WO2015155298A1 - Assembly for packaging a composition for coating keratin fibres - Google Patents

Assembly for packaging a composition for coating keratin fibres Download PDF

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Publication number
WO2015155298A1
WO2015155298A1 PCT/EP2015/057748 EP2015057748W WO2015155298A1 WO 2015155298 A1 WO2015155298 A1 WO 2015155298A1 EP 2015057748 W EP2015057748 W EP 2015057748W WO 2015155298 A1 WO2015155298 A1 WO 2015155298A1
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WO
WIPO (PCT)
Prior art keywords
composition
equal
weight
nonionic surfactant
hlb value
Prior art date
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PCT/EP2015/057748
Other languages
French (fr)
Inventor
Nathalie Jager Lezer
Philippe Ilekti
Original Assignee
L'oreal
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Publication of WO2015155298A1 publication Critical patent/WO2015155298A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/044Suspensions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/10Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26Optical properties
    • A61K2800/262Transparent; Translucent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/87Application Devices; Containers; Packaging

Definitions

  • the present invention relates to an assembly for packaging a cosmetic composition for coating keratin fibres, comprising a cosmetic composition for coating keratin fibres, and in particular the eyelashes, and a packaging device configured to store said composition.
  • the present invention also relates to a process for coating keratin fibres, in particular a process for making up and optionally caring for the eyelashes.
  • the composition used may in particular be in the form of an eyelash product such as a mascara, or an eyebrow product. More preferentially, the invention relates to a mascara.
  • the term "mascara” is intended to mean a composition intended to be applied to the eyelashes: it may be an eyelash makeup composition, an eyelash makeup base (also known as a base coat), a composition to be applied over a mascara, also known as a top coat, or else a cosmetic composition for treating the eyelashes.
  • the mascara is more particularly intended for human eyelashes, but also false eyelashes.
  • Mascaras are in particular prepared according to two types of formulation: water-based mascaras known as cream mascaras, in the form of a dispersion of waxes in water; anhydrous mascaras or mascaras with a low water content, known as waterproof mascaras, in the form of dispersions of waxes in organic solvents.
  • water-based mascaras known as cream mascaras, in the form of a dispersion of waxes in water
  • anhydrous mascaras or mascaras with a low water content known as waterproof mascaras, in the form of dispersions of waxes in organic solvents.
  • the present patent application more specifically relates to water-based mascaras.
  • Water-based mascaras are conventionally presented in opaque packaging devices. The reason for this is that the intensity of the colour of mascaras is often dull and greyish, which makes them relatively unattractive.
  • water-based mascaras based on waxes are relatively unstable and may aggregate under the action of heat, which tends towards further accentuating their greyish colour.
  • one aim of the present invention is to produce a mascara that is attractive to the user, especially by proposing an assembly comprising a water-based mascara with good colour intensity and good stability over time.
  • one aim of the present invention consists in stabilizing a direct emulsion that is rich in fatty substances, especially in waxes, without phase separation over time.
  • An aim of the present patent application is more particularly to provide a stable mascara which has a texture that is sufficiently thick to obtain a charging deposit, of satisfactory consistency, allowing easy application to the eyelashes and an even deposit, i.e. a deposit that is smooth and uniform, even after two months stored at 4°C.
  • An aim of the present patent application is more particularly to provide a stable mascara which has a texture that is sufficiently thick to obtain a charging deposit, of satisfactory consistency, allowing easy application to the eyelashes and an even deposit, i.e. a deposit that is smooth and uniform, even after two months stored at 45°C.
  • An aim of the present patent application is more particularly to provide a stable mascara which has a texture that is sufficiently thick to obtain a charging deposit, of satisfactory consistency, allowing easy application to the eyelashes and an even deposit, i.e. a deposit that is smooth and uniform, even after two months stored at temperatures oscillating between 4°C and 45°C.
  • An aim of the present patent application is more particularly to provide a mascara in which the waxes are uniformly dispersed.
  • An aim of the present patent application is more particularly to provide a mascara in which the pigments are uniformly dispersed.
  • An aim of the present invention is also to produce water-based mascaras of good colour intensity and good stability making it possible to exceed a high solids content, for example of greater than or equal to 40%.
  • one subject of the present invention is an assembly for packaging a composition, preferably for coating keratin fibres such as the eyelashes, comprising:
  • composition in particular for coating keratin fibres such as the eyelashes, more preferentially a mascara composition, comprising:
  • particles comprising at least one hard wax, preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition, iii) a lamellar phase ⁇ formed by an aqueous phase-structuring surfactant system, said surfactant system comprising a content of surfactant(s), preferably nonionic surfactant(s), of greater than or equal to 15% by weight relative to the total weight of the composition,
  • a packaging device comprising a container for storing said composition, this container being at least partly transparent so that said composition contained in the container is directly visible through the container.
  • the surfactant system forming the lamellar phase ⁇ _ ⁇ comprises:
  • the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula (I) below:
  • - ALK is a C7-C23, preferably Cn-C 2 i and more preferentially C15-C17 alkyl group,
  • a and b are integers between 0 and 100
  • c is an integer between 1 and 100, in particular between 1 and 3, preferably equal to 1
  • a and b preferably being equal to 0,
  • X is a (poly)oxyalkylene group optionally substituted and/or terminated with a hydroxyl group, X preferably being an oxyethylene group (CH2CH 2 0) n or (OCH 2 CH2) n in which n is greater than or equal to 1 , for example between 1 and 200, said (poly)oxyalkylene group preferably being a polyethylene glycol or being the result of at least one substitution of a hydroxyl group, preferably chosen from (poly)glycerols.
  • the total content of hard wax(es) and optionally of additional wax(es) and the total content of surfactant system are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the surfactant system is less than or equal to 1 .75, preferably strictly less than 1 .5, in particular between 1/3 and 1 .25, the composition comprising a solids content of greater than or equal to 42%, preferably 45% and more preferentially 48%.
  • additional wax(es) means any wax other than a hard wax, such as one or more soft waxes.
  • the total content of hard wax(es) relative to the total content of surfactant system, and preferentially of nonionic surfactants corresponding to formula (I) below, should be considered for calculating the preferred weight ratio in the invention.
  • Such a ratio is preferably less than or equal to 1.75, preferably strictly less than 1 .5 and in particular between 1/3 and 1.25.
  • the group X is preferably chosen from:
  • - ALK which may be identical or different, representing a C1 -C6 and in particular C1 -C4 alkylene group, preferably ethylene,
  • x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
  • - ALK which may be identical or different, representing a C1 -C6 and in particular C1 -C4 ethylene group, preferably ethylene,
  • nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula ( ⁇ ) below:
  • - ALK is a C 8 -C 2 4, preferably C12-C22 and more preferentially Ci 6 -Ci 8 alkyl group,
  • n being an integer other than 0, between 1 and 200, preferably between 1 and 10 and better still between 2 and 6 for the nonionic surfactant(s) with an HLB value at 25°C of less than 8, preferably between 20 and 200 for the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8.
  • the invention comprises:
  • At least one hard wax preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition, and
  • a composition in accordance with the invention gives rise to a water-based mascara composition which gives a strong colour intensity.
  • the invention makes it possible to formulate water-based mascaras that may be rich in solids, especially in fatty substances, and that are stable, having a homogeneous and uniform dispersion of waxes, even after 2 months whether at 45°C or at 4°C.
  • this mascara has good dispersion of the pigments and waxes, and is smooth and glossy.
  • Such a composition is still pleasant upon application, comfortable and has a volumizing effect.
  • this composition has a reinforced water content when film-forming polymer particles are present.
  • the combination of surfactants as described above allows an excellent compromise in terms of colour intensity, texture and cosmeticity and makes it possible, contrary to all expectation in the field of water-based mascaras, to condition these mascaras in a transparent container. Furthermore, it would have been difficult to envisage such surfactants with thickening nature in a formula rich in hard waxes and with a high solids content.
  • an "alky group is a linear or branched, preferably linear, C7-C23, preferably Cn-C 2 i and more preferentially C15-C17 hydrocarbon-based group or chain;
  • hydrocarbon-based chain is optionally “(poly)unsaturated” when it comprises one or more double bonds and/or one or more triple bonds, which may be conjugated or non-conjugated; preferably, this hydrocarbon-based chain is saturated;
  • ALK-[C(0)] a -[0]b generally means that the alkyl group ALK may be derived from a fatty acid or from a fatty alcohol;
  • the compounds of formula (I) preferably result from an esterification, more preferentially from a mono-esterification, or from an etherification (or alkoxylation), more preferentially a mono-etherification (or mono-alkoxylation);
  • (poly)oxyalkylene means that one or more -OH functions, in particular derived from a hydroxyl function or a carboxylic function, may be substituted with an oxyalkylene group, in particular an oxyethylene group;
  • acyl means a linear or branched, saturated C 8 -C 2 4, better still C12-C2 0 and more preferentially C14-C18 hydrocarbon-based chain, comprising a carboxylic function whose hydroxyl function (-OH) has been substituted.
  • the aqueous phase represents from 30% to 80% by weight and preferably from 40% to 70% by weight relative to the total weight of the composition
  • composition comprises a fatty phase dispersed in the aqueous phase, the fatty phase predominantly comprising hard wax particles, preferentially in the form of aqueous dispersion(s);
  • the at least one from among the nonionic surfactant(s) with an HLB value at 25°C of less than 8 are chosen from:
  • esters of fatty acids especially of C 8 -C 2 4 and preferably of Ci 6 -C 2 2, and of (poly)oxyalkylenated polyol, especially of (poly)oxyalkylenated glycerol or of oxyalkylenated sorbitol, preferably of (poly)oxyalkylenated glycerol;
  • the at least one from among the nonionic surfactant(s) with an HLB value at 25°C of less than 8 comprises a (poly)oxyalkylenated alcohol comprising an ether of a
  • nonionic surfactant(s) with an HLB value at 25°C greater than or equal to 8, preferably greater than or equal to 10 are chosen from:
  • esters of a fatty acid and of (poly)oxyalkylenated polyethylene glycol are esters of a fatty acid and of (poly)oxyalkylenated polyethylene glycol
  • esters of a fatty acid and of (poly)oxyalkylenated glycerol ethers
  • esters of a fatty acid and of (poly)oxyalkylenated sorbitol ethers
  • the at least one from among the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 comprises a (poly)oxyalkylenated alcohol comprising at least an ether of a C 8 -C 2 4 fatty alcohol and of polyethylene glycol, said ether comprising at least 20 ethylene glycol units and better still between 20 and 200 ethylene glycol units;
  • nonionic surfactant(s) with an HLB value at 25°C of less than 8, preferably corresponding to formula (I) are present in a content of greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition;
  • nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, preferably corresponding to formula (I) are present in a content of greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition;
  • the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, both preferably corresponding to formula (I), are present in a total content of greater than or equal to 10%, better still 12% and in particular between 15% and 25% by weight relative to the total weight of the composition;
  • the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, both preferably corresponding to formula (I), are present in a respective total content such that the weight ratio of the nonionic surfactant(s) with an HLB value at 25°C of less than 8 to the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 ranges from 1/5 to 5, preferably from 1/3 to 3, preferably from 2/3 to 3/2;
  • the total content of hard wax(es) and optionally of additional wax(es) and the total content of surfactant system(s) are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the surfactant system(s) is less than or equal to 1 .75, preferably less than or equal to 1 .5, in particular between 1/3 and 1 .25;
  • the total content of hard wax(es) and optionally of additional wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 and of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 1 .75, preferably less than or equal to 1 .5, in particular between 1/3 and 1.25;
  • the total content of hard wax(es) and optionally of additional wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
  • the total content of hard wax(es) and optionally of additional wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
  • the total content of hard wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 are such that the weight ratio of the hard wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
  • the total content of hard wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
  • the total content of hard wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 and of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 1 .75, preferably less than or equal to 1 .5, in particular between 1/3 and 1 .25;
  • composition is free of oil or organic solvent
  • the fatty phase represents from 15% to 30% by weight relative to the total weight of the composition
  • composition comprises a solids content of greater than or equal to 42%, preferentially 45%, more preferentially 48%, or even 50%;
  • the hard wax particles have in said (final) composition a mean size expressed as the volume-mean "effective" diameter D[4.3] of less than or equal to 5 ⁇ , preferentially less than or equal to 2 ⁇ , even more preferentially 1 ⁇ , for example between 0.01 and 5 ⁇ , and more preferentially between 0.05 and 2 ⁇ ;
  • the film-forming polymer particles introduced in aqueous dispersion form into said composition have in said composition a mean size expressed as the volume-mean
  • composition comprises a total content of hard wax particles, preferentially present in aqueous dispersion form, of greater than or equal to 12% by weight, preferably 15% by weight, preferably 18% by weight and more preferentially 20% by weight, relative to the total weight of the composition, for example between 16% and 30% by weight relative to the total weight of the composition;
  • composition comprises a total content of hard wax particles, preferentially in aqueous dispersion form, representing at least 80% by weight, preferentially at least 90% by weight and more preferentially 100% by weight relative to the total weight of wax(es);
  • the total content of hard wax particles, preferentially in aqueous dispersion form, is greater than or equal to 30% by weight and preferentially 40% by weight relative to the total weight of the particles;
  • the total content of hard wax particles, preferentially in aqueous dispersion form, represents at least 80% relative to the total weight of fatty substances;
  • the hard wax(es) in the form of particles, preferentially in aqueous dispersion form, are polar;
  • a cosmetic composition according to the invention preferentially a mascara, in the form of an aqueous dispersion of pre-prepared particles;
  • the film-forming polymer particles are introduced into the preparation of the composition in the form of a pre-prepared aqueous dispersion of film-forming polymer(s);
  • composition comprises a total content of film-forming polymer particles in aqueous dispersion form of greater than or equal to 10% by weight and preferably 15% by weight relative to the total weight of the composition;
  • the film-forming polymer(s) in accordance with the invention are, during the manufacture of a cosmetic composition according to the invention, preferentially a mascara, introduced in the form of an aqueous dispersion of pre-dispersed film-forming polymer particles, advantageously having its own surfactant system, varied according to the chemistry of the film-forming polymer(s) used;
  • the film-forming polymer particles have their own surfactant system, i.e. different from the surfactant system in accordance with the present invention, more particularly different from the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, or preferably greater than or equal to 10, suited to dispersing the hard wax(es);
  • the hard wax particles and the film-forming polymer particles in aqueous dispersion have a respective surfactant system, more precisely a respective surfactant;
  • the film-forming polymer particles in aqueous dispersion form are chosen from synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and mixtures thereof;
  • the film-forming polymer particles in aqueous dispersion form are chosen from acrylic polymer dispersions, polyurethane dispersions, sulfopolyester dispersions, vinyl dispersions, polyvinyl acetate dispersions, vinylpyrrolidone, dimethylaminopropylmethacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride terpolymer dispersions, dispersions of polyurethane/polyacrylic hybrid polymers, dispersions of core-shell particle type and mixtures thereof, preferably from acrylic polymer dispersions, dispersions of polyurethane/polyacrylic hybrid polymers, and derivatives thereof, and mixtures thereof, preferentially from acrylic polymer dispersions, in particular styrene-acrylic, and polyurethane dispersions, in particular polyester- polyurethane, and derivatives thereof, and mixtures thereof;
  • the total content of hard wax particles and the total content of film-forming polymer particles are such that the weight ratio of the hard wax particles to the film-forming polymer particles is greater than or equal to 1/2, preferably greater than 2/3, advantageously between 1/2 and 2 and preferably between 2/3 and 3/2;
  • composition comprises one or more additional surfactants (i.e. other than a surfactant of formula (I)) chosen from nonionic surfactants with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, nonionic surfactants with an HLB value at 25°C of less than 8, anionic surfactants, and mixtures thereof; preferably from nonionic surfactants with an HLB value at 25°C of less than 8;
  • additional surfactants i.e. other than a surfactant of formula (I)
  • additional surfactants chosen from nonionic surfactants with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, nonionic surfactants with an HLB value at 25°C of less than 8, anionic surfactants, and mixtures thereof; preferably from nonionic surfactants with an HLB value at 25°C of less than 8;
  • composition comprises at least one water-soluble film-forming polymer, more preferentially said composition is free of water-soluble film-forming polymer;
  • composition comprises at least one dyestuff chosen from one or more pulverulent dye(s), preferably metal oxides, and in particular iron oxides;
  • the metal oxide(s) are preferably present in a content of greater than or equal to 2% by weight relative to the total weight of the composition, and advantageously inclusively between 3% and 22% by weight relative to the total weight of the composition;
  • composition comprises at least one hydrophilic and/or lipophilic gelling agent, preferably at least one hydrophilic gelling agent;
  • composition has a viscosity at 25°C ranging from 5 to 50 Pa.s, in particular measured using a Rheomat RM100® machine;
  • composition may be a makeup composition, a makeup base or "base coat”, or a "top coat” composition to be applied onto a makeup;
  • the container defines internally a storage volume for a composition in accordance with the invention
  • the container comprises a body, which is preferably cylindrical, closed at one end by a base and open at an opposite end;
  • the composition is in direct contact with the container so that the user directly sees the composition packaged inside the container by looking through a constituent wall of said container;
  • the container has no inner coating intended to mask the composition from the user;
  • the body of the container comprises a neck forming a shoulder from which the aperture raises;
  • the aperture houses internally a wiper configured to free the applicator of surplus composition
  • the lid supports an applicator configured to apply said composition in accordance with the invention to keratin fibres, in particular to the eyelashes;
  • said applicator is configured to come into the position dipping into the composition in accordance with the invention in the closed position of the lid on the container;
  • the body, the neck and the base of the container are transparent;
  • the container is made of a transparent thermoplastic material, for example by injection-moulding, or of glass, for example by injection blow-moulding;
  • this assembly comprises means for heating said composition, for example integrally fastened to the applicator.
  • a packaging assembly in accordance with the invention comprises:
  • a specific composition in particular for coating keratin fibres such as the eyelashes, more preferentially a mascara composition, and a packaging device comprising a container for storing said composition, this container being at least partly transparent so that said composition contained in the container can be seen through the container.
  • a composition of an assembly according to the invention in particular for coating keratin fibres such as the eyelashes, more preferentially a mascara composition, comprises:
  • particles comprising at least one hard wax, preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition, iii) a lamellar phase ⁇ _ ⁇ formed by an aqueous phase-structuring surfactant system, said surfactant system comprising a content of surfactant(s) of greater than or equal to 15% by weight relative to the total weight of the composition.
  • Aqueous phase ⁇ _ ⁇ formed by an aqueous phase-structuring surfactant system, said surfactant system comprising a content of surfactant(s) of greater than or equal to 15% by weight relative to the total weight of the composition.
  • composition of an assembly according to the invention comprises an aqueous phase, which may form a continuous phase of the composition.
  • the aqueous phase comprises water. It may also comprise at least one water-soluble solvent.
  • water-soluble solvent denotes a compound that is liquid at room temperature and water-miscible.
  • the water-soluble solvents that may be used in the compositions according to the invention may also be volatile.
  • the aqueous phase (water and optionally the water-miscible solvent) is generally present in the composition according to the present patent application in a content ranging from 30% to 80% by weight and preferably ranging from 40% to 70% by weight relative to the total weight of the composition.
  • This aqueous phase content includes not only the water originating from the aqueous dispersions of film-forming polymers, and, where appropriate, aqueous dispersions of hard waxes, in accordance with the invention, but also, where appropriate, the water deliberately added to the composition.
  • composition according to the invention advantageously comprises a solids content of greater than or equal to 40%, in particular 42%, more particularly 45%, or even 48%, and preferentially 50%.
  • solids content denotes the content of non-volatile matter.
  • the solids content (abbreviated as SC) of a composition according to the invention is measured using a "Halogen Moisture Analyzer HR 73" commercial halogen desiccator from Mettler Toledo. The measurement is performed on the basis of the weight loss of a sample dried by halogen heating, and thus represents the percentage of residual matter once the water and the volatile matter have evaporated off.
  • the measuring protocol is as follows:
  • sample Approximately 2 g of the composition, referred to hereinbelow as the sample, are spread out on a metal crucible, which is placed in the halogen desiccator mentioned above. The sample is then subjected to a temperature of 105°C until a constant weight is obtained. The wet mass of the sample, corresponding to its initial mass, and the dry mass of the sample, corresponding to its mass after halogen heating, are measured using a precision balance.
  • the experimental error associated with the measurement is of the order of plus or minus 2%.
  • the solids content is calculated in the following manner:
  • a composition according to the invention comprises wax particles, film- forming polymer particles and at least one particular surfactant system.
  • a composition of an assembly according to the invention comprises a surfactant system for structuring the aqueous phase so as to form a lamellar phase ⁇ , comprising:
  • - ALK is a C7-C23, preferably Cn-C 2 i and more preferentially C15-C17 alkyl group,
  • - a and b are integers between 0 and 100
  • c is an integer between 1 and 100, in particular between 1 and 3, preferably equal to 1
  • a and b preferably being equal to 0,
  • X is a (poly)oxyalkylene group optionally substituted and/or terminated with a hydroxyl group, X preferably being an oxyethylene group (CH 2 CH 2 0) n or (OCH 2 CH 2 ) n in which n is greater than or equal to 1 , for example between 1 and 200, said (poly)oxyalkylene group preferably being a polyethylene glycol or being the result of at least one substitution of a hydroxyl group, preferably chosen from (poly)glycerols.
  • the group X is preferably chosen from:
  • - ALK which may be identical or different, representing a C1 -C6 and in particular C1 -C4 alkylene group, preferably ethylene,
  • x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
  • - ALK which may be identical or different, representing a C1 -C6 and in particular C1 -C4 ethylene group, preferably ethylene,
  • - x is an integer other than 0 and preferably between 1 and 200.
  • nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula ( ⁇ ) below:
  • - ALK is a C 8 -C 2 4, preferably C12-C22 and more preferentially Ci 6 -Ci 8 alkyl group,
  • n being an integer other than 0, between 1 and 200, preferably between 1 and 10 and better still between 2 and 6 for the nonionic surfactant(s) with an HLB value at 25°C of less than 8, preferably between 20 and 200 for the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8.
  • This surfactant system is capable of dispersing the hard wax particles and optionally the additional wax(es). It may also be capable of dispersing the film-forming polymer particles, but the film-forming polymer particles may have their own surfactant system, different from that which is suitable for dispersing the hard wax particles and optionally the additional wax(es).
  • the nonionic surfactant(s) with an HLB value, in the Griffin sense, at 25°C, of greater than or equal to 8 may be advantageously chosen from:
  • - (poly)oxyalkylenated glycerol ethers in particular oxyethylenated and/or oxypropylenated glycerol ethers, which may comprise from 20 to 200 oxyethylene and/or oxypropylene units;
  • - (poly)oxyalkylenated alcohols in particular oxyethylenated and/or oxypropylenated alcohols, which may comprise from 20 to 200 oxyethylene and/or oxypropylene units, preferably from 20 to 100 oxyethylene units, in particular ethoxylated C 8 -C 2 4 and preferably Ci 2 -Ci 8 fatty alcohols such as ethoxylated stearyl alcohol comprising 20 oxyethylene units (CTFA name: Steareth-20) such as Brij 78 sold by the company Uniqema, or ethoxylated cetearyl alcohol comprising 30 oxyethylene units (CTFA name: Steareth-30);
  • esters of a fatty acid in particular of a C 8 -C 2 4 and preferably Ci 6 -C 2 2 fatty acid, and of polyethylene glycol (or
  • PEG (which may comprise from 20 to 200 oxyethylene units), such as PEG-50 stearate and PEG-40 monostearate sold under the name Myrj 52P® by the company Uniqema;
  • esters of a fatty acid in particular a C 8 -C 2 4 and preferably Ci 6 -C 22 fatty acid
  • (poly)oxyalkylenated glycerol ethers which are in particular oxyethylenated and/or oxypropylenated (which may comprise from 20 to 200 oxyethylene and/or oxypropylene units), for instance glyceryl monostearate polyoxyethylenated with 200 oxyethylene units, sold under the name Simulsol 220 TM® by the company SEPPIC; glyceryl stearate polyoxyethylenated with 30 oxyethylene units, for instance the product Tagat S® sold by the company Goldschmidt, glyceryl oleate polyoxyethylenated with 30 oxyethylene units, for instance the product Tagat O® sold by the company Goldschmidt, glyceryl cocoate polyoxyethylenated with 30 oxyethylene units, for instance the product Varionic LI
  • esters of a fatty acid in particular a C 8 -C 24 and preferably Ci 6 -C 22 fatty acid
  • (poly)oxyalkylenated sorbitol ethers which are in particular oxyethylenated and/or oxypropylenated (which may comprise from 20 to 200 oxyethylene and/or oxypropylene units), for instance the polysorbate 60 sold under the name Tween 60® by the company Uniqema;
  • a composition comprises at least one nonionic surfactant with an
  • HLB value in the Griffin sense, at 25°C, of greater than or equal to 8 and preferably greater than or equal to 10, chosen from at least one ether of a C 8 -C 2 4 , preferably Ci 2 - C 2 2 and more preferentially Ci 6 -Ci 8 , fatty alcohol and of polyethylene glycol, said ether comprising at least 20 ethylene glycol units and better still between 20 and 200 ethylene glycol units.
