Patent Description:
For sun care products, good UV protecting effects and good usability are among the key functions. In addition, in order to satisfy consumer's preference, it is preferable that sun care products show a clear appearance.

Bi-phase compositions comprising an aqueous phase and an oily phase have a benefit regarding their usability thanks to their low viscosity. In addition, they have another benefit regarding their appearance since they do not show a whitish appearance as emulsion compositions do.

To date, some prior art documents exist relating to sun care compositions having the bi-phase form. For example, <CIT> discloses a composition separated into two phases and containing (A) an oil soluble ultraviolet absorber, (B) a water soluble polymer thickener; and (C) a nonionic surfactant, which can be easily mixed homogenously at the time of use and can be sprayed in a misty state. In addition, <CIT> discloses a double layered cosmetic containing the following components (A)-(D) in an aqueous phase: (A) water-soluble ultraviolet absorber with a sulfonic acid group, (B) a basic substance, (C) water , and (D) a polyhydric alcohol; and the following components (E) and (F) in an oily phase: (E), an oil soluble ultraviolet absorber and (F) a liquid oil.

However, there is still a need for sun care compositions in the bi-phase form, having a better UV protection property and mist-forming quality.

An objective of the present invention is to provide a bi-phase sun-care composition having a good UV protecting property and mist-forming quality.

The above objective can be achieved by a bi-phase composition comprising an aqueous phase and an oily phase, wherein the composition comprises:.

wherein the aqueous phase and the oily phase are visually separated at rest.

The viscosity of the oily phase can be more than <NUM> mPa·s.

The (a) semi-crystalline or crystalline lipophilic thickener may be selected from semi-crystalline polymers.

The (b) UV filter may comprise at least one lipophilic organic UV filter, and may further comprise at least one hydrophilic organic UV filter.

The amount of the semi-crystalline or crystalline lipophilic thickener(s) in the composition may be from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight, and more preferably from <NUM> to <NUM>% by weight, relative to the total weight of the composition.

The composition according to the present invention may comprise at least one oil.

The composition according to the present invention may comprisie cationic, anionic, non-ionic, amphoteric or zwitterionic surfactants or emulsifiers in an amount of <NUM>% by weight or less, preferably <NUM>% by weight or less, and more preferably <NUM>% by weight or less, relative to the total amount of the composition.

The composition according to the present invention may be free of any kind of surfactant or emulsifier.

The composition according to the present invention may be transparent.

The present invention also relates to the composition according to the present invention, for use in a process for protecting keratinous substances, preferably skin, from UV radiation, which is applied to the keratinous substances.

The present invention also relates to a product comprising the composition according to the present invention and a containerselected from a bottle, a tube, a vessel, or a container equipped with a mist-pump, a spray bottle, and a pump bottle.

After diligent research, the inventors have discovered that a bi-phase composition comprising semi-crystalline or crystalline lipophilic thickener and UV filter can provide good UV protecting property and mist-forming quality.

Thus, the composition according to the present invention is a bi-phase composition comprising an aqueous phase and an oily phase, wherein the composition comprises:.

Hereinafter, the composition according to the present invention will be explained in a more detailed manner.

The composition according to the present invention may be intended for use as a cosmetic topical composition. Thus, the composition according to the present invention may be intended for application onto a keratinous substance. Keratinous substance here means a material containing keratin as a main constituent element, and examples thereof include the skin, scalp, nails, lips, hair, and the like. In particular, the composition according to the present invention may be a skin sun care cosmetic composition for protecting skin from UV rays.

The composition according to the present invention has a bi-phase form comprising an aqueous phase and an oily phase.

The bi-phase composition according to the present invention means a composition consisting of two phases of the aqueous phase and the oily phase which are visually and/or macroscopically separated at rest.

The term "aqueous phase" here means a phase that is liquid at room temperature, comprising or consisting of hydrophilic, water-soluble, or water-dispersible substances.

The term "oily phase" here means a phase that is liquid at room temperature, comprising or consisting of lipophilic, oil-soluble, or oil-dispersible substances.

It is preferable that each of the aqueous and oily phases be a continuous phase at rest. Therefore, the bi-phase composition according to the present invention has two distinct layers at rest, each layer consisting of either the aqueous phase or the oily phase. In other words, the aqueous phase and the oily phase are separated at rest by a single interface. This state is clearly different from an emulsion in which one of the phases is dispersed in the other in the form of droplets and thus the phases do not form layers, and are separated by multiple interfaces.

The composition according to the present invention is preferably transparent. The transparency of the composition can be determined by measuring the turbidity with, for example, a turbidimeter (2100Q portable, Hach Company). Preferably, the composition has a turbidity of more than <NUM>, preferably more than <NUM>, and less than <NUM>, preferably less than <NUM>.

The oily phase of the present invention preferably has a viscosity of more than <NUM> mPa·s, more preferably more than <NUM> mPa·s at room temperature (<NUM>). The upper limit of the viscosity of the oily phase is not limited, but in general, the oily phase has a viscosity of less than <NUM> mPa·s at room temperature.

The viscosity of the aqueous phase of the present invention is not particularly limited. Preferably, the viscosity of the aqueous phase can range from <NUM> to <NUM> Pa·s, more preferably from <NUM> to <NUM> Pa·s at room temperature.

For the viscosity measurement, VISCOMAN™(GILSON Technology) can be used. The bulk viscosity (mPaS, PaS) is automatically calculated from the needed aspiration force in the small pipet (<NUM>µL).

The composition according to the present invention is intended for use after mixing the aqueous phase and the oily phase homogenously, for example, by simply shaking it. Since the homogenous composition of the present invention after mixing has a relatively lower viscosity, especially a lower viscosity than an emulsion composition, the present invention has a benefit in that it can be easily sprayed in a misty state without using an aerosol device and easily spread on keratinous substances. Therefore, the composition according to the present invention may be contained in a non-aerosol device, such as a container equipped with a mist generating means, such as a mist-pump, a spray bottle, or a pump bottle.

The pH of the aqueous phase of the present invention is not particularly limited. The pH of the aqueous phase may range from <NUM> to <NUM>, preferably from <NUM> to <NUM>. The pH of the aqueous phase of the present invention can be adjusted to the desired value using acidifying or basifying agents commonly used in the cosmetics field.

The inventors of the present invention surprisingly found that the mixed composition according to the present invention, in particular applied as mist, can form a homogenous and fine film on keratinous substances, such as skin. Accordingly, the composition can provide improved UV protecting effects.

The amount of the aqueous phase in the composition according to the present invention may range from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight, and more preferably from <NUM> to <NUM>% by weight, relative to the total weight of the composition.

The amount of the oily phase in the composition according to the present invention may range from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight, and more preferably from <NUM> to <NUM>% by weight, relative to the total weight of the composition.

The composition according to the present invention comprises (a) at least one semi-crystalline or crystalline lipophilic thickener, (b) at least one UV filter, and (c) water. These ingredients will be explained in a more detailed manner below.

