WO2016012515A2

WO2016012515A2 - Emulsions stabilized with a crosslinked silicone polymer and a semi-crystalline polymer

Info

Publication number: WO2016012515A2
Application number: PCT/EP2015/066796
Authority: WO
Inventors: Raluca Lorant; Mathieu CHABRILLANGEAS
Original assignee: L'oreal
Priority date: 2014-07-22
Filing date: 2015-07-22
Publication date: 2016-01-28
Also published as: FR3024034A1; WO2016012515A3

Abstract

The invention relates to a composition in the form of an emulsion, comprising, in a physiologically acceptable medium, at least: (i) one aqueous phase, (ii) one oily phase, (iii) one silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain, and (iv) one semi-crystalline polymer.

Description

"EMULSIONS STABILIZED WITH A CROSSLINKED SILICONE POLYMER AND A SEMI-CRYSTALLINE POLYMER" FIELD OF THE INVENTION

The invention relates to a composition in the form of an oil-in-water or a water-in-oil emulsion type.

It in particular relates to a cosmetic composition in the form of an oil-in-water or a water-in-oil emulsion type. Said cosmetic composition is in particular intended to be applied to keratin materials, in particular the skin and the lips, the hair and the nails.

More particularly, the invention relates to a cosmetic composition which is in the form of an emulsion, comprising at least one silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain and one semi-crystalline polymer.

TECHNICAL BACKGROUND

In the cosmetics field, and more particularly in the skincare, makeup and photoprotection field, emulsions containing at least one silicone elastomer are very advantageous for their application properties (particularly the slippery effect) and their very characteristic sensory effect (in particular, the provision of softness and the silky effect).

The stability of these emulsions is fragile and easily deteriorates when active molecules or ingredients such as UV -screening agents are added. To stabilize these emulsions, it has been proposed to use high contents of emulsifiers in order to increase the robustness of the architecture, which results in compromising the sensoriality and sometimes the innocuousness and the comfort on the skin of these products.

For example, document FR 2912 651 describes a composition in the form of a water-in-oil (W/O) emulsion containing at least one emulsifying silicone elastomer and at least one semi-crystalline polymer, providing a freshness effect during application and a very effective skin nutrition. However, these compositions exhibit medium stability in the presence of organic oils or of sunscreens. Furthermore, the application qualities of these emulsions could be improved. Finally, the formulation perimeter is restricted, since these emulsions are limited to only water-in-oil emulsions.

Moreover, these silicone emulsions are not persistent and do not always provide good wear of the effects during the day. As it happens, the wear qualities are essential for ensuring the effectiveness of the active molecules, and maintaining moisturization, comfort, emollience and photoprotective properties, when the emulsion contains screening agents.

There is therefore a need to provide emulsions, and in particular water-in-oil emulsions, which have good stability. Advantageously, the emulsions according to the invention exhibit uniform application qualities and good comfort, and persistent properties over time, and exhibit good sensory attractiveness.

The term "stable" is intended to mean stable for at least one month, preferably at least 2 months, at 45°C.

SUMMARY OF THE INVENTION

According to a first aspect, the invention relates to a composition in the form of an emulsion comprising at least:

(i) one aqueous phase,

(ii) one oily phase,

(iii) one silicone polymer crosslinked with at least one poiyoxyalkylene chain and comprising at least one pendant poiyoxyalkylene chain, and

(iv) one semi-crystalline polymer.

In certain embodiments, said composition is a cosmetic composition. Said cosmetic composition is in particular suitable for topical application. The composition may be intended to be applied to keratin materials, in particular the skin and the lips, the hair and the nails.

According to another aspect, the invention relates to a cosmetic use of a composition according to the invention, for caring for keratin materials, preferably the skin, the lips, the hair and the nails.

According to another aspect, the invention relates to a method for the cosmetic treatment of keratin materials, comprising a topical admimstration of a composition according to the invention. According to another aspect, the invention relates to a method for preparing a composition comprising at least:

(i) one aqueous phase,

(ii) one oily phase,

(iii) one silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain, and

(iv) one semi-crystalline polymer.

DETAILED DESCRIPTION OF THE INVENTION

Surprisingly, the inventors have developed emulsions based on at least one specific crosslinked silicone polymer, as emulsifier, and on at least one semi-crystalline polymer, which make it possible to obtain, after application, a feeling of softness, a good penetration quality, an absence of sensation of a residual oily or greasy effect, good stability and therefore good comfort immediately and over time. Notably, the effects observed are obtained both with water-in-oil (W/O) emulsions and with oil -in- water (O/W) emulsions. Finally, in the presence of UV-screening agents, the compositions according to me invention make it possible to increase the UV protection index.

1/ Composition

Physiologically acceptable medium

Since the compositions according to the invention are intended for topical application to the skin or skin appendages, they contain a physiologically acceptable medium. The term "physiologically acceptable medium'' is intended to mean a medium compatible with the skin, the lips, the mucous membranes, the nails, the scalp and/or the hair. In other words, a composition according to the invention must not contain compounds known to be toxic to human beings or animals.

Aqueous phase

In the context of the present invention, the aqueous phase comprises water and optionally at least one organic solvent which is water-miscible at ambient temperature (25°C) and/or at least one hydrophilic adjuvant The term "adjuvant" is intended to mean an active agent or additive, known in the prior art to have a physical, chemical and/or biological property of interest in the context of skincare, dermatology, cosmetics and/or makeup.

As water-miscible organic solvent, mention may be made, in a non-limiting way, of in particular monoalcohols comprising from 2 to 8, preferably from 2 to 6 carbon atoms, such as ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, polyols having in particular from 2 to 20 carbon atoms, for instance glycerol, arabitol, adonitol, dulcitol, erythritol, pentylene glycol, propylene glycol, butylene glycol, isoprene glycol, hexylene glycol, (Methylene glycol, dipropylene glycol, polyglycerols with 2 to 6 glycerolated units, such as diglycerol, sorbitol; sugars such as glucose, fructose, maltose, lactose, sucrose, saccharose, xylose or trehalose; and mixtures thereof.

The composition may also contain thickening hydrophilic polymers such as homopolymers and copolymers of AMPS (for instance Hostacerin AMPS sold by the company Clariant), celluloses or acrylic polymers (such as carbopols, etc). Oilv phase

The oily phase consists of at least one oil or of any other fatty substance and lipophilic constituent which may be present in the composition of the invention, including the crosslinked silicone polymer. Any cosmetically acceptable oil may be used.

The term "oil" is intended to mean a fatty substance that is liquid at ambient temperature (25°C).

As oils that may be used in the composition of the invention, examples that may be mentioned include:

- hydrocarbon-based oils of animal origin, such as perhydrosqualene and squalane;

- hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of C₄- C₁₀ fatty acids, for instance heptanoic or octanoic acid triglycerides, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those available under the trade names Miglyol 810, Miglyol 812 and Miglyol 818 from the company Dynamit Nobel, or else, for example, sunflower oil, corn oil, soya bean oil, marrow oil, grape seed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, castor oil, avocado oil, jojoba oil and shea butter oil; - synthetic esters and ethers, in particular of fatty acids, for instance the oils of formulae R₁COOR₂ and R₁OR₂ in which Ri represents a C₈ to C₂₉ fatty acid residue and R₂ represents a C₃ to C₃₀ branched or unbranched hydrocarbon-based chain, for instance purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2- octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, octanoates and decanoates of C₈- C₃₀ fatty alcohols; esters of hydroxylated acid and of C₈-C₃₀ fatty alcohol, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate; polyol esters, for instance propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, for instance pentaerythrityl tetraisostearate (for instance Crodamol ΡTIS from Croda);

- linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or non-volatile liquid paraffins, and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam oil;

- silicone oils, for instance volatile or non-volatile polymethyisiloxanes

(PDMSs) containing a linear or cyclic silicone chain, which are liquid or pasty at ambient temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasUoxane and cyclopentasiloxane; polydimethylsiloxanes (or dimethicones) comprising alkyl, alkoxy or phenyl groups, which are pendant or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenylsilicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates and polymethylphenylsiloxanes;

- fait y alcohols containing from 8 to 26 carbon atoms, for instance cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol);

- partially hydrocarbon-based and/or silicone-based fluoro oils, for instance those described in document JP-A-2-295 912;

- and mixtures thereof.