  • a composition according to the invention has a content of nonionic surfactant(s) with an H LB value, in the Griffin sense, at 25°C of greater than or equal to 8, preferably greater than or equal to 10, of greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition.
  • the nonionic surfactant(s) with an HLB value, in the Griffin sense, at 25°C, of less than 8 may be advantageously chosen from:
  • esters of fatty acids especially of C 8 -C 2 4 and preferably of Ci 6 - C22, and of (poly)oxyalkylenated polyol, especially of (poly)oxyalkylenated glycerol or of (poly)oxyalkylenated sorbitol, preferably of (poly)oxyalkylenated glycerol;
  • (poly)oxyalkylenated means from 1 to 10 oxyethylene groups (or units) and better still from 2 to 6 oxyethylene groups.
  • 25°C of less than 8 preferably comprises a (poly)oxyalkylenated alcohol comprising an ether of a C 8 -C 2 4 fatty alcohol and of polyethylene glycol, said ether comprising from 1 to 10 and better still between 2 and 6 ethylene glycol units.
  • a composition according to the invention has a content of nonionic surfactant(s) with an HLB value, in the Griffin sense, at 25°C, of less than 8, preferably greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition.
  • composition in accordance with the invention is free of anionic surfactant(s).
  • composition in accordance with the invention is free of amphoteric surfactant(s).
  • the surfactant system may comprise one or more co-surfactants chosen from fatty alcohols comprising from 10 to 26 carbon atoms, better still from 12 to 24 carbon atoms and even better still from 14 to 22 carbon atoms.
  • Lamellar phase LB Lamellar phase LB
  • the surfactant system in accordance with the invention is organized in the form of a lamellar phase 1_ ⁇ , or paracrystalline phase ⁇ , or lamellar gel phase.
  • This composition is stable at a room temperature of 25°C, having a viscosity preferentially ranging from 5 to 50 Pa.s, measured at a room temperature of 25°C using a Rheomat RM 100® rheometer.
  • lamellar gel phase or paracrystalline phase ⁇ means a phase in which the surfactant molecules and/or more generally the molecules of amphiphilic compounds are organized in the form of bimolecular layers spaced apart by aqueous leaflets. Within the bimolecular layers, the molecules are distributed in a hexagonal geometry, their hydrocarbon-based chains are in a crystalline state and are oriented perpendicular to the plane of the bimolecular layers but have no specific orientation relative to each other in the plane of these layers.
  • the paracrystalline phases ⁇ , ⁇ are metastable phases in which the fatty chains are in solid form and are arranged randomly relative to each other, unlike the miceliar, hexagonal, cubic and lamellar fluid paracrystalline phases (La) in which the fatty chains are in liquid form, and unlike the crystalline phases in which the fatty chains are in solid form and oriented in an ordered manner relative to each other.
  • the paracrystalline phases 1_ ⁇ are metastable and, in general, they have a tendency to evolve towards crystallization.
  • the Applicant has found a particular surfactant system that makes it possible to obtain a stable paracrystalline phase ⁇ _ ⁇ , and thus cosmetic compositions for coating keratin fibres, in particular the eyelashes, which are stable and comfortable to apply, with good wear property and volume, by using a particular system of surfactant type in particular contents.
  • a particular system of surfactant type in particular contents.
  • To identify the lamellar gel phase or paracrystalline phase 1_ ⁇ of the surfactant system present in the composition of the invention use may be made of various techniques, and especially the technique of X-ray scattering.
  • Wide-angle X-ray scattering (WAXS) X-ray diagrams were recorded by a Mar345 image plate detector
  • the flux after the output mica windows was 3 x 10 8 photons/s.
  • a 2-mm diameter circular metal wire beam stop was placed in air at 150 mm after the sample, and the detector was positioned at 360 mm.
  • the repetitive distances d 27i/q should be between 200 A and 3.5 A.
  • the samples were placed in 1.2-1 .3 mm glass capillaries (Glas W. Muller, Germany) and introduced into a home-made capillary holder accommodating up to 20 capillaries at controlled temperature.
  • compositions of an assembly according to the present invention comprise hard wax particles and preferably film-forming polymers, which are preferentially in aqueous dispersion form.
  • Such particles may be characterized by a mean particle size.
  • Such particles are generally isotropic, especially substantially spherically shaped or spherically shaped.
  • a particle size can be measured by various techniques. Mention may in particular be made of the (dynamic and static) light scattering techniques, Coulter capture methods, measurements of sedimentation rates (related to the size via Stokes law) and microscopy.
  • the particle sizes and size distributions of the compositions according to the invention are measured by static light scattering using a commercial particle size analyser such as the MasterSizer 2000 from Malvern.
  • the data are processed on the basis of the Mie scattering theory.
  • This theory which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter.
  • This theory is especially described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.
  • V represents the volume of the particles of effective diameter d. This parameter is in particular described in the technical documentation of the particle size analyser.
  • the measurements are carried out at 25°C, on a diluted dispersion of particles.
  • the "effective" diameter is obtained by taking a refractive index of 1.33 for water and an average refractive index of 1.45 for the particles.
  • the particles of the compositions in accordance with the invention comprising at least one hard wax and preferably at least one film-forming polymer, which are preferentially present in the form of aqueous dispersions, have a mean size expressed as the volume-mean "effective" diameter D[4,3] of less than or equal to 5 ⁇ , in particular strictly less than ⁇ , more preferentially 2 ⁇ and even more preferentially less than or equal to 1 ⁇ .
  • Such particle sizes preferentially correspond to the size of the particles in the final composition.
  • compositions in accordance with the present invention are advantageous as regards the use of the composition in accordance with the present invention when compared with compositions comprising hard wax particles and film-forming polymers of larger sizes, which result in a mascara that is difficult or even impossible to formulate, granular, too thick, which cannot be applied (too compact and does not disintegrate), which is uncomfortable, which has poor dispersion of the pigments and fillers, and which has a matt colour.
  • the surfactant system(s) will have a tendency to position itself (themselves) at the interface of the aqueous phase and of the hard wax particles, and optionally of the film-forming polymer particles, in order to stabilize them.
  • the measured particle sizes are thus measured in the presence of the surfactants, since they are difficult to dissociate from the particles.
  • the sizes measured and given take this feature into account.
  • the other particles of the composition for example dyestuffs and fillers, these compounds will be dealt with independently in another paragraph of the description, the size characteristics of particles of this type differing from the particle sizes of the waxes and film-forming polymers in accordance with the invention. Wax(es)
  • the wax(es) are generally a lipophilic compound that is solid at room temperature (25°C), with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30°C, which may be up to 200°C and in particular up to 120°C.
  • the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in standard ISO 1 1357-3; 1999.
  • the melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments.
  • DSC differential scanning calorimeter
  • the waxes have a heat of fusion AHf of greater than or equal to
  • the waxes comprise at least one crystallizable part, which is visible by X-ray observation.
  • the measurement protocol is as follows:
  • a 5 mg sample of wax placed in a crucible is subjected to a first temperature increase from -20°C to 120°C, at a heating rate of
  • the melting point (Mp) of the wax as mentioned previously corresponding to the temperature of the most endothermic peak of the melting curve observed, representing the variation of the difference in power absorbed as a function of the temperature
  • - AHf the heat of fusion of the wax, corresponding to the integral of the entire melting curve obtained. This heat of fusion of the wax is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.
  • the wax(es) may be hydrocarbon-based waxes, fluoro waxes and/or silicone waxes and may be of plant, mineral, animal and/or synthetic origin.
  • the wax(es) may be present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition and better still 15% by weight relative to the total weight of the composition. Preferably, they are present in a content ranging from 10% to 30% by weight and better still from 15% to 30% by weight relative to the total weight of the composition.
  • a composition according to the invention comprises at least one hard wax, preferably present in the preparation of the composition in the form of an aqueous dispersion of wax particles.
  • the composition more specifically comprises at least one hard wax.
  • hard wax means a wax with a melting point ranging from 65 to 120°C and more preferentially between 70 and 100°C.
  • the term "hard” wax means a wax having, at 20°C, a hardness of greater than 5 MPa, especially ranging from 5 to 30 MPa, preferably greater than 6 MPa and better still ranging from 6 to 25 MPa.
  • the wax is melted at a temperature equal to the melting point of the wax +20°C. To do this, 30 g of wax are placed in a 100 ml beaker 50 mm in diameter, which is itself placed on a magnetic-stirring hotplate.
  • the mechanical properties of the wax or of the mixture of waxes are determined in a room thermostatically maintained at 20°C, using a texturometer sold under the name TA-XT2i by the company Swantech, equipped with a stainless-steel cylinder 2 mm in diameter.
  • the measurement comprises three steps: a first step after automatic detection of the surface of the sample, where the spindle moves at a measuring speed of 0.1 mm/s, and penetrates into the wax to a penetration depth of 0.3 mm, the software notes the maximum force value reached; a second “relaxation” step where the spindle remains at this position for one second and the force is noted after 1 second of relaxation; finally, a third “withdrawal” step in which the spindle returns to its initial position at a speed of 1 mm/s, and the probe withdrawal energy (negative force) is noted.
  • the hardness value corresponds to the maximum measured compression force in newtons divided by the area of the texturometer cylinder, expressed in mm 2 , in contact with the wax.
  • the hardness value obtained is expressed in megapascals or MPa.
  • hard wax examples include carnauba wax, candelilla wax, the wax Bis-PEG-12 Dimethicone Candelillate, for instance Siliconyl Candelilla wax sold by the company Koster Keunen, hydrogenated jojoba wax, for instance the product sold by the company Desert Whale, hydrogenated palm oil such as the product sold by the company SIO, rice bran wax, sumach wax, ceresin waxes, laurel wax, Chinese insect wax, shellac wax, hydrogenated olive oil such as Waxolive from the company Soliance, the waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols, such as the products sold by the company Sophim under the trade names Phytowax Olive 12L44, 14L48, 16L55 and 18L57, the waxes obtained by hydrogenation of castor oil esterified with cetyl or behenyl alcohol, for instance the products sold under the names Phytowax Ricin 16L64 and
  • Use is preferably made of waxes of plant origin such as carnauba wax, candelilla wax, hydrogenated jojoba wax, sumach wax, the waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols sold by the company Sophim under the name Phytowax (12L44, 14L48, 16L55 and 18L57), rice bran wax, stearyl and behenyl alcohols, lauryl wax or ouricury wax.
  • waxes of plant origin such as carnauba wax, candelilla wax, hydrogenated jojoba wax, sumach wax, the waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols sold by the company Sophim under the name Phytowax (12L44, 14L48, 16L55 and 18L57), rice bran wax, stearyl and behenyl alcohols, lauryl wax or ouricury wax.
  • the wax particles used in the preparation of a composition in accordance with the present invention are not introduced in the form of a microdispersion of pre-prepared hard waxes, as described in patent applications FR 2 687 569 or FR 2 815 849.
  • the hard wax(es) used in a composition in accordance with the present invention are introduced in powder or solid fatty substance form.
  • the final composition may be defined as comprising an aqueous dispersion of hard wax(es).
  • the hard wax dispersion is prepared in situ, making it possible, surprisingly and advantageously, to achieve high solids contents and high contents of hard wax(es), which would be unachievable if a pre- prepared microdispersion of hard waxes were to be introduced as such for manufacturing a cosmetic composition according to the invention.
  • the water derived from the aqueous dispersion of film-forming polymer(s) serves to prepare the dispersion of hard wax(es).
  • the hard wax(es) are preferably polar.
  • polar wax means a wax whose solubility parameter calculated above its melting point ⁇ 3 is other than 0 (J/cm 3 ) 1 ⁇ 2 .
  • polar wax means a wax whose chemical structure is formed essentially from, or even constituted of, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.
  • the parameters ⁇ ⁇ , 8 h , 5 D and 8 a are expressed in (J/cm 3 ) 1 ⁇ 2 .
  • the composition according to the invention comprises a content of hard wax(es), preferentially present in aqueous dispersion form, of greater than or equal to 10% by weight relative to the total weight of the composition and better still 15% by weight relative to the total weight of the composition.
  • the composition according to the invention advantageously comprises a total content of hard wax(es), preferentially present in aqueous dispersion form, ranging from 10% to 30% by weight and better still from 15% to 30% by weight, relative to the total weight of the composition.
  • the composition according to the invention comprises a total content of hard wax particles preferentially present in aqueous dispersion form such that they represent at least 80% by weight, preferentially at least 90% by weight and even more preferentially 100% by weight relative to the total weight of wax(es).
  • the total content of hard wax(es), preferentially present in aqueous dispersion form is greater than or equal to 30% by weight and preferentially 40% by weight relative to the total weight of solid particles.
  • the total content of hard wax(es), preferentially present in aqueous dispersion form represents at least 80% by weight, preferentially at least 90% by weight and even more preferentially 100% by weight relative to the total weight of fatty substances.
  • composition according to the invention may comprise at least one soft wax, present in the form of an aqueous dispersion of wax or non-wax particles, i.e. particles whose melting point is strictly less than 50°C, and optionally whose hardness is strictly less than 5 MPa.
  • a composition according to the invention preferably comprises less than 5% by weight of soft wax(es), preferably less than 2% by weight of soft wax(es), and even more preferentially is free of soft wax(es).
  • composition of an assembly according to the invention preferably comprises at least an aqueous dispersion of film-forming polymer particles and optionally at least one additional film-forming polymer (not present in the form of an aqueous dispersion of particles, such as a water-soluble film-forming polymer).
  • film-forming polymer is intended to mean a polymer that is capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous deposit, and preferably a cohesive deposit, and even better still a deposit of which the cohesion and mechanical properties are such that said deposit can be isolated and manipulated individually, for example when said deposit is prepared by pouring onto a non-stick surface such as a Teflon- coated or silicone-coated surface.
  • a composition according to the invention preferably comprises a total solids content of film-forming polymer(s) of greater than or equal to 5% by weight, preferably 10% by weight, relative to the total weight of the composition, and better still 12% by weight, relative to the total weight of the composition.
  • a composition according to the invention preferably comprises a total solids content of film-forming polymer(s) ranging from 10% to 30% by weight and better still from 12% to 25% relative to the total weight of the composition.
  • composition according to the invention preferably comprises more specifically at least an aqueous dispersion of particles formed from one or more film- forming polymers.
  • a composition may comprise at least one additional film-forming polymer, different from the film-forming polymer particles present in aqueous dispersion form.
  • the content of these "water-soluble" additional film-forming polymer(s) is preferably less than or equal to 10% by weight relative to the total weight of the composition, even more preferentially 5% by weight and better still 2% by weight relative to the total weight of the composition.
  • Such a film-forming polymer present in said preparation of the composition in the form of particles in aqueous dispersion is generally known as a (pseudo)latex, i.e. a latex or psuedolatex.
  • a (pseudo)latex i.e. a latex or psuedolatex.
  • Techniques for preparing these dispersions are well known to those skilled in the art.
  • a dispersion that is suitable for use in the invention may comprise one or more types of particle, these particles possibly varying as regards their size, their structure and/or their chemical nature.
  • a composition according to the invention comprises a total solids content of film-forming polymer particles in aqueous dispersion form of greater than or equal to 10% by weight.
  • a composition according to the invention comprises a total solids content of film-forming polymer particles in aqueous dispersion form of greater than or equal to 12% by weight relative to the total weight of the composition and preferably 15% by weight relative to the total weight of the composition.
  • a composition according to the invention preferably comprises a total solids content of film-forming polymer particles ranging from 10% to 30% by weight and better still from 12% to 25% by weight relative to the total weight of the composition.
  • the total content of film-forming polymer particles present in aqueous dispersion form is preferably greater than or equal to 30% by weight and preferentially 40% by weight relative to the total weight of the particles.
  • These particles may be of anionic, cationic or neutral nature and may constitute a mixture of particles of different nature.
  • film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, and polymers of natural origin, and mixtures thereof. In general, these polymers may be statistical polymers, block copolymers of A-B type, of A- B-A or ABCD, etc. multiblock type, or even grafted polymers.
  • free-radical polymer means a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopolymerizing (unlike polycondensates).
  • the film-forming polymers of free-radical type may especially be acrylic and/or vinyl homopolymers or copolymers.
  • the vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers.
  • Ethylenically unsaturated monomers bearing at least one acid group or monomer bearing an acid group that may be used include ⁇ , ⁇ -ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid.
  • (Meth)acrylic acid and crotonic acid are in particular used, and more particularly (meth)acrylic acid.
  • esters of acidic monomers are advantageously chosen from (meth)acrylic acid esters (also known as (meth)acrylates), especially (meth)acrylates of an alkyl, in particular of a Ci-C 2 o and more particularly Ci-C 8 alkyl, (meth)acrylates of an aryl, in particular of a C 6 -Ci 0 aryl, and (meth)acrylates of a hydroxyalkyl, in particular of a C 2 -
  • alkyl (meth)acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate.
  • hydroxyalkyl (meth)acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2- hydroxypropyl methacrylate.
  • aryl (meth)acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.
  • the (meth)acrylic acid esters are in particular alkyl (meth)acrylates.
  • the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • amides of the acid monomers for example, of (meth)acrylamides and especially N-alkyl(meth)acrylamides, in particular N-(C 2 -Ci 2 alkyl)(meth)acrylamides.
  • N-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide and N-t-octylacrylamide.
  • the vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers.
  • these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned previously.
  • vinyl esters examples include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
  • Styrene monomers that may be mentioned include styrene and o methylstyrene.
  • Vinyl polymers that may also be used include silicone acrylic polymers.
  • Hybrid polymers Mention may also be made of polymers resulting from free-radical polymerization of one or more free-radical monomers inside and/or partially at the surface of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and/or alkyds. These polymers are generally referred to as "hybrid polymers”.
  • polycondensate As film-forming polymer of polycondensate type, mention may be made of anionic, cationic, nonionic or amphoteric polyurethanes, acrylic polyurethanes, polyvinylpyrrolidone-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea/polyurethanes and silicone polyurethanes, and mixtures thereof.
  • anionic, cationic, nonionic or amphoteric polyurethanes acrylic polyurethanes, polyvinylpyrrolidone-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea/polyurethanes and silicone polyurethanes, and mixtures thereof.
  • the film-forming polyurethane may be, for example, an aliphatic, cycloaliphatic or aromatic polyurethane, polyurea/urethane or polyurea copolymer comprising, alone or as a mixture, at least one block chosen from:
  • branched or non-branched silicone block for example polydimethylsiloxane or polymethylphenylsiloxane, and/or
  • the film-forming polyurethanes as defined in the invention may also be obtained from branched or unbranched polyesters or from alkyds comprising mobile hydrogens, which are modified by reaction with a diisocyanate and a difunctional organic compound (for example dihydroxy, diamino or hydroxyamino), also comprising either a carboxylic acid or carboxylate group, or a sulfonic acid or sulfonate group, or alternatively a neutralizable tertiary amine group or a quaternary ammonium group.
  • a diisocyanate for example dihydroxy, diamino or hydroxyamino
  • a difunctional organic compound for example dihydroxy, diamino or hydroxyamino
  • polyesters examples include polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxyester resins.
  • the polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.
  • the dicarboxylic acid may be aliphatic, alicyclic or aromatic.
  • acids that may be mentioned include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1 ,3-cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid.
  • These dicarboxylic acid monomers may be used alone or as a combination of
  • the diol may be chosen from aliphatic, alicyclic and aromatic diols.
  • the diol used is chosen in particular from: ethylene glycol, diethylene glycol, triethylene glycol, 1 ,3-propanediol, cyclohexanedimethanol and 4-butanediol.
  • Other polyols that may be used are glycerol, pentaerythritol, sorbitol and trimethylolpropane.
  • the polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycondensation of diacids with diamines or amino alcohols.
  • Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para- phenylenediamine.
  • An amino alcohol that may be used is monoethanolamine.
  • polymers of natural origin such as shellac resin, sandarac gum, dammar resins, elemi gums, copal resins, water-insoluble cellulose-based polymers such as nitrocellulose, modified cellulose esters especially including carboxyalkyl cellulose esters such as those described in patent application US 2003/185 774, and mixtures thereof.
  • said at least one film- forming polymer in dispersed form is chosen from acrylic polymer dispersions, polyurethane dispersions, sulfopolyester dispersions, vinyl dispersions, polyvinyl acetate dispersions, vinylpyrrolidone, dimethylaminopropylmethacrylamide lauryldimethylpropylmethacrylamidoammonium chloride terpolymer dispersions, polyurethane/polyacrylic hybrid polymer dispersions and dispersions of particles of core- shell type, and mixtures thereof.
  • aqueous dispersion especially commercial dispersions, which are suited to the preparation of the composition in accordance with the present invention are detailed below.
  • the aqueous dispersion of polymer particles is an aqueous dispersion of acrylic polymer.
  • the acrylic polymer can be a styrene/acrylate copolymer and especially a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one Ci-Ci 8 alkyl (meth)acrylate monomer.
  • styrene monomers that may be used in the invention, examples that may be mentioned include styrene and omethylstyrene, and in particular styrene.
  • the C-i-C-18 alkyl (meth)acrylate monomer is in particular a C1-C12 alkyl (meth)acrylate and more particularly a C1-C1 0 alkyl (meth) acrylate.
  • the C Ci 8 alkyl (meth)acrylate monomer may be chosen from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate.
  • acrylic polymer in aqueous dispersion use may be made according to the invention of the styrene/acrylate copolymer sold under the name Joncryl SCX-821 1 ® by the company BASF or Syntran 5760cg by the company Interpolymer, the acrylic polymer sold under the reference Acronal ® DS-6250 by the company BASF, or the acrylic copolymer Joncryl ® 95 by the company BASF.
  • the aqueous dispersion of polymer particles is an aqueous dispersion of polyester-polyurethane and/or polyether-polyurethane particles, in particular in anionic form.
  • the anionic nature of the polyester-polyurethanes and of the polyether- polyurethanes used according to the invention is due to the presence in their constituent units of groups bearing a carboxylic acid or sulfonic acid function.
  • polyester-polyurethane or polyether-polyurethane particles used according to the invention are generally sold in aqueous dispersion form.
  • the particle content of said dispersions currently available on the market ranges from approximately 20% to approximately 60% by weight relative to the total weight of the dispersion.
  • anionic polyester-polyurethane dispersions that may be used in the compositions according to the invention, mention may be made in particular of the product sold under the name Avalure UR 405 ® by the company Noveon or Baycusan C1004 by the company Bayer Material Science.
  • anionic polyether-polyurethane particle dispersions that may be used according to the invention, mention may be made in particular of the products sold under the name Avalure UR 450 ® by the company Noveon and under the name Neorez R 970 ® by the company DSM.
  • the aqueous dispersion used comprises a mixture of at least two film-forming polymers in the form of particles that differ by their respective glass transition temperatures (Tg).
  • the composition in accordance with the invention may comprise at least a first film-forming polymer in dispersed form and at least a second film-forming polymer in dispersed form, said first and second polymers having different Tg values and, preferably, the Tg of the first polymer (Tg1 ) is higher than the Tg of the second polymer (Tg2).
  • the difference between the Tg1 and Tg2 values is, as an absolute value, at least 10°C and preferably at least 20°C.
  • it comprises in an acceptable aqueous medium: a) particles dispersed in the aqueous medium of a first film-forming polymer having at least one glass transition temperature Tg1 greater than or equal to 20°C, and b) particles dispersed in the aqueous medium of a second film-forming polymer having at least one glass transition temperature Tg2 less than or equal to 70°C.
  • This dispersion generally results from a mixing of two aqueous dispersions of film-forming polymer.
  • the first film-forming polymer has at least one, and especially has one, glass transition temperature Tg1 of greater than or equal to 20°C, especially ranging from 20°C to 150°C and advantageously greater than or equal to 40°C, especially ranging from 40°C to 150°C and in particular greater than or equal to 50°C, especially ranging from 50°C to 150°C.
  • the second film-forming polymer has at least one, and especially has one, glass transition temperature Tg2 less than or equal to 70°C, especially ranging from
  • -120°C to 70°C in particular less than 50°C, especially ranging from -60°C to +50°C and more particularly ranging from -30°C to 30°C.
  • Tg glass transition temperature
  • Tg glass transition temperature
  • DMTA glass transition temperature
  • This film is prepared by pouring the aqueous dispersion of film-forming polymer in a Teflon-coated matrix followed by drying at 120°C for 24 hours. A film is then obtained, from which specimens are cut out (for example using a punch). These specimens are typically about 150 ⁇ thick, from 5 to 10 mm wide and have a useful length of about 10 to 15 mm. A tensile stress is imposed on this sample. The sample undergoes a static force of 0.01 N on which is superimposed a sinusoidal displacement of ⁇ 8 m at a frequency of 1 Hz. The test is thus performed in the linear range, at low levels of deformation. This tensile stress is performed on the sample at temperatures ranging from -150°C to +200°C, with a temperature variation of 3°C per minute.
  • the curve of the Tg8 values is then plotted as a function of the temperature; this curve presents at least one peak.
  • the glass transition temperature Tg of the polymer corresponds to the temperature at the top of this peak.
  • the value taken as the Tg of the polymer tested is the temperature for which the curve presents a peak of the largest amplitude (i.e. corresponding to the largest Tg value; in this case, only the "major" Tg is considered as the Tg value of the polymer tested).
