WO2017110152A1

WO2017110152A1 - High internal phase emulsion composition for improving its spf and rheology

Info

Publication number: WO2017110152A1
Application number: PCT/JP2016/075741
Authority: WO
Inventors: Mohammad Mydul ALAM; Rui Niimi; Ritesh Sinha
Original assignee: L'oreal
Priority date: 2015-12-22
Filing date: 2016-08-26
Publication date: 2017-06-29
Also published as: EP3393599A1; JP2017114799A; CN108367177B; JP6789631B2; CN108367177A

Abstract

The present invention relates to a sun care cosmetic composition, in particular a sun care cosmetic composition in the form of an oil-in-water-in-oil (O/W/O) multiple emulsion 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 with HLB of less than 13; (b) at least one oil; (c) at least one UV filter; and (d) water; wherein the amount of the high internal aqueous phase is 60% by weight or more relative to the total weight of the composition and the droplet size of the internal oil phase is less than 200 nm.

Description

DESCRIPTION

HIGH INTERNAL PHASE EMULSION COMPOSITION FOR IMPROVING ITS SPF AND

RHEOLOGY

TECHNICAL FIELD

The present invention relates to a cosmetic composition, in particular a cosmetic composition in the form of an oil-in-water-in-oil (0/W/O) multiple emulsion, for a keratin substance such as skin.

BACKGROUND ART

Emulsion compositions are commonly used in a cosmetics and dermatological fields, since they are pleasant to use due to the feeling of freshness that the aqueous phase can provide. Emulsions may be in a form of an oil-in-water emulsion (O/W type emulsion), a water-in-oil emulsion (W/O type emulsion), a water-in-oil-in-water multiple emulsion (W/O/W type emulsion), and an oil-in-water-in-oil multiple emulsion (0/W/O type emulsion). To date, some prior art documents disclose a composition in a form of a multiple emulsion.

For example, US-A-5, 814,321 discloses a water-in-oil-in-water type oil adjuvant vaccine comprising a water-in-oil type oil adjuvant phase comprising 30 to 90% by weight of an oil phase A), 0.5 to 30% by weight of an emulsifying agent comprising a non-ionic surfactant B) which is a partial ester derived from a polyhydric alcohol carrying at least three hydroxyl groups and a fatty acid, and a hydroxy fatty acid triglyceride C) wherein a hydroxy group of the fatty acid is polyoxyethylenated with 20 to 60 ethylene oxide units, E) 0.01 to 10% by weight of an amino acid or a salt thereof and 0.01 to 10% by weight of a non-reducing sugar or a sugar alcohol having at least 5 hydroxyl groups in the molecule and 5 to 65% by weight of an aqueous phase D) containing a biologically acceptable and effective amount of antigens; and an outer aqueous phase F) comprising 0.2 to 20% by weight of an emulsifying agent which comprises a non-ionic surfactant.

Also, a high internal aqueous phase W/O emulsion, which is comprised with a large amount of water, is also known in the cosmetics and dermatological fields.

For example, US-A-2003/0064046 discloses a high internal aqueous phase water-in-oil type emulsion cosmetic composition comprising (A) one or more cross-linkable

polyether-modified silicone having a certain structure in an amount of 0.1 to 10.0% by weight and (B) one or more polyether-modified silicone having a certain structure, and having a content of an aqueous phase component of at least 50% by weigh.

In addition, JP-A-2010-132620 discloses a water-in-oil type emulsified cosmetic which contains the following components (A), (B), (C) and (D), and satisfies the requirements (1) and (2) below. Components: (A) one or two or more selected from among glycerin

monooleate, glycerine monoisostearate and polyoxyethylene glyceryl monostearate; (B) an aqueous component; (C) an oily component; and (D) a powder. Requirements: (1) The internal water phase ratio which is obtained by dividing the sum of the mass of the aqueous component of the component (B), by the sum of the mass of the aqueous component of the component (A) and the component (B), and of the oily component of the component (C), is at least 50%; (2) for the component (A), the purity of glycerine monooleate is at least 90 mass% based on the total amount of glycerin monooleate, glycerine dioleate and glycerine trioleate; the purity of glycerine monoisostearate is at least 90 mass% based on the total amount of glycerine monoisostearate, glycerine diisostearate and glycerine triisostearate; and the purity of polyoxyethylene glyceryl monostearate is at least 90 mass% based on the total amount of polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl distearate and

polyoxyethylene glyceryl tristearate.

In sun care cosmetic products for a keratinous substance, such as skin, these emulsion compositions are commonly used. For sun care products, good UV protecting effect is among the key functions.

DISCLOSURE OF INVENTION

An objective of the present invention is to provide a 0/W/O multiple emulsion composition, preferably a cosmetic sun care 0/W/O multiple emulsion composition for a keratin substance, such as skin, which has improved UV protecting effects.

The above objective of the present invention can be achieved by a composition in a 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 as droplets, comprising:

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

(b) at least one oil;

(c) at least one UV filter; and

' (d) water,

wherein the amount of the high internal aqueous phase is 60% by weight or more relative to the total weight of the composition, and the size of the droplets of the internal oil phase is less than 200 nm. The size of the droplets of the internal oil phase may be less than 150 nm, preferably less than 120 nm.

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

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

A viscosity of the composition may be from 1 to 500 Pa-s, preferably from 10 to 400 Pa-s, and more preferably from 50 to 350 Pa-s, and even more preferably from 100 to 300 Pa-s at 25°C.

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

The (b) oil in the internal oil phase may be selected from ester oils Such as isopropyl myristate, isopropyl palmitate, ethyl hexyl palmitate, triglycerides such as capryl caprylyl glycerides, sarcosinate such as isopropyl lauroyl sarcosinate, hydrocarbon oil such as isohexadecane, and mineral oil such as paraffin. The (a) surfactant may be selected from nonionic surfactants which are mono-esters of a polyol and a fatty acid containing from 8 to 24 carbon atoms, wherein the polyol is preferably selected from glycerol, sorbitan, and diglycerol and the fatty acid is preferably selected from isolauric acid and oleic acid, in particular esters of polyglyceryl-2 laurate, glyceryl laurate, sorbitan oleate, and glyceryl oleate, and silicone surfactants which are preferably polyether modified dimethicone such as PEG/PPG- 18/18 dimethicone, and polyether and alkyl modified dimethicone cross polymer such as PEG-15/lauryl dimethicone cross polymer, and anionic surfactants which are polyoxyethylene alkyl ether carboxylic acids such as polyoxyethylene (3) to (17) lauryl ether carboxylic acids.

The amount of the (a) surfactant may be ranging from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 1 to 10% by weight, relative to the total weight of the composition. The amount of the external oil phase may be ranging from 1% by weight to 40% by weight, preferably from 2% by weight to 30% by weight to, and more preferably from 5% by weight to 20% by weight, relative to the total weight of the composition.

The (b) oil in the external oil phase may be selected from ester oils such as isopropyl myristate, isopropyl palmitate, ethyl hexyl palmitate, triglycerides such as capryl caprylyl glycerides, sarcosinate such as isopropyl lauroyl sarcosinate, hydrocarbon oil such as isohexadecane, mineral oil such as paraffin, and silicone oil.

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

The (c) UV filter may include both of a hydrophilic and hydrophobic UV filter, and the amount of the (c) UV filter may be ranging from 1 to 40% by weight, preferably from 2 to 30% by weight, more preferably from 5 to 20% by weight, relative to the total weight of the composition.

The

such as skin; comprising the step of: applying onto the keratin substance the composition according to the present invention.

The present invention also relates to a process of protecting a keratin substance from ultraviolet radiation comprising applying to the keratin substance the composition according to the present invention. BRIEF DESCRIPTION OF DRAWINGS

[Fig.l] Figure 1 shows an example of a schematic view of the 0/W/O emulsion of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have found that, in sun care 0/W/O emulsion compositions, an introduction of nano-sized oil phase into aqueous phase can surprisingly improve UV protecting effects. In addition, the inventors also found that employing nano-sized oil phase in an 0/W/O emulsion can improve its stability.

Thus, the composition, preferably a cosmetic composition for keratin substance, preferably skin, according to the present invention is an O/W/0 type emulsion having an external oil phase, a high internal aqueous phase in the external oil phase, and internal oil phase dispersed in the high internal aqueous phase, comprising:

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

(b) at least one oil;

(c) at least one UV filter; and

(d) water,

wherein the amount of the high internal aqueous phase is 60% by weight or more relative to the total weight of the composition, and the size of the internal oil phase is less than 200 nm.

The composition according to the present invention can exhibit improved UV protecting effects.

Hereafter, the composition according to the present invention will be described in a detailed manner.

[Composition]

The composition according to the present invention is in a form of an O/W/0 emulsion having an external oil phase, a high internal aqueous phase in the external oil phase, and internal oil phase dispersed in the high internal aqueous phase. The external oil phase forms a continuous oil phase. The high internal aqueous phase is in an amount of 60% by weight or more relative to the total weight of the composition. The internal oil phase forms nano-sized droplets having a size of less than 200 nm. The composition comprises (a) at least one surfactant with HLB of less than 13, (b) at least one oil, (c) at least one UV filter; and (d) water.

