COSMETIC USE OF CONCAVE OR ANNULAR PARTICLES OF
SILICONS MATERIAL AS AGENTS MAKING IT POSSIBLE TO
INCREASE THE SUN PROTECTION FACTOR; AQUEOUS
PHOTOPROTECTIVE COMPOSITION COMPRISING THEM
A subject-matter of the present invention is the use of concave or annular particles of silicone material, in particular in the form of portions of hollow spheres, in a composition comprising, in a physiologically acceptable medium, at least one aqueous phase and at least one organic UV screening agent and/or one inorganic UV screening agent for the purpose of increasing the sun protection factor (SPF).
The present patent application relates more particularly to a composition comprising, in a physiologically acceptable medium:
a) at least one aqueous phase;
b) concave or annular particles of silicone material,
in particular in the form of portions of hollow
spheres;
c) at least one wetting agent;
d) at least one organic UV screening agent and/or one
inorganic UV screening agent.
It is well known that light radiation with wavelengths of between 280 nm and 400 nm makes possible browning of the human epidermis and that rays with wavelengths of between 280 and 320 nm, known under the name of UV-B radiation, cause erythemas and skin burns which may be harmful to the development of natural tanning; this UV-B radiation must therefore be screened out.
It is also known that UV-A rays, with wavelengths of between 320 and 400 nm, which cause browning of the skin, are capable of bringing about a detrimental change in the latter, in particular in the case of sensitive skin or of skin continually exposed to solar radiation. UV-A rays cause in particular a loss in

elasticity of the skin and the appearance of wrinkles, resulting in premature ageing. They promote the triggering of the erythemal reaction or accentuate this reaction in some subjects and can even be the cause of phototoxic or photoallergic reactions. It is therefore desirable also to screen out UV-A radiation.
UV-A and UV-B rays should thus be screened out and there currently exist protective cosmetic compositions for the human epidermis which include UV-A and/or UV-B screening agents in the context of everyday and antisun photoprotection.
However, one of the major objectives of these applications is, for cosmetic pleasantness or tolerance reasons but also for formulation reasons, to limit as much as possible the level of sunscreens in the composition.
Patent US 6 039 935 has already provided antisun formulations in the form of an oil/water emulsion comprising organic UV screening agents and a nonemulsifying crosslinked elastomeric silicone and volatile silicone for increasing the level of protection and minimizing the amount of screening agent. Oily microgels formed of crosslinked elastomeric silicone are concerned; these microgels have the disadvantages of modifying the viscosity of the composition.
The aim will thus be to find materials which, introduced into the composition, make it possible not only to significantly improve the effectiveness of the suncreens but without the disadvantages set out above, in particular without increasing the viscosity, and which make it possible to obtain a nongreasy dry feel.
Concave particles of crosslinked organopolysiloxane material which have the form of portions of hollow

spheres, obtained by condensation of silanols resulting from the hydrolysis of organosilicone compounds, are known in the prior art, in particular from Patent Applications JP-A-2000-191789, JP-A-2003-128788, EP 1 579 849, EP 1 579 841, FR 2 867 677 and FR 2 877 839. In these patent applications, their use is indicated in particular in cosmetic products for the face or in makeup products, in particular in compact foundation powders or lipstick sticks. In Patent Applications EP 1 642 619 and EP 1 642 620, these same particles have been provided in hair compositions for fixing and/or retaining the form of the hairstyle. Silicone particles of annular shape are also known in Patent Application US 2006/0089778, it being possible for these silicone particles to be used as powder in products for caring for the face, makeup products, products for the body, hair products or deodorants.
The Applicant Company has discovered, surprisingly and unexpectedly, that this objective can be achieved by using concave particles of silicone material in an aqueous composition comprising at least one organic UV screening agent and/or one inorganic UV screening agent.
Furthermore, the Applicant Company has found that these concave particles of silicone material in combination with a wetting agent in an aqueous composition comprising at least one organic UV screening agent and/or one inorganic UV screening agent also make it possible to significantly increase the photoprotective effectiveness, which is reflected in particular by the sun protection factor (SPF).
A subject-matter of the present invention is thus the use of concave or annular particles of silicone material, in particular in the form of portions of hollow spheres, in an aqueous composition comprising, in a physiologically acceptable medium, at least one

aqueous phase and at least one organic UV screening agent and/or one inorganic UV screening agent for the purpose of increasing the sun protection factor (SPF)
Another subject-matter of the present invention is the use of concave or annular particles of silicone material, in particular in the form of portions of hollow spheres, in combination with a wetting agent in an aqueous composition comprising, in a physiologically acceptable medium, at least one organic UV screening agent and/or one inorganic UV screening agent for the purpose of increasing the sun protection factor (SPF).
Another subject-matter of the present invention is an aqueous composition comprising, in a physiologically acceptable medium:
a) concave or annular particles of silicone material,
in particular in the form of portions of hollow
spheres;
b) at least one wetting agent;
c) at least one organic UV screening agent and/or one
inorganic UV screening agent.
The term "physiologically acceptable medium" is understood to mean a nontoxic medium capable of being applied to the skin, lips, hair, eyelashes, eyebrows or nails. The composition of the invention can constitute in particular a cosmetic or dermatological composition.
The term "wetting agent" is understood to mean any compound which, introduced at 0.05% (by weight) in aqueous solution, makes it possible to reduce the surface tension of water to a value of less than 35 mN/m and preferably of less than 30 mN/m.
The sun protection factor (SPF) is expressed mathematically by the ratio of the dose of UV radiation necessary to reach the erythemogenic threshold with the UV screening agent to the dose of UV radiation

necessary to reach the erythemogenic threshold without UV screening agent.
The term "composition comprising at least one aqueous phase" is understood to mean a formulation of the oil-in-water (0/W) or water-in-oil (W/0) or multiple (triple: W/O/W or 0/W/O) type. The proportion by weight of the aqueous phase preferably varies from 25 to 95%, preferably from 30 to 90% and more preferably still from 40 to 80%. The emulsions of the oil-in-water type or of the water-in-oil-in-water type will more particularly be chosen.
Concave or annular particles of silicone material
The concave or annular particles present in the composition according to the invention are silicone particles, in particular particles of portions of hollow spheres composed of a silicone material.
The said particles preferably have a mean diameter of less than or equal to 10 urn, in particular ranging from 0.1 urn to 8 urn, preferably from 0.2 to 7 urn, more preferably ranging from 0.5 to 6 um and preferably again ranging from 0.5 to 4 um.
The term "mean diameter" is understood to mean the greatest dimension of the particle.
Advantageously, these particles have a density of greater than 1.
The portions of hollow spheres used in the composition according to the invention can have the shape of truncated hollow spheres exhibiting a single orifice communicating with their central cavity and having a transverse cross section with the shape of a horseshoe or arch.

The silicone material is a crosslinked polysiloxane with a three-dimensional structure; it preferably comprises, indeed even is composed of, units of formula (I) Si02 and of formula (II) R1SiO1.5
in which R1 denotes an organic group having a carbon atom directly connected to the silicon atom.
The organic group R1 can be a reactive organic group; R1 can more particularly be an epoxy group, a (meth)acryloyloxy group, an alkenyl group, a mercaptoalkyl, aminoalkyl or haloalkyl group, a glyceroxy group, a ureido group or a cyano group and preferably an epoxy group, a (meth)acryloyloxy group, an alkenyl group or a mercaptoalkyl or aminoalkyl group. These groups generally comprise from 2 to 6 carbon atoms, in particular from 2 to 4 carbon atoms.
The organic group R1 can also be an unreactive organic group; R1 can then more particularly be a Ci-C4 alkyl group, in particular a methyl, ethyl, propyl or butyl group, or a phenyl group and preferably a methyl group.
Mention may be made, as epoxy group, of a 2-glycidoxyethyl group, a 3-glycidoxypropyl group or a 2-(3,4-epoxycyclohexyl)propyl group.
Mention may be made, as (meth)acryloyloxy group, of a 3-methacryloyloxypropyl group or a 3-acryloyloxypropyl group.
Mention may be made, as alkenyl group, of the vinyl, allyl or isopropenyl groups.
Mention may be made, as mercaptoalkyl group, of the mercaptopropyl or mercaptoethyl groups.
Mention may be made, as aminoalkyl group, of a 3-[(2-aminoethyl)amino]propyl group, a 3-aminopropyl group or an N,N-dimethylaminopropyl group.

