FR2834916A1 - Solid composition in the form of a water-in-oil emulsion useful for make-up removal or cleansing, comprises an oil phase thickened with a semi crystalline solid polymer - Google Patents

Abstract

Solid composition in the form of a water-in-oil emulsion containing an emulsifier with a hydrophilic-lipophilic balance (HLB) of 1-8 includes, in the oil phase, a semi crystalline solid polymer with a m.pt. below 70degreesC comprising a crystallizable organic side chain and/or a crystallizable organic sequence in the main chain, the polymer having a number-average molecular weight above 2000. An Independent claim is also included for a cosmetic method for make-up removal or for cleansing the skin, lips and visible organs, comprising applying a composition as above.

Description

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The present invention relates to a solid composition for removing make-up and / or cleansing of the skin, including the scalp, the integuments and / or the lips of the face of human beings, in the form of a water-in-water emulsion. oil (W / O), containing at least one particular polymer in the liquid oily phase. This solid composition can be in particular in the form of a stick, the application of which leads to a fresh deposit.

The cleansers and facial cleansers conventionally used to date are compositions having a high fat concentration whose function, when applied to the skin, is to dissolve the various fatty substances present on the skin and in particular those contained in makeup products, so as to eliminate them. However, the use of such high-fat makeup removal compositions causes, at the time of their application, an inconvenience or discomfort that results in a feeling of heaviness on the face or a veil on the eyes. The application of these compositions to the eyes may, moreover, cause swelling of the eyelids.

In addition, these products are generally in the form of creams, lotions or milks, which makes their transport difficult because of the risk of overturning. In addition, the dosage and the application of liquid or semiliquid products can be difficult because the product can flow and for example flow between the fingers at the time of application and possibly stain clothes.

Skincare products are known in solid form, so more easily transportable without risk of pouring. However, the majority of skincare products in solid form consist of anhydrous gels that do not contain water. These gels, on application, do not bring a fresh effect because there is no or little evaporation on the surface of the skin.

Examples of solid emulsions in the prior art relate in particular to products containing a high level of waxes or fillers. However, although waxes bring the viscosity to the emulsion, the transfer properties on the skin decrease sharply when the rate of these waxes increases. As a result, the cleansing ability of the product can decrease. In addition, the presence of waxes makes it difficult to remove the makeup remover when wiped or rinsed (poor rinsability). There remains therefore the need for a solid composition capable of removing make-up and / or cleansing of the skin, having at the same time the desired qualities of rigidity so that the solid composition does not break and the transfer properties are sufficient for the deposit of product on the skin allows a good make-up removal and / or cleaning.

The subject of the invention is precisely a makeup removal and / or cleaning composition for keratin materials such as the skin and / or the lips of the face and / or the integuments that make it possible to remedy these drawbacks. The applicant

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 envisaged the manufacture of a solid makeup remover composition, including a stick, with little or no charge, and giving a good makeup removal or skin cleansing while being fresh to the application.

 Surprisingly, the Applicant has found that the use of particular polymers made it possible to structure, even in the absence of conventional wax and filler, the liquid oily phases in the form of a stick whose application to the skin led to a deposit. not sticky and fresh.

By "oily phase", in the sense of the application, is meant a liquid fatty phase at ambient temperature (25 ° C.) and atmospheric pressure (760 mm).
Hg), composed of one or more fats liquid at room temperature, also called oils, compatible with each other. This fatty phase is macroscopically homogeneous.

 The invention applies to cleansing products and / or cleaning the skin, lips and / or integuments (eyelashes for example).

 More specifically, the subject of the invention is a solid composition in the form of a water-in-oil emulsion, comprising an aqueous phase dispersed in an oily phase, at least one emulsifier having an HLB value of 1 to 8, the oily phase containing at least one semicrystalline solid polymer at room temperature and having a melting temperature below 70 C comprising a) a polymer backbone and b) at least one crystallizable side organic chain and / or crystallizable organic block forming part of said polymeric backbone, said polymer having a number average molecular weight greater than 2,000.

 The solid composition according to the invention is intended for topical application, especially on the skin, lips or superficial body growths, it comprises a physiologically acceptable medium. The term "physiologically acceptable medium" means a non-toxic medium that can be applied to the skin (including the inside of the eyelids), the lips, the nails or the hair of human beings. The composition of the invention may constitute in particular a cosmetic or dermatological composition.

 For the purposes of the present invention, the term "solid composition" is intended to mean any composition which does not flow under its own weight and which has a hardness as defined below (shearing force of 100 to 350 gf).

 For the purposes of the invention, the term "semicrystalline polymer" is intended to mean polymers comprising a crystallizable part, pendant chain or sequence in the backbone, and an amorphous part in the backbone and having a reversible phase change temperature of the first order, in particular of fusion (solid-liquid transition). For the purposes of the invention, the term "polymers" means compounds comprising at least 2 repeating units, preferably at least 3 repeating units and more especially at least 10 repeating units. When the crystallizable part is a sequence of the polymeric backbone, this sequence

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 crystallizable is of a different chemical nature from that of the amorphous sequences; the semicrystalline polymer is in this case a sequenced polymer, for example of the diblock, triblock or multiblock type.

 Advantageously, the semi-crystalline polymer (s) of the composition of the invention have a number-average molecular mass Mn greater than or equal to 2000, for example ranging from 2,000 to 800,000, preferably from 3,000 to 500,000. for example, from 4,000 to 150,000, and more preferably from 4,000 to 99,000.

In the composition according to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase at at least 1% by weight, at a temperature above their melting temperature. Apart from crystallizable chains or blocks, the sequences of the polymers are amorphous. For the purposes of the invention, the term "chain or crystallizable block" means a chain or sequence which, if it were alone, would pass from the amorphous state to the crystalline state, in a reversible manner, depending on whether above or below the melting temperature. A chain within the meaning of the invention is a group of atoms, during or lateral to the backbone of the polymer. A sequence is a group of atoms belonging to the backbone, a group constituting one of the repeating units of the polymer.

Preferably, the polymer backbone of the semi-crystalline polymers is soluble in the oily phase.

pF telle que 25 C : : : ; pF 70 C et mieux 30 C : : : ; pF < 50 C. La température de fusion peut être mesurée notamment par toute méthode connue et en particulier avec un calorimètre à balayage différentiel (D. S. C). Preferably, the semi-crystalline polymers used in the composition of the invention have a melting temperature (or melting point) pF of less than 70 ° C., preferably less than 50 ° C., this temperature being at least equal to the temperature keratinous support to receive the composition according to the invention. The semi-crystalline polymer preferably has a melting temperature

pF such that C::; pF 70 C and better 30 C::; pF <50 C. The melting temperature can be measured in particular by any known method and in particular with a differential scanning calorimeter (DS C).