It is preferable that the composition according to the'present'invention'is a cosmetic composition, in particular a cosmetic sun care composition for a keratin substance such as skin.

The composition according to the present invention can exhibit improved UV protecting effects. In addition, the composition according to the present invention can have a good stability, even when it does not include any thickeners or includes only a tiny amount of thickeners.

First, the O/W/0 structure of the composition according to the present invention will be explained below.

(External Oil Phase)

The external oil phase in the O/W/0 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 comprise 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 in general ranges from 1% by weight to 40% by weight, preferably from 2% by weight to 30% by weight to, and more preferably from 5% by weight to 20% by weight, relative to the total weight of the composition. (High Internal Aqueous Phase)

The high internal aqueous phase in the 0/W/O emulsion of the present 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 neutralizers.

The high internal aqueous phase provides a high internal phase emulsion (HIPE). Due to a high amount of the aqueous phase, in general, the droplet shape of the aqueous phase becomes polyhedral. In addition, the high amount of the aqueous phase may include a high amount of water, and thus this can provide the composition according to the present invention with a feeling of freshness when it is applied to the skin.

The high internal aqueous phase forms a micro-sized droplet. The size of the internal aqueous phase may be 1 μιη or more, preferably less than 20 μπι, and more preferably less than 10 μηι. The size of the aqueous droplet can be measured by using, for example, Particle size analyzer (Vasco, Cordoun Technologies).

The amount of the high internal aqueous phase is 60% by weight or more, preferably 70 % by more, and more preferably 80% by more relative to the total weight of the composition. The upper limit of the amount of the high internal aqueous phase is not limited, but in general, less than 99% by weigh, preferably less than 95% by weight, and more preferably less than 90% by weight relative to the total weight of the composition.

(Internal Oil Phase)

The external oil phase in the 0/W/O emulsion of the present invention forms droplets dispersed n the high internal aqueous phase and¾omprises (b) at least one oil. In addition to the (b) oil, the internal oil phase may comprise other hydrophobic/oil-soluble ingredients, such as hydrophobic UV filters and oil-soluble cosmetic active ingredients.

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

The amount of the internal oil phase is not limited, but in general ranges from 0.5% by weight to 15% by weight, preferably from 1% by weight to 10% by weight, and more preferably from 2% by weight to 5% by weight, relative to the total weight of the composition.

Surprisingly, the inventors found that the nano-sized internal oil droplet in the 0/W/O emulsion can improve UV protecting effects of the composition according to the present invention. In addition, the inventors found that the nano-sized internal oil droplet in the 0/W/O emulsion can improve the stability of the composition, since it can provide a composition with a viscosity. Therefore, the composition according to the present invention is stable even if it does not substantially include any thickeners or includes only a tiny amount of thickener.

In one embodiment of the present invention, the composition according to the present invention is substantially free from thickeners, preferably comprises less than 5% by weight, and more preferably comprises 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 by using a rheometer, for example, DHR2 rheometer (TA instrument) with a parallel-plate geometry at 25°C. Preferably, the viscosity of the composition which does not includes any thickeners can range, for example, from 1 to 500 Pa · s, preferably from 10 to 400 Pa · s, and more preferably from 50 to 350 Pa · s, and even more preferably from 100 to 300 Pa- s at 25°C and 0.01 to 1000 1/s. In addition, the composition may possess a Newtonian nature.

Also, the stability of the composition according to the present invention can be characterized by its high yield stress value. Yield stress used herein means the maximum stress up to which materials keep its structure. Beyond this stress, the materials tend to flow or destabilize. In other word, high yield stress helps to improve the stability. The high yield stress value can be calculated, for example, from the share rate vs stress curve measured by using a rheometer, for example, DHR2 rheometer (TA instrument) with a parallel-plate geometry at 25°C. Preferably, the yield stress value of the 0/W/O multiple emulsion according to the present invention can be, for example, more than 30 Pa, preferably more than 50 Pa, and more preferably more than 70 Pa at 25°C and 0.01 to 1000 1/s.

Fig. 1 sho ws an example of a schematic view of the 0/W/O emulsion of the present invention. This figure is only for reference 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 external oil phase forms a continuous oil phase in the emulsion; the high internal aqueous phase may form polyhedral droplets in the external oil phase, and the internal oil phase forms nano-sized droplets dispersed in the high internal aqueous phase.

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

(a) Surfactant

The composition according to the present invention comprises (a) at least one surfactant with HLB (Hydrophilic Lipophilic Balance) of less than 13. Two or more (a) surfactants may be used in combination. Thus, a single type of a 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 denotes the hydrophilic-lipophilic balance of a surfactant. The HLB or

hydrophilic-lipophilic balance of the surfactant(s) used according to the invention is the HLB according to Griffin, defined in the publication J. Soc. Cosm. Chem., 1954 (Vol 5), pages 249-256 or the HLB determined experimentally and as described in the publication from the authors F. Puisieux and M. Seiller, entitled "Galenica 5: Les systemes disperses [Dispersed systems] - Volume I - Agents de surface et emulsions [Surface agents and emulsions] - Chapter IV - Notions de HLB et de HLB critique [Notions of HLB and of critical HLB], pages 153-194 - paragraph 1.1.2. Determination de HLB par voie experimental

[Experimental determination of HLB], pages 164- 180.

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

It is preferable that the calculated HLB values are taken into account. The calculated HLB is defined as being the following coefficient:

calculated HLB = 20 ^χ molar mass of the hydrophilic part/total molar mass. Preferably, the lipophilic part of the surfactant is comprised of either carbon and hydrogen atoms or silicon and hydrogen atoms.

The surfactant used in the composition according to the present invention can be selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric

surfactants. Preferably, the (a) surfactants are selected from nonionic surfactants and anionic surfactants.

Nonionic Surfactant The nonionic surfactants are compounds well known in themselves (see, e.g., in this regard, "Handbook of Surfactants" by M. R. Porter, Blackie & Son publishers (Glasgow and London), 1991, pp. 116-178).

Thus, the (a) surfactant can, for example, be chosen from alcohols, alpha-diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, it being possible for the number of ethylene-oxide or propylene oxide groups to range from 2 to 50, and for the number of glycerol groups to range from 1 to 30. The (a) surfactant may preferably be chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, and are preferably oxy ethylene units. Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned include:

monooxyalkylenated or polyoxyalkylenated (C₈-C2₄)alkylphenols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated

C₈-C₃₀ alcohols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C₈-C₃₀ amides,

esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of polyalkylene glycols,

monooxyalkylenated or polyoxyalkylenated esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of sorbitol, saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated plant oils, condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures.

The surfactants preferably contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100 and most preferably between 2 and 50. Advantageously, the nonionic surfactants do not comprise any oxypropylene units.

According to one of the embodiments of the present invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylenated fatty ester (polyethylene glycol ester of fatty acid).

Examples of polyoxyethylenated fatty alcohol (or Cg-C₃o alcohols) that may be mentioned include the adducts of ethylene oxide with lauryl alcohol, especially those containing from 7 to 50 oxyethylene units and more particularly those containing from 6 to 12 oxyethylene units (Laureth-7 to Laureth-12, as the CTFA names); the adducts of ethylene oxide with behenyl alcohol, especially those containing from 5 to 50 oxyethylene units (Beheneth-5 to

Beheneth-50, as the CTFA names); the adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing from 7 to 30 oxyethylene units (Ceteareth-7 to Ceteareth-30, as the CTFA names); the adducts of ethylene oxide with cetyl alcohol, especially those containing from 7 to 30 oxyethylene units (Ceteth-7 to Ceteth-30, as the CTFA names); the adducts of ethylene oxide with stearyl alcohol, especially those containing from 7 to 30 oxyethylene units (Steareth-7 to Steareth-30, as the CTFA names); the adducts of ethylene oxide with isostearyl alcohol, especially those containing from 8 to 50 oxyethylene units (Isosteareth-8 to Isosteareth-50, as the CTFA names); and mixtures thereof.

As examples of monoglycerolated or polyglycerolated nonionic surfactants,

monoglycerolated or polyglycerolated C₈-C₄₀ alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C₈-C₄o alcohols correspond to the following formula:

RO-[CH₂-CH(CH₂OH)-0]_m-H or RO-[CH(CH₂OH)-CH₂0]_m-H in which R represents a linear or branched C₈-C₄₀ and preferably Q-C30 alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

As examples of compounds that are suitable in the context of the present invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4

Lauryl Ether), lauryl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohol may coexist in the form of a mixture. Among the monoglycerolated or polyglycerolated alcohols, it is preferable to use the C₈/C₁₀ alcohol containing 1 mol of glycerol, the C₁₀/C₁₂ alcohol containing 1 mol of glycerol and the Ci₂ alcohol containing 1.5 mol of glycerol.