Mention may be made, as haloalkyl group, of a 3-chloropropyl group or a trifluoropropyl group.
Mention may be made, as glyceroxy group, of a 3-glyceroxypropyl group or a 2-glyceroxyethyl group.
Mention may be made, as ureido group, of a 2-ureidoethyl group.
Mention may be made, as cyano group, of the cyanopropyl or cyanoethyl groups.
Preferably, in the unit of formula (II), R1 denotes a methyl group.
Advantageously, the silicone material comprises the units (I) and (II) according to a unit (I)/unit (II) molar ratio ranging from 30/70 to 50/50, preferably ranging from 35/65 to 45/55.
The particles of silicone material can in particular be capable of being obtained according to a process comprising:
(a) the introduction into an aqueous medium, in the
presence of at least one hydrolysis catalyst and
optionally of at least one surfactant, of a compound
(III) of formula SiX4 and of a compound (IV) of formula
RSiY3, where X and Y denote, independently of one another, a C1-C4 alkoxy group, an alkoxyethoxy group including a C1-C4 alkoxy group, a C2-C4 acyloxy group, an N,N-dialkylamino group including C1-C4 alkyl groups, a hydroxyl group, a halogen atom or a hydrogen atom and R denotes an organic group comprising a carbon atom connected directly to the silicon atom; and
(b) the operation in which the mixture resulting from
stage (a) is brought into contact with an aqueous
solution including at least one polymerization catalyst
and optionally at least one surfactant, at a

temperature of between 30 and 85°C, for at least two hours.
Stage (a) corresponds to a hydrolysis reaction and stage (b) corresponds to a condensation reaction.
In stage (a) , the molar ratio of the compound (III) to the compound (IV) generally ranges from 30/70 to 50/50, advantageously from 35/65 to 45/45, and is preferentially 40/60. The ratio by weight of the water to the total of the compounds (III) and (IV) preferably ranges from 10/90 to 70/30. The order of introduction of the compounds (III) and (IV) generally depends on their rate of hydrolysis. The temperature of the hydrolysis reaction generally ranges from 0 to 40°C and usually does not exceed 30°C in order to prevent premature condensation of the compounds.
For the X and Y groups of the compounds (III) and (IV) :
mention may be made, as C1-C4 alkoxy group, of the methoxy or ethoxy groups;
mention may be made, as alkoxyethoxy group including a Ci-C4 alkoxy group, of the methoxyethoxy or butoxyethoxy groups;
mention may be made, as C2-C4 acyloxy group, of the acetoxy or propionyloxy groups;
mention may be made, as N,N-dialkylamino group including a C1-C4 alkyl group, of the dimethylamino or diethylamino groups;
mention may be made, as halogen atom, of the chlorine or bromine atoms.
Mention may be made, as compounds of formula (III), of tetramethoxysilane, tetraethoxysilane, tetrabutoxy-

