resorcinol or resorcinol derivatives.

As the anti-aging ingredient, for example, vitamins such as retinol, and saponin and allantoin may be mentioned.

As the antioxidant ingredient, there may be mentioned, for example, carotenoids such as β -zeaxanthin, and tocopherol and its derivatives, and flavonoids.

These cosmetic active ingredients may be formulated in the external oil phase and/or the internal oil phase. The amount of the cosmetic active ingredient in the inner oil phase is not limited, but may be 0.1 to 5% by weight, preferably less than 2% by weight, of the total weight of the composition. The amount of the cosmetic active in the external oil phase is not limited, but may be from 1 to 15% by weight, preferably less than 5% by weight, of the total weight of the composition.

The degree of saturation of these cosmetic active ingredients in the oil phase is preferably from 0.7 to 1. Saturation is defined herein as the ratio between the concentration of the active ingredient in the oil phase and the maximum solubility of the active ingredient in the oil phase measured at room temperature and atmospheric pressure.

The compositions according to the invention may comprise at least one cosmetically acceptable hydrophilic organic solvent (water-soluble solvent) in the high internal aqueous phase. The hydrophilic solvent used in the composition according to the present invention may include, for example, substantially linear or branched lower monoalcohols having 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol and isobutanol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, ethylene glycol monomethyl ether, monoethyl ether and monobutyl ether, propylene glycol ethers such as propylene glycol monomethyl ether, diethylene glycol alkyl ethers such as diethylene glycol monoethyl ether or monobutyl ether; polyethylene glycols, such as PEG-4, PEG-6 and PEG-8, and derivatives thereof.

The amount of hydrophilic organic solvent or solvents in the composition may be less than 10 wt%, preferably less than 5 wt%, of the total weight of the composition. In one embodiment of the invention, the composition is free of hydrophilic organic solvents.

Furthermore, the composition according to the invention may comprise a neutralizing agent, such as ethanolamine, in the high internal water phase. The amount of the neutralizing agent is not limited, but may be 1 to 10% by weight based on the total weight of the composition.

The compositions according to the invention may comprise further additives customary for cosmetics. The additive may be selected from anionic, cationic, nonionic or amphoteric polymers; peptides and derivatives thereof; a protein hydrolysate; swelling agents and penetrants; a natural or synthetic thickener for the oil (b); an acidifying agent; an inorganic or organic filler; an antioxidant; a preservative; a bactericide; a suspending agent; a chelating agent; an opacifying agent; a dye; inorganic ultraviolet filters; vitamins or provitamins; a humectant; a tanning compound; an anti-wrinkle active ingredient; antistaling agent, stabilizer; and mixtures thereof.

The amount of the one or more additional ingredients is not limited, but may be 0.1 to 30 wt% of the total weight of the composition according to the present invention.

The composition may be in the form of a lotion, emulsion, cream, gel, cream or essence.

The composition preferably exhibits a pH that is compatible with the skin and is generally from 3 to 8, preferably from 4.5 to 7.

The composition according to the invention can be manufactured in two steps comprising a nanoemulsion preparation step and a high internal phase emulsion preparation step. The nanoemulsion preparation step can be performed by low energy methods known in the art. Specifically, the nanoemulsion preparation step can be carried out by gently mixing together the components of (a) surfactant, (b) oil and (d) water (with or without the presence of (c) UV filter and other ingredients), for example, at room temperature (25 ℃). The high internal phase emulsion preparation step can be carried out by mixing the resulting nanoemulsion, (b) oil and (a) surfactant (with or without (c) UV filter) at high speed at 2750 rpm, for example with a high speed mixer (DAC 400FVZ, HAUSCHILD, Engineering) at room temperature for 2 to 4 minutes.

[ cosmetic method ]

The composition according to the invention can preferably be used as a sunscreen composition. In particular, the compositions according to the invention are intended to be applied to keratin materials such as the skin, the scalp and/or the lips, preferably the skin. Thus, the composition according to the invention can be used in a cosmetic method of the skin.

The cosmetic process or the cosmetic use according to the invention for keratin materials such as the skin comprises at least a step of applying the composition according to the invention to the keratin materials. The invention also relates to a method for protecting keratinous substances from ultraviolet radiation, comprising applying a composition according to the invention to the keratinous substances, and to a method for absorbing ultraviolet radiation, comprising applying a composition according to the invention and applying ultraviolet radiation to the keratinous substances. These methods may be defined as non-therapeutic methods.

The composition according to the invention can be used in topical sunscreen compositions in the form of lotions, milks, creams, gels, pastes or essences.

Examples

The present invention will be described in more detail by way of examples. However, these examples should not be construed as limiting the scope of the invention.

Example 1 and comparative example 1

The following compositions according to example 1 shown in table 1 were prepared as follows. The numerical values of the component amounts in table 1 are all based on "wt%" as an active raw material.