The monoglycerolated or polyglycerolated C₈-C₄₀ fatty esters may correspond to the following formula:

R'0-[CH₂-CH(CH₂OR'")-0]_m-R" or R'0-[CH(CH₂OR"')-CH₂0]_m-R" in which each of R', R" and R'" independently represents a hydrogen atom, or a linear or branched C₈-C₄o and preferably Cg-C₃₀ alkyl-CO- or alkenyl-CO-radical, with the proviso that at least one of R', R" and R'" is not a hydrogen atom, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

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

According to one of the embodiments according to the present invention, the nonionic surfactant may be selected from esters of polyols with fatty acids with a saturated or unsaturated chain containing, for example, from 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units, such as mono glyceryl esters or poly glyceryl esters of a C -C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and

polyoxyalkylenated derivatives thereof, preferably containing from-10 to 200, and-more preferably from 10 to 100 oxyalkylene units; sorbitol esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sugar (sucrose, maltose, glucose, fructose, sorbitol, sorbitan, and/or alkylglycose) esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; ethers of fatty alcohols; ethers of sugar and a C₈-C₂₄, preferably Ci₂-C₂₂, fatty alcohol or alcohols; and mixtures thereof.

As glyceryl esters of fatty acids, glyceryl laurate (glyceryl mono, di, and/or tri-laurate), in particular glyceryl monolaurate (CTFA name: glyceryl laurate, sold by Taiyo Kagaku), glyceryl stearate (glyceryl mono-, di- and/or tri-stearate) (CTFA name: glyceryl stearate), glyceryl monooleate (CTFA name: glyceryl oleate, sold by Taiyo Kagaku) or glyceryl ricinoleate and mixtures thereof can be cited, and as polyoxyalkylenated derivatives thereof, mono-, di- or triester of fatty acids with a polyoxyalkylenated glycerol (mono-, di- or triester of fatty acids with a polyalkylene glycol ether of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), such as PEG-20 glyceryl stearate (mono-, di- and/or tristearate) can be cited. Mixtures of these surfactants, such as, for example, the product containing glyceryl stearate and PEG- 100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEGIN by Goldschmidt (CTFA name: glyceryl stearate SE), can also be used.

As polyglyceryl esters of (a) fatty acid(s), mention be made the product containing 2 to 10 glycerol units, such as polyglyceryl monolaurate, in particular diglyceryl monolaurate (CTFA name: polyglyceryl-2 laurate, sold by Taiyo Kagaku), oleate, myristate, caprylate, or stearate comprising 2 to 10 glycerol units, polyglyceryl mono(iso)stearate comprising 2 to 10 glycerol units, polyglyceryl dioleate comprising 2 to 10 glycerol units, polyglyceryl dilaurate comprising 2 to 10 glycerol units, polyglyceryl dimyristate comprising 2 to 10 glycerol units, polyglyceryl trimyristate comprising 2 to 10 glycerol units, polyglyceryl trioleate comprising 2 to 10 glycerol units, and polyglyceryl tricaprylate comprising 2 to 10 glycerol units.

The sorbitol esters of C₈-C₂₄ fatty acids and polyoxyalkylenated derivatives thereof can 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, from 20 to 100 EO, such as, for example, sorbitan monooleate (CTFA name: sorbitan oleate, sold by Croda), sorbitan monostearate (CTFA name: sorbitan stearate), sold by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate), sold by the company ICI under the name Span 40, and sorbitan tristearate 20 EO (CTFA name: polysorbate 65), sold by the company ICI under the name Tween 65, polyethylene sorbitan trioleate (polysorbate 85) or the compounds marketed under the trade names Tween 20 or Tween 60 by Uniqema.

As esters of fatty acids and glucose or alkylglucose, glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters, the diester of methylglucoside and oleic acid (CTFA name: Methyl glucose dioleate), the mixed ester of methylglucoside and the mixture of oleic acid/hydroxystearic acid (CTFA name: Methyl glucose dioleate/hydroxystearate), the ester methylglucoside"and^risostear.i'e'acid-^'(CTFA name: Methyl glucose isostearate), the ester of methylglucoside and lauric acid (CTFA name: Methyl glucose laurate), the mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesqui-isostearate), the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by AMERCHOL, and mixtures thereof can be cited. As ethoxylated ethers of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and methylglucose, and in particular the polyethylene glycol ether of the diester of methylglucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methyl-glucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof, can, for example, be cited. As sucrose esters, saccharose palmito-stearate, saccharose stearate and saccharose monolaurate can, for example, be cited.

As sugar ethers, alkylpolyglucosides can be used, and, for example, ethers of a sugar and of C_8-C₂₄ fatty alcohols including decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel, and the product marketed under the name ORAMIX NS 10 by Seppic,

caprylyl/capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818/UP by

Henkel, cetostearyl glucoside possibly mixed with cetostearyl alcohol, marketed, for example, under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by

Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example, in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example, in the form of the mixture (35/65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof can in particular be cited.

Mixtures of glycerides of alkoxylated plant oils such as mixtures of ethoxylated (200 EO) palm and copra (7 EO) glycerides can also be cited.

The nonionic surfactant according to the present invention preferably contains alkenyl or branched C₁₂-C₂₂ acyl chain such as oleyl or isostearyl group. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

According to one of the embodiments according to the present invention, the nonionic surfactant may be selected from copolymers of ethylene oxide and of propylene oxide, in particular copolymers of the following formula: HO(C₂H₄0)_a(C₃H₆0)_b(C₂H₄0)_cH in which a; b and c are'integers-suc^that'a+c ranges-from^ to 100^' and b ranges from 14 t -60. and mixtures thereof. In particular, among these nonionic surfactants, mono-esters of a polyol and a fatty acid are preferably used in the present invention. As the polyol, glycerol, sorbitan, and diglycerol are especially preferable, and as the fatty acid, lauric acid and oleic acid are especially preferable. The most preferable esters are polyglyceryl-2 laurate, glyceryl laurate, sorbitan oleate, and glyceryl oleate.

According to one of the embodiments according to the present invention, the nonionic surfactant may be selected from copolymers of ethylene oxide and of propylene oxide, in particular copolymers of the following formula: HO(C₂H₄0)_a(C₃H₆0)_b(C₂H₄0)_cH in which a, b and c are integers such that a+c ranges from 2 to 100 and b ranges from 14 to 60, and mixtures thereof. According to one of the embodiments according to the present invention, the nonionic surfactant may be selected from silicone surfactants. Non-limiting mention may be made of those disclosed in documents US-A-5364633 and US-A-5411744.

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

in which:

Ri, R₂ and R₃, independently of each other, represent a Q-Q alkyl radical or a radical -(CH₂)_x-(OCH₂CH₂)_y-(OCH₂CH₂CH₂)_z-OR₄, at least one radical R_1; R₂ or R₃ not being an alkyl radical; R₄ being a hydrogen, an alkyl radical or an acyl radical;

A is an integer ranging from 0 to 200;

B is an integer ranging from 0 to 50; with the proviso that A and B are not simultaneously equal to zero;

x is an integer ranging from 1 to 6;

y is an integer ranging from 1 to 30;

z is an integer ranging from 0 to 5.

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

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

(CH₃)₃SiO - [(CH₃)₂SiO]_A - (CH₃SiO)_B - Si(CH₃)₃

I (ID

(CH₂)r(OCH₂CH₂)_y-OH

in which A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10 and y is an integer ranging from 10 to 20.

As examples of silicone surfactants of formula (I), mention may also be made of the compounds of formula (III): H-(OCH₂CH₂)_y-(CH₂)₃-[(CH₃)₂SiG]_A'-(CH₂)₃-(OCH₂CH₂)_y-OH (III) in which A' and y are integers ranging from 10 to 20.

Compounds of the present invention which may be used are those sold by the company Dow Corning under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667. The compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (III) in which, respectively, A is 22, B is 2 and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12. The compound Q4-3667 is a compound of formula (III) in which A is 15 and y is 13. In particular, the silicone surfactants may include alkyl dimethicone copolyols, notably those having an alkyl radical with 10 to 22 carbon atoms and having 2 to 50 oxyethylene groups and 2 to 50 oxypropylene groups, such as cetyl dimethicone copolyol (INCI name: Cetyl PEG/PPG- 10/1 Dimethicone) such as the product marketed under the designation Abil EM-90 by the company Goldschmidt; lauryl dimethicone copolyol (INCI name: Lauryl

PEG/PPG- 18/ 18 Methicone) and, for example, a mixture of about 91% lauryl dimethicone copolyol and about 9% isostearyl alcohol, marketed under the designation DOW CORNING 5200 FORMULATION AID by the company Dow Corning; dimethicone copolyols, notably among those having 2 to 50 oxyethylene groups and 2 to 50 oxypropylene groups, which are polyether modified linear or branched polysiloxane polymer, for example, that having 18 oxyethylene groups and 18 oxypropylene groups (PEG/PPG- 18/18 Dimethicone, sold by Shinetsu Chemical), such as the mixture of dimethicone copolyol having 18 oxyethylene groups and 18 oxypropylene groups, cyclopentasiloxane and water (10/88/2), marketed by the company Dow Corning under the designation DC-3225C or DC2-5225C (INCI name:

Cyclopentasiloxane/PEG/PPG-18/18 Dimethicone), or that having 14 oxyethylene groups and 14 oxypropylene groups (PEG/PPG- 14/ 14 Dimethicone) such as, notably, the mixture of dimethicone copolyol having 14 oxyethylene groups and 14 oxypropylene groups and cyclopentasiloxane (85/15) marketed under the designation Abil EM-97 by the company Goldschmidt (INCI name: Bis-PEG/PPG-14/14 Dimethicone/Cyclopentasiloxane).