silane, trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane, tetrapropioxysilane, tetra-(dimethylamino)silane, tetra(diethylamino)silane, silanetetraol, chlorosilanetriol, dichlorodisilanol, tetrachlorosilane or chlorotrihydrosilane. Preferably, the compound of formula (III) is chosen from tetra-methoxysilane, tetraethoxysilane, tetrabutoxysilane and their mixtures.
The compound of formula (III) results, after the polymerization reaction, in the formation of the units of formula (I).
The compound of formula (IV) results, after the polymerization reaction, in the formation of the units of formula (II).
The R group in the compound of formula (IV) has the meaning as described for the R1 group for the compound of formula (II).
Mention may be made, as examples of compounds of formula (IV) comprising an unreactive organic group R, of methyltrimethoxysilane, ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane, phenyltri-methoxyethoxysilane, methyltributoxyethoxysilane, methyltriacetoxysilane, methyltripropioxysilane, methyltri(dimethylamino)silane, methyltri(diethylamino) silane, methylsilanetriol, methylchlorodisilanol, methyltrichlorosilane or methyltrihydrosilane.
Mention may be made, as examples of compounds of formula (IV) comprising a reactive organic group R, of: - silanes having an epoxy group, such as (3-glycidoxy-propyl)trimethoxysilane, (3-glycidoxypropyl)triethoxy-silane, [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (2-glycidoxy-ethyl)methyldimethoxysilane, (3-glycidoxypropyl)-dimethylmethoxysilane or (2-glycidoxyethyl)dimethyl-
methoxysilane;
- silanes having a (meth)acryloyloxy group, such as
(3-methacryloyloxypropyl)trimethoxysilane or (3-acryl-
oyloxypropyl)trimethoxysilane;
- silanes having an alkenyl group, such as vinyltri-
methoxysilane, allyltrimethoxysilane or isopropenyltri-
methoxysilane;
- silanes having a mercapto group, such as mercapto-
propyltrimethoxysilane or mercaptoethyltrimethoxy-
silane;
- silanes having an aminoalkyl group, such as (3-amino-
propyl)trimethoxysilane, (3-[(2-aminoethyl)amino]-
propyl)trimethoxysilane, (N,N-dimethylaminopropyl)-
trimethoxysilane or (N,N-dimethylaminoethyl)trimethoxy
silane;
- silanes having a haloalkyl group, such as (3-chloro-
propyl)trimethoxysilane or trifluoropropyltrimethoxy-
s i1ane;
- silanes having a glyceroxy group, such as
(3-glyceroxypropyl)trimethoxysilane or di(3-
glyceroxypropyl)dimethoxysilane;
- silanes having a ureido group, such as (3-ureido-
propyl)trimethoxysilane, (3-ureidopropyl)methyl-
dimethoxysilane or (3-ureidopropyl)dimethylmethoxy-
silane;
- silanes having a cyano group, such as cyanopropyltri-
methoxysilane, cyanopropylmethyldimethoxysilane or
cyanopropyldimethyImethoxysilane.
Preferably, the compound of formula (IV) comprising a reactive organic group R is chosen from silanes having an epoxy group, silanes having a (meth)acryloyloxy group, silanes having an alkenyl group, silanes having a mercapto group or silanes having an aminoalkyl group.
Examples of compounds (III) and (IV) which are preferred for the implementation of this invention are respectively tetraethoxysilane and methyltri-methoxysilane.
Use may independently be made, as hydrolysis and polymerization catalysts, of basic catalysts, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, ammonia or amines, such as trimethylamine, triethylamine or tetramethyl-ammonium hydroxide, or acidic catalysts, such as organic acids, for example citric acid, acetic acid, methanesulphonic acid, p-toluenesulphonic acid, dodecylbenzenesulphonic acid or dodecylsulphonic acid, or inorganic acids, such as hydrochloric acid, sulphuric acid or phosphoric acid.
When it is present, the surfactant used is preferably a nonionic or anionic surfactant or a mixture of the two. Sodium dodecylbenzenesulphonate can be used as anionic surfactant. The end of the hydrolysis is marked by the disappearance of the products (III) and (IV), which are insoluble in water, and the production of a homogeneous liquid layer.
The condensation stage (b) can use the same catalyst as the hydrolysis stage or another catalyst chosen from those mentioned above.
On conclusion of this process, a suspension in water of fine organosilicone particles is obtained, which particles can optionally be separated subsequently from their medium. The process described above can thus comprise an additional stage of filtration, for example on a membrane filter, of the product resulting from stage (b) , optionally followed by a stage of centrifuging the filtrate, intended to separate the particles from the liquid medium, and then by a stage of drying the particles. Other separation methods can, of course, be employed.
The shape of the portions of hollow spheres obtained according to the above process and their dimensions will depend in particular on the method used to bring
the products into contact in stage (b).
A somewhat basic pH and introduction under cold conditions of the polymerization catalyst into the mixture resulting from stage (a) will result in portions of hollow spheres with the shape of round-bottomed "bowls", whereas a somewhat acidic pH and dropwise introduction of the mixture resulting from stage (a) into the hot polymerization catalyst will result in portions of hollow spheres having a transverse cross section with the shape of a "horseshoe".
According to a preferred embodiment of the invention, portions of hollow spheres with the shape of "bowls" are used. These can be obtained as described in Application JP-A-2003-128788.
Portions of hollow spheres with the shape of a horseshoe are described in Application JP-A-2000-191789.
A concave particle in the form of portions of spheres with the shape of a bowl is illustrated in transverse cross section in the appended Figure 1. The width W2 corresponds to the diameter of the particles.
As emerges from this figure, these concave particles are formed (in cross section perpendicular to the plane of the opening delimited by the portion of hollow sphere) of a small internal arc (11) , of a large external arc (21) and of segments (31) which connect the ends of the respective arcs, the width (Wl) between the two ends of the small internal arc (11) ranging from 0.01 to 8 µm, preferably from 0.02 to 6 µm, on average, the width (W2) between the two ends of the large external arc (21) ranging from 0.05 to 10 µm, preferably from 0.06 to 8 µm, on average, and the height (H) of the large external arc (21) ranging from
0.015 to 8 µm, preferably from 0.03 to 6 um, on average.
The dimensions mentioned above are obtained by calculating the mean of the dimensions of one hundred particles chosen on an image obtained with a scanning electron microscope.
Mention may be made, as concave particles in the form of portions of spheres which can be used according to the invention, of, for example:
- particles composed of the crosslinked organosilicone
TAK-110 (crosslinked methylsilanol/silicate polymer)
from Takemoto Oil & Fat, with the shape of a bowl, with
a width of 2.5 urn, a height of 1.2 urn and a thickness
of 150 nm (particles sold under the name NLK-506 by
Takemoto Oil & Fat);
- particles composed of the crosslinked organosilicone
TAK-110 (crosslinked methylsilanol/silicate polymer)
from Takemoto Oil & Fat, with the shape of a bowl, with
a width of 0.8 um, a height of 0.4 um and a thickness
of 130 nm (particles sold under the name NLK-515 by
Takemoto Oil & Fat);
- particles composed of the crosslinked organosilicone
TAK-110 (crosslinked methylsilanol/silicate polymer)
from Takemoto Oil & Fat, with the shape of a bowl, with
a width of 7 um, a height of 3.5 um and a thickness of
200 nm (particles sold under the name NLK-510 by
Takemoto Oil & Fat).
These particles have the INCI name: methylsilanol/ silicate crosspolymer.
Advantageously, the concave silicone particles have a mean diameter of less than or equal to 5 um, in particular ranging from O.lpm to 5 µm, preferably ranging from 0.2 to 5 um, more preferably ranging from 0.5 to 4 um and preferably again ranging from 0.5 to 3 µm.
These particles make possible, in addition to the reduction, indeed even the elimination, of the sticky feel, the optimization of the properties of slip, of spreading and of comfort of the composition according to the invention.
The silicone particles of annular shape are preferably chosen from those described and synthesized in Patent Application US-A-2006/0089478. They exhibit a mean external diameter of 0.05 to 15 µm and a mean internal diameter of 0.01 to 10 um, the difference between the mean external diameter and the mean internal diameter being from 0.04 to 5 µm.
They exhibit a polysiloxane network comprising siloxane units of formulae (1), (2), (3), (4), (5) and (6):
Si04/2 (1)
Si(OH)3/2 (2)
RiSi03/2 (3)
R2Si03/2 (4)
R3Si03/2 (5)
R4Si03/2 (6)
in which:
- RI and R3 denote unreactive hydrocarbon groups, in
particular alkyl, cycloalkyl, aryl, alkylaryl or
aralkyl groups, preferably C1-C3 alkyl groups, in
particular methyl, ethyl or propyl groups and
preferably a methyl group,
and R2 and R4 each denote a hydrocarbon group chosen
from the acryloyloxy, methacryloyloxy, vinyl or
mercapto groups;
the siloxane units of formula (1)/siloxane units of
formulae (2), (3), (4), (5) and (6) molar ratio being
from 20/80 to 50/50;
the siloxane units of formulae (2), (3) and (4)/siloxane units of formulae (5) and (6) molar ratio being from 50/50 to 75/25;
the siloxane units of formulae (3) and (5)/siloxane units of formulae (4) and (6) molar ratio being from 20/80 to 60/40.