The term "hydrocarbon-based oil" above is intended to mean any oil mainly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and/or alcohol groups. In addition to the oils indicated above, the composition of the invention may contain other fatty substances in the oily phase, such as C₈ to C₃₀ fatty acids, for instance stearic acid; silicone resins such as trifluoromethyl(C₁-C₄ alkyl) dimethicone and trifluoropropyl dimethicone; silicone gums (dimethiconol), non-emulsifying silicone elastomers, for instance the products sold under the names KSG 6 and KSG 16 by the company Shin-Etsu, under the names Trefll, BY29 and EPSX by the company Dow Corning, or under the name Gransil by the company Grant Industries; waxes, for example mineral waxes, waxes of animal origin, for instance beeswax, waxes of plant origin, hydrogenated oils that are solid at 25°C, glycerides that are solid at 25°C, synthetic waxes and silicone waxes; and mixtures thereof.

Finally, the oily phase may contain one or more waxes chosen from those described above, and in particular a synthetic wax such as polymethylene wax or polyethylene wax, or alternatively one or more pasty fatty compounds such as petroleum jelly.

For the purposes of the present invention, the term "pasty compound'' is intended to mean a compound that is water-immiscible and that undergoes a reversible solid/liquid change of state and that comprises in the solid state an anisotropic crystal organization, and comprises, at a temperature of 23°C, a liquid fraction and a solid fraction.

According to one particular embodiment, the oily phase may also comprise one or more lipophilic adjuvant(s), such as, for example, one or more oily thickeners.

By way of thickener, mention may be made, for example, of organomodified clays, which are clays treated with compounds chosen in particular from quaternary amines and tertiary amines. Organomodified clays that may be mentioned include organomodified bentonites such as those which are commercially available under the name Bentone from the company Rheox, for instance those modified with distearyldimethylammonium chloride (Bentone 38 and Bentone 34), or the product modified with stearylbenzyldimethylammonium chloride (Bentone 27).

The oily-phase thickener may advantageously be chosen from C₈- C₃₀ fatty acid esters of glycerol, and in particular C₈-C₃₀ fatty acid triesters of glycerol, such as glyceryl tristearate (tristearine), such as the mixture of acetylated glycol stearate and of glyceryl tristearate, sold under the name Unitwix by the company United Guardian. The oily-phase thickener may also be chosen from C₈-C₃₀ fatty acid esters of dextrin, such as, in particular, dextrin palmitate, in particular those sold under the name Rheopearl by the company Chiba Flour Milling.

The thickeners) may be present in an amount ranging, for example, from approximately 0.1% to 5% by weight, preferably approximately 0.1% to 3% by weight and preferably approximately 0.2% to 2% by weight, relative to the total weight of the composition.

In the context of the present invention, it is understood mat the term "approximately" means that the value to which it refers encompasses said value +/-10%. Thus, 5% represents a value included strictly between 4.5% and 5.5%.

Oil-in-water (O/W) emulsion

In the context of the present invention, when the composition is in the form of an oil-in-water emulsion, the aqueous phase may represent approximately 60% to 98% by weight, preferably approximately 65% to 95% by weight, preferably approximately 70% to 90% by weight and preferably approximately 70% to 85% by weight, relative to the total weight of the composition.

The hydrophilic adjuvant(s), for instance the polyols and the monoalcohols, may represent approximately 0% to 30% by weight, preferably approximately 0.1% to 30% by weight, and preferably approximately 1% to 20% by weight, relative to the total weight of the composition.

When the composition is in the form of an oil-in-water emulsion, the water may be present in a content ranging from 60% to 98% by weight, preferably from 65% to 95% by weight, preferably approximately 70% to 90% by weight and preferably approximately 70% to 85% by weight, relative to the total weight of the composition.

According to another aspect of the invention, the oily phase, within the composition in the form of an oil-in-water emulsion, represents a value less than or equal to approximately 35% by weight, preferably a value less than or equal to approximately 33% by weight, preferably a value less than or equal to approximately 32% by weight, relative to the total weight of the composition.

According to another aspect of the invention, the oily phase may represent approximately 2% to 35% by weight, preferably approximately 5% to 33% by weight, preferably approximately 10% to 33% by weight and preferably approximately 15% to 30% by weight, relative to the total weight of the composition.

According to another particular embodiment, a composition in the form of an oil-in-water emulsion comprises an oil(s) content of less than or equal to approximately 35% by weight, preferably less than or equal to approximately 33% by weight and preferably less than or equal to 32% by weight, relative to the total weight of the composition.

Water-in-oil (W/O) emulsion

In the context of the present invention, when the composition is in the form of a water-in-oil W/O emulsion, the aqueous phase may represent approximately 30% to 95% by weight, preferably approximately 35% to 90% by weight and preferably approximately 40% to 85% by weight, relative to the total weight of the composition.

In one particular embodiment, the water preferably represents at least approximately 30% by weight, preferably at least approximately 40% by weight, preferably at least approximately 50% by weight, relative to the total weight of the composition. This amount may represent, for example, approximately 30% to 90% by weight, preferably approximately 40% to 80% by weight and preferably approximately 50% to 75% by weight, relative to the total weight of the composition.

According to one preferred embodiment, the oily phase represents approximately 0.5% to 50% by weight, relative to the total weight of the composition, preferably approximately 10% to 35% by weight, relative to the total weight of the composition. Crosslinked silicone polymer

In the context of the invention, a crosslinked silicone polymer is in particular described in PCT international application WO 2010/080755.

The crosslinked silicone polymer, in particular in the form of an organic silicone elastomer gel, contains an organic silicone elastomer and a hydrophobic liquid carrier.

The organic silicone elastomer may represent approximately 2% to 95% by weight, relative to the total weight of the elastomer gel, while the hydrophobic liquid carrier may represent approximately 5% to 98% by weight, relative to the total weight of the elastomer gel.

Additional constituents, in addition to the organic silicone elastomer and the hydrophobic liquid carrier, may be added to the organic silicone elastomer gel; in this case, the amounts of all the constituents used must correspond exactly to 100% by weight.

According to one preferred embodiment, the silicone elastomer gel comprises: - 2% to 95% by weight, relative to the total weight of the silicone elastomer gel, of an organic silicone elastomer, obtained by reacting:

A) an organohydrogenosiloxane comprising siloxy units of average formula: (R¹ ₃SiO_0.5)_v (R² ₂SiO)_x (R²HSiO)_y

in which:

- R¹ represents a hydrogen or R²,

- R² represents a monovalent hydrocarbon-based (hydrocarbyl) group, - v≥2, x≥ 0, y≥ 2,

B) a first polyoxyalkylene having the average formula:

R³O-[(C₂H₄O)_c(C₃H₆O)_d(C₄H₈O)_e]-R³

in which:

- R³ is a monovalent unsaturated aliphatic hydrocarbon-based group containing from 2 to 12 carbon atoms,

- c ranges from 0 to 50, d ranges from 0 to 100, e ranges from 0 to 100, with the condition that the ratio of (d+e)/(c+d+e) is greater than 0.5,

C) a hydrosilylation catalyst,

D) a second polyoxyalkylene having the average formula:

R³O[(C₂H₄O)_c' (C₃H₆O)_d' (C₄H₈O)_e]-R⁴

in which:

- R³ represents a monovalent unsaturated aliphatic hydrocarbon-based group containing from 2 to 12 carbon atoms,

- c' represents a value greater than 4, d' and e represent a value which can range from 0 to 100,

- R⁴ represents a hydrogen atom, an acyl group, or a monovalent hydrocarbon-based group containing 1 to 8 carbon atoms, in which said organic silicone elastomer has from 2% to 25% of ethylene oxide units,

- 5% to 98% by weight, relative to the total weight of the silicone elastomer gel, of a hydrophobic liquid carrier.

The silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain makes it possible to confer, on the composition, slippery properties on application and after penetration, in particular while reducing the greasy effect sensation. Furthermore, the crosslinked silicone polymer is used for its emulsifying properties.

According to one preferred embodiment, the silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain is a silicone polymer crosslinked with a polyoxypropylene chain, preferably having from 4 to 50 and better still from 10 to 30 propylene oxide units, and comprising at least one pendant polyoxyethylene chain, preferably having from 4 to 20 ethylene oxide units.