Also, the silicone surfactants may include crosslinked siloxane elastomers, such as polyether substituted or unsubstituted dimethicone/copolyol crosspolymer, dimethicone and

dimethicone/PEG-10/15 crosspolymers, substituted or unsubstituted dimethicone/polyglyceryl crosspolymer, dimethicone and dimethicone/polyglycerin-3 crosspolymer. Such suitable emulsifying crosslinked siloxane elastomers are sold or made, for example, under the names of "KSG-210" a polyether-modified dimethicone cross polymer with an INCI name of dimethicone (and) dimethicone/PEG-10/15 crosspolymer, and "KSG-710" a

polyglycerin-modified dimethicone crosspolymer with an INCI name of dimethicone (and) dimethicone/polyglycerin-3 crosspolymer, both available from ShinEtsu Silicones of America, Inc. (Akron, Ohio). Among polyether modified crosslinked siloxane elastomers, polyether and alkyl chain modified crosslinked siloxane elastomers, such as PEG-10/lauryl dimethicone cross polymer and PEG-15/lauryl dimethicone cross polymer, which are sold by Shinetsu Chemical under the name of "KSG-310", " SG-320", " SG-330", or " SG-340, are preferably used in the present invention. In the polyetherand alkyl chain-modified" crosslinked siloxane 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 Surfactant

The anionic surfactants may be chosen in particular from phosphates and alkyl phosphates, carboxylates, sulphosuccinates, amino acid derivatives, alkyl sulphates, alkyl ether sulphates, sulphonates, isethionates, taurates, polyoxyethylene alkyl ether carboxylic acids, alkyl sulphoacetates, polypeptides, and their mixtures.

1) Mention may be made, as phosphates and alkyl phosphates, for example, of monoalkyl phosphates and dialkyl phosphates, such as lauryl monophosphate, sold under the name MAP 20® by Kao Chemicals, the potassium salt of dodecyl phosphate, the mixture of mono- and diesters (predominantly diester) sold under the name Crafol AP-31® by Cognis, the mixture of octyl phosphate monoester and diester, sold under the name Crafol AP-20® by Cognis, the mixture of ethoxylated (7 mol of EO) 2-butyloctyl phosphate monoester and diester, sold under the name Isofol 12 7 EO-Phosphate Ester® by Condea, the potassium or triethanolamine salt of mono(C₁₂-C₁₃)alkyl phosphate, sold under the references Arlatone MAP 230K-40® and Arlatone MAP 230T-60® by Uniqema, potassium lauryl phosphate, sold under the name Dermalcare MAP XC-99/09® by Rhodia Chimie, and potassium cetyl phosphate, sold under the name Arlatone MAP 160K by Uniqema. 2) Mention may be made, as carboxylates, of:

amido ether carboxylates (AEC), such as sodium lauryl amido ether carboxylate (3 EO), sold under the name Akypo Foam 30® by Kao Chemicals;

polyoxyethylenated carboxylic acid salts, such as oxyethylenated (6 EO) sodium lauryl ether carboxylate (65/25/10 C₁₂-C₁₄-C₁₆), sold under the name Akypo Soft 45 NV® by Kao Chemicals, polyoxyethylenated and carboxymethylated fatty acids originating from olive oil, sold under the name Olivem 400® by Biologia E Tecnologia, or oxyethylenated (6 EO) sodium tridecyl ether carboxylate, sold under the name Nikkol ECTD-6NEX® by Nikkol; and salts of fatty acids (soaps) having a C₆ to C₂₂ alkyl chain which are neutralized with an organic or inorganic base, such as potassium hydroxide, sodium hydroxide,

triethanolamine, N-methylglucamine, lysine and arginine.

3) Mention may in particular be made, as amino acid derivatives, of alkali salts of amino acids, such as:

sarcosinates, such as sodium lauroyl sarcosinate, sold under the name Sarkosyl NL 97® by Ciba or sold under the name Oramix L 30® by Seppic, sodium myristoyl sarcosinate, sold under the name Nikkol Sarcosinate MN® by Nikkol, or sodium palmitoyl sarcosinate, sold under the name Nikkol Sarcosinate PN® by Nikkol;

alaninates, such as sodium N-lauroyl-N-methylamidopropionate, sold under the name Sodium Nikkol Alaninate LN 30® by Nikkol or sold under the name Alanone ALE® by Kawaken, or triethanolamine N-lauroyl-N-methylalanine, sold under the name Alanone ALTA® by Kawaken;

glutamates, such as triethanolamine monococoyl glutamate, sold under the name Acylglutamate CT-12® by Ajinomoto, triethanolamine lauroyl glutamate, sold under the name Acylglutamate LT-12® by Ajinomoto;

- aspartates, such as the mixture of triethanolamine N-lauroyl aspartate and

triethanolamine N-myristoyl aspartate, sold under the name Asparack® by Mitsubishi;

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

citrates, such as the citric monoester of oxyethylenated (9 mol) coco alcohols, sold under the name Witconol EC 1129 by Goldschmidt; and

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

4) Mention may be made, as sulphosuccinates, for example, of oxyethylenated (3 EO) lauryl (70/30 C₁₂/C₁₄) alcohol monosulphosuccinate, sold under the names Setacin 103 Special® and Rewopol SB-FA 30 K 4® by Witco, the disodium salt of a hemisulphosuccinate of Ci₂-Ci₄ alcohols, sold under the name Setacin F Special Paste® by Zschimmer Schwarz, oxyethylenated (2 EO) disodium oleamidosulphosuccinate, sold under the name Standapol SH 135® by Cognis, oxyethylenated (5 EO) lauramide monosulphosuccinate, sold under the name Lebon A-5000® by Sanyo, the disodium salt of oxyethylenated (10 EO) lauryl citrate monosulphosuccinate, sold under the name Rewopol SB CS 50® by Witco, or ricinoleic monoethanolamide monosulphosuccinate, sold under the name Rewoderm S 1333® by Witco. Use may also be made of polydimethylsiloxane sulphosuccinates, such as disodium PEG- 12 dimethicone sulphosuccinate, sold under the name Mackanate-DC 30 by Maclntyre. 5) Mention may be made, as alkyl sulphates, for example, of triethanolamine lauryl sulphate (CTFA name: TEA lauryl sulphate), such as the product sold by Huntsman under the name Empicol TL40 FL or the product sold by Cognis under the name Texapon T42, which products are at 40% in aqueous solution. Mention may also be made of ammonium lauryl sulphate (CTFA name: ammonium lauryl sulphate), such as the product sold by Huntsman under the name Empicol AL 30FL, which is at 30% in aqueous solution.

6) Mention may be made, as alkyl ether sulphates, for example, of sodium lauryl ether sulphate (CTFA name: sodium laureth sulphate), such as that sold under the names Texapon N40 and Texapon AOS 225 UP by Cognis, or ammonium lauryl ether sulphate (CTFA name: ammonium laureth sulphate), such as that sold under the name Standapol EA-2 by Cognis.

7) Mention may be made, as sulphonates, for example, of α-olefinsulphonates,. such as sodium a-olefinsulphonate (C₁₄-C₁₆), sold under the name Bio-Terge AS-40® by Stepan, sold under the names Witconate AOS Protege® and Sulframine AOS PH 12® by Witco or sold under the name Bio-Terge AS-40 CG® by Stepan, secondary sodium olefinsulphonate, sold under the name Hostapur SAS 30® by Clariant; or linear alkylarylsulphonates, such as sodium xylenesulphonate, sold under the names Manrosol SXS30®, Manrosol SXS40® and Manrosol SXS93® by Manro. 8) Mention may be made, as isethionates, of acylisethionates, such as sodium

cocoylisethionate, such as the product sold under the name Jordapon CI P® by Jordan.