Preferably, the crystallizable sequences or chains of the semicrystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. The semicrystalline polymers of the invention with crystallizable sequences are polymers, sequenced or multiblocked. They can be obtained by reactive (or ethylenic) double bond monomer polymerization or by polycondensation. When the polymers of the invention are crystallizable side chain polymers, the latter are advantageously in random or statistical form.

Preferably, the semi-crystalline polymers of the invention are of synthetic origin. In addition, they do not have a polysaccharide backbone.

The semi-crystalline polymers that can be used in the invention are in particular: 1. Block copolymers of polyolefins with controlled crystallization, the monomers of which are described in document EP-A-951897;

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2. polycondensates and in particular polyester polycondensates, aliphatic or aromatic, and aliphatic / aromatic copolyesters; 3. the homo-or co-polymers carrying at least one crystallizable side chain and homo-or co-polymers carrying in the backbone at least one crystallizable block, such as those described in document US Pat.
5,156,911; 4. the homo-or co-polymers carrying at least one crystallizable side chain with fluorinated group (s), as described in WO-A-4.
01/19333; 5. and their mixtures.

 In the last two cases (3 and 4), the side chain or crystallizable sequences are hydrophobic.

 Crystalline polymers with crystallizable side chains or bearing in the backbone at least one crystallizable block are described below.

A) Crystallizable Side-chain Semi-Crystalline Polymers Particularly those defined in US-A-5,156, 911 and WO-A-01/19333 may be mentioned. These are homopolymers or copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers bearing hydrophobic side chain (s) (s) crystallizable (s).

où M représente un atome du squelette polymérique, S représente un espaceur These homo- or co-polymers are of any kind as long as they have the conditions indicated below with, in particular, the characteristic of being soluble or dispersible in the oily phase by heating above their melting point. pF. They can result from: - the radical polymerization of one or more monomers with double bond (s) reactive (s) or ethylenic vis-à-vis a polymerization, namely vinyl group, (meth) acrylic or allylic; polycondensation of one or more monomers bearing co-reactive groups (carboxylic or sulphonic acid, alcohol, amine or isocyanate), such as, for example, polyesters, polyurethanes, polyethers, polyureas or polyamides. a) In general, the crystallizable units (chains or sequences) of the semi-crystalline polymers according to the invention, come from monomer (s) with a sequence (s) or crystallizable chain (s), used (s) for the manufacture of semi-crystalline polymers. These polymers are chosen in particular from homopolymers and copolymers resulting from the polymerization of at least one crystallizable chain monomer (s) which may be represented by the formula X:

where M represents an atom of the polymer backbone, S represents a spacer

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 and C represents a crystallizable group.

The crystallizable -S-C chains may be aliphatic or aromatic, optionally fluorinated or perfluorinated. S represents in particular a linear or branched or cyclic (CH 2) n or (CH 2 CH 2 O) n or (CH 2 O) group, 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 are aliphatic chains (alkyl), they contain at least 11 carbon atoms and at most 40 carbon atoms and better still at most 24 carbon atoms. These include alkyl chains having at least 12 carbon atoms, and preferably they are alkyl chains having from 14 to 24 carbon atoms (CC).)) May be hydrocarbon alkyl chains ( carbon and hydrogen atoms) or fluorinated or perfluorinated alkyl chains (carbon atoms, and hydrogen and / or fluorine atoms). When it is fluorinated or perfluorinated alkyl chains, they comprise at least 11 carbon atoms of which at least 6 carbon atoms are fluorinated.

Examples of semicrystalline polymers or copolymers with crystallizable chain (s) include those resulting from the polymerization of at least one crystallizable chain monomer chosen from (C14) saturated alkyl (meth) acrylates. C24 (C14-C24 means that the alkyl group has from 14 to 24 carbon atoms); C -C perfluoroalkyl (meth) acrylates (alkyl group with 11 to 15 carbon atoms); C -C 24 N-alkyl (meth) acrylamides with or without fluorine atom (alkyl group with 14 to 24 carbon atoms); vinyl esters with alkyl or perfluoroalkyl (C to C24) chains (alkyl group with 14 to 24 carbon atoms), with a perfluoroalkyl chain containing at least 6 fluorine atoms; vinyl ethers with C14 to C24 alkyl chains or perfluoroalkyl (alkyl group with 14 to 24 carbon atoms), with a perfluoroalkyl chain having at least 6 fluorine atoms; C14-C24 alpha-olefins (alkyl group with 14 to 24 carbon atoms), such as, for example, octadecene; C14-C24 para-alkyl styrenes (alkyl group with 14 to 24 carbon atoms), and mixtures thereof.

For the purposes of the invention, the term "alkyl" means a saturated group in particular containing from 8 to 24 carbon atoms (Ce to C24), unless expressly mentioned.

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

When the polymers used in the composition of the invention are copolymers, they contain, in addition, from 0 to 50% of Y or Z groups resulting from the copolymerization: a) with Y which is a polar or non-polar monomer or a mixture of both:

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 When Y is a polar monomer, it is either a monomer carrying polyoxyalkylenated groups (especially oxyethylenated and / or oxypropylenated), a hydroxyalkyl (meth) acrylate such as hydroxyethyl acrylate, (meth) acrylamide, a N-alkyl (meth) acrylamide, an NN-dialkyl (meth) acrylamide, for example NN-diisopropylacrylamide or N-vinylpyrrolidone (NVP), N-vinyl-caprolactam, a monomer carrying at least one group carboxylic acid such as (meth) acrylic, crotonic, itaconic, maleic, fumaric or carboxylic acid anhydride groups such as maleic anhydride, and mixtures thereof.

When Y is a non-polar monomer, it may be a branched or cyclic linear alkyl (meth) acrylate ester, a vinyl ester, an alkyl vinyl ether, an alpha-olefin, styrene or styrene substituted with a alkyl group having 1 to 10 carbon atoms (C1 to C1), such as α-methylstyrene, a vinyl-unsaturated polyorganosiloxane macromonomer.

 ss) with Z which is a polar monomer or a mixture of polar monomers. Z has the same definition as the "polar Y" defined above.

Preferably, the semicrystalline crystallizable side chain polymers are chosen from homopolymers of alkyl (meth) acrylate or of alkyl (meth) acrylamide with an alkyl group as defined above, and in particular with C14-C24; copolymers of these monomers with a hydrophilic monomer preferably of a different nature from (meth) acrylic acid; and their mixtures. It may be, for example as copolymers, copolymers of alkyl (meth) acrylate or alkyl (meth) acrylamide with a C14 to C24 alkyl group, with N-vinylpyrrolidone, hydroxyethyl (meth) acrylate; or their mixtures.

