WO2008074870A2 - Lash coating kit comprising silicone compounds x and y and fibres - Google Patents

Lash coating kit comprising silicone compounds x and y and fibres Download PDF

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Publication number
WO2008074870A2
WO2008074870A2 PCT/EP2007/064348 EP2007064348W WO2008074870A2 WO 2008074870 A2 WO2008074870 A2 WO 2008074870A2 EP 2007064348 W EP2007064348 W EP 2007064348W WO 2008074870 A2 WO2008074870 A2 WO 2008074870A2
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WO
WIPO (PCT)
Prior art keywords
compound
kit according
composition
compounds
groups
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Application number
PCT/EP2007/064348
Other languages
French (fr)
Other versions
WO2008074870A3 (en
Inventor
Nathalie Jager Lezer
Stéphane Arditty
Original Assignee
L'oreal
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Publication date
Priority claimed from FR0655741A external-priority patent/FR2910305B1/en
Application filed by L'oreal filed Critical L'oreal
Publication of WO2008074870A2 publication Critical patent/WO2008074870A2/en
Publication of WO2008074870A3 publication Critical patent/WO2008074870A3/en

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Classifications

    • 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
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • A61K8/027Fibers; Fibrils
    • 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
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • 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
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/892Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
    • 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
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/893Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
    • 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
    • A61K8/89Polysiloxanes
    • A61K8/895Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • 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
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/594Mixtures of polymers

Definitions

  • Lash coating kit comprising silicone compounds X and Y and fibres .
  • the present invention relates to a lash coating composition or mascara, in particular a non-therapeutic eyelash makeup or care composition, comprising at least two compounds X and Y that are capable of reacting together, one at least of the compounds being a silicone compound, and fibres.
  • a cosmetic kit comprising the said compounds X and Y.
  • the composition may be a lash makeup composition, a lash makeup base, a composition for application over a mascara, also known as top-coat, or else a cosmetic lash treatment composition.
  • the mascara is intended more particularly for the lashes of human beings, but also for false eyelashes.
  • anhydrous mascaras or mascaras with a low level of water and/or water-soluble solvents are known in particular, being known as "waterproof" mascaras, which are formulated as a dispersion of waxes in nonaqueous solvents and which exhibit effective resistance to water and/or sebum.
  • the makeup film obtained after these compositions have been applied is not sufficiently water-resistant, on bathing or showering, for example, to tears or perspiration, or else to sebum.
  • the mascara thus tends to disintegrate over time: grains are deposited, and unattractive lines appear around the eyes.
  • the use of fibres to produce a lash- lengthening effect is not beneficial to a smooth, homogeneous deposit on the lashes, thereby giving rise to poor hold on the part of the fibres, which have a tendency to become detached more easily.
  • the invention allows another formulation pathway to be proposed for a lash coating composition, allowing the lashes to receive a makeup which exhibits very good hold, which leads to lengthening and which leads to a continuous smooth, intense black and glossy film.
  • the compositions lead to lash makeup which exhibits good hold both of the fibres and of the overall makeup film.
  • compositions according to the invention permit smooth and homogeneous application.
  • the mascaras according to the invention allow a makeup result which holds for more than 1 day, more preferably for more than 3 days, and more preferably still for more than a week.
  • compositions comprising fibres and compounds, preferably silicone compounds, which polymerize and/or crosslink in situ so as to adhere more effectively to the lashes. These compounds additionally exhibit a high level of biocompatibility .
  • These compounds are able to react together on the lashes or on a substrate so as to form an adherent film with good hold on the lashes.
  • the present invention provides a lash coating kit comprising: - at least one first composition and at least one second composition, which are packaged separately,
  • the kit comprising at least one compound (X) , at least one compound (Y) and optionally at least one catalyst or one peroxide, at least one of the compounds, X or Y, being a silicone compound,
  • the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide, when they are brought into contact with one another, and fibres.
  • the present invention provides a lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately,
  • the kit comprising at least one compound (X) , at least one compound (Y) and at least one catalyst, at least one of the compounds, X or Y, being a silicone compound, - with the proviso that the compounds X and Y and the catalyst are not present simultaneously in the same composition,
  • the said compounds X and Y being able to react together by a hydrosilylation reaction, when they are brought into contact with one another in the presence of a catalyst, fibres, and at least one phenyl silicone oil.
  • the present invention likewise provides a lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately, - the kit comprising at least one compound (X) , at least one compound (Y) and optionally at least one catalyst, at least one of the compounds, X or Y, being a silicone compound,
  • the compound or compounds X and the compound or compounds Y may be applied to the lashes from two or more compositions containing the compound or compounds X, the compound or compounds Y and the fibres, alone or in a mixture, or from a single composition containing the compound or compounds X, the compound or compounds Y and the fibres.