9) Mention may be made, as taurates, of the sodium salt of palm kernel oil

methyltaurate, sold under the name Hostapon CT Pate® by Clariant; N-acyl-N-methyltaurates, such as sodium N-cocoyl-N-methyltaurate, sold under the name Hostapon LT-SF® by

Clariant or sold under the name Nikkol CMT-30-T® by Nikkol, sodium palmitoyl

methyltaurate, sold under the name Nikkol PMT® by Nikkol, or sodium steraroyl

methyltaurate, sold under the name Sunsoft O-30S by Taiyo Kagaku. 10) Mention may be made of polyoxyethylene alkyl ether carboxylic acids, such as compounds corresponding to formula (IV):

RO[CH₂0]_u[(CH₂)_xCH(R')(CH₂)_y(eH₂)_zO]v[e¾GH20] eH₂COOH (IV)

wherein:

R is a hydrocarbon radical containing from 6 to 40 carbon atoms;

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

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

R' represents hydrogen, alkyl, preferably C_\-Cn alkyl; and

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 the substituent, mention may be made of a monovalent functional group such as a halogen atom, a hydroxyl group, a Ci-C₆ alkoxy group, an amino group, a C C₆ alkylamino group, a Cy-C dialkylamino group, a nitro group, a carbonyl group, an acyl group, a carboxyl group, a cyano group and the like.

Typically, R is a linear or branched, acyclic C₆-C₄₀ alkyl or alkenyl group or a C₁-C₄₀ alkyl phenyl group, more typically a C₈-C₂₄ alkyl or alkenyl group or a C₄-C₂₀ alkyl phenyl group, and even more typically a Ci₀-C₁₈ alkyl group or alkenyl group or a C₆-C₁₆ alkyl phenyl group, which may be substituted; u, v, w, independently of one another, is typically a number from 2 to 20, more typically a number from 3 to 17, and most typically a number from 5 to 15; x, y, z, independently of one another, is typically a number from 2 to 13, more typically a number from 1 to 10, and most typically a number from 0 to 8;

The polyoxyethylene alkyl ether carboxylic acids corresponding to formula (IV) can be obtained by alkoxylation of alcohols ROH with ethylene oxide as the sole alkoxide or with several alkoxides and subsequent oxidation. The numbers u, v, and w each represent the degree of alkoxylation. Whereas, on a molecular level, the numbers u, v and w and the total degree of alkoxylation can only be integers, including zero, on a macroscopic level they are mean values in the form of broken numbers. The fatty ether carboxylic acids may include polyoxyalkylenated (C₆-C₃o)alkyl ether carboxylic acid and their salts, more specifically polyoxyethylenated (C -C₃₀) alkyl ether carboxylic acids and their salts; polyoxyalkylenated (C₆-C₃o)alkylaryl ether carboxylic acids and their salts; and polyoxyalkylenated

(C₆-C₃o)alkylamido ether carboxylic acids. Preferably, the fatty ether carboxylic acids are polyoxyethylene (3) to (17) lauryl ether carboxylic acid. Suitable polyoxyethylene alkyl ether carboxylic acids, include, but are not limited to, the following representatives referred to by their INCI names: Butoxynol-5 to 19 Carboxylic Acid, Capryleth-4 to 25 Carboxylic Acid, Coceth-7 Carboxylic Acid, C_9-15 Pareth-6 to 8

Carboxylic Acid, Deceth-7 Carboxylic Acid, Laureth-3 to 17 Carboxylic Acid, such as

Laureth-5 carboxylic acid, PPG-6-Laureth-6 Carboxylic Acid, PPG-8-Steareth-7 Carboxylic Acid, Myreth-3 to 5 Carboxylic Acid, Nonoxynol-5 to 10 Carboxylic Acid, Octeth-3

Carboxylic Acid, Octoxynol-20 Carboxylic Acid, Oleth-3 t olO Carboxylic Acid,

PPG-3-Deceth-2 Carboxylic Acid, Capryleth-2 Carboxylic Acid, Ceteth-13 Carboxylic Acid, Deceth-2 Carboxylic Acid, Hexeth-4 Carboxylic Acid, Isosteareth-6 to 11 Carboxylic Acid, Trudeceth-3 to 12 Carboxylic Acid, Trideceth-3 to 19 Carboxylic Acid, Undeceth-5

Carboxylic Acid, and mixtures thereof.

Preferably, the (a) surfactant used in the composition according to the present invention can be selected from nonionic surfactants which are mono-esters of a polyol and a fatty acid containing from 8 to 24 carbon atoms, wherein the polyol is preferably selected from glycerol, sorbitan, and diglycerol and the fatty acid is preferably selected from isolauric acid and oleic acid, in particular esters of polyglyceryl-2 laurate, glyceryl laurate, sorbitan oleate, and glyceryl oleate, and silicone surfactants which are prefcrably polyether modified dimethicone such as PEG/PPG- 18/18 dimethicone, and polyether and alkyl modified dimethicone cross polymer such as PEG-15/lauryl dimethicone cross polymer, and anionic surfactants which are polyoxyethylene alkyl ether carboxylic acids such as polyoxyethylene (3) to (17) lauryl ether carboxylic acids.

The representative examples of the surfactants used in the present invention and the HLB values are shown below. Name of Surfactants HLB

PEG/PPG-18/18 Dimethicone < 9

Polyglyceryl-2 Laurate 8.5

PEG-15/Lauryl Dimethicone Cross < 8

polymer

Glyceryl Laurate 5.3

Sorbitan Oleate 4.3

Glyceryl Oleate 2.8

Laureth-5 Carboxylic Acid 9.5

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

(b) Oil

The composition according to the present 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, the (b) oil may be included in both the external and internal oil phases.

As used herein, the expression "oil" means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). These oil(s) may be volatile or non-volatile, preferably non-volatile.

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

Hydrocarbon oils may be chosen from:

linear or branched, optionally cyclic, C₆-C₁₆ lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane; and

- linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam®, and squalane.

As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosane, and decene/butene copolymer; and mixtures thereof.

As examples of silicone oils, mention may be made of, for example, linear

organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane,

methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as

octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,

dodecamethylcyclohexasiloxane, and the like; and mixtures thereof. Preferably, silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group. These silicone oils may also be organomodified. The organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprising in their structure one or more organofunctional groups attached via a

hydrocarbon-based group. Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry 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 between 60°C and 260°C, and even more particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia,

decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the type such as

dimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 3109 sold by the company Union Carbide, of formula:

- D"— D' D" - D' -

CH CH₃

I I

with D" : ^— Si - O— and with D' : - Si - O—

CH₃ C₈H₁₇

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture, of octamethylcyclotetrasiloxane and

tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-l,r-bis(2,2,2',2',3,3'-hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5 ^χ 10^"6 m²/s at 25°C. An example is

decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM standard 445 Appendix C.

Non-volatile 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, mention may be made, in a non-limiting manner, of the following commercial products:

the Silbione^® oils of the 47 and 70 047 series or the Mirasil^® oils sold by Rhodia, for instance the oil 70 047 V 500 000;

- the oils of the Mirasil^® series sold by the company Rhodia; the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm /s;

the Viscasil^® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia. Among the silicones containing aryl groups are polydiarylsiloxanes, especially

polydiphenylsiloxanes and polyalkylarylsiloxanes. Examples that may be mentioned include the products sold under the following names:

the Silbione® oils of the 70 641 series from Rhodia;

the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;

- the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;

the silicones of the PK series from Bayer, such as the product PK20;

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

As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado 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 oils are preferably liquid esters of saturated or unsaturated, linear or branched CrC₂₆ aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Q-C₂₆ aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.

Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the invention are derived is branched.

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

Esters of C₄-C₂₂ dicarboxylic or tricarboxylic acids and of C C₂₂ alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C₄-C₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.

Mention may especially be made of: diethyl sebacate; isopropyl lauroyl sarcosinate;

diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As ester oils, one can use sugar esters and diesters of C₆-C₃₀ and preferably Ci₂-C₂₂ fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C₆-C₃₀ and preferably C₁₂-C₂₂ fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated 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, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.

More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates.

An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleater

As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl

isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate),

pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

As examples of artificial triglycerides, mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/liholenate).

It may be preferable that the (b) oil be chosen from apolar hydrocarbon oils which are in the form of a liquid at a room temperature, in particular a mineral oil, such as paraffin. It may be also preferable that the (b) oil be chosen from oils with molecular weight below 600 g/mol. Preferably, the (b) oil has a low molecular weight such as below 600 g/mol, more preferably below 500 g/mol, in particular below 400 g/mol, chosen among ester or ether oils with a short hydrocarbon chain or chains (Cj-C₁₈, e.g., isopropyl myristate, isopropyl palmitate, isononyl isononanoate, dicaprylyl carbonate, ethyl hexyl palmitate, dicaprylyl ether, and in particular sarcosinate such as isopropyl lauroyl sarcosinate), hydrocarbon oils with a short alkyl chain or chains (Ci-C₁₈, e.g., isododecane, isohexadecane, and squalane), and short alcohol type oils such as octyldodecanol.

It is also preferable that the (b) oil be selected from the group consisting of hydrocarbon oils, esters of C₄-C₂₂ dicarboxylic or tricarboxylic acids and of C1-C22 alcohols, and esters of C₄-C₂2 monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C₄-C₂₆ dihydroxy, C₄-C₁₅ trihydroxy, tetrahydroxy or pentahydroxy alcohols, and mixtures thereof.