  • the transition temperature Tg1 corresponds to the "major” Tg (in the predefined sense) of the first film-forming polymer when the latter has at least two Tg values; the glass transition temperature Tg2 corresponds to the "major"
  • Tg of the second film-forming polymer when the latter has at least two Tg values.
  • the first film-forming polymer and the second film-forming polymer may be chosen, independently of each other, from free-radical polymers, polycondensates and polymers of natural origin as defined previously having the glass transition temperature characteristics defined previously.
  • first film-forming polymer in aqueous dispersion use may be made of the aqueous polymer dispersions sold under the names Neorez R-989 ® by the company
  • aqueous polymer dispersions sold under the names Avalure ® UR-405,
  • the film-forming polymer of the aqueous dispersion Avalure ® UR-460 is a polyurethane obtained by polycondensation of polytetramethylene oxide, tetramethylxylylene diisocyanate, isophorone diisocyanate and dimethylolpropionic acid.
  • first and second film-forming polymers in aqueous dispersion use is made, as first and second film-forming polymers in aqueous dispersion, of the combination of styrene/acrylate polymer dispersion such as the dispersion sold under the reference Joncryl 821 1 ® by BASF and of acrylic polymer dispersion such as the dispersion sold under the reference Neocryl A-45 ® by DSM.
  • first film-forming polymer in aqueous dispersion of an acrylic polymer dispersion such as the dispersion sold under the reference Joncryl 95 ® by BASF and, as second film-forming polymer, of a dispersion of anionic polyurethane polymer sold under the reference Avalure UR405 ® by DSM.
  • aqueous dispersions of film-forming polymer use may be made of:
  • Neorez R- 981 ® and Neorez R-974 ® by the company DSM
  • Avalure UR-405 ® Avalure UR-410 ®
  • Avalure UR-425 ® Avalure UR-450 ®
  • Sancure 875 ® Avalure UR 445 ® and Avalure UR 450 ® by the company Noveon
  • Impranil 85 ® by the company Bayer
  • Baycusan C1004 ® by the company Bayer Material Science
  • - vinyl dispersions such as Mexomer PAM, aqueous dispersions of polyvinyl acetate such as Vinybran ® from the company Nisshin Chemical or the products sold by the company Union Carbide, aqueous dispersions of vinylpyrrolidone, dimethylaminopropylmethacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride terpolymer such as Styleze W ® from ISP,
  • aqueous dispersions of polyurethane/polyacrylic hybrid polymer such as the products sold under the references Hybridur ® by the company Air Products or Duromer ® from National Starch,
  • core-shell type such as the products sold by the company Arkema under the reference Kynar ® (core: fluid - shell: acrylic) or alternatively those described in US 5 188 899 (core: silica - shell: silicone), and mixtures thereof.
  • a composition in accordance with the invention comprises an aqueous dispersion of particles chosen from aqueous dispersions of acrylic film-forming polymer(s) and derivatives, in particular of styrene-acrylic and derivatives, and aqueous dispersions of polyurethane polymer(s), in particular of polyester-polyurethane, and derivatives thereof, and a mixture thereof.
  • the total content of hard wax(es) and the total content of film-forming polymer particles are such that the weight ratio of the hard wax(es) to the film-forming polymer particles is greater than or equal to 1/2 and better still 2/3.
  • this ratio is inclusively between 1/2 and 2 and even more preferentially between 2/3 and 3/2.
  • the total content of hard wax(es) and the total content of film-forming polymer particles which are both preferentially present in the form of particles in aqueous dispersion, with the film-forming polymer(s) chosen from aqueous dispersions of acrylic film-forming polymer(s) and derivatives, in particular styrene-acrylic and derivatives, and the aqueous dispersions of polyester- polyurethane hybrid polymer(s), and a mixture thereof, are such that the weight ratio of the hard wax particles to said film-forming polymer particles is greater than or equal to 1/2 and better still 2/3.
  • this ratio is inclusively between 1/2 and 2 and even more preferentially between 2/3 and 3/2.
  • compositions of an assembly according to the present invention comprise at least one water-soluble film-forming polymer.
  • a composition according to the invention is free of water-soluble film-forming polymer.
  • the total solids content of "water-soluble film-forming polymer(s)" may range from 0.1 % to 10%, preferably from 0.5% to 8% and better still from 1 % to 5% by weight relative to the total weight of the composition.
  • water-soluble film-forming polymers examples include:
  • proteins of plant origin such as wheat proteins and soybean proteins
  • proteins of animal origin such as keratins, for example keratin hydrolysates and sulfonic keratins
  • cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose and carboxymethyl cellulose, and also quaternized cellulose derivatives;
  • vinyl polymers for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and of caprolactam; polyvinyl alcohol;
  • anionic, cationic, amphoteric or nonionic chitin or chitosan polymers anionic, cationic, amphoteric or nonionic chitin or chitosan polymers
  • compositions of an assembly according to the present invention may also contain at least one hydrophilic, or water-soluble, gelling agent, and may be chosen from:
  • associative polymers and in particular associative polyurethanes such as the Ci 6 -OE 12 o-Ci 6 polymer from the company Elementis (sold under the name Rheolate FX1 100, this molecule bearing a urethane function and having a weight-average molecular weight of 1300), OE being an oxyethylene unit, Rheolate 205 bearing a urea function, sold by the company Rheox, or Rheolate 208 or 204 (these polymers being sold in pure form) or DW 1206B from Rohm & Haas bearing a C 20 alkyl chain and a urethane bond, sold at 20% solids in water.
  • Ci 6 -OE 12 o-Ci 6 polymer from the company Elementis (sold under the name Rheolate FX1 100, this molecule bearing a urethane function and having a weight-average molecular weight of 1300), OE being an oxyethylene unit, Rheolate 205 bearing a
  • solutions or dispersions of these associative polyurethanes especially in water or in aqueous-alcoholic medium.
  • examples of such polymers include Rheolate FX1010, Rheolate FX1035, Rheolate1070, Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Elementis.
  • Rheolate FX1010 Rheolate FX1035, Rheolate1070, Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Elementis.
  • water-soluble film-forming polymers also act as water-soluble gelling agent.
  • the hydrophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 10% by weight, preferably from 0.1 % to 5% by weight and better still from 0.5% to 2% by weight, relative to the total weight of the composition.
  • a composition according to the invention advantageously comprises one of the abovementioned gelling agents, preferably chosen from AMPS (polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked), AMPS/acrylamide copolymers, and a mixture thereof.
  • AMPS polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked
  • AMPS/acrylamide copolymers preferably chosen from AMPS (polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked), AMPS/acrylamide copolymers, and a mixture thereof.
  • AMPS polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked
  • AMPS/acrylamide copolymers preferably chosen from AMPS/acrylamide copolymers
  • a composition of an assembly according to the invention may comprise at least one lipophilic or liposoluble gelling agent.
  • the gelling agent(s) that may be used may be organic or mineral, polymeric or molecular lipophilic gelling agents.
  • Mineral lipophilic gelling agents that may be mentioned include clays, modified clays, such as Bentone 38 VCG by the company Elementis, and optionally hydrophobically surface-treated fumed silica.
  • the polymeric organic lipophilic gelling agents are, for example, partially or completely crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6 ® , KSG16 ® and KSG18 ® by Shin-Etsu, Trefil E-505C ® and Trefil E-506C ® by Dow Corning, Gransil SR-CYC ® , SR DMF10 ® , SR- DC556 ® , SR 5CYC gel ® , SR DMF 10 gel ® and SR DC 556 gel ® by Grant Industries and SF 1204 ® and JK 1 13 ® by General Electric; ethyl cellulose, for instance the product sold under the name Ethocel ® by Dow Chemical; polycondensates of polyamide type resulting from the condensation between (a) at least one acid chosen from dicarboxylic acids containing at least 32 carbon atoms, such as fatty acid dimers, and ( ⁇ ) an al
  • Block copolymers of "diblock”, “triblock” or “radial” type, of the polystyrene/polyisoprene or polystyrene/polybutadiene type such as the products sold under the name Luvitol HSB ® by the company BASF, of the polystyrene/copoly(ethylene-propylene) type, such as the products sold under the name Kraton ® by the company Shell Chemical Co., or of the polystyrene/copoly(ethylene- butylene) type, and mixtures of triblock and radial (star) copolymers in isododecane, such as those sold by the company Penreco under the name Versagel ® , for instance the mixture of butylene/ethylene/styrene triblock copolymer and of ethylene/propylene/styrene star copolymer in isododecane (Versagel M 5960).
  • compositions according to the invention may also comprise a non- emulsifying silicone elastomer as lipophilic gelling agent.
  • a non- emulsifying silicone elastomer as lipophilic gelling agent.
  • lipophilic gelling agents that may also be mentioned are organogelling agents.
  • a composition according to the invention is preferably free of lipophilic gelling agent.
  • compositions of an assembly in accordance with the invention comprise at least one dyestuff.
  • This (or these) dyestuffs are preferably chosen from pulverulent dyes, liposoluble dyes and water-soluble dyes, and mixtures thereof.
  • compositions according to the invention comprise at least one pulverulent colorant.
  • the pulverulent dyestuffs may be chosen from pigments and nacres, and preferably from pigments.
  • the pigments may be white or coloured, mineral and/or organic, and coated or uncoated.
  • mineral pigments mention may be made of metal oxides, in particular titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxide, and also iron, titanium or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue.
  • organic pigments that may be mentioned are carbon black, pigments of D&C type and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium.
  • the nacres may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica with iron oxides, titanium mica in particular with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.
  • white nacreous pigments such as mica coated with titanium or with bismuth oxychloride
  • coloured nacreous pigments such as titanium mica with iron oxides, titanium mica in particular with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.
  • the liposoluble dyes are, for example, Sudan Red, D&C Red 17, D&C Green
  • the pigments contained in the compositions according to the invention are chosen from metal oxides.
  • dyestuffs may be present in a content ranging from 0.01 % to 30% by weight relative to the total weight of the composition and in particular from 3% to 22% by weight relative to the total weight of the composition.
  • the dyestuff(s) are chosen from one or more metal oxides that are present in a content of greater than or equal to 2% by weight relative to the total weight of the composition, and advantageously inclusively between 3% and 22% by weight relative to the total weight of the composition.
  • compositions of an assembly in accordance with the invention may also comprise at least one filler.
  • the fillers may be selected from those that are well known to those skilled in the art and commonly used in cosmetic compositions.
  • the fillers may be mineral or organic, and lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders, for instance the Nylon ® sold under the name Orgasol ® by the company Atochem, poly-p-alanine powders and polyethylene powders, powders of tetrafluoroethylene polymers, for instance Teflon ® , lauroyllysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance the products sold under the name Expancel ® by the company Nobel Industrie, acrylic powders such as those sold under the name Polytrap ® by the company Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (for example Tospearls ® from Toshiba), precipitated
  • the fillers may represent from 0.1 % to 15% by weight and in particular from
  • compositions of an assembly in accordance with the invention may also comprise at least one cosmetic active agent.
  • cosmetic active agents that may be used in the compositions in accordance with the invention, mention may be made especially of antioxidants, preserving agents, fragrances, neutralizers, emollients, coalescers, moisturizers, vitamins and screening agents, in particular sunscreens, and mixtures thereof.
  • the composition according to the invention is a leave-in composition.
  • the composition is a makeup composition and in particular a mascara.
  • compositions of an assembly according to the invention may comprise at least one oil or organic solvent.
  • compositions according to the invention may in particular comprise at least one oil chosen from at least one non-volatile oil, at least one volatile oil, and a mixture thereof.
  • oil means a fatty substance that is liquid at room temperature and at atmospheric pressure.
  • non-volatile oil means an oil that remains on the skin or the keratin fibre at room temperature and pressure. More precisely, a non-volatile oil has an evaporation rate strictly less than 0.01 mg/cm 2 /min.
  • Said at least one non-volatile oil may be chosen from hydrocarbon-based oils and silicone oils, and mixtures thereof, preferably from hydrocarbon-based oils.
  • non-volatile hydrocarbon-based oils that are suitable for the present invention may be chosen in particular from:
  • oils of plant origin such as triglycerides formed from fatty acid esters of glycerol, the fatty acids of which may have varied chain lengths from C4 to C28, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, palm oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil and musk rose oil; or alternatively caprylic/capric acid triglycerides such as
  • esters such as oils of formula R1 COOR2 in which R1 represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R2 represents an in particular branched hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R1 + R2 ⁇ 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, alkyl or polyalkyl octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate and diisostearyl malate; and pentaerythr
  • octyldodecanol isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol; and
  • - higher fatty acids such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof.
  • non-volatile silicone oils that are suitable for the present invention may be chosen in particular from:
  • non-volatile silicone oils that may be used in the composition in accordance with the invention may be non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicat.es.
  • PDMSs non-volatile polydimethylsiloxanes
  • polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon
  • a composition according to the invention optionally comprises at least one hydrocarbon-based non-volatile oil of plant origin, such as triglycerides consisting of fatty acid esters of glycerol in which the fatty acids may have chain lengths ranging from C4 to C28, in particular palm oil and hydrogenated jojoba oil(s).
  • a composition according to the invention is preferably free of silicone non-volatile oil(s).
  • a composition according to the invention is preferably free of non-volatile oil.
  • the total content of non-volatile oil(s) in a composition in accordance with the invention may range from 0.01 % to 10% by weight, in particular from 0.1 % to 8% by weight and preferably from 0.25% to 5% by weight relative to the total weight of the composition.
  • a composition according to the invention comprises less than 5% by weight of non-volatile oil(s) relative to the total weight of the composition. Volatile oil
  • composition of an assembly according to the invention may comprise at least one volatile oil.
  • volatile oil means an oil (or non-aqueous medium) that can evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure.
  • the volatile oil is a cosmetic volatile oil, which is liquid at room temperature. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg/cm 2 /min, limits included.
  • This volatile oil may be hydrocarbon-based.
  • the volatile hydrocarbon-based oil may be chosen from hydrocarbon-based oils containing from 7 to 16 carbon atoms.
  • composition according to the invention may contain one or more volatile branched alkane(s).
  • volatile branched alkane(s) means, without preference, “one or more volatile branched alkane oil(s)”.
  • volatile hydrocarbon-based oils containing from 7 to 16 carbon atoms mention may be made especially of C 8 -Ci 6 branched alkanes, for instance C 8 -Ci 6 isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and for example the oils sold under the trade names Isopar or Permethyl, C 8 -Ci 6 branched esters such as isohexyl neopentanoate, and mixtures thereof.
  • the volatile hydrocarbon-based oil containing from 8 to 16 carbon atoms is chosen from isododecane, isodecane and isohexadecane, and mixtures thereof, and is especially isododecane.
  • composition according to the invention may contain one or more volatile linear alkane(s).
  • volatile linear alkane(s) means, without preference, “one or more volatile linear alkane oil(s)”.
  • a volatile linear alkane that is suitable for the invention is liquid at room temperature (about 25°C) and at atmospheric pressure (760 mmHg).
  • a "volatile linear alkane” that is suitable for the invention means a cosmetic linear alkane, which is capable of evaporating on contact with the skin in less than one hour, at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e. 101 325 Pa), which is liquid at room temperature, especially having an evaporation rate ranging from 0.01 to 15 mg/cm 2 /min, at room temperature (25°C) and atmospheric pressure (760 mmHg).
  • the linear alkanes preferably of plant origin, comprise from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms and more particularly from 1 1 to 13 carbon atoms.
  • linear alkanes that are suitable for use in the invention, mention may be made of the alkanes described in patent applications WO 2007/068 371 or WO 2008/155 059 by the company Cognis (mixtures of distinct alkanes that differ by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut oil or palm oil.
  • linear alkanes that are suitable for the invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C1 1 ), n- dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15), and mixtures thereof, and in particular the mixture of n-undecane (C1 1 ) and n-tridecane (C13) described in Example 1 of patent application WO 2008/155 059 by the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof.
  • the linear alkane may be used alone or as a mixture of at least two distinct alkanes that differ from each other by a carbon number of at least 1 , and especially a mixture of at least two linear alkanes comprising from 10 to 14 distinct carbon atoms that differ from each other by a carbon number of at least 2, and in particular a mixture of C1 1/C13 volatile linear alkanes or a mixture of C12/C14 linear alkanes, in particular an n- undecane/n-tridecane mixture (such a mixture may be obtained according to Example 1 or Example 2 of WO 2008/155 059).
  • composition prepared may comprise at least one volatile silicone oil or solvent that is compatible with cosmetic use.
  • silicon oil means an oil containing at least one silicon atom, and especially containing Si-0 groups. According to one embodiment, said composition comprises less than 10% by weight of volatile silicone oil(s), relative to the total weight of the composition, better still less than 5% by weight, or even is free of volatile silicone oil.
  • Volatile silicone oils that may be mentioned include cyclic polysiloxanes and linear polysiloxanes, and mixtures thereof.
  • Volatile linear polysiloxanes that may be mentioned include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane.
  • Volatile cyclic polysiloxanes that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
  • the composition prepared may comprise at least one volatile fluoro oil.
  • fluoro oil means an oil containing at least one fluorine atom.
  • Volatile fluoro oils that may be mentioned include nonafluoromethoxybutane and perfluoromethylcyclopentane, and mixtures thereof.
  • a composition according to the invention is preferably free of non-volatile oil.
  • at least one volatile oil may be present in a total content ranging from 0.1 % to 10% by weight.
  • the volatile oil may be present in the composition in a content ranging from 0.5% to 5% relative to the total weight of the composition.
  • a composition according to the invention comprises less than 5% by weight of volatile oil(s) relative to the total weight of the composition.
  • a packaging assembly according to the present invention comprises a packaging device that is capable of receiving said cosmetic composition in accordance with the invention.
  • the packaging device comprises a transparent container for housing the composition for coating keratin fibres.
  • This composition may then be withdrawn from the container by immersing an applicator therein.
  • This applicator may be firmly attached to a member for closing the container.
  • This closing member may form a member for gripping the applicator.
  • This gripping member may form a cap to be removably mounted on said container by any suitable means, such as screwing, click-fastening, coupling, etc. Such a container may thus reversibly house said applicator.
  • This container may be optionally equipped with a wiper suitable for removing surplus product taken up by the applicator.
  • the container is transparent.
  • this container advantageously comprises a body, which is closed at one end by a base and open at an opposite end. More particularly, the body of the container may comprise a neck forming a shoulder from which the aperture raises. This aperture may receive the wiper inside. Such an aperture may be reversibly closed by a cap. This cap preferably supports the applicator intended to coat the keratin fibres with a composition according to the invention.
  • At least the body of the container is transparent.
  • the body, the neck and the base of the container are transparent.
  • this container of a transparent thermoplastic material, for example by injection-moulding, or of glass, for example by injection blow-moulding.
  • such a container may be made of a transparent thermoplastic material chosen from the group consisting of PET and PMMA.
  • such a device may comprise means for heating a composition in accordance with the invention.
  • a packaging device in accordance with the invention may comprise heating means so that a composition in accordance with the invention can be subjected to these heating means before and/or during application.
  • heating means may be integrally fastened to an assembly for coating keratin fibres and more particularly to an applicator configured to apply said cosmetic composition for coating keratin fibres, and optionally, where appropriate, to a conditioning device suitable for receiving said composition.
  • heating means are then suitable for melting at least part of the fatty phase, and especially at least part of the surfactant system and, where appropriate, at least part of the soft wax(es), and optionally at least part of the hard wax particles.
  • the wax particles are heated to a temperature T c such that only part of the crystallizable chains are melted.
  • the heating means may also come into contact with or face the composition to be heated.
  • the composition may be heated while it is contained in a packaging device.
  • the composition may be heated while it is at least partially exposed to the ambient air.
  • the composition may be locally heated to a temperature greater than or equal to 45°C, or even greater than or equal to 50°C, or even greater than or equal to 55°C.
  • the temperature of the composition should not entail any risk of burning at the time of application. This is why when the composition is heated before application, a waiting time between the moment at which the composition is heated and the application to the keratin materials may optionally be necessary.
  • the composition is heated simultaneously with its application to the keratin fibres.
  • the composition is heated before and during its application to the keratin fibres.
  • the temperature to which at least part of the composition is heated may be inclusively between 45°C and 95°C, better still 50°C to 85°C and better still 55°C to 75°C.
  • the temperature may be measured, for example, at the surface using an infrared pyrometer, for example a Fluke® brand machine.
  • composition in accordance with the invention is capable of passing from a solid state to an at least partially liquid or even totally liquid state, and of doing so reversibly.
  • the solid/liquid change of state is at least partly due to the melting of a crystalline part, in particular of the wax(es) described previously in the present description.
  • the total heat of fusion of the composition is the heat consumed by the composition between -20°C and 120°C.
  • the total heat of fusion of the composition is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5°C or 10°C per minute, according to standard ISO 1 1357-3:1999.
  • DSC differential scanning calorimeter
  • a 5 mg sample of composition is placed in a crucible and subjected to a first temperature rise ranging from -20°C to 120°C, at a heating rate of 10°C/minute, and is then cooled from 120°C to -20°C at a cooling rate of 10°C/minute.
  • the sample is maintained at -20°C for 5 minutes and finally subjected to a second temperature rise ranging from -20°C to 100°C at a heating rate of 5°C / minute.
  • the variation in the difference in power absorbed by an empty crucible and by the crucible containing the sample of the composition is measured as a function of the temperature.
  • the melting point of the compound is the value of the temperature corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
  • the heat of fusion of the composition consumed at the temperature T c is the amount of energy required to make the compound pass from the solid or very viscous state at -20°C to the state of the composition at the temperature T c . It is expressed in J/g.
  • the composition is chosen such that the ratio of the heat consumed between -20°C and T c by the product to the total heat consumed between -20°C and 120°C is less than or equal to 0.7.
  • the choice of the temperature T c to which the composition is brought by the heating means may thus be made so that said ratio is less than or equal to 0.7, for example inclusively between 0.3 and 0.6.
  • heating is performed to a temperature such that the ratio of the heat supplied to heat the sample of composition to the temperature T c to the total heat is less than or equal to 0.7, such a parameter being measured according to the DSC protocol described above.
  • a device of an assembly according to the invention preferably comprises an applicator for smoothing and/or separating keratin fibres, such as the eyelashes or the eyebrows, especially in the form of teeth, bristles or other reliefs.
  • the applicator is arranged to apply the composition to the eyelashes or the eyebrows, and may comprise, for example, a brush or a comb.
  • the applicator may also be used for finishing of the makeup, over a region of the eyelashes or eyebrows that is made up or laden with composition.
  • the brush may comprise a twisted core and bristles held between the turns of the core, or may be made in yet another way.
  • the comb is, for example, produced from a single part by moulding of a plastic.
  • the application member is mounted at the end of a wand, which wand may be flexible, which may contribute to improving the comfort during application.
  • the packaging and application assembly may be in the form of a kit, it being possible for the applicator and the packaging device to be housed separately in the same packaging article.
  • a process for applying the composition according to the invention to the eyelashes or the eyebrows may also include the following steps:
  • a mascara composition of an assembly in accordance with the invention is described below:
  • Phase B Steareth 2 (B rij 72 fro m U n i q e m a ) 8
  • Steareth 20 (B rij 78P from U n iq e ma) 8
  • Phase D Preserving agents qs This composition was prepared as follows:
  • Phase A is added to phase B and the mixture is emulsified for 5 minutes at 95°C using a Moritz blender. iv. Preparation of phase C
  • Phase A+B (hot emulsion at 95°C) is poured into the thermostatic bath containing phase C. vi. Addition of phase D
  • Phase D is poured into the phase A+B+C mixture when the temperature of the mixture is less than or equal to 45°C. vii. End of formulation
  • the mascara thus obtained is transferred into a closed jar to prevent it from drying out on contact with air; it is then necessary to wait 24 hours to check the homogeneity of the formulation and the correct dispersion of the pigments.
  • Such a composition is packaged in a packaging device comprising a transparent container through which the mascara composition is directly visible.
  • the composition prepared is observed with the naked eye and by microscope.
  • the composition according to the invention is a fine emulsion with a fine grain of well-distributed (homogeneous) wax(es). It has a fluid texture (viscosity at 25°C of 14.4 Pa.s measured using a Rheomat RM100® machine).
  • the pigments are well dispersed and the composition has an intense black colour.
  • these compositions are stable at 4 and 45°C for two months.
  • the composition obtained has good gloss and a particularly satisfactory black intensity.
  • these compositions When tested on a sample of naked eyelashes, these compositions, applied using a brush, are pleasant on application.
  • the deposit is constructed coat after coat, the composition coats the eyelashes well, the makeup result is uniform and the eyelash fringe is well developed.
  • the properties of a mascara in accordance with the invention are such that a transparent container containing it makes it possible to magnify the mascara and to give an idea of the black intensity qualities and optionally the gloss qualities of the packaged mascara, even after a long period of storage of the assembly.