Mention may be made, as acryloyloxy group, of a 2-methacryloyloxyethyl group or a 3-acryloyloxypropyl group.
Mention may be made, as (meth)acryloyloxy group, of a 3-methacryloyloxypropyl group or a 3-acryloyloxypropyl group.
Mention may be made, as mercaptoalkyl group, of a mercaptopropyl or mercaptoethyl group.
Mention may be made, as vinyl group, of the allyl, isopropenyl or 2-methylallyl groups.
The concave or annular silicone particles can be present in the composition according to the invention in a content ranging from 0.1 to 15% by weight, preferably ranging from 0.5 to 10% by weight and preferably ranging from 0.5 to 7.5% by weight, with respect to the total weight of the composition.
UV screening agents
The screening compositions in accordance with the invention comprise organic and/or inorganic UV screening agents active in the UV-A and/or UV-B region which are hydrophilic and/or lipophilic and/or properly insoluble in the cosmetic solvents commonly used.
The hydrophilic, lipophilic or insoluble organic UV screening agents are chosen in particular from anthranilates; dibenzoylmethane derivatives; cinnamic
derivatives; salicylic derivatives; camphor
derivatives; benzophenone derivatives;
(J, 3-diphenylacrylate derivatives; triazine derivatives;
benzotriazole derivatives; benzalmalonate derivatives,
in particular those cited in Patent US 5 624 663;
benzimidazole derivatives; imidazolines;
bis-benzoazolyl derivatives, such as described in
Patents EP 669 323 and US 2 463 264; p-aminobenzoic
acid (PABA) derivatives;
methylenebis(hydroxyphenylbenzotriazole) derivatives, such as described in Applications US 5 237 071, US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 119; benzoxazole derivatives, such as described in Patent Applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 10162844; screening polymers and screening silicones, such as those described in particular in Application WO 93/04665; dimers derived from a-alkylstyrene, such as those described in Patent Application DE 19855649; 4,4-diarylbutadienes, such as described in Applications EP 0 967 200, DE 19746654, DE 19755649, EP-A-1 008 586, EP 1 133 980 and EP 133 981; and their mixtures.
Mention may be made, as examples of organic UV screening agents, of those denoted below under their INCI names:
para-Aminobenzoic acid derivatives:
PABA,
Ethyl PABA,
Ethyl Dihydroxypropyl PABA,
Ethylhexyl Dimethyl PABA, sold in particular under the
name "Escalol 507" by ISP,
Glyceryl PABA,
PEG-25 PABA, sold under the name "Uvinul P25" by BASF,
Dibenzoylmethane derivatives:
Butyl Methoxydibenzoylmethane, sold in particular
under the trade name "Parsol 1789" by Hoffmann-
LaRoche,
Isopropyl Dibenzoylmethane,
Salicylic derivatives:
Homosalate, sold under the name "Eusolex HMS" by
Rona/EM Industries,
Ethylhexyl Salicylate, sold under the name "Neo
Heliopan OS" by Haarmann and Reimer,
Dipropyleneglycol Salicylate, sold under the name
"Dipsal" by Scher,
TEA Salicylate, sold under the name "Neo Heliopan TS"
by Haarmann and Reimer,
Cinnamic derivatives:
Ethylhexyl Methoxycinnamate, sold in particular under
the trade name "Parsol MCX" by Hoffmann-LaRoche,
Isopropyl Methoxycinnamate,
Isoamyl Methoxycinnamate, sold under the trade name
"Neo Heliopan E 1000" by Haarmann and Reimer,
Cinoxate,
DBA Methoxycinnamate,
Diisopropyl Methylcinnamate,
Glyceryl Ethylhexanoate Dimethoxycinnamate,
(3, ft-Diphenylacrylate derivatives :
Octocrylene, sold in particular under the trade name
"Uvinul N539" by BASF,
Etocrylene, sold in particular under the trade name
"Uvinul N35" by BASF,
Benzophenone derivatives:
Benzophenone-1, sold under the trade name "Uvinul 400"
by BASF,
Benzophenone-2, sold under the trade name "Uvinul D50"
by BASF,
Benzophenone-3 or Oxybenzone, sold under the trade
name "Uvinul M40" by BASF,
Benzophenone-4, sold under the trade name "Uvinul MS40" by BASF, Benzophenone- 5,
Benzophenone-6, sold under the trade name "Helisorb 11" by Norquay,
Benzophenone-8, sold under the trade name "Spectra-Sorb UV-24" by American Cyanamid,
Benzophenone-9, sold under the trade name "Uvinul DS-49" by BASF, Benzophenone-12, n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
Benzylidenecamphor derivatives:
3-Benzylidene camphor, manufactured under the name
"Mexoryl SD" by Chimex,
4-Methylbenzylidene camphor, sold under the name
"Eusolex 6300" by Merck,
Benzylidene Camphor Sulfonic Acid, manufactured under
the name "Mexoryl SL" by Chimex,
Camphor Benzalkonium Methosulfate, manufactured under
the name "Mexoryl SO" by Chimex,
Terephthalylidene Dicamphor Sulfonic Acid,
manufactured under the name "Mexoryl SX" by Chimex,
Polyacrylamidomethyl Benzylidene Camphor, manufactured
under the name "Mexoryl SW" by Chimex,
Phenylbenzimidazole derivatives:
Phenylbenzimidazole Sulfonic Acid, sold in particular
under the trade name "Eusolex 232" by Merck,
Disodium Phenyl Dibenzimidazole Tetrasulfonate, sold
under the trade name "Neo Heliopan AP" by Haarmann and
Reimer,
Phenylbenzotriazole derivatives:
Drometrizole Trisiloxane, sold under the name
"Silatrizole" by Rhodia Chimie,
Methylene Bis-Benzotriazolyl Tetramethylbutylphenol,
sold in the solid form under the trade name "Mixxim
BB/100" by Fairmount Chemical or in the micronized
form in aqueous dispersion under the trade name "Tinosorb M" by Ciba Specialty Chemicals,
Triazine derivatives:
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, sold
under the trade name "Tinosorb S" by Ciba-Geigy,
Ethylhexyl Triazone, sold in particular under the
trade name "Uvinul T150" by BASF,
Diethylhexyl Butamido Triazone, sold under the trade
name "Uvasorb HEB" by Sigma 3V,
2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-
triazine,
the symmetrical triazine screening agents described in
Patent US 6 225 467, Application WO 2004/085412 (see
compounds 6 and 9) or the document "Symmetrical
Triazine Derivatives", IP.COM Journal, IP.COM INC,
WEST HENRIETTA, NY, US (20 September 2004), in
particular the 2,4,6-tris(biphenyl)-1,3,5-triazines
(especially 2,4,6-tris(biphenyl-4-yl)-1,3,5-triazine)
and 2,4,6-tris(terphenyl)-1,3 , 5-triazine, which is
taken up again in Patent Applications WO 06/035000, WO
06/034982, WO 06/034991, WO 06/035007, WO 2006/034992
and WO 2006/034985.
Anthranilic derivatives:
Menthyl anthranilate, sold under the trade name "Neo
Heliopan MA" by Haarmann and Reimer,
Imidazoline derivatives:
Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline
Propionate,
Benzalmalonate derivatives: Dineopentyl 4'-methoxybenzalmalonate,
Polyorganosiloxane comprising benzalmalonate functional groups, such as Polysilicone-15, sold under the trade name "Parsol SLX" by Hoffmann-LaRoche,
4,4-Diarylbutadiene derivatives:
1,1-Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene,
Benzoxazole derivatives:
2,4-bis [5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine, sold under the name of Uvasorb K2A by Sigma 3V and their mixtures.
The preferred organic UV screening agents are chosen
from:
Ethylhexyl Methoxycinnamate,
Homosalate,
Ethylhexyl Salicylate,
Octocrylene,
Phenylbenzimidazole Sulfonic Acid,
Benzophenone-3,
Benzophenone- 4,
Benzophenone- 5,
n-Hexyl 2- (4-diethylamino-2-hydroxybenzoyl)benzoate,
4-Methylbenzylidene Camphor,
Terephthalylidene Dicamphor Sulfonic Acid,
Disodium Phenyl Dibenzimidazole Tetrasulfonate,
Ethylhexyl triazone,
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine,
Diethylhexyl Butamido Triazone,
2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-
triazine,
2,4,6-Tris(diisobutyl 4'-aminobenzalmalonate)-s-
triazine,
2,4,6-Tris(biphenyl-4-yl)-1,3,5-triazine,
2,4,6-Tris(terphenyl)-1,3,5-triazine,
Methylene Bis-Benzotriazolyl Tetramethylbutylphenol,
Drometrizole Trisiloxane,
Polysilicone-15,
Dineopentyl 4'-methoxybenzalmalonate,
1,1-Dicarboxy(2,2'-dimethylpropyl)-4,4-
diphenylbutadiene,
2,4-Bis [5-1(dimethylpropyl)ben2oxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1, 3,5-triazine, and their mixtures.
The inorganic screening agents are chosen from pigments (mean size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) formed of metal oxides which may or may not be coated, 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 well known per se.
The pigments may or may not be coated.
The coated pigments are pigments which have been subjected to one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (titanium or aluminium alkoxides), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
In a known way, the silicones are organosilicon polymers or oligomers comprising a linear or cyclic and branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitable functional silanes and essentially composed of a repetition of 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 the said silicon atoms via a carbon atom.
The term "silicones" also encompasses the silanes necessary for their preparation, in particular alkylsilanes.
The silicones used for the coating of the pigments suitable for the present invention are preferably chosen from the group consisting of alkylsilanes, polydialkylsiloxanes and polyalkylhydrosiloxanes. More preferably still, the silicones are chosen from the group consisting of octyltrimethylsilane, polydimethylsiloxanes and polymethylhydrosiloxanes.
Of course, the pigments formed of metal oxides may, before their treatment with silicones, have been treated with other surfacing agents, in particular with cerium oxide, alumina, silica, aluminium compounds, silicon compounds or their mixtures.
The coated pigments are more particularly titanium oxides coated:
- with silica, such as the product "Sunveil" from