It may be also preferable that the (b) oil be chosen from ester oils such as isopropyl myristate, isopropyl palmitate, isononyl isononanoate, dicaprylyl carbonate, ethyl hexyl palmitate, dicaprylyl ether, and in particular sarcosinate such as isopropyl lauroyl sarcosinate, artificial triglycerides such as capryl caprylyl glycerides, and silicon oils.

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

Preferably, the (b) oils which constitute the internal oil phase are selected from a group consisting of the ester oils such as isopropyl myristate, isopropyl palmitate, ethyl hexyl palmitate, triglycerides such as capryl caprylyl glycerides, sarcosinate such as isopropyl lauroyl sarcosinate, hydrocarbon oils such as isohexadecane, mineral oils such as paraffin.

The amount of the (b) oil in the internal oil phase of the- presenHnvention is preferably 70% by weight or more, more preferably 80% by weight or more, and more preferably 90% by weight or more.

Preferably, the (b) oils which constitute the external oil phase are selected from a group consisting of the ester oils such as isopropyl myristate, isopropyl palmitate, ethyl hexyl palmitate, triglycerides such as capryl caprylyl glycerides, sarcosinate such as isopropyl lauroyl sarcosinate, hydrocarbon oils such as isohexadecane, mineral oils such as paraffin, and the silicone oils.

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

(c) UV Filter

The composition according to the present 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" here comprises the UV-B region (260-320 run in wavelength) and the UV-A region (320-400 nm in wavelength). Therefore, a UV filter means any material which has filtering effects in the wavelength of UV-A and/or UV-B regions. Preferably, the

composition according to the present invention may cover both the UV-A and UV-B regions.

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

The term "hydrophilic UV filter" used herein is understood to mean any agent which screens out UV radiation and which is capable of being completely dissolved in the molecular state in the aqueous phase or of being dispersed in the colloidal form (for example in the micelle form) in the aqueous phase of the 0/W/O emulsion. Therefore, the hydrophilic UV filters may be formulated in the internal aqueous phase of the present invention.

The term "hydrophobic UV filter" used herein is understood to mean any agent which screens out UV radiation and which is capable of being completely dissolved in the molecular state in an oil phase or of being dispersed in the colloidal form (for example in the micelle form) in the oil phase of the 0/W/O emulsion. Therefore, the hydrophobic UV filters may be formulated in the external and internal oil phases of the present invention.

(Hydrophilic UV Filter) The hydrophilic UV filter(s) used for the present invention may be active in the UV-A and/or UV-B region, preferably in the both the UV-A and UV-B regions in alone or a combination.

The hydrophilic UV-A filter includes, but not limited to:

Benzylidenecamphor derivatives, such as Terephthalylidene Dicamphor Sulfonic Acid, for exmple, manufactured under the name "Mexoryl SX" by Chimex,

Bisbenzoxazolyl derivatives, such as described in Patent, EP 669 323 and US 2,463,264, more particularly the compound Disodium Phenyl Dibenzimidazole Tetrasulfonate, sold under the trade name "Neo Heliopan AP" by Haarmann and Reimer. The hydrophilic UV-B filter includes, but not limited to:

p-Aminobenzoic (PABA) derivatives, such as PABA, Glyceryl PABA and PEG-25 PABA, such as sold under the name "Uvinul P25" by BASF,

Phenylbenzimidazole deruvatuves, such as phenylbenzimidazole sulfonic acid, marketed under the name "Eusolex 232" by Merck, and disodium phenyl dibenzimidazole

tetrasulfonate, marketed under the name "Neo Heliopan AP" by Haarmann,

Reimer.Phenylbenzimidazole Sulfonic Acid, such as sold in particular under the trade name

"Eusolex 232" by Merck,

Ferulic Acid,

Salicylic Acid,

DEA methoxycinnamate,

Benzylidene Camphor Sulfonic Acid, such as manufactured under the name "Mexoryl SL" by

Chimex,

Camphor Benzalkonium Methosulfate, such as manufactured under the name "Mexoryl SO" by Chimex. The hydrophilic UV-A and UV-B filter includes, but not limited to:

Benzophenone-4, such as sold under the trade name "Uvinul MS40" by

BASF,Benzophenone-5, and Benzophenone-9. Preferably, the hydrophilic UV filters are selected from a group consisting of

benzylidenecamphor derivatives, such as terephthalylidene dicamphor sulfonic acid, and phenylbenzimidazole deruvatuves, such as phenylbenzimidazole sulfonic acid.

The amount of the hydrophilic UV filter(s) in the composition may be from 1 to 40% by weight, preferably from 3 to 30% by weight, and more preferably from 5 to 20% by weight, relative to the total weight of the composition.

(Hydrophobic UV Filter) The hydrophobic filters of the present invention can be formulated in both the external oil phase and the internal oil phase, or either the external oil phase or the internal oil phase.

The hydrophobic UV filter(s) used for the present invention may be active in the UV-A and/or UV-B region, preferably in the both of the UV-A and UV-B regions alone or a combination.

Hydrophobic UV-A filters used in the present invention may include, but are not limited to, aminobenzophenone compounds, dibenzoylmethane compounds, anthranilic acid compounds, and 4,4-diarylbutadiene compounds. As the aminobenzophenone compounds, mention may be made of n-hexyl

2-(4-diethylamino-2-hydroxybenzoyl)benzoate, the alternative name of which is diethylamino hydroxybenzoyl hexyl benzoate (DHHB), sold under the trade nomw "Uvinul A+" from BASF. As the dibenzoylmethane compounds, mention may be made of 4-isopropyldibenzoylmethane, sold under the name of "Eusolex 8020" from Merck,

l-(4-methoxy-l-benzofuran-5-yl)-3-phenylpropane-li3-dronej sold under the name of

"Pongamol" from Quest, l-(4-(tert-butyl)phenyl)-3-(2-hydroxyphenyl)propane-l,3-dione, and butyl methoxydibenzoylmethane, sold under the trade name "Parsol 1789" from Hoffmann-La Roche.

As the anthranilic acid compounds, mention may be made of menthyl anthranilate marketed under the name "NEC- HELIPAN MA" by Symrise. As the 4,4-diarylbutadiene compounds, mention may be made of 1 , 1 -dicarboxy

(2,2'-dimethylpropyl)-4,4-diphenylbutadiene and diphenyl butadinene malonates and malononitriles.

Hydrophobic UV-B filters used in the present invention may include, but are not limited to, triazine compounds, para-aminobenzoic acid compounds, salicylic compounds, cinnnamate compounds, β,β-diphenylacrylate compounds, benzylidenecamphor compounds, imidazoline compounds, benzalmalonate compounds, and mecocyanine compounds.

As the triazine compounds, mention may be made of ethylhexyl triazone, marketed under the name "UVINUL T-150" by BASF, diethylhexyl butamido triazone, marketed under the name "UVASORB HEB" by SIGMA 2V, 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4' -aminobenzalmalonate)-s-triazine, 2,4-bis(dineopentyl

4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s-triazine, 2,4-bis(n-butyl

4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine.

As the para-aminobenzoic acid derivates, mention may be made of para-aminobenzoates (PABA), for example, ethyl PAB A (para-aminobenzoate), ethyl dihydroxypropyl PABA, and ethylhexyl dimethyl PABA, marketed under the name "ESCALOL 5972 from ISP. As the salicylic compounds, mention may be made of homosalate, marketed under the name "Eusolex HMS" by Rona/EM industries, and ethylhexyl salicylate, marketed under the name "NEO HELIOPAN OS" by Symrise.

As the cinnnamate compounds, mention may be made of ethylhexyl methoxycinnamate, marketed under the name "PARSOL MCX" by DSM NUTRITIONAL PRODUCTS, isopropyl ethoxy cinnamate, isoamyl methoxy cinnamate, marketed under the name "NEO HELIOPAN E 1000" by Symrise, diisopropyl methylcinnamate, cinoxate, and glyceryl ethylhexanoate dimethoxycynnamate. As the β,β-diphenylacrylate compounds, mention may be made of octocrylene, marketed under the name "UVINUL N539" by BASF, and

etocrylene, marketed under the name "UNIVUL N35" by BASF.

As the benzylidenecamphor compounds, mention may be made of 3 -benzylidene camphor, marketed under the name "MEXORYL SD" from CHIMEX, methylbenzylidene camphor, marketed under the name "EUSOLEX 6300" by MERCK, polyacrylamidomethyl benzylidene Camphor, marketed under the name "MEXORYL SW" by CHIMEX.

As the imidazoline compounds, mention may be made of ethylhexyl dimetoxybenzylidene dioxoimidazoline propionate.

As the benzalmalonate compounds, mention may be made of polyorganosiloxane containing a^j benzalmalonate moiety, for example, Polysilicone-15, marketed under the name "Parsol SLX" by DSM NUTRITIONAL PRODUCTS, and di-neopentyl 4'-mefhoxybenzalmalonate.