  • the compound or compounds X and the compound or compounds Y may in particular be present in the first and/or in the second composition.
  • the fibres may in particular be present in the first and/or in the second composition.
  • a first composition comprising the compound or compounds X, the compound or compounds Y and the fibres is applied to the lashes.
  • a first composition comprising the fibres and a second composition comprising the compound or compounds X and the compound or compounds Y are applied to the lashes, the order in which the first and second compositions are applied being arbitrary.
  • a first composition comprising the fibres, a second composition comprising the compound or compounds X and a third composition comprising the compound or compounds Y are applied to the lashes, the order in which the said compositions are applied being arbitrary.
  • a first composition comprising the compound or compounds X and fibres and a second composition comprising the compound or compounds Y are applied to the lashes, the order in which the said compositions are applied being arbitrary.
  • a first composition comprising the compound or compounds X and a second composition comprising the compound or compounds Y and the fibres are applied to the lashes, the order in which the said compositions are applied being arbitrary.
  • At least one catalyst as defined below is applied to the lashes in order to activate the reaction between the compound or compounds X and the compound or compounds Y.
  • the catalyst or catalysts may be present in one or other or in each of the first and second compositions that are applied to the lashes, or in an additional composition, in which case the order in which the various compositions are applied to the lashes is arbitrary.
  • the catalysts advantageously selected are those described hereinbelow.
  • the first composition comprises at least one compound X and at least one compound Y
  • the second composition comprises at least one compound X and a catalyst
  • one at least of the first and second compositions comprises fibres.
  • At least one additional reactive compound as defined hereinbelow is applied to the lashes.
  • the additional reactive compound or compounds may be present in one or the other or in each of the first and second compositions applied to the lashes, or in an additional composition, in which case the order in which the various compositions are applied to the lashes is arbitrary.
  • the kit further comprises a supplementary composition intended to remove the coating obtained on the lashes by reaction of the compounds X and Y, the said composition preferably comprising at least one organic solvent or oil selected from the organic solvents or oils described later on.
  • Each composition of the kit may be packaged separately in a single pack, as for example in a twin-compartment pen, the base composition being delivered by one end of the pen and the top composition being delivered by the other end of the pen, with each end being closed, more particularly closed tightly, by a cap.
  • Each composition may also be packaged in a compartment within a single pack, the mixing of the two compositions taking place at the end or ends of the pack at the time of delivery of each composition.
  • each composition may be packaged in a different pack.
  • the invention further provides for the use of a kit or of a composition as described above to give a film deposited on the lashes that exhibits enhanced properties of hold, gloss and/or comfort and also a lengthening effect.
  • the present invention provides a cosmetic lash coating method comprising applying to the said lashes at least one layer of a mixture of a first composition and a second composition, each of the first and second compositions comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide; one at least of the compounds X and Y being a silicone compound, the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide when they are brought into contact with one another, the compounds X and Y and the catalyst, when present, or the peroxide not being present simultaneously in the same composition, the said mixture being obtained either at the time of use, before application to the lashes, or simultaneously with its application to the lashes, and one at least of the said first and second compositions comprising fibres.
  • the compounds X and Y are mixed at the time of use and then the mixture is applied to the lashes .
  • the invention provides a cosmetic lash coating method comprising: a. mixing, at the time of use, at least one first composition and at least one second composition, each of the first and second compositions comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide, one at least of the compounds X and Y being a silicone compound, the compounds X and Y and the catalyst, when present, or the peroxide not being present simultaneously in the same composition, the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide when they are brought into contact with one another, and one at least of the said first and second compositions comprising fibres, and then b. applying at least one layer of the said mixture to the said lashes.
  • each composition comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide.
  • the present invention provides a cosmetic lash coating method comprising applying to the lashes: a. at least one layer of a first composition, b. at least one layer of a second composition, each of the first and second compositions comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide, one at least of the compounds X and Y being a silicone compound, the compounds X and Y and the catalyst, when present, or the peroxide not being present simultaneously in the same composition, the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide when they are brought into contact with one another, and one at least of the said first and second compositions comprising fibres.
  • the order in which the first and second compositions are applied is arbitrary. It is also possible to apply a plurality of layers of each of the first and second compositions in alternation to the lashes.
  • At least one catalyst as defined later on is applied to the lashes in order to activate the reaction between the compound or compounds X and the compound or compounds Y.
  • the catalyst or catalysts may be present in one or the other or in each of the first and second compositions applied to the lashes, or in an additional composition, in which case the order in which the various compositions are applied to the lashes is arbitrary.
  • the catalysts advantageously selected are those described hereinbelow.