Ikeda,
- with silica and with iron oxide, such as the product
"Sunveil F" from Ikeda,
- with silica and with alumina, such as the products
"Microtitanium Dioxide MT 500 SA" and "Microtitanium
Dioxide MT 100 SA" from Tayca, "Tioveil" from Tioxide
and "Mirasun TiW 60" from Rhodia,
- with alumina, such as the products "Tipaque TTO-55
(B) " and "Tipaque TTO-55 (A)" from Ishihara and "UVT
14/4" from Kemira,
- with alumina and with aluminium stearate, such as
the product "Microtitanium Dioxide MT 100 T, MT 100
TX, MT 100 Z or MT-01" from Tayca, the products
"Solaveil CT-10 W" and "Solaveil CT 100" from Uniqema
and the product "Eusolex T-AVO" from Merck,
- with silica, with alumina and with alginic acid,
such as the product "MT-100 AQ" from Tayca,
- with alumina and with aluminium laurate, such as the
product "Microtitanium Dioxide MT 100 S" from Tayca,
- with iron oxide and with iron stearate, such as the
product "Microtitanium Dioxide MT 100 F" from Tayca,
- with zinc oxide and with zinc stearate, such as the
product "BR351" from Tayca,
- with silica and with alumina and treated with a
silicons, such as the products "Microtitanium Dioxide
MT 600 SAS", "Microtitanium Dioxide MT 500 SAS" or
"Microtitanium Dioxide MT 100 SAS" from Tayca,
with silica, with alumina and with aluminium stearate and treated with a silicone, such as the product "STT-30-DS" from Titan Kogyo,
- with silica and treated with a silicone, such as the
product "UV-Titan X 195" from Kemira,
- with alumina and treated with a silicone, such as
the products "Tipaque TTO-55 (S)" from Ishihara or "UV
Titan M 262" from Kemira,
- with triethanolamine, such as the product "STT-65-S"
from Titan Kogyo,
- with stearic acid, such as the product "Tipaque TTO-
55 (C)" from Ishihara,
- with sodium hexametaphosphate, such as the product
"Microtitanium Dioxide MT 150 W" from Tayca.
Other titanium oxide pigments treated with a silicone are preferably Ti02 treated with octyltrimethylsilane and for which the mean size of the individual particles is between 25 and 40 nm, such as that sold under the trade name "T 805" by Degussa Silices, TiO2 treated with a polydimethylsiloxane and for which the mean size of the individual particles is 21 nm, such as that sold under the trade name "70250 Cardre UF TiO2S13" by Cardre, anatase/rutile TiO2 treated with a polydimethylhydrosiloxane and for which the mean size of the individual particles is 25 nm, such as that sold under the trade name "Microtitanium Dioxide USP Grade Hydrophobic" by Color Techniques.
The uncoated titanium oxide pigments are, for example, sold by Tayca under the trade names "Microtitanium Dioxide MT 500 B" or "Microtitanium Dioxide MT600 B", by Degussa under the name "P 25", by Wacker under the name "Oxyde de titane transparent PW", by Miyoshi Kasei under the name "UFTR" , by Tomen under the name "ITS" and by Tioxide under the name "Tioveil AQ".
The uncoated zinc oxide pigments are, for example:
- those sold under the name "Z-cote" by Sunsmart;
- those sold under the name "Nanox" by Elementis;
- those sold under the name "Nanogard WCD 2025" by
Nanophase Technologies.
The coated zinc oxide pigments are, for example:
those sold under the name "Oxide zinc CS-5" by Toshibi (ZnO coated with polymethylhydrosiloxane);
- those sold under the name "Nanogard Zinc Oxide FN"
by Nanophase Technologies (as a 40% dispersion in
Finsolv TN, C12-Ci5 alkyl benzoate) ;
- those sold under the name "Daitopersion Zn-30" and
"Daitopersion Zn-50" by Daito (dispersions in
oxyethylenated
polydimethylsiloxane/cyclopolymethylsiloxane comprising 30% or 50% of zinc nanooxides coated with silica and polymethylhydrosiloxane);
- those sold under the name "NFD Ultrafine ZnO" by
Daikin (ZnO coated with phosphate of perfluoroalkyl
and copolymer based on perfluoroalkylethyl as a
dispersion in cyclopentasiloxane);
- those sold under the name "SPD-Z1" by Shin-Etsu (ZnO
coated with silicone-grafted acrylic polymer dispersed
in cyclodimethylsiloxane);
- those sold under the name "Escalol Z100" by ISP
(alumina-treated ZnO dispersed in the ethylhexyl
methoxycinnamate/PVP-hexadecene copolymer/methicone mixture);
- those sold under the name "Fuji ZnO-SMS-10" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);
those sold under the name "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate).
The uncoated cerium oxide pigments are sold, for example, under the name "Colloidal Cerium Oxide" by Rhone-Poulenc.
The uncoated iron oxide pigments are, for example, sold by Arnaud under the names "Nanogard WCD 2002 (FE 45B)", "Nanogard Iron FE 45 BL AQ", "Nanogard FE 45R AQ" or "Nanogard WCD 2006 (FE 45R)", or by Mitsubishi under the name "TY-220".
The coated iron oxide pigments are, for example, sold by Arnaud under the names "Nanogard WCD 2008 (FE 45B FN)", "Nanogard WCD 2009 (FE 45B 556)", "Nanogard FE 45 BL 345" or "Nanogard FE 45 BL" or by BASF under the name "Oxyde de fer transparent".
Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and of cerium dioxide, including the mixture of equal weights of titanium dioxide coated with silica and of cerium dioxide coated with silica sold by Ikeda under the name "Sunveil A", and also the mixture of titanium dioxide and of zinc dioxide coated with alumina, with silica and with silicone, such as the product "M 261" sold by Kemira, or coated with alumina, with silica and with glycerol, such as the product "M 211" sold by Kemira.
The UV screening agents are generally present in the compositions according to the invention in proportions ranging from 0.01 to 20% by weight, with respect to the total weight of the composition, and preferably
ranging from 0.1 to 10% by weight, with respect to the total weight of the composition.
According to a particularly preferred form of the invention, the compositions additionally comprise at least one wetting agent.
The wetting agents in accordance with the invention are preferably chosen from water-soluble silicones comprising at least one terminal or pendent monovalent polyoxyalkylene group and which, introduced at 0.05% by weight into an aqueous solution, are capable of reducing the surface tension of water to a value of less than 35 mN/m and preferably of less than 30 mN/m.
The wetting agents in accordance with the invention are more preferably chosen from water-soluble silicones comprising at least one polyoxyalkylene group of following general formula (a):
(Formula Removed)
in which:
- the R2 radicals, which are identical or different, denote a monovalent hydrocarbon radical chosen from alkyl, aryl and aralkyl radicals having at most 10 carbon atoms; some of the R2 radicals can also additionally comprise an ethylcyclohexylene monoxide group of formula:
and are in low proportion in the polysiloxane chain;
- p varies from 0 to 150, preferably from 0 to 100 and
more preferably from 0 to 30;
- q varies from 1 to 12, preferably from 1 to 10 and
more preferably from 1 to 8;
- the polyether group PE has the following formula (b):
(Formula Removed)
in which:
x varies from 1 to 8 and preferably varies from 2 to 4
and more preferably is equal to 3;
y is greater than 0;
z is greater than or equal to 0; the values of y and z
are such that the total molecular weight of the
polyoxyalkylene portion of the polyether group PE
varies from 200 to 10 000 and more preferably from 350
to 4000;
R3 denotes hydrogen, a d-C8 alkyl group or a C2-C8 acyl
group.
It should be noted that, when z is other than 0, the polyoxyethylene and polyoxypropylene units can be distributed randomly along the polyether chain PE or distributed as blocks or indeed simultaneously distributed as blocks and randomly.
Preferably, the R2 radicals are chosen from lower C1-C6 alkyls, such as methyl, ethyl, butyl or hexyl, phenyl and benzyl. More particularly, the R2 radicals are chosen from lower C1-C4 alkyls and more particularly still denote methyl.
Preferably, the R3 radicals are chosen from lower C1-C4 alkyls and more particularly still denote methyl.
The number of oxyethylene units of the PE group must be sufficient to produce a cloud point in water between 25 and 90°C and more preferably from 40 to 70°C.
The water-soluble silicones of formula (a) can be obtained according to the process described in Patent US 4 847 398.
Use will preferably be made, among the water-soluble silicones of formula (a), of that of following formula (a') :
(Formula Removed)
where Me denotes methyl; PE denotes:
(Formula Removed)
where x, z and z have the same values indicated above and R3 denotes hydrogen or a C1-C4 alkyl group and more particularly methyl.
Mention may be made, as other family of water-soluble silicones which can be used according to the invention, of the branched silicones of following formula (c):
(Formula Removed)
where p and q have the same values indicated above in the formula (a); Me signifies methyl; PE denotes the group of following formula (d):
(Formula Removed)
where y and z have the same values indicated above in the formula (b) and R3 denotes a C1-C4 alkyl group and more particularly methyl.
Such silicones are, for example, sold by OSI under the trade names Silwet L-720®, Silwet L-7002®, Silwet L-7600®, Silwet L-7604®, Silwet L-7605®, Silwet L-7607®, Silwet 1614, Silwet L-7657® , Silwet L-7200®, Silwet L7230, Silsoft 305, Silsoft 820 and Silsoft 880 or by Goldschmidt under the trade names Tegowet 260®, Tegowet 500®, Tegowet 505® and Tegowet 510®.
Values of surface tensions at 25°C of aqueous solutions comprising 0.05% (by weight) of different wetting agents are collated in the following table.