The hydrophobic UV- A and UV-B filters used in the present invention include, but not limited to:

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

- benzotriazole compounds such as drometrizole trisiloxane marketed under the name

"Silatrizole" by Rhodia Chimie and bumetrizole marketed under the name "TINOGUARTD AS" by CIBA-GEIGY;

- bis-resorcinyl triazines, such as bis-ethylhexyloxyphenyl methoxyphenyl triazine marketed under the name "TINOSORB S" by CIBA-GEIGY; and

- benzoxazole compounds, such as 2,4-bis[5-(l-dimethylpropyl)

benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-l,3,5-triazine marketed under the name "Uvasorb K2A" by Sigma 3V.

Preferably, the hydrophobic UV filters are selected from cinnnamate compounds, such as ethylhexyl methoxycinnamate, isopropyl ethoxy cinnamate, isoamyl methoxy cinnamate, diisopropyl methylcinnamate, cinoxate, and glyceryl ethylhexanoate dimethoxycynnamate.

The amount of the hydrophobic UV filter(s) in the internal oil phase is not limited, but may be from 0.1 to 5% by weight, preferably less than 2% by weight relative to the total weight of the composition. The amount of the hydrophobic UV filter(s) in the external oil phase is not limited, but may be from 1 to 15% by weight, preferably less than 5% by weight relative to the total weight of the composition.

In general, the amount of the (c) UV filter(s) including hydrophilic and hydrophobic UV filter(s) may be from 1 to 40% by weight, preferably from 2 to 30% by weight, more preferably from 5 to 20% by weight, relative to the total weight of the composition.

(d) Water

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

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

(Other Ingredients) The composition according to the present invention may also comprise at least one additional ingredient.

The composition according to the present invention may comprise at least one thickener. The thickener used in the composition according to the present invention may include water soluble polymers such as, for example, high molecular weight crosslinked homopolymers of acrylic acid, and Acrylates/Ci₀-₃o Alkyl Acrylate Crosspolymer, such as the Carbopol® and Pemulen®; anionic acrylate polymers such as Salcare® AST and cationic acrylate polymers such as Salcare® SC96; acrylamidopropylttrimonium chloride/acrylamide; hydroxyethyl methacrylate polymers, Steareth-10 Allyl Ether/ Acrylate Copolymer; Acrylates/Beheneth-25 Metacrylate Copolymer, known as Aculyn® 28; glyceryl polymethacrylate,

Acrylates/Steareth-20 Methacrylate Copolymer; bentonite; gums such as alginates, carageenans, gum acacia, gum arabic, gum ghatti, gum karaya, gum tragacanth, guar gum; guar hydroxypropyltrimonium chloride, xanthan gum or gellan gum; cellulose derivatives such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl

carboxyethyl cellulose, hydroxymethyl carboxypropyl cellulose, ethyl cellulose, sulfated cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, macrocrystalline cellulose; agar; pectin; gelatin; starch and its derivatives; chitosan and its derivatives such as hydroxyethyl chitosan; polyvinyl alcohol, PVM/MA copolymer, PVM/MA decadiene crosspolymer, poly(ethylene oxide) based gelling agents, sodium carbomer, and mixtures thereof. Preferably, the composition according to the present invention is substantially free from thickeners. Preferentially, the composition according to the present invention includes less than 5% by weight, preferably less than 2% by weight, and more preferably less than 1% by weight of thickeners, relative to the total weight of the composition.

The composition according to the present invention may include at least one cosmetic active ingredient. The term "active ingredient" used herein means an organic compound having any cosmetic or dermatological effects. Preferably, the active ingredients used in the composition are selected from skin- whitening ingredients, antiaging ingredients, antioxidant ingredients, and fragrances.

As the skin-whitening ingredients, mention can be made, for example, L-ascorbic acid and its derivatives, such as ascorbyl tetraisopalmitate, alkoxysalicylic acids, hydroquinone glycosides and its derivatives, tranexamic acids and its derivatives, resorcinol or resorcinol derivatives, such as phenylethyl resorcinol, koji acids and its derivatives, ellagic acid, and resveratrol. Preferably, the skin-whitening ingredients are selected from resorcinol or resorcinol derivatives. As the antiaging ingredients, mention can be made, for example, vitamins such as retinol, and saponin, and allantoin.

As the antioxidant ingredients, mention can be made, for example, carotenoids such as β-cryptoxanthin, and tocopherol and its derivatives, and flavonoids.

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

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

The composition according to the present 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 mono-alcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol, and isobutanol; aromatic alcohols, such asbenzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol ethers, such as propylene glycol monomethylether, diethylene glycol alkyl ethers, such as diethylene glycol monoethylether or monobutylether; polyethylene glycols, such as PEG-4, PEG-6, and PEG-8, and their derivatives.

The amount of the hydrophilic organic solvent(s) in the composition may be less than 10% by weight, preferably less than 5% by weight, relative to the total weight of the composition. In one embodiment of the present invention, the composition is free from the hydrophilic organic solvent. In addition, the composition according to the present invention may comprise a neutralizer, such as ethanol amine in the high internal aqueous phase. The amount of the neutralizer is not limited, but may be from 1 to 10% by weight relative to the total weight of the

composition. The composition according to present invention may comprise other additives usually used in cosmetics. The additives may be selected from the group consisting of anionic, cationic, nonionic or amphoteric polymers; peptides and derivatives thereof; protein hydrolyzates; swelling agents and penetrating agents; natural or synthetic thickeners for (b) oils; acidifying agents; inorganic or organic fillers; antioxidants; preservatives; bactericides; suspending agents; sequestering agents; opacifying agents; dyes; inorganic UV filters; vitamins or provitamins; moisturizing agents; self-tanning compounds; antiwrinkle active principles; preserving agents, stabilizers; and mixtures thereof.

The amount of the additional ingredient(s) is not limited, but may be from 0.1 to 30% by weight relative to the total weight of the composition according to the present invention.

The composition can be in the form of a lotion, a milky lotion, a cream, a gel, a paste, or a serum. The composition preferably exhibits a pH which respects the skin and which generally ranges from 3 to 8 and preferably from 4.5 to 7.

The composition according to the present invention can be manufactured by two steps comprising a nano-emulsion preparing step and a high internal phase emulsion preparing step. The nano-emulsion preparing step can be carried out by a low energy method which is known in the art. Concretely, the nano-emulsion preparing step can be carried out by gently mixing the components of the (a) surfactant, the (b) oil, and the (d) water, : with'orwithout'the (c) UV filter and other ingredients together, for example, at room temperature (25°C). The high internal phase emulsion preparing step can be carried out by mixing the obtained

nano-emulsion, the (b) oil, and the (a) surfactant with or without the (c) UV filter at a high speed, for example with a high speed mixer (DAC 400FVZ, HAUSCHILD, Engineering) at 2750 rpm for 2 to 4 minutes at room temperature.

[Cosmetic Process]

The composition according to the present invention may preferably be used as a sun care composition. In particular, the composition according to the present invention may be intended for application onto a keratin substance such as the skin, the scalp and/or the lips, preferably the skin. Thus, the composition according to the present invention can be used for a cosmetic process for the skin.

The cosmetic process or cosmetic use for a keratin substance such as skin, according to the present invention comprises, at least, the step of applying the composition according to the present invention onto the keratin substance. The present invention can also relates to a process of protecting a keratin substance from ultraviolet radiation comprising applying to the keratin substance the composition according to the present invention, as well as a process of absorbing ultraviolet light comprising applying the composition according to the present invention and subjecting the keratin substance to ultraviolet light. These processes can be defined as non-therapeutic processes.

The composition according to the present invention can be used in the topical sun care composition in the form of a lotion, a milky lotion, a cream, a gel, a paste, or a serum.

EXAMPLES

The present invention will be described in a more detailed manner by way of examples.

However, these examples should not be construed as limiting the scope of the present invention. [Example 1 and Comparative Example 1]

The following composition according to Example 1, shown in Table 1, was prepared as following. The numerical values for the amounts of the ingredients are all based on "% by weight" as active raw materials in Table 1.

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

20g of ethyl hexyl palmitate, lOg of ethylhexyl methoxycinnamate, 30 g of laureth-5 carboxylic acid (HLB = 9.5, obtained from KAO Chemicals) and 40 g of water was mixed using a magnetic stirrer. This premix was diluted 20 times with an aqueous phase, which contains 3g of phenylbenzimidazole sulfonic acid, 13g of terephthalylidene dicamphor sulfonic acid, 4g of triethanolamine and 75g of water. The final composition of the nanoemulsion is composed of lg of ethyl hexyl palmitate, 0.5g of ethyl hexyl methoxycinnamate, 1.5 g of laureth-5 carboxylic acid, 2.85g of phenylbenzimidazole sulfonic acid, 12.35g of terephthalylidene dicamphor sulfonic acid, 3.8g of triethanolamine and 78 g of water.