First, an O/W nanoemulsion was prepared in the following manner:

using a magnetic stirrer, 20 grams ethylhexyl palmitate, 10 grams ethylhexyl methoxycinnamate, 30 grams laureth-5 carboxylic acid (HLB = 9.5, available from KAO Chemicals), and 40 grams water were mixed. This premix was diluted 20-fold with an aqueous phase containing 3 g of phenylbenzimidazole sulfonic acid, 13 g of terephthalylidene dicamphor sulfonic acid, 4 g of triethanolamine and 75 g of water. The final composition of the nanoemulsion consisted of 1 g ethylhexyl palmitate, 0.5 g ethylhexyl methoxycinnamate, 1.5 g laureth-5 carboxylic acid, 2.85 g phenylbenzimidazole sulfonic acid, 12.35 g terephthalylidene dicamphor sulfonic acid, 3.8 g triethanolamine and 78 g water.

Next, an O/W/O multiple emulsion was prepared in the following manner:

85 grams of the O/W nanoemulsion was premixed with 10 grams of isohexadecane and 5 grams of PEG-15/lauryl dimethicone crosspolymer (HLB <8, available from Shinetsu Chemical). The resulting premix was further mixed using a high speed mixer (DAC 400FVZ, HAUSCHILD, Engineering) at 2750 rpm for 3 minutes to obtain an O/W/O multiple emulsion.

For comparative example 1 in table 1, an O/W emulsion was prepared in the following manner:

1 g of ethylhexyl palmitate, 0.5 g of ethylhexyl methoxycinnamate, 1.5 g of laureth-5 carboxylic acid, 2.85 g of phenylbenzimidazole sulfonic acid, 12.35 g of p-xylylene dicamphor sulfonic acid, 3.8 g of triethanolamine and 78 g of water were mixed together using a magnetic stirrer and a milky white O/W emulsion was prepared.

Next, 85 grams of the O/W emulsion was premixed with 10 grams of isohexadecane and 5 grams of PEG-15/lauryl dimethicone crosspolymer (HLB <8, available from Shinetsu Chemical). The resulting premix was further mixed using a high speed mixer (DAC 400FVZ, HAUSCHILD, Engineering) at 2750 rpm for 3 minutes to obtain an O/W/O multiple emulsion.

[ evaluation ]

The compositions according to example 1 and comparative example 1 were evaluated as follows.

(droplet size)

The droplet size of the oil phase of the O/W nanoemulsion of example 1 and of the O/W emulsion of comparative example 1 obtained during the preparation of the O/W/O emulsion was determined using a particle size analyzer (Vasco, Cordoun Technologies). The refractive index and viscosity of water at 25 ℃ were 1.33 and 0.89 cp.

The droplet size of the internal aqueous phase of the O/W/O multiple emulsion was determined using OLYMPUS GX 71 (OLYMPUS) microscopy.

(SPF)

Samples for SPF value measurement were prepared by placing 20 mg of each of the compositions according to example 1 and comparative example 1 in spots on a board (Helio plate HD 6, PMMA, 50 mm x 50 mm), and then rubbing 3 times with a finger on the board. The in vitro SPF value was calculated from UV absorbance data measured with a UV spectrophotometer (UV-2000S, Labsphere Inc) on the diffuse transmittance of the sample in the wavelength range of 250 to 450 nm.

(viscosity)

The steady state shear viscosity was measured at 25 ℃ using a DHR2 rheometer (TA instrument) with a parallel plate geometry (40 mm) with a set gap of 0.2 mm. The sample amount is 2 g and a shear rate of 0.01 to 10001/s is applied.

(yield stress)

The yield stress values of the compositions according to example 1 and comparative example 1 were calculated from the shear rate vs stress curve, wherein these parameters were measured at 25 ℃ with a set gap of 0.2 mm using a DHR2 rheometer (TA instrument) with a parallel plate geometry (40 mm). The sample amount is 2 g and a shear rate of 0.01 to 10001/s is applied.

The compositions of example 1 and comparative example 1 and the results of these evaluations are shown in table 1.

TABLE 1

	Example 1	Comparative example 1
			Laureth-5-carboxylic acid	1.2	1.2
PEG-15/lauryl dimethicone crosspolymer	5	5
			Ethylhexyl methoxycinnamate	0.4	0.4
Ethyl hexyl palmitate	0.9	0.9
			Isohexadecane	10	10
Water (W)	66.4	66.4
			Phenylbenzimidazole sulfonic acids	2.4	2.4
P-xylylene dicamphor sulfonic acid	10.5	10.5
			Triethanolamine	3.2	3.2
Inner oil droplet size (nm)	50	10,000
			Aqueous phase droplet size (μm)	1-10	1-10
SPF value	54	10
			Viscosity at 25 ℃ (Pa ∙ s)	274	66
Yield stress at 25 ℃ (Pa ∙ s)	90	45

As shown in table 1, the composition according to example 1 shows improved UV protection due to its high SPF value. Furthermore, it also shows good stability due to the high viscosity. In contrast, the composition according to comparative example 1, which included macro-sized oil droplets as an internal oil phase, exhibited poor UV protection and lower viscosity.