(Table Removed)
According to the invention, the wetting agent or agents are present at concentrations ranging from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight and more particularly from 0.1% to 3% by weight, with respect to the total weight of the final composition.
The compositions according to the invention can be prepared according to the techniques for the preparation of emulsions well known to a person skilled in the art. They are generally provided in the form of a simple or complex emulsion (O/W, W/0, 0/W/O or W/O/W).
The compositions which can be used according to the invention can be more or less fluid and have the appearance of a white or coloured cream, of an ointment, of a milk, of a lotion, of a serum or of a paste. They can also be provided in the solid form, for example in the stick form. They can optionally be packaged in an aerosol and be provided in the foam or spray form.
The choice will more particularly be made of the emulsions of the oil-in-water type or of the water-in-oil-in-water type.
The compositions in accordance with the invention generally comprise at least one oily phase which
comprises at least one oil, in particular a cosmetic
oil. The term "oil" is understood to mean a fatty
substance which is liquid at ambient temperature
(25°C).
Use may be made, as oils which can be used in the composition of the invention, for example, of hydrocarbon oils of animal origin, such as perhydrosqualene (or squalane) ; hydrocarbon oils of vegetable origin, such as triglycerides of caprylic/capric acids, for example those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel, or oils of vegetable origin, for example sunflower, maize, soybean, cucumber, grape seed, sesame, hazelnut, apricot, macadamia, arara, coriander, castor, avocado or jojoba oil or shea butter oil; synthetic oils; silicone oils, such as volatile or nonvolatile polymethylsiloxanes (PDMSs) comprising a linear or cyclic silicone chain which are liquid or pasty at ambient temperature; fluorinated oils, such as those which are partially hydrocarbon and/or silicone, for example those described in the document JP-A-2-295912; ethers, such as dicaprylyl ether (CTFA name); and esters, such as benzoate C12-C15 fatty alcohols (Finsolv TN from Finetex); arylalkyl benzoate derivatives, such as 2-phenylethyl benzoate (X-Tend 226 from ISP) ; amidated oils, such as isopropyl N-lauroylsarcosinate (Eldew SL-205 from Ajinomoto), and their mixtures.
The oily phase can also comprise one or more fatty substances chosen, for example, from fatty alcohols (cetyl alcohol, stearyl alcohol, cetearyl alcohol), fatty acids (stearic acid) or waxes (paraffin wax, polyethylene waxes, carnauba wax, beeswax). The oily phase can comprise lipophilic gelling agents, surfactants or also organic or inorganic particles. The oily phase can preferably represent from 1 to 70% of
oil by weight, with respect to the total weight of the composition.
The compositions according to the invention in the emulsion form generally comprise emulsifying surfactants which are appropriately chosen according to the type of emulsion chosen. When the emulsion is a triple emulsion, it generally comprises an emulsifier in the primary emulsion and an emulsifier in the external phase into which the primary emulsion is introduced.
In the case of the simple oil-in-water emulsion, the dispersed oily phase can represent from 1 to 70% by weight, preferably from 5 to 60% by weight and better still from 10 to 50% by weight, with respect to the total weight of the simple emulsion.
In the case of the water-in-oil-in-water triple emulsion, the W/0 primary emulsion can represent, for example, from 5 to 70% by weight, preferably from 10 to 60% by weight and better still from 15 to 50% by weight, with respect to the total weight of the triple emulsion. The internal aqueous phase of the W/0 primary emulsion preferably represents from 5 to 90%, better still from 30 to 90% and even better still from 40 to 80% of the total weight of the primary emulsion.
The emulsifying surfactants are generally present at a minimum concentration of 0.5% by weight, with respect to the total weight of the composition.
They are preferably used at proportions ranging from 0.5 to 30% by weight, preferably from 0.5 to 20% by weight and better still from 0.5 to 15% by weight, with respect to the total weight of the composition.
Mention may be made, as emulsifying surfactants which can be used for the preparation of the W/0 emulsions,
for example, of sorbitan, glycerol or sugar alkyl esters or ethers; silicone surfactants, such as dimethicone copolyols, for example the mixture of cyclomethicone and of dimethicone copolyol sold under the name "DC 5225 C" by Dow Corning, and alkyl dimethicone copolyols, such as lauryl methicone copolyol, sold under the name "Dow Corning 5200 Formulation Aid" by Dow Corning, cetyl dimethicone copolyol, such as the product sold under the name Abil EM 90R by Goldschmidt, and the mixture of cetyl dimethicone copolyol, of polyglycerol (4 mol) isostearate and of hexyl laurate sold under the name Abil WE 09 by Goldschmidt. It is also possible to add thereto one or more coemulsifiers which, advantageously, can be chosen from the group consisting of polyol alkyl esters.
Mention may in particular be made, as polyol alkyl esters, of polyethylene glycol esters, such as PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by ICI.
Mention may be made, as esters of glycerol and/or of sorbitan, for example, of polyglycerol isostearate, such as the product sold under the name Isolan GI 34 by Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by ICI; glycerol sorbitan isostearate, such as the product sold under the name Arlacel 986 by ICI, and their mixtures.
Mention may be made, for the 0/W emulsions, for example, as emulsifiers, of nonionic emulsifiers, such as oxyalkylenated (more particularly polyoxyethylenated) esters of fatty acids and of glycerol; oxyalkylenated esters of fatty acids and of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acid esters, such as the PEG-100 stearate/glyceryl stearate mixture sold, for
example, by ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters, such as sucrose stearate; ethers of fatty alcohol and of sugar, in particular alkyl polyglucosides (APG), such as decyl glucoside and lauryl glucoside, for example sold by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetearyl glucoside, optionally as a mixture with cetearyl alcohol, for example sold under the name Montanov 68 by Seppic, under the name Tegocare CG90 by Goldschmidt and under the name Emulgade KE3302 by Henkel, and arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and of arachidyl glucoside sold under the name Montanov 202 by Seppic. According to a specific embodiment of the invention, the mixture of the alkyl polyglucoside as defined above with the corresponding fatty alcohol can be in the form of a self-emulsifying composition, for example as disclosed in the document WO-A-92/06778.
When an emulsion is involved, the aqueous phase of the latter can comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol. Biol. , 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
According to a specific embodiment of the invention, the emulsions according to the invention can comprise only 1% by weight or less and can even be devoid of emulsifying surfactants while being stable on storage. In this case, they can be stabilized by various techniques, such as the use of hydrophilic or lipophilic thickening agents, such as those of Patent EP 864 320, of amphiphilic polymers, such as those cited in Patent EP 1 093 796 or in Patent Application WO 02/44231, or of solid particles (Pickering-type emulsions), such as the emulsions cited in Patent Applications WO 98/42300, WO 98/42301, EP 987 001,
EP 987 002, EP 987 003, EP 987 004, EP 987 005, EP 987 006, EP-987 007, EP-987 008, WO 2000/07548, WO 2000/07549 or EP 992 233.
In the W/O/W triple emulsions according to the invention, the W/0 primary emulsion advantageously comprises at least one emulsifier with an HLB of less than 10 (HLP = hydrophilic-lipophilic balance). The emulsifiers can be chosen, for example, from the group consisting of alkoxylated and in particular ethoxylated fatty alcohols, alkoxylated and in particular ethoxylated fatty esters, glycerolated esters or ethers (such as, for example, polyglycerol-4 isostearate), salts of fatty acids, such as aluminium stearate, sugar-derived surfactants, such as methyl glucose isostearate, polymeric surfactants derived from polyolefins and silicone emulsifiers and their mixtures.
For the polymeric surfactants derived from polyolefins, the nonpolar part is chosen from polyolefins, such as polymers and/or copolymers of ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptedecene and 1-octadecene. The polymer chains are or are not hydrogenated. They are composed of at least 40 carbons and preferably of 60 to 700 carbons.
The polar part of these polymeric surfactants can be anionic, cationic, nonionic, zwitterionic or amphoteric. It is, for example, composed of acrylic derivatives, of polyalkylene glycols or polyalkyleneimine. The polymeric surfactants comprising a carboxylic acid polar part result, for example, from the reaction of a polyolefin with carboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid,
aconitic acid, and the like. Preferably, their polar part is composed of succinic acid or anhydride, their ester or amide derivatives, the corresponding salts of alkali metal, alkaline earth metal or organic ions, or alternatively of polyoxyethylene.
The polymeric surfactants derived from polyolefins are also chosen from the polyolefin derivatives of succinic acid described in Patents US 4 234 435, US 4 708 753, US 5 129 972, US 4 931 110, GB 2 156 799 and US 4 919 179. The polyolefin part can be composed of hydrogenated or nonhydrogenated polyisobutylene. The succinic anhydride or acid can be modified by alcohols, amines, alkanolamines or polyols, or can also occur in the form of salts of alkali metal or alkaline earth metal ions, or also of organic ions, such as the diethanolammonium or triethanolammonium ions. Mention may in particular be made of the polyisobutylenes comprising a modified succinic ending, such as the products sold under the names L2724, L2721, L2722, OS156565 and Lubrizol 5603 by Lubrizol or also Chemcinnate 2000, supplied by Chemron. Another example of a polymeric surfactant which can be used in the invention is the product of the reaction of maleic anhydride with polyisobutylene, such as Glissopal SA, sold by BASF.
The silicone emulsifiers can be chosen, for example, from the group consisting of dimethicone copolyols, alkyl dimethicone copolyols which can comprise heteroatoms, such as fluorine, and the mixtures comprising them, for example the polyglyceryl-4 isostearate/cetyl dimethicone copolyol/hexyl laurate mixture sold under the name Abil WE 09 by Goldschmidt, the cetyl dimethicone copolyol sold under the name Abil EM 90 by Goldschmidt and the cyclomethicone/dimethicone copolyol mixture sold under the name Q2-3225C by Dow Corning. The level of emulsifier in the primary emulsion generally ranges from 0.1 to 10% by weight of
active material and preferably from 0.5 to 5% by weight, with respect to the total weight of the primary emulsion.
The compositions of the invention can comprise all the
additives commonly used in cosmetics and will find
applications in the care field, makeup field and field
of antisun products.
The aqueous compositions in accordance with the present invention can additionally comprise conventional cosmetic adjuvants chosen in particular from organic solvents, ionic or nonionic and hydrophilic or lipophilic thickeners, softening agents, moisturizing agents, opacifiers, stabilizing agents, emollients, silicones, antifearning agents, fragrances, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, active principles, fillers, polymers, propellants, basifying or acidifying agents or any other ingredient generally used in the cosmetic and/or dermatological field.
Mention may be made, as hydrophilic thickeners, of carboxyvinyl polymers, such as the Carbopols
(carbomers) and the Pemulens (acrylate/C10-C30 alkyl acrylate copolymer); the terpolymer of methacrylic acid, methyl acrylate and dimethyl(meta-isopropenyl)benzyl isocyanate of ethoxylated alcohol
(INCI name: Polyacrylate-3) , such as the product sold by Amerchol under the name Viscophobe DB 1000; polyacrylamides, such as, for example, the crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide/C13-14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/poly-sorbate 80) by Seppic; optionally crosslinked and/or neutralized polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, such as the poly(2-acrylamido-2-methylpropanesulphonic acid) sold
by Clariant under the trade name "Hostacerin AMPS" (CTFA name: ammonium polyacryldimethyltauramide); cellulose derivatives, such as hydroxyethylcellulose; polysaccharides and in particular gums, such as xanthan gum; and their mixtures.
Mention may be made, as lipophilic thickeners, of synthetic polymers, such as the poly(Ci0-3o alkyl acrylate) sold under the name "Doresco IPA 13-1" by Landec, or also of modified clays, such as hectorite and its derivatives, for example the products sold under the Bentone names.
The organic solvents can be chosen from the group consisting of hydrophilic organic solvents, lipophilic organic solvents, amphiphilic solvents and their mixtures.
Mention may be made, among hydrophilic organic solvents, for example, of linear or branched monohydric alcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol or isobutanol; polyethylene glycols having from 6 to 80 ethylene oxides; polyols, such as propylene glycol, isoprene glycol, butylene glycol, glycerol or sorbitol; mono- or dialkyl isosorbides, the alkyl groups of which have from 1 to 5 carbon atoms, such as dimethyl isosorbide; or glycol ethers, such as diethylene glycol monomethyl or monoethyl ether and propylene glycol ethers, such as dipropylene glycol methyl ether.
Mention may be made, as amphiphilic organic solvents, of polypropylene glycol (PPG) derivatives, such as esters of polypropylene glycol and of fatty acid or ethers of PPG and of fatty alcohol, such as PPG-23 oleyl ether and PPG-36 oleate.
Mention may be made, as lipophilic organic solvents, for example, of fatty esters, such as diisopropyl adipate, dioctyl adipate or alkyl benzoates.
Mention may be made, as preservatives, of esters of para-hydroxybenzoic acid, also known as Parabens® (in particular methylparaben, ethylparaben or propylparaben), phenoxyethanol, releasers of formaldehyde, such as, for example, imidazolidinyl urea or diazolidinyl urea, chlorhexidine digluconate, sodium benzoate, caprylyl glycol, iodopropynyl butylcarbamate, pentylene glycol, alkyltrimethylammonium bromide, such as myristyltrimethylammonium bromide (CTFA name: myrtrimonium bromide), dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide and their mixtures, such as the mixture sold under the name Cetrimide® by FEF Chemicals. The preservative can be present in the composition according to the invention in a content ranging from 0.001 to 10% by weight, with respect to the total weight of the composition, in particular ranging from 0.1 to 5% by weight and especially ranging from 0.2 to 3% by weight.
Mention may be made, as fillers which can be used in the composition of the invention, for example, of pigments; silica powder; talc; polyamide particles and in particular those sold under the name Orgasol by Atochem; polyethylene powders; powders formed of natural organic materials, such as starch powders, in particular powders formed of crosslinked or noncrosslinked maize, wheat or rice starches, such as powders formed of starch crosslinked by octenylsuccinic anhydride, sold under the name Dry-Flo by National Starch; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate/lauryl methacrylate copolymer sold by Dow Corning under the name of Polytrap; poly(methyl methacrylate) powders, such as those sold under the name Micropearl M 100 by Matsumoto; expanded powders, such as hollow
microspheres and in particular the microspheres sold under the name Expancel by Kemanord Plast or under the name Micropearl F 80 ED by Matsumoto; silicone resin microbeads, such as those sold under the name Tospearl by Toshiba Silicone; polyurethane powders, such as the powder formed of hexamethylene diisocyanate/trimethylol hexyllactone copolymer sold under the name Plastic Powder D-400 by Toshiba Pigment (CTFA name: HDI/Trimethylol Hexyllactone Crosspolymer); and their mixtures. When they are present, these fillers can be in amounts ranging from 0.001 to 20% by weight, preferably from 0.1 to 10% by weight and better still from 1 to 5% by weight, with respect to the total weight of the composition.
Mention may be made, among active principles, of:
- vitamins (A, C, E, K, PP, and the like) and their
derivatives or precursors, alone or as mixtures;
- agents for combating pollution and/or agents for
combating free radicals;
- depigmenting agents and/or propigmenting agents;
- antiglycation agents;
- soothing agents;
- NO-synthase inhibitors;
- agents which stimulate the synthesis of dermal or
epidermal macromolecules and/or which prevent their
decomposition;
- agents which stimulate the proliferation of
fibroblasts;
- agents which stimulate the proliferation of
keratinocytes;
- muscle-relaxing agents;
- tightening agents;
- matifying agents;
- keratolytic agents;
- desquamating agents;
- moisturizing agents;
- antiinflammatory agents;
- agents which act on the energy metabolism of the
cells;
- insect repellents;
- substance P or substance CRGP antagonists;
- agents for combating hair loss and/or for the
regrowth of the hair;
- antiwrinkle agents.
Of course, a person skilled in the art will take care to choose the additional optional compound or compounds mentioned above and/or their amounts so that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or not substantially, detrimentally affected by the envisaged addition or additions.
Another subject-matter of the present invention is composed of the use of the compositions according to the invention as defined above in the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and/or scalp, in particular care products, sun protection products and makeup products.
The composition according to the invention can constitute a product for caring for the skin, in particular for the face, neck, outline of the eye or body; or alternatively a makeup product, such as a product for the complexion (in particular foundation), concealer or sun protection product; or indeed a product for cleaning the skin. Preferably, the composition according to the invention will be a sun protection product.
The cosmetic compositions according to the invention can, for example, be used as care product and/or sun protection product for the face and/or the body with a liquid to semiliquid consistency, such as lotions, milks, more or less smooth creams, gels or cream gels.
- ,4-i -
They can also be packaged in an aerosol and be provided in the foam or spray form.
The compositions according to the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or hair in the form of fine particles using pressurization devices. The devices in accordance with the invention are well known to a person skilled in the art and comprise nonaerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as propellant. The latter are described in Patents US 4 077 441 and US 4 850 517 (forming an integral part of the content of the description).
The compositions packaged in aerosol in accordance with the invention generally comprise conventional propellant, such as, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. They are preferably present in amounts ranging from 15 to 50% by weight, with respect to the total weight of the composition.
The invention will now be described with reference to the following examples, given by way of illustration and without implied limitation. In these examples, unless otherwise indicated, the amounts are expressed as percentages by weight. The following antisun formulations were prepared; the amounts are shown as percentages by weight:
Examples