B) Polymers carrying at least one crystallizable block in the backbone Again, they are polymers which are soluble or dispersible in the oily phase by heating above their melting point pF. These polymers are especially block copolymers consisting of at least 2 sequences of different chemical nature, one of which is crystallizable.

The following can be used: 1) Polymers defined in US-A-5, 156, 911; 2) block copolymers of olefin or cycloolefin with a crystallizable chain, such as those resulting from the sequential polymerization of: cyclobutene, cyclohexene, cyclooctene, norbornene (that is to say bicyclo (2,2, 1) heptene-2 ), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6-trimethyl norbornene, 5-ethylidene norbornene, 5-phenylnorbonene, 5-benzylnorbornene, 5-vinylnorbornene, 1.4, 5.8 1,2, 3,4, 4a, 5,8a-octahydronaphthalene, dicyclopentadiene, or mixtures thereof; with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, eicosene or their mixtures.

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These block copolymers may in particular be copoly (ethylene / norbornene) blocks and block terpolymers (ethylene / propylene / ethylidene norbornene).

It is also possible to use those resulting from the block copolymerization of at least 2 C 2 -C 16 and better still C 2 -C 12 α-olefins such as those mentioned above, and in particular block bipolymers of ethylene and octene.

3) The copolymers having at least one crystallizable block, the remainder of the copolymer being amorphous (at room temperature). These copolymers may, in addition, have two crystallizable blocks of different chemical nature.

The preferred copolymers are those which have both at room temperature, a crystallizable block and an amorphous sequence both hydrophobic and lipophilic distributed sequentially; for example, polymers having one of the crystallizable blocks and one of the following amorphous blocks: Sequence crystallizable by nature: a) polyester such as poly (alkylene terephthalate), b) polyolefin such as polyethylenes or polypropylenes.

. Amorphous and lipophilic sequence such as: amorphous polyolefins or copoly (olefins) such as poly (isobutylene), hydrogenated polybutadiene, hydrogenated poly (isoprene).

a) les copo ! ymères séquences po) y (e-capro) actone)-b-po) y (butadiène), utilisés de préférence hydrogénés, tels que ceux décrits dans l'article D6 "Melting behavior of poly (-caprolactone)-block-polybutadiène copolymers"de S. Nojima, Macromolécules, 32,3727-3734 (1999). As examples of such crystallizable block and amorphous block copolymers, mention may be made of:

a) copo! ymerized (po) y (e-capro) actone) -b-po) y (butadiene) sequences, preferably hydrogenated, such as those described in article D6 "Melting behavior of poly (-caprolactone) -block-polybutadiene copolymers "S. Nojima, Macromolecules, 32, 3727-3734 (1999).

hydrogénés séquencés ou multiséquencés, cités dans l'article D7"Study of morphological and mechanical properties of PP/PBT"de B. Boutevin et al., Polymer Bulletin, 34,117-123 (1995). y) les copolymères séquencés poly (éthylène)-b-copoly (éthylène/propylène) cités dans les articles D8 "Morphology of semi-crystalline block copolymers of ethylene- (ethylene-ait-propylene)" de P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) et D9 "Polymer agregates with crystalline cores : the system poly (ethylene)-poly (ethylene-propylene)" P. Richter et al., Macromolécules, 30, 1053-1068 (1997). â) les copolymères séquencés poly (éthylène)-b-poly (éthyléthylène) cités dans l'article général D10 "Cristallizatin in block copolymers" de I.W. Hamley, Advances in Polymer Science, vol 148,113-137 (1999). ss) poly (butylene terephthalate) -b-poly (isoprene) block copolymers

hydrogenated sequenced or multisequenced, cited in article D7 "Study of morphological and mechanical properties of PP / PBT" B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995). y) the poly (ethylene) -b-copoly (ethylene / propylene) block copolymers mentioned in articles D8 "Morphology of semi-crystalline block copolymers of ethylene- (ethylene-α-propylene)" by P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) and D9 "Polymer agglates with crystalline cores: the poly (ethylene) -poly (ethylene-propylene) system" P. Richter et al., Macromolecules, 30, 1053-1068 (1997) . a) the poly (ethylene) -b-poly (ethylethylene) block copolymers listed in the general article D10 "Crystallizatin in block copolymers" of IW Hamley, Advances in Polymer Science, vol 148, 113-137 (1999).

The semi-crystalline polymers of the composition of the invention may be uncrosslinked or partially crosslinked as long as the degree of crosslinking does not interfere with their dissolution or dispersion in the oily phase by heating above their melting point. It can then be a chemical crosslinking, by

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 reaction with a multifunctional monomer during the polymerization. It may also be a physical crosslinking which may then be due either to the establishment of hydrogen or dipolar type bonds between groups carried by the polymer, such as for example dipolar interactions between ionomers carboxylates, these interactions being weak. amount and carried by the polymer backbone; or at a phase separation between the crystallizable blocks and the amorphous blocks carried by the polymer.

Preferably, the semi-crystalline polymers of the composition according to the invention are uncrosslinked.

As a particular example of structuring semicrystalline polymer usable in the composition according to the invention, mention may be made of the Intelimer &commat; from Landec described in the brochure "Intelimer &commat; polymers". These polymers are in solid form at room temperature (25OC). They carry crystallizable side chains and have the above formula X. Mention may in particular be made of Landec IP22, having a melting temperature pF of 56 C, which is a viscous product at room temperature, impermeable, non-sticky.

It is also possible to use the semi-crystalline polymers described in Examples 3, 4,5, 7,9 of US-A-5,156,911, resulting from the copolymerization of acrylic acid and Cs alkyl (meth) acrylate. at C16 having a pF of from 20 ° C to 35 ° C, and more particularly those resulting from the copolymerization: of acrylic acid, hexadecylacrylate and isodecylacrylate in a 1/16/3 ratio, of acrylic acid and pentadecylacrylate in a 1/19 ratio, of acrylic acid, hexadecylacrylate, ethyl acrylate in a ratio of 2, 5/76, 5/20, acrylic acid, hexadecylacrylate and methylacrylate in a 5/85/10 ratio, of acrylic acid, polyoctadecylmethacrylate in a ratio of 2.5 / 97.5.

It is also possible to use the structure polymer marketed by National Starch, such as that described in US Pat. No. 5,736,125, of pF 44 C, as well as semi-crystalline crystalline pendant chain polymers containing fluorinated groups. as described in Examples 1,4, 6,7 and 8 of WO-A-01/19333.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of stearyl acrylate and acrylic acid or of NVP as described in document US Pat. No. 5,519,063 or EP-A-0550745, and more especially those described. in Examples 1 and 2, hereinafter, of polymer preparation, melting temperature of 400C and 38C, respectively.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of behenyl acrylate and acrylic acid or NVP, as described in documents US-A-5,519,063 and EP-A-0 550745, and especially those

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 described in Examples 3 and 4, below, of polymer preparation, melting temperature respectively of 600C and 58 C.

Preferably, the semi-crystalline polymers do not contain a carboxylic group.

According to a preferred embodiment of the invention, the composition comprises at least two semi-crystalline polymers, that is to say at least one semicrystalline polymer having a pF ranging from 500 to 700 ° C. and at least one semi-crystalline polymer. having a pF of 250C to 50C and better still of 300 to 500C.

The total amount of semi-crystalline polymer is chosen according to the hardness of the desired composition and depending on the particular application envisaged. This hardness is such that the composition is self-supporting, that is to say that it supports itself while remaining in its solid form (for example stick) and it does not sag under its weight as do the creams or liquids, and that it can disintegrate easily to form a satisfactory deposit on the skin and lips. The hardness of the sticks obtained is measured at 200 ° C. by means of a DFGHS 2 dynanometer of INDELCO-CHATILLON company moving at a speed of 100 mm / minute. This hardness is expressed as the shear force (expressed in gram force, gf) required to cut a 12.7 mm diameter stick under these conditions. In the present application, the shearing force of the composition is preferably from 100 to 350 g, more preferably from 120 to 250 g, and most preferably from 150 to 220 g.

In practice, the total amount of semicrystalline polymer represents from 0.1 to 50% by weight of active material relative to the total weight of the composition, preferably from 1 to 40% by weight and better still from 5 to 20% by weight. of active material relative to the total weight of the composition. Preferably, the polymer represents more than 10% by weight of active material relative to the total weight of the composition of the composition.

Advantageously, the weight ratio of semicrystalline polymer relative to the oily phase is from 0.20 to 0.60 and better still from 0.25 to 0.50, to obtain a hard stick which disintegrates in contact with the skin or lips and in particular hardness ranging from 100 to 350 gf.

The oily phase structured by the semi-crystalline polymer constitutes the continuous phase of the W / O emulsion. It may be present in an amount ranging for example from 10 to 95% by weight, preferably from 20 to 80% by weight and better still from 30 to 70% by weight relative to the total weight of the composition.

This oily phase contains at least one oil, and it may contain several oils and possibly other fatty substances.

Preferably, the oily phase of the composition according to the invention contains at least one cleansing oil and in particular an oil chosen from fatty acid esters comprising at least 12 carbon atoms.

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The fatty acid esters having at least 12 carbon atoms are preferably obtained from a straight or branched chain alcohol having from 1 to 17 carbon atoms and a straight or branched chain fatty acid comprising at least 12 carbon atoms and preferably from 14 to 22 carbon atoms. It is preferably mono-or di-esters.

Preferably, the makeup-removing oil is chosen from the group of esters which contain no unsaturation and / or no ether or hydroxyl group. Even more advantageously, the makeup removal oil is a saturated ester which contains no ether or hydroxyl group.

Thus, the cleansing oil used in the composition according to the invention may be chosen in particular from the group comprising 2-ethylhexyl palmitate (or octyl palmitate), 2-ethylhexyl myristate (or myristate). of octyl), isopropyl palmitate, isopropyl myristate, di-isopropyl adipate, di-octyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, methyl myristate, octyldodecyl octanoate, isodecyl neopentanoate, ethyl myristate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate , 2-ethylhexyl caprate / caprylate, methyl palmitate, butyl myristate, isobutyl myristate, ethyl palmitate, isohexyl laurate, hexyl laurate, isostearate, isopropyl, and mixtures thereof.

The amount of cleansing oil (s) may be all or part of the oil phase oil. It preferably constitutes at least 10% by weight relative to the total weight of the composition. This amount may range, for example, from 10 to 95%, preferably from 10 to 80% by weight and better still from 10 to 60% by weight relative to the total weight of the composition.

The oily phase may also contain one or more oils other than the fatty esters indicated above, and in particular animal, vegetable, mineral, silicone, fluorinated and / or synthetic oil oils.

Other components of the oil phase that may be mentioned include paraffin oil, liquid petroleum jelly, perhydrosqualene, vegetable oils (sweet almond, palm oil, castor oil, avocado oil, jojoba oil, apricot kernels), nonvolatile silicone oils such as polydimethylsiloxanes, optionally phenylated such as phenyltrimethicones, volatile silicone oils such as cyclomethicones, straight or branched chain hydrocarbon oils, synthetic oils such as polyisobutene hydrogenated (Parteam oil &commat;), fluorinated oils and their mixtures.

As branched chain hydrocarbon oils, there may be mentioned in particular those comprising from 10 to 20 carbon atoms, and for example isohexadecane, isododecane, isoparaffins and mixtures thereof.

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 As volatile silicone oils, mention may in particular be made of cyclodimethylsiloxanes such as cyclohexadimethylsiloxane (or cyclohexamethicone) and cyclopentadimethylsiloxane (or cyclopentamethicone) and their mixtures.

The oily phase may also contain one or more other fatty substances such as, for example, fatty acids, fatty alcohols, waxes and mixtures thereof.

It is also possible to use in the composition of the invention at least one wax such as those used up to now in cosmetics.

à température ambiante (25 C) et pression atmosphérique (760 mm de Hg), à changement d'état solide/liquide réversible, ayant une température de fusion supérieure à 40 C et mieux supérieure à 50 C, pouvant aller jusqu'à 200 C, et présentant à l'état solide une organisation cristalline anisotrope. A wax, within the meaning of the present invention, is a lipophilic, solid fatty compound

at room temperature (25 ° C.) and at atmospheric pressure (760 mmHg), with reversible solid / liquid state change, having a melting temperature of greater than 40 ° C. and better still greater than 50 ° C., up to 200 ° C. and having in the solid state an anisotropic crystalline organization.

The conventional waxes, in the sense of the demand, are those generally used in the cosmetic and dermatological fields; they are notably of natural origin, such as beeswax, Candelilla, Ouricoury, Japan, cork or sugar cane fibers, paraffin waxes, lignite waxes, microcrystalline waxes with a melting point> 500C, lanolin wax, Montan wax, ozokerites, hydrogenated oils such as hydrogenated jojoba oil (CTFA name: hydrogenated jojoba oil), but also waxes of synthetic origin such as polyethylene waxes derived from polymerization of ethylene, waxes obtained by Fischer-Tropsch synthesis with melting point> 500C, fatty acid esters and glycerides at 500C, silicone waxes such as alkyl, alkoxy and / or poly esters (di) methylsiloxane solid at 50 C.

It is possible to use, for example, as wax, a polyethylene wax such as that marketed under the name PERFOMALENE 655 by the company New Phase Technologies, which has a melting point of 93 ° C., and the hydrogenated jojoba oil marketed by Desert Whale, which has a melting point of 700C.

According to a particular embodiment of the invention, the composition contains at least one wax chosen from polyethylene waxes, hydrogenated jojoba waxes and mixtures thereof.

The emulsifier of the composition according to the invention has a value of HLB (hydrophilic-lipophilic balance) ranging from 1 to 8. The emulsifier may be chosen in particular from silicone emulsifiers, alkylpolyglycosides and mixtures thereof.

As silicone emulsifiers that can be used in the composition according to the invention, mention may be made, for example, of dimethicone copolyols and alkyl dimethicone copolyols. As dimethicone copolyol, there may be mentioned for example the mixture of dimethicone copolyol and dimethicone (polydimethylsiloxane) (10/90) marketed by Dow Corning under the name DC3225C. According to a preferred embodiment of the invention, use is made of

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 silicone emulsifier, an alkyl dimethicone copolyol having an alkyl radical containing from 10 to 22 carbon atoms, such as cetyl dimethicone copolyol, for instance the product sold under the name Abil EM-90 by the company Goldschmidt and such as the cetyl dimethicone copolyol mixture; of polyglycerol isostearate (4 moles) and hexyl laurate, sold under the name ABIL WE 09 by the company Goldschmidt; lauryl dimethicone copolyol and for example the mixture of about 91% lauryl dimethicone copolyol and about 9% isostearyl alcohol, sold under the name Q2-5200 by Dow Corning, and mixtures thereof.

One or more coemulsifiers may also be added, which advantageously may be selected from the group consisting of alkylated polyol esters. As alkylated esters of polyol, mention may in particular be made of glycerol and / or sorbitan esters and for example polyglyceryl isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt, sorbitan isostearate, such as the product sold under the name Arlacel 987 by ICI, sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

The emulsifier may also be chosen from alkylpolyglycosides having an HLB of less than 7 and preferably less than or equal to 5, for example those represented by the following general formula (1): -O- (G) x (1) in which R represents a branched and / or unsaturated alkyl radical containing from 14 to 24 carbon atoms, G represents a reduced sugar containing from 5 to 6 carbon atoms, and x represents a value ranging from 1 to 10 and preferably from 1 to 4, and G denotes, in particular, glucose, fructose or galactose.

The unsaturated alkyl radical may comprise one or more ethylenic unsaturations, and in particular one or two ethylenic unsaturations.

As alkylpolyglycosides of this type, there may be mentioned alkylpolyglucosides (G = glucose in formula (1)) and in particular those of formula (1) in which R represents more particularly an oleyl radical (unsaturated C18 radical) or isostearyl radical (saturated radical at C18), G denotes glucose, x is a value ranging from 1 to 2, especially isostearyl glucoside, oleyl glucoside and mixtures thereof.

This alkylpolyglucoside may be used in admixture with a co-emulsifier, more particularly with a fatty alcohol and in particular a fatty alcohol having the same fatty chain as that of the alkylpolyglucoside, that is to say comprising from 14 to 24 carbon atoms. carbon and having a branched and / or unsaturated chain, and for example isostearyl alcohol when the alkylpolyglucoside is isostearylglucoside, and oleyl alcohol when the alkylpolyglucoside is oleylglucoside, optionally in the form of a composition self-emulsifying, as described for example in WO-A-92/06778. In particular, it is possible to use

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 mixture of isostearyl glucoside and isostearyl alcohol (15/85) sold by the company SEPPIC under the name MONTANOV WO 18.

The emulsifier is preferably used in an amount of active material ranging for example from 0.1 to 20% and preferably from 0.5 to 10% by weight relative to the total weight of the composition.

The aqueous phase of the composition of the invention generally represents from 5 to 90% by weight and preferably from 20 to 60% by weight relative to the total weight of the composition. It may contain, in addition to water, solvents such as primary alcohols having 1 to 6 carbon atoms such as ethanol, or polyols such as butylene glycol, glycerine, sorbitol, hexylene glycol and the like. isoprene glycol, or sugars such as glucose, fructose. The solvent or solvents may be present in an amount ranging from 0.1 to 30% by weight relative to the total weight of the composition.

The composition of the invention may furthermore comprise any additive usually used in the field in question, chosen from thickeners or gelling agents, dyestuffs, antioxidants, essential oils, preservatives, perfumes, fillers and dispersants. , neutralizers, lipophilic or hydrophilic active agents, and mixtures thereof. These additives may be present in the composition according to the amounts generally used in the cosmetic and dermatological field and in particular in a proportion of from 0.01 to 50% of the total weight of the composition and better still from 0.1 to 20%.

les sphingolipides et céramides ; les composés auto-bronzants tels que la DHA (dihydroxyacétone) ; les filtres solaires comme par exemple l'octylméthoxycinnamate (Parsol MCX), la 3-benzophénone (Uvinul M40), le butylméthoxydibenzoyl-méthane (Parsol 1789) ; l'urée ; les dépigmentants tels que l'acide kojique et l'acide caféique ; les bêta-hydroxyacides tels que l'acide salicylique et ses dérivés ; les alpha-hydroxyacides tels que l'acide lactique, l'acide citrique et l'acide glycolique ; les rétinoïdes tels que le rétinol et ses esters comme le palmitat ou l'acétate de rétinyle, le rétinal, les caroténoïdes ; et leurs mélanges. Examples of active ingredients that may be mentioned include moisturizers and, for example, hydrolysas of proteins and polyols such as glycerine, glycols such as polyethylene glycols, and sugar derivatives; natural extracts; procyannidol oligomers; vitamins such as vitamin E (tocopherol) and its derivatives (for example acetate), vitamin A (retinol) and its derivatives (for example retinyl palmitate), vitamin C (ascorbic acid) and its derivatives (for example palmitate) ascorbyl), the derivatives of these vitamins being in particular esters including palmitate and acetate; essential fatty acids;

sphingolipids and ceramides; self-tanning compounds such as DHA (dihydroxyacetone); sunscreens such as, for example, octyl methoxycinnamate (Parsol MCX), 3-benzophenone (Uvinul M40), butylmethoxydibenzoylmethane (Parsol 1789); urea; depigmenting agents such as kojic acid and caffeic acid; beta-hydroxy acids such as salicylic acid and its derivatives; alpha-hydroxy acids such as lactic acid, citric acid and glycolic acid; retinoids such as retinol and its esters such as palmitate or retinyl acetate, retinal, carotenoids; and their mixtures.

As gelling agents, it is possible to use in particular hydrophilic gelling agents such as carboxyvinyl polymers, such as carbomers; polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally cross-linked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by the company Cariant under the

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dénomination commerciale Hostacerin AMPS (nom CTFA : ammonium polyacryldimethyltauramide) ; ou le copolymère acrylamide lacrylamido-2methylpropane sulfonate de sodium en émulsion inverse à 40 % dans le polysorbate, commercialisé sous la dénomination SIMULGEL 600 par la société SEPPIC ; les polysaccharides tels que la gomme de xanthane ; et leurs mélanges.

trademark Hostacerin AMPS (CTFA name: ammonium polyacryldimethyltauramide); or the acrylamide acrylamide-2-methylpropanesulphonate copolymer in 40% inverse emulsion in polysorbate, sold under the name SIMULGEL 600 by the company SEPPIC; polysaccharides such as xanthan gum; and their mixtures.

These gelling agents, when present, are generally used at concentrations ranging from 0.05 to 7% and preferably from 0.1 to 5% by weight of active material relative to the total weight of the composition.

par la société Matsumoto ; les poudres de matériaux organiques naturels tels que les poudres d'amidon, notamment d'amidons de maïs, de blé ou de riz, réticulés ou non, telles que les poudres d'amidon réticulé par l'anhydride octénylsuccinate, commercialisées sous la dénomination DRY-FLO par la société National Starch ; les microbilles de résine de silicone telles que celles commercialisées sous la dénomination TOSPEARL par la société Toshiba Silicone, notamment TOSPEARL 240 ; la silice ; les oxydes métalliques tels que le dioxyde de titane ou l'oxyde de zinc ; le mica ; et leurs mélanges. La quantité de charge (s) peut aller par exemple de 0,05 à 20 % en poids et mieux 0,1 à 10 % en poids par rapport au poids total de la composition. As fillers, mention may be made, for example, of polyamide (nylon) particles and in particular those sold under the names ORGASOL by the company Atochem; polyethylene powders; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate / lauryl methacrylate copolymer sold by Dow Corning under the name Polytrap; polymethyl methacrylate microspheres, sold under the name MICROSPHERE M-100 by the company Matsumoto or under the name COVABEAD LH85 by the company Wackherr; ethylene-acrylate copolymer powders, such as those sold under the name FLOBEADS by Sumitomo Seika Chemicals; expanded powders such as hollow microspheres and in particular microspheres formed of a terpolymer of vinylidene chloride, acrylonitrile and methacrylate and sold under the name Expancel by the company Kemanord Plast under the references 551 DE 12 (particle size distribution). about 12 μm and density 40 kg / m 3), 551 DE (particle size about 30 μm and density 65 kg / m 3), 551 DE 50 (particle size about 40 μm), or the microspheres marketed under the name MICROPEARL F 80 ED

by the company Matsumoto; powders of natural organic materials such as starch powders, especially corn starch, wheat or rice, crosslinked or otherwise, such as starch powders crosslinked with octenylsuccinate anhydride, sold under the name DRY -FLO by the company National Starch; silicone resin microbeads such as those sold under the name Tospearl by the company Toshiba Silicone, in particular Tospearl 240; silica; metal oxides such as titanium dioxide or zinc oxide; mica; and their mixtures. The amount of filler (s) may range, for example, from 0.05 to 20% by weight and better still from 0.1 to 10% by weight relative to the total weight of the composition.

Of course, those skilled in the art will take care to choose the possible additional additives and / or their quantity in such a way that the advantageous properties of the composition according to the invention, namely in particular solidity of the stick, non-sticking, good transfer and good make-up removal, are not or not substantially impaired by the proposed addition.

The composition according to the invention can be manufactured by known methods, generally used in the cosmetic or dermatological field. It can be manufactured by the process of heating the polymer at least to its

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 melting temperature, to add the emulsifier (s) and other components of the oil phase, to prepare the aqueous phase at a temperature above the melting point (pF) of the polymer used in the oily phase, and to introduce the aqueous phase into the oily phase with stirring, then pouring the resulting mixture into a suitable mold such as a stick mold or directly into the packaging articles (housing or cup in particular).

 Advantageously, the composition of the invention constitutes a make-up removal or cleaning composition for the skin, lips and integuments, which can be in the form of a stick (or stick) or in cast form. It is able to remove make-up or clean the skin, lips or dander of human beings.

 The invention also relates to a cosmetic process for removing makeup or cleaning the skin, lips and integuments, comprising applying to the skin, the lips or integuments, the particular cosmetic composition as defined above.

The subject of the invention is also the use of at least one solid semi-crystalline polymer at ambient temperature and having a melting point of less than
70 C, comprising a) a polymer backbone and b) at least one crystallizable side organic chain and / or a crystallizable organic block forming part of the backbone of said polymer, said polymer having a number average molecular weight greater than or equal to 2000, in an W / O emulsion comprising an aqueous phase dispersed in an oily phase, as an agent for structuring the continuous oily phase and obtaining a solid with a hardness ranging from 100 to 350 gf.

 The invention is illustrated in more detail in the following examples. Quantities are given as a percentage by mass.

1) Examples of manufacture of semi-crystalline polymers
EXAMPLE 1 Acid Polymer with a Melting Point of 40 ° C.
In an 11 reactor equipped with a central stirrer with anchor, a condenser and a thermometer, 120 g of oil of Parleam oil are introduced. (mineral oil) which is heated from room temperature to 80 C in 45 minutes. At 80 ° C., the following mixture C1 is introduced in 2 hours:
40 g of cyclohexane + 4 g of Triganox 141 [2,5 bis (2-ethyl hexanoyl peroxy) -2,5-dimethylhexane].

30 min after the start of the casting of the mixture C1, is introduced in 1 h30 the mixture C2 consisting of:
190 g of stearyl acrylate + 10 g of acrylic acid + 400 g of cyclohexane.

 At the end of the two flows, the mixture is allowed to act for a further 3 hours at 80 ° C. and then the entire cyclohexane present in the reaction medium is distilled at atmospheric pressure.

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 The polymer with 60% by weight of active material in Par oil is then obtained! ASM &commat;.

Its weight average molecular weight Mw is 35,000 expressed in polystyrene equivalent and its melting temperature pF is 400C IIC, measured by D. S. C.

Example 2: Basic polymer with a melting point of 38 ° C. The same procedure as in Example 1 is applied except that N-vinyl pyrrolidone is used instead of acrylic acid.

The polymer obtained is 60% by weight of active material in Parleam® oil (S), its weight average molecular weight Mw is 38,000 and its mp 38 C.

EXAMPLE 3 Polymer Acid with a Melting Point of 600 ° C. The same procedure as in Example 1 is applied, except that behenyl acrylate is used in place of stearyl acrylate. The polymer obtained is 60% by weight of active ingredient in Parleam® oil (D. Its weight average molecular weight Mw is 42,000 and its mp 60 C.

Example 4: Basic polymer with a melting point of 58 ° C. The same procedure as in Example 2 is applied except that behenyl acrylate is used in place of stearyl acrylate. The polymer obtained is 60% by weight of active ingredient in Parleam® oil. His Mw is 45,000 and his pF is 58 C.

 H) Examples of composition Example 5: makeup remover stick Oily phase Stearyl acrylate / acrylic acid copolymer with 60% of active ingredient in Parleam oil according to Example 1 12% Copolymer of behenyl acrylate / acrylic acid at 60% of material active ingredient in Parleamam oil according to Example 3 10% Isopropyl palmitate 45% Cetyl dimethicone copolyol mixture, polyglycerol isostearate (4 moles), hexyl laurate (ABIL WE 09 from Goldschmidt) 5%

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 Water phase Glycerine 5% Magnesium sulphate 0.7% Preservatives 0.8% Demineralized water qs 100% Procedure: the oil phase is heated to 80 ° C. The aqueous phase is prepared at 80 ° C. and the aqueous phase is added with stirring. in the oily phase.

We obtain a homogeneous stick, with a melting touch, which spreads well and is not sticky. This stick ensures a good make-up removal of the skin.

EXAMPLE 6 Cleaning Stick Oil Phase Stearyl acrylate / acrylic acid copolymer with 60% active ingredient in Parleam oil according to Example 1 12% Copolymer behenyl acrylate / acrylic acid at 60% active ingredient in oil of Parleam by Example 3 10% Isoparaffin 15% Isopropyl palmitate 45% Cetyl dimethicone copolyol mixture, polyglycerol isostearate (4 moles), hexyl laurate (ABIL WE 09 from Goldschmidt) 5% Acrylate copolymer (EXPANCEL 551 DE 20D60 from Expancel) 0.8% Aqueous phase Glycerine 5% Magnesium sulphate 0.7% Preservatives 0.8% Demineralized water qs 100% Procedure: the oily phase is heated to 80 ° C. The aqueous phase is prepared at 800C and the aqueous phase is added with stirring to the oily phase.

A homogeneous stick with a soft, soft, slippery and non-sticky feel is obtained. This stick makes it possible to obtain a cleansing of the skin effective and soft.

Example 7: makeup remover stick Oily phase Hydrogenated jojoba oil from the company

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 Desert Whale (melting point 70 ° C.) 5% polyethylene wax (PERFOMALENE 655 1% copolymer of behenyl acrylate / acrylic acid with 60% of active ingredient in Parleam® according to example 3 8% mixture of cetyl dimethicone copolyol, isostearate polyglycerol (4 moles), hexyl laurate (ABIL WE 09 from Goldschmidt) 5% isopropyl palmitate 45% nylon-12 (ORGASOL 2002 EXD NAT COS from Atochem) 1.5% aqueous phase Glycerine 5% magnesium sulphate 0.7% Preservatives 0.8% Demineralized water qs 100% Procedure: the oil phase is heated to 80 ° C. The aqueous phase is prepared at 800 ° C. and the aqueous phase is added with stirring to the oily phase.

We obtain a homogeneous stick of rich texture, soft to the application and ensuring a good make-up removal of the skin.

EXAMPLE 8 Cleaning Stick Oil Phase Hydrogenated Jojoba Oil from Desert Whale (Melting Point 700C) 5% Polyethylene Wax (PERFOMALENE 655 1% Copolymer Behenyl Acrylate / Acrylic Acid with 60% Active Ingredient in Parleam According to Example 3 8% Mixture of cetyl dimethicone copolyol, isostearate polyglycerol (4 moles), hexyl laurate (ABIL WE 09 from Goldschmidt) 5% Palmitat isopropyl 39% silicone oil (DC 200 FLUID - 5 CST from the company Dow Corning) 5% Apricot oil 1% Nylon-12 (ORGASOL 2002 EXD NAT COS from Atochem) 1.5% Water phase Glycerine 5% Magnesium sulphate 0.7% Preservatives 0.8% Demineralized water qs 100 %

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 Procedure: The oil phase is heated to 80 ° C. The aqueous phase is prepared at 80 ° C. and the aqueous phase is added with stirring to the oily phase.

We obtain a homogeneous stick having a rich and melting texture, very comfortable to the application and to obtain a make-up removal of the skin, soft and effective.

EXAMPLE 9 Bi-gel makeup remover stick Oily phase Stearyl acrylate / acrylic acid copolymer with 60% active ingredient in Parleam oil according to Example 1 12% Behenyl acrylate / acrylic acid copolymer containing 60% of active ingredient in Parleamam oil according to Example 3 10% Isopropyl palmitate 45% Cetyl dimethicone copolyol mixture, isostearate polyglycerol (4 moles), hexyl laurate (ABIL WE 09 from Goldschmidt) 5% Nylon-12 ( ORGASOL 2002 EXD NAT COS from Atochem) 1.5% Aqueous phase Glycerin 5% Ammonium polyacryloyldimethyl tau spleen (HOSTACER1N AMPS) 0.5% Preservatives 0.8% Demineralized water qs 100% Operating mode: the oil phase is heated to C. The aqueous phase is prepared at 80 ° C. and the aqueous phase is added with stirring to the oily phase.

We obtain a homogeneous stick of melting and fresh texture at the same time, which ensures a good make-up removal of the skin.

Claims (28)

 1. A solid composition in the form of a water-in-oil emulsion, comprising an aqueous phase dispersed in an oily phase, at least one emulsifier having an HLB value of 1 to 8, the oily phase containing at least one semi-synthetic polymer. crystalline solid at room temperature and having a melting temperature of less than 70 ° C, comprising a) a polymer backbone and b) at least one crystallizable side organic chain and / or a crystallizable organic block forming part of said polymer backbone, said polymer having an average molecular weight in excess of 2,000. 2. Composition according to claim 1, characterized in that it has a shear force of 100 to 350 gf. 3. Composition according to claim 1 or 2, characterized in that the polymer has a number average molecular weight ranging from 3,000 to 500,000 and preferably from 4,000 to 99,000. 4. Composition according to any one of the preceding claims, characterized in that the polymer is soluble in the oily phase to at least 1% by weight at a temperature above its melting point. 5. Composition according to any one of the preceding claims, characterized in that the polymer has a melting temperature pF such that C <pF <70 C and preferably such as C:; pF <50C. 6. Composition according to any one of the preceding claims, characterized in that the polymer is chosen from: - block copolymers of polyolefins with controlled crystallization, - aliphatic or aromatic polyester polycondensates and aliphatic / aromatic copolyesters, - homo- or co-polymers carrying at least one crystallizable side chain, and homo-or co-polymers carrying in the skeleton at least one crystallizable block, homo-or co-po! ymers carrying at least one crystallizable side chain with fluorinated group (s), and mixtures thereof. 7. Composition according to any one of the preceding claims, characterized in that the polymer is chosen from homopolymers and copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers carrying chain ( s) Hydrophobic lateral (s) crystallizable (s). 8. Composition according to any one of the preceding claims, characterized in that the polymer is chosen from homopolymers and copolymers resulting from the polymerization of at least one crystallizable chain monomer (s) of formula X: <Desc / Clms Page number 21>  where M represents an atom of the polymer backbone, S represents a spacer and C represents a crystallizable group.

9. Composition according to any one of the preceding claims, characterized in that the polymer is chosen from homopolymers and copolymers resulting from the polymerization of at least one crystallizable chain monomer chosen from saturated alkyl (meth) acrylates. C14-C24, C11-C15 perfluoroalkyl (meth) acrylates, C14-C24 N alkyl (meth) acrylamides with or without fluorine atom, C14-C24 alkyl chain or perfluoroalkyl vinyl esters, vinyl ethers with C14-C24 alkyl or perfluoroalkyl chains, C14-C24 alpha-olefins, para-alkyl styrenes with an alkyl group having from 14 to 24 carbon atoms, and mixtures thereof. 10. Composition according to any one of the preceding claims, characterized in that the polymer is chosen from homopolymers of alkyl (meth) acrylate or alkyl (meth) acrylamide C14 to C24; copolymers of these monomers with a hydrophilic monomer; and their mixtures. 11. Composition according to any one of the preceding claims, characterized in that the polymer is chosen from copolymers of alkyl (meth) acrylate or alkyl (meth) acrylamide with a C14 to C24 alkyl group, with N vinylpyrrolidone, hydroxymethyl (meth) acrylate; or their mixtures.

 1 12. Composition according to any one of the preceding claims, characterized in that it comprises at least one semicrystalline polymer having a melting temperature ranging from 50 to 700 ° C. and at least one semicrystalline polymer having a melting point ranging from at 50 C. 13. Composition according to any one of the preceding claims, characterized in that the polymer represents from 0.1 to 50% by weight of active material, and preferably from 1 to 40% by weight of active ingredient relative to the total weight. of the composition. 14. Composition according to any one of the preceding claims, characterized in that the oily phase represents from 10 to 95% by weight and preferably from 20 to 80% by weight relative to the total weight of the composition. 15. Composition according to any one of the preceding claims, characterized in that the oily phase contains at least one oil selected from fatty acid esters having at least 12 carbon atoms. <Desc / Clms Page number 22> 16. Composition according to the preceding claim, characterized in that the oil is chosen from the group comprising 2-ethylhexyl palmitate, 2-ethylhexyl myristate, isopropyl palmitate and isopropyl myristate. , di-isopropyl adipate, di-octyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, methyl myristate, octyldodecyl octanoate, isodecyl neopentanoate , ethyl myristate, myristyl propionate, 2-ethylhexyl 2-hexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprate / caprylate, methyl palmitate , butyl myristate, isobutyl myristate, ethyl palmitate, isohexyl laurate, hexyl laurate, isopropyl isostearate, and mixtures thereof. 17. Composition according to any one of the preceding claims, characterized in that the oily phase additionally contains one or more oils chosen from paraffin oil, liquid petroleum jelly, perhydrosqualene,

 vegetable oils, non-volatile silicone oils, volatile silicone oils, straight or branched chain hydrocarbon oils, synthetic oils, fluorinated oils and mixtures thereof. 18. Composition according to any one of the preceding claims, characterized in that the oily phase further contains one or more fatty substances chosen from fatty acids, fatty alcohols, waxes and mixtures thereof. 19. Composition according to the preceding claim, characterized in that the wax is chosen from polyethylene waxes, hydrogenated jojoba waxes and mixtures thereof. 20. Composition according to any one of the preceding claims, characterized in that the emulsifier is chosen from silicone emulsifiers, alkylpolyglycosides and mixtures thereof. 21. Composition according to the preceding claim, characterized in that the emulsifier is a silicone emulsifier selected from dimethicone copolyols and alkyl dimethicone copolyols. 22. Composition according to Claim 20, characterized in that the emulsifier is chosen from alkylpolyglycosides represented by the following general formula (1): RO - (G), (1) wherein R represents a branched and / or unsaturated alkyl radical having from 14 to 24 carbon atoms, G represents a reduced sugar containing from 5 to 6 carbon atoms, x denotes a value ranging from from 1 to 10, and G denotes glucose, fructose or galactose. 23. Composition according to any one of the preceding claims, characterized in that the emulsifier is present in an amount of <Desc / Clms Page number 23>  active compound ranging from 0.1 to 20% by weight and preferably from 0.5 to 10% by weight relative to the total weight of the composition. 24. Composition according to any one of the preceding claims, characterized in that it comprises at least one filler. 25. Composition according to any one of the preceding claims, characterized in that it constitutes a make-up removing composition and / or cleaning the skin, lips and / or integuments. 26. Composition according to any one of the preceding claims, characterized in that it is in stick form or in cast form. 27. A cosmetic process for removing makeup or cleaning the skin, lips and superficial body growths, comprising applying to the skin, the lips or the integuments, a cosmetic composition according to any one of the preceding claims. 28. Use of at least one semi-crystalline solid polymer at ambient temperature and having a melting point of less than 70 ° C., comprising a) a polymer backbone and b) at least one crystallizable lateral organic chain and / or crystallizable organic block forming part of the backbone of said polymer, said polymer having a number average molecular weight greater than or equal to 2,000, in an W / O emulsion comprising an aqueous phase dispersed in an oily phase, as an agent for structuring the continuous oily phase and obtaining a solid hardness ranging from 100 to 350 gf.