  • At least one additional layer of at least one composition comprising a cosmetically acceptable medium and preferably at least one film- forming polymer and at least one organic (or oily) or aqueous solvent medium is applied to the layer or layers of the composition or compositions comprising the compounds X and/or Y for the purpose, for example, of enhancing its or their hold, gloss and/or comfort.
  • the invention additionally provides a lash coating composition
  • a lash coating composition comprising: - at least one compound X and at least one compound Y, one at least of the compounds X and Y being a silicone compound, and optionally at least one catalyst or a peroxide, the said compounds X and Y being able to react together by a hydrosilylation reaction, a condensation reaction or a crosslinking reaction in the presence of the catalyst or the peroxide when they are brought into contact with one another, and fibres.
  • one at least of the compounds X and Y may be present in an encapsulated form. In one version the two compounds X and Y are both present in separate encapsulated forms.
  • the compounds X and/or Y may be present in the form of microcapsules, and more particularly of core/shell nanocapsules, the lipophilic core containing the compound X or the compound Y.
  • composition comprises a cosmetically acceptable medium, in other words a medium which is not toxic and can be applied to the lashes of human beings, and with a pleasant appearance, odour and feel.
  • a silicone compound is a compound comprising at least two organosiloxane units.
  • the compounds X and the compounds Y are silicone compounds .
  • the compounds X and the compounds Y may be aminated or non-aminated.
  • At least one of the compounds X and Y is a polymer whose main chain is formed predominantly of organosiloxane units.
  • silicone compounds mentioned below may have both film-forming properties and adhesive properties, depending, for example, on their proportion of silicone or on whether they are used in a mixture with a specific additive. It is possible, consequently, to modify the film-forming properties or the adhesive properties of such compounds in accordance with the intended use; this is the case in particular for the reactive elastomeric silicones known as "room temperature vulcanization" silicones.
  • the compounds X and Y may react together at a temperature varying between ambient temperature and 180 0 C.
  • the compounds X and Y are able to react together at ambient temperature (20 ⁇ 5 0 C) and atmospheric pressure, alone or advantageously in the presence of a catalyst, by a hydrosilylation reaction or a condensation reaction, or a crosslinking reaction in the presence of a peroxide.
  • one at least of the compounds X and Y carries at least one polar group able to form at least one hydrogen bond with the lashes.
  • a polar group is a group which contains carbon atoms and hydrogen atoms in its chemical structure and also at least one heteroatom (such as O, N, S and P) such that the said group is capable of establishing at least one hydrogen bond with the lashes.
  • Compounds which carry at least one group capable of establishing a hydrogen bond are particularly advantageous, since they provide the compositions containing them with improved adhesion to the lashes, owing to the capacity of these groups to establish a hydrogen bond with the lashes.
  • the polar group or groups carried by at least one of the compounds X and Y is or are capable of establishing a hydrogen bond, and include or includes either a hydrogen atom bonded to an electronegative atom, or an electronegative atom such as, for example, O, N or S .
  • the hydrogen atom can interact with another electronegative atom carried, for example, by another molecule, such as keratin, to form a hydrogen bond.
  • the electronegative atom can interact with a hydrogen atom bonded to an electronegative atom carried, for example, by another molecule, such as keratin, to form a hydrogen bond.
  • these polar groups may be selected from the following groups: carboxylic acids -COOH, alcohols, such as -CH 2 OH or -CH(R)OH, R being an alkyl radical containing 1 to 6 carbon atoms, amino of formula -NRiR 2 , in which the radicals
  • Ri and R 2 which are identical or different, represent an alkyl radical containing 1 to 6 carbon atoms, or one of the radicals, Ri or R 2 , denotes a hydrogen atom, pyridino, amido of formula -NH-COR' or -CO-NH-R' in which
  • R' represents a hydrogen atom or an alkyl radical containing 1 to 6 carbon atoms, pyrrolidino selected preferably from the groups of formula:
  • these polar groups are present in an amount of less than or equal to 10% by weight relative to the weight of each compound X or Y, preferably less than or equal to 5% by weight, for example in an amount of from 1 to 3% by weight.
  • the polar group or groups may be situated in the main chain of the compound X and/or Y or are pendant to the main chain or are situated at the ends of the main chain of the compound X and/or Y.
  • the compounds X and Y are able to react by hydrosilylation, a reaction which can be depicted in a simplified way as follows: where W represents a carbon and/or silicone chain containing one or more unsaturated aliphatic groups.
  • the compound X may be selected from silicone compounds comprising at least two unsaturated aliphatic groups.
  • the compound X may comprise a main silicone chain whose unsaturated aliphatic groups are pendant to the main chain (side group) or are situated at the ends of the main chain of the compound (terminal group) .
  • these specific compounds will be referred to as polyorganosiloxanes having unsaturated aliphatic groups.