The composition according to the present invention comprises (a) at least one semi-crystalline or crystalline lipophilic thickener. Two or more semi-crystalline or crystalline lipophilic thickeners may be used in combination. Thus, a single type of semi-crystalline or crystalline lipophilic thickener or a combination of different types of semi-crystalline or crystalline lipophilic thickeners may be used.

The term "lipophilic" here means a substance which is soluble in oil(s) at a concentration of at least1 % by weight relative to the total weight of the oil(s) at room temperature (<NUM>) and atmosphere pressure (<NUM><NUM> Pa). Therefore, the semi-crystalline or crystalline lipophilic thickener(s) is(are) present in the oily phase of the present invention.

The semi-crystalline or crystalline lipophilic thickener used in the present invention is selected from poly C10-C30 alkyl acrylate and crystalline apolar hydrocarbon-based waxes constituted solely of carbon and hydrogen atoms.

The term "semi-crystalline polymer" means polymers comprising a crystallizable portion, a crystallizable pendent and/or end chain or a crystallizable block in the backbone and/or at the ends, and an amorphous portion in the backbone, and having a first-order reversible temperature of change of phase, in particular of melting (solid-liquid transition). When the crystallizable portion is in the form of a crystallizable block of the polymer backbone, the amorphous portion of the polymer is in the form of an amorphous block; the semi-crystalline polymer is, in this case, a block copolymer, for example of the diblock, triblock or multiblock type, comprising at least one crystallizable block and at least one amorphous block. The term "block" generally means at least five identical repeating units. The crystallizable block(s) are then of different chemical nature from the amorphous block(s).

A semi-crystalline polymer has a melting point of greater than or equal to <NUM> (especially ranging from <NUM> to <NUM>), preferably ranging from <NUM> to <NUM>,and in particular ranging from <NUM> to <NUM>. This melting point is a first-order temperature of change of state.

This melting point may be measured by any known method and in particular using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments.

Advantageously, a tbesemi-crystalline polymer(s) has a number-average molecular mass of greater than or equal to <NUM>.

Advantageously, a semi-crystalline polymer(s) has a number-average molecular mass Mn ranging from <NUM> to <NUM><NUM>, preferably from <NUM> to <NUM><NUM>, better still from <NUM> to <NUM><NUM> and especially less than <NUM><NUM> and better still from <NUM> to <NUM><NUM>. Preferably, they have a number-average molecular mass of greater than <NUM>, for example ranging from <NUM> to <NUM><NUM>.

The expression "crystallizable chain or block" means a chain or block which, if it were obtained alone, would change from the amorphous state to the crystalline state reversibly, depending on whether the temperature is above or below the melting point. A "chain" is a group of atoms, which are pendent or lateral relative to the polymer backbone. A "block" is a group of atoms belonging to the backbone, this group constituting one of the repeating units of the polymer. Advantageously, the "pendent crystallizable chain" may be a chain containing at least <NUM> carbon atoms.

Preferably, the crystallizable block(s) or chain(s) of the semi-crystalline polymers represent at least <NUM>% of the total weight of each polymer and better still at least <NUM>%. The semi-crystalline polymers containing crystallizable blocks are block or multiblock polymers. They may be obtained via polymerization of a monomer containing reactive double bonds (or ethylenic bonds) or via polycondensation. When the polymers are polymers containing crystallizable side chains, these side chains are advantageously in random or statistical form.

Semi-crystalline polymers may be of synthetic origin. Moreover, they do not comprise a polysaccharide backbone. In general, the crystallizable units (chains or blocks) of the semi-crystalline polymers originate from monomer(s) containing crystallizable block(s) or chain(s), used for the manufacture of the semi-crystalline polymers.

Semi-crystalline polymers may be chosen from block copolymers comprising at least one crystallizable block and at least one amorphous block, and homopolymers and copolymers bearing at least one crystallizable side chain per repeating unit, and mixtures thereof.

Examples of semi-crystalline polymers are in particular:.

In the last two cases, the crystallizable side chain(s) or block(s) are hydrophobic.

Mention may be made in particular of those defined in documents <CIT> and <CIT>. They are homopolymers or copolymers comprising from <NUM>% to <NUM>% by weight of units resulting from the polymerization of one or more monomers bearing a crystallizable hydrophobic side chain.

These homopolymers or copolymers are of any nature, provided that they meet the conditions mentioned previously.

In general, these polymers are chosen especially from homopolymers and copolymers resulting from the polymerization of at least one monomer containing crystallizable chain(s) that may be represented by formula (I):
<CHM>
with M representing an atom of the polymer backbone, S representing a spacer and C representing a crystallizable group.

The crystallizable chains "-S-C" may be aliphatic or aromatic, and optionally fluorinated or perfluorinated. "S" especially represents the group (CH<NUM>)n or (CH<NUM>CH<NUM>O)n or (CH<NUM>O), which may be linear or branched or cyclic, with n being an integer ranging from <NUM> to <NUM>. Preferably, "S" is a linear group. Preferably, "S" and "C" are different.

When the crystallizable chains "-S-C" are hydrocarbon-based aliphatic chains, they comprise hydrocarbon-based alkyl chains containing at least <NUM> carbon atoms and not more than <NUM> carbon atoms and better still not more than <NUM> carbon atoms. They are especially aliphatic chains or alkyl chains containing at least <NUM> carbon atoms, and they are preferably C<NUM>-C<NUM> alkyl chains. When they are fluoroalkyl or perfluoroalkyl chains, they contain at least six fluorinated carbon atoms and especially at least <NUM> carbon atoms, at least six of which carbon atoms are fluorinated.

As examples of semi-crystalline polymers or copolymers bearing crystallizable chain(s), mention may be made of those resulting from the polymerization of one or more of the following monomers: (meth)acrylates of saturated alkyl with the alkyl group being C<NUM>-C<NUM>, perfluoroalkyl (meth)acrylates with a C<NUM>-C<NUM> perfluoroalkyl group, N-alkyl(meth)acrylamides with the alkyl group being C<NUM> to C<NUM> with or without a fluorine atom, vinyl esters containing alkyl or perfluoro(alkyl) chains with the alkyl group being C<NUM> to C<NUM> (with at least <NUM> fluorine atoms per perfluoroalkyl chain), vinyl ethers containing alkyl or perfluoro(alkyl) chains with the alkyl group being C<NUM> to C<NUM> and at least <NUM> fluorine atoms per perfluoroalkyl chain, C<NUM> to C<NUM> alpha-olefins such as, for example, octadecene, para-alkylstyrenes with an alkyl group containing from <NUM> to <NUM> carbon atoms, and mixtures thereof.

When the polymers result from a polycondensation, the hydrocarbon-based and/or fluorinated crystallizable chains as defined above are borne by a monomer that may be a diacid, a diol, a diamine or a diisocyanate.

When the polymers are copolymers, they may additionally contain from <NUM> to <NUM>% of groups Y or Z resulting from the copolymerization:
α) of Y which is a polar or non-polar monomer or a mixture of the two:
When Y is a polar monomer, it is either a monomer bearing polyoxyalkylenated groups (especially oxyethylenated and/or oxypropylenated groups), a hydroxyalkyl (meth)acrylate, for instance hydroxyethyl acrylate, (meth)acrylamide, an N-alkyl(meth)acrylamide, an N,N-dialkyl(meth)acrylamide such as, for example, N,N-diisopropylacrylamide or N-vinylpyrrolidone (NVP), N-vinylcaprolactam, a monomer bearing at least one carboxylic acid group, for instance (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, or bearing a carboxylic acid anhydride group, for instance maleic anhydride, and mixtures thereof.

When Y is a non-polar monomer, it may be an ester of the linear, branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an α-olefin, styrene or styrene substituted with a C<NUM> to C<NUM> alkyl group, for instance α-methylstyrene.

The term "alkyl" means a saturated group especially of C<NUM> to C<NUM>, except where otherwise mentioned, and better still of C<NUM> to C<NUM>.

β) of Z which is a polar monomer or a mixture of polar monomers. In this case, Z has the same definition as the "polar Y" defined above.

Preferably, the semi-crystalline polymers containing a crystallizable side chain are alkyl (meth)acrylate or alkyl(meth)acrylamide homopolymers with an alkyl group as defined above, and especially of C<NUM>-C<NUM>, copolymers of these monomers with a hydrophilic monomer preferably of different nature from (meth)acrylic acid, for instance N-vinylpyrrolidone or hydroxyethyl (meth)acrylate, and mixtures thereof.

These polymers are especially block copolymers consisting of at least two blocks of different chemical nature, one of which is crystallizable.

As examples of such copolymers containing a crystallizable block and a separate amorphous block, mention may be made of:.

The semicrystalline polymers may or may not be partially crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the liquid fatty phase optionally present in the composition by heating above their melting point. It may then be a case of chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It may also be a case of physical crosslinking, which may then be due either to the establishment of bonds of hydrogen or dipolar type between groups borne by the polymer, for instance dipolar interactions between carboxylate ionomers, these interactions being in small amount and borne by the polymer backbone; or to a phase separation between the crystallizable blocks and the amorphous blocks, borne by the polymer.

The polymers may be copolymers resulting from the polymerization of at least one monomer containing a crystallizable chain chosen from saturated C<NUM> to C<NUM> alkyl (meth)acrylates, C<NUM> to C<NUM> perfluoroalkyl (meth)acrylates, C<NUM> to C<NUM> N-alkyl(meth)-acrylamides with or without a fluorine atom; vinyl esters containing C<NUM>-to C<NUM> alkyl or perfluoroalkyl chains, vinyl ethers containing C<NUM> to C<NUM> alkyl or perfluoroalkyl chains, C<NUM> to C<NUM> alpha-olefins, para-alkylstyrenes with an alkyl group containing from <NUM> to <NUM> carbon atoms, with at least one optionally fluorinated C<NUM> to C<NUM> monocarboxylic acid ester or amide, which may be represented by the following formula (ω):
<CHM>
in which R<NUM> is H or CH<NUM>, R represents an optionally fluorinated C<NUM>-C<NUM> alkyl group and X represents O, NH or NR<NUM> in which R<NUM> represents an optionally fluorinated C<NUM>-C<NUM> alkyl group.

The polymers may be derived from a monomer containing a crystallizable chain chosen from saturated C<NUM> to C<NUM> alkyl (meth)acrylates and even more particularly poly(stearyl acrylate) or poly(behenyl acrylate).

The structuring semi-crystalline polymers used in the composition according to the present are polymers having the INCI name "Poly C<NUM>-C<NUM> alkyl acrylate", for instance the Intelimer® products from the company Air Products, for instance the product Intelimer® IPA <NUM>-<NUM>, which is a polystearyl acrylate of a melting point of <NUM>, or the product Intelimer® IPA <NUM>-<NUM>, which is a behenyl polymer.

Other examples of semi-crystalline polymers may especially be: those described in Examples <NUM>, <NUM>, <NUM>, <NUM>, <NUM> and <NUM> of patent <CIT> containing a -COOH group, resulting from the copolymerization of acrylic acid and of C<NUM> to C<NUM> alkyl (meth)acrylate and more particularly of the copolymerization:.

Other examples are the structure "O" from National Starch, as described in document <CIT>, with a melting point of <NUM>, and also semi-crystalline polymers with crystallizable pendent chains comprising fluoro groups, as described in Examples <NUM>, <NUM>, <NUM>, <NUM> and <NUM> of document <CIT>.

Other examples are semi-crystalline polymers obtained by copolymerization of stearyl acrylate and of acrylic acid or NVP as described in document <CIT> or <CIT>, with melting points of <NUM> and <NUM>, respectively.

Other examples are semi-crystalline polymers obtained by copolymerization of behenyl acrylate and of acrylic acid or NVP, as described in documents <CIT> and <CIT>, with melting points of <NUM> and <NUM>, respectively.

Finally, the semi-crystalline polymers may be waxy polymers obtained by metallocene catalysis, such as those described in patent application <CIT>.

These polymers are homopolymers or copolymers of ethylene and/or propylene prepared via metallocene catalysis, i.e. by polymerization at low pressure and in the presence of a metallocene catalyst.

The weight-average molecular mass (Mw) of the waxes obtained via metallocene catalysis described in that document is less than or equal to <NUM><NUM>/mol and ranges, for example, from <NUM> to <NUM><NUM>/mol and better still from <NUM> to <NUM><NUM>/mol.

The number-average molecular mass (Mn) of the waxes obtained via metallocene catalysis described in that document is preferably less than or equal to <NUM><NUM>/mol and ranges, for example, from <NUM> to <NUM><NUM>/mol and better still from <NUM> to <NUM><NUM>/mol.

The polydispersity index I of the polymer is equal to the ratio of the weight-average molecular mass Mw to the number-average molecular mass Mn. Preferably, the polydispersity index of the waxy polymers is between <NUM> and <NUM>, moer preferably between <NUM> and <NUM>, even more preferably between <NUM> and <NUM> and better still between <NUM> and <NUM>.

The waxy homopolymers and copolymers may be obtained in a known manner from ethylene and/or propylene monomers, for example via metallocene catalysis according to the process described in document <CIT>.

The homopolymers and copolymers of ethylene and/or propylene prepared via metallocene catalysis may be unmodified or "polar"-modified (polar-modified waxes, i.e. waxes modified such that they have the properties of a polar wax). The polar-modified waxy homopolymers and copolymers may be prepared in a known manner from unmodified waxy homopolymers and copolymers such as those described previously by oxidation with gases containing oxygen, such as air, or by grafting with polar monomers such as maleic acid or acrylic acid or alternatively derivatives of these acids. These two routes enabling polar modification of the polyolefins obtained via metallocene catalysis are described, respectively, in documents <CIT> and <CIT>, for example, the content of these two documents being incorporated herein by reference.

The polar-modified homopolymers and copolymers of ethylene and/or propylene prepared via metallocene catalysis may be modified such that they have hydrophilic properties. Examples that may be mentioned include ethylene and/or propylene homopolymers or copolymers modified by the presence of hydrophilic groups such as maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc..

Waxy ethylene and/or propylene homopolymers or copolymers modified by the presence of hydrophilic groups such as maleic anhydride or acrylate are an example,.

Semi-crystalline or crystalline waxes are chosen from polar and apolar hydrocarbon-based waxes, or mixtures thereof.

The term "wax(es)", under consideration in the context of the present invention are generally lipophilic compounds that are solid at room temperature (<NUM>), with a solid/liquid reversible change of state, having a melting point of greater than or equal to <NUM>, which may be up to <NUM> and especially up to <NUM>.

In particular, the semi-crystalline or crystalline waxes may have a melting point ot greater than or equal to <NUM>, preterably greater than or equal to <NUM>, and in particular greater than or equal to <NUM>. Furthermore, the semi-crystalline or crystalline waxes may have a melting point of less than or equal to <NUM>, preferably less than or equal to <NUM>, and especially less than or equal to <NUM>.

For the purposes of the present invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the standard ISO <NUM>-<NUM>; <NUM>. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments.

The semi-crystalline or crystalline waxes comprise at least one crystallizable part, which can be visible by X-ray observation.

The exemplified measurement protocol of the melting point is as follows:
A sample of <NUM> of wax placed in a crucible is subjected to a first temperature rise ranging from -<NUM> to <NUM>, at a heating rate of <NUM>/minute, it is then cooled from <NUM> to -<NUM> at a cooling rate of <NUM>/minute and is finally subjected to a second temperature increase ranging from -<NUM> to <NUM> at a heating rate of <NUM>/minute. During the second temperature increase, the following parameters are measured. The melting point (Mp) of the wax, as mentioned previously, corresponds to the temperature of the most endothermic peak of the melting curve observed, and represents the variation of the difference in power absorbed as a function of the temperature.

A semi-crystalline or crystalline wax may have a molecular weight between <NUM> and <NUM>,<NUM> Dalton, preferable between <NUM> and <NUM>,<NUM> Dalton, and more preferably between <NUM> and <NUM>,<NUM> Dalton.

The waxes used in the present invention are crystalline apolar waxes.

For the purposes of the present invention, the term "apolar wax" means a wax whose solubility parameter at <NUM> as defined below, δa, is equal to <NUM> (J/cm<NUM>)½.

Apolar waxes according to the present invention are hydrocarbon-based waxes constituted solely of carbon and hydrogen atoms, and free of heteroatoms such as N, O, Si and P.

The term "hydrocarbon-based wax" means a wax formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The definition and calculation of the solubility parameters in the Hansen three-dimensional solubility space are described in the article by <NPL>).

The parameters δp, δh, δD and δa are expressed in (J/cm<NUM>)½.

More particularly, the apolar wax may be chosen from microcrystalline waxes, paraffin waxes, ozokerite, polyethylene waxes, polymethylene waxes and microwaxes, and mixtures thereof.

As microcrystalline waxes that may be used, mention may be made of Multiwax W <NUM>® sold by the company Sonneborn, and Microwax HW® and Base Wax <NUM>® sold by the company Paramelt.

An ozokerite that may be mentioned is Ozokerite Wax SP <NUM> P.

Polyethylene waxes that may be mentioned include Performalene <NUM>-L Polyethylene and Performalene <NUM> Polyethylene sold by New Phase Technologies.

Polymethylene waxes that may be mentioned include the Polymethylene Wax sold under the reference Cirebelle <NUM>, which has a melting point of <NUM> to <NUM>; and the Polymethylene Wax sold under the reference Cirebelle <NUM>, which has a melting point of <NUM> to <NUM>, sold by Cirebelle.

As microwaxes that may be used in the compositions according to the present invention as apolar wax, mention may be made especially of polyethylene microwaxes such as those sold under the names Micropoly <NUM>®, <NUM>®, <NUM>® and <NUM>® by the company Micro Powders.

For the purposes of the present invention, the term "polar wax" means a wax whose solubility parameter at <NUM>, δa, is other than <NUM> (J/cm<NUM>)½.

The term "polar wax" here means a wax whose chemical structure is formed essentially from, or even constituted of, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.

As the hydrocarbon-based polar wax, a wax chosen from ester waxes may be an example.

The term "hydrocarbon-based" means a compound formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms.

According to the present invention, the term "ester wax" means a wax comprising at least one ester function.

The following are examples of an ester wax:.

Particular examples of an ester wax is C<NUM>-C<NUM> alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from <NUM> to <NUM> carbon atoms), alone or as a mixture, or a C<NUM>-C<NUM> alkyl stearate. Such waxes are especially sold under the names Kester Wax K <NUM> P®, Hydroxypolyester K <NUM> P®, Kester Wax K <NUM> P® and Kester Wax K82H by the company Koster Keunen.

According to the present invention, the wax is a crystalline apolar hydrocarbon-based wax constituted solely of carbon and hydrogen atoms, such as a polymethylene wax.

The amount of the semi-crystalline or crystalline lipophilic thickener(s) in the composition according to the present invention may be <NUM>% by weight or more, preferably <NUM>% by weight or more, and more preferably <NUM>% by weight or more, relative to the total weight of the composition.

The amount of the semi-crystalline or crystalline lipophilic thickener(s) in the composition according to the present invention may be <NUM>% by weight or less, preferably <NUM>% by weight or less, and more preferably <NUM>% by weight or less, relative to the total weight of the composition. Specifically, the amount of the semi-crystalline or crystalline lipophilic thickener(s) in the composition according to the present invention may be from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight, and more preferably from <NUM> to <NUM>% by weight, relative to the total weight of the composition.

The composition according to the present invention comprises (b) 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.

There is no limitation to the type of UV filter. The UV filter can be selected from organic UV filters, inorganic UV filters, and mixtures thereof.

The term "UV" here means ultraviolet radiation and comprises the UV-B region (<NUM>-<NUM> in wavelength) and the UV-A region (<NUM>-<NUM> in wavelength). Therefore, a UV filter means any material which has filtering effects on ultraviolet radiation in wavelengths of the UV-A and/or UV-B regions.

The UV filter(s) used for the present invention may be active in the UV-A and/or UV-B region, preferably in both of the UV-A and UV-B regions alone or in combination. Therefore, the UV filter(s) used in the present invention include(s) a UV-A filter capable of absorbing UV radiation from <NUM> to <NUM>, a UV-B filter capable of absorbing UV radiation from <NUM> to <NUM>, and a UV-A and UV-B filter capable of absorbing UV radiation from <NUM> to <NUM>.

The organic UV filters used for the present invention can be lipophilic organic UV filters and/or hydrophilic organic UV filters. Preferably, the composition according to the present invention comprises at least one lipophilic organic UV filter, and more preferably comprises a combination of at least one lipophilic organic UV filter and at least one hydrophilic organic UV filter.

The term "lipophilic organic UV filter" here means organic UV filters which are soluble in oils at a concentration of at least <NUM> % by weight relative to the total weight of the oils at room temperature (<NUM>) and atmosphere pressure (<NUM><NUM> Pa). Therefore, the lipophilic organic UV filter(s) is(are) present in the oily phase of the present invention.

The lipophilic organic UV-A filters used in the present invention may include, but are not limited to, aminobenzophenone compounds, dibenzoylmethane compounds, anthranilic acid compounds, and <NUM>,<NUM>-diarylbutadiene compounds.

As the aminobenzophenone compounds, mention may be made of n-hexyl <NUM>-(<NUM>-diethlamino-<NUM>-hydroxybenzoyl)benzoate, the alternative name of which is diethylamino hydroxybenzoyl hexyl benzoate (DHHB), sold under the trade name "Uvinul A+" from BASF.

As the dibenzoylmethane compounds, mention may be made of <NUM>-isopropyldibenzoylmethane, sold under the name of "Eusolex <NUM>" from Merck, <NUM>-(<NUM>-methoxy-<NUM>-benzofuran-<NUM>-yl)-<NUM>-phenylpropane-<NUM>,<NUM>-dione, sold under the name of "Pongamol" from Quest, <NUM>-(<NUM>-(tert-butyl)phenyl)-<NUM>-(<NUM>-hydroxyphenyl)propane-<NUM>,<NUM>-dione, and butyl methoxydibenzoylmethane, sold under the trade name "Parsol <NUM>" from Hoffmann-La Roche.

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

As the <NUM>,<NUM>-diarylbutadiene compounds, mention may be made of <NUM>,<NUM> -dicarboxy (<NUM>,<NUM>'-dimethylpropyl)-<NUM>,<NUM>-diphenylbutadiene and diphenyl butadiene malonates and malononitriles.

The lipophilic organic UV-B filters used in the present invention may include, but are not limited to, triazine compounds, para-aminobenzoic acid compounds, salicylic compounds, cinnamate compounds, β,β-diphenylacrylate compounds, benzylidenecamphor compounds, phenylbenzimidazole 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-<NUM>" by BASF, diethylhexyl butamido triazone, marketed under the name "UVASORB HEB" by SIGMA 2V, <NUM>,<NUM>,<NUM>-tris(dineopentyl <NUM>'-aminobenzalmalonate)-s-triazine, <NUM>,<NUM>,<NUM>-tris(diisobutyl <NUM>'-aminobenzalmalonate)-s-triazine, <NUM>,<NUM>-bis(dineopentyl <NUM>'-aminobenzalmalonate)-<NUM>-(n-butyl <NUM>'-aminobenzoate)-s-triazine, <NUM>,<NUM>-bis(n-butyl <NUM>'-aminobenzoate)-<NUM>-(aminopropyltrisiloxane)-s-triazine.

As the para-aminobenzoic acid derivatives, mention may be made of para-aminobenzoates (PABA), for example, ethyl PABA (para-aminobenzoate), ethyl dihydroxypropyl PABA, and ethylhexyl dimethyl PABA, marketed under the name "ESCALOL <NUM> 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 cinnamate compounds, mention may be made of ethylhexyl methoxycinnamate, marketed under the name "PARSOL CX" by DSM NUTRITIONAL PRODUCTS, isopropyl ethoxy cinnamate, isoamyl methoxy cinnamate, marketed under the name "NEO HELIOPAN E <NUM>" by Symrise, diisopropyl methylcinnamate, cinoxate, and glyceryl ethylhexanoate dimethoxycinnamate.

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 "UVINUL N35" by BASF.

As the benzylidenecamphor compounds, mention may be made of <NUM>-benzylidene camphor, marketed under the name "MEXORYL SD" from CHIMEX, methylbenzylidene camphor, marketed under the name "EUSOLEX <NUM>" by MERCK, polyacrylamidomethyl benzylidene Camphor, marketed under the name "MEXORYL SW" by CHIMEX, and terephthalylidene dicamphor sulfonic acid, marketed under the name "Mexoryl SX" by Chimex.

As the phenylbenzimidazole compounds, mention may be made of phenylbenzimidazole sulfonic acid, marketed under the name "Eusolex <NUM>" by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, marketed under the name "Neo Heliopan AP" by Haarmann and Reimer.

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

As the benzalmalonate compounds, mention may be made of polyorganosiloxane containing a benzalmalonate moiety, for example, Polysilicone-<NUM>, marketed under the name "Parsol SLX" by DSM NUTRITIONAL PRODUCTS, and di-neopentyl <NUM>'-methoxybenzalmalonate.

The lipophilic organic UV filters of the present invention may comprise lipophilic UV-A and UV-B filters. The following are non-limited examples of the lipophilic organic UV-A and UV-B filters:.

Preferably, the lipophilic organic UV filter of the present invention is selected from a combination of at least one lipophilic organic UV-A filter and at least one lipophilic organic UV-B filter. Preferably, the lipophilic organic UV filter may be selected from dibenzoylmethane compounds, triazine compounds, salicylic compounds, β,β-diphenylacrylate compounds, bis-resorcinyl triazine compounds, and mixtures thereof.

In one preferred embodiment of the present invention, the amount of the lipophilic organic UV filter(s) in the composition according to the present invention is at least <NUM>% by weight, preferably at least <NUM>% by weight, and more preferably at least <NUM>% by weight, and is less than or equal to <NUM>% by weight, preferably less than or equal to <NUM>% by weight, and more preferably less than or equal to <NUM>% by weight, relative to the total weight of the composition.

In one particular embodiment of the present invention, the amount of the lipophilic organic UV filter(s) in the oily phase of the present invention is at least <NUM>% by weight, preferably at least <NUM>% by weight, and more preferably at least <NUM>% by weight, and is less than or equal to <NUM>% by weight, preferably less than or equal to <NUM>% by weight, and more preferably less than or equal to <NUM>% by weight, relative to the total weight of the oily phase.

The term "hydrophilic organic UV filter" here means organic UV filters which are soluble in water at a concentration of at least <NUM> % by weight relative to the total weight of the water at room temperature (<NUM>) and atmosphere pressure (<NUM><NUM> Pa). Therefore, the hydrophilic organic UV filter(s) is(are) present in the aqueous phase of the present invention.

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

The hydrophilic organic UV-B filter includes, but is not limited to:.

The hydrophilic organic UV-A and UV-B filter includes, but is not limited to:.