The composition according to example 1 comprising nano-sized oil droplets as the inner oil phase also shows better stability in terms of its high yield stress value. In contrast, the composition according to comparative example 2 comprising macro-sized oil droplets as the inner oil phase showed lower stability.

Examples 2 to 3 and comparative example 2

The following compositions according to examples 2 to 3 and comparative example 2 as shown in table 2 were prepared in the same manner as in example 1 above, except that instead of the PEG-15/lauryl polydimethylsiloxane crosspolymer, glyceryl oleate (HLB = 2.8, obtained from Taiyo Kagaku) was used in example 2, polyglycerol-2 laurate (HLB = 8.5, obtained from Taiyo Kagaku) was used in example 3, and polysorbate 80 (HLB = 15, obtained from Croda) was used in comparative example 2.

[ evaluation ]

The compositions according to examples 2 to 3 and comparative example 2 were evaluated as follows.

(appearance inspection)

The appearance of the O/W/O multiple emulsions according to examples 2 to 3 and comparative example 2 was observed with naked eyes to confirm the formation of the multiple emulsion.

The compositions of examples 2 to 3 and comparative example 2 and the results of appearance observation are shown in table 2.

TABLE 2

	Example 2	Example 3	Comparative example 2
				Laureth-5-carboxylic acid	1.2	1.2	1.2
Oleic acid glyceride	5
				Polyglycerol-2 laurate		5
Polysorbate 80			5
				Ethylhexyl methoxycinnamate	0.4	0.4	0.4
Ethyl hexyl palmitate	0.9	0.9	0.9
				Isohexadecane	10	10	10
Water (W)	66.4	66.4	66.4
				Phenylbenzimidazole sulfonic acids	2.4	2.4	2.4
P-xylylene dicamphor sulfonic acid	10.5	10.5	10.5
				Triethanolamine	3.2	3.2	3.2
Multiple emulsions	Is that	Is that	Whether or not

As shown in table 2, the compositions according to examples 2 and 3 including surfactants having HLB less than 13 can form multiple emulsions. In contrast, the composition according to comparative example 2 including the surfactant having HLB of 13 failed to form a multiple emulsion.

Claims (11)

1. A composition in the form of an oil-in-water-in-oil multiple emulsion having an outer oil phase, a high inner aqueous phase in the outer oil phase and an inner oil phase dispersed in the high inner aqueous phase in the form of droplets, the composition comprising:

(a) at least one surfactant having an HLB of less than 10;

(b) at least one oil;

(c) at least one UV filter; and

(d) water;

wherein the amount of the high internal aqueous phase is 70% by weight or more based on the total weight of the composition,

the droplets of the internal oil phase are less than 120 nanometers in size,

the amount of the inner oil phase is from 0.5 wt% to 15 wt% of the total weight of the composition,

the (a) surfactant is selected from the group consisting of a nonionic surfactant, a silicone surfactant and an anionic surfactant, wherein the nonionic surfactant is a monoester of a polyhydric alcohol and a fatty acid having 8 to 24 carbon atoms, and the anionic surfactant is a polyoxyethylene alkyl ether carboxylic acid, and

the amount of the external oil phase is 1 to 40% by weight of the total weight of the composition.

2. The composition of claim 1, wherein the amount of the high internal aqueous phase is from 70 to 99 weight percent of the total weight of the composition.

3. The composition of claim 1, wherein the viscosity of the composition is from 1 to 500 Pa ∙ s at 25 ℃.

4. The composition of claim 1, wherein the amount of the inner oil phase is from 1 weight percent to 10 weight percent of the total weight of the composition.

5. The composition of claim 1 wherein the (b) oil in the inner oil phase is selected from ester oils, hydrocarbon oils, and mineral oils.

6. The composition of claim 1, wherein the amount of the (a) surfactant is 0.1 to 20 wt% based on the total weight of the composition.

7. The composition of claim 1, wherein the amount of the external oil phase is from 2 to 30 weight percent of the total weight of the composition.

8. The composition of claim 1 wherein (b) the oil in the outer oil phase is selected from ester oils, hydrocarbon oils, mineral oils and silicone oils.

9. The composition according to claim 1, wherein the composition comprises less than 10% by weight of water-soluble solvent relative to the total weight of the composition.

10. The composition of claim 1, wherein the (c) UV filter comprises hydrophilic and hydrophobic UV filters, and the amount of the (c) UV filter is 1 to 40 wt% of the total weight of the composition.

11. A non-therapeutic cosmetic process of keratin substances, comprising the steps of:

applying a composition according to any one of claims 1 to 10 to a keratinous material.

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