Abstract

The present invention relates to an assembly for packaging a composition, preferably for coating keratin fibres such as the eyelashes, comprising: - a composition, preferably for coating keratin fibres such as the eyelashes, comprising: i) an aqueous phase, ii) particles comprising at least one hard wax, preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition, iii) a lamellar phase Lβ formed by an aqueous phase-structuring surfactant system, said surfactant system comprising a content of surfactant(s) of greater than or equal to 15% by weight relative to the total weight of the composition, - a packaging device comprising a container for storing said composition, this container being at least partly transparent so that said composition contained in the container is directly visible through the container.

Description

Assembly for packaging a composition for coating keratin fibres
The present invention relates to an assembly for packaging a cosmetic composition for coating keratin fibres, comprising a cosmetic composition for coating keratin fibres, and in particular the eyelashes, and a packaging device configured to store said composition. The present invention also relates to a process for coating keratin fibres, in particular a process for making up and optionally caring for the eyelashes.
The composition used may in particular be in the form of an eyelash product such as a mascara, or an eyebrow product. More preferentially, the invention relates to a mascara. The term "mascara" is intended to mean a composition intended to be applied to the eyelashes: it may be an eyelash makeup composition, an eyelash makeup base (also known as a base coat), a composition to be applied over a mascara, also known as a top coat, or else a cosmetic composition for treating the eyelashes. The mascara is more particularly intended for human eyelashes, but also false eyelashes.
Mascaras are in particular prepared according to two types of formulation: water-based mascaras known as cream mascaras, in the form of a dispersion of waxes in water; anhydrous mascaras or mascaras with a low water content, known as waterproof mascaras, in the form of dispersions of waxes in organic solvents.
The present patent application more specifically relates to water-based mascaras. Water-based mascaras are conventionally presented in opaque packaging devices. The reason for this is that the intensity of the colour of mascaras is often dull and greyish, which makes them relatively unattractive.
Furthermore, water-based mascaras based on waxes are relatively unstable and may aggregate under the action of heat, which tends towards further accentuating their greyish colour.
Thus, one aim of the present invention is to produce a mascara that is attractive to the user, especially by proposing an assembly comprising a water-based mascara with good colour intensity and good stability over time.
More particularly, one aim of the present invention consists in stabilizing a direct emulsion that is rich in fatty substances, especially in waxes, without phase separation over time.
An aim of the present patent application is more particularly to provide a stable mascara which has a texture that is sufficiently thick to obtain a charging deposit, of satisfactory consistency, allowing easy application to the eyelashes and an even deposit, i.e. a deposit that is smooth and uniform, even after two months stored at 4°C.
An aim of the present patent application is more particularly to provide a stable mascara which has a texture that is sufficiently thick to obtain a charging deposit, of satisfactory consistency, allowing easy application to the eyelashes and an even deposit, i.e. a deposit that is smooth and uniform, even after two months stored at 45°C.
An aim of the present patent application is more particularly to provide a stable mascara which has a texture that is sufficiently thick to obtain a charging deposit, of satisfactory consistency, allowing easy application to the eyelashes and an even deposit, i.e. a deposit that is smooth and uniform, even after two months stored at temperatures oscillating between 4°C and 45°C.
An aim of the present patent application is more particularly to provide a mascara in which the waxes are uniformly dispersed.
An aim of the present patent application is more particularly to provide a mascara in which the pigments are uniformly dispersed. An aim of the present invention is also to produce water-based mascaras of good colour intensity and good stability making it possible to exceed a high solids content, for example of greater than or equal to 40%.
Consequently, one subject of the present invention is an assembly for packaging a composition, preferably for coating keratin fibres such as the eyelashes, comprising:
- a composition, in particular for coating keratin fibres such as the eyelashes, more preferentially a mascara composition, comprising:
i) an aqueous phase,
ii) particles comprising at least one hard wax, preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition, iii) a lamellar phase ίβ formed by an aqueous phase-structuring surfactant system, said surfactant system comprising a content of surfactant(s), preferably nonionic surfactant(s), of greater than or equal to 15% by weight relative to the total weight of the composition,
- a packaging device comprising a container for storing said composition, this container being at least partly transparent so that said composition contained in the container is directly visible through the container.
Preferably, the surfactant system forming the lamellar phase Ι_β comprises:
* at least one nonionic surfactant with an HLB value at 25°C of less than 8, and
* at least one nonionic surfactant with an HLB value at 25°C of greater than or equal to 8.
Preferably, the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula (I) below:
(ALK-[C(0)]a-[0]b)c-X (I)
in which formula (I):
- ALK is a C7-C23, preferably Cn-C2i and more preferentially C15-C17 alkyl group,
a and b are integers between 0 and 100, c is an integer between 1 and 100, in particular between 1 and 3, preferably equal to 1 , a and b preferably being equal to 0,
X is a (poly)oxyalkylene group optionally substituted and/or terminated with a hydroxyl group, X preferably being an oxyethylene group (CH2CH20)n or (OCH2CH2)n in which n is greater than or equal to 1 , for example between 1 and 200, said (poly)oxyalkylene group preferably being a polyethylene glycol or being the result of at least one substitution of a hydroxyl group, preferably chosen from (poly)glycerols.
Preferably, the total content of hard wax(es) and optionally of additional wax(es) and the total content of surfactant system are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the surfactant system is less than or equal to 1 .75, preferably strictly less than 1 .5, in particular between 1/3 and 1 .25, the composition comprising a solids content of greater than or equal to 42%, preferably 45% and more preferentially 48%.
The term "additional wax(es)" means any wax other than a hard wax, such as one or more soft waxes.
Preferably, the total content of hard wax(es) relative to the total content of surfactant system, and preferentially of nonionic surfactants corresponding to formula (I) below, should be considered for calculating the preferred weight ratio in the invention. Such a ratio is preferably less than or equal to 1.75, preferably strictly less than 1 .5 and in particular between 1/3 and 1.25.
The group X is preferably chosen from:
i) HO-(ALK-0)z-CH2-CH[(OALK)y-OH]-CH2-(0-ALK)x-(*)
in which:
- ALK, which may be identical or different, representing a C1 -C6 and in particular C1 -C4 alkylene group, preferably ethylene,
- x, y and z being an integer between 0 and 200, it being understood that x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
ii) H-(ALK-0)x-(*) and H-(0-ALK)x-(*), preferably is H-(0-ALK)x-(*)
in which:
- ALK, which may be identical or different, representing a C1 -C6 and in particular C1 -C4 ethylene group, preferably ethylene,
- x is an integer other than 0 and preferably between 1 and 200. The nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula (Γ) below:
ALK-(0-CH2-CH2)n-OH (Ι') in which formula (Γ):
- ALK is a C8-C24, preferably C12-C22 and more preferentially Ci6-Ci8 alkyl group,
n being an integer other than 0, between 1 and 200, preferably between 1 and 10 and better still between 2 and 6 for the nonionic surfactant(s) with an HLB value at 25°C of less than 8, preferably between 20 and 200 for the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8.
According to one particular embodiment, the invention comprises:
* at least one hard wax, preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition, and
* preferably at least an aqueous dispersion of particles of at least one film-forming polymer, the film-forming polymer(s) preferably being present in a solids content of greater than or equal to 5% by weight and preferably 10% by weight relative to the total weight of said composition.
Surprisingly and unexpectedly, the inventors of the present application have solved this (these) problem(s) by means of such a composition. In particular, a composition in accordance with the invention gives rise to a water-based mascara composition which gives a strong colour intensity. Furthermore, the invention makes it possible to formulate water-based mascaras that may be rich in solids, especially in fatty substances, and that are stable, having a homogeneous and uniform dispersion of waxes, even after 2 months whether at 45°C or at 4°C. Finally, this mascara has good dispersion of the pigments and waxes, and is smooth and glossy. Such a composition is still pleasant upon application, comfortable and has a volumizing effect. Furthermore, this composition has a reinforced water content when film-forming polymer particles are present.
According to the inventors, the combination of surfactants as described above allows an excellent compromise in terms of colour intensity, texture and cosmeticity and makes it possible, contrary to all expectation in the field of water-based mascaras, to condition these mascaras in a transparent container. Furthermore, it would have been difficult to envisage such surfactants with thickening nature in a formula rich in hard waxes and with a high solids content.
Throughout the description that follows, and unless otherwise mentioned: an "alky group is a linear or branched, preferably linear, C7-C23, preferably Cn-C2i and more preferentially C15-C17 hydrocarbon-based group or chain;
- the "hydrocarbon-based chain" is optionally "(poly)unsaturated" when it comprises one or more double bonds and/or one or more triple bonds, which may be conjugated or non-conjugated; preferably, this hydrocarbon-based chain is saturated;
ALK-[C(0)]a-[0]b generally means that the alkyl group ALK may be derived from a fatty acid or from a fatty alcohol;
[C(0)]a-[0]b means that the ALK group may comprise at least one function chosen from an ester function COO (when a+b=1 ), a carbonyl function CO (when a=1 and b=0), an oxy function O (when a=0 and b=1 ), or may be directly linked to the oxyalkylene group (when a+b=0);
the compounds of formula (I) preferably result from an esterification, more preferentially from a mono-esterification, or from an etherification (or alkoxylation), more preferentially a mono-etherification (or mono-alkoxylation);
the term "(poly)oxyalkylene" means that one or more -OH functions, in particular derived from a hydroxyl function or a carboxylic function, may be substituted with an oxyalkylene group, in particular an oxyethylene group;
the term "acyl" means a linear or branched, saturated C8-C24, better still C12-C20 and more preferentially C14-C18 hydrocarbon-based chain, comprising a carboxylic function whose hydroxyl function (-OH) has been substituted.
According to particular preferred embodiments of an assembly in accordance with the invention directed towards solving at least one of the abovementioned problems: - the aqueous phase represents from 30% to 80% by weight and preferably from 40% to 70% by weight relative to the total weight of the composition;
- said composition comprises a fatty phase dispersed in the aqueous phase, the fatty phase predominantly comprising hard wax particles, preferentially in the form of aqueous dispersion(s);
- the at least one from among the nonionic surfactant(s) with an HLB value at 25°C of less than 8 are chosen from:
* (poly)oxyalkylenated saccharide esters and ethers;
* esters of fatty acids, especially of C8-C24 and preferably of Ci6-C22, and of (poly)oxyalkylenated polyol, especially of (poly)oxyalkylenated glycerol or of oxyalkylenated sorbitol, preferably of (poly)oxyalkylenated glycerol;
* (poly)oxyalkylenated alcohols;
and mixtures thereof, preferably from (poly)oxyalkylenated alcohols;
- the at least one from among the nonionic surfactant(s) with an HLB value at 25°C of less than 8 comprises a (poly)oxyalkylenated alcohol comprising an ether of a
C8-C24 fatty alcohol and of polyethylene glycol, said ether comprising from 1 to 10 and better still between 2 and 6 ethylene glycol units.
- the nonionic surfactant(s) with an HLB value at 25°C greater than or equal to 8, preferably greater than or equal to 10, are chosen from:
* (poly)oxyalkylenated glycerol ethers,
* (poly)oxyalkylenated alcohols,
* esters of a fatty acid and of (poly)oxyalkylenated polyethylene glycol,
* esters of a fatty acid and of (poly)oxyalkylenated glycerol ethers,
* esters of a fatty acid and of (poly)oxyalkylenated sorbitol ethers,
and mixtures thereof, preferably from (poly)oxyalkylenated alcohols;
- the at least one from among the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 comprises a (poly)oxyalkylenated alcohol comprising at least an ether of a C8-C24 fatty alcohol and of polyethylene glycol, said ether comprising at least 20 ethylene glycol units and better still between 20 and 200 ethylene glycol units;
- the nonionic surfactant(s) with an HLB value at 25°C of less than 8, preferably corresponding to formula (I), are present in a content of greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition; - the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, preferably corresponding to formula (I), are present in a content of greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition;
- the nonionic surfactant(s) with an HLB value at 25°C of less than 8, and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, both preferably corresponding to formula (I), are present in a total content of greater than or equal to 10%, better still 12% and in particular between 15% and 25% by weight relative to the total weight of the composition;
- the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, both preferably corresponding to formula (I), are present in a respective total content such that the weight ratio of the nonionic surfactant(s) with an HLB value at 25°C of less than 8 to the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 ranges from 1/5 to 5, preferably from 1/3 to 3, preferably from 2/3 to 3/2;
- the total content of hard wax(es) and optionally of additional wax(es) and the total content of surfactant system(s) are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the surfactant system(s) is less than or equal to 1 .75, preferably less than or equal to 1 .5, in particular between 1/3 and 1 .25;
- the total content of hard wax(es) and optionally of additional wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 and of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 1 .75, preferably less than or equal to 1 .5, in particular between 1/3 and 1.25;
- the total content of hard wax(es) and optionally of additional wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
- the total content of hard wax(es) and optionally of additional wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
- the total content of hard wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 are such that the weight ratio of the hard wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
- the total content of hard wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 4, preferably less than or equal to 3, in particular between 2/5 and 5/2;
- the total content of hard wax(es) and the total content of nonionic surfactant(s) with an HLB value at 25°C of less than 8 and of nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are such that the weight ratio of the hard wax(es) to the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 is less than or equal to 1 .75, preferably less than or equal to 1 .5, in particular between 1/3 and 1 .25;
- said composition is free of oil or organic solvent;
- the fatty phase represents from 15% to 30% by weight relative to the total weight of the composition;
- said composition comprises a solids content of greater than or equal to 42%, preferentially 45%, more preferentially 48%, or even 50%;
- the hard wax particles have in said (final) composition a mean size expressed as the volume-mean "effective" diameter D[4.3] of less than or equal to 5 μηη, preferentially less than or equal to 2 μηη, even more preferentially 1 μηη, for example between 0.01 and 5 μηη, and more preferentially between 0.05 and 2 μηη;
- the film-forming polymer particles introduced in aqueous dispersion form into said composition have in said composition a mean size expressed as the volume-mean
"effective" diameter D[4.3] of less than or equal to 5 μηη, preferentially less than or equal to 2 μηη, even more preferentially 1 μηη, for example between 0.01 and 5 μηη, and more preferentially between 0.05 and 2 μηη;
- said composition comprises a total content of hard wax particles, preferentially present in aqueous dispersion form, of greater than or equal to 12% by weight, preferably 15% by weight, preferably 18% by weight and more preferentially 20% by weight, relative to the total weight of the composition, for example between 16% and 30% by weight relative to the total weight of the composition;
- said composition comprises a total content of hard wax particles, preferentially in aqueous dispersion form, representing at least 80% by weight, preferentially at least 90% by weight and more preferentially 100% by weight relative to the total weight of wax(es);
- the total content of hard wax particles, preferentially in aqueous dispersion form, is greater than or equal to 30% by weight and preferentially 40% by weight relative to the total weight of the particles;
- the total content of hard wax particles, preferentially in aqueous dispersion form, represents at least 80% relative to the total weight of fatty substances;
- the hard wax(es) in the form of particles, preferentially in aqueous dispersion form, are polar;
- the hard wax(es) are not introduced into the manufacture of a cosmetic composition according to the invention, preferentially a mascara, in the form of an aqueous dispersion of pre-prepared particles;
- the film-forming polymer particles are introduced into the preparation of the composition in the form of a pre-prepared aqueous dispersion of film-forming polymer(s);
- said composition comprises a total content of film-forming polymer particles in aqueous dispersion form of greater than or equal to 10% by weight and preferably 15% by weight relative to the total weight of the composition;
- unlike the hard wax(es), the film-forming polymer(s) in accordance with the invention are, during the manufacture of a cosmetic composition according to the invention, preferentially a mascara, introduced in the form of an aqueous dispersion of pre-dispersed film-forming polymer particles, advantageously having its own surfactant system, varied according to the chemistry of the film-forming polymer(s) used;
- the film-forming polymer particles have their own surfactant system, i.e. different from the surfactant system in accordance with the present invention, more particularly different from the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, or preferably greater than or equal to 10, suited to dispersing the hard wax(es);
- the hard wax particles and the film-forming polymer particles in aqueous dispersion have a respective surfactant system, more precisely a respective surfactant;
- the film-forming polymer particles in aqueous dispersion form are chosen from synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and mixtures thereof;
- the film-forming polymer particles in aqueous dispersion form are chosen from acrylic polymer dispersions, polyurethane dispersions, sulfopolyester dispersions, vinyl dispersions, polyvinyl acetate dispersions, vinylpyrrolidone, dimethylaminopropylmethacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride terpolymer dispersions, dispersions of polyurethane/polyacrylic hybrid polymers, dispersions of core-shell particle type and mixtures thereof, preferably from acrylic polymer dispersions, dispersions of polyurethane/polyacrylic hybrid polymers, and derivatives thereof, and mixtures thereof, preferentially from acrylic polymer dispersions, in particular styrene-acrylic, and polyurethane dispersions, in particular polyester- polyurethane, and derivatives thereof, and mixtures thereof;
- the total content of hard wax particles and the total content of film-forming polymer particles, preferentially both in aqueous dispersion form, are such that the weight ratio of the hard wax particles to the film-forming polymer particles is greater than or equal to 1/2, preferably greater than 2/3, advantageously between 1/2 and 2 and preferably between 2/3 and 3/2;
- said composition comprises one or more additional surfactants (i.e. other than a surfactant of formula (I)) chosen from nonionic surfactants with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, nonionic surfactants with an HLB value at 25°C of less than 8, anionic surfactants, and mixtures thereof; preferably from nonionic surfactants with an HLB value at 25°C of less than 8;
- said composition comprises at least one water-soluble film-forming polymer, more preferentially said composition is free of water-soluble film-forming polymer;
- said composition comprises at least one dyestuff chosen from one or more pulverulent dye(s), preferably metal oxides, and in particular iron oxides;
- the metal oxide(s) are preferably present in a content of greater than or equal to 2% by weight relative to the total weight of the composition, and advantageously inclusively between 3% and 22% by weight relative to the total weight of the composition;
- said composition comprises at least one hydrophilic and/or lipophilic gelling agent, preferably at least one hydrophilic gelling agent; - said composition has a viscosity at 25°C ranging from 5 to 50 Pa.s, in particular measured using a Rheomat RM100® machine;
- said composition may be a makeup composition, a makeup base or "base coat", or a "top coat" composition to be applied onto a makeup;
- the container defines internally a storage volume for a composition in accordance with the invention;
- the container comprises a body, which is preferably cylindrical, closed at one end by a base and open at an opposite end;
- the composition is in direct contact with the container so that the user directly sees the composition packaged inside the container by looking through a constituent wall of said container;
- the container has no inner coating intended to mask the composition from the user;
- the body of the container comprises a neck forming a shoulder from which the aperture raises;
- the aperture houses internally a wiper configured to free the applicator of surplus composition;
- the aperture is reversibly closed by a lid;
- the lid supports an applicator configured to apply said composition in accordance with the invention to keratin fibres, in particular to the eyelashes;
- said applicator is configured to come into the position dipping into the composition in accordance with the invention in the closed position of the lid on the container;
- at least the body of the container is transparent;
- the body, the neck and the base of the container are transparent;
- the container is made of a transparent thermoplastic material, for example by injection-moulding, or of glass, for example by injection blow-moulding;
- this assembly comprises means for heating said composition, for example integrally fastened to the applicator.
ASSEMBLY
A packaging assembly in accordance with the invention comprises:
a specific composition, in particular for coating keratin fibres such as the eyelashes, more preferentially a mascara composition, and a packaging device comprising a container for storing said composition, this container being at least partly transparent so that said composition contained in the container can be seen through the container.
The description that follows is directed towards describing in greater detail this composition and this device.
COMPOSITION
A composition of an assembly according to the invention, in particular for coating keratin fibres such as the eyelashes, more preferentially a mascara composition, comprises:
i) an aqueous phase,
ii) particles comprising at least one hard wax, preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition, iii) a lamellar phase Ι_β formed by an aqueous phase-structuring surfactant system, said surfactant system comprising a content of surfactant(s) of greater than or equal to 15% by weight relative to the total weight of the composition. Aqueous phase
The composition of an assembly according to the invention comprises an aqueous phase, which may form a continuous phase of the composition.
The aqueous phase comprises water. It may also comprise at least one water-soluble solvent.
In the present invention, the term "water-soluble solvent" denotes a compound that is liquid at room temperature and water-miscible.
The water-soluble solvents that may be used in the compositions according to the invention may also be volatile.
Among the water-soluble solvents that may be used in the compositions in accordance with the invention, mention may be made in particular of lower monoalcohols containing from 1 to 5 carbon atoms such as ethanol and isopropanol, and glycols containing from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1 ,3- butylene glycol and dipropylene glycol.
The aqueous phase (water and optionally the water-miscible solvent) is generally present in the composition according to the present patent application in a content ranging from 30% to 80% by weight and preferably ranging from 40% to 70% by weight relative to the total weight of the composition. This aqueous phase content includes not only the water originating from the aqueous dispersions of film-forming polymers, and, where appropriate, aqueous dispersions of hard waxes, in accordance with the invention, but also, where appropriate, the water deliberately added to the composition.
Solids content
The composition according to the invention advantageously comprises a solids content of greater than or equal to 40%, in particular 42%, more particularly 45%, or even 48%, and preferentially 50%.
For the purposes of the present invention, the "solids content" denotes the content of non-volatile matter.
The solids content (abbreviated as SC) of a composition according to the invention is measured using a "Halogen Moisture Analyzer HR 73" commercial halogen desiccator from Mettler Toledo. The measurement is performed on the basis of the weight loss of a sample dried by halogen heating, and thus represents the percentage of residual matter once the water and the volatile matter have evaporated off.
This technique is fully described in the machine documentation supplied by
Mettler Toledo.
The measuring protocol is as follows:
Approximately 2 g of the composition, referred to hereinbelow as the sample, are spread out on a metal crucible, which is placed in the halogen desiccator mentioned above. The sample is then subjected to a temperature of 105°C until a constant weight is obtained. The wet mass of the sample, corresponding to its initial mass, and the dry mass of the sample, corresponding to its mass after halogen heating, are measured using a precision balance.