According to one preferred embodiment, the silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain represents, in terms of active material, approximately 0.01% to 10% by weight, preferably approximately 0.15% to 7% by weight, relative to the total weight of the composition. According to another preferred embodiment, the silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain represents, in terms of active material, approximately 0.18% to 5.4% by weight, preferably approximately 0.36% to 3.6% by weight, relative to the total weight of the composition.

In practice, the active material is first of all mixed with a hydrophobic liquid carrier so as to obtain a silicone elastomer gel. Subsequently, the silicone elastomer gel can then be mixed with a solvent. In certain embodiments, said solvent is chosen from water and a hydrophilic solvent. In certain embodiments, the silicone elastomer gel is then mixed with a solvent in a ratio of 100 parts by weight of solvent for 1 part by weight of the elastomer gel, and up to a ratio of 600 parts by weight of solvent for 1 part by weight of the elastomer gel, respectively, in order to obtain a crosslinked silicone elastomer paste. A. organohvdrosiloxane

The compound A is a branched or linear organohydrosiloxane of average formula: (R¹ ₃SiO_0.5)_v (R² ₂SiO)_x(R²HSiO)_y in which:

- R¹ represents a hydrogen or R²,

- R² represents a monovalent hydrocarbon-based group,

- v≥ 2,

- x≥ 0, preferably x ranges from 1 to 500, preferably x ranges from 1 to

200,

- y≥ 2, preferably y ranges from 2 to 200, preferably y ranges from 2 to

100.

R² may be a substituted or unsubstituted, aliphatic or aromatic hydrocarbon- based radical.

As monovalent, unsubstituted aliphatic hydrocarbon-based radicals, mention may, for example, be made of alkyl groups, such as methyl, ethyl, propyl, pentyl, octyl, undecyl and octadecyl groups; and also cycloalkyl groups such as the cyclohexyl group.

As monovalent, substituted aliphatic hydrocarbon-based radicals, mention may, for example, be made of halogenated alkyl groups, such as chloromethyi, 3- chloropropyl and 3,3,3-trifluoropropyl.

By way of example of a hydrocarbon-based aromatic group, mention may be made of phenyl, tolyl, xylyl, benzyl, styryl and 2-phenylethyl groups.

According to one embodiment, the organohydrosiloxane may comprise an additional siloxy unit, in particular of average formula:

(R¹ ₃SiO_0.5)_v (R² ₂SiO)_x(R²HSiO)_y(R²SiO_1.5)_z,

(R¹ ₃SiO_0.5)_v(R² ₂SiO)_x(R²HSiO)_y(SiO₂)w,

(R¹ ₃SiO_0.5)_v (R² ₂SiO)_x(R²HSiO)_y(SiO2)w(R²SiO_1.5)z

or mixtures thereof,

in which R¹ represents a hydrogen atom or R²,

R² represents a monovalent hydrocarbon-based group, and v≥2, w≥ 0, x≥0, y≥ 2, and z≥0.

According to one embodiment, the organohydrosiloxane is chosen from the following groups: dimethyl, methylhydropolysiloxane of average formula (CH₃)3SiO[(CH₃)2SiO3x[(CH₃)HSiO]ySi(CH₃)3 in which x≥ 0, preferably x ranges from 1 to 500, preferably x ranges from 1 to 200, and y≥ 2, preferably y ranges from 2 to 200, preferably y ranges from 2 to 100.

B, first polvoxvalkvlene

The compound B is a polyoxyalkylene of average formula:

R³O-[(C₂H₄O)_c(C₃H₆O)_d(C₄H₈O)_e]-R³

in which:

- c ranges from 0 to 50, preferably from 0 to 10, preferably less than 2,

- d ranges from 0 to 100, preferably from 1 to 100, preferably from 5 to 50,

- e ranges from 0 to 100, preferably from 0 to 50, preferably from 0 to 30,

with the condition that the ratio of (d+e)/(c+d+e) is greater than 0.5, preferably greater than 0.8, preferably greater than 0.95.

The compound B is preferably a polyoxyalkylene with, at each chain end (i.e. alpha and omega positions), an unsaturated aliphatic hydrogenated group comprising from 2 to 12 carbon atoms. The polyoxyalkylene may result from the polymerization of ethylene oxide, of propylene oxide, of butylene oxide, of 1,2-epoxyhexane, of 1,2- epoxyoctane, or of cyclic epoxides such as cyclohexene oxide or exo-2,3- epoxynorbomane.

The polyoxyalkylene group may comprise oxyethylene units (C₂H₄O), oxypropylene units (C₃H₆O), oxybutylene units (C₄H₈O), or mixtures thereof. For example, the polyoxyalkylene group may comprise a mole majority of oxypropylene and oxybutylene units.

The unsaturated aliphatic hydrocarbon-based group may be an alkenyl or alkynyl group.

By way of examples, mention may be made of the alkenyl groups having the following structures: H₂C=CH-, H₂C=CHCH₂-, H₂C=C(CH₃)CH₂- , H₂C=CHCH₂CH₂-, H₂C=CHCH₂CH₂CH₂ -, and H₂C=CHCH₂CH₂CH₂CH₂-, preferably H₂C=CHCH₂. By way of examples, mention may be made of the alkynyl groups having the following structures: HC≡C-, HC≡CCH₂-, HC≡CCH(CH₃)- , HC≡CC(CH₃)₂- , HC≡CC(CH₃)2CH₂- .

According to one embodiment, the polyoxyalkylene is chosen from:

H₂C=CHCH₂O[C₃H₆O]_dCH₂CH=CH₂

H₂C=C(CH₃)CH₂O[C₃H₆O]_dCH₂C(CH₃)=CH₂

HC≡CCH₂O[C₃H₆O]_dCH₂C≡CH, or

HC≡CC(CH₃)₂O[C₃H₆O]_dC(CH₃)2C≡CH

preferably H₂C=CHCH₂O[C₃H₆O]_dCH₂CH=CH₂

with d being as defined above.

C. hvdrosilvlation catalyst

The compound C comprises any catalyst commonly used for hydrosilylation reactions.

According to one preferred embodiment, a catalyst based on a metal of the platinum group is used. The term "metal of the platinum group" is intended to mean ruthenium, rhodium, palladium, osmium, iridium and platinum, and complexes thereof.

Catalysts based on a metal of the platinum group which can be used to prepare the silicone elastomer according to the invention are the platinum complexes prepared as described by Willing, U. S. Pat. No. 3,419,593, and Brown et al, U. S. Pat. No. 5,175,325, incorporated by way of reference. As other examples of catalysts based on a metal of the platinum group which can be used, mention may be made of those in Lee et al., U. S. Pat. No. 3,989,668; Chang et al., U. S. Pat. No. 5,036,117; Ashby, U. S. Pat No. 3,159,601; Lamoreaux, U. S. Pat No. 3,220,972; Chalk et al., U. S. Pat. No. 3,29631; Modic, U. S. Pat. No. 3,516,946; Karstedt, U. S. Pat. No. 3,814,730; and Chandra et al., U.S. Pat No. 3,928,629 incorporated by way of reference.

The catalyst based on a metal of the platinum group may be a metal of the platinum group, said metal being deposited on a carrier such as silica gel or powdered carbon, or a compound or complex of said metal. Mention may be made, by way of examples, of: chloroplatinic acid, either in its hexahydrate form or in its anhydrous form, a catalyst containing platinum obtained by means of a method reacting chloroplatinic acid with an unsaturated aliphatic organosilicone, such as divinyltetramethyldisiloxane, or the alkene-platinum-silyl complexes as described in U.S. Patent Application No. 10/017229, such as (COD)Pt(SiMeCl₂)_2, where COD is 1 ,5-cyclooctadiene and Me is methyl. These alkene-platinum-silyl complexes can be prepared, for example, by mixing 0.015 mol of (COD)PtCI₂ with 0.045 mol of COD and 0.0612 mol of HMeSiCl₂.

The amount of catalyst required depends on the catalyst used. The catalyst must be present in sufficient amount to provide at least 2 parts per million (ppm), preferably from 4 to 200 ppm, of platinum relative to the weight of total solids of the silicone elastomer gel (all the non-solvent compounds). For example, the catalyst is present in sufficient amount to provide 4 to 150 ppm by weight of platinum.

D. second polvoxvalkvlene

The silicone elastomer comprises non-crosslinked pendant polyoxyalkylene groups. These groups are formed on the silicone elastomer via a hydrosilylation reaction by addition of the second polyoxyalkylene compound D) of average formula:

R³O[(C₂H₄O)c' (C₃H₆O)_d' (C₄H₈O)_e]-R⁴

in which

- R⁴ represents a hydrogen atom, an acyl group, or a monovalent hydrocarbon-based group containing 1 to 8 carbon atoms.

The unsaturated aliphatic hydrogenated group in D may be an alkyl or alkenyl group.

By way of examples, mention may be made of the alkenyl groups having the following structures: H₂C=CH-, H₂C=CHCH₂-, H₂C=C(CH₃)CH₂- , H₂C=CHCH₂CH₂-, H₂C=CHCH₂CH₂CH₂ -, and H₂C=CHCH₂CH₂CH₂CH₂-.

By way of examples, mention may be made of the alkynyl groups having the following structures: HC≡C-, HC≡CCH₂-, HC≡CCH(CH₃)- , HC≡CC(CH₃)₂- , HC≡CC(CH₃)₂CH₂- .

By way of examples of polyoxyalkylenes, that may be used as compound D), mention may be made of:

with c* and d' being as defined above.

The polyether may also be chosen from those described in US 6 987 157, incorporated by way of reference.

The compound D may be added to the silicone elastomer either during its formation (i.e. simultaneous reaction of the compounds A), B), C) and D)), or in a first reaction (for example by reacting a part of the SiH groups of the compound A) with C) and D)), subsequently followed by reaction with B), or subsequently added to the formed silicone elastomer having SiH groups (for example, unreacted SiH units present on the silicone elastomer).

The amounts of compounds A, B and D used in the hydrosilylation reaction can vary, as long as the mole amount of the total unsaturated aliphatic groups present in the reaction of the compounds B) and D) is such that the mole ratio of the SiH units of the compound A) to the aliphatic unsaturated groups of the compounds B) and D) ranges from 10/1 to 1/10. However, the mole ratio of the aliphatic unsaturated groups of the compounds B) and D) to the SiH units of the compound A) is greater than 1 so as to have complete consumption of the SiH groups.

The amounts and structures of B) and D) used may also vary. However, the amounts used and the structures of B) and D) are such that the organic silicone elastomer has a content of ethylene oxide units ranging from 2% to 25% by weight, preferably from 3% to 20% by weight, preferably from 4% to 18% by weight For the purposes of the present invention, the content of ethylene oxide units means the average amount of ethylene oxide ("EO", i.e. CH₂CH₂O-) units present in the structure of the organic silicone elastomer.

According to one embodiment, the organic silicone elastomer is crosslinked with a polyoxypropylene chain and the organic silicone elastomer also comprises pendant polyoxyethylene chains. According to this embodiment, the compound B is a polyoxypropylene (having in particular from 4 to 50, preferably 10 to 30 propylene oxide units) having an al!yl group at its two ends. Thus, according to this embodiment, the compound B has the general formula R³O-[(C₃H₆O)<r]-R³ _> with R³ as defined above, and d' greater than 0, preferably d' ranges from 4 to 50, preferably from 10 to 30. According to this embodiment, the compound D is a polyoxyethylene (having in particular from 4 to 20 ethylene oxide units) having an allyl group at one end

According to one embodiment, a sufficient amount of compound B is used to obtain a silicone elastomer with a content of propylene oxide units ranging from 5% to 50% by weight According to this embodiment, the compound B has the general formula R³O-[(C₂H₄O)_c']-R⁴ with R³ and R⁴ as defined above, and c' greater than 4, preferably c' ranges from 4 to 50, preferably from 10 to 30. Sufficient amounts of compound D are used to obtain a silicone elastomer with an ethylene oxide content ranging from 2% to 25% by weight

The order of addition of the compounds A), B), C) and D) can vary. However, according to one embodiment, the reaction for the synthesis of the silicone elastomer is carried out in 2 steps. Firstly, the compounds A), C) and D) react so as to form a polyoxyethylene organohydrosiloxane copolymer, then the polyoxyethylene organohydrosiloxane copolymer reacts with the compound B) and additional amounts of C).

E. hydrophobic fluid carrier

The organic silicone elastomers are in a liquid carrier.

According to one embodiment, the liquid carrier is the solvent used for the hydrosilylation reaction so as to form the organic silicone elastomer.

By way of examples of liquid carriers, mention may be made of organic liquids (oils and solvents), silicones and mixtures thereof.

According to one embodiment, the liquid carrier is an organic liquid. The organic liquids include oils and solvents. The organic liquids are, for example, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than 6 carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides and aromatic halides. The hydrocarbons may be, for example: isododecane, isohexadecane, isoparaffins such as Isopar L (C11-C13) or Isopar H (C11-C12), or hydrogenated polydecene. The ethers and esters may be, for example: isodecyl neopentanoate, neopentylglycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, and octyl palmitate. Organic fluid carriers may be fatty substances, oils, fatty acids and fatty alcohols.

The liquid carrier may also be an organopolysiloxane of low viscosity or a volatile methylsiloxane or a volatile ethylsiloxane or a volatile methylethylsiloxane having a viscosity at 25°C ranging from 1 to 1000 mm²/dry, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethy1-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyI-3,3- bis{(trimethylsilyl)oxy}trisiloxane, pentamemyl{(trimemylsilyl)oxy}cyclotrisiloxane and also polydimethylsiloxanes, polyethylsiloxanes, polymethylethylsiloxanes, polymethylphenylsiloxanes, polydiphenylsiloxanes, and mixtures thereof.

The liquid carrier may be a (C₆-C₂₀) alkyl methicone. By way of examples of (C₆-C₂₀) alkyl methicone, mention may be made of caprylyl methicone, cetearyl methicone, ethyl methicone, hexyl methicone, lauryl methicone, myristyl methicone and stearyl methicone, preferably caprylyl methicone.

The content of organic silicone elastomer and of liquid carrier is such that the silicone elastomer gel comprises from 2% to 95% by weight, preferably from 5% to 95% by weight, preferably from 10% to 90% by weight of organic silicone elastomer, and from 5% to 98% by weight, preferably from 95% to 5% by weight, preferably from 90% to 10% by weight of liquid carrier, such that the sum of the contents of silicone elastomer and of liquid carrier, and of any other compound, is equal to 100%.

According to one preferred embodiment, the silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain is a polyoxyethylenated dimethicone polymer, in particular with 12 ethylene oxide units, crosslinked with bis-allyl polypropylene glycol in particular 20 ethylene oxide units, in particular used in the form of a gel carried in caprylyl methicone. Such an elastomer gel is in particular sold under the name EL-7040 Hydro elastomer blend by the company Dow Corning, and it has the INCI name [Caprylyl Methicone (and) PEG-12 Dimethicone/PPG- 20 Crosspolymer].

Thus, in this particular embodiment, the content of silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain of approximately 0.18% to 5.4% by weight, relative to the total weight of the composition, is obtained by using approximately 1% to 30% by weight, relative to the total weight of the composition, of a crosslinked silicone elastomer paste as defined above.

Likewise, a content of silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain of approximately 0.36% to 3.6% by weight, relative to the total weight of the composition, is obtained by using approximately 2% to 20% by weight, relative to the total weight of the composition, of a crosslinked silicone elastomer paste as defined above. Semi-crvstalline polymer

The composition according to the invention contains at least one semi- crystalline polymer, preferably derived from acrylic or methacrylic acid. For the purposes of the invention, the term "semi-crystalline polymer" is intended to mean polymers comprising a crystallizable, pendant-chain or block portion in the backbone, and an amorphous portion in the backbone, and having a first-order reversible change of phase temperature, in particular melting point (solid-liquid transition). When the crystallizable portion is a block of the polymer backbone, this crystallizable block is of chemical nature different than that of the amorphous blocks; the semi-crystalline polymer is, in this case, a block polymer, for example of the diblock, triblock or multiblock type, comprising at least one crystallizable block and at least one amorphous block. The term "block¹¹ is generally intended to mean at least 5 identical repeating units. The crystallizable block(s) are then of different chemical nature from the amorphous bIock(s).

Advantageously, the semi-crystalline polymer of the composition of the invention has an average molecular weight (Mn) greater than or equal to about 2000, preferably from about 2000 to 800000, preferably from about 3000 to 500000, preferably from about 4000 to 150000, and preferably from about 4000 to 99000.

In the composition according to the invention, the semi-crystalline polymers are advantageously soluble in the oily phase at least 1% by weight, at a temperature that is higher than their melting point. Besides the crystallizable chains or blocks, the blocks of the polymers are amorphous. For the purposes of the invention, the term "crystallizable chain or block" is intended to mean a chain or block which, if it were alone, would change from the amorphous state to the crystalline state reversibly, depending on whether one is above or below the melting point. For the purposes of the invention, a chain is a group of atoms, which are pendant 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 "pendant crystallizable chain" may be a chain containing at least 6 carbon atoms.

Preferably, the polymer backbone of the semi-crystalline polymers is soluble in the oily phase. Thus, the semi-crystalline polymer used in the composition of the invention is generally introduced into the oily phase of the composition. Preferably, the semi-crystalline polymers used in the composition of the invention have a melting point, Mp, below 70°C (25°C≤Mp< 70°C), this temperature being at least equal to the temperature of the keratin material which must receive the composition according to the invention, in particular the skin. The melting point may be measured in particular by any known method and in particular with a differential scanning calorimeter (DSC).

Preferably, the crystallizable blocks or chains of the semi-crystalline polymers represent at least approximately 30% by weight and preferably at least approximately 40% by weight relative to the total weight of each polymer. The semi-crystalline polymers comprising crystallizable blocks used according to the invention are block or multiblock polymers. They may be obtained via polymerization of monomers containing double bonds which are reactive (or which are ethylenic) or via polycondensation. When the polymers of the invention are polymers containing crystallizable side chains, they are advantageously in random or statistical form.

The semi-crystalline polymers of the invention may be of synthetic origin. Moreover, they do not comprise a polysaccharide backbone.

The semi-crystalline polymers that may be used in the invention are in particular:

- block copolymers of polyolefins with controlled crystallization,

- polycondensates of aliphatic or aromatic polyester or aliphatic/aromatic copolyester type,

- homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or copolymers bearing at least one crystallizable block in the backbone,

- homopolymers or copolymers bearing at least one crystallizable side chain, in particular containing fluoro group(s), and

- mixtures thereof.

For example, the block copolymers of polyolefins with controlled crystallization suitable for the present invention are in particular those of which the monomers are described in EP-A-0951 897. For example, homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or copolymers bearing at least one crystallizable block in the backbone that are particularly suitable for implementing the invention are those described in particular in document US-A-5 156911-

Finally, the homopolymers or copolymers bearing at least one crystallizable side chain, in particular containing fluoro group(s), are preferably those described in document WO-A-01/19333.

In one particular embodiment, the crystallizable side chain(s) or block(s) are hydrophobic. a) Semi-crystalline polymers containing crystallizable side chains:

Mention may be made in particular of those defined in documents US-A- 5 156911 and WO-A-01/19333. They are homopolymers or copolymers comprising from 50% to 100% 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.

They can result:

- from the polymerization, in particular the free-radical polymerization, of one or more monomers containing double bond(s) which is (are) reactive, or which is (are) ethylenic, with respect to a polymerization, namely a vinyl, (meth)acrylic or allyiic group,

- from the polycondensation of one or more monomers bearing co-reactive groups (carboxylic acid, sulfonic acid, alcohol, amine or isocyanate), such as, for example, polyesters, polyurethanes, polyethers, polyureas or polyamides.

In general, these polymers are chosen in particular from homopolymers and copolymers resulting from the polymerization of at least one monomer containing crystallizable chain(s) that may be represented by the following formula:

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" represents in particular a group (CH₂)n or (CH₂CH₂O)_n or (CH₂O), which may be linear or branched or cyclic, with n being an integer ranging from 0 to 22. 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 11 carbon atoms and at most 40 carbon atoms and preferably at most 24 carbon atoms. They are in particular aliphatic chains or alkyl chains containing at least 12 carbon atoms, and they are preferably C₁₄-C₂₄ alkyl chains. When they are fluoroalkyl or perfluoroalkyl chains, they contain at least six fluorinated carbon atoms and in particular at least 11 carbon atoms, at least six of which carbon atoms are fluorinated.

According to one particular embodiment, the invention relates to a composition for which the semi-crystalline polymer is chosen from a group comprising homopolymers and copolymers resulting from the polymerization of at least one monomer containing crystallizable chain(s), said chain being chosen from alkyl chains comprising at least 11 carbon atoms and at most 40 carbon atoms.

As examples of semi-crystalline polymers or copolymers containing crystallizable chain(s), mention may be made of those resulting from the polymerization of one or more of the following monomers: saturated alkyl (meth)acrylates with the alkyl group being C₁₄-C₂₄, perfluoroalkyl (meth)acrylates with a C₁₁-C₁₅ perfluoroalkyl group, N-alkyl(meth)acrylamides with the alkyl group being C₁₄ to C₂₄ with or without a fluorine atom, vinyl esters containing alkyl or perfluoro(alkyl) chains with the alkyl group being C₁₄ to C₂₄ (with at least 6 fluorine atoms per perfluoroalkyl chain), vinyl ethers containing alkyl or perfluoro(alkyl) chains with the alkyl group being Ct4 to C₂₄ and at least 6 fluorine atoms per perfluoroalkyl chain, C₁₄ to C₂₄ alpha-olefins such as, for example, octadecene, para-alkylstyrenes with an alkyl group containing from 12 to 24 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 diacicl, a diol, a diamine or a diisocyanate.

According to one embodiment, when the polymers that are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y resulting from the copolymerization of a monomer containing a crystallizable chain with 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 (in particular 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- cliisopropylacrylamide 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, the alkyl groups denoting a saturated group which is in particular C₈ to C₂₄, and better still C₁₄ to C₂₄;

- 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 alpha-olefin, styrene or styrene substituted with a C₁ to C₁₀ alkyl group, for instance a-methylstyrene, the alkyl groups denoting a saturated group which is in particular Cg to C₂₄, and better still C₁₄ to C₂₄.

For the purposes of the invention, the term "alkyl" is intended to mean a saturated group which is in particular C₈ to C₂₄, unless expressly mentioned, and better still C₁₄ to C₂₄.

According to one embodiment, when the polymers mat are subjects of the invention are copolymers, they additionally contain from 0 to 50% of groups Z resulting from the copolymerization of a monomer containing a crystallizable chain with 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 in particular of C₁₄-C₂₄, 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. b) Polymers bearing in the backbone at least one crvstallizable block:

These polymers are in particular block copolymers consisting of at least 2 blocks of different chemical nature, one of which is crystalHzable.

For example, the block polymers defined in patent US-A-5 156 911 are particularly suitable.

They are, for example, block copolymers of olefin or of cycloolefin containing a crystalHzable chain, for instance those resulting from the block polymerization of:

- cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo(2,2,1)-2- heptene), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimelhylnorbornene, 5,5,6- trimethylnorbomene, 5-ethylidenenorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene, dicyclopentadiene, or mixtures thereof,

- with ethylene, propylene, 1-butene, 3-methy1- 1-butene, 1-hexene, 4-methyl- 1-pentene, 1-octene, 1-decene or 1-eicosene, or mixtures thereof, and in particular block copoly(ethylene/norbornene)s and (ethylene/propylene/emylidene-norbomene) block terpolymers.

The polymers resulting from the block copolymerization of at least two Ci- C₁₆, preferably C₂-C₁₂ and preferably C₄-C₁₂ a-olefins such as those mentioned above and in particular block bipolymers of ethylene and of 1 -octene may also be used.

The copolymers of interest may also be copolymers containing at least one crystalHzable block, the rest of the copolymer being amorphous (at ambient temperature). These copolymers may also contain two crystallizable blocks of different chemical nature. The preferred copolymers are those that simultaneously contain at ambient temperature a crystallizable block and an amorphous block that are both hydrophobic and lipophilic, sequentially distributed; mention may be made, for example, of polymers containing one of the crystallizable blocks and one of the amorphous blocks below: - block that is crystallizable by nature: a) of polyester type, for instance poly(alkylene terephthalate), b) of polyolefin type, for instance polyethylenes or polypropylenes;

- amorphous and lipophilic block, for instance amorphous polyolefins or copoly(olefin)s such as poly(isobutylene), hydrogenated polybutadiene or hydrogenated poly(isoprene).

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

- poly(ε-caprolactone)-b-poly(butadiene) block copolymers, preferably used hydrogenated, such as those described by Nojima (Macromolecules, vol. (32), p. 3727-

3734, 1999);

- the hydrogenated block or multiblock poly(butylene terephthalate)-b- poly(isoprene) block copolymers, mentioned by Boutevin et al. (Polymer Bulletin, vol. (34), p. 117-123, 1995);

- the poly(ethylene)-b-copoly(emylene/propylene) block copolymers mentioned by Rangarajan et al. (Macromolecules, vol. (26), p. 4640-4645, 1993) et Richter et al. (Macromolecules, vol. (30), p. 1053-1068, 1997);

- the poly(ethylene)-b-poly(emylethylene) block copolymers mentioned by Hamley (Advances in Polymer Science, vol. (148), p. 113-137, 1999).

The semi-crystalline polymers of the composition of the invention may or may not be partially crosslinked, provided mat the degree of crosslinking is not detrimental to their dissolution or dispersion in the oily phase, 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.

Preferably, the semi-crystalline polymers of the composition according to the invention are not crosslinked. According to one particular embodiment of the invention, the polymer is chosen from copolymers resulting from the polymerization of at least one monomer containing a crystallizable chain chosen from saturated C₁₄ to C₂₄ alkyl (meth)acrylates, C₁₁ to C₁₅ perfluoroalkyl (meth)acrylates, Cu to C₂₄ N-aIkyl(meth)acrylamides with or without a fluorine atom, vinyl esters containing C₁₄ to C₂₄ alkyl or perfluoroalkyl chains, vinyl ethers containing C₁₄ to C₂₄ alkyl or perfluoroalkyl chains, C₁₄ to C₂₄ alpha-olefins, para-alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, with at least one optionally fluorinated C₁ to C₁₀ monocarboxylic acid ester or amide, which may be represented by the following formula:

in which R₁ is H or CH₃, R represents an optionally fluorinated C₁-C₁₀ alkyl group and X represents O, NH or NR₂ in which R₂ represents an optionally fluorinated C₁- C₁₀ alkyl group.

According to one more particular embodiment of the invention, the polymer is derived from a monomer containing a crystallizable chain chosen from saturated C₁₄ to C₂₂ alkyl (meth)acrylates and even more particularly poly(stearyl acrylate)s or poly(behenyl acrylate)s.

According to one particular embodiment, the semi-crystalline polymer is chosen from homopolymers obtained by polymerization of a monomer chosen from C₁₄- C₂₄ alkyl acrylates and C₁₄-C₂₄ alkyl methacrylates and from copolymers obtained by copolymerization of a monomer chosen from C₁₄-C₂₄ alkyl acrylates and C₁₄-C₂₄ alkyl methacrylates, with a hydrophilic monomer.

As particular examples of structuring semi-crystalline polymers that may be used in the composition according to the invention, mention may be made of polymers having the INCI name Poly C₁₀-C₃₀ alkyl acrylate, for instance the Intelimer products from the company Air Products, for instance the product Intelimer IPA 13-1, which is a polystearyl acrylate, or the product Intelimer IPA 13-6, which is a behenyl polymer.

According to one particular embodiment, the semi-crystalline polymer is a polymer having the INCI name: Poly C₁₀-C₃₀ alkyl acrylate. The Inteliraer semi-crystalline polymer IPA 13-1 NG is known for its SPF booster effects, but it is barely or not at all compatible with the conventional silicone emulsifiers and, more generally, with conventional silicone ingredients.

The semi-crystalline polymers may in particular be those described in Examples 3, 4, 5, 7, 9 and 13 of patent US-A-5 156 911 containing a -COOH group, resulting from the copolymerization of acrylic acid and of C₅ to C₁₆ alkyl (meth)acrylate and more particularly from the copolymerization:

- of acrylic acid, of hexadecyl aery late and of isodecyl acrylate in a 1/16/3 weight ratio,

- of acrylic acid and of pentadecyl acrylate in a 1/19 weight ratio,

- of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in a 2.5/76.5/70 weight ratio,

- of acrylic acid, of hexadecyl acrylate and of methyl acrylate in a 5/85/10 weight ratio,

- of acrylic acid and of octadecyl methacrylate in a 2.5/97.5 weight ratio,

- of hexadecyl acrylate, of polyethylene glycol methacrylate monomethyl ether containing 8 ethylene glycol units, and of acrylic acid in an 8.5/1/0.5 weight ratio.

It is also possible to use the polymer of structure "O" from National Starch, such as that described in document US-A-5 736 125, with a melting point of 44°C, and also semi-crystalline polymers with crystallizable pendant chains comprising fluoro groups, as described in Examples 1, 4, 6, 7 and 8 of document WO-A-01/19333.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of stearyl acrylate and of acrylic acid or NVP as described in document US-A-5 519 063 or EP-A-550 745, with melting points of 40°C and 38°C, respectively.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of behenyl acrylate and of acrylic acid or NVP, as described in documents US-A-5 519 063 and EP-A-550 745, with melting points of 60°C and 58°C, respectively.

Preferably, the semi-crystalline polymers do not comprise any carboxylic groups.

According to one embodiment of the invention, the semi-crystalline polymer(s) may represent, within the composition, approximately 0.05% to 10% by weight, preferably from 0.1% to 5% by weight and preferably from 0.2% to 3% by weight, relative to the total weight of the composition.

UV-screeninz agents

According to one preferred embodiment, the composition according to the invention also comprises at least one UV-screening agent.

As will be illustrated in the examples below, the inventors have noticed that the presence of at least one crosslinked silicone polymer and at least one semi-crystalline polymer, as described in the present invention, stabilizes an emulsion which comprises at least one UV-screening agent.

Any UV-screening agent known from the prior art is capable of being able to be formulated in the composition according to the present invention. For the purposes of illustration, mention may in particular be made of the following compounds, represented by their INCI names:

- para-amino benzoic acid (PABA) and derivatives thereof:

PABA,

Ethyl PABA,

Ethyl Dihydroxypropyl PABA,

Ethylhexyl Dimethyl PABA, in particular commercially available under the name Escalol 507 from the company ISP,

Glyceryl PABA,

- dibenzoylmethane derivatives:

Butyl Methoxydibenzoylmethane, in particular commercially available under the name Parsol 1789 from Hofrmann-LaRoche,

Isopropyl Dibenzoylmethane,

- salicylic acid derivatives:

Homosalate, in particular commercially available under the name Eusolex HMS from the company Rona/EM Industries,

Ethylhexyl Salicylate, in particular commercially available under the name Neo Heliopan OS from Haarmann and Reimer,

Dipropylene Glycol Salicylate, in particular commercially available under the name Dipsal from Scher, TEA Salicylate, in particular commercially available under the name Neo Heliopan TS from Haarmann and Reimer,

- cinnamic acid derivatives:

Ethylhexyl Methoxycinnamate, in particular commercially available under the name Parsol MXC from the company Hoffmann-LaRoche,

Isopropyl Methoxycinnamate,

Isoamyl Methoxycinnamate, in particular commercially available under the name Neo Heliopan E 1000 from Haarmann and Reimer,

Cinoxate,

DEA Methoxycinnamate,

Diisopropyl Methylcinnamate,

Glyceryl Ethylhexanoate Dimethoxycinnamate,

- β,β-diphenyl acrylate derivatives:

Octocrylene, in particular commercially available under the name Uvinul N539 from BASF,

Etocrylene, in particular commercially available under the name Uvinul N35 from BASF,

- benzophenone derivatives:

Benzophenone-1, in particular commercially available under the name Uvinul 400 from BASF,

Benzophenone-2, in particular commercially available under the name Uvinul D50 from BASF,

Benzophenone-3 or Oxybenzone, in particular commercially available under the name Uvinul M40 from BASF,

Benzophenone-4, in particular commercially available under the name Uvinul

MS40 from BASF,

Benzophenone-5,

Benzophenone-6, in particular commercially available under the name Helisorb 11 from Norquay,

- other preferred UV-screening agents

- Ethylhexyl triazone, for example the product sold under the name Uvinul® T 150 by the company BASF, - Drometrizole trisiloxane, and in particular the product sold under the name Silatrizole® by the company Rhodia,

- Bis-ethylhexyloxyphenol methoxyphenyl triazine, for instance the product sold under the name Tinosorb® by the company BASF,

- Diethylhexylbutamidotriazone, for instance the product sold under the name

Uvasorb® HEB by the company Sigma 3 V,

- Phenylbenzimidazolesulfonic acid, in particular the product sold under the name Eusolex® 232 by the company Merck,

- Terephthalylidenedicamphorsulfonic acid, in particular the product sold under the name Mexoryl® SX by the company Chimex, and

- Diemylamidohydroxybenzoylhexyl benzoate, in particular the product sold under the name Uvinul® A Plus Granular by the company BASF,

- and mixtures thereof. Adjuvants

In the context of the present invention, the composition in the form of a oil-in- water or water-in-oil emulsion may also contain at least one adjuvant chosen from the adjuvants which are customary in the cosmetics field.

These adjuvants are, for example, active ingredients, preservatives, antioxidants, complexing agents, thickeners, gelling agents, film-forming agents, surfactants, co-surfactants, moisturizing agents, solvents, fragrances, fillers, bactericides, fungicides, parasiticides, odour absorbers, pH regulators, anti-inflammatory agents, colorants (dyes and pigments), and also lipid vesicles.

The term "pigments¹* should be understood as meaning white or coloured, mineral or organic particles that are insoluble in an aqueous solution, which are intended to colour and/or opacify the composition containing them.

As mineral pigments that may be used in the invention, mention may be made of titanium oxide, titanium dioxide, zirconium oxide, zirconium dioxide, cerium oxide or cerium dioxide and also zinc oxide, iron oxide or chromium oxide, ferric blue, manganese violet, ultramarine blue and chromium hydrate, and mixtures thereof.

It may also be a pigment having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals and Catalysts, and has a contrast ratio in the region of 30.

They may also be pigments having a structure that may be, for example, of silica microsphere type containing iron oxide. An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL- 100 P, this pigment consisting of silica microspheres containing yellow iron oxide.

Advantageously, the pigments in accordance with the invention are iron oxides and/or titanium dioxides.

The amounts of these various adjuvants are those conventionally used in the field under consideration, and for example from 0.01% to 20% of the total weight of the composition. These adjuvants, depending on their nature, can be introduced into the oily phase, into the aqueous phase and/or into lipid vesicles.

These adjuvants and the concentrations thereof should be such that they do not modify the property desired for the composition of the invention.

2/Use

The compositions of the invention can be used in any cosmetic or dermatological application, for example in the cosmetics industry for caring for keratin materials, which includes any cosmetic application for caring for the skin, the hair, the scalp, the eyelashes, the eyebrows, the nails or the mucous membranes, for instance the lips.

In particular, the compositions according to the invention can be part of the production of protective, treatment or care products for the face, for the hands or for the body, as products for cleansing the skin, in particular of the face or of the body, as makeup products, for example foundations, or as hair products.

The cosmetic compositions according to the invention have applications in a large number of cosmetic treatments for keratin materials, and more especially the skin, in particular for obtaining a feeling of softness of the skin and a silky effect. By virtue of its pleasantness and its effects, the composition of the invention is particularly suitable for treating skin showing imperfections and also dehydrated, rough or sensitive skin. Thus, a subject of the present invention is the cosmetic use of a composition as defined above, for caring for the skin, in particular dehydrated skin or skin comprising imperfections.

A subject of the present invention is also the cosmetic use of a composition as defined above, for caring for the hair, in particular for conferring thereon a silky appearance.

A composition according to the invention may be in various galenical forms conventionally used for topical applications and in particular in the form of dispersions of the serum type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing an oily phase in an aqueous phase (O/W) or vice versa (W/O), or suspensions or emulsions of soft, semi-solid or solid consistency of the cream or gel type, or alternatively multiple emulsions (W/O/W or O/W/O), microemulsions, vesicular dispersions of ionic and/or nonionic type. These compositions are prepared according to the usual methods.

In addition, the compositions used according to the invention may be more or less fluid and may have the appearance of a gel, of a white or coloured cream, an ointment, a milk, a serum, a paste or a foam.

According to another particular embodiment, the composition according to the invention is in the form of a water-in-oil emulsion comprising a continuous oily phase and an aqueous phase dispersed in said oily phase, or in the form of an oil-in-water emulsion comprising a continuous aqueous phase and an oily phase dispersed in said aqueous phase.

3/Cosmetic method

A subject of the present invention is also a cosmetic method for attenuating the visible or tactile irregularities of the surface of the skin, comprising a topical administration of a composition according to the invention to the skin and/or the lips.

Indeed, the good penetration and the feeling of softness of the skin, which are obtained after application of a composition according to the invention, reinforce the consumer's sensation of skin which has a smooth and uniform appearance.

Likewise, a subject of the present invention is also a cosmetic method for improving the appearance of the hair and/or the nails, comprising a topical administration of a composition according to the invention to the hair and/or the nails. The topical application of a composition makes it possible to reinforce the silky appearance of the hair and thus reduces the rough, coarse, brittle appearance.

According to another aspect, the topical administration can be carried out at a rate of at least once a day, of at least once every 2 days, of once every 3 days, or of once a week. The term "at least once a day" encompasses twice a day, 3 times a day, 4 times a day.

Thus, as will be shown by the examples below, the combination of a crosslinked silicone polymer as described in the invention with a semi-crystalline polymer, in care, makeup or screening emulsions, makes it possible to optimize the feelings of softness, comfort, penetration and persistence.

The examples that follow will allow the invention to be understood more clearly, without, however, being limiting in nature. The raw materials are referred to by their chemical or INCI name. The amounts indicated are given as % by weight of raw materials, unless otherwise mentioned.

EXAMPLES

1) Materials and methods

1. 1) Process for preparing compositions according to the invention The aqueous phase is prepared in a Rayneri mixer, by dissolving hydrophilic adjuvant(s) and or water-miscible solvents) in water (at the required temperature), and then a hydrophilic gelling agent is added with stirring at a temperature of approximately 70°C until the gel is homogeneous. The fatty phase is then homogenized, at a temperature suitable for obtaining a homogeneous liquid phase. When the mixtures of the two phases are homogeneous, an emulsion is conventionally produced by adding the aqueous phase to the oily phase with stirring in a Rayneri mixer. The emulsion is then cooled with stirring until a homogeneous smooth cream is obtained.

1.2) Evaluation of the cosmetic properties of the emulsions

The cosmetic properties were evaluated according to the following protocol. The cosmetic properties on application are evaluated, monadically, by a panel of experts trained in the description of care products. The sensory evaluation of the care products by this panel is performed as follows: the products are packaged in opaque jars or pump- dispenser bottles depending on the viscosity of the products. Within the same session, the samples are presented in random order to each panellist.

In each case, 15 experts evaluated the comfort during application to the skin and after penetration.

The parameter is evaluated on a 5-level scale: no, little, medium, quite, very. A score was assigned to each level: no (0), little (1), medium (2), quite (3) and very (4). Subsequently, the scores assigned by each of the 15 experts are added so as to obtain an overall score.

A ratio between the score obtained for the compositions according to the invention and the score obtained for the comparative compositions was calculated. A ratio greater than 1.25 was considered to be statistically significant for the parameter under consideration.

1.3) Stability

The immediate stability at ambient temperature and the stability after 2 months of storage under different temperature conditions, i.e. 4°C, ambient temperature (25°C) and 45°C, were evaluated.

For the water-in-oil emulsions, a cycle stability was performed (10 cycles -20/+20°C).

2) Results

2.1) Comparative Example 1: Screening water-in-oil emulsions

Example 1 illustrates the evaluation of the stability properties of an emulsion according to the invention in comparison with an emulsion of which the formulation is adapted from document FR 2 912 651. Table 1; formulations of water-in-oil emulsions 1 and 2 (as % by weight relative to the total weight of the composition)

KSG-210 from Shin Etsu, (25% of active material in dmiethicone); EL-7040 from Dow Corning (HSOEB, 18% of active material in CAPRYLYL METHICONE); ³ Sunscreens; ⁴ INTELIMER IPA 13-1; ⁵ The content is represented as % by weight of raw material relative to the total weight of the composition, which corresponds to a weight of active material of 3.24% by weight relative to the total weight of the composition; ⁶ Luvigel EM from BASF.

In conclusion: the screening composition of the invention, in which the crosslinked silicone polymer (PEG-12 Dimethicone/PPG-20 Crosspolymer) is used as an emulsifying elastomer, is more stable compared with the screening composition of the comparative example in which KSG210 is used as an emulsifying elastomer.

2.2) Comparative example 2 - Screening compositions with lipophilic screening agents In order to demonstrate the advantage of the combination, the stability and the cosmetic properties of 2 water-in-oil emulsions containing the combination of crosslinked silicone polymer (PEG-12 Dimethicone/PPG-20 Crosspolymer) and semi-crystalline polymer (Poly C₁₀-C₃₀ Alkyl acrylate) (emulsions 4 and 5) were compared with the same parameters of an emulsion not containing the semi-crystalline polymer (emulsion 3).

Table 2: formulations of water-in-oil emulsions 3.4 and 5 (as % by weight relative to the total weight of the composition)

¹ EL-7040 from Dow Corning (HSOEB, 18% of active material in CAPRYLYL METfflCONE); ² Sunscreens; ³ INTELIMER IPA 13-1; ⁴ The content is represented as % by weight of raw material relative to the total weight of the composition, which corresponds to a weight of active material of 3.24% by weight relative to the total weight of the composition; ⁵ Rheoluxe 811 from Elementis. a) Evaluation of the performance levels of the water-in-oil emulsions W/O 3, W/O 4 and W/0 5

For each of the 3 compositions, the following were evaluated:

- the immediate stability at ambient temperature and the stability after 2 months of storage at 45°C;

- the application, comfort and persistence qualities and, in the presence of screening agents, a good SPF effect after application to the skin. Table 3; stability of water-in-oil emulsions 3. 4 and 5

With regard to the stability parameter, the screening compositions according to the invention, in which the crosslinked silicone polymer of HSOEB type (PEG- 12 Dimethicone/PPG-20 Crosspolymer) is used as an emulsifying elastomer and comprising a semi-crystalline polymer (Poly C₁₀-C₃₀ Alkyl acrylate), are more stable than the composition of the comparative example not containing semi-crystalline polymer (Poly C₁₀-C₃₀ Alkyl acrylate).

With regard to the protective index performance parameter, the use of the semi-crystalline polymer (Intelimer IPA 13-1 NG) in combination with the crosslinked silicone polymer (PEG-12 Dimethicone/PPG-20 Crosspolymer), i.e. emulsions 4 and 5, makes it possible to significantly increase the SPF performance of the product compared with a formulation without semi-crystalline polymer (emulsion 3), without degrading the sensory effect. b) Evaluation of the sensory effect:

Table 4: cosmetic performance levels of water-in-oil emulsions 3. 4 and 5

With the addition of the semi-crystalline polymer of Intelimer IPA 13-1 NG type in a composition comprising a crosslinked silicone polymer (PEG-12 Dimethicone/PPG-20 Crosspolymer) makes possible to guarantee a more uniform application on the skin. The screening emulsions according to the invention are also very fresh on application and very nourishing while at the same time retaining the qualities of softness, both on application and after application.

Claims

1. Composition in the form of an emulsion comprising at least:

(i) one aqueous phase,

(ii) one oily phase,

(iv) one semi-crystalline polymer.

2. Composition according to Claim 1, which is a cosmetic composition, preferably a cosmetic composition for topical application.

3. Composition according to either of Claims 1 and 2, characterized in that the silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain is present in the form of a silicone elastomer gel, said silicone elastomer gel comprising:

- 2% to 95% by weight, relative to the total weight of the silicone elastomer gel, of an organic silicone elastomer, obtained by reacting:

A) an organohydrogenosiloxane comprising siloxy units of average formula: (R¹ ₃SiO_0.5)_v (R² ₂SiO)_x (R²HSiO)_y in which:

- R¹ represents a hydrogen or R²,

- R² represents a monovalent hydrocarbyl group,

- v≥ 2, x≥ 0, y≥≥ 2,

B) a first polyoxyalkylene having the average formula:

R³O-[(C₂H₄O)_c(C₃H₆O)_d(C₄H₈O)_e]-R³

in which:

- R³ is a monovalent unsaturated aliphatic hydrocarbon- based group containing from 2 to 12 carbon atoms,

C) a hydrosilylation catalyst,

D) a second polyoxyalkylene having the average formula: R³O[(C₂H₄O)c' (C₃H₆O)_d' (C₄H₈O)_e]-R⁴

in which:

- R⁴ represents a hydrogen atom, an acyl group, or a monovalent hydrocarbon-based group containing 1 to 8 carbon atoms,

in which said organic silicone elastomer comprises from 2% to 25% of ethylene oxide units,

4. Composition according to one of Claims 1 to 3, characterized in that the emulsion is chosen from an O/W emulsion and a W/O emulsion, preferably a W/O emulsion.

5. Composition according to one of Claims 1 to 4, characterized in that the silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain represents approximately 0.01% to 10% by weight, preferably approximately 0.15% to 7% by weight, preferably approximately 0.18% to 5.4% by weight, preferably approximately 0.36% to 3.6% by weight, relative to the total weight of the composition.

6. Composition according to one of Claims 1 to 5, characterized in that the polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain is a silicone polymer crosslinked with a polyoxypropylene chain, preferably having from 4 to 50 and better still from 10 to 30 propylene oxide units, and comprising at least one pendant polyoxyethylene chain, preferably having from 4 to 20 ethylene oxide units.

7. Composition according to one of Claims 1 to 6, characterized in that the silicone polymer crosslinked with at least one polyoxyalkylene chain and comprising at least one pendant polyoxyalkylene chain is a polyoxyethylenated dimethicone polymer, in particular having 12 ethylene oxide units, crosslinked with bis-allyl polypropylene glycol, in particular having 20 propylene oxide units.

S. Composition according to one of Claims 1 to 7, characterized in that the semi-crystalline polymer represents approximately 0.05% to 10% by weight, preferably approximately 0.1% to 5% by weight, preferably approximately 0.2% to 3% by weight, relative to the total weight of the composition.

9. Composition according to one of Claims 1 to 8, characterized in that the semi-crystalline polymer is chosen from a group comprising homopolymers and copolymers resulting from the polymerization of at least one monomer containing crystallizable chain(s), said chain being chosen from alkyl chains comprising at least 11 carbon atoms and at most 40 carbon atoms.

10. Composition according to one of Claims 1 to 9, characterized in that the semi-crystalline polymer is chosen from homopolymers obtained by polymerization of a monomer chosen from C₁₄-C₂₄ alkyl acrylates and C₁₄-C₂₄ alkyl methacrylates and from copolymers obtained by copolymerization of a monomer chosen from C₁₄-C₂₄ alkyl acrylates and C₁₄-C₂₄ alkyl methacrylates, with a hydrophilic monomer.

11. Composition according to one of Claims 1 to 10, characterized in that the semi-crystalline polymer is chosen from saturated C₁₄ to C₂₂ alkyl (meth)acrylates and preferably from poly(stearyl acrylate)s or poly(behenyl acrylate)s.

12. Composition according to one of Claims 1 to 11, characterized in that the water-in-oil W/O emulsion comprises an oily phase representing approximately 0.5% to 50% by weight, preferably approximately 10% to 35% by weight, relative to the total weight of the composition.

13. Composition according to one of Claims 1 to 12, characterized in that the composition also comprises at least one UV-screening agent.

14. Composition according to one of Claims 1 to 13, characterized in that the composition also comprises at least one adjuvant, in particular chosen from active ingredients, preservatives, antioxidants, complexing agents, thickeners, gelling agents, film-forming agents, surfactants, co-surfactants, moisturizing agents, solvents, fragrances, fillers, bactericides, fungicides, parasiticides, odour absorbers, pH regulators, antiinflammatory agents, colorants (dyes and pigments), and lipid vesicles.

15. Cosmetic use of a composition according to one of Claims 1 to 14, for caring for keratin materials, preferably the skin, the lips, the hair and the nails.

16. Method for the cosmetic treatment of keratin materials, comprising a topical administration of a composition according to one of Claims 1 to 14.