  • the compound X and/or the compound Y carries at least one polar group, as described above, able to form at least one hydrogen bond with the lashes.
  • This polar group is advantageously carried by the compound X which comprises at least two unsaturated aliphatic groups.
  • the compound X is selected from polyorganosiloxanes comprising at least two unsaturated aliphatic groups, for example two or three vinyl or allyl groups, each bonded to a silicon atom. In one advantageous embodiment the compound X is selected from polyorganosiloxanes containing siloxane units of formula:
  • the polyorganosiloxane further comprises units of formula R SiO , ,
  • the compound X may be a silicone resin containing at least two ethylenic unsaturations, the said resin being capable of reacting with the compound Y by hydrosilylation .
  • silicone resins are crosslinked organosiloxane polymers.
  • the nomenclature of silicone resins is known by the name of "MDTQ", the resin being described as a function of the different monomeric siloxane units it comprises, with each of the letters MDTQ characterizing one type of unit.
  • the letter M represents the monofunctional unit of formula (CH 3 ) 3 Si0i / 2, the silicon atom being joined to a single oxygen atom in the polymer comprising this unit.
  • the letter D signifies a difunctional unit (CH 3 ) 2 Si ⁇ 2 / 2 in which the silicon atom is joined to two oxygen atoms .
  • the letter T represents a trifunctional unit of formula (CH 3 )SiO 372 .
  • the units M, D and T defined above at least one of the methyl groups may be substituted by a group R other than the methyl group, such as a hydrocarbon radical (more particularly alkyl) having 2 to 10 carbon atoms, or a phenyl group, or else a hydroxyl group.
  • the letter Q signifies a tetrafunctional unit Si ⁇ 4 / 2 in which the silicon atom is bonded to four hydrogen atoms which are themselves bonded to the remainder of the polymer.
  • MT silicone resins such as the poly (phenylvinylsilsesquioxanes) like those sold under the name SST-3PV1 by Gelest.
  • the compounds X preferably contain from 0.01% to 1% by weight of unsaturated aliphatic groups.
  • the compound X is selected from polyorganopolysiloxanes, more particularly those comprising the siloxane units (I) and optionally (II) described above.
  • the compound Y preferably comprises at least two free Si-H groups (hydrogenosilane groups) .
  • R represents a monovalent linear or cyclic hydrocarbon group containing 1 to 30 carbon atoms, such as, for example, an alkyl radical having 1 to 30 carbon atoms, preferably 1 to 20 and more preferably 1 to 10 carbon atoms, in particular a methyl radical, or else a phenyl group, and p is 1 or 2.
  • R is a hydrocarbon group, preferably methyl.
  • organosiloxane compounds Y having alkylhydrogeno- siloxane units may further comprise units of formula:
  • the compound Y may be a silicone resin comprising at least one unit selected from the M, D, T and Q units as defined above and comprising at least one Si-H group, such as the poly (methylhydridosilsesquioxanes) sold under the name SST-3MH1.1 by Gelest.
  • these organosiloxane compounds Y contain from 0.5% to 2.5% by weight of Si-H groups.
  • the radicals R represent a methyl group in the formulae (I), (II) and (III) above.
  • these organosiloxanes Y comprise terminal groups of formula (CH 3 ) 3 Si0i / 2.
  • the organosiloxanes Y comprise at least two alkylhydrogenosiloxane units of formula (H 2 C) (H) SiO and optionally comprise units (H 3 C) 2SiO.
  • Organosiloxane compounds Y of this kind containing hydrogenosilane groups are described for example in document EP 0465744.
  • the compound X is selected from organic oligomers or polymers (organic compounds are those whose main chain is not a silicone chain, preference being given to compounds containing no silicon atoms) or from hybrid organic/silicone polymers or oligomers, the said oligomers or polymers carrying at least two reactive unsaturated aliphatic groups, and the compound Y being selected from the aforementioned hydrogenosiloxanes .
  • organic or organic/silicone hybrid compounds X carrying at least two reactive unsaturated aliphatic groups carry at least one polar group as described above.
  • the compound X which is organic in nature, may then be selected from vinyl and (meth) acrylic oligomers or polymers, polyesters, polyurethanes and/or polyureas, polyethers, perfluoropolyethers, polyolefins such as polybutene and polyisobutylene, dendrimers or hyperbranched organic polymers, or mixtures thereof.
  • organic polymer or the organic part of the hybrid polymer may be selected from the following polymers: a) ethylenically unsaturated polyesters: this is a group of polymers of polyester type having at least 2 ethylenic double bonds distributed anywhere in the main chain of the polymer.
  • These unsaturated polyesters are obtained by polycondensation of a mixture: - of linear or branched aliphatