EP1469815A1 - Composition containing a semi-crystalline polymer and an ester - Google Patents

Composition containing a semi-crystalline polymer and an ester

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Publication number
EP1469815A1
EP1469815A1 EP20020795370 EP02795370A EP1469815A1 EP 1469815 A1 EP1469815 A1 EP 1469815A1 EP 20020795370 EP20020795370 EP 20020795370 EP 02795370 A EP02795370 A EP 02795370A EP 1469815 A1 EP1469815 A1 EP 1469815A1
Authority
EP
European Patent Office
Prior art keywords
semi
composition according
composition
polymer
crystalline polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20020795370
Other languages
German (de)
French (fr)
Inventor
Véronique Ferrari
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR0200885A external-priority patent/FR2834888B1/en
Application filed by LOreal SA filed Critical LOreal SA
Publication of EP1469815A1 publication Critical patent/EP1469815A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06—Lipsticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

  • the present invention relates to a composition, in particular a cosmetic composition, containing at least one semi-crystalline polymer and one ester which is in particular in the form of a stick which slips when applied and leads to a shiny and comfortable deposit.
  • Cosmetic compositions the fatty phase of which is gelled by semi-crystalline polymers, have been described in application FR 0106047 not yet published.
  • the lipstick formulas resulting from these inventions are in the form of a stick which deposits a shiny, non-sticky and covering film. These compositions however have the drawback of not depositing easily when they are applied to keratin materials.
  • the present invention therefore aims to provide a composition comprising a liquid fatty phase structured by a semi-crystalline polymer with solid organic structure at room temperature, the deposition on the skin or the lips is shiny and comfortable and easy to deposit.
  • the invention applies in particular to makeup products for the lips but also for the eyes, such as the eyeliners, in particular in the form of a pencil, and the mascaras, in particular in the form of bread, or of the skin, such as foundations.
  • the subject of the invention is a makeup composition
  • a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, the melting point of which is greater than or equal to 30 ° C., b) a coloring matter and c) an ester comprising 10 to 40 carbon atoms, the liquid fatty phase, the coloring matter, the ester and the polymer forming a physiologically acceptable medium.
  • the melting temperature of the semi-crystalline polymer is preferably less than 150 ° C.
  • composition of the invention can be in the form of a paste, a solid, a cream. It can be an oil-in-water or water-in-oil emulsion, an anhydrous, solid or flexible gel. Preferably, it is in anhydrous form, and more especially in the form of an anhydrous gel, in particular poured in a stick or in a dish.
  • crystallizable part is either a side chain (or pendant chain) or a sequence in the skeleton.
  • polymers in the sense of the invention compounds comprising at least 2 repeating units, preferably at least 3 repeating units and more especially at least 10 repeating units.
  • the crystallizable part is a sequence of the polymer backbone, this crystallizable sequence is of a chemical nature different from that of the amorphous sequences; the semi-crystalline polymer is in this case a block copolymer, for example of the diblock, triblock or multiblock type.
  • the semi-crystalline polymer can be a homopolymer or a copolymer.
  • organic compound or “with organic structure” is meant compounds containing carbon atoms and hydrogen atoms and optionally heteroatoms such as S, O, N, P alone or in combination.
  • the semi-crystalline polymer or polymers of the composition of the invention comprise a weight-average molecular mass Mp ranging from 5,000 to 1,000,000, preferably from 10,000 to 800,000, preferably from 15,000 to 500 000.
  • the semi-crystalline polymer (s) according to the invention serving as a structuring agent are solids at ambient temperature (25 ° C) and atmospheric pressure (760 mm Hg), the melting point is greater than or equal to 30 ° C.
  • the melting point values correspond to the melting point measured using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name DSC 30 by the company METTLER, with a rise in temperature of 5 or 10 ° C per minute. (The melting point considered is the point corresponding to the temperature of the most endothermic peak of the thermogram).
  • the semi-crystalline polymer (s) according to the invention preferably have a melting temperature higher than the temperature of the keratinous support intended to receive said composition, in particular the skin or the lips.
  • the semi-crystalline polymer (s) according to the invention are capable of structuring, alone or as a mixture, the composition without adding any particular surfactant, nor filler, nor wax.
  • the semi-crystalline polymers are advantageously soluble in the fatty phase, in particular at least 1% by weight, at a temperature above their melting temperature.
  • the sequences of the polymers are amorphous.
  • crystallizable chain or sequence within the meaning of the invention a chain or sequence which if it were alone would pass from the amorphous state to the crystalline state, reversibly, depending on whether one is above or below the melting temperature.
  • a chain within the meaning of the invention is a group of atoms, pendant or lateral with respect to the polymer backbone.
  • a sequence is a group of atoms belonging to the skeleton, a group constituting one of the repeating units of the polymer.
  • the polymer backbone of semi-crystalline polymers is soluble in the liquid fatty phase.
  • the crystallizable blocks or chains of the semi-crystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%.
  • the semi-crystalline polymers with crystallizable side chains are homo or copolymers.
  • the semi-crystalline polymers of the invention with crystallizable blocks are copolymers, block or multiblock. They can be obtained by polymerization of monomer with reactive (or ethylenic) double bonds or by polycondensation.
  • the polymers of the invention are chain polymers lateral crystallizable, the latter are advantageously in random or statistical form.
  • the semi-crystalline polymers of the invention are of synthetic origin. In addition, they do not have a polysaccharide backbone.
  • the semi-crystalline polymers which can be used in the invention are in particular:
  • the side chain (s) or crystallizable blocks are hydrophobic.
  • They are homopolymers or copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers carrying a hydrophobic crystallizable side chain.
  • 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 liquid fatty phase, by heating above their melting point. Pf. They may result: - from the radical polymerization in particular of one or more monomers with reactive double bond (s) or ethylenic towards a polymerization, namely with vinyl group, ( meth) acrylic or allylic.
  • the crystallizable units (chains or sequences) of the semi-crystalline polymers according to the invention come from monomer (s) with crystallizable block (s) or chain (s), used for the production of semi-crystalline polymers.
  • These polymers are chosen in particular from homopolymers and copolymers resulting from the polymerization of at least one monomer with a crystallizable chain (s) which can be represented by formula X:
  • the crystallizable “-SC” chains can be aliphatic or aromatic, optionally fluorinated or perfluorinated.
  • “S” represents in particular a group (CH 2 ) n or (CH 2 CH 2 O) n or (CH 2 O), linear or branched or cyclic, with n integer ranging from 0 to 22.
  • Preferably “S” is a linear group.
  • "S" and "C” are different.
  • the crystallizable chains are aliphatic hydrocarbon chains, they comprise alkyl hydrocarbon chains with at least 11 carbon atoms and at most 40 carbon atoms and better still at most 24 carbon atoms. These are in particular aliphatic chains or alkyl chains having at least 12 carbon atoms and preferably, they are C 14 -C 24 alkyl chains. preferably in C ⁇ 6 -C 22 . When it is fluorinated or perfluorinated alkyl chains, they contain at least 11 carbon atoms of which at least 6 carbon atoms are fluorinated.
  • alkyl (meth) acrylates saturated with the alkyl group in C u - C 24 perfluoroalkyl (meth) acrylates with a Cn-C ⁇ 5 perfluoro alkyl group
  • the crystallizable hydrocarbon and / or fluorinated chains as defined above are carried by a monomer which can be a diacid, a diol, a diamine, a di-isocyanate.
  • polymers which are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y or Z resulting from the copolymerization:
  • Y which is a polar or non-polar monomer or a mixture of the two:
  • Y is a polar monomer, it is either a monomer carrying polyoxyalkylenated groups (in particular oxyethylenated and / or oxypropylenated), a hydroxyalkyl (meth) acrylate such as hydroxyethyl acrylate, (meth) acrylamide, an N - alkyl (meth) acrylamide, an NN-dialkyl (meth) acrylamide such as for example NN-diisopropylacrylamide or N-vinyl-pyrolidone (NVP), N-vinyl caprolactam, a monomer carrying at least one carboxylic acid group such as (meth) acrylic, crotonic, itaconic, maleic, fumaric acids or carrying a carboxylic acid anhydride group such as maleic anhydride, and mixtures thereof.
  • a hydroxyalkyl (meth) acrylate such as hydroxyethyl acrylate, (meth) acrylamide, an N
  • Y is a non-polar monomer, it can be an ester of the branched or cyclic linear (meth) acrylate type, a vinyl ester, an alkyl vinyl ether, an alpha-olefin, styrene or styrene substituted by an alkyl group. in C 1 to C 10 , such as ⁇ -methylstyrene, a macromonomer of the polyorganosiloxane type with vinyl unsaturation.
  • alkyl is meant in the sense of the invention a saturated group in particular C 8 to C 24 , unless expressly mentioned.
  • Z which is a polar monomer or a mixture of polar monomers.
  • Z has the same definition as the "polar Y" defined above.
  • semi-crystalline side chain polymers are homopolymers of alkyl (meth) acrylate or of alkyl (meth) acrylamide with an alkyl group as defined above, and in particular in C ⁇ 4 -C 24 , copolymers of these monomers with a hydrophilic monomer preferably of a different nature from (meth) acrylic acid such as N-vinylpyrrolidone or hydroxyethyl (methjacrylate and their mixtures).
  • the polymers bearing in the backbone at least one crystallizable block. They are also polymers which are soluble or dispersible in the liquid fatty phase by heating above their melting point Pf. These polymers are in particular block copolymers consisting of at least two sequences of different chemical nature, one of which is crystallizable.
  • Block copolymers of olefin or of cycloolefin with a crystallizable chain such as those resulting from the block polymerization of:
  • cyclobutene cyclohexene, cyclooctene, norbornene (i.e. bicyclo (2,2,1) heptene-2), 5-methylnorbomene, 5-ethylnorbomene, 5,6-dimethylnorbomene, 5,5,6-trimethyl norbornene , 5-ethylidene-norbornene, 5-phenyl-norbonene, 5-benzylnorbomene, 5-vinyl norbornene, 1, 4,5,8-dimethano-1,2,3,4,4a, 5,8a-octahydronaphthalene, dicyclopentadiene or their mixtures,
  • the copolymers can be copolymers having at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers can, moreover, 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 block both hydrophobic and lipophilic distributed sequentially; mention may, for example, be made of 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 (olefin) such as poly (isobutylene), hydrogenated polybutadiene, hydrogenated poly (isoprene).
  • copolymers with crystallizable block and with amorphous block mention may be made of: ⁇ ) poly ( ⁇ -caprolactone) -b-poly (butadiene) block copolymers, preferably used hydrogenated, such as those described in article D6 "Melting behavior of poly (- caprolactone) -block-polybutadiene copolymers" by S. Nojima, Macromolecules, 32, 3727- 3734 (1999).
  • the semi-crystalline polymers of the composition of the invention may or may not be crosslinked in part as long as the crosslinking rate does not hinder their dissolution or dispersion in the liquid fatty phase by heating above their melting temperature. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It can also be a physical crosslinking which can then be due either to the establishment of hydrogen type or dipolar bonds between groups carried by the polymer such as for example the dipolar interactions between ionomeres carboxylates, these interactions being in small quantity and carried by the polymer backbone; or to a phase separation between the crystallizable blocks and the amorphous blocks, carried by the polymer.
  • the semi-crystalline polymers of the composition according to the invention are non-crosslinked.
  • a structuring semi-crystalline polymer which can be used in the composition according to the invention, mention may be made of the mtelimer® products from the company Landec described in the brochure "Intelimer® polymers", Landec IP22 (Rev. 4-97 ). These polymers are in solid form at room temperature (25 ° C). They carry crystallizable side chains and have the above formula X.
  • the semi-crystalline polymer (s) having a melting point Pf 2 of less than 50 ° C will be called “low melting point polymers” and the crystalline or semi-crystalline compound (s) having a temperature of Pf-i melting greater than or equal to 50 ° C will be referred to as "high melting point compounds".
  • the melting point can be measured in particular by any known method and in particular with a differential scanning calorimeter (DSC).
  • the composition advantageously contains a mixture of a polymer chosen from polymers with a low melting point having a melting temperature below 50 ° C., and a polymer chosen from polymers with a high melting point having a melting temperature at less than 50 ° C.
  • the semi-crystalline compound (s) with a high melting point are advantageously polymers having a melting temperature Pfi such that 50 ° C ⁇ Pfi ⁇ 150 ° C, better still 55 ° C ⁇ P ⁇ ⁇ 150 ° C, and preferably 60 ° C ⁇ Pf, ⁇ 130 ° C and the polymers with low melting point advantageously have a melting temperature Pf 2 such that 30 ° C ⁇ Pf 2 ⁇ 50 ° C, and better still 35 ° C ⁇ Pf 2 ⁇ 45 ° C.
  • This melting temperature is a first order state change temperature.
  • polymers with a low melting point have a melting point Pf 2 at least equal to the temperature of the keratinous support which is to receive the composition according to the invention.
  • high melting point waxes such as certain polyethylene waxes such as Epolene N-14 sold by Eastman Chemical Co., the Carnauba waxes and certain microcrystalline waxes such as those sold by Tisco under the brand "Tisco wax 88", as well as polymers semi-crystalline with a high melting point.
  • the high melting point compound is a second organic solid semi-crystalline polymer with high melting point.
  • the semi-crystalline polymers whose melting point is less than 50 ° C. are in particular those described in Examples 3, 4, 5, 7, 9 of US Pat. No. 5,156,911 with a -COOH group, resulting from the copolymerization of acrylic acid and of C 5 to C 16 alkyl (meth) acrylate with a melting temperature ranging from 20 ° C to 35 ° C and more particularly of the copolymerization:. acrylic acid, hexadecylacrylate and isodecylacrylate in a 1/16/3 ratio,. of acrylic acid and pentadecylacrylate in a ratio 1/19,.
  • the semi-crystalline polymers having a melting point greater than or equal to 50 ° C. are in particular the Intelimer described in the brochure "Intelimer® polymers", Landec IP22 (Rev. 4-97) with a melting point of 56 ° C, which is a viscous product at room temperature, waterproof, non-sticky. 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-055 0745 and more especially those described in Examples 3 and 4, below, of polymer preparation.
  • the semi-crystalline polymers with a low melting point and / or those with a high melting point do not contain a carboxylic group.
  • the compound with a high melting point (crystalline or semi-crystalline) and that with a low melting point are in a weight ratio ranging from 10/90 to 90/10 and better still 40 / 60 to 60/40, more preferably in a weight ratio close to 50/50.
  • the weight ratio of semi-crystalline polymer with organic structure relative to the liquid fatty phase is from 0.20 to 0.60 and better still from 0.25 to 0.50, obtaining a hard stick which disintegrates at skin or lip contact and in particular of hardness ranging from 100 to 350 gf.
  • the gelation of the fatty phase is adjustable according to the nature of the polymer (s) and their respective concentrations and can be such that a rigid structure is obtained in the form of a stick or a stick.
  • the level of each polymer is chosen according to the hardness of the desired composition and according to the particular application envisaged.
  • the respective amounts of polymer may be such that they make it possible to obtain a disintegrable solid, in particular having a hardness ranging from 100 to 350 gf.
  • This hardness can be measured by the so-called "butter cutting wire” method, which consists of cutting a stick of lipstick 12.7 mm in diameter and measuring the hardness at 20 ° C, using uri DFGHS 2 dynamometer from the company Indelco-Chatillon moving at a speed of 100mm / minute. It is expressed as the shear force (expressed in gram-force) necessary to cut a stick under these conditions.
  • composition of the invention in cast form, in particular in stick form, withstands impact well.
  • the composition of the invention is in the form of a solid stick, of hardness ranging from 100 gf to 350 gf, measured according to the "butter cutting wire" method. It is however possible to use an amount of semi-crystalline polymer such that the composition is in the form of a flexible paste applicable with the finger or with the aid of an applicator on keratin materials.
  • the total amount of semi-crystalline polymer (s) represents from 0.1 to 80% of the total weight of the composition and better still from 0.5 to 40% and even better still from 3 to 30%; Preferably, it represents from 15% to 25% by weight of the composition.
  • the sticks or sticks according to the invention make it possible, after application, to obtain a glossy deposit, uniform in color, non-sticky, with good coverage (that is to say that the skin or the lips do not appear under the makeup).
  • ester means a monoester
  • the ester according to the invention comprises 10 to 40 carbon atoms, preferably from 10 to 30 carbon atoms, more preferably from 12 to 26 carbon atoms, more preferably from 16 to 22 carbon atoms.
  • the ester according to the invention is preferably liquid at room temperature (25 ° C). It is advantageously aliphatic and / or linear.
  • the ester preferably represents from 10 to 40%, and better still from 15 to 30%, preferably from 20 to 25% by weight of the composition.
  • the ester preferably represents 15 to 50%, preferably 25 to 40% of the liquid fatty phase.
  • the weight ratio of the ester relative to the semi-crystalline polymer is advantageously between 1 and 2, preferably between 1.3 and 1.7.
  • the ester according to the invention can be chosen from - synthetic esters, in particular of fatty acids such as oils of formula R 1 COOR 2 in which Ri represents the remainder of a higher fatty acid containing from 1 to 38 carbon atoms and R 2 represents a hydrocarbon chain containing from 1 to 38 carbon atoms with 39> Ri + R 2 > 10 such as Purcellin oil, isononyl isononanoate, isopropyl isostearate, isopropyl myristate, ethyl 2-hexyl palmitate , octyl 2-dodecyl stearate, octyl 2-dodecyl erucate, isostearyl isostearate;
  • fatty acids such as oils of formula R 1 COOR 2 in which Ri represents the remainder of a higher fatty acid containing from 1 to 38 carbon atoms and R 2 represents a hydrocarbon chain containing from 1 to 38 carbon atoms with 39> Ri + R 2 > 10
  • esters such as isostearyl lactate, octyl hydroxy stearate, octyl dodecyl hydroxy stearate, heptanoates, octanoates, decanoates of fatty alcohols;
  • liquid fatty phase in the sense of the demand, is meant a fatty phase liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mm of Hg), composed of one or more fatty substances liquid at ambient temperature, also called oils, compatible with each other. This fatty phase is macroscopically homogeneous.
  • the liquid fatty phase structured by the semi-crystalline polymers, constitutes the continuous phase of the composition.
  • This fatty phase can contain one or more non-polar oils or a mixture of non-polar oil (s) and polar oil (s) or a mixture of polar oils, different from aliphatic alcohol. previously described.
  • apolar oils according to the invention are in particular silicone oils such as polydimethylsiloxanes (PDMS), linear or cyclic, liquid at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, pendant and / or at the end of the silicone chain, groups having 2 to 24 carbon atoms, liquid at room temperature; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl.
  • silicone oils such as polydimethylsiloxanes (PDMS), linear or cyclic, liquid at room temperature
  • polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, pendant and / or at the end of the silicone chain, groups having 2 to 24 carbon atoms, liquid at room temperature
  • phenylated silicones such
  • the nonpolar oils used are nonpolar oils of the hydrocarbon type, liquids, of mineral or synthetic origin, chosen in particular from Parleam® oil (hydrogenated isoparaffin), isoparaffins, squalane and their mixtures.
  • the liquid fatty phase contains at least one polar oil and at least one slightly polar oil, such as isononyl isononanonoate.
  • polar oils of the invention are:
  • oils with a high triglyceride content consisting of fatty acid esters (C 8 to C 24 ) and glycerol, the fatty acids of which can have varied chain lengths, the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular the oils of wheat germ, corn, sunflower, shea, castor, sweet almonds, macadamia, apricot, soy, rapeseed, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grapeseed or blackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye, safflower, and nutmeg , passion flower, muscat rose; or the triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel
  • R 5 COOR 6 synthetic oils of formula R 5 COOR 6 in which R 5 represents the remainder of a linear or branched higher fatty acid containing from 7 to 40 carbon atoms and R 6 represents a branched hydrocarbon chain containing from 3 to 40 carbon atoms carbon such as, for example, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C 12 to C 15 alcohol benzoate;
  • esters and ethers such as isopropyl myristate, ethyl 2-hexyl palmitate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, hydroxylated esters such as isostearyl lactate, malate di-isostearyl; and pentaerythritol esters;
  • - fatty acids having from 12 to 22 carbon atoms such as oleic, linoleic or linolenic acid;
  • the liquid fatty phase represents, in practice, from 5 to 99% of the total weight of the composition, preferably from 20 to 80%. Advantageously, it represents at least 60% of the total weight of the composition.
  • the composition contains a coloring material which can be chosen from lipophilic dyes, hydrophilic dyes, pigments and nacres usually used in cosmetic or dermatological compositions, and mixtures thereof.
  • This coloring material is generally present in an amount of 0.01 to 50% (in dry matter) of the total weight of the composition, preferably from 5 to 30% (if present).
  • the liposoluble dyes are for example Sudan red, D & C Red 17, D & C Green 6, ⁇ -carotene, soybean oil, Sudan brown, D & C Yellow 11, D & C Violet 2, D & C orange 5, quinacii ⁇ e yellow, annatto. They can represent from 0 to 20% of the weight of the composition and better still from 0.01 to 6% (if present).
  • the water-soluble dyes are, for example, beet juice, methylene blue and can represent up to 6% of the total weight of the composition.
  • the pigments can be white or colored, mineral and / or organic, coated or not. Mention may be made, among the mineral pigments, of titanium or zinc dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chromium and ferric blue.
  • the organic pigments there may be mentioned carbon black, pigments of the D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum (such as D & C red 27, 21 , 7, D & C yellow 5, 6, FD & C blue n ° 1).
  • the pigments can represent from 0 to 40% (0.01 to 40%), in particular from 0.5 to 35% and better still from 2 to 25% of the total weight of the composition (if present).
  • the pearlescent pigments can be chosen from white pearlescent pigments such as mica, in particular coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica titanium with iron oxides, mica titanium with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. They can represent from 0 to 25% (0.05 to 25%) of the total weight of the composition and better still from 0.1 to 15% (if present).
  • the pigments and pearlescent agents are introduced into the composition in the form of a pigment paste.
  • pigment paste in the sense of the invention a concentrated colloidal dispersion of colored particles coated or not in a continuous medium, optionally stabilized using a dispersing agent.
  • the makeup composition of the invention may be in the form of a colored product in particular of the skin, optionally having care or treatment properties, and may in particular be a foundation, a blush, a blush. cheeks or eyeshadow, a concealer, an eyeliner, a body makeup product; lip makeup such as a lipstick, a lip gloss or a lip pencil possibly having properties. care or treatment; make-up of the integuments such as nails, eyelashes in the form of mascara, eyebrows and hair. It is preferably anhydrous or in cast form.
  • composition of the invention must be cosmetically acceptable, ie contain a physiologically acceptable medium which is non-toxic and capable of being applied to. the skin, the integuments or the lips of the face of human beings.
  • cosmetically acceptable is meant in the sense of the invention a composition of appearance, odor, touch and possibly of pleasant taste.
  • composition of the invention at least one wax such as those used to date in cosmetics.
  • a wax within the meaning of the present invention, is a lipophilic fatty compound, solid at room temperature (25 ° C) and atmospheric pressure (760 mm Hg), with reversible solid / liquid state change, having a melting temperature greater than 40 ° C and better still greater than 50 ° C, up to 200 ° C, and having an anisotropic crystalline organization in the solid state.
  • the size of the crystals is such that the crystals diffract and / or scatter light, giving the composition a cloudy, more or less opaque appearance.
  • the wax By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, the wax is recrystallized from the oils of the mixed. This recrystallization from the mixture may be responsible for the reduction in the gloss of said mixture.
  • the composition contains little or no conventional waxes and in particular less than 10%, by weight, of conventional wax and better still less than 5% relative to the total weight of the composition.
  • waxes in the sense of demand, are those generally used in the cosmetic and dermatological fields; they are in particular of natural origin such as beeswax, Candellila, Ouricoury, Japan, cork fibers or sugar cane, paraffin waxes, lignite, microcrystalline waxes of melting point> 50 ° C, lanolin wax, Montan wax, ozokerites, hydrogenated oils such as hydrogenated jojoba oil, but also of synthetic origin such as polyethylene waxes resulting from the polymerization of ethylene and waxes obtained by Fischer-Tropsch synthesis at melting point> 50 ° C, fatty acid esters and concrete glycerides at 50 ° C, silicone waxes such as alkyl, alkoxy and / or poly (di) methylsiloxane esters solid at 50 ° C.
  • the composition of the invention contains little or no "mattifying" fillers and in particular less than 5% of mattifying filler. This is particularly the case when it is desired to obtain a shiny deposit on keratin materials such as the lips, the eyelashes and the hair. On the contrary, for a foundation, this type of filler can be used.
  • a mattifying filler is generally a filler which absorbs sweat and / or sebum from the skin such as silicas, talcs, clays, kaolins, polyamide powders (Nylon®).
  • composition according to the invention can be produced by known methods, generally used in the cosmetic field.
  • the subject of the invention is also a cosmetic process for caring for, making up or treating keratin materials of human beings and in particular of the skin, facial lips and integuments of human beings, comprising the application to keratin materials of the composition, in particular cosmetic, as defined above.
  • Another subject of the invention is the use of an ester comprising 10 to 40 carbon atoms, in a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, the melting point is greater than or equal to 30 ° C, b) a coloring matter, the liquid fatty phase, the coloring matter, the ester and the polymer forming a physiologically acceptable medium.
  • Another subject of the invention is the use of a sufficient quantity of an ester comprising 10 to 40 carbon atoms, in a composition containing a physiologically acceptable medium comprising a) at least one liquid fatty phase structured by at least one polymer semi-crystalline with an organic structure, the melting point of which is greater than or equal to 30 ° C, and b) a coloring matter, as an agent for imparting slipperiness on application and gloss to said composition.
  • the subject of the invention is also the use of an ester comprising 10 to 40 carbon atoms in a cosmetic composition containing a physiologically acceptable medium comprising at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, to obtain a composition that is slippery on application and shiny.
  • the mixture C 2 consisting of: 200 g of stearyl acrylate + 400 g of cyclohexane is introduced over 1 hour 30 minutes.
  • the reaction is left to act for an additional 3 hours at 80 ° C., then all of the cyclohexane present in the reaction medium is distilled.
  • the polymer is then obtained at 60% by weight of active material in the Parléam.
  • Example 2 Copolymer with a Melting Point of 48 ° C
  • Example 2 The same procedure is applied as in Example 1, except that a mixture of 10 g of N-Vinyl Pyrrolidone and 190 g of stearyl acrylate is used.
  • the polymer obtained is 60% by weight of active material in Parleam, its weight average molecular weight is 43,000-53,000 and its T f is 48 ° C.
  • Example 2 The same procedure is applied as in Example 1, except that behenyl acrylate is used in place of stearyl acrylate.
  • the polymer obtained is 60% by weight of active material in Parléam. Its weight average molecular weight is 17000-27000 and its T f of 58 ° C.
  • Example 4 Copolymer with a Melting Point of 58 ° C
  • Example 2 The same procedure is applied as in Example 2, except that behenyl acrylate is used in place of stearyl acrylate.
  • the polymer obtained is 60% by weight of active material in Parléam®. Its weight average molecular mass is 23500-33500 and its T f is 58 ° C.

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Abstract

The invention relates to a makeup composition comprising a) at least one liquid fatty phase structured with at least one semi-crystalline polymer having an organic structure, whose melting temperature is greater than or equal to 30° C., b) a colorant and c) a volatile oil, the liquid fatty phase, colorant, volatile oil and polymer forming a physiologically acceptable medium. This composition is in the form in particular of a stick which on keratin materials, particularly the lips, lays down a glossy film which does not undergo transfer to objects with which the keratin materials come into contact.

Description

COMPOSITION CONTENANT UN POLYMERE SEMI-CRISTALLIN ET UN ESTERCOMPOSITION CONTAINING SEMICRYSTALLINE POLYMER AND ESTER
La présente invention se rapporte à une composition, notamment cosmétique, contenant au moins un polymère semi-cristallin et un ester se présentant notamment sous forme d'un stick glissant à l'application et conduisant à un dépôt brillant et confortable.The present invention relates to a composition, in particular a cosmetic composition, containing at least one semi-crystalline polymer and one ester which is in particular in the form of a stick which slips when applied and leads to a shiny and comfortable deposit.
Des compositions cosmétiques dont la phase grasse est gélifiée par des polymères semi- cristallins ont été décrites la demande FR 0106047 non encore publiée. Les formules de rouge à lèvres issues de ces inventions se présentent sous la forme d'un stick qui dépose un film brillant, non-collant et couvrant. Ces compositions ont cependant l'inconvénient de ne pas de déposer facilement lors de leur application sur les matières kératiniques.Cosmetic compositions, the fatty phase of which is gelled by semi-crystalline polymers, have been described in application FR 0106047 not yet published. The lipstick formulas resulting from these inventions are in the form of a stick which deposits a shiny, non-sticky and covering film. These compositions however have the drawback of not depositing easily when they are applied to keratin materials.
La présente invention a donc pour but de fournir une composition comprenant une phase grasse liquide structurée par un polymère semi-cristallin à structure organique solide à température ambiante, dont le dépôt sur la peau ou les lèvres est brillant et confortable et facile à déposer.The present invention therefore aims to provide a composition comprising a liquid fatty phase structured by a semi-crystalline polymer with solid organic structure at room temperature, the deposition on the skin or the lips is shiny and comfortable and easy to deposit.
Les brevets US 5 736 125 et US 5 156 911, ainsi que la demande WO 01/19333 illustrent certains types de polymères semi-cristallins qui peuvent entrer dans la composition des formules de l'invention. Néanmoins, ces documents ne décrivent pas des compositions cosmétiques.US Patents 5,736,125 and US 5,156,911, as well as Application WO 01/19333 illustrate certain types of semi-crystalline polymers which can enter into the composition of the formulas of the invention. However, these documents do not describe cosmetic compositions.
De façon surprenante, le demandeur a trouvé que l'ajout d'un ester comprenant 10 à 40 atomes de carbone dans une composition contenant un polymère semi-cristallin permet d'améliorer le dépôt de la composition et d'améliorer sa brillance.Surprisingly, the applicant has found that the addition of an ester comprising 10 to 40 carbon atoms in a composition containing a semi-crystalline polymer makes it possible to improve the deposition of the composition and to improve its gloss.
L'invention s'applique en particulier aux produits de maquillage des lèvres mais aussi des yeux comme les eye-liners en particulier sous forme de crayon et les mascaras notamment sous forme de pain, ou de la peau, comme les fonds de teint.The invention applies in particular to makeup products for the lips but also for the eyes, such as the eyeliners, in particular in the form of a pencil, and the mascaras, in particular in the form of bread, or of the skin, such as foundations.
De façon plus précise, l'invention a pour objet une composition de maquillage comprenant a) au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique dont la température de fusion est supérieure ou égale à 30°C, b) une matière colorante et c) un ester comprenant 10 à 40 atomes de carbone, la phase grasse liquide, la matière colorante, l'ester et le polymère formant un milieu physiologiquement acceptable. La température de fusion du polymère semi-cristallin est de préférence inférieure à 150°C.More specifically, the subject of the invention is a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, the melting point of which is greater than or equal to 30 ° C., b) a coloring matter and c) an ester comprising 10 to 40 carbon atoms, the liquid fatty phase, the coloring matter, the ester and the polymer forming a physiologically acceptable medium. The melting temperature of the semi-crystalline polymer is preferably less than 150 ° C.
La composition de l'invention peut se présenter sous forme de pâte, de solide, de crème. Elle peut être une émulsion huile-dans-eau ou eau-dans-huile, un gel anhydre, solide ou souple. De préférence, elle se présente sous forme anhydre, et plus spécialement sous forme de gel anhydre, notamment coulée en stick ou en coupelle.The composition of the invention can be in the form of a paste, a solid, a cream. It can be an oil-in-water or water-in-oil emulsion, an anhydrous, solid or flexible gel. Preferably, it is in anhydrous form, and more especially in the form of an anhydrous gel, in particular poured in a stick or in a dish.
Par "polymère semi-cristallin", on entend au sens de l'invention, des polymères comportant une partie cristallisable et une partie amorphe dans le squelette et présentant une température de changement de phase réversible du premier ordre, en particulier de fusion (transition solide-liquide). La partie cristallisable est soit une chaîne latérale (ou chaîne pendante), soit une séquence dans le squelette.By "semi-crystalline polymer" is meant within the meaning of the invention, polymers comprising a crystallizable part and an amorphous part in the skeleton and having a reversible phase change temperature of the first order, in particular of fusion (solid transition -liquid). The crystallizable part is either a side chain (or pendant chain) or a sequence in the skeleton.
Par "polymères", on entend au sens de l'invention des composés comportant au moins 2 motifs de répétition, de préférence au moins 3 motifs de répétition et plus spécialement au moins 10 motifs répétitifs.By "polymers" is meant in the sense of the invention compounds comprising at least 2 repeating units, preferably at least 3 repeating units and more especially at least 10 repeating units.
Lorsque la partie cristallisable est une séquence du squelette polymérique, cette séquence cristallisable est de nature chimique différente de celle des séquences amorphes; le polymère semi-cristallin est dans ce cas un copolymère séquence par exemple du type dibloc, tribloc ou multibloc. Lorsque la partie cristallisable est une chaîne pendante au squelette, le polymère semi cristallin peut être un homopolymère ou un copolymère.When the crystallizable part is a sequence of the polymer backbone, this crystallizable sequence is of a chemical nature different from that of the amorphous sequences; the semi-crystalline polymer is in this case a block copolymer, for example of the diblock, triblock or multiblock type. When the crystallizable part is a chain hanging from the skeleton, the semi-crystalline polymer can be a homopolymer or a copolymer.
Par "composé organique" ou "à structure organique", on entend des composés contenant des atomes de carbone et des atomes d'hydrogène et éventuellement des hétéroatomes comme S, O, N, P seuls ou en association.By "organic compound" or "with organic structure" is meant compounds containing carbon atoms and hydrogen atoms and optionally heteroatoms such as S, O, N, P alone or in combination.
Les polymères semi-cristallinsSemi-crystalline polymers
De façon avantageuse, le ou les polymères semi-cristallins de la composition de l'invention comprennent une masse moléculaire moyenne en poids Mp allant de 5 000 à 1 000 000, de préférence de 10 000 à 800 000, préférentiellement de 15 000 à 500 000.Advantageously, the semi-crystalline polymer or polymers of the composition of the invention comprise a weight-average molecular mass Mp ranging from 5,000 to 1,000,000, preferably from 10,000 to 800,000, preferably from 15,000 to 500 000.
Le ou les polymères semi-cristallins selon l'invention servant d'agent structurant sont des solides à température ambiante (25°C) et pression atmosphérique (760 mm de Hg), dont la température de fusion est supérieure ou égale à 30°C. Les valeurs de point de fusion correspondent au point de fusion mesuré à l'aide d'un calorimètre à balayage différentiel (D. S. C), tel que le calorimètre vendu sous la dénomination DSC 30 par la société METTLER, avec une montée en température de 5 ou 10°C par minute. (Le point de fusion considéré est le point correspondant à la température du pic le plus endotherme du thermogramme).The semi-crystalline polymer (s) according to the invention serving as a structuring agent are solids at ambient temperature (25 ° C) and atmospheric pressure (760 mm Hg), the melting point is greater than or equal to 30 ° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name DSC 30 by the company METTLER, with a rise in temperature of 5 or 10 ° C per minute. (The melting point considered is the point corresponding to the temperature of the most endothermic peak of the thermogram).
Le ou les polymères semi-cristallins selon l'invention ont de préférence une température de fusion supérieure à la température du support kératinique destiné à recevoir ladite composition, en particulier la peau ou les lèvres.The semi-crystalline polymer (s) according to the invention preferably have a melting temperature higher than the temperature of the keratinous support intended to receive said composition, in particular the skin or the lips.
Le ou les polymères semi-cristallins selon l'invention sont capables de structurer seuls ou en mélange, la composition sans ajout de tensioactif particulier, ni de charge, ni de cire.The semi-crystalline polymer (s) according to the invention are capable of structuring, alone or as a mixture, the composition without adding any particular surfactant, nor filler, nor wax.
Selon l'invention les polymères semi-cristallins sont avantageusement solubles dans la phase grasse, notamment à au moins 1 % en poids, à une température supérieure à leur température de fusion. En dehors des chaînes ou séquences cristallisables, les séquences des polymères sont amorphes.According to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase, in particular at least 1% by weight, at a temperature above their melting temperature. Apart from the crystallizable chains or sequences, the sequences of the polymers are amorphous.
Par "chaîne ou séquence cristallisable", on entend au sens de l'invention une chaîne ou séquence qui si elle était seule passerait de l'état amorphe à l'état cristallin, de façon réversible, selon qu'on est au-dessus ou en dessous de la température de fusion. Une chaîne au sens de l'invention est un groupement d'atomes, pendant ou latéral par rapport au squelette du polymère. Une séquence est un groupement d'atomes appartenant au squelette, groupement constituant un des motifs répétitif du polymère.By "crystallizable chain or sequence" is meant within the meaning of the invention a chain or sequence which if it were alone would pass from the amorphous state to the crystalline state, reversibly, depending on whether one is above or below the melting temperature. A chain within the meaning of the invention is a group of atoms, pendant or lateral with respect to the polymer backbone. A sequence is a group of atoms belonging to the skeleton, a group constituting one of the repeating units of the polymer.
De préférence, le squelette polymérique des polymères semi-cristallins est soluble dans la phase grasse liquide.Preferably, the polymer backbone of semi-crystalline polymers is soluble in the liquid fatty phase.
De préférence, les séquences ou chaînes cristallisables des polymères semi-cristallins représentent au moins 30 % du poids total de chaque polymère et mieux au moins 40 %. Les polymères semi-cristallins à chaînes latérales cristallisables sont des homo ou des copolymères. Les polymères semi-cristallins de l'invention à séquences cristallisables sont des copolymères, séquences ou multiséquencés. Ils peuvent être obtenus par polymérisation de monomère à double liaisons réactives (ou éthyléniques) ou par polycondensation. Lorsque les polymères de l'invention sont des polymères à chaînes latérales cristallisables, ces derniers sont avantageusement sous forme aléatoire ou statistique.Preferably, the crystallizable blocks or chains of the semi-crystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. The semi-crystalline polymers with crystallizable side chains are homo or copolymers. The semi-crystalline polymers of the invention with crystallizable blocks are copolymers, block or multiblock. They can be obtained by polymerization of monomer with reactive (or ethylenic) double bonds or by polycondensation. When the polymers of the invention are chain polymers lateral crystallizable, the latter are advantageously in random or statistical form.
De préférence, les polymères semi-cristallins de l'invention sont d'origine synthétique. En outre, ils ne comportent pas de squelette polysaccharidique.Preferably, the semi-crystalline polymers of the invention are of synthetic origin. In addition, they do not have a polysaccharide backbone.
Les polymères semi-cristallins utilisables dans l'invention sont en particulier :The semi-crystalline polymers which can be used in the invention are in particular:
- les copolymères séquences de polyoléfines à cristallisation contrôlée, dont les monomères sont décrits dans EP-A-0 951 897. - les polycondensats et notamment de type polyester, aliphatique ou aromatique ou aliphatique/aromatique,- block copolymers of polyolefins with controlled crystallization, the monomers of which are described in EP-A-0 951 897. - polycondensates and in particular of polyester, aliphatic or aromatic or aliphatic / aromatic type,
- les homo- ou co-polymères portant au moins une chaîne latérale cristallisable et les homo- ou co-polymères portant dans le squelette au moins une séquence cristallisable, comme ceux décrits dans le document US-A-5 156 911, - les homo- ou co-polymères portant au moins une chaîne latérale cristallisable en particulier à groupement(s) fluoré(s), tels que décrits dans le document WO-A-01/19333,- 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-A-5,156,911, - homo - or co-polymers carrying at least one crystallizable side chain, in particular with fluorinated group (s), as described in document WO-A-01/19333,
- et leurs mélanges. Dans ces deux derniers cas, la ou les chaînes latérales ou séquences cristallisables sont hydrophobes.- and their mixtures. In the latter two cases, the side chain (s) or crystallizable blocks are hydrophobic.
A) Polymères semi-cristallins à chaînes latérales cristallisablesA) Semi-crystalline polymers with crystallizable side chains
On peut citer en particulier ceux définis dans les documents US-A-5 156 911 et WO-A-Mention may be made in particular of those defined in documents US-A-5,156,911 and WO-A-
01/19333.01/19333.
. Ce sont des homopolymères ou copolymères comportant de 50 à 100 % en poids de motifs résultant de la polymérisation de un ou plusieurs monomères porteurs de chaîne latérale hydrophobe cristallisable.. They are homopolymers or copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers carrying a hydrophobic crystallizable side chain.
. Ces homo- ou co-polymères sont de toute nature du moment qu'ils présentent les conditions indiquées ci-après avec en particulier la caractéristique d'être solubles ou dispersables dans la phase grasse liquide, par chauffage au-dessus de leur température de fusion Pf. Ils peuvent résulter : - de la polymérisation notamment radicalaire d'un ou plusieurs monomères à double(s) liaison(s) réactive(s) ou éthyléniques vis-à-vis d'une polymérisation, à savoir à groupe vinylique, (méth)acrylique ou allylique.. 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 liquid fatty phase, by heating above their melting point. Pf. They may result: - from the radical polymerization in particular of one or more monomers with reactive double bond (s) or ethylenic towards a polymerization, namely with vinyl group, ( meth) acrylic or allylic.
- de la polycondensation d'un ou plusieurs monomères porteurs de groupes co-réactifs- polycondensation of one or more monomers carrying co-reactive groups
(acide carboxylique ou sulfonique, alcool, aminé ou isocyanate), comme par exemple les polyesters, les polyuréthanes, les polyéthers, les polyurées, les polyamides. a) D'une façon générale les motifs (chaînes ou séquences) cristallisables des polymères semi-cristallins selon l'invention, proviennent de monomère(s) à séquence(s) ou chaîne(s) cristallisable(s), utilisé(s) pour la fabrication des polymères semi-cristallins. Ces polymères sont choisis notamment parmi les homopolymères et copolymères résultant de la polymérisation d'au moins un monomère à chaîne(s) cristallisable(s) qui peut être représenté par la formule X :(carboxylic or sulfonic acid, alcohol, amino or isocyanate), such as, for example, polyesters, polyurethanes, polyethers, polyureas, polyamides. a) In general, the crystallizable units (chains or sequences) of the semi-crystalline polymers according to the invention come from monomer (s) with crystallizable block (s) or chain (s), used for the production of semi-crystalline polymers. These polymers are chosen in particular from homopolymers and copolymers resulting from the polymerization of at least one monomer with a crystallizable chain (s) which can be represented by formula X:
— M — avec M représentant un atome du squelette polymérique | S représentant un espaceur- M - with M representing an atom of the polymer backbone | S representing a spacer
S C représentant un groupe cristallisableS C representing a crystallizable group
Les chaînes « -S-C » cristallisables peuvent être aliphatiques ou aromatiques, éventuellement fluorées ou perfluorees. « S » représente notamment un groupe (CH2)n ou (CH2CH2O)n ou (CH2O), linéaire ou ramifié ou cyclique, avec n entier allant de 0 à 22. De préférence « S » est un groupe linéaire. De préférence, « S » et « C » sont différents.The crystallizable “-SC” chains can be aliphatic or aromatic, optionally fluorinated or perfluorinated. “S” represents in particular a group (CH 2 ) n or (CH 2 CH 2 O) n or (CH 2 O), linear or branched or cyclic, with n integer ranging from 0 to 22. Preferably “S” is a linear group. Preferably, "S" and "C" are different.
Lorsque les chaînes cristallisables sont des chaînes aliphatiques hydrocarbonées, elles comportent des chaînes alkyle hydrocarbonées à au moins 11 atomes de carbone et au plus 40 atomes de carbone et mieux au plus 24 atomes de carbone. Il s'agit notamment de chaînes aliphatiques ou chaînes alkyle possédant au moins 12 atomes de carbone et de préférence, il s'agit de chaînes alkyle en C14-C24. de préférence en Cι6-C22 .Lorsqu'il s'agit de chaînes alkyle fluorées ou perfluorees, elles comportent au moins 11 atomes de carbone dont au moins 6 atomes de carbone sont fluorés.When the crystallizable chains are aliphatic hydrocarbon chains, they comprise alkyl hydrocarbon chains with at least 11 carbon atoms and at most 40 carbon atoms and better still at most 24 carbon atoms. These are in particular aliphatic chains or alkyl chains having at least 12 carbon atoms and preferably, they are C 14 -C 24 alkyl chains. preferably in Cι 6 -C 22 .When it is fluorinated or perfluorinated alkyl chains, they contain at least 11 carbon atoms of which at least 6 carbon atoms are fluorinated.
Comme exemple d'homopolymères ou de copolymères semi-cristallins à chaîne(s) cristallisable(s), on peut citer ceux résultant de la polymérisation d'un ou plusieurs monomères suivants : les (méth)acrylates d'alkyle saturés avec le groupe alkyle en Cu- C24, les (méth)acrylates de perfluoroalkyle avec un groupe alkyle perfluoro en Cn-Cι5, les N-alkyl (méth)acrylamides avec le groupe alkyle en Cu à C24 avec ou sans atome de fluor, les esters vinyliques à chaînes alkyle ou perfluoro (alkyle) avec le groupe alkyle en C14 à C24 (avec au moins 6 atomes de fluor pour une chaîne perfluoro alkyle), les éthers vinyliques à chaînes alkyle ou perfluoro (alkyle) avec le groupe alkyle en C14 à C24 et au moins 6 atomes de fluor pour une chaîne perfluoro alkyle, les alpha-oléfines en Cu à C2 comme par exemple l'octadécène, les para-alkyl styrènes avec un groupe alkyle comportant de 12 à 24 atomes de carbone, leurs mélanges.As an example of homopolymers or semi-crystalline copolymers with crystallizable chain (s), mention may be made of those resulting from the polymerization of one or more of the following monomers: alkyl (meth) acrylates saturated with the alkyl group in C u - C 24 , perfluoroalkyl (meth) acrylates with a Cn-Cι 5 perfluoro alkyl group, N-alkyl (meth) acrylamides with the Cu to C 24 alkyl group with or without fluorine atom, vinyl esters with alkyl or perfluoro (alkyl) chains with the C 14 to C 24 alkyl group (with at least 6 fluorine atoms for a perfluoro alkyl chain), vinyl ethers with alkyl or perfluoro (alkyl) chains with the alkyl group in C 14 to C 24 and in at least 6 fluorine atoms for a perfluoro alkyl chain, the C 2 to C 2 alpha-olefins such as for example octadecene, para-alkyl styrenes with an alkyl group comprising from 12 to 24 carbon atoms, their mixtures.
Lorsque les polymères résultent d'une polycondensation, les chaînes cristallisables hydrocarbonées et/ou fluorées telles que définies ci-dessus, sont portées par un monomère qui peut être un diacide, un diol, une diamine, un di-isocyanate.When the polymers result from a polycondensation, the crystallizable hydrocarbon and / or fluorinated chains as defined above, are carried by a monomer which can be a diacid, a diol, a diamine, a di-isocyanate.
Lorsque les polymères objets de l'invention sont des copolymères, ils contiennent, en plus, de 0 à 50 % de groupes Y ou Z résultant de la copolymérisation :When the polymers which are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y or Z resulting from the copolymerization:
α ) de Y qui est un monomère polaire ou non polaire ou un mélange des deux :α) of Y which is a polar or non-polar monomer or a mixture of the two:
. Lorsque Y est un monomère polaire, c'est soit un monomère porteur de groupes polyoxyalkylénés (notamment oxyéthyléné et/ou oxypropyléné), un (méth)acrylate d'hydroxyalkyle comme l'acrylate d'hydroxyéthyle, le (méth)acrylamide, un N- alkyl(méth)acrylamide, un NN-dialkyl(méth)acrylamide comme par exemple le NN- diisopropylacrylamide ou la N-vinyl-pyrolidone (NVP), le N-vinyl caprolactame, un monomère porteur d'au moins un groupe acide carboxylique comme les acides (méth)acryliques, crotonique, itaconique, maléique, fumarique ou porteur d'un groupe anhydride d'acide carboxylique comme l'anhydre maléique, et leurs mélanges.. When Y is a polar monomer, it is either a monomer carrying polyoxyalkylenated groups (in particular oxyethylenated and / or oxypropylenated), a hydroxyalkyl (meth) acrylate such as hydroxyethyl acrylate, (meth) acrylamide, an N - alkyl (meth) acrylamide, an NN-dialkyl (meth) acrylamide such as for example NN-diisopropylacrylamide or N-vinyl-pyrolidone (NVP), N-vinyl caprolactam, a monomer carrying at least one carboxylic acid group such as (meth) acrylic, crotonic, itaconic, maleic, fumaric acids or carrying a carboxylic acid anhydride group such as maleic anhydride, and mixtures thereof.
. Lorsque Y est un monomère non polaire il peut être un ester du type (méth)acrylate d'alkyle linéaire ramifié ou cyclique, un ester vinylique, un alkyl vinyl éther, une alpha- oléfine, le styrène ou le styrène substitué par un groupe alkyle en Ci à C10, comme l'α- méthylstyrène, un macromonomère du type polyorganosiloxane à insaturation vinylique.. When Y is a non-polar monomer, it can be an ester of the branched or cyclic linear (meth) acrylate type, a vinyl ester, an alkyl vinyl ether, an alpha-olefin, styrene or styrene substituted by an alkyl group. in C 1 to C 10 , such as α-methylstyrene, a macromonomer of the polyorganosiloxane type with vinyl unsaturation.
Par "alkyle", on entend au sens au sens de l'invention un groupement saturé notamment en C8 à C24, sauf mention exprès.By "alkyl" is meant in the sense of the invention a saturated group in particular C 8 to C 24 , unless expressly mentioned.
β) de Z qui est un monomère polaire ou un mélange de monomères polaires. Dans ce cas, Z a la même définition que le "Y polaire" défini ci-dessus.β) of Z which is a polar monomer or a mixture of polar monomers. In this case, Z has the same definition as the "polar Y" defined above.
De préférence, les polymères semi-cristallins à chaîne latérale . cristallisable sont des homopolymères d'alkyl(méth)acrylate ou d'alkyl(méth)acrylamide avec un groupe alkyle tel que défini ci-dessus, et notamment en Cι4-C24, des copolymères de ces monomères avec un monomère hydrophile de préférence de nature différente de l'acide (méth)acrylique comme la N-vinylpyrrolidone ou l'hydroxyéthyl (méthjacrylate et leurs mélanges.Preferably, semi-crystalline side chain polymers. crystallizable are homopolymers of alkyl (meth) acrylate or of alkyl (meth) acrylamide with an alkyl group as defined above, and in particular in Cι 4 -C 24 , copolymers of these monomers with a hydrophilic monomer preferably of a different nature from (meth) acrylic acid such as N-vinylpyrrolidone or hydroxyethyl (methjacrylate and their mixtures).
B) Les polymères portant dans le squelette au moins une séquence cristallisable II s'agit encore de polymères solubles ou dispersables dans la phase grasse liquide par chauffage au-dessus de leur point de fusion Pf. Ces polymères sont notamment des copolymères séquences constitués d'au moins deux séquences de nature chimique différente dont l'une est cristallisable.B) The polymers bearing in the backbone at least one crystallizable block. They are also polymers which are soluble or dispersible in the liquid fatty phase by heating above their melting point Pf. These polymers are in particular block copolymers consisting of at least two sequences of different chemical nature, one of which is crystallizable.
- On peut utiliser les polymères définis dans le brevet US-A-5 156 911 ,- The polymers defined in US-A-5,156,911 can be used,
- Les copolymères séquences d'oléfine ou de cyclooléfine à chaîne cristallisable comme ceux issus de la polymérisation séquencée de :- Block copolymers of olefin or of cycloolefin with a crystallizable chain such as those resulting from the block polymerization of:
. cyclobutène, cyclohexène, cyclooctène, norbornène (c'est-à-dire bicyclo(2,2,1)heptène-2), 5-méthylnorbomène, 5-éthylnorbomène, 5,6-diméthylnorbomène, 5,5,6-triméthyl norbornène, 5-éthylidène-norbomène, 5-phényl-norbonène, 5-benzylnorbomène, 5-vinyl norbornène, 1 ,4,5,8-diméthano-1,2,3,4,4a,5,8a-octahydronaphtalène, dicyclopentadiène ou leurs mélanges,. cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo (2,2,1) heptene-2), 5-methylnorbomene, 5-ethylnorbomene, 5,6-dimethylnorbomene, 5,5,6-trimethyl norbornene , 5-ethylidene-norbornene, 5-phenyl-norbonene, 5-benzylnorbomene, 5-vinyl norbornene, 1, 4,5,8-dimethano-1,2,3,4,4a, 5,8a-octahydronaphthalene, dicyclopentadiene or their mixtures,
. avec l'éthylène, le propylène, le 1 -butène, le 3-méthyl-1 -butène, le 1-hexène, le 4-méthyl- 1-pentène, le 1-octène, le 1 -décène, le 1-éicosène ou leurs mélanges, . et en particulier les copoly(éthylène/norbomène) blocs et les terpolymères (éthylène/propylène/éthylidène-norbornène), blocs. On peut aussi utiliser ceux résultants de la copolymérisation séquencée d'au moins 2 α-oléfines en C2-Cι6 et mieux en C2-C12 tels que ceux cités précédemment et en particulier les bipolymères séquences d'éthylène et d'1-octène.. with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-eicosene or their mixtures,. and in particular the copoly (ethylene / norbornene) blocks and the terpolymers (ethylene / propylene / ethylidene-norbornene), blocks. One can also use those resulting from the block copolymerization of at least 2 α-olefins C 2 -Cι 6 and better C 2 -C 12 such as those mentioned above and in particular the block polymers of ethylene and 1 octene.
- Les copolymères peuvent être des copolymères présentant au moins une séquence cristallisable, le reste du copolymère étant amorphe (à température ambiante). Ces copolymères peuvent, en outre, présenter deux séquences cristallisables de nature chimique différente. Les copolymères préférés sont ceux qui possèdent à la fois à température ambiante, une séquence cristallisable et une séquence amorphe à la fois hydrophobe et lipophile réparties séquentiellement ; on peut citer par exemple les polymères possédant une des séquences cristallisables et une des séquences amorphes suivantes :- The copolymers can be copolymers having at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers can, moreover, 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 block both hydrophobic and lipophilic distributed sequentially; mention may, for example, be made of polymers having one of the crystallizable blocks and one of the following amorphous blocks:
. Séquence cristallisable par nature : a) polyester comme les poly(alkylène téréphtalate), b) polyoléfine comme les polyéthylènes ou polypropylènes. . Séquence amorphe et lipophile comme : les polyoléfines ou copoly(oléfine)s amorphes telles que le poly(isobutylène), le polybutadiène hydrogéné, le poly(isoprène) hydrogéné.. 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 (olefin) such as poly (isobutylene), hydrogenated polybutadiene, hydrogenated poly (isoprene).
Comme exemple de tels copolymères à séquence cristallisable et à séquence amorphe, on peut citer : α) les copolymères séquences poly(ε-caprolactone)-b-poly(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). β) les copolymères séquences poly(butylènetéréphtalate)-b-poly(isoprène) hydrogénés séquences ou multiséquencès, 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). γ) les copolymères séquences poly(éthylène)-b-copoly(éthylène/propylène) cités dans les articles D8 "Morphology of semi-crystalline block copolymers of ethylene-(ethylene-alt- propylene)" de P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) et D9 "Polymer agregates with crystalline cores : the System poly(ethylene)-poly(ethy!ene- propylene)" P. Richter et al., Macromolécules, 30, 1053-1068 (1997). δ) les copolymères séquences poly(éthylène)-b-poly(éthyléthylène) cités dans l'article général D10 "Cristallization in block copolymers" de I.W. Hamiey, Advances in Polymer Science, vol 148, 113-137 (1999).As an example of such copolymers with crystallizable block and with amorphous block, mention may be made of: α) poly (ε-caprolactone) -b-poly (butadiene) block copolymers, preferably used hydrogenated, such as those described in article D6 "Melting behavior of poly (- caprolactone) -block-polybutadiene copolymers" by S. Nojima, Macromolecules, 32, 3727- 3734 (1999). β) block copolymers poly (butyleneterephthalate) -b-poly (isoprene) hydrogenated block or multisequence, cited in article D7 "Study of morphological and mechanical properties of PP / PBT" by B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995). γ) poly (ethylene) -b-copoly (ethylene / propylene) block copolymers cited in articles D8 "Morphology of semi-crystalline block copolymers of ethylene- (ethylene-alt-propylene)" by P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) and D9 "Polymer agregates with crystalline cores: the System poly (ethylene) -poly (ethy! Ene-propylene)" P. Richter et al., Macromolecules, 30, 1053-1068 ( 1997). δ) the poly (ethylene) -b-poly (ethylethylene) block copolymers mentioned in general article D10 "Crystallization in block copolymers" by I.W. Hamiey, Advances in Polymer Science, vol 148, 113-137 (1999).
Les polymères semi-cristallins de la composition de l'invention peuvent être ou non réticulés en partie du moment où le taux de réticulation ne gène pas leur dissolution ou dispersion dans la phase grasse liquide par chauffage au-dessus de leur température de fusion. Il peut s'agir alors d'une réticulation chimique, par réaction avec un monomère multifonctionnel lors de la polymérisation. Il peut aussi s'agir d'une réticulation physique qui peut alors être due soit à l'établissement de liaisons type hydrogène ou dipolaire entre des groupes portés par le polymère comme par exemple les interactions dipolaires entre ionomeres carboxylates, ces interactions étant en faible quantité et portées par le squelette du polymère ; soit à une séparation de phase entre les séquences cristallisables et les séquences amorphes, portées par le polymère.The semi-crystalline polymers of the composition of the invention may or may not be crosslinked in part as long as the crosslinking rate does not hinder their dissolution or dispersion in the liquid fatty phase by heating above their melting temperature. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It can also be a physical crosslinking which can then be due either to the establishment of hydrogen type or dipolar bonds between groups carried by the polymer such as for example the dipolar interactions between ionomeres carboxylates, these interactions being in small quantity and carried by the polymer backbone; or to a phase separation between the crystallizable blocks and the amorphous blocks, carried by the polymer.
De préférence, les polymères semi-cristallins de la composition selon l'invention sont non réticulés. A titre d'exemple particulier de polymère semi-cristallins structurant utilisable dans la composition selon l'invention, on peut citer les produits mtelimer® de la société Landec décrits dans la brochure "Intelimer® polymers", Landec IP22 (Rev. 4-97). Ces polymères sont sous forme solide à température ambiante (25°C). Ils sont porteurs de chaînes latérales cristallisables et présentent la formule X précédente.Preferably, the semi-crystalline polymers of the composition according to the invention are non-crosslinked. As a specific example of a structuring semi-crystalline polymer which can be used in the composition according to the invention, mention may be made of the mtelimer® products from the company Landec described in the brochure "Intelimer® polymers", Landec IP22 (Rev. 4-97 ). These polymers are in solid form at room temperature (25 ° C). They carry crystallizable side chains and have the above formula X.
Mélange de polymère semi-cristallin à haut point de fusion et de polymère semi- cristallin à bas point de fusionMixture of semi-crystalline polymer with high melting point and semi-crystalline polymer with low melting point
Dans la suite de la description, le ou les polymères semi-cristallins ayant une température de fusion Pf2 inférieure à 50°C seront dénommés "polymères à bas point de fusion" et le ou les composés cristallins ou semi-cristallins ayant une température de fusion Pf-i supérieure ou égale à 50°C seront dénommés "composés à haut point de fusion". Selon l'invention, le point de fusion peut être mesuré notamment par toute méthode connue et en particulier avec un calorimètre à balayage différentiel (D.S.C).In the following description, the semi-crystalline polymer (s) having a melting point Pf 2 of less than 50 ° C will be called "low melting point polymers" and the crystalline or semi-crystalline compound (s) having a temperature of Pf-i melting greater than or equal to 50 ° C will be referred to as "high melting point compounds". According to the invention, the melting point can be measured in particular by any known method and in particular with a differential scanning calorimeter (DSC).
La composition contient avantageusement un mélange d'un polymère choisi parmi les polymères à bas point de fusion ayant une température de fusion inférieure à 50°C, et d'un polymère choisi parmi les polymères à haut point de fusion ayant une température de fusion au moins égale à 50°C.The composition advantageously contains a mixture of a polymer chosen from polymers with a low melting point having a melting temperature below 50 ° C., and a polymer chosen from polymers with a high melting point having a melting temperature at less than 50 ° C.
Selon l'invention le ou les composés semi-cristallins à haut point de fusion sont avantageusement des polymères ayant une température de fusion Pfi telle que 50°C < Pfi < 150°C, mieux 55°C < P^ < 150°C, et de préférence 60°C < Pf, < 130°C et les polymères à bas point de fusion ont avantageusement une température de fusion Pf2 telle que 30°C < Pf2 < 50°C, et mieux 35°C < Pf2 < 45°C. Cette température de fusion est une température de changement d'état du premier ordre.According to the invention, the semi-crystalline compound (s) with a high melting point are advantageously polymers having a melting temperature Pfi such that 50 ° C <Pfi <150 ° C, better still 55 ° C <P ^ <150 ° C, and preferably 60 ° C <Pf, <130 ° C and the polymers with low melting point advantageously have a melting temperature Pf 2 such that 30 ° C <Pf 2 <50 ° C, and better still 35 ° C <Pf 2 <45 ° C. This melting temperature is a first order state change temperature.
De façon générale, les polymères à bas point de fusion présentent une température de fusion Pf2 au moins égale à la température du support kératinique devant recevoir la composition selon l'invention.In general, polymers with a low melting point have a melting point Pf 2 at least equal to the temperature of the keratinous support which is to receive the composition according to the invention.
Comme composé à. haut point de fusion utilisable dans l'invention, on peut citer les cires à haut point de fusion comme certaines cires de polyéthylène telle que l'Epolène N-14 vendu par Eastman Chemical Cie, les cires, de Carnauba et certaines cires microcristallines comme celles vendues par Tisco sous la marque "Tisco wax 88", ainsi que des polymères semi-cristallins à haut point de fusion. De préférence, le composé à haut point de fusion est un second polymère semi-cristallin solide organique à haut point de fusion. Il est toutefois possible d'utiliser comme composé à haut point de fusion des polymères cristallins, solides à température ambiante et ayant une température de fusion supérieure à 50°C des polymères statistiques comportant une cristallisation contrôlée, tels que décrits dans le document EP-A-0 951 897 et plus spécialement les produits commerciaux Engage 8 401 et Engage 8 402 de Dupont de Nemours, respectivement de température de fusion de 51 °C et 64°C et qui sont des bipolymères statistiques éthylène/1-octène.As composed at. high melting point which can be used in the invention, mention may be made of high melting point waxes such as certain polyethylene waxes such as Epolene N-14 sold by Eastman Chemical Co., the Carnauba waxes and certain microcrystalline waxes such as those sold by Tisco under the brand "Tisco wax 88", as well as polymers semi-crystalline with a high melting point. Preferably, the high melting point compound is a second organic solid semi-crystalline polymer with high melting point. However, it is possible to use, as a compound with a high melting point, crystalline polymers, solid at room temperature and having a melting temperature above 50 ° C., random polymers comprising controlled crystallization, as described in document EP-A -0 951 897 and more specifically the commercial products Engage 8 401 and Engage 8 402 from Dupont de Nemours, with melting temperatures of 51 ° C and 64 ° C respectively and which are random ethylene / 1-octene bipolymers.
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i) Les polymères semi-cristallins dont le point de fusion est inférieur à 50°C sont notamment ceux décrits dans les exemples 3, 4, 5, 7, 9 du brevet US-A-5 156 911 à groupement -COOH, résultant de la copolymérisation d'acide acrylique et d'alkyl(méth)acrylate en C5 à C16 de température de fusion allant de 20°C à 35°C et plus particulièrement de la copolymérisation : . d'acide acrylique, d'hexadécylacrylate et d'isodécylacrylate dans un rapport 1/16/3, . d'acide acrylique et de pentadécylacrylate dans un rapport 1/19, . d'acide acrylique, d'hexadécylacrylate, éthylacrylate dans un rapport 2,5/76,5/20, . d'acide acrylique, d'hexadécylacrylate et de méthylacrylate dans un rapport 5/85/10, . d'acide acrylique, de polyoctadécylméthacrylate dans un rapport 2,5/97,5.i) The semi-crystalline polymers whose melting point is less than 50 ° C. are in particular those described in Examples 3, 4, 5, 7, 9 of US Pat. No. 5,156,911 with a -COOH group, resulting from the copolymerization of acrylic acid and of C 5 to C 16 alkyl (meth) acrylate with a melting temperature ranging from 20 ° C to 35 ° C and more particularly of the copolymerization:. acrylic acid, hexadecylacrylate and isodecylacrylate in a 1/16/3 ratio,. of acrylic acid and pentadecylacrylate in a ratio 1/19,. acrylic acid, hexadecylacrylate, ethylacrylate in a ratio 2.5 / 76.5 / 20,. of acrylic acid, hexadecylacrylate and methylacrylate in a 5/85/10 ratio,. acrylic acid, polyoctadecylmethacrylate in a ratio 2.5 / 97.5.
On peut aussi utiliser le polymère Structure « O » de National Starch tel que celui décrit dans le document US-A-5 736 125 de température de fusion de 44°C ainsi que les polymères semi-cristallins à chaînes pendantes cristallisables comportant des groupements fluorés tels que décrits dans les exemples 1, 4, 6, 7 et 8 du document WO- A-01/19333.One can also use the polymer 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 fluorinated groups. as described in examples 1, 4, 6, 7 and 8 of document WO-A-01/19333.
On peut encore utiliser les polymères semi-cristallins de bas point de fusion obtenus par copolymérisation d'acrylate de stéaryle et d'acide acrylique ou de NVP tels que décrits dans le document US-A-5 519 063 ou EP-A- 550 745 et plus spécialement ceux décrits dans les exemples 1 et 2, ci-après, de préparation de polymère.It is also possible to use the semi-crystalline polymers of low melting point obtained by copolymerization of stearyl acrylate and acrylic acid or NVP as described in document US-A-5,519,063 or EP-A-550,745 and more particularly those described in Examples 1 and 2, below, of polymer preparation.
ii) Les polymères semi-cristallins présentant un point de fusion supérieur ou égal à 50°C sont notamment l'Intelimer décrit dans la brochure "Intelimer® polymers", Landec IP22 (Rev. 4-97) de température de fusion de 56°C, qui est un produit visqueux à température ambiante, imperméable, non-collant. On peut aussi utiliser les polymères semi-cristallins obtenus par copolymérisation de l'acrylate de béhényle et de l'acide acrylique ou de NVP, tels que décrits dans les documents US-A-5 519 063 et EP-A- 055 0745 et plus spécialement ceux décrits dans les exemples 3 et 4, ci-après, de préparation de polymère.ii) The semi-crystalline polymers having a melting point greater than or equal to 50 ° C. are in particular the Intelimer described in the brochure "Intelimer® polymers", Landec IP22 (Rev. 4-97) with a melting point of 56 ° C, which is a viscous product at room temperature, waterproof, non-sticky. 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-055 0745 and more especially those described in Examples 3 and 4, below, of polymer preparation.
De préférence, les polymères semi-cristallins à bas point de fusion et/ou ceux à haut point de fusion ne comportent pas de groupement carboxylique.Preferably, the semi-crystalline polymers with a low melting point and / or those with a high melting point do not contain a carboxylic group.
Selon l'invention et de façon avantageuse, le composé à haut point de fusion (cristallin ou semi-cristallin) et celui à bas point de fusion sont dans un rapport en poids allant de 10/90 à 90/10 et mieux de 40/60 à 60/40, de préférence encore dans un rapport pondéral proche de 50/50.According to the invention and advantageously, the compound with a high melting point (crystalline or semi-crystalline) and that with a low melting point are in a weight ratio ranging from 10/90 to 90/10 and better still 40 / 60 to 60/40, more preferably in a weight ratio close to 50/50.
De façon avantageuse, le rapport pondéral de polymère semi-cristallin à structure organique par rapport à la phase grasse liquide est de 0,20 à 0,60 et mieux de 0,25 à 0,50, obtenir un stick dur qui se délite au contact de la peau ou des lèvres et en particulier de dureté allant de 100 à 350 gf.Advantageously, the weight ratio of semi-crystalline polymer with organic structure relative to the liquid fatty phase is from 0.20 to 0.60 and better still from 0.25 to 0.50, obtaining a hard stick which disintegrates at skin or lip contact and in particular of hardness ranging from 100 to 350 gf.
La gélification de la phase grasse est modulable selon la nature du ou des polymères et leurs concentrations respectives et peut être telle que l'on obtienne une structure rigide sous forme d'un bâton ou d'un stick.The gelation of the fatty phase is adjustable according to the nature of the polymer (s) and their respective concentrations and can be such that a rigid structure is obtained in the form of a stick or a stick.
Le taux de chaque polymère est choisi selon la dureté de la composition désirée et en fonction de l'application particulière envisagée. Les quantités respectives de polymère peuvent être telles qu'elles permettent l'obtention d'un solide délitable, présentant en particulier une dureté allant de 100 à 350 gf. Cette dureté peut être mesurée par la méthode dite du "fil à couper le beurre", qui consiste à couper un bâton de rouge à lèvres de 12,7 mm de diamètre et à mesurer la dureté à 20°C, au moyen d'uri dynamomètre DFGHS 2 de la société Indelco-Chatillon se déplaçant à une vitesse de 100mm/minute. Elle est exprimée comme la force de cisaillement (exprimée en gramme-force) nécessaire pour couper un stick dans ces conditions .The level of each polymer is chosen according to the hardness of the desired composition and according to the particular application envisaged. The respective amounts of polymer may be such that they make it possible to obtain a disintegrable solid, in particular having a hardness ranging from 100 to 350 gf. This hardness can be measured by the so-called "butter cutting wire" method, which consists of cutting a stick of lipstick 12.7 mm in diameter and measuring the hardness at 20 ° C, using uri DFGHS 2 dynamometer from the company Indelco-Chatillon moving at a speed of 100mm / minute. It is expressed as the shear force (expressed in gram-force) necessary to cut a stick under these conditions.
Cette dureté est telle que la composition est autoportée et peut se déliter aisément pour former un dépôt satisfaisant sur la peau et les lèvres. En outre, avec cette dureté, la composition de l'invention sous forme coulée notamment en stick résiste bien aux chocs. De préférence, la composition de l'invention se présente sous forme d'un stick solide, de dureté allant de 100 gf à 350 gf, mesurée selon la méthode du "fil à couper le beurre". Il est toutefois possible d'utiliser une quantité de polymère semi-cristallin telle que la composition soit sous forme de pâte souple applicable au doigt ou à l'aide d'un applicateur sur les matières kératiniques.This hardness is such that the composition is self-supporting and can disintegrate easily to form a satisfactory deposit on the skin and the lips. In addition, with this hardness, the composition of the invention in cast form, in particular in stick form, withstands impact well. Preferably, the composition of the invention is in the form of a solid stick, of hardness ranging from 100 gf to 350 gf, measured according to the "butter cutting wire" method. It is however possible to use an amount of semi-crystalline polymer such that the composition is in the form of a flexible paste applicable with the finger or with the aid of an applicator on keratin materials.
En pratique, la quantité totale de polymère(s) semi-cristallin(s) représente de 0,1 à 80 % du poids total de la composition et mieux de 0,5 à 40 % et encore mieux de 3 à 30 %; De préférence, il représente de 15 % à 25% en poids de la composition.In practice, the total amount of semi-crystalline polymer (s) represents from 0.1 to 80% of the total weight of the composition and better still from 0.5 to 40% and even better still from 3 to 30%; Preferably, it represents from 15% to 25% by weight of the composition.
Les bâtons ou sticks selon l'invention permettent, après application, d'obtenir un dépôt brillant, homogène en couleur, non collant, de bonne couvrance (c'est-à-dire que la peau ou les lèvres n'apparaît pas sous le maquillage).The sticks or sticks according to the invention make it possible, after application, to obtain a glossy deposit, uniform in color, non-sticky, with good coverage (that is to say that the skin or the lips do not appear under the makeup).
L'esterThe ester
Le mot ester selon l'invention signifie un monoester.The word ester according to the invention means a monoester.
L'ester selon l'invention comprend 10 à 40 atomes de carbone, de préférence de 10 à 30 atomes de carbone, de préférence encore de 12 à 26 atomes de carbone, de préférence encore de 16 à 22 atomes de carbone.The ester according to the invention comprises 10 to 40 carbon atoms, preferably from 10 to 30 carbon atoms, more preferably from 12 to 26 carbon atoms, more preferably from 16 to 22 carbon atoms.
L'ester selon l'invention est de préférence liquide à température ambiante (25°C). Il est avantageusement aliphatique et/ou linéaire.The ester according to the invention is preferably liquid at room temperature (25 ° C). It is advantageously aliphatic and / or linear.
L'ester représente de préférence de 10 à 40%, et mieux de 15 à 30 %, de préférence de 20 à 25% en poids de la composition.The ester preferably represents from 10 to 40%, and better still from 15 to 30%, preferably from 20 to 25% by weight of the composition.
L'ester représente de préférence 15 à 50 % , de préférence de 25 à 40% de la phase grasse liquide.The ester preferably represents 15 to 50%, preferably 25 to 40% of the liquid fatty phase.
Le rapport pondéral de l'ester par rapport au polymère semi-cristallin est avantageusement compris entre 1 et 2, de préférence entre 1,3 et 1,7.The weight ratio of the ester relative to the semi-crystalline polymer is advantageously between 1 and 2, preferably between 1.3 and 1.7.
L'ester selon invention peut être choisi parmi - les esters de synthèse notamment d'acides gras comme les huiles de formule R1COOR2 dans laquelle Ri représente le reste d'un acide gras supérieur comportant de 1 à 38 atomes de carbone et R2 représente une chaîne hydrocarbonée contenant de 1 à 38 atomes de carbone avec 39 > Ri + R2 > 10 comme par exemple l'huile de Purcellin, l'isononanoate d'isononyle, l'isostéarate d'isopropyle, le myristate d'isopropyle, le palmitate d'éthyl 2-hexyle, le stéarate d'octyl 2-dodécyle, l'érucate d'octyl 2-dodécyle, l'isostéarate d'isostéaryle ;The ester according to the invention can be chosen from - synthetic esters, in particular of fatty acids such as oils of formula R 1 COOR 2 in which Ri represents the remainder of a higher fatty acid containing from 1 to 38 carbon atoms and R 2 represents a hydrocarbon chain containing from 1 to 38 carbon atoms with 39> Ri + R 2 > 10 such as Purcellin oil, isononyl isononanoate, isopropyl isostearate, isopropyl myristate, ethyl 2-hexyl palmitate , octyl 2-dodecyl stearate, octyl 2-dodecyl erucate, isostearyl isostearate;
- les esters hydroxylés comme le lactate d'isostéaryle, l'hydroxy stéarate d'octyle, l'hydroxy stéarate d'octyl dodécyle, des heptanoates, octanoates, décanoates d'alcools gras ;- hydroxylated esters such as isostearyl lactate, octyl hydroxy stearate, octyl dodecyl hydroxy stearate, heptanoates, octanoates, decanoates of fatty alcohols;
- l'érucate d'oléyle ;- oleyl erucate;
- un ester benzoate d'alkyle en C12- C15 (comme le Finsolv TN commercialisé par la société FINETEX),a C 12 -C 15 alkyl benzoate ester (such as Finsolv TN sold by the company FINETEX),
- et leurs mélanges- and their mixtures
La phase grasse liquideThe liquid fatty phase
Par "phase grasse liquide", au sens de la demande, on entend une phase grasse liquide à température ambiante (25°C) et pression atmosphérique (760 mm de Hg), composée d'un ou plusieurs corps gras liquides à température ambiante, appelés aussi huiles, compatibles entre eux. Cette phase grasse est macroscopiquement homogène.By “liquid fatty phase”, in the sense of the demand, is meant a fatty phase liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mm of Hg), composed of one or more fatty substances liquid at ambient temperature, also called oils, compatible with each other. This fatty phase is macroscopically homogeneous.
Avantageusement, la phase grasse liquide, structurée par les polymères semi-cristallins, constitue la phase continue de la composition. Cette phase grasse peut contenir une ou plusieurs huiles apolaires ou non ou un mélange d'huile(s) apolaire(s) et d'huile(s) polaire(s)ou un mélange d'huiles polaires, différentes de l'alcool aliphatique décrit précédemment.Advantageously, the liquid fatty phase, structured by the semi-crystalline polymers, constitutes the continuous phase of the composition. This fatty phase can contain one or more non-polar oils or a mixture of non-polar oil (s) and polar oil (s) or a mixture of polar oils, different from aliphatic alcohol. previously described.
Les huiles apolaires selon l'invention sont en particulier les huiles siliconées telles que les polydiméthylsiloxanes (PDMS), linéaires ou cycliques, liquides à température ambiante ; les polydiméthylsiloxanes comportant des groupements alkyle, alcoxy ou phényle, pendant et/ou en bout de chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone, liquides à température ambiante ; les silicones phénylées comme les phényl triméthicones, les phényl diméthicones, les phényl triméthylsiloxy diphénylsiloxanes, des diphényl diméthicones, les diphényl méthyldiphényl . trisiloxanes, les 2-phényléthyl triméthylsiloxysilicates, liquides ; les hydrocarbures ou fluorocarbures linéaires ou ramifiés d'origine synthétique ou minérale, liquides, comme les huiles de paraffine et leurs dérivés, la vaseline, les polydécènes, le polyisobutène hydrogéné tel que le Parléam® vendu par la société Nippon Oil Fats, le squalane ; leurs mélanges. De préférence, les huiles apolaires utilisées sont des huiles apolaires du type hydrocarboné, liquides, d'origine minérale ou synthétique, choisies notamment parmi l'huile de Parleam® (isoparaffine hydrogénée), les isoparaffines, le squalane et leurs mélanges.The apolar oils according to the invention are in particular silicone oils such as polydimethylsiloxanes (PDMS), linear or cyclic, liquid at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, pendant and / or at the end of the silicone chain, groups having 2 to 24 carbon atoms, liquid at room temperature; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl. trisiloxanes, 2-phenylethyl trimethylsiloxysilicates, liquids; linear or branched hydrocarbons or fluorocarbons of synthetic or mineral origin, liquids, such as paraffin oils and their derivatives, petrolatum, polydecenes, hydrogenated polyisobutene such as Parléam® sold by the company Nippon Oil Fats, squalane; their mixtures. Preferably, the nonpolar oils used are nonpolar oils of the hydrocarbon type, liquids, of mineral or synthetic origin, chosen in particular from Parleam® oil (hydrogenated isoparaffin), isoparaffins, squalane and their mixtures.
Avantageusement, la phase grasse liquide contient au moins une huile polaire et au moins une huile peu polaire, comme l'isononyl isononanonoate.Advantageously, the liquid fatty phase contains at least one polar oil and at least one slightly polar oil, such as isononyl isononanonoate.
En particulier, les huiles polaires de l'invention sont :In particular, the polar oils of the invention are:
- les huiles végétales hydrocarbonées à forte teneur en triglycérides constitués d'esters d'acides gras (en C8 à C24) et de glycérol dont les acides gras peuvent avoir des longueurs de chaînes variées, ces dernières pouvant être linéaires ou ramifiées, saturées ou insaturées ; ces huiles sont notamment les huiles de germe de blé, de maïs, de tournesol, de karité, de ricin, d'amandes douces, de macadamia, d'abricot, de soja, de colza, de coton, de luzerne, de pavot, de potimarron, de sésame, de courge, d'avocat, de noisette, de pépins de raisin ou de cassis, d'onagre, de millet, d'orge, de quinoa, d'olive, de seigle, de carthame, de bancoulier, de passiflore, de rosier muscat ; ou encore les triglycérides des acides caprylique/caprique comme ceux vendus par la société Stearineries Dubois ou ceux vendus sous les dénominations Miglyol 810, 812 et 818 par la société Dynamit Nobel- hydrocarbon-based vegetable oils with a high triglyceride content consisting of fatty acid esters (C 8 to C 24 ) and glycerol, the fatty acids of which can have varied chain lengths, the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular the oils of wheat germ, corn, sunflower, shea, castor, sweet almonds, macadamia, apricot, soy, rapeseed, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grapeseed or blackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye, safflower, and nutmeg , passion flower, muscat rose; or the triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel
- les huiles de synthèse de formule R5COOR6 dans laquelle R5 représente le reste d'un acide gras supérieur linéaire ou ramifié comportant de 7 à 40 atomes de carbone et R6 représente une chaîne hydrocarbonée ramifiée contenant de 3 à 40 atomes de carbone comme par exemple l'huile de Purcellin (octanoate de cétostéaryle), l'isononanoate d'isononyle, le benzoate d'alcool en C12 à C15 ;- synthetic oils of formula R 5 COOR 6 in which R 5 represents the remainder of a linear or branched higher fatty acid containing from 7 to 40 carbon atoms and R 6 represents a branched hydrocarbon chain containing from 3 to 40 carbon atoms carbon such as, for example, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C 12 to C 15 alcohol benzoate;
- les esters et les éthers de synthèse comme le myristate d'isopropyle, le palmitate d'éthyl 2-hexyle, des octanoates, décanoates ou ricinoléates d'alcools ou de polyalcools, les esters hydroxylés comme le lactate d'isostéaryle, le malate de di-isostéaryle ; et les esters du pentaérythritol ;- synthetic esters and ethers such as isopropyl myristate, ethyl 2-hexyl palmitate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, hydroxylated esters such as isostearyl lactate, malate di-isostearyl; and pentaerythritol esters;
- les acides gras ayant de 12 à 22 atomes de carbone comme l'acide oléique, linoléique ou linolénique ;- fatty acids having from 12 to 22 carbon atoms such as oleic, linoleic or linolenic acid;
- leurs mélanges. La phase grasse liquide représente, en pratique, de 5 à 99 % du poids total de la composition, de préférence de 20 à 80 %. Avantageusement, elle représente au moins 60 % du poids total de la composition.- their mixtures. The liquid fatty phase represents, in practice, from 5 to 99% of the total weight of the composition, preferably from 20 to 80%. Advantageously, it represents at least 60% of the total weight of the composition.
La matière coloranteThe coloring matter
Avantageusement, la composition contient une matière colorante qui peut être choisie parmi les colorants lipophiles, les colorants hydrophiles, les pigments et les nacres habituellement utilisés dans les compositions cosmétiques ou dermatologiques, et leurs mélanges. Cette matière colorante est généralement présente à raison de 0,01 à 50 % (en matière sèche) du poids total de la composition, de préférence de 5 à 30 % (si présente).Advantageously, the composition contains a coloring material which can be chosen from lipophilic dyes, hydrophilic dyes, pigments and nacres usually used in cosmetic or dermatological compositions, and mixtures thereof. This coloring material is generally present in an amount of 0.01 to 50% (in dry matter) of the total weight of the composition, preferably from 5 to 30% (if present).
Les colorants liposolubles sont par exemple le rouge Soudan, le D & C Red 17, le D & C Green 6, le β-carotène, l'huile de soja, le brun Soudan, le D & C Yellow 11 , le D & C Violet 2, le D & C orange 5, le jaune quinoléiήe, le rocou. Ils peuvent représenter de 0 à 20 % du poids de la composition et mieux de 0,01 à 6 % (si présents). Les colorants hydrosolubles sont par exemple le jus de betterave, le bleu de méthylène et peuvent représenter jusqu'à 6 % du poids total de la composition.The liposoluble dyes are for example Sudan red, D & C Red 17, D & C Green 6, β-carotene, soybean oil, Sudan brown, D & C Yellow 11, D & C Violet 2, D & C orange 5, quinoléiήe yellow, annatto. They can represent from 0 to 20% of the weight of the composition and better still from 0.01 to 6% (if present). The water-soluble dyes are, for example, beet juice, methylene blue and can represent up to 6% of the total weight of the composition.
Les pigments peuvent être blancs ou colorés, minéraux et/ou organiques, enrobés ou non. On peut citer, parmi les pigments minéraux, le dioxyde de titane ou de zinc, éventuellement traité en surface, les oxydes de zirconium ou de cérium, ainsi que les oxydes de fer ou de chrome, le violet de manganèse, le bleu outremer, l'hydrate de chrome et le bleu ferrique. Parmi les pigments organiques, on peut citer le noir de carbone, les pigments de type D & C, et les laques à base de carmin de cochenille, de baryum, strontium, calcium, aluminium (tels que le D & C red 27, 21 , 7, D & C yellow 5, 6, le F D & C blue n°1). Les pigments peuvent représenter de 0 à 40 % (0,01 à 40 %) notamment de 0,5 à 35 % et mieux de 2 à 25 % du poids total de la composition (si présents).The pigments can be white or colored, mineral and / or organic, coated or not. Mention may be made, among the mineral pigments, of titanium or zinc dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chromium and ferric blue. Among the organic pigments, there may be mentioned carbon black, pigments of the D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum (such as D & C red 27, 21 , 7, D & C yellow 5, 6, FD & C blue n ° 1). The pigments can represent from 0 to 40% (0.01 to 40%), in particular from 0.5 to 35% and better still from 2 to 25% of the total weight of the composition (if present).
Les pigments nacrés peuvent être choisis parmi les pigments nacrés blancs tels que le mica notamment recouvert de titane ou d'oxychlorure de bismuth, les pigments nacrés colorés tels que le mica titane avec des oxydes de fer, le mica titane avec notamment du bleu ferrique ou de l'oxyde de chrome, le mica titane avec un pigment organique du type précité ainsi que les pigments nacrés à base d'oxychlorure de bismuth. Ils peuvent représenter de 0 à 25 % (0,05 à 25 %) du poids total de la composition et mieux de 0,1 à 15 % (si présents). Avantageusement, les pigments et les nacres sont introduits dans la composition sous forme de pâte pigmentaire.The pearlescent pigments can be chosen from white pearlescent pigments such as mica, in particular coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica titanium with iron oxides, mica titanium with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. They can represent from 0 to 25% (0.05 to 25%) of the total weight of the composition and better still from 0.1 to 15% (if present). Advantageously, the pigments and pearlescent agents are introduced into the composition in the form of a pigment paste.
Par "pâte pigmentaire", on entend au sens de l'invention une dispersion colloïdale concentrée de particules colorées enrobées ou non dans un milieu continu, éventuellement stabilisée à l'aide d'un agent dispersant.By "pigment paste" is meant in the sense of the invention a concentrated colloidal dispersion of colored particles coated or not in a continuous medium, optionally stabilized using a dispersing agent.
Bien entendu l'homme du métier veillera à choisir les éventuels additifs complémentaires, et/ou leur quantité de telle manière que les propriétés avantageuses de la composition selon l'invention ne soient pas ou substantiellement pas, altérées par l'adjonction envisagée.Of course, a person skilled in the art will take care to choose any additional additives, and / or their amount in such a way that the advantageous properties of the composition according to the invention are not or not substantially altered by the envisaged addition.
La composition de maquillage de l'invention peut se présenter sous la forme d'un produit coloré en particulier de la peau, présentant éventuellement des propriétés de soin ou de traitement, et être en particulier un fond de teint, un blush, un fard à joues ou à paupières, un produit anti-cerne, un eye-liner, un produit de maquillage du corps ; de maquillage des lèvres comme un rouge à lèvres, un brillant à lèvres ou un crayon à lèvres présentant éventuellement des propriétés . de soin ou de traitement ; de maquillage des phanères comme les ongles, les cils sous forme de mascara, les sourcils et les cheveux. Elle est de préférence anhydre ou sous forme coulée.The makeup composition of the invention may be in the form of a colored product in particular of the skin, optionally having care or treatment properties, and may in particular be a foundation, a blush, a blush. cheeks or eyeshadow, a concealer, an eyeliner, a body makeup product; lip makeup such as a lipstick, a lip gloss or a lip pencil possibly having properties. care or treatment; make-up of the integuments such as nails, eyelashes in the form of mascara, eyebrows and hair. It is preferably anhydrous or in cast form.
Bien entendu la composition de l'invention doit être cosmétiquement acceptable, à savoir contenir un milieu physiologiquement acceptable non toxique et susceptible d'être appliqué sur. la peau, les phanères ou les lèvres du visage d'êtres humains. Par cosmétiquement acceptable, on entend au sens de l'invention une composition d'aspect, d'odeur, de toucher et éventuellement de goût agréables.Of course, the composition of the invention must be cosmetically acceptable, ie contain a physiologically acceptable medium which is non-toxic and capable of being applied to. the skin, the integuments or the lips of the face of human beings. By cosmetically acceptable is meant in the sense of the invention a composition of appearance, odor, touch and possibly of pleasant taste.
On peut aussi utiliser dans la composition de l'invention au moins une cire telle que celles utilisées jusqu'à ce jour en cosmétique.It is also possible to use in the composition of the invention at least one wax such as those used to date in cosmetics.
Une cire, au sens de la présente invention, est un composé gras lipophile, solide 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. La taille des cristaux est telle que les cristaux diffractent et/ou diffusent la lumière, conférant à la composition un aspect trouble, plus ou moins opaque. En portant la cire à sa température de fusion, il est possible de la rendre miscible aux huiles et de former un mélange homogène microscopiquement, mais en ramenant la température du mélange à la température ambiante, on obtient une recristallisation de la cire dans les huiles du mélange. Cette recristallisation dans le mélange peut être responsable de la diminution de la brillance dudit mélange. Aussi, avantageusement, la composition contient peu ou pas de cires classiques et notamment moins de 10 %, en poids, de cire classique et mieux moins de 5% par rapport au poids total de la composition.A wax, within the meaning of the present invention, is a lipophilic fatty compound, solid at room temperature (25 ° C) and atmospheric pressure (760 mm Hg), with reversible solid / liquid state change, having a melting temperature greater than 40 ° C and better still greater than 50 ° C, up to 200 ° C, and having an anisotropic crystalline organization in the solid state. The size of the crystals is such that the crystals diffract and / or scatter light, giving the composition a cloudy, more or less opaque appearance. By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, the wax is recrystallized from the oils of the mixed. This recrystallization from the mixture may be responsible for the reduction in the gloss of said mixture. Also, advantageously, the composition contains little or no conventional waxes and in particular less than 10%, by weight, of conventional wax and better still less than 5% relative to the total weight of the composition.
Les cires classiques, au sens de la demande, sont celles généralement utilisées dans les domaines cosmétique et dermatologique ; elles sont notamment d'origine naturelle comme la cire d'abeilles, de Candellila, d'Ouricoury, du Japon, de fibres de liège ou de canne à sucre, les cires de paraffine, de lignite, les cires microcristallines de point de fusion > 50°C, la cire de lanoline, la cire de Montan, les ozokérites, les huiles hydrogénées comme l'huile de jojoba hydrogénée, mais aussi d'origine synthétique comme les cires de polyéthylène issues de la polymérisation de l'éthylène et les cires obtenues par synthèse de Fischer- Tropsch à point de fusion > 50°C, les esters d'acides gras et les glycérides concrets à 50°C, les cires de silicone comme les alkyle, alcoxy et/ou esters de poly(di)méthylsiloxane solide à 50°C.Conventional waxes, in the sense of demand, are those generally used in the cosmetic and dermatological fields; they are in particular of natural origin such as beeswax, Candellila, Ouricoury, Japan, cork fibers or sugar cane, paraffin waxes, lignite, microcrystalline waxes of melting point> 50 ° C, lanolin wax, Montan wax, ozokerites, hydrogenated oils such as hydrogenated jojoba oil, but also of synthetic origin such as polyethylene waxes resulting from the polymerization of ethylene and waxes obtained by Fischer-Tropsch synthesis at melting point> 50 ° C, fatty acid esters and concrete glycerides at 50 ° C, silicone waxes such as alkyl, alkoxy and / or poly (di) methylsiloxane esters solid at 50 ° C.
Avantageusement, la composition de l'invention contient peu ou pas de charges "matifiantes" et en particulier moins de 5 % de charge matifiante. Ceci est notamment le cas lorsqu'on souhaite obtenir un dépôt brillant sur les matières kératiniques comme les lèvres, les cils et les cheveux. Pour un fond de teint, on peut au contraire utiliser ce type de charges. Une charge matifiante est en général une charge qui absorbe la sueur et/ou le sébum de la peau comme les silices, talcs, argiles, kaolins, poudres de polyamide (Nylon®).Advantageously, the composition of the invention contains little or no "mattifying" fillers and in particular less than 5% of mattifying filler. This is particularly the case when it is desired to obtain a shiny deposit on keratin materials such as the lips, the eyelashes and the hair. On the contrary, for a foundation, this type of filler can be used. A mattifying filler is generally a filler which absorbs sweat and / or sebum from the skin such as silicas, talcs, clays, kaolins, polyamide powders (Nylon®).
La composition selon l'invention peut être fabriquée par les procédés connus, généralement utilisés dans le domaine cosmétique.The composition according to the invention can be produced by known methods, generally used in the cosmetic field.
L'invention a encore pour objet un procédé cosmétique de soin, de maquillage ou de traitement des matières kératiniques des êtres humains et notamment de la peau, des lèvres du visage et des phanères des êtres humains, comprenant l'application sur les matières kératiniques de la composition notamment cosmétique telle que définie ci-dessus. L'invention a encore pour objet l'utilisation d'un ester comprenant 10 à 40 atomes de carbone, dans une composition de maquillage comprenant a) au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique dont la température de fusion est supérieure ou égale à 30°C, b) une matière colorante, la phase grasse liquide, la matière colorante, l'ester et le polymère formant un milieu physiologiquement acceptable.The subject of the invention is also a cosmetic process for caring for, making up or treating keratin materials of human beings and in particular of the skin, facial lips and integuments of human beings, comprising the application to keratin materials of the composition, in particular cosmetic, as defined above. Another subject of the invention is the use of an ester comprising 10 to 40 carbon atoms, in a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, the melting point is greater than or equal to 30 ° C, b) a coloring matter, the liquid fatty phase, the coloring matter, the ester and the polymer forming a physiologically acceptable medium.
L'invention a encore pour objet l'utilisation d'une quantité suffisante d'un ester comprenant 10 à 40 atomes de carbone, dans une Composition contenant un milieu physiologiquement acceptable comprenant a) au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique, dont la température de fusion est supérieure ou égale à 30°C, et b) une matière colorante, comme agent pour conférer du glissant à l'application et de la brillance à ladite composition.Another subject of the invention is the use of a sufficient quantity of an ester comprising 10 to 40 carbon atoms, in a composition containing a physiologically acceptable medium comprising a) at least one liquid fatty phase structured by at least one polymer semi-crystalline with an organic structure, the melting point of which is greater than or equal to 30 ° C, and b) a coloring matter, as an agent for imparting slipperiness on application and gloss to said composition.
L'invention a encore pour objet l'utilisation d'un ester comprenant 10 à 40 atomes de carbone dans une composition cosmétique contenant un milieu physiologiquement acceptable comprenant au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique, pour obtenir une composition glissante à l'application et brillante.The subject of the invention is also the use of an ester comprising 10 to 40 carbon atoms in a cosmetic composition containing a physiologically acceptable medium comprising at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, to obtain a composition that is slippery on application and shiny.
L'invention est illustrée plus en détail dans les exemples suivants. Les quantités sont données en pourcentage massique.The invention is illustrated in more detail in the following examples. The quantities are given in percentage by mass.
I) Exemples de fabrication de polymères semi-cristallinsI) Examples of manufacturing semi-crystalline polymers
Exemple 1 : Homopolymère de point de fusion de 48°CEXAMPLE 1 Homopolymer with a Melting Point of 48 ° C
Dans un réacteur d'il muni d'une agitation centrale avec ancre, d'un réfrigérant et d'un thermomètre, on introduit 120g de Parléam que l'on chauffe de la température ambiante à 80°C en 45 min. A 80°C, on introduit en 2h le mélange Ci suivant :120 g of Parleam are introduced into a reactor with a central agitation with an anchor, a condenser and a thermometer, which are heated from room temperature to 80 ° C. in 45 min. At 80 ° C., the following mixture Ci is introduced over 2 hours:
40g de cyclohexane + 4g de Trigonox 141 [ 2,5 bis (2-éthyl hexanoyl peroxy) - 2,5 - diméthyl hexane].40g of cyclohexane + 4g of Trigonox 141 [2,5 bis (2-ethyl hexanoyl peroxy) - 2,5 - dimethyl hexane].
30 min après le début de la coulée du mélange Ci, on introduit en 1h30 le mélange C2 constitué de : 200 g d'acrylate de stéaryle + 400 g de cyclohexane. A la fin des deux coulées, on laisse agir 3h supplémentaires à 80°C puis on distille à pression atmosphérique la totalité du cyclohexane présent dans le milieu réactionnel. On obtient alors le polymère à 60 % en poids en matière active dans le Parléam.30 min after the start of the pouring of the mixture Ci, the mixture C 2 consisting of: 200 g of stearyl acrylate + 400 g of cyclohexane is introduced over 1 hour 30 minutes. At the end of the two flows, the reaction is left to act for an additional 3 hours at 80 ° C., then all of the cyclohexane present in the reaction medium is distilled. The polymer is then obtained at 60% by weight of active material in the Parléam.
Sa masse moléculaire moyenne en poids est de l'ordre 20 000-30 000 et sa température de fusion Tf est de 48°C, mesurée par D.S.C.Its weight average molecular mass is around 20,000-30,000 and its melting temperature T f is 48 ° C, measured by DSC
Exemple 2 : Copolymère de point de fusion de 48°CExample 2 Copolymer with a Melting Point of 48 ° C
On applique le même mode opératoire que dans l'exemple 1, sauf que l'on utilise un mélange de 10 g de N-Vinyl Pyrrolidone et de 190 g d'acrylate de stéaryle. Le polymère obtenu est à 60% en poids en matière active dans le Parléam, sa masse moléculaire moyenne en poids est de 43 000-53 000 et sa Tf de 48°C.The same procedure is applied as in Example 1, except that a mixture of 10 g of N-Vinyl Pyrrolidone and 190 g of stearyl acrylate is used. The polymer obtained is 60% by weight of active material in Parleam, its weight average molecular weight is 43,000-53,000 and its T f is 48 ° C.
Exemple 3 : Homopolymère de point de fusion de 58°CExample 3 Homopolymer with a Melting Point of 58 ° C
On applique le même mode opératoire que dans l'exemple 1, sauf que l'on utilise de l'acrylate de béhényle en lieu et place de l'acrylate de stéaryle. Le polymère obtenu est à 60% en poids en matière active dans le Parléam. Sa masse moléculaire moyenne en poids est de 17000-27000 et sa Tf de 58°C.The same procedure is applied as in Example 1, except that behenyl acrylate is used in place of stearyl acrylate. The polymer obtained is 60% by weight of active material in Parléam. Its weight average molecular weight is 17000-27000 and its T f of 58 ° C.
Exemple 4 : Copolymère de point de fusion de 58°CExample 4 Copolymer with a Melting Point of 58 ° C
On applique le même mode opératoire que dans l'exemple 2, sauf que l'on utilise de l'acrylate de béhényle en lieu et place de l'acrylate de stéaryle. Le polymère obtenu est à 60% en poids en matière active dans le Parléam®. Sa masse moléculaire moyenne en poids est de 23500-33500 et sa Tf de 58°C. The same procedure is applied as in Example 2, except that behenyl acrylate is used in place of stearyl acrylate. The polymer obtained is 60% by weight of active material in Parléam®. Its weight average molecular mass is 23500-33500 and its T f is 58 ° C.
II) Exemples de compositionII) Examples of composition
Exemple 5 : Formule de rouge à lèvresExample 5: Lipstick Formula
Pourcentage en poidsPercentage by weight
2-Octyl-dodécanol 14,52-Octyl-dodecanol 14.5
Diisostéaryl malate 9,5Diisostearyl malate 9.5
Acide polyhydroxystéarique 2Polyhydroxystearic acid 2
Coco-glycérides hydrogénés 2 Homopolymère préparé selon l'exemple 1 11Hydrogenated coco-glycerides 2 Homopolymer prepared according to Example 1 11
Homopolymère préparé selon l'exemple 3 11Homopolymer prepared according to Example 3 11
Pigments 9Pigments 9
Charge 1Charge 1
Nacre 3 Isononanoate d'isononyle qsp 100Nacre 3 Isononyle isononanoate qs 100
Cette formule est glissante à l'application et son dépôt est brillant et confortable. This formula is slippery on application and its deposit is shiny and comfortable.

Claims

REVENDICATIONS
1. Composition de maquillage comprenant a) au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique dont la température de fusion est supérieure ou égale à 30°C, b) une matière colorante et c) un ester comprenant 10 à 40 atomes de carbone, la phase grasse liquide, la matière colorante, l'ester et le polymère formant un milieu physiologiquement acceptable.1. Make-up composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose melting point is greater than or equal to 30 ° C, b) a coloring matter and c) an ester comprising 10 to 40 carbon atoms, the liquid fatty phase, the coloring matter, the ester and the polymer forming a physiologically acceptable medium.
2. Composition selon la revendication l'ester est choisi parmi - les esters de synthèse notamment d'acides gras comme les huiles de formule2. Composition according to claim the ester is chosen from - synthetic esters in particular of fatty acids such as the oils of formula
RîCOOR2 dans laquelle R^ représente le reste d'un acide gras supérieur comportant de 1 à 38 atomes de carbone et R2 représente une chaîne hydrocarbonée contenant de 1 à 38 atomes de carbone avec 39 > Ri + R2 > 10 comme par exemple l'huile de Purcellin, l'isononanoate d'isononyle, l'isostéarate d'isopropyle, le myristate d'isopropyle, le palmitate d'éthyl 2-hexyle, le stéarate d'octyl 2-dodécyle, l'érucate d'octyl 2-dodécyle, l'isostéarate d'isostéaryle ;RîCOOR 2 in which R ^ represents the remainder of a higher fatty acid containing from 1 to 38 carbon atoms and R 2 represents a hydrocarbon chain containing from 1 to 38 carbon atoms with 39> Ri + R 2 > 10 as for example Purcellin oil, isononyl isononanoate, isopropyl isostearate, isopropyl myristate, ethyl 2-hexyl palmitate, octyl 2-dodecyl stearate, octyl erucate 2-dodecyl, isostearyl isostearate;
- les esters hydroxylés comme le lactate d'isostéaryle, l'hydroxy stéarate d'octyle, l'hydroxy stéarate d'octyl dodécyle, des heptanoates, octanoates, décanoates d'alcools gras ; - l'érucate d'oléyle ;- hydroxylated esters such as isostearyl lactate, octyl hydroxy stearate, octyl dodecyl hydroxy stearate, heptanoates, octanoates, decanoates of fatty alcohols; - oleyl erucate;
- un ester benzoate d'alkyle en C12- C15,a C 12 -C 15 alkyl benzoate ester,
- et leurs mélanges- and their mixtures
3. Composition selon la revendication 1, caractérisée en ce que l'ester est un ester comprend 12 à 26, de préférence de 16 à 22 atomes de carbone.3. Composition according to claim 1, characterized in that the ester is an ester comprises 12 to 26, preferably from 16 to 22 carbon atoms.
4. Composition selon l'une des revendications précédentes, caractérisée en ce que l'ester représente 15 à 40 % en poids de la composition, de préférence de 15 à 30%.4. Composition according to one of the preceding claims, characterized in that the ester represents 15 to 40% by weight of the composition, preferably from 15 to 30%.
5. Composition selon l'une des revendications précédentes, dans laquelle le rapport pondéral de l'ester par rapport au polymère semi-cristallin est avantageusement compris entre 1 et 2, de préférence entre 1,3 et 1,7.5. Composition according to one of the preceding claims, in which the weight ratio of the ester relative to the semi-crystalline polymer is advantageously between 1 and 2, preferably between 1.3 and 1.7.
6. Composition selon l'une des revendications précédentes, caractérisée en ce que l'ester représente 15 à 50%, de préférence 25 à 40% de la phase grasse liquide. 6. Composition according to one of the preceding claims, characterized in that the ester represents 15 to 50%, preferably 25 to 40% of the liquid fatty phase.
7. Composition selon l'une quelconque des revendications précédentes, dans laquelle le polymère semi-cristallin a une masse moléculaire moyenne en poids allant de 5 000 à 1 000 000, de préférence de 10 000 à 800 000, préférentiellement de 15 000 à 500 000.7. Composition according to any one of the preceding claims, in which the semi-crystalline polymer has a weight-average molecular mass ranging from 5,000 to 1,000,000, preferably from 10,000 to 800,000, preferably from 15,000 to 500 000.
8. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère semi-cristallin est soluble dans la phase grasse liquide à une température supérieure à sa température de fusion.8. Composition according to any one of the preceding claims, characterized in that the semi-crystalline polymer is soluble in the liquid fatty phase at a temperature above its melting temperature.
9. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère semi-cristallin a une température de fusion supérieure à la température du support kératinique destiné à recevoir ladite composition.9. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer has a melting temperature higher than the temperature of the keratinous support intended to receive said composition.
10. Composition selon la revendication précédente, caractérisée en ce que le support destiné à recevoir la composition est la peau ou les lèvres.10. Composition according to the preceding claim, characterized in that the support intended to receive the composition is the skin or the lips.
11. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère semi-cristallin est choisi parmi :11. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from:
- les copolymères séquences de polyoléfines à cristallisation contrôlée,- block copolymers of polyolefins with controlled crystallization,
- les polycondensats polyesters aliphatiques ou aromatiques et les copolyesters aliphatiques/aromatiques,- aliphatic or aromatic polyester polycondensates and aliphatic / aromatic copolyesters,
- les homo- ou co-polymères portant au moins une chaîne latérale cristallisable,- homo- or co-polymers carrying at least one crystallizable side chain,
- leurs mélanges.- their mixtures.
12. Composition selon l'une des revendications précédentes, caractérisée en ce le polymère semi-cristallin est choisi parmi les homopolymères et copolymères comportant de12. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from homopolymers and copolymers comprising
50 à 100 % en poids de motifs résultant de la polymérisation de un ou plusieurs monomères porteurs de chaîne(s) latérale(s) hydrophobe(s) cristallisable(s).50 to 100% by weight of units resulting from the polymerization of one or more monomers carrying hydrophobic side chain (s) which can be crystallized.
13. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère semi-cristallin est choisi parmi les homopolymères et copolymères résultant de la polymérisation d'au moins un monomère à chaîne(s) cristallisable(s) de formule X :13. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from homopolymers and copolymers resulting from the polymerization of at least one monomer with crystallizable chain (s) of formula X:
— M — avec M représentant un atome du squelette polymérique I S représentant un espaceur- M - with M representing an atom of the polymer backbone IS representing a spacer
S C représentant un groupe cristallisableS C representing a crystallizable group
C et leurs mélanges, avec « S-C » représentant une chaîne alkyle à au moins 11 atomes de carbone, éventuellement fluorée ou perfluorée.C and their mixtures, with “S-C” representing an alkyl chain with at least 11 carbon atoms, optionally fluorinated or perfluorinated.
14. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère semi-cristallin est choisi parmi les polymères résultant de la polymérisation d'au moins un monomère choisi parmi l'acide acrylique, méthacrylique, crotonique, itaconique, maléique, l'anhydride maléique et leurs mélanges.14. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from polymers resulting from the polymerization of at least one monomer chosen from acrylic, methacrylic, crotonic, itaconic, maleic acid, maleic anhydride and mixtures thereof.
15. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère semi-cristallin est choisi parmi les homopolymères et copolymères résultant de la polymérisation d'au moins un monomère à chaîne cristallisable choisis parmi les (méth)acrylates d'alkyle saturés en C 4-C24, les (méth)acrylates de perfluoroalkyle en Cι Cι5, les N alkyl (méth)acrylamides en C14 à C24 avec ou sans atome de fluor, les esters vinyliques à chaînes alkyle ou perfluoroalkyle en Cι4 à C24, les éthers vinyliques à chaînes alkyle ou perfluoroalkyle en Cu à C24, les alpha-oléfines en C1 à C24, les para-alkyl styrènes avec un groupe alkyle comportant de 12 à 24 atomes de carbone, leurs' mélanges.15. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from homopolymers and copolymers resulting from the polymerization of at least one monomer with a crystallizable chain chosen from alkyl (meth) acrylates saturated with C 4 -C 24 , C ι Cι 5 (meth) acrylates of perfluoroalkyl, C 14 to C 24 N (meth) acrylamides with or without fluorine atom, vinyl esters with alkyl or perfluoroalkyl chains Cι 4 to C 24 vinyl ethers, alkyl or perfluoroalkyl chains Cu to C 24 alpha-olefins, C 1 -C 24, para-alkylstyrenes with an alkyl group having 12 to 24 carbon atoms, and 'mixtures.
16. Composition selon l'une des revendications précédentes, caractérisée en ce que les polymères semi-cristallins sont des homopolymères d'alkyl(méth)acrylate ou d'alkyl(méth)acrylamide avec un groupe alkyle en C,4 à C24, des copolymères de ces monomères avec un monomère hydrophile.16. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymers are homopolymers of alkyl (meth) acrylate or of alkyl (meth) acrylamide with a C 4 to C 24 alkyl group, copolymers of these monomers with a hydrophilic monomer.
17. Composition selon l'une des revendications précédentes, caractérisée en ce que les polymères semi-cristallins sont des copolymères d'alkyl(méth)acrylate ou d'alkyl (méth)acrylamide avec un groupe alkyle en C14 à C2 avec un monomère de nature différente de l'acide (méth)acrylique comme la N-vinylpyrolidone ou l'hydroxyéthyl (méth)acrylate, et leurs mélanges.17. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymers are copolymers of alkyl (meth) acrylate or of alkyl (meth) acrylamide with a C 14 to C 2 alkyl group with a monomer of a different nature from (meth) acrylic acid such as N-vinylpyrolidone or hydroxyethyl (meth) acrylate, and mixtures thereof.
18. Composition selon l'une des revendications précédentes, caractérisée en ce que le ou les polymères semi-cristallins représentent de 0,1 à 80 % du poids total de la composition et mieux de 0,5 à 40 % et encore mieux de 3 à 30 %, de préférence de 15 % à 25% en poids de la composition.18. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer (s) represent from 0.1 to 80% of the total weight of the composition and better still from 0.5 to 40% and even better still from 3 to 30%, preferably from 15% to 25% by weight of the composition.
19. Composition selon l'une des revendications précédentes, caractérisée en ce que la composition contient un mélange d'un polymère choisi parmi les polymères à bas point de fusion ayant une température de fusion inférieure à 50°C, et d'un polymère choisi parmi les polymères à haut point de fusion ayant une température de fusion au moins égale à 50°C.19. Composition according to one of the preceding claims, characterized in that the composition contains a mixture of a polymer chosen from polymers with a low melting point having a melting temperature below 50 ° C, and a polymer chosen among polymers with a high melting point having a melting temperature at least equal to 50 ° C.
20. Composition selon la revendication précédente, caractérisée en ce que le polymère à haut point de fusion a une température de fusion Pfi telle que 55°C < P^ < 150°C et de préférence 60°C < Pf 1 < 130°C.20. Composition according to the preceding claim, characterized in that the polymer with a high melting point has a melting point Pfi such that 55 ° C <P ^ <150 ° C and preferably 60 ° C <Pf 1 <130 ° C .
21. Composition selon la revendication 21 ou 22, caractérisée en ce que le polymère à bas point de fusion a une température de fusion Pf2 telle que 30°C < Pf2 < 50°C.21. Composition according to claim 21 or 22, characterized in that the polymer with a low melting point has a melting temperature Pf 2 such that 30 ° C <Pf 2 <50 ° C.
22. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère semi-cristallin est un mélange d'un polymère à bas point de fusion ayant une température de fusion inférieure à 50°C, et d'un polymère à haut point de fusion ayant une température de fusion au moins égale à 50°C, dans un rapport en poids compris entre 90/10 et 10/90, de préférence entre 40/60 et 60/40, de préférence encore dans un rapport pondéral proche de 50/50.22. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is a mixture of a polymer with low melting point having a melting temperature below 50 ° C, and a polymer with high melting point having a melting temperature at least equal to 50 ° C, in a weight ratio between 90/10 and 10/90, preferably between 40/60 and 60/40, more preferably in a close weight ratio 50/50.
23. Composition selon l'une des revendications précédentes, caractérisée en ce que la phase grasse contient au moins une huile polaire, et une huile peu polaire.23. Composition according to one of the preceding claims, characterized in that the fatty phase contains at least one polar oil, and a slightly polar oil.
24. Composition selon l'une des revendications précédentes, caractérisée en ce le rapport pondéral du polymère semi-cristallin et de la phase grasse liquide est compris entre 0,20 et 0,60, de préférence entre 0,25 et 0,50.24. Composition according to one of the preceding claims, characterized in that the weight ratio of the semi-crystalline polymer and of the liquid fatty phase is between 0.20 and 0.60, preferably between 0.25 and 0.50.
25. Composition selon l'une des revendications précédentes, caractérisée en ce qu'elle contient moins de 10 %, en poids, de cire et/ou moins de 5 % en poids de charge matifiante, par rapport au poids total de la composition.25. Composition according to one of the preceding claims, characterized in that it contains less than 10%, by weight, of wax and / or less than 5% by weight of mattifying filler, relative to the total weight of the composition.
26. Composition selon l'une des revendications précédentes, caractérisée en ce que la composition est soύs forme anhydre. 26. Composition according to one of the preceding claims, characterized in that the composition is soύs anhydrous form.
27. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle se présente sous forme coulée.27. Composition according to any one of the preceding claims, characterized in that it is in cast form.
28. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle se présente sous forme de mascara, d'eye-liner, de fond de teint, de rouge à lèvres, de déodorant, de produit de maquillage du corps, de fard à paupières ou à joues, de produit anti-cerne.28. Composition according to any one of the preceding claims, characterized in that it is in the form of mascara, eyeliner, foundation, lipstick, deodorant, body makeup product. , eyeshadow or blush, concealer.
29. Composition selon la revendication 28, caractérisé en ce qu'elle se présente sous forme d'un stick solide, de dureté allant de 100 à 350 gf.29. Composition according to claim 28, characterized in that it is in the form of a solid stick, of hardness ranging from 100 to 350 gf.
30. Rouge à lèvres comprenant a) au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique dont la température de fusion P^ est telle que 55°C < Pfi < 150°C, et au moins un polymère semi-cristallin à structure organique dont la température de fusion Pf2 est telle que 30°C < Pf2 < 50°C b) une matière colorante et c) un alcool aliphatique comprenant 8 à 26 atomes de carbone.30. Lipstick comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose melting point P ^ is such that 55 ° C <Pfi <150 ° C, and at least one semi-crystalline polymer with organic structure whose melting point Pf 2 is such that 30 ° C <Pf 2 <50 ° C b) a coloring matter and c) an aliphatic alcohol comprising 8 to 26 carbon atoms.
31. Procédé cosmétique de maquillage comprenant l'application sur les matières kératiniques de la composition conforme à l'une des revendications 1 à 30.31. Cosmetic make-up process comprising the application to keratin materials of the composition according to one of claims 1 to 30.
32. Utilisation d'un ester comprenant 10 à 40 atomes de carbone, dans une composition de maquillage comprenant a) au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique dont la température de fusion est supérieure ou égale à 30°C, b) une matière colorante, la phase grasse liquide, la matière colorante, l'alcool aliphatique et le polymère formant un milieu physiologiquement acceptable.32. Use of an ester comprising 10 to 40 carbon atoms, in a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose melting point is greater than or equal at 30 ° C, b) a coloring matter, the liquid fatty phase, the coloring matter, the aliphatic alcohol and the polymer forming a physiologically acceptable medium.
33. Utilisation d'une quantité suffisante d'un ester comprenant 10 à 40 atomes de carbone, dans une composition contenant un milieu physiologiquement acceptable comprenant a) au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique, dont la température de fusion est supérieure ou égale à 30°C, et b) urte matière colorante, comme agent pour conférer du glissant à l'application et de la brillance à ladite composition.33. Use of a sufficient amount of an ester comprising 10 to 40 carbon atoms, in a composition containing a physiologically acceptable medium comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, whose melting point is greater than or equal to 30 ° C, and b) urte coloring matter, as an agent for imparting slipperiness to the application and gloss to said composition.
34. Utilisation d'un ester comprenant 10 à 40 atomes de carbone dans une composition cosmétique contenant un milieu physiologiquement acceptable comprenant au moins une phase grasse liquide structurée par au moins un polymère semi-cristallin à structure organique, pour obtenir une composition glissante à l'application et brillante. 34. Use of an ester comprising 10 to 40 carbon atoms in a cosmetic composition containing a physiologically acceptable medium comprising at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, in order to obtain a composition which is slippery on application and shiny.
EP20020795370 2002-01-24 2002-11-06 Composition containing a semi-crystalline polymer and an ester Withdrawn EP1469815A1 (en)

Applications Claiming Priority (5)

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FR0200885A FR2834888B1 (en) 2002-01-24 2002-01-24 COSMETIC COMPOSITION GELIFIED BY A SEMI-CRYSTALLINE POLYMER
FR0200885 2002-01-24
FR0202358 2002-02-25
FR0202358 2002-02-25
PCT/FR2002/003802 WO2003061613A1 (en) 2002-01-24 2002-11-06 Composition containing a semi-crystalline polymer and an ester

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DE60222701D1 (en) 2007-11-08
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DE60222701T2 (en) 2008-07-17
WO2003061612A1 (en) 2003-07-31
US20050142082A1 (en) 2005-06-30
EP1469814A1 (en) 2004-10-27
US20050123493A1 (en) 2005-06-09
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WO2003061613A1 (en) 2003-07-31
US8142765B2 (en) 2012-03-27
EP1469814B1 (en) 2007-09-26
JP5112604B2 (en) 2013-01-09
EP1469814B9 (en) 2008-11-05

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