The experimental error associated with the measurement is of the order of plus or minus 2%.
The solids content is calculated in the following manner:
Solids content (expressed as weight percentage) = 100 χ (dry mass/wet mass). A composition according to the invention comprises wax particles, film- forming polymer particles and at least one particular surfactant system.
Surfactant system
A composition of an assembly according to the invention comprises a surfactant system for structuring the aqueous phase so as to form a lamellar phase ίβ, comprising:
* at least one nonionic surfactant with an HLB value at 25°C of less than
8, and
* at least one nonionic surfactant with an HLB value at 25°C of greater than or equal to 8,
at least one from among the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and at least one from among the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 corresponding to formula (I) below:
(ALK-[C(0)]a-[0]b)c-X (I)
in which formula (I):
- ALK is a C7-C23, preferably Cn-C2i and more preferentially C15-C17 alkyl group,
- a and b are integers between 0 and 100, c is an integer between 1 and 100, in particular between 1 and 3, preferably equal to 1 , a and b preferably being equal to 0,
X is a (poly)oxyalkylene group optionally substituted and/or terminated with a hydroxyl group, X preferably being an oxyethylene group (CH2CH20)n or (OCH2CH2)n in which n is greater than or equal to 1 , for example between 1 and 200, said (poly)oxyalkylene group preferably being a polyethylene glycol or being the result of at least one substitution of a hydroxyl group, preferably chosen from (poly)glycerols.
The group X is preferably chosen from:
i) HO-(ALK-0)z-CH2-CH[(OALK)y-OH]-CH2-(0-ALK)x-(*)
in which:
- ALK, which may be identical or different, representing a C1 -C6 and in particular C1 -C4 alkylene group, preferably ethylene,
- x, y and z being an integer between 0 and 200, it being understood that x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
ii) H-(ALK-0)x-(*) and H-(0-ALK)x-(*), preferably is H-(0-ALK)x-(*)
in which:
- ALK, which may be identical or different, representing a C1 -C6 and in particular C1 -C4 ethylene group, preferably ethylene,
- x is an integer other than 0 and preferably between 1 and 200.
The nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula (Γ) below:
ALK-(0-CH2-CH2)n-OH (Ι') in which formula (Γ):
- ALK is a C8-C24, preferably C12-C22 and more preferentially Ci6-Ci8 alkyl group,
n being an integer other than 0, between 1 and 200, preferably between 1 and 10 and better still between 2 and 6 for the nonionic surfactant(s) with an HLB value at 25°C of less than 8, preferably between 20 and 200 for the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8.
This surfactant system is capable of dispersing the hard wax particles and optionally the additional wax(es). It may also be capable of dispersing the film-forming polymer particles, but the film-forming polymer particles may have their own surfactant system, different from that which is suitable for dispersing the hard wax particles and optionally the additional wax(es).
The Griffin HLB (hydrophilic/lipophilic balance) value is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256. Reference may be made to the Kirk- Othmer Encyclopedia of Chemical Technology, volume 22, p. 333-432, 3rd edition, 1979, Wiley, for the definition of the emulsifying properties and functions of surfactants, in particular p. 347-377 of this reference. Nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8
The nonionic surfactant(s) with an HLB value, in the Griffin sense, at 25°C, of greater than or equal to 8 may be advantageously chosen from:
- (poly)oxyalkylenated glycerol ethers, in particular oxyethylenated and/or oxypropylenated glycerol ethers, which may comprise from 20 to 200 oxyethylene and/or oxypropylene units;
- (poly)oxyalkylenated alcohols, in particular oxyethylenated and/or oxypropylenated alcohols, which may comprise from 20 to 200 oxyethylene and/or oxypropylene units, preferably from 20 to 100 oxyethylene units, in particular ethoxylated C8-C24 and preferably Ci2-Ci8 fatty alcohols such as ethoxylated stearyl alcohol comprising 20 oxyethylene units (CTFA name: Steareth-20) such as Brij 78 sold by the company Uniqema, or ethoxylated cetearyl alcohol comprising 30 oxyethylene units (CTFA name: Steareth-30);
- (poly)oxyalkylenated fatty acid esters, in particular esters of a fatty acid, in particular of a C8-C24 and preferably Ci6-C22 fatty acid, and of polyethylene glycol (or
PEG) (which may comprise from 20 to 200 oxyethylene units), such as PEG-50 stearate and PEG-40 monostearate sold under the name Myrj 52P® by the company Uniqema;
- esters of a fatty acid, in particular a C8-C24 and preferably Ci6-C22 fatty acid, and of (poly)oxyalkylenated glycerol ethers, which are in particular oxyethylenated and/or oxypropylenated (which may comprise from 20 to 200 oxyethylene and/or oxypropylene units), for instance glyceryl monostearate polyoxyethylenated with 200 oxyethylene units, sold under the name Simulsol 220 TM® by the company SEPPIC; glyceryl stearate polyoxyethylenated with 30 oxyethylene units, for instance the product Tagat S® sold by the company Goldschmidt, glyceryl oleate polyoxyethylenated with 30 oxyethylene units, for instance the product Tagat O® sold by the company Goldschmidt, glyceryl cocoate polyoxyethylenated with 30 oxyethylene units, for instance the product Varionic LI 13® sold by the company Sherex, glyceryl isostearate polyoxyethylenated with 30 oxyethylene units, for instance the product Tagat L® sold by the company Goldschmidt, and glyceryl laurate polyoxyethylenated with 30 oxyethylene units, for instance the product Tagat I ® from the company Goldschmidt;
- esters of a fatty acid, in particular a C8-C24 and preferably Ci6-C22 fatty acid, and of (poly)oxyalkylenated sorbitol ethers, which are in particular oxyethylenated and/or oxypropylenated (which may comprise from 20 to 200 oxyethylene and/or oxypropylene units), for instance the polysorbate 60 sold under the name Tween 60® by the company Uniqema;
- and mixture(s) thereof; preferably, among the (poly)oxyalkylenated alcohols preferably comprising from 20 to 200 oxyethylene (or ethylene glycol) units.
Preferably, a composition comprises at least one nonionic surfactant with an
HLB value, in the Griffin sense, at 25°C, of greater than or equal to 8 and preferably greater than or equal to 10, chosen from at least one ether of a C8-C24 , preferably Ci2- C22 and more preferentially Ci6-Ci8, fatty alcohol and of polyethylene glycol, said ether comprising at least 20 ethylene glycol units and better still between 20 and 200 ethylene glycol units.
A composition according to the invention has a content of nonionic surfactant(s) with an H LB value, in the Griffin sense, at 25°C of greater than or equal to 8, preferably greater than or equal to 10, of greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition.
Nonionic surfactant(s) with an HLB value at 25°C of less than 8
The nonionic surfactant(s) with an HLB value, in the Griffin sense, at 25°C, of less than 8 may be advantageously chosen from:
- (poly)oxyalkylenated saccharide esters and ethers;
- esters of fatty acids, especially of C8-C24 and preferably of Ci6- C22, and of (poly)oxyalkylenated polyol, especially of (poly)oxyalkylenated glycerol or of (poly)oxyalkylenated sorbitol, preferably of (poly)oxyalkylenated glycerol;
- (poly)oxyalkylenated alcohols;
- and mixture(s) thereof; preferably, from (poly)oxyalkylenated alcohols preferably comprising from 1 to 10 oxyethylene units.
The term "(poly)oxyalkylenated" means from 1 to 10 oxyethylene groups (or units) and better still from 2 to 6 oxyethylene groups. The at least one from among the nonionic surfactant(s) with an HLB value at
25°C of less than 8 preferably comprises a (poly)oxyalkylenated alcohol comprising an ether of a C8-C24 fatty alcohol and of polyethylene glycol, said ether comprising from 1 to 10 and better still between 2 and 6 ethylene glycol units. A composition according to the invention has a content of nonionic surfactant(s) with an HLB value, in the Griffin sense, at 25°C, of less than 8, preferably greater than or equal to 5% by weight relative to the total weight of the composition, preferably between 8% and 20% by weight relative to the total weight of the composition.
Preferably, a composition in accordance with the invention is free of anionic surfactant(s).
Preferably, a composition in accordance with the invention is free of amphoteric surfactant(s).
Moreover, the surfactant system may comprise one or more co-surfactants chosen from fatty alcohols comprising from 10 to 26 carbon atoms, better still from 12 to 24 carbon atoms and even better still from 14 to 22 carbon atoms.
Lamellar phase LB
The surfactant system in accordance with the invention is organized in the form of a lamellar phase 1_β, or paracrystalline phase ίβ, or lamellar gel phase.
This composition is stable at a room temperature of 25°C, having a viscosity preferentially ranging from 5 to 50 Pa.s, measured at a room temperature of 25°C using a Rheomat RM 100® rheometer.
The term "lamellar gel phase or paracrystalline phase ίβ" means a phase in which the surfactant molecules and/or more generally the molecules of amphiphilic compounds are organized in the form of bimolecular layers spaced apart by aqueous leaflets. Within the bimolecular layers, the molecules are distributed in a hexagonal geometry, their hydrocarbon-based chains are in a crystalline state and are oriented perpendicular to the plane of the bimolecular layers but have no specific orientation relative to each other in the plane of these layers.
The paracrystalline phases ί,β are metastable phases in which the fatty chains are in solid form and are arranged randomly relative to each other, unlike the miceliar, hexagonal, cubic and lamellar fluid paracrystalline phases (La) in which the fatty chains are in liquid form, and unlike the crystalline phases in which the fatty chains are in solid form and oriented in an ordered manner relative to each other. The paracrystalline phases 1_β are metastable and, in general, they have a tendency to evolve towards crystallization. Now, the Applicant has found a particular surfactant system that makes it possible to obtain a stable paracrystalline phase Ι_β, and thus cosmetic compositions for coating keratin fibres, in particular the eyelashes, which are stable and comfortable to apply, with good wear property and volume, by using a particular system of surfactant type in particular contents. To identify the lamellar gel phase or paracrystalline phase 1_β of the surfactant system present in the composition of the invention, use may be made of various techniques, and especially the technique of X-ray scattering.
Wide-angle X-ray scattering (WAXS) X-ray diagrams were recorded by a Mar345 image plate detector
(Maresearch, Norderstedt, Germany) mounted on a FR591 rotary anode X-ray generator (Brijker, Courtaboeuf, France), used at 50 kV and at 50 mA. The monochromatic CuKa radiation (λ = 1 .541 A) was focused with a 350 μηη focal spot at 320 mm by double reflection on an elliptic cross section multilayer Montel mirror (Incoatec, Geesthacht, Germany). The beam was defined under vacuum by four motorized carbon-tungsten slits (JJ-Xray, Roskilde, Denmark) positioned in front of the mirror (500 μηη). Four additional guard slits were placed at the focal point with a 220 mm slit separation. The flux after the output mica windows was 3 x 108 photons/s. A 2-mm diameter circular metal wire beam stop was placed in air at 150 mm after the sample, and the detector was positioned at 360 mm. The X-ray diagrams were therefore recorded for a range of reciprocal spacing q = 47i*sin θ/λ of 0.03-1.8 A"1, in which Θ is the scattering angle. The repetitive distances d = 27i/q should be between 200 A and 3.5 A. The samples were placed in 1.2-1 .3 mm glass capillaries (Glas W. Muller, Germany) and introduced into a home-made capillary holder accommodating up to 20 capillaries at controlled temperature.
Particles
The compositions of an assembly according to the present invention comprise hard wax particles and preferably film-forming polymers, which are preferentially in aqueous dispersion form.
These particles may be characterized by a mean particle size. Such particles are generally isotropic, especially substantially spherically shaped or spherically shaped.
Particle size
A particle size can be measured by various techniques. Mention may in particular be made of the (dynamic and static) light scattering techniques, Coulter capture methods, measurements of sedimentation rates (related to the size via Stokes law) and microscopy.
These techniques make it possible to measure a particle diameter and some make it possible to measure a particle size distribution.
Preferably, the particle sizes and size distributions of the compositions according to the invention are measured by static light scattering using a commercial particle size analyser such as the MasterSizer 2000 from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is especially described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.
In the context of the present invention, the "mean particle size" is expressed as volume mean "effective" diameter D[4,3], defined in the following way:
Figure imgf000022_0001
i
where V, represents the volume of the particles of effective diameter d,. This parameter is in particular described in the technical documentation of the particle size analyser.
The measurements are carried out at 25°C, on a diluted dispersion of particles. The "effective" diameter is obtained by taking a refractive index of 1.33 for water and an average refractive index of 1.45 for the particles.
Thus, preferentially, the particles of the compositions in accordance with the invention, comprising at least one hard wax and preferably at least one film-forming polymer, which are preferentially present in the form of aqueous dispersions, have a mean size expressed as the volume-mean "effective" diameter D[4,3] of less than or equal to 5 μηη, in particular strictly less than δμηη, more preferentially 2 μηη and even more preferentially less than or equal to 1 μηη. Such particle sizes preferentially correspond to the size of the particles in the final composition.
This mean particle size is advantageous as regards the use of the composition in accordance with the present invention when compared with compositions comprising hard wax particles and film-forming polymers of larger sizes, which result in a mascara that is difficult or even impossible to formulate, granular, too thick, which cannot be applied (too compact and does not disintegrate), which is uncomfortable, which has poor dispersion of the pigments and fillers, and which has a matt colour.
It is understood that the surfactant system(s) will have a tendency to position itself (themselves) at the interface of the aqueous phase and of the hard wax particles, and optionally of the film-forming polymer particles, in order to stabilize them. The measured particle sizes are thus measured in the presence of the surfactants, since they are difficult to dissociate from the particles. The sizes measured and given take this feature into account. As regards the other particles of the composition, for example dyestuffs and fillers, these compounds will be dealt with independently in another paragraph of the description, the size characteristics of particles of this type differing from the particle sizes of the waxes and film-forming polymers in accordance with the invention. Wax(es)
The wax(es) are generally a lipophilic compound that is solid at room temperature (25°C), with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30°C, which may be up to 200°C and in particular up to 120°C.
For the purposes of the invention, the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in standard ISO 1 1357-3; 1999. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments. Preferably, the waxes have a heat of fusion AHf of greater than or equal to
70 J/g.
Preferably, the waxes comprise at least one crystallizable part, which is visible by X-ray observation.
The measurement protocol is as follows:
A 5 mg sample of wax placed in a crucible is subjected to a first temperature increase from -20°C to 120°C, at a heating rate of
10°C/minute, and then is cooled from 120°C to -20°C at a cooling rate of 10°C/rminute and finally subjected to a second temperature increase from - 20°C to 120°C at a heating rate of 5°C/minute. During the second temperature increase, the following parameters are measured:
- the melting point (Mp) of the wax, as mentioned previously corresponding to the temperature of the most endothermic peak of the melting curve observed, representing the variation of the difference in power absorbed as a function of the temperature, - AHf: the heat of fusion of the wax, corresponding to the integral of the entire melting curve obtained. This heat of fusion of the wax is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.
The wax(es) may be hydrocarbon-based waxes, fluoro waxes and/or silicone waxes and may be of plant, mineral, animal and/or synthetic origin.
The wax(es) may be present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition and better still 15% by weight relative to the total weight of the composition. Preferably, they are present in a content ranging from 10% to 30% by weight and better still from 15% to 30% by weight relative to the total weight of the composition. A composition according to the invention comprises at least one hard wax, preferably present in the preparation of the composition in the form of an aqueous dispersion of wax particles.
Hard wax
According to the invention, the composition more specifically comprises at least one hard wax.
For the purposes of the present invention, the term "hard wax" means a wax with a melting point ranging from 65 to 120°C and more preferentially between 70 and 100°C.
Advantageously, for the purposes of the present invention, the term "hard" wax means a wax having, at 20°C, a hardness of greater than 5 MPa, especially ranging from 5 to 30 MPa, preferably greater than 6 MPa and better still ranging from 6 to 25 MPa.
To take these hardness measurements, the wax is melted at a temperature equal to the melting point of the wax +20°C. To do this, 30 g of wax are placed in a 100 ml beaker 50 mm in diameter, which is itself placed on a magnetic-stirring hotplate.
An amount of about 15 g of molten wax is poured into a stainless-steel container 80 mm in diameter and 15 mm deep preheated to 45°C in an oven. The wax is then left to recrystallize in a room thermostatically maintained at 20°C for 24 hours before taking the measurement.
The mechanical properties of the wax or of the mixture of waxes are determined in a room thermostatically maintained at 20°C, using a texturometer sold under the name TA-XT2i by the company Swantech, equipped with a stainless-steel cylinder 2 mm in diameter.
The measurement comprises three steps: a first step after automatic detection of the surface of the sample, where the spindle moves at a measuring speed of 0.1 mm/s, and penetrates into the wax to a penetration depth of 0.3 mm, the software notes the maximum force value reached; a second "relaxation" step where the spindle remains at this position for one second and the force is noted after 1 second of relaxation; finally, a third "withdrawal" step in which the spindle returns to its initial position at a speed of 1 mm/s, and the probe withdrawal energy (negative force) is noted.
The hardness value corresponds to the maximum measured compression force in newtons divided by the area of the texturometer cylinder, expressed in mm2, in contact with the wax. The hardness value obtained is expressed in megapascals or MPa.
As examples of hard wax, mention may be made especially of carnauba wax, candelilla wax, the wax Bis-PEG-12 Dimethicone Candelillate, for instance Siliconyl Candelilla wax sold by the company Koster Keunen, hydrogenated jojoba wax, for instance the product sold by the company Desert Whale, hydrogenated palm oil such as the product sold by the company SIO, rice bran wax, sumach wax, ceresin waxes, laurel wax, Chinese insect wax, shellac wax, hydrogenated olive oil such as Waxolive from the company Soliance, the waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols, such as the products sold by the company Sophim under the trade names Phytowax Olive 12L44, 14L48, 16L55 and 18L57, the waxes obtained by hydrogenation of castor oil esterified with cetyl or behenyl alcohol, for instance the products sold under the names Phytowax Ricin 16L64 and Phytowax Ricin 22L73 by the company Sophim, hydrogenated camellina wax, ouricury wax, montan wax, ozokerite waxes, for instance Wax SP 1020 P sold by the company Strahl & Pitsch, microcrystalline waxes, for instance the product sold under the trade name Microwax HW by the company Paramelt, lauric, palmitic, cetylic and stearic acid triglycerides (INCI name: hydrogenated cocoyl glycerides), for instance the product sold under the trade name Softisan 100 by the company Sasol, polymethylene waxes, for instance the product sold under the trade name Cirebelle 303 by the company Sasol, polyethylene waxes, for instance the products sold under the trade names Performalene 400 polyethylene, Performalene 655 polyethylene and Performalene 500-L polyethylene by the company New Phase Technologies, alcohol-polyethylene waxes, for instance the product sold under the name Performacol 425 Alcohol by the company Bareco, the 95/5 ethylene/acrylic acid copolymer sold under the trade name Wax AC 540 by the company Honeywell, hydroxyoctacosanyl hydroxystearate, for instance the product sold under the trade name Elfacos C 26 by the company Akzo, octacosanyl stearate, for instance the product sold under the name Kester Wax K 82 H by the company Koster Keunen, stearyl stearate, for instance the product sold under the name Liponate SS by the company Lipo Chemicals, pentaerythrityl distearate, for instance the product sold under the name Cutina PES by the company Cognis, the mixture of dibehenyl adipate, dioctadecyl adipate and dieicosanyl adipate (INCI name: C18-22 dialkyl adipate), the mixture of dilauryl adipate and ditetradecyl adipate (INCI name: C12-14 dialkyl adipate), the mixture of dioctadecyl sebacate, didocosyl sebacate and dieicosyl sebacate (INCI name: C18-22 dialkyl sebacate), the mixture of dioctadecyl octadecanedioate, didocosyl octanedioate and dieicosyl octanedioate (INCI name: C18-22 dialkyl octanedioate), for instance the products sold by the company Cognis, pentaerythrityl tetrastearate, for instance Liponate PS-4 from the company Lipo Chemicals, tetracontanyl stearate, for instance Kester Wax K76 H from the company Koster Keunen, stearyl benzoate, for instance Finsolv 1 16 from the company Finetex, behenyl fumarate, for instance Marrix 222 from the company Akzo Bernel, bis(1 ,1 ,1 -trimethylolpropane) tetrastearate, for instance the product sold under the name Hest 2T-4S by the company Heterene, didotriacontanyl distearate, for instance Kester Wax K82D from the company Koster Keunen, polyethylene glycol montanate containing 4 oxyethylene units (PEG-4), for instance the product sold under the trade name Clariant Licowax KST1 , hexanediol disalicylate, for instance Betawax RX-13750 sold by the company CP Hall, d i pentaeryth rity I hexastearate, for instance the product sold under the trade name Hest 2P-6S by the company Heterene, ditrimethylolpropane tetrabehenate, for instance the product sold under the trade name Hest 2T-4B by the company Heterene, jojoba esters, for instance the product sold under the trade name Floraester HIP by the company Floratech, mixtures of linear carboxylic acid (C20- 40)/saturated hydrocarbons (INCI name: C20-40 acid polyethylene), for instance Performacid 350 acid from the company New Phase Technologies, synthetic wax of Fisher-Tropsch type, such as the product sold under the reference Rosswax 100 by the company Ross, stearyl alcohol, behenyl alcohol, dioctadecyl carbonate and, for instance Cutina KE3737, sucrose polybehenate, for instance Crodaderm B from the company Croda, and mixtures thereof.
Use may also be made of the waxes mentioned above in the form of commercially available mixtures, for example under the names Koster KPC-56 (mixture of 87.5% by weight of cetyl stearate, 7.5% by weight of behenyl alcohol and 5% by weight of palm kernel glycerides), KPC-60 (mixture of 87.5% by weight of stearyl stearate, 7.5% by weight of behenyl alcohol and 5% by weight of palm kernel glycerides), KPC-63 (mixture of 87.5% by weight of behenyl stearate, 7.5% by weight of behenyl alcohol and 5% by weight of palm kernel glycerides) and KPC-80 (mixture of 86% by weight of synthetic beeswax, 7.5% of hydrogenated plant oil and 6.5% by weight of behenyl alcohol) from the company Koster Keunen.
Use is preferably made of waxes of plant origin such as carnauba wax, candelilla wax, hydrogenated jojoba wax, sumach wax, the waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols sold by the company Sophim under the name Phytowax (12L44, 14L48, 16L55 and 18L57), rice bran wax, stearyl and behenyl alcohols, lauryl wax or ouricury wax.
Preferably, the wax particles used in the preparation of a composition in accordance with the present invention are not introduced in the form of a microdispersion of pre-prepared hard waxes, as described in patent applications FR 2 687 569 or FR 2 815 849. Specifically, the hard wax(es) used in a composition in accordance with the present invention are introduced in powder or solid fatty substance form. However, the final composition may be defined as comprising an aqueous dispersion of hard wax(es). Specifically, according to the present manufacturing process, the hard wax dispersion is prepared in situ, making it possible, surprisingly and advantageously, to achieve high solids contents and high contents of hard wax(es), which would be unachievable if a pre- prepared microdispersion of hard waxes were to be introduced as such for manufacturing a cosmetic composition according to the invention. Specifically, in the present invention, the water derived from the aqueous dispersion of film-forming polymer(s) serves to prepare the dispersion of hard wax(es).
The hard wax(es) are preferably polar.
The term "polar" wax means a wax whose solubility parameter calculated above its melting point δ3 is other than 0 (J/cm3)½.
In particular, the term "polar" wax means a wax whose chemical structure is formed essentially from, or even constituted of, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.
The definition and calculation of the solubility parameters in the Hansen three- dimensional solubility space are described in the article by CM. Hansen: The three- dimensional solubility parameters, J. Paint Technol. 39, 105 (1967).
According to this Hansen space:
- δ0 characterizes the London dispersion forces derived from the formation of dipoles induced during molecular impacts;
- δρ characterizes the Debye interaction forces between permanent dipoles and also the Keesom interaction forces between induced dipoles and permanent dipoles;
- 8h characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.); and
- 8a is determined by the equation: 8a = (δρ 2 + 8h 2)½
The parameters δρ, 8h, 5D and 8a are expressed in (J/cm3)½. The composition according to the invention comprises a content of hard wax(es), preferentially present in aqueous dispersion form, of greater than or equal to 10% by weight relative to the total weight of the composition and better still 15% by weight relative to the total weight of the composition.
More generally, the composition according to the invention advantageously comprises a total content of hard wax(es), preferentially present in aqueous dispersion form, ranging from 10% to 30% by weight and better still from 15% to 30% by weight, relative to the total weight of the composition.
According to an advantageous embodiment, the composition according to the invention comprises a total content of hard wax particles preferentially present in aqueous dispersion form such that they represent at least 80% by weight, preferentially at least 90% by weight and even more preferentially 100% by weight relative to the total weight of wax(es).
Preferably, the total content of hard wax(es), preferentially present in aqueous dispersion form, is greater than or equal to 30% by weight and preferentially 40% by weight relative to the total weight of solid particles.
According to an advantageous embodiment, the total content of hard wax(es), preferentially present in aqueous dispersion form, represents at least 80% by weight, preferentially at least 90% by weight and even more preferentially 100% by weight relative to the total weight of fatty substances.
Additionally, a composition according to the invention may comprise at least one soft wax, present in the form of an aqueous dispersion of wax or non-wax particles, i.e. particles whose melting point is strictly less than 50°C, and optionally whose hardness is strictly less than 5 MPa.
However, a composition according to the invention preferably comprises less than 5% by weight of soft wax(es), preferably less than 2% by weight of soft wax(es), and even more preferentially is free of soft wax(es).
Film-forming polymer(s)
The composition of an assembly according to the invention preferably comprises at least an aqueous dispersion of film-forming polymer particles and optionally at least one additional film-forming polymer (not present in the form of an aqueous dispersion of particles, such as a water-soluble film-forming polymer).
In the present patent application, the term "film-forming polymer" is intended to mean a polymer that is capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous deposit, and preferably a cohesive deposit, and even better still a deposit of which the cohesion and mechanical properties are such that said deposit can be isolated and manipulated individually, for example when said deposit is prepared by pouring onto a non-stick surface such as a Teflon- coated or silicone-coated surface.
A composition according to the invention preferably comprises a total solids content of film-forming polymer(s) of greater than or equal to 5% by weight, preferably 10% by weight, relative to the total weight of the composition, and better still 12% by weight, relative to the total weight of the composition.
A composition according to the invention preferably comprises a total solids content of film-forming polymer(s) ranging from 10% to 30% by weight and better still from 12% to 25% relative to the total weight of the composition.
The composition according to the invention preferably comprises more specifically at least an aqueous dispersion of particles formed from one or more film- forming polymers.
It may also comprise at least one water-soluble film-forming polymer. Thus, a composition may comprise at least one additional film-forming polymer, different from the film-forming polymer particles present in aqueous dispersion form. The content of these "water-soluble" additional film-forming polymer(s) is preferably less than or equal to 10% by weight relative to the total weight of the composition, even more preferentially 5% by weight and better still 2% by weight relative to the total weight of the composition.
Film-forming polymer(s) in aqueous dispersion
Such a film-forming polymer present in said preparation of the composition in the form of particles in aqueous dispersion is generally known as a (pseudo)latex, i.e. a latex or psuedolatex. Techniques for preparing these dispersions are well known to those skilled in the art.
A dispersion that is suitable for use in the invention may comprise one or more types of particle, these particles possibly varying as regards their size, their structure and/or their chemical nature.
A composition according to the invention comprises a total solids content of film-forming polymer particles in aqueous dispersion form of greater than or equal to 10% by weight.
Advantageously, a composition according to the invention comprises a total solids content of film-forming polymer particles in aqueous dispersion form of greater than or equal to 12% by weight relative to the total weight of the composition and preferably 15% by weight relative to the total weight of the composition.
A composition according to the invention preferably comprises a total solids content of film-forming polymer particles ranging from 10% to 30% by weight and better still from 12% to 25% by weight relative to the total weight of the composition. The total content of film-forming polymer particles present in aqueous dispersion form is preferably greater than or equal to 30% by weight and preferentially 40% by weight relative to the total weight of the particles.
These particles may be of anionic, cationic or neutral nature and may constitute a mixture of particles of different nature.
Among the film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, and polymers of natural origin, and mixtures thereof. In general, these polymers may be statistical polymers, block copolymers of A-B type, of A- B-A or ABCD, etc. multiblock type, or even grafted polymers.
Free-radical film-forming polymer
The term "free-radical polymer" means a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopolymerizing (unlike polycondensates).
The film-forming polymers of free-radical type may especially be acrylic and/or vinyl homopolymers or copolymers. The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers.
Ethylenically unsaturated monomers bearing at least one acid group or monomer bearing an acid group that may be used include α,β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid and crotonic acid are in particular used, and more particularly (meth)acrylic acid.
The esters of acidic monomers are advantageously chosen from (meth)acrylic acid esters (also known as (meth)acrylates), especially (meth)acrylates of an alkyl, in particular of a Ci-C2o and more particularly Ci-C8 alkyl, (meth)acrylates of an aryl, in particular of a C6-Ci0 aryl, and (meth)acrylates of a hydroxyalkyl, in particular of a C2-
C6 hydroxyalkyl.
Among the alkyl (meth)acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate.
Among the hydroxyalkyl (meth)acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2- hydroxypropyl methacrylate.
Among the aryl (meth)acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.
The (meth)acrylic acid esters are in particular alkyl (meth)acrylates.
According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
Mention may be made, as amides of the acid monomers, for example, of (meth)acrylamides and especially N-alkyl(meth)acrylamides, in particular N-(C2-Ci2 alkyl)(meth)acrylamides. Among the N-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide and N-t-octylacrylamide.
The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned previously.
Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
Styrene monomers that may be mentioned include styrene and o methylstyrene.
The list of monomers given is not limiting, and it is possible to use any monomer known to those skilled in the art included in the categories of acrylic and vinyl monomers (including monomers modified with a silicone chain).
Vinyl polymers that may also be used include silicone acrylic polymers.
Mention may also be made of polymers resulting from free-radical polymerization of one or more free-radical monomers inside and/or partially at the surface of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and/or alkyds. These polymers are generally referred to as "hybrid polymers".
Polycondensate As film-forming polymer of polycondensate type, mention may be made of anionic, cationic, nonionic or amphoteric polyurethanes, acrylic polyurethanes, polyvinylpyrrolidone-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea/polyurethanes and silicone polyurethanes, and mixtures thereof.
The film-forming polyurethane may be, for example, an aliphatic, cycloaliphatic or aromatic polyurethane, polyurea/urethane or polyurea copolymer comprising, alone or as a mixture, at least one block chosen from:
- one block of aliphatic and/or cycloaliphatic and/or aromatic polyester origin, and/or
- one branched or non-branched silicone block, for example polydimethylsiloxane or polymethylphenylsiloxane, and/or
- a block comprising fluoro groups.
The film-forming polyurethanes as defined in the invention may also be obtained from branched or unbranched polyesters or from alkyds comprising mobile hydrogens, which are modified by reaction with a diisocyanate and a difunctional organic compound (for example dihydroxy, diamino or hydroxyamino), also comprising either a carboxylic acid or carboxylate group, or a sulfonic acid or sulfonate group, or alternatively a neutralizable tertiary amine group or a quaternary ammonium group.
Among the film-forming polycondensates, mention may also be made of polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxyester resins.
The polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.
The dicarboxylic acid may be aliphatic, alicyclic or aromatic. Examples of such acids that may be mentioned include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1 ,3-cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or as a combination of at least two dicarboxylic acid monomers. Among these monomers, the ones chosen in particular are phthalic acid, isophthalic acid and terephthalic acid.
The diol may be chosen from aliphatic, alicyclic and aromatic diols. The diol used is chosen in particular from: ethylene glycol, diethylene glycol, triethylene glycol, 1 ,3-propanediol, cyclohexanedimethanol and 4-butanediol. Other polyols that may be used are glycerol, pentaerythritol, sorbitol and trimethylolpropane.
The polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycondensation of diacids with diamines or amino alcohols. Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para- phenylenediamine. An amino alcohol that may be used is monoethanolamine.
Polymer of natural origin
Use may be made in the present invention of optionally modified polymers of natural origin, such as shellac resin, sandarac gum, dammar resins, elemi gums, copal resins, water-insoluble cellulose-based polymers such as nitrocellulose, modified cellulose esters especially including carboxyalkyl cellulose esters such as those described in patent application US 2003/185 774, and mixtures thereof. According to a particular embodiment of the invention, said at least one film- forming polymer in dispersed form is chosen from acrylic polymer dispersions, polyurethane dispersions, sulfopolyester dispersions, vinyl dispersions, polyvinyl acetate dispersions, vinylpyrrolidone, dimethylaminopropylmethacrylamide lauryldimethylpropylmethacrylamidoammonium chloride terpolymer dispersions, polyurethane/polyacrylic hybrid polymer dispersions and dispersions of particles of core- shell type, and mixtures thereof.
Various types of aqueous dispersion, especially commercial dispersions, which are suited to the preparation of the composition in accordance with the present invention are detailed below.
1/ Thus, according to a preferred embodiment of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of acrylic polymer.
The acrylic polymer can be a styrene/acrylate copolymer and especially a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one Ci-Ci8 alkyl (meth)acrylate monomer.
As styrene monomers that may be used in the invention, examples that may be mentioned include styrene and omethylstyrene, and in particular styrene.
The C-i-C-18 alkyl (meth)acrylate monomer is in particular a C1-C12 alkyl (meth)acrylate and more particularly a C1-C10 alkyl (meth) acrylate. The C Ci8 alkyl (meth)acrylate monomer may be chosen from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate.
As acrylic polymer in aqueous dispersion, use may be made according to the invention of the styrene/acrylate copolymer sold under the name Joncryl SCX-821 1® by the company BASF or Syntran 5760cg by the company Interpolymer, the acrylic polymer sold under the reference Acronal® DS-6250 by the company BASF, or the acrylic copolymer Joncryl® 95 by the company BASF.
21 According to one embodiment variant of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of polyester-polyurethane and/or polyether-polyurethane particles, in particular in anionic form.
The anionic nature of the polyester-polyurethanes and of the polyether- polyurethanes used according to the invention is due to the presence in their constituent units of groups bearing a carboxylic acid or sulfonic acid function.
The polyester-polyurethane or polyether-polyurethane particles used according to the invention are generally sold in aqueous dispersion form.
The particle content of said dispersions currently available on the market ranges from approximately 20% to approximately 60% by weight relative to the total weight of the dispersion.
Among the anionic polyester-polyurethane dispersions that may be used in the compositions according to the invention, mention may be made in particular of the product sold under the name Avalure UR 405® by the company Noveon or Baycusan C1004 by the company Bayer Material Science.
Among the anionic polyether-polyurethane particle dispersions that may be used according to the invention, mention may be made in particular of the products sold under the name Avalure UR 450® by the company Noveon and under the name Neorez R 970® by the company DSM.
According to a particular embodiment of the invention, use may be made of a mixture of commercial dispersions consisting of anionic polyester-polyurethane particles as defined above and of anionic polyether-polyurethane particles also defined above.
For example, use may be made of a mixture consisting of the dispersion sold under the name Sancure 861® or a mixture of the product sold under the name Avalure UR 405® and of the product sold under the name Avalure UR 450®, these dispersions being sold by the company Noveon. 3/ According to another particular embodiment of the invention, the aqueous dispersion used comprises a mixture of at least two film-forming polymers in the form of particles that differ by their respective glass transition temperatures (Tg).
In particular, according to one embodiment of the invention, the composition in accordance with the invention may comprise at least a first film-forming polymer in dispersed form and at least a second film-forming polymer in dispersed form, said first and second polymers having different Tg values and, preferably, the Tg of the first polymer (Tg1 ) is higher than the Tg of the second polymer (Tg2). In particular, the difference between the Tg1 and Tg2 values is, as an absolute value, at least 10°C and preferably at least 20°C.
More precisely, it comprises in an acceptable aqueous medium: a) particles dispersed in the aqueous medium of a first film-forming polymer having at least one glass transition temperature Tg1 greater than or equal to 20°C, and b) particles dispersed in the aqueous medium of a second film-forming polymer having at least one glass transition temperature Tg2 less than or equal to 70°C.
This dispersion generally results from a mixing of two aqueous dispersions of film-forming polymer.
The first film-forming polymer has at least one, and especially has one, glass transition temperature Tg1 of greater than or equal to 20°C, especially ranging from 20°C to 150°C and advantageously greater than or equal to 40°C, especially ranging from 40°C to 150°C and in particular greater than or equal to 50°C, especially ranging from 50°C to 150°C.
The second film-forming polymer has at least one, and especially has one, glass transition temperature Tg2 less than or equal to 70°C, especially ranging from
-120°C to 70°C, in particular less than 50°C, especially ranging from -60°C to +50°C and more particularly ranging from -30°C to 30°C.
The measurement of the glass transition temperature (Tg) of a polymer is performed by DMTA (dynamic and mechanical temperature analysis) as described below.
To measure the glass transition temperature (Tg) of a polymer, viscoelasticity tests are performed with a "Polymer Laboratories" DMTA machine, on a sample of film. This film is prepared by pouring the aqueous dispersion of film-forming polymer in a Teflon-coated matrix followed by drying at 120°C for 24 hours. A film is then obtained, from which specimens are cut out (for example using a punch). These specimens are typically about 150 μηι thick, from 5 to 10 mm wide and have a useful length of about 10 to 15 mm. A tensile stress is imposed on this sample. The sample undergoes a static force of 0.01 N on which is superimposed a sinusoidal displacement of ± 8 m at a frequency of 1 Hz. The test is thus performed in the linear range, at low levels of deformation. This tensile stress is performed on the sample at temperatures ranging from -150°C to +200°C, with a temperature variation of 3°C per minute.
The complex modulus E* = E' + iE" of the polymer tested is thus measured as a function of the temperature.
From these measurements, the dynamic moduli E' and E" and the damping power: tg8 = E7E' are deduced.
The curve of the Tg8 values is then plotted as a function of the temperature; this curve presents at least one peak. The glass transition temperature Tg of the polymer corresponds to the temperature at the top of this peak.
When the curve presents at least two peaks (in this case, the polymer has at least two Tg values), the value taken as the Tg of the polymer tested is the temperature for which the curve presents a peak of the largest amplitude (i.e. corresponding to the largest Tg value; in this case, only the "major" Tg is considered as the Tg value of the polymer tested).
In the present invention, the transition temperature Tg1 corresponds to the "major" Tg (in the predefined sense) of the first film-forming polymer when the latter has at least two Tg values; the glass transition temperature Tg2 corresponds to the "major"
Tg of the second film-forming polymer when the latter has at least two Tg values.
The first film-forming polymer and the second film-forming polymer may be chosen, independently of each other, from free-radical polymers, polycondensates and polymers of natural origin as defined previously having the glass transition temperature characteristics defined previously.
As first film-forming polymer in aqueous dispersion, use may be made of the aqueous polymer dispersions sold under the names Neorez R-989® by the company
DSM, Joncryl 95 and Joncryl®821 1 by the company BASF.
As second film-forming polymer in aqueous dispersion, use may be made, for example, of the aqueous polymer dispersions sold under the names Avalure® UR-405,
Avalure® UR-460 by the company Noveon or Acrilem IC89RT® by the company ICAP, and Neocryl A-45 by the company DSM. The film-forming polymer of the aqueous dispersion Avalure® UR-460 is a polyurethane obtained by polycondensation of polytetramethylene oxide, tetramethylxylylene diisocyanate, isophorone diisocyanate and dimethylolpropionic acid. According to a most particularly preferred embodiment of the invention, use is made, as first and second film-forming polymers in aqueous dispersion, of the combination of styrene/acrylate polymer dispersion such as the dispersion sold under the reference Joncryl 821 1® by BASF and of acrylic polymer dispersion such as the dispersion sold under the reference Neocryl A-45® by DSM.
According to another preferred embodiment of this particular embodiment of point 3/ above of the invention, use is made, as first film-forming polymer in aqueous dispersion, of an acrylic polymer dispersion such as the dispersion sold under the reference Joncryl 95® by BASF and, as second film-forming polymer, of a dispersion of anionic polyurethane polymer sold under the reference Avalure UR405® by DSM.
As aqueous dispersions of film-forming polymer, use may be made of:
the acrylic dispersions sold under the names Acronal DS-6250® by the company BASF, Neocryl A-45®, Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the company DSM, Joncryl 95®, Joncryl 821 1® by the company BASF, Daitosol 5000 AD® or Daitosol 5000 SJ by the company Daito Kasey Kogyo; Syntran 5760 CG by the company Interpolymer,
the aqueous polyurethane dispersions sold under the names Neorez R- 981 ® and Neorez R-974® by the company DSM, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Avalure UR 445® and Avalure UR 450® by the company Noveon, Impranil 85® by the company Bayer, and Baycusan C1004® by the company Bayer Material Science,
the sulfopolyesters sold under the brand name Eastman AQ® by the company EASTMAN CHEMICAL PRODUCTS,
- vinyl dispersions such as Mexomer PAM, aqueous dispersions of polyvinyl acetate such as Vinybran® from the company Nisshin Chemical or the products sold by the company Union Carbide, aqueous dispersions of vinylpyrrolidone, dimethylaminopropylmethacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride terpolymer such as Styleze W® from ISP,
aqueous dispersions of polyurethane/polyacrylic hybrid polymer such as the products sold under the references Hybridur® by the company Air Products or Duromer® from National Starch,
dispersions of particles of core-shell type such as the products sold by the company Arkema under the reference Kynar® (core: fluid - shell: acrylic) or alternatively those described in US 5 188 899 (core: silica - shell: silicone), and mixtures thereof.
According to a preferred embodiment, a composition in accordance with the invention comprises an aqueous dispersion of particles chosen from aqueous dispersions of acrylic film-forming polymer(s) and derivatives, in particular of styrene-acrylic and derivatives, and aqueous dispersions of polyurethane polymer(s), in particular of polyester-polyurethane, and derivatives thereof, and a mixture thereof.
According to an advantageous embodiment, the total content of hard wax(es) and the total content of film-forming polymer particles are such that the weight ratio of the hard wax(es) to the film-forming polymer particles is greater than or equal to 1/2 and better still 2/3. Preferably, this ratio is inclusively between 1/2 and 2 and even more preferentially between 2/3 and 3/2.
According to an advantageous embodiment, the total content of hard wax(es) and the total content of film-forming polymer particles, which are both preferentially present in the form of particles in aqueous dispersion, with the film-forming polymer(s) chosen from aqueous dispersions of acrylic film-forming polymer(s) and derivatives, in particular styrene-acrylic and derivatives, and the aqueous dispersions of polyester- polyurethane hybrid polymer(s), and a mixture thereof, are such that the weight ratio of the hard wax particles to said film-forming polymer particles is greater than or equal to 1/2 and better still 2/3.
Preferably, this ratio is inclusively between 1/2 and 2 and even more preferentially between 2/3 and 3/2.
Water-soluble film-forming polymer The compositions of an assembly according to the present invention comprise at least one water-soluble film-forming polymer.
Preferably, a composition according to the invention is free of water-soluble film-forming polymer. However, the total solids content of "water-soluble film-forming polymer(s)" may range from 0.1 % to 10%, preferably from 0.5% to 8% and better still from 1 % to 5% by weight relative to the total weight of the composition.
Examples of water-soluble film-forming polymers that may be mentioned include:
- proteins, for instance proteins of plant origin such as wheat proteins and soybean proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and sulfonic keratins;
- cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose and carboxymethyl cellulose, and also quaternized cellulose derivatives;
- acrylic polymers or copolymers, such as polyacrylates or polymethacrylates;
- vinyl polymers, for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and of caprolactam; polyvinyl alcohol;
anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;
- gum arabic, guar gum, xanthan derivatives, karaya gum, acacia gum;
- alginates and carrageenans;
- glycoaminoglycans, hyaluronic acid and its derivatives;
- deoxyribonucleic acid;
- mucopolysaccharides such as chondroitin sulfates;
and mixtures thereof.
Gelling agents
Hydrophilic gelling agents
The compositions of an assembly according to the present invention may also contain at least one hydrophilic, or water-soluble, gelling agent, and may be chosen from:
- acrylic or methacrylic acid homopolymers or copolymers or the salts thereof and esters thereof and in particular the products sold under the names Versicol F® or Versicol K® by the company Allied Colloid, Ultrahold 8® by the company Ciba Geigy, and polyacrylic acids of Synthalen K type,
- copolymers of acrylic acid and of acrylamide sold in the form of the sodium salt thereof under the names Reten® by the company Hercules, and the sodium salts of polyhydroxycarboxylic acids sold under the name Hydagen F® by the company Henkel,
- polyacrylic acid/alkyl acrylate copolymers of Pemulen type,
- AMPS (polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked) sold by the company Clariant,
- AMPS/acrylamide copolymers of Sepigel® or Simulgel® type sold by the company SEPPIC, and
- AMPS/polyoxyethylenated alkyl methacrylate copolymers (crosslinked or non-crosslinked), and mixtures thereof.
associative polymers and in particular associative polyurethanes such as the Ci6-OE12o-Ci6 polymer from the company Elementis (sold under the name Rheolate FX1 100, this molecule bearing a urethane function and having a weight-average molecular weight of 1300), OE being an oxyethylene unit, Rheolate 205 bearing a urea function, sold by the company Rheox, or Rheolate 208 or 204 (these polymers being sold in pure form) or DW 1206B from Rohm & Haas bearing a C20 alkyl chain and a urethane bond, sold at 20% solids in water. It is also possible to use solutions or dispersions of these associative polyurethanes, especially in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned include Rheolate FX1010, Rheolate FX1035, Rheolate1070, Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Elementis. It is also possible to use the products DW 1206F and DW 1206J, and also Acrysol RM 184 or Acrysol 44 from the company Rohm & Haas, or alternatively Borchigel LW 44 from the company Borchers,
- and mixtures thereof.
Some of the water-soluble film-forming polymers also act as water-soluble gelling agent.
The hydrophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 10% by weight, preferably from 0.1 % to 5% by weight and better still from 0.5% to 2% by weight, relative to the total weight of the composition.
A composition according to the invention advantageously comprises one of the abovementioned gelling agents, preferably chosen from AMPS (polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked), AMPS/acrylamide copolymers, and a mixture thereof. Lipophilic gelling agents
A composition of an assembly according to the invention may comprise at least one lipophilic or liposoluble gelling agent.
The gelling agent(s) that may be used may be organic or mineral, polymeric or molecular lipophilic gelling agents.
Mineral lipophilic gelling agents that may be mentioned include clays, modified clays, such as Bentone 38 VCG by the company Elementis, and optionally hydrophobically surface-treated fumed silica.
The polymeric organic lipophilic gelling agents are, for example, partially or completely crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6®, KSG16® and KSG18® by Shin-Etsu, Trefil E-505C® and Trefil E-506C® by Dow Corning, Gransil SR-CYC®, SR DMF10®, SR- DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® by Grant Industries and SF 1204® and JK 1 13® by General Electric; ethyl cellulose, for instance the product sold under the name Ethocel® by Dow Chemical; polycondensates of polyamide type resulting from the condensation between (a) at least one acid chosen from dicarboxylic acids containing at least 32 carbon atoms, such as fatty acid dimers, and (β) an alkylenediamine and in particular ethylenediamine, in which the polyamide polymer comprises at least one carboxylic acid end group esterified or amidated with at least one saturated and linear monoalcohol or monoamine containing from 12 to 30 carbon atoms, and in particular ethylenediamine/stearyl dilinoleate copolymers such as the product sold under the name Uniclear 100 VG® by the company Arizona Chemical; silicone polyamides of the polyorganosiloxane type such as those described in documents US-A- 5 874 069, US-A-5 919 441 , US-A-6 051 216 and US-A-5 981 680, for instance the products sold under the references Dow Corning 2-8179 and Dow Corning 2-8178 Gellant by the company Dow Corning. Block copolymers of "diblock", "triblock" or "radial" type, of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as the products sold under the name Luvitol HSB® by the company BASF, of the polystyrene/copoly(ethylene-propylene) type, such as the products sold under the name Kraton® by the company Shell Chemical Co., or of the polystyrene/copoly(ethylene- butylene) type, and mixtures of triblock and radial (star) copolymers in isododecane, such as those sold by the company Penreco under the name Versagel®, for instance the mixture of butylene/ethylene/styrene triblock copolymer and of ethylene/propylene/styrene star copolymer in isododecane (Versagel M 5960).
The compositions according to the invention may also comprise a non- emulsifying silicone elastomer as lipophilic gelling agent. Among the lipophilic gelling agents that may also be mentioned are organogelling agents.
A composition according to the invention is preferably free of lipophilic gelling agent.
Dyestuffs
The compositions of an assembly in accordance with the invention comprise at least one dyestuff.
This (or these) dyestuffs are preferably chosen from pulverulent dyes, liposoluble dyes and water-soluble dyes, and mixtures thereof.
Preferably, the compositions according to the invention comprise at least one pulverulent colorant. The pulverulent dyestuffs may be chosen from pigments and nacres, and preferably from pigments.
The pigments may be white or coloured, mineral and/or organic, and coated or uncoated. Among the mineral pigments, mention may be made of metal oxides, in particular titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxide, and also iron, titanium or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments that may be mentioned are carbon black, pigments of D&C type and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium.
The nacres may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica with iron oxides, titanium mica in particular with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.
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 1 1 , D&C Violet 2, D&C Orange 5, quinoline yellow and annatto. Preferably, the pigments contained in the compositions according to the invention are chosen from metal oxides.
These dyestuffs may be present in a content ranging from 0.01 % to 30% by weight relative to the total weight of the composition and in particular from 3% to 22% by weight relative to the total weight of the composition.
Preferably, the dyestuff(s) are chosen from one or more metal oxides that are present in a content of greater than or equal to 2% by weight relative to the total weight of the composition, and advantageously inclusively between 3% and 22% by weight relative to the total weight of the composition.
Fillers
The compositions of an assembly in accordance with the invention may also comprise at least one filler.
The fillers may be selected from those that are well known to those skilled in the art and commonly used in cosmetic compositions. The fillers may be mineral or organic, and lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders, for instance the Nylon® sold under the name Orgasol® by the company Atochem, poly-p-alanine powders and polyethylene powders, powders of tetrafluoroethylene polymers, for instance Teflon®, lauroyllysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance the products sold under the name Expancel® by the company Nobel Industrie, acrylic powders such as those sold under the name Polytrap® by the company Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (for example Tospearls® from Toshiba), precipitated calcium carbonate, magnesium carbonate and magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms and in particular from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate and magnesium myristate.
The fillers may represent from 0.1 % to 15% by weight and in particular from
0.5% to 10% by weight relative to the total weight of the composition.
Cosmetic active agents
The compositions of an assembly in accordance with the invention may also comprise at least one cosmetic active agent.
As cosmetic active agents that may be used in the compositions in accordance with the invention, mention may be made especially of antioxidants, preserving agents, fragrances, neutralizers, emollients, coalescers, moisturizers, vitamins and screening agents, in particular sunscreens, and mixtures thereof.
Needless to say, a person skilled in the art will take care to select the optional additional ingredients and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.
Preferably, the composition according to the invention is a leave-in composition. Advantageously, the composition is a makeup composition and in particular a mascara.
Oil or organic solvent
The compositions of an assembly according to the invention may comprise at least one oil or organic solvent.
The compositions according to the invention may in particular comprise at least one oil chosen from at least one non-volatile oil, at least one volatile oil, and a mixture thereof.
Non-volatile oil
The term "oil" means a fatty substance that is liquid at room temperature and at atmospheric pressure.
The term "non-volatile oil" means an oil that remains on the skin or the keratin fibre at room temperature and pressure. More precisely, a non-volatile oil has an evaporation rate strictly less than 0.01 mg/cm2/min.
To measure this evaporation rate, 15 g of oil or of oil mixture to be tested are placed in a crystallizing dish 7 cm in diameter, which is placed on a balance in a large chamber of about 0.3 m3 that is temperature-regulated, at a temperature of 25°C, and hygrometry-regulated, at a relative humidity of 50%. The liquid is allowed to evaporate freely, without stirring it, while providing ventilation by means of a fan (Papst-Motoren, reference 8550 N, rotating at 2700 rpm) placed in a vertical position above the crystallizing dish containing said oil or said mixture, the blades being directed towards the crystallizing dish, 20 cm away from the bottom of the crystallizing dish. The mass of oil remaining in the crystallizing dish is measured at regular intervals. The evaporation rates are expressed in mg of oil evaporated per unit of area (cm2) and per unit of time (minutes).
Said at least one non-volatile oil may be chosen from hydrocarbon-based oils and silicone oils, and mixtures thereof, preferably from hydrocarbon-based oils.
The non-volatile hydrocarbon-based oils that are suitable for the present invention may be chosen in particular from:
- hydrocarbon-based oils of plant origin, such as triglycerides formed from fatty acid esters of glycerol, the fatty acids of which may have varied chain lengths from C4 to C28, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, palm oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil and musk rose oil; or alternatively caprylic/capric acid triglycerides such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Sasol;
- synthetic ethers containing from 10 to 40 carbon atoms;
- linear or branched hydrocarbons of mineral or synthetic origin other than the polymers according to the invention, such as petroleum jelly, polybutenes, polydecenes and squalane, and mixtures thereof;
- synthetic esters such as oils of formula R1 COOR2 in which R1 represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R2 represents an in particular branched hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R1 + R2≥ 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, alkyl or polyalkyl octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate and diisostearyl malate; and pentaerythritol esters;
- fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol; and
- higher fatty acids such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof.
The non-volatile silicone oils that are suitable for the present invention may be chosen in particular from:
- the non-volatile silicone oils that may be used in the composition in accordance with the invention may be non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicat.es.
A composition according to the invention optionally comprises at least one hydrocarbon-based non-volatile oil of plant origin, such as triglycerides consisting of fatty acid esters of glycerol in which the fatty acids may have chain lengths ranging from C4 to C28, in particular palm oil and hydrogenated jojoba oil(s). A composition according to the invention is preferably free of silicone non-volatile oil(s). A composition according to the invention is preferably free of non-volatile oil. However, the total content of non-volatile oil(s) in a composition in accordance with the invention may range from 0.01 % to 10% by weight, in particular from 0.1 % to 8% by weight and preferably from 0.25% to 5% by weight relative to the total weight of the composition.
According to one preferred embodiment, a composition according to the invention comprises less than 5% by weight of non-volatile oil(s) relative to the total weight of the composition. Volatile oil
The composition of an assembly according to the invention may comprise at least one volatile oil.
The term "volatile oil" means an oil (or non-aqueous medium) that can evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a cosmetic volatile oil, which is liquid at room temperature. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg/cm2/min, limits included.
This volatile oil may be hydrocarbon-based.
The volatile hydrocarbon-based oil may be chosen from hydrocarbon-based oils containing from 7 to 16 carbon atoms.
The composition according to the invention may contain one or more volatile branched alkane(s). The expression "one or more volatile branched alkane(s)" means, without preference, "one or more volatile branched alkane oil(s)".
As volatile hydrocarbon-based oils containing from 7 to 16 carbon atoms, mention may be made especially of C8-Ci6 branched alkanes, for instance C8-Ci6 isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and for example the oils sold under the trade names Isopar or Permethyl, C8-Ci6 branched esters such as isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon-based oil containing from 8 to 16 carbon atoms is chosen from isododecane, isodecane and isohexadecane, and mixtures thereof, and is especially isododecane.
The composition according to the invention may contain one or more volatile linear alkane(s). The term "one or more volatile linear alkane(s)" means, without preference, "one or more volatile linear alkane oil(s)".
A volatile linear alkane that is suitable for the invention is liquid at room temperature (about 25°C) and at atmospheric pressure (760 mmHg).
A "volatile linear alkane" that is suitable for the invention means a cosmetic linear alkane, which is capable of evaporating on contact with the skin in less than one hour, at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e. 101 325 Pa), which is liquid at room temperature, especially having an evaporation rate ranging from 0.01 to 15 mg/cm2/min, at room temperature (25°C) and atmospheric pressure (760 mmHg).
The linear alkanes, preferably of plant origin, comprise from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms and more particularly from 1 1 to 13 carbon atoms.
As examples of linear alkanes that are suitable for use in the invention, mention may be made of the alkanes described in patent applications WO 2007/068 371 or WO 2008/155 059 by the company Cognis (mixtures of distinct alkanes that differ by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut oil or palm oil.
As examples of linear alkanes that are suitable for the invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C1 1 ), n- dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15), and mixtures thereof, and in particular the mixture of n-undecane (C1 1 ) and n-tridecane (C13) described in Example 1 of patent application WO 2008/155 059 by the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof.
The linear alkane may be used alone or as a mixture of at least two distinct alkanes that differ from each other by a carbon number of at least 1 , and especially a mixture of at least two linear alkanes comprising from 10 to 14 distinct carbon atoms that differ from each other by a carbon number of at least 2, and in particular a mixture of C1 1/C13 volatile linear alkanes or a mixture of C12/C14 linear alkanes, in particular an n- undecane/n-tridecane mixture (such a mixture may be obtained according to Example 1 or Example 2 of WO 2008/155 059).
As a variant or additionally, the composition prepared may comprise at least one volatile silicone oil or solvent that is compatible with cosmetic use.
The term "silicone oil" means an oil containing at least one silicon atom, and especially containing Si-0 groups. According to one embodiment, said composition comprises less than 10% by weight of volatile silicone oil(s), relative to the total weight of the composition, better still less than 5% by weight, or even is free of volatile silicone oil.
Volatile silicone oils that may be mentioned include cyclic polysiloxanes and linear polysiloxanes, and mixtures thereof. Volatile linear polysiloxanes that may be mentioned include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane. Volatile cyclic polysiloxanes that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
As a variant or additionally, the composition prepared may comprise at least one volatile fluoro oil. The term "fluoro oil" means an oil containing at least one fluorine atom.
Volatile fluoro oils that may be mentioned include nonafluoromethoxybutane and perfluoromethylcyclopentane, and mixtures thereof.
A composition according to the invention is preferably free of non-volatile oil. However, at least one volatile oil may be present in a total content ranging from 0.1 % to 10% by weight. In particular, the volatile oil may be present in the composition in a content ranging from 0.5% to 5% relative to the total weight of the composition.
According to one preferred embodiment, a composition according to the invention comprises less than 5% by weight of volatile oil(s) relative to the total weight of the composition.
PACKAGING DEVICE
A packaging assembly according to the present invention comprises a packaging device that is capable of receiving said cosmetic composition in accordance with the invention.
The packaging device comprises a transparent container for housing the composition for coating keratin fibres.
This composition may then be withdrawn from the container by immersing an applicator therein.
This applicator may be firmly attached to a member for closing the container. This closing member may form a member for gripping the applicator. This gripping member may form a cap to be removably mounted on said container by any suitable means, such as screwing, click-fastening, coupling, etc. Such a container may thus reversibly house said applicator.
This container may be optionally equipped with a wiper suitable for removing surplus product taken up by the applicator.
According to the invention, the container is transparent. In particular, this container advantageously comprises a body, which is closed at one end by a base and open at an opposite end. More particularly, the body of the container may comprise a neck forming a shoulder from which the aperture raises. This aperture may receive the wiper inside. Such an aperture may be reversibly closed by a cap. This cap preferably supports the applicator intended to coat the keratin fibres with a composition according to the invention.
According to an advantageous embodiment, at least the body of the container is transparent.
According to a particular embodiment, the body, the neck and the base of the container are transparent.
To produce such a packaging device, it is possible to make this container of a transparent thermoplastic material, for example by injection-moulding, or of glass, for example by injection blow-moulding.
For example, such a container may be made of a transparent thermoplastic material chosen from the group consisting of PET and PMMA.
According to a particular embodiment, such a device may comprise means for heating a composition in accordance with the invention.
HEATING MEANS
A packaging device in accordance with the invention may comprise heating means so that a composition in accordance with the invention can be subjected to these heating means before and/or during application.
These heating means may be integrally fastened to an assembly for coating keratin fibres and more particularly to an applicator configured to apply said cosmetic composition for coating keratin fibres, and optionally, where appropriate, to a conditioning device suitable for receiving said composition.
These heating means are then suitable for melting at least part of the fatty phase, and especially at least part of the surfactant system and, where appropriate, at least part of the soft wax(es), and optionally at least part of the hard wax particles. The wax particles are heated to a temperature Tc such that only part of the crystallizable chains are melted.
The heating means may also come into contact with or face the composition to be heated.
The composition may be heated while it is contained in a packaging device.
The composition may be heated while it is at least partially exposed to the ambient air.
The composition may be locally heated to a temperature greater than or equal to 45°C, or even greater than or equal to 50°C, or even greater than or equal to 55°C. The temperature of the composition should not entail any risk of burning at the time of application. This is why when the composition is heated before application, a waiting time between the moment at which the composition is heated and the application to the keratin materials may optionally be necessary.
According to one embodiment variant, the composition is heated simultaneously with its application to the keratin fibres.
According to another variant, the composition is heated before and during its application to the keratin fibres.
The temperature to which at least part of the composition is heated may be inclusively between 45°C and 95°C, better still 50°C to 85°C and better still 55°C to 75°C.
The temperature may be measured, for example, at the surface using an infrared pyrometer, for example a Fluke® brand machine.
The composition in accordance with the invention is capable of passing from a solid state to an at least partially liquid or even totally liquid state, and of doing so reversibly.
The solid/liquid change of state is at least partly due to the melting of a crystalline part, in particular of the wax(es) described previously in the present description.
The total heat of fusion of the composition is the heat consumed by the composition between -20°C and 120°C. The total heat of fusion of the composition is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5°C or 10°C per minute, according to standard ISO 1 1357-3:1999.
Measuring protocol:
A 5 mg sample of composition is placed in a crucible and subjected to a first temperature rise ranging from -20°C to 120°C, at a heating rate of 10°C/minute, and is then cooled from 120°C to -20°C at a cooling rate of 10°C/minute. The sample is maintained at -20°C for 5 minutes and finally subjected to a second temperature rise ranging from -20°C to 100°C at a heating rate of 5°C / minute.
During the second temperature rise, the variation in the difference in power absorbed by an empty crucible and by the crucible containing the sample of the composition is measured as a function of the temperature. The melting point of the compound is the value of the temperature corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
The heat of fusion of the composition consumed at the temperature Tc is the amount of energy required to make the compound pass from the solid or very viscous state at -20°C to the state of the composition at the temperature Tc. It is expressed in J/g.
According to one embodiment of the invention, the composition is chosen such that the ratio of the heat consumed between -20°C and Tc by the product to the total heat consumed between -20°C and 120°C is less than or equal to 0.7.
This relationship is confirmed, for example, for a temperature Tc of the composition of between 45°C and 80°C.
The choice of the temperature Tc to which the composition is brought by the heating means may thus be made so that said ratio is less than or equal to 0.7, for example inclusively between 0.3 and 0.6. In other words, heating is performed to a temperature such that the ratio of the heat supplied to heat the sample of composition to the temperature Tc to the total heat is less than or equal to 0.7, such a parameter being measured according to the DSC protocol described above.
Only the heated composition can come into contact with the keratin fibres, for example the eyelashes, during the application. Applicator
A device of an assembly according to the invention preferably comprises an applicator for smoothing and/or separating keratin fibres, such as the eyelashes or the eyebrows, especially in the form of teeth, bristles or other reliefs.
The applicator is arranged to apply the composition to the eyelashes or the eyebrows, and may comprise, for example, a brush or a comb.
The applicator may also be used for finishing of the makeup, over a region of the eyelashes or eyebrows that is made up or laden with composition.
The brush may comprise a twisted core and bristles held between the turns of the core, or may be made in yet another way.
The comb is, for example, produced from a single part by moulding of a plastic.
In certain embodiments, the application member is mounted at the end of a wand, which wand may be flexible, which may contribute to improving the comfort during application. Finally, it should be noted that the packaging and application assembly may be in the form of a kit, it being possible for the applicator and the packaging device to be housed separately in the same packaging article.
A process for applying the composition according to the invention to the eyelashes or the eyebrows may also include the following steps:
- forming a deposit of the cosmetic composition on the eyelashes or the eyebrows,
- leaving the deposit on the eyelashes or the eyebrows, it being possible for the deposit to dry.
The examples above and that follow are given as illustrations of the present invention, and shall not limit the scope thereof.
EXAMPLE
A mascara composition of an assembly in accordance with the invention is described below:
Composition
Ingredients according to with percentage contents the
invention
Phase A Carnauba Wax SP 63 from Strahl & Pitsch 12
Polymethylene wax (Cirebelle 108 from Cirebelle) 5
Oxyethylenated glyceryl monostearate (30 OE) (Tagat
4
S from Evonik Goldschmidt)
Phase B Steareth 2 (B rij 72 fro m U n i q e m a ) 8
Steareth 20 (B rij 78P from U n iq e ma) 8
Pigments 10
Water 33
Phase C Water qs 100
Phase D Preserving agents qs This composition was prepared as follows:
/'. Preparation of phase A:
All the starting materials used are carefully weighed out using a balance (accuracy 0.01 g). The various waxes are melted in a 500 mL jacketed heating pan with circulation of hot oil to control the temperature. The mixture is heated to about 95-98°C. Once the waxes have melted, they are homogenized by stirring using a Moritz blender, which is stirring of rotor-stator type: this machine consists of a fixed part in which a second mobile part rotates at variable speed, and is used for making emulsions since it can produce a very high shear.
Once the waxes are melted and homogenized, the oxyethylenated (30 OE) glyceryl monostearate is added and the mixture is emulsified for 10 minutes. ii. Preparation of phase B
The ingredients are weighed out, the Steareth 2 and Steareth 20 in accordance with the invention are melted at 80°C, and the water preheated in an electric kettle to 95°C and the pigments are then added. iii. Mixing of phase B with phase A
Phase A is added to phase B and the mixture is emulsified for 5 minutes at 95°C using a Moritz blender. iv. Preparation of phase C
The water is poured into a bath thermostatically maintained at 5°C. v. Mixing of phase A+B with phase C
Phase A+B (hot emulsion at 95°C) is poured into the thermostatic bath containing phase C. vi. Addition of phase D
Phase D is poured into the phase A+B+C mixture when the temperature of the mixture is less than or equal to 45°C. vii. End of formulation The mascara thus obtained is transferred into a closed jar to prevent it from drying out on contact with air; it is then necessary to wait 24 hours to check the homogeneity of the formulation and the correct dispersion of the pigments. Such a composition is packaged in a packaging device comprising a transparent container through which the mascara composition is directly visible.
21 Protocols and results
The composition prepared is observed with the naked eye and by microscope. The composition according to the invention is a fine emulsion with a fine grain of well-distributed (homogeneous) wax(es). It has a fluid texture (viscosity at 25°C of 14.4 Pa.s measured using a Rheomat RM100® machine). Moreover, the pigments are well dispersed and the composition has an intense black colour. In addition, these compositions are stable at 4 and 45°C for two months. Furthermore, the composition obtained has good gloss and a particularly satisfactory black intensity.
It should be noted that the protocols for measuring the gloss and the black intensity to be used in the context of the present invention are described in patent application FR 2 968 978, page 44, lines 1 -21 .
When tested on a sample of naked eyelashes, these compositions, applied using a brush, are pleasant on application. The deposit is constructed coat after coat, the composition coats the eyelashes well, the makeup result is uniform and the eyelash fringe is well developed.
In contrast with other water-based mascaras, the properties of a mascara in accordance with the invention are such that a transparent container containing it makes it possible to magnify the mascara and to give an idea of the black intensity qualities and optionally the gloss qualities of the packaged mascara, even after a long period of storage of the assembly.
It is understood that, in the context of the present invention, the weight percentages given for a compound or a family of compounds are always expressed as weight of solids of the compound in question. Throughout the application, the wording "comprising one" or "including one" "comprising at least one" or "including at least one", unless otherwise specified.