The salts of the compounds that may be used are chosen in particular from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminum, manganese or copper; salts of ammonium of formula NH<NUM>+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, <NUM>-hydroxyethylamine, bis(<NUM>-hydroxyethyl)amine or tris(<NUM>-hydroxyethyl)amine; lysine or arginine salts. Salts chosen from sodium, potassium, magnesium, strontium, copper, manganese or zinc salts are preferably used. The sodium salt is preferentially used.

Preferably, the hydrophilic organic UV filter of the present invention is selected from a combination of at least one hydrophilic organic UV-A filter and at least one hydrophilic organic UV-B filter. In particular, the hydrophilic organic UV filter is a combination of phenylbenzimidazole sulfonic acid and terephthalylidene dicamphor sulfonic acid.

In one preferred embodiment of the present invention, the amount of the hydrophilic organic UV filter(s) in the composition according to the present invention is at least <NUM>% by weight, preferably at least <NUM>% by weight, and more preferably at least <NUM>% by weight, and is less than or equal to <NUM>% by weight, preferably less than or equal to <NUM>% by weight, and more preferably less than or equal to <NUM>% by weight, relative to the total weight of the composition.

In one particular embodiment of the present invention, the amount of the hydrophilic organic UV filter(s) in the aqueous phase of the present invention is at least <NUM>% by weight, preferably at least <NUM>% by weight, and more preferably at least <NUM>% by weight, and is less than or equal to <NUM>% by weight, preferably less than or equal to <NUM>% by weight, and more preferably less than or equal to <NUM>% by weight, relative to the total weight of the aqueous phase.

The inorganic UV filter may be hydrophilic and/or lipophilic. The inorganic UV filter is preferably insoluble in solvents such as water and ethanol commonly used in cosmetics.

It is preferable that the inorganic UV filter be in the form of a fine particle such that the mean (primary) particle diameter thereof ranges from <NUM> to <NUM>, preferably <NUM> to <NUM>, and more preferably <NUM> to <NUM>. The mean (primary) particle size or mean (primary) particle diameter here is an arithmetic mean diameter.

The inorganic UV filter can be selected from the group consisting of metal oxides which may or may not be coated, and mixtures thereof.

Preferably, the inorganic UV filter is selected from pigments (mean size of the primary particles: generally from <NUM> to <NUM>, preferably from <NUM> to <NUM>) formed of metal oxides, such as, for example, pigments formed of titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide, or cerium oxide, which are all UV photoprotective agents that are well known per se. Preferably, the inorganic UV filter is selected from titanium oxide, zinc oxide, and more preferably titanium oxide.

The inorganic UV filter may or may not be coated. The inorganic UV filter may have at least one coating. The coating may comprise at least one compound selected from the group consisting of alumina, silica, aluminum hydroxide, silicones, silanes, fatty acids or salts thereof (such as sodium, potassium, zinc, iron, or aluminum salts), fatty alcohols, lecithin, amino acids, polysaccharides, proteins, alkanolamines; waxes such as beeswax, (meth)acrylic polymers, organic UV filters, and (per)fluoro compounds.

It is preferable for the coating to include at least one organic UV filter. As the organic UV filter in the coating, a dibenzoylmethane derivative such as butyl methoxydibenzoylmethane (Avobenzone) and <NUM>,<NUM>'-Methylenebis[<NUM>-(<NUM>-Benzotriazol-<NUM>-yl)-<NUM>-(<NUM>,<NUM>,<NUM>,<NUM>-Tetramethyl-Butyl) Phenol] (Methylene Bis-Benzotriazolyl Tetramethylbutylphenol) marketed as "TINOSORB M" by BASF may be preferable.

In a known manner, the silicones in the coating(s) may be organosilicon polymers or oligomers comprising a linear or cyclic and branched or cross-linked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitable functional silanes and essentially composed of repeated main units in which the silicon atoms are connected to one another via oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being connected directly to said silicon atoms via a carbon atom.

The term "silicones" also encompasses silanes necessary for their preparation, in particular alkylsilanes.

The silicones used for the coating(s) can preferably be selected from the group consisting of alkylsilanes, polydialkylsiloxanes, and polyalkylhydrosiloxanes. More preferably still, the silicones are selected from the group consisting of octyltrimethylsilane, polydimethylsiloxanes, and polymethylhydrosiloxanes.

Of course, the inorganic UV filters made of metal oxides may, before their treatment with silicones, have been treated with other surfacing agents, in particular with cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or their mixtures.

The coated inorganic UV filter may have been prepared by subjecting the inorganic UV filter to one or more surface treatments of a chemical, electronic, mechanochemical, and/or mechanical nature with any of the compounds as described above, as well as polyethylenes, metal alkoxides (titanium or aluminum alkoxides), metal oxides, sodium hexametaphosphate, and those shown, for example, in <NPL>.

The coated inorganic UV filters may be titanium oxides coated:.

Other titanium oxide pigments treated with a silicone are preferably TiO<NUM> treated with octyltrimethylsilane for which the mean size of the individual particles is from <NUM> and <NUM>, such as that marketed under the trademark "T <NUM>" by Degussa Silices, TiO<NUM> treated with a polydimethylsiloxane for which the mean size of the individual particles is <NUM>, such as that marketed under the trademark "<NUM> Cardre UF TiO<NUM>Si<NUM>" by Cardre, and anatase/rutile TiO<NUM> treated with a polydimethylhydrosiloxane for which the mean size of the individual particles is <NUM>, such as that marketed under the trademark "Microtitanium Dioxide USP Grade Hydrophobic" by Color Techniques.

Preferably, the following coated TiO<NUM> can be used as the coated inorganic UV filter:.

In terms of UV filtering ability, TiO<NUM> coated with at least one organic UV filter is more preferable. For example, Avobenzone (and) Stearic Acid (and) Aluminum Hydroxide (and) TiO<NUM>, such as the product "HXMT-100ZA" from Tayca, with a mean primary particle diameter of <NUM>, can be used.

The uncoated titanium oxide pigments are, for example, marketed by Tayca under the trademarks "Microtitanium Dioxide MT500B" or "Microtitanium Dioxide MT600B", by Degussa under the trademark "P <NUM>", by Wacker under the trademark "Oxyde de titane transparent PW", by Miyoshi Kasei under the trademark "UFTR", by Tomen under the trademark "ITS" and by Tioxide under the trademark "Tioveil AQ".

The uncoated zinc oxide pigments are, for example:.

The coated zinc oxide pigments are, for example:.

The uncoated cerium oxide pigments are marketed, for example, under the trademark "Colloidal Cerium Oxide" by Rhone-Poulenc.

The uncoated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD <NUM> (FE 45B)", "Nanogard Iron FE <NUM> BL AQ", "Nanogard FE 45R AQ", and "Nanogard WCD <NUM> (FE 45R)", or by Mitsubishi under the trademark "TY-<NUM>".