(Table Removed)

The sun protection factor (SPF) is determined according to the "in vitro" method described by B.L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133 (1989). The measurements were carried out using a UV-1000S spectrophotometer from Labsphere. Each composition is applied to a quartz slide in the form of a homogeneous and uniform deposit in a proportion of 1.33 mg/cm2.
It is found that the SPF is significantly improved when hollow hemispherical particles are added to the reference composition. The in vitro SPF values are improved by 68% and 134% respectively with 3 and 5% of Takemoto NLK 506 particles. Furthermore, these particles make it possible to significantly reduce the shine, after application, of the screening formulations comprising them.

WE CLAIM:
1. Use of concave or annular particles of silicone
material, in particular in the form of portions of
hollow spheres, in a composition comprising, in a
physiologically acceptable medium, at least one aqueous
phase and at least one organic UV screening agent
and/or one inorganic UV screening agent for the purpose
of increasing the sun protection factor (SPF).
2. Use according to Claim 1, where the particles of
silicone material are in combination with at least one
wetting agent.
3. Use according to Claim 1 or 2, characterized in
that the concave particles of silicone material have a
mean diameter of less than or equal to 10 µm.
4. Use according to Claim 3, characterized in that
the concave particles of silicone material have a mean
diameter ranging from 0.1 µm to 8 µm.
5. Use according to any one of Claims 1 to 4,
characterized in that the concave particles of silicone
material are in the form of portions of hollow spheres
having a transverse cross section with the shape of a
horseshoe or arch.
6. Use according to any one of the preceding claims,
characterized in that the silicone material is a
crosslinked polysiloxane with a three-dimensional
structure comprising or composed of units of formula
(I) : Si02 and of formula (II) : R1iO1.5
in which R1 denotes an organic group having a carbon atom directly connected to the silicon atom.
7. Use according to Claim 6, characterized in that R1
is a C1-C4 alkyl group or a phenyl group.
8. Use according to Claim 7, characterized in that R1
is a methyl group.
9. Use according to Claim 6, characterized in that R1
is chosen from epoxy, (meth)acryloyloxy, alkenyl,
mercaptoalkyl, aminoalkyl, haloalkyl, glyceroxy, ureido
or cyano groups.
10. Use according to any one of Claims 5 to 9,
characterized in that the silicone material comprises
the units (I) and (II) according to a unit (I)/unit
(II) molar ratio ranging from 30/70 to 50/50,
preferably ranging from 35/65 to 45/55.
11. Use according to any one of the preceding claims,
characterized in that the concave particles made of
silicone material are capable of being obtained
according to a process comprising:
(a) the introduction into an aqueous medium, in the
presence of at least one hydrolysis catalyst and
optionally of at least one surfactant, of a compound
(III) of formula SiX4 and of a compound (IV) of formula
RSiY3, where X and Y denote, independently of one
another, a C1-C4 alkoxy group, an alkoxyethoxy group
including a C1-C4 alkoxy group, a C2-C4 acyloxy group,
an N,N-dialkylamino group including a C1-C4 alkyl group,
a hydroxyl group, a halogen atom or a hydrogen atom and
R denotes an organic group comprising a carbon atom
connected directly to the silicon atom; and
(b) the operation in which the mixture resulting from
stage (a) is brought into contact with an aqueous
solution including at least one polymerization catalyst
and optionally at least one surfactant, at a
temperature of between 30 and 85°C, for at least two
hours.
12. Use according to Claim 11, characterized in that,
in stage (a) , the molar ratio of the compound (III) to
the compound (IV) ranges from 30/70 to 50/50.
13. Use according to Claim 11 or 12, characterized in
that the ratio by weight of the water to the total of
the compounds (III) and (IV) ranges from 10/90 to 70/30
in stage (a).
14. Use according to Claim 11, characterized in that R
is a Ci-C4 alkyl group or a phenyl group.
15. Use according to Claim 14, characterized in that R
is a methyl group.
16. Use according to Claim 11, characterized in that R
is chosen from epoxy, (meth)acryloyloxy, alkenyl,
mercaptoalkyl, aminoalkyl, haloalkyl, glyceroxy, ureido
or cyano groups.
17. Use according to any one of the preceding claims,
characterized in that the concave particles are formed
of a small internal arc (11) , of a large external arc
(21) and of segments (31) which connect the ends of the
respective arcs, the width (Wl) between the two ends of
the small internal arc (11) ranging from 0.01 to 8 urn,
preferably from 0.02 to 6 urn, on average, the width
(W2) between the two ends of the large external arc
(21) ranging from 0.05 to 10 urn, preferably from 0.06
to 8 urn, on average, and the height (H) of the large
external arc (21) ranging from 0.015 to 8 urn,
preferably from 0.03 to 6 um, on average.
18. Use according to Claim 1 or 2, characterized in
that the particles of annular shape exhibit a mean
external diameter of 0.05 to 15 um and a mean internal
diameter of 0.01 to 10 um, the difference between the
mean external diameter and the mean internal diameter
being from 0.04 to 5 µm.
19. Use according to Claim 18, exhibiting a
polysiloxane network comprising siloxane units of
formulae (1), (2), (3), (4), (5) and (6):
Si04/2 (1)
Si (OH) 3/2 (2)
RiSi03/2 (3)
R2Si03/2 (4)
R3Si03/2 (5)
R4Si03/2 (6)
in which Rx and R3 denote alkyl, cycloalkyl, aryl, alkylaryl or aralkyl groups and R2 and R4 each denote a hydrocarbon group chosen from the acryloyloxy, methacryloyloxy, vinyl or mercapto groups; the siloxane units of formula (1)/siloxane units of formulae (2), (3), (4), (5) and (6) molar ratio being from 20/80 to 50/50;
the siloxane units of formulae (2), (3) and (4)/siloxane units of formulae (5) and (6) molar ratio being from 50/50 to 75/25;
the siloxane units of formulae (3) and (5)/siloxane units of formulae (4) and (6) molar ratio being from 20/80 to 60/40.
20. Use according to any one of the preceding claims,
where the wetting agent is chosen from water-soluble
silicones comprising at least one terminal or pendent
monovalent polyoxyalkylene group.
21. Use according to Claim 20, where the wetting agent
is chosen from water-soluble silicones comprising at
least one polyoxyalkylene group of following general
formula (a):
(Formula Removed)
which:
- the R2 radicals, which are identical or different, denote a monovalent hydrocarbon radical chosen from alkyl, aryl and aralkyl radicals having at most 10 carbon atoms; some of the R2 radicals can also additionally comprise an ethylcyclohexylene monoxide group of formula
- (Formula Removed)