Secondly, the 0/W/O multiple emulsions were prepared in-the following way:

85 g of O/W nanoemulsion was premixed with 10 g of isohexadecane and 5g of PEG-15/lauryl dimethicone cross polymer (HLB<8, obtained from Shinetsu Chemical). The obtained premix was further mixed by using a speed mixer (DAC 400FVZ, HAUSCHILD, Engineering) at 2750 rpm for 3 minutes to obtain an 0/W/O multiple emulsion.

For the comparative example 1 in Table 1, O/W emulsion was prepared in the following way: lg of ethyl hexyl palmitate, 0.5g of ethyl hexyl methoxycinnamate, 1.5 g of laureth-5 carboxylic acid, 2.85g of phenylbenzimidazole sulfonic acid, 12.35g of terephthalylidene dicamphor sulfonic acid, 3.8g of triethanolamine and 78 g of water were mixed together by using a magnetic stirrer and milky O/W emulsion was prepared. Secondly, the 85 g of O/W emulsion was premixed with 10 g of isohexadecane and 5g of PEG-15/lauryl dimethicone cross polymer (HLB<8, obtained from Shinetsu Chemical). The obtained pre-mixture was further mixed by using a speed mixer (DAC 400FVZ, HAUSCHILD, Engineering) at 2750 rpm for 3 minutes to obtain an 0/W/O multiple emulsion. [Evaluation]

The compositions according to Example 1 and Comparative Example 1 were evaluated as follows.

(Droplet size)

Particle size analyzer (Vasco, Cordoun Technologies) was used to determine the droplet size of the oil phase of the O/W nanoemulsion of Example 1 and O/W emulsion of Comparative Example 1, which were obtained during the preparing process of the 0/W/O emulsions. The refractive index and viscosity of the water were 1.33 and 0.89 cp at 25 °C.

The droplet size of the internal aqueous phase of the 0/W/O multiple emulsion was determined by using OLYMPUS GX 71 (OLYMPUS) microscopy.

(SPF)

The sample for SPF value measurement was prepared by placing 20mg of each of the compositions according to Example 1 and Comparative Example 1 on the plate (Helio plate HD 6, PMMA, 50 mm x 50 mm) like dots, then spreading them 3 times with finger over the plate. The in vitro SPF value was calculated from the UV absorbance data, which was measured with a UV spectrophotometer (UV-2000S, Labsphere Inc) on the diffuse

transmittance of the samples in the wavelength range from 250 to 450 nm. (Viscosity)

The steady shear viscosity was measured using DHR2 rheometer (TA instrument) with a parallel-plate geometry (40 mm) with set gap 0.2 mm at 25 °C. The sample amount was 2g and 0.01 to 1000 1/s of shear rate was applied.

(Yield Stress)

The yield stress value of the compositions according to Example 1 and Comparative Example 1 was calculated from the shear rate vs stress curve where those parameters were measured using DHR2 rheometer (TA instrument) with a parallel-plate geometry (40 mm) with set gap 0.2 mm at 25 °C. The sample amount was 2g and 0.01 to 1000 1/s of shear rate was applied.

The compositions of Examples 1 and Comparative Example 1 and results of these evaluations are shown in Table 1. Table 1

As shown in Table 1 , the composition according to Example 1 exhibited improved UV protecting effect due to its high SPF value. In addition, it also exhibited a good stability according to high viscosity. In contrast, the composition according to Comparative Example 1, which includes macro-sized oil droplets as the internal oil phase, exhibited poor UV protecting effect and a lower viscosity.

Also, the composition according to Example 1 , which includes nano-sized oil droplets as the internal oil phase, exhibited a better stability according to its high yield stress value. In contrast, the composition according to Comparative Example 2, which includes macro-sized^" oil droplets as the internal oil phase, exhibited a 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 PEG-15/Lauryl dimethicone cross polymer, Glyceryl Oleate (HLB = 2.8, obtained from Taiyo Kagaku) was used in Example 2, Polyglyceryl-2 Laurate (HLB = 8.5, obtained from Taiyo Kagaku) was used in Example 3, and Polysorbate 80 (HLB = 15, obtained from Croda) was used for Comparative Example 2. [Evaluation]

The compositions according to Examples2 to 3 and Comparative Example 2 were evaluated as follows.

(Appearance Observation) Appearances of the 0/W/O multiple emulsions according to Examples 2 to 3 and

Comparative Example 2 were observed with the naked eye to confirm the formation of a multiple emulsion. The compositions of Examples 2 to 3 and Comparative Example 2 as well as results of appearance observation are shown in Table 2.

Table 2

As shown in Table 2, the composition according to each of Examples 2 and 3, which include surfactant with HLB of less than 13, could form a multiple emulsion. In contrast, the composition according to Comparative Example 2, which includes a surfactant with HLB of 13, could not form a multiple emulsion.

Claims

A composition in the form of an oil-in- water-in-oil multiple 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 as droplets, comprising:

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

(b) at least one oil;

(c) at least one UV filter; and

(d) water;

wherein the amount of the high internal aqueous phase is 60% by weight or more relative to the total weight of the composition, and the size of the droplets of the internal oil phase is less than 200 nm.

The composition according to Claim 1, wherein the size of the droplets of the internal oil phase is less than 150 nm, preferably less than 120 nm.

The composition according to any one of Claims 1 or 2, wherein the amount of the high internal aqueous phase is ranging from 60 to 99% weight, preferably from 70 to 95% by weight, and more preferably from 80 to 90% by weight, relative to the total weight of the composition.

The composition according to any one of Claims 1 to 3, wherein the HLB of the (a) surfactant is less than 12, preferably less than 10.

The composition according to any one of Claims 1 to 4, wherein a viscosity of the composition is from 1 to 500 Pa-s, preferably from 10 to 400 Pa-s, and more preferably from 50 to 350 Pa-s, and even more preferably from 100 to 300 Pa-s at 25°C.

The composition according to any one of Claims 1 to 5, wherein the amount of the internal oil phase is ranging from 0.5% by weight to Γ5°/ό by-weight; preferably fronr 1% by weight to 10% by weight, and more preferably from 2% by weight to 5% by weight, relative to the total weight of the composition.

The composition according to any one of Claims 1 to 6, wherein the (b) oil in the internal oil phase is selected from ester oils such as isopropyl myristate, isopropyl palmitate, ethyl hexyl palmitate, triglycerides such as capryl caprylyl glycerides, sarcosinate such as isopropyl lauroyl sarcosinate, hydrocarbon oil such as isohexadecane, and mineral oil such as paraffin.

The composition according to any one of Claims 1 to 7, wherein the (a) surfactant is selected from nonionic surfactants which are mono-esters of a polyol and a fatty acid containing from 8 to 24 carbon atoms, wherein the polyol is preferably selected from glycerol, sorbitan, and diglycerol and the fatty acid is preferably selected from isolauric acid and oleic acid, in particular esters of polyglyceryl-2 laurate, glyceryl laurate, sorbitan oleate, and glyceryl oleate, and silicone surfactants which are preferably polyether modified dimethicone such as PEG/PPG-18/18 dimethicone, and polyether and alkyl modified dimethicone cross polymer such as PEG-15/lauryl dimethicone cross polymer, and anionic surfactants which are polyoxyethylene alkyl ether carboxylic acids such as polyoxyethylene (3) to (17) lauryl ether carboxylic acids.

The composition according to any one of Claims 1 to 8, wherein the amount of the (a) surfactant is ranging from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 1 to 10%» by weight, relative to the total weight of the composition.

The composition according to any one of Claims 1 to 8, wherein the amount of the external oil phase is ranging from 1 % by weight to 40% by weight, preferably from 2%i by weight to 30%> by weight to, and more preferably from 5% by weight to 20% by weight, relative to the total weight of the composition.

The composition according to any one of Claims 1 to 10, wherein the (b) oil in the external oil phase is selected from ester oils such as isopropyl myristate, isopropyl palmitate, ethyl hexyl palmitate, triglycerides such as capryl caprylyl glycerides, sarcosinate such as isopropyl lauroyl sarcosinate, hydrocarbon oil such as

isohexadecane, mineral oil such as paraffin, and silicone oil.

The composition according to any one of Claims 1 to 11, wherein the composition includes water soluble solvent of less than 10% by weight, preferably less than 5% by weight relative to the total weight of the composition.

The composition according to any one of Claims 1 to 12, wherein the amount of the (c) UV filter includes both of a hydrophilic and hydrophobic UV filter, and the amount of the (c) UV filter is ranging from 1 to 40% by weight, preferably from 2 to 30%) by weight, more preferably from 5 to 20%> by weight, relative to the total weight of the composition.

A cosmetic process for a keratin substance such as skin, comprising the step of:

applying onto the keratin substance the composition according to any one of Claims 1 to 13.

A process of protecting a keratin substance from ultraviolet radiation comprising applying to the keratin substance the composition according to any one of Claims 1 to 13.