The coated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD <NUM> (FE 45B FN)", "Nanogard WCD <NUM> (FE 45B <NUM>)", "Nanogard FE <NUM> BL <NUM>", and "Nanogard FE <NUM> BL", or by BASF under the trademark "Oxyde de fer transparent".

Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and of cerium dioxide, including a mixture of equal weights of titanium dioxide coated with silica and of cerium dioxide coated with silica marketed by Ikeda under the trademark "Sunveil A", and also a mixture of titanium dioxide and of zinc dioxide coated with alumina, with silica and with silicone, such as the product "M <NUM>" marketed by Kemira, or coated with alumina, with silica and with glycerol, such as the product "M <NUM>" marketed by Kemira.

Coated inorganic UV filters are preferable, because the UV filtering effects of the inorganic UV filters can be enhanced. In addition, the coating(s) may help uniformly or homogeneously disperse the UV filters in the composition according to the present invention.

The amount of the UV filter(s)_in the composition according to the present invention may be <NUM>% by weight or more, preferably <NUM>% by weight or more, more preferably <NUM>% by weight or more, and even more preferably <NUM>% by weight or more, relative to the total weight of the composition.

The amount of the UV filter(s) in the composition according to the present invention may be <NUM>% by weight or less, preferably <NUM>% by weight or less, and more preferably <NUM>% by weight or less, relative to the total weight of the composition.

Specifically, the amount of the UV filter(s) in the composition according to the present invention may be from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight, more preferably from <NUM> to <NUM>% by weight, and even more preferably from <NUM> to <NUM>% by weight, relative to the total weight of the composition.

The composition according to the present invention comprises (c) water. In the present invention, water forms the aqueous phase.

The amount of water may be <NUM>% by weight or more, preferably <NUM>% by weight or more, and more preferably <NUM>% by weight or more, relative to the total weight of the composition.

The amount of the water may be <NUM>% by weight or less, preferably <NUM>% by weight or less, and more preferably <NUM>% by weight or less, relative to the total weight of the composition according to the present invention.

Specifically, the amount of the water in the composition according to the present invention may be from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight, and more preferably from <NUM> to <NUM>% by weight, relative to the total weight of the composition.

The composition according to the present invention may comprise at least one oil. If two or more oils are used, they may be the same or different.

Here, "oil" means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (<NUM>) under atmospheric pressure (<NUM> mmHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile. Preferably the oil is different from the UV filter.

The oil can form the oily phase of the composition according to the present invention.

The 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.

The oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

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 C<NUM>-C<NUM> aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C<NUM>-C<NUM> aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to <NUM>.

Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the present 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, <NUM>-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate.

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

Mention may especially be made of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis(<NUM>-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(<NUM>-ethylhexyl) adipate; diisostearyl adipate; bis(<NUM>-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 C<NUM>-C<NUM> and preferably C<NUM>-C<NUM> 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 <NUM> 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 C<NUM>-C<NUM> and preferably C<NUM>-C<NUM> 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.

As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, <NUM>-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, <NUM>-ethylhexyl <NUM>-ethylhexanoate, <NUM>-ethylhexyl octanoate, <NUM>-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(<NUM>-ethylhexanoate), pentaerythrithyl tetra(<NUM>-ethylhexanoate), <NUM>-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

As examples of ether oils, mention may be made of, for example, ether oils with a short hydrocarbon chain or chains, such as dicaprylyl ether.

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/linolenate).

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 cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.

Preferably, the 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 comprise in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

Organopolysiloxanes are defined in greater detail in<NPL>. 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 <NUM> and <NUM>.

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:.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the <NUM> series from the company Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oil.

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

As the phenyl silicone oil, phenyl trimethicone is preferable.

The organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-<NUM> proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.

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, isoeicosan, and decene/butene copolymer; and mixtures thereof.

The term "fatty" in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have <NUM> or more, preferably <NUM> or more, and more preferably <NUM> or more carbon atoms are encompassed within the scope of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.

The fatty alcohol may have the structure R-OH wherein R is chosen from saturated and unsaturated, linear and branched radicals containing from <NUM> to <NUM> carbon atoms, preferably from <NUM> to <NUM> carbon atoms, and more preferably from <NUM> to <NUM> carbon atoms. In at least one embodiment, R may be chosen from C<NUM>-C<NUM> alkyl and C<NUM>-C<NUM> alkenyl groups. R may or may not be substituted with at least one hydroxyl group.

As examples of the fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

It is preferable that the fatty alcohol be a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from straight or branched, saturated or unsaturated C<NUM>-C<NUM> alcohols, preferably straight or branched, saturated C<NUM>-C<NUM> alcohols, and more preferably straight or branched, saturated C<NUM>-C<NUM> alcohols.

The term "saturated fatty alcohol" here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C<NUM>-C<NUM> fatty alcohols. Among the linear or branched, saturated C<NUM>-C<NUM> fatty alcohols, linear or branched, saturated C<NUM>-C<NUM> fatty alcohols may preferably be used. Any linear or branched, saturated C<NUM>-C<NUM> fatty alcohols may be more preferably used. Branched C<NUM>-C<NUM> fatty alcohols may be even more preferably used.

As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol, can be used as a saturated fatty alcohol.

According to at least one embodiment, the fatty alcohol used in the composition according to the present invention is preferably chosen from cetyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof.

It is preferable that the oil be chosen from hydrocarbon oils, ester oils, silicone oils, and mixtures thereof.

In one embodiment, it is preferable that the oil be selected from the group consisting of mineral oil, octyldodecanol, petrolatum, isododecane, hydrogenated polyisobutene, isopropyl myristate, isononyl isononanoate, dimethicone, cyclohexasiloxane, C<NUM>-C<NUM> alcohol, cetyl palmitate, oleyl alcohol, cetyl alcohol, and mixtures thereof.

The amount of the oil in the composition according to the present invention may range from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight, and more preferably from <NUM> to <NUM>% by weight, relative to the total weight of the composition.

The composition according to the present invention may comprise at least one cosmetically acceptable hydrophilic organic solvent. If two or more oils are used, they may be the same or different.

The cosmetically acceptable hydrophilic organic solvent can form the aqueous phase of the composition according to the present invention.

The cosmetically acceptable hydrophilic organic solvent(s) may include, for example, substantially linear or branched lower mono-alcohols having from <NUM> to <NUM> carbon atoms, such as ethanol, propanol, butanol, isopropanol, and isobutanol; aromatic alcohols, such as benzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerine, propanediol, caprylyl glycol, 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-<NUM>, PEG-<NUM>, and PEG-<NUM>, and their derivatives.

The amount of the cosmetically acceptable hydrophilic organic solvent(s) in the composition according to the present invention may range from <NUM>% to <NUM>% by weight, preferably from <NUM>% to <NUM>% by weight, and more preferably from <NUM>% to <NUM>% by weight, relative to the total weight of the composition.

The compositions according to the present invention may also contain various adjuvants conventionally used in compositions for sun care products, which may be selected from a physiologically acceptable medium, cationic, anionic, non-ionic, amphoteric or zwitterionic polymers, or mixtures thereof, cationic, anionic, non-ionic, amphoteric or zwitterionic surfactants or emulsifiers, or mixtures thereof, antioxidants, such as tocopherol, neutralizing agents, such as triethanolamine, sequestering agents, such as disodium EDTA, fragrances, dispersing agents, dyes and/or pigments, such as VIOLET <NUM> and GREEN <NUM>, film-forming agents and/or thickeners other than the (a) semi-crystalline or crystalline oil thickener, ceramides, preservatives, such as phenoxy ethanol, co-preservatives and opacifying agents.

In one preferred embodiment of the present invention, the composition according to the present invention comprises cationic, anionic, non-ionic, amphoteric or zwitterionic surfactants or emulsifiers in an amount of <NUM>% by weight or less, preferably <NUM>% by weight or less, and more preferably <NUM> % by weight or less, relative to the total amount of the composition.

In one particular embodiment of the present invention, the composition according to the present invention is free of any kind of surfactant or emulsifier.

The adjuvants may be present in the composition of the present invention in an amount preferably ranging from <NUM>% to <NUM>% by weight, preferably from <NUM>% to <NUM>% by weight, and more preferably from <NUM>% to <NUM>% by weight, relative to the total weight of the composition.

The composition according to the present invention can be prepared by mixing the ingredients (a) to (c), as essential ingredients, as well as optional ingredient(s), as explained above.

The method and means to mix the above essential and optional ingredients are not limited. Any conventional method and means can be used to mix the above essential and optional ingredients to prepare the composition according to the present invention. In general, the aqueous phase and the oily phase are prepared separately, and then they are mixed to prepare the composition according to the present invention. The mix ratio of the aqueous phase and the oily phase are not particularly limited, but generally from <NUM>:<NUM> to <NUM>:<NUM>, preferably from <NUM>:<NUM> to <NUM>:<NUM>, and more preferably from <NUM>:<NUM> to <NUM>:<NUM>. It is also possible to heat the ingredients, for example, to <NUM> to <NUM>, to ensure that they are dissolved completely during the method.

The composition according to the present invention may preferably be used as a cosmetic composition. The cosmetic composition may be a sun care composition for protecting keratinous substances, such as skin, from UV rays.

Therefore, the present invention relates to a composition as defined in the claims for use in a process for protecting keratinous substances, preferably skin, from UV radiation, which is applied to the keratinous substances. The process according to the present invention can further comprise another step of mixing the aqueous phase and the oily phase of the present invention prior to the application on the keratinous substance, so as to be a homogenous composition.

The present invention also relates to a cosmetic product comprising the composition according to the present invention. The product according to the present invention comprises the composition according to the present invention and a container or a package in which the composition is contained.

The container or package is not particularly limited; however, since the composition according to the present invention has a relatively low viscosity, there is a benefit in that the composition can be applied without using an aerosol device. Therefore, the container or package are preferably selected from non-aerosol devices, such as a bottle, a tube, a vessel, or a container equipped with a mist generating means, such as a mist-pump, a spray bottle, and a pump bottle.

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

Each of the compositions according to Examples <NUM> to <NUM> (Ex. <NUM> to Ex. <NUM>) and Comparative Examples <NUM> to <NUM> (Comp. <NUM> to Comp. <NUM>) was prepared in accordance with the following preparation protocol. The compositions are shown in the following Table <NUM>.

Among the ingredients, polystearyl acrylate was obtained from the company Air Products (product name: Intelimer® IPA <NUM>-<NUM>) and the polymethylene wax was obtained from Cirebelle (product name: Cirebelle <NUM>). The numerical values for the amounts of the ingredients are all based on "% by weight" as active raw materials.

Each of the oily phases of Examples <NUM> to <NUM> and Comparative Examples <NUM> to <NUM> was measured with VISCOMAN™(GILSON Technology) at room temperature. The bulk viscosity (mPaS, PaS) was automatically calculated from the needed aspiration force in the small pipet (<NUM>µL). The viscosity was measured <NUM> times and its average data was used.

Each of the compositions was shaken <NUM> times in a capped container to be homogeneous. Each of the homogenous compositions was applied to a polypropylene sheet (thickness: <NUM>, PX-P from Sekisui Kagaku) using an applicator called "Elecometer <NUM>" with a force of 1kgf, so as to obtain <NUM> of coating of the composition on the sheet. The sheet was then exposed to a UV lamp (UV black ray B-100AP, wave length: <NUM>) and a picture was taken. The film homogeneity was evaluated based on the visual appearance of the coated sheet in five grades (Very Good, Good, Fair, Bad, and Very Bad). If the appearance was homogeneous intensive black, it was ranked as "Very Good". If the appearance was non-homogenous blue translucent, it was ranked as "Very Bad).

Each of the compositions was shaken <NUM> times in a capped container to be homogeneous. Each of the homogenous compositions was transferred onto a plate (Helio plate HD <NUM>, PMMA, roughness: <NUM>) with an adjustable pipette in an amount of <NUM>/cm<NUM> of the plate and then uniformly spread by finger. The coated plate was air dried for <NUM> minutes at room temperature. The obtained sample plate was placed into a Labsphere Ultraviolet Transmittance Analyzer (Model UV-<NUM> from Solar Light Company, Philadelphia, Pennsylvania). Irradiation took place at <NUM> points on the sample plate. The in vitro SPF level was estimated from absorbance intensity at <NUM>.

Each of the compositions was shaken <NUM> times in a spray bottle to be homogeneous. The mist quality of each of the homogeneous compositions was evaluated visually based on its sprayed droplet size and spray angle. If the sprayed droplet size was fine and the spray angle was wide, it was scored as "Good". If the sprayed droplet size was big and the spray angle was narrow, it was scored as "Bad". In this evaluation, ALBEA mechanical pump was used as a standard spray bottle.

The evaluation results are summarized in Table <NUM> below.

As can be seen from Table <NUM>, the compositions according to each of Examples <NUM> to <NUM>, which include the specific combination of the ingredients (a) to (c) of the present invention exhibited a good film homogeneity and thus a high absorbance intensity at <NUM>.

On the other hand, each of the compositions according to Comparative Examples <NUM> to <NUM>, which lacks semi-crystalline or crystalline lipophilic thickeners as defined in claim <NUM>, showed inferior film homogeneity and thus a low absorbance intensity at <NUM>.

Claim 1:
A bi-phase composition comprising an aqueous phase and an oily phase, wherein the composition comprises:
(a) at least one semi-crystalline or crystalline lipophilic thickener selected from poly C<NUM>-C<NUM> alkyl acrylate and crystalline apolar hydrocarbon-based waxes constituted solely of carbon and hydrogen atoms,
(b) at least one UV filter, and
(c) water, and
wherein the aqueous phase and the oily phase are visually separated at rest.