and are in low proportion in the polysiloxane chain;
- p varies from 0 to 150, preferably from 0 to 100 and
more preferably from 0 to 30;
- q varies from 1 to 12, preferably from 1 to 10 and
more preferably from 1 to 8;
- the polyether group PE has the following formula (b):
(Formula Removed)
in which:
x varies from 1 to 8 and preferably varies from 2 to 4
and more preferably is equal to 3;
y is greater than 0;
z is greater than or equal to 0; the values of y and z
are such that the total molecular weight of the
polyoxyalkylene portion of the polyether group PE
varies from 200 to 10 000 and more preferably from 350
to 4000;
R3 denotes hydrogen, a C1-CB alkyl group or a C2-C8 acyl
group.
22. Use according to Claim 21, where the R2 radicals
are chosen from lower C alkyls, phenyl and benzyl._C
23. Use according to Claim 22, where the R2 radicals
are chosen from lower C1-C4 alkyls and more particularly
still denote methyl.
24. Use according to any one of Claims 20 to 23, where
the R3 radicals are chosen from lower C1-C4 alkyls and
more particularly still denote methyl.
25. Use according to any one of Claims 20 to 24, where
the water-soluble silicones of formula (a) are chosen
from those of following formula (a'):
(Formula Removed)
where Me denotes methyl; PE denotes the group of formula (b' ) :
(Formula Removed)
where x, z and z have the same values indicated in Claim 29 and R3 denotes hydrogen or a C1-C4 alkyl group and more particularly methyl.
26. Use according to Claim 20, where the water-soluble
silicone is chosen from the branched silicones of
following formula (c):
(Formula Removed)
where:
- p varies from 0 to 150, preferably from 0 to 100 and
more preferably from 0 to 30;
- q varies from 1 to 12, preferably from 1 to 10 and
more preferably from 1 to 8;
- Me signifies methyl;
- PE denotes the group of following formula (d):
(Formula Removed)
where:
- y is greater than 0;
- z is greater than or equal to 0; the values of y and
z are such that the total molecular weight of the
polyoxyalkylene portion of the polyether group PE varies from 200 to 10 000 and more preferably from 350 to 4000; - R3 denotes a C1-C4 alkyl group.
27. Use according to any one of the preceding claims,
where the organic UV screening agent is chosen from
anthranilates; dibenzoylmethane derivatives; cinnamic
derivatives; salicylic derivatives; camphor
derivatives; benzophenone derivatives; (3, p-diphenyl-
acrylate derivatives; triazine derivatives;
benzotriazole derivatives; benzalmalonate derivatives;
benzimidazole derivatives; imidazolines; bis-
benzoazolyl derivatives; p-aminobenzoic acid (PABA)
derivatives; methylenebis(hydroxyphenylbenzotriazole)
derivatives; benzoxazole derivatives; screening
polymers and screening silicones; dimers derived from
a-alkylstyrene; 4,4-diarylbutadienes; and their
mixtures.
28. Composition according to Claim 27, where the
organic UV screening agent is chosen from
Ethylhexyl Methoxycinnamate,
Homosalate,
Ethylhexyl Salicylate,
Octocrylene,
Phenylbenzimidazole Sulfonic Acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
n-Hexyl 2- (4-diethylamino-2-hydroxybenzoyl)benzoate,
4-Methylbenzylidene Camphor,
Terephthalylidene Dicamphor Sulfonic Acid,
Disodium Phenyl Dibenzimidazole Tetrasulfonate,
Ethylhexyl triazone,
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine,
Diethylhexyl Butamido Triazone,
2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-
triazine,
2,4,6-Tris(diisobutyl 4'-aminobenzalmalonate)-s-
triazine,
2,4,6-Tris(biphenyl-4-yl)-1,3,5-triazine,
2,4,6-Tris(terphenyl)-1,3,5-triazine,
Methylene Bis-Benzotriazolyl Tetramethylbutylphenol,
Drometrizole Trisiloxane,
Polysilicone-15,
Dineopentyl 4'-methoxybenzalmalonate,
1,1-Dicarboxy(2,2'-dimethyIpropyl)-4,4-
diphenylbutadiene,
2,4-Bis[5-1(dimethyIpropyl)benzoxazol-2-yl-(4-
phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,
and their mixtures.
29. Use according to any one of the preceding claims,
where the inorganic UV screening agents are chosen from
metal oxide pigments which may or may not be coated.
30. Use according to Claim 29, where the said pigments
are chosen from titanium oxide, zinc oxide, iron oxide,
zirconium oxide, cerium oxide and their mixtures, which
may or may not be coated.
31. Use according to Claim 30, characterized in that
the pigments are based on titanium oxide, which may or
may not be coated.
32. Use according to Claim 31, characterized in that
the titanium oxide is in the rutile, anatase or
amorphous form.
33. Use according to any one of Claims 29 to 32,
characterized in that the pigments have a mean
elementary particle size of greater than 5 nm and less
than 100 nm.
34. Use according to any one of Claims 29 to 33,
characterized in that the composition is in the form of
an oil-in-water emulsion, a water-in-oil emulsion, a
water-in-oil-in-water triple emulsion or an oil-in-water-in-oil triple emulsion.
35. Use according to Claim 34, characterized in that
the composition is in the form of an oil-in-water
emulsion or of a water-in-oil-in-water triple emulsion.
36. Composition comprising, in a physiologically
acceptable medium:

a) at least one aqueous phase;
b) concave or annular particles of silicone material,
in particular in the form of portions of hollow spheres
as defined in the preceding claims;
c) at least one organic UV screening agent and/or one
inorganic UV screening agent as defined in the
preceding claims;
d) at least one wetting agent as defined in the
preceding claims.

37. Composition according to Claim 36, characterized
in that it is in the form of an oil-in-water emulsion,
a water-in-oil emulsion, a water-in-oil-in-water triple
emulsion or an oil-in-water-in-oil triple emulsion.
38. Composition according to Claim 36 or 37,
characterized in that it is in the form of an oil-in-
water emulsion or of a water-in-oil-in-water triple
emulsion.
39. Composition according to any one of Claims 36 to
38, characterized in that the concave or annular
particles are present in a content ranging from 0.1 to
15% by weight, with respect to the total weight of the
composition.
40. Composition according to any one of Claims 36 to
39, where the UV screening agent or agents are present
in proportions ranging from 0.01 to 20% by weight, with
respect to the total weight of the composition, and
preferably ranging from 0.1 to 10% by weight, with respect to the total weight of the composition.
41. Composition according to any one of Claims 36 to
40, where the proportion by weight of the aqueous phase
varies from 25 to 95% by weight, preferably from 30 to
90% by weight and more preferably still from 40 to 80%
by weight, with respect to the total weight of the
composition.
42. Composition according to any one of Claims 36 to
41, where the wetting agent is chosen from water-
soluble silicones comprising at least one terminal or
pendent monovalent polyoxyalkylene group.
43. Composition according to any one of Claims 36 to
42, additionally comprising at least one cosmetic
adjuvant chosen from organic solvents, ionic or
nonionic and hydrophilic or lipophilic thickeners,
softening agents, moisturizing agents, opacifiers,
stabilizing agents, emollients, silicones, antifoaming
agents, fragrances, preservatives, anionic, cationic,
nonionic, zwitterionic or amphoteric surfactants,
active principles, fillers, polymers, propellants or
basifying or acidifying agents.
44 . Composition according to any one of Claims 36 to
43, characterized in that it is provided in the form of
a white or coloured cream, of a milk, of a lotion or of
a cream gel or in a solid form.
45. Composition according to any one of Claims 36 to
44, characterized in that it is packaged in an aerosol
and can form a foam or a spray.
46. Use of a composition as defined in any one of
Claims 36 to 45 in the manufacture of products for the
cosmetic treatment of the skin, lips, nails, hair,
eyelashes, eyebrows and/or scalp.
47. Use of a composition as defined in any one of
Claims 36 to 45 in the manufacture of a care product
and/or sun protection product for the face and/or body.
48. Use of a composition as defined in any one of
Claims 36 to 45 in the manufacture of a makeup product.
49. Use of concave or annular particles of silicone
material and composition substantially as herein
described with reference to the accompanying drawings
and as illustrated in the foregoing examples.