Claims

1 . Assembly for packaging a composition, preferably for coating keratin fibres such as the eyelashes, comprising:
- a composition, preferably for coating keratin fibres such as the eyelashes, comprising:
i) an aqueous phase,
ii) particles comprising at least one hard wax, preferentially in the form of at least an aqueous dispersion of hard wax particles, the hard wax(es) having a melting point ranging from 65 to 120°C, the hard wax(es) being present in a total content of greater than or equal to 10% by weight relative to the total weight of the composition,
iii) a lamellar phase ίβ formed by an aqueous phase-structuring surfactant system, said surfactant system comprising a content of surfactant(s), preferably nonionic surfactant(s), of greater than or equal to 15% by weight relative to the total weight of the composition,
a packaging device comprising a container for storing said composition, this container being at least partly transparent so that said composition contained in the container is directly visible through the container.
2. Assembly according to Claim 1 , in which the surfactant system forming the lamellar phase ίβ comprises:
* at least one nonionic surfactant with an HLB value at 25°C of less than
8, and
* at least one nonionic surfactant with an HLB value at 25°C of greater than or equal to 8,
at least one from among the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and at least one from among the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 corresponding to formula (I) below:
(ALK-[C(0)]a-[0]b)c-X (I)
in which formula (I):
- ALK is a C7-C23, preferably Cn-C2i and more preferentially C15-C17 alkyl group, a and b are integers between 0 and 100, c is an integer between 1 and 100, in particular between 1 and 3, preferably equal to 1 , a and b preferably being equal to 0,
X is a (poly)oxyalkylene group optionally substituted and/or terminated with a hydroxyl group, X preferably being an oxyethylene group (CH2CH20)n or (OCH2CH2)n in which n is greater than or equal to 1 , for example between 1 and 200, said (poly)oxyalkylene group preferably being a polyethylene glycol or being the result of at least one substitution of a hydroxyl group, preferably chosen from (poly)glycerols.
3. Assembly according to Claim 2, in which the group X is chosen from:
i) HO-(ALK-0)z-CH2-CH[(OALK)y-OH]-CH2-(0-ALK)x-(*)
in which:
- ALK, which may be identical or different, representing a C1 -C6 and in particular C1 -C4 alkylene group, preferably ethylene,
- x, y and z being an integer between 0 and 200, it being understood that x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
ii) H-(ALK-0)x-(*) and H-(0-ALK)x-(*), preferably is H-(0-ALK)x-(*)
in which:
- ALK, which may be identical or different, representing a C1 -C6 and in particular C1 -C4 ethylene group, preferably ethylene,
- x is an integer other than 0 and preferably between 1 and 200.
4. Assembly according to Claim 2 or 3, in which the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula (Γ) below:
ALK-(0-CH2-CH2)n-OH (Ι') in which formula (Γ):
- ALK is a C8-C24, preferably Ci2-C22 and more preferentially Ci6-Ci8 alkyl group,
n being an integer other than 0, between 1 and 200, preferably between 1 and 10 and better still between 2 and 6 for the nonionic surfactant(s) with an HLB value at 25°C of less than 8, preferably between 20 and 200 for the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8.
5. Assembly according to Claim 2, 3 or 4, in which the nonionic surfactant(s) with an HLB value at 25°C of less than 8 are chosen from:
- (poly)oxyalkylenated saccharide esters and ethers;
- esters of fatty acids, especially of C8-C24 and preferably of Ci6-C22, and of (poly)oxyalkylenated polyol, especially of (poly)oxyalkylenated glycerol or of oxyalkylenated sorbitol, preferably of (poly)oxyalkylenated glycerol;
- (poly)oxyalkylenated alcohols;
and mixture(s) thereof; preferably, from (poly)oxyalkylenated alcohols preferably comprising from 1 to 10 oxyethylene units.
6. Assembly according to any one of Claims 2 to 5, in which the nonionic surfactant(s) with an HLB value at 25°C of less than 8 comprise a (poly)oxyalkylenated alcohol comprising an ether of a C8-C24 fatty alcohol and of polyethylene glycol, said ether comprising from 1 to 10 and better still between 2 and 6 ethylene glycol units.
7. Assembly according to any one of Claims 2 to 6, in which the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, are chosen from:
- (poly)oxyalkylenated glycerol ethers,
- (poly)oxyalkylenated alcohols,
- (poly)oxyalkylenated esters of a fatty acid and of polyethylene glycol,
- esters of a fatty acid and of (poly)oxyalkylenated glycerol ethers,
- esters of a fatty acid and of (poly)oxyalkylenated sorbitol ethers,
and mixture(s) thereof; preferably, from (poly)oxyalkylenated alcohols preferably comprising from 20 to 200 oxyethylene units.
8. Assembly according to any one of Claims 2 to 7, in which the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 comprise a (poly)oxyalkylenated alcohol comprising at least one ether of a C8-C24 fatty alcohol and of polyethylene glycol, said ether comprising at least 20 ethylene glycol units and better still between 20 and 200 ethylene glycol units.
9. Assembly according to any one of Claims 2 to 8, in which the aqueous phase represents from 30% to 80% by weight and preferably from 40% to 70% by weight, relative to the total weight of the composition.
10. Assembly according to any one of Claims 2 to 9, in which the hard wax particles are not introduced into the preparation of the composition in the form of a pre- prepared aqueous microdispersion of hard wax(es).
1 1 . Assembly according to any one of Claims 2 to 10, comprising a total content of hard wax particles, preferentially present in aqueous dispersion form, of greater than or equal to 12% by weight, preferably 15% by weight, preferably 18% by weight and more preferentially 20% by weight, relative to the total weight of the composition, for example between 16% and 30% by weight relative to the total weight of the composition.
12. Assembly according to any one of Claims 2 to 1 1 , comprising a total content of hard wax particles, preferentially in aqueous dispersion form, representing at least 80% by weight, preferentially at least 90% by weight and more preferentially 100% by weight relative to the total weight of wax(es).
13. Assembly according to any one of Claims 2 to 12, in which the hard wax(es) are polar.
14. Assembly according to any one of Claims 2 to 13, in which the nonionic surfactant(s) of formula (I) with an HLB value at 25°C of greater than or equal to 8 are present in a content of greater than or equal to 5% by weight relative to the total weight of the composition, preferably ranging from 8% to 20% by weight relative to the total weight of the composition.
15. Assembly according to any one of Claims 2 to 14, in which the nonionic surfactant(s) of formula (I) with an HLB value at 25°C of less than 8 are present in a content of greater than or equal to 5% by weight relative to the total weight of the composition, preferably ranging from 8% to 20% by weight relative to the total weight of the composition.
16. Assembly according to any one of Claims 2 to 15, in which the nonionic surfactant(s) with an HLB value at 25°C of less than 8 and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 are present in a total content of greater than or equal to 10%, better still 12% and in particular between 15% and 25% by weight relative to the total weight of the composition.
17. Assembly according to any one of Claims 2 to 16, in which the nonionic surfactant(s) with an HLB value at 25°C of less than 8 of formula (I) and the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 of formula (I) are present in a respective total content such that the weight ratio of the nonionic surfactant(s) with an HLB value at 25°C of less than 8 of formula (1 ) to the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 of formula (I) ranges from 1/5 to 5, preferably from 1/3 to 3, preferably from 2/3 to 3/2.
18. Assembly according to any one of Claims 2 to 17, in which the total content of hard wax(es), and optionally of additional wax(es), and the total content of surfactant system are such that the weight ratio of the hard wax(es) plus the additional wax(es) to the surfactant system is less than or equal to 1.75, preferably strictly less than 1 .5, in particular between 1/3 and 1.25.
19. Assembly according to any one of Claims 2 to 18, comprising a solids content of greater than or equal to 40%, in particular 42%, preferably 45% and more preferentially 48%.
20. Assembly according to any one of Claims 2 to 19, comprising at least one dyestuff chosen from one or more pulverulent materials, preferably metal oxides and in particular iron oxides.
21 . Assembly according to any one of Claims 2 to 20, comprising a viscosity at
25°C ranging from 5 to 50 Pa.s.
PCT/EP2015/057748 2014-04-11 2015-04-09 Assembly for packaging a composition for coating keratin fibres WO2015155298A1 (en)

Applications Claiming Priority (2)

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FR1453260A FR3019738B1 (en) 2014-04-11 2014-04-11 CONDITIONING ASSEMBLY OF A COSMETIC COMPOSITION FOR COATING KERATIN FIBERS
FR1453260 2014-04-11

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100278770A1 (en) * 2009-04-30 2010-11-04 L'oreal Wax-in-water emulsion comprising a combination of a glutamic acid derivative and an alkylpolyglycoside
FR2996757A1 (en) * 2012-10-15 2014-04-18 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100278770A1 (en) * 2009-04-30 2010-11-04 L'oreal Wax-in-water emulsion comprising a combination of a glutamic acid derivative and an alkylpolyglycoside
FR2996757A1 (en) * 2012-10-15 2014-04-18 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS

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FR3019738A1 (en) 2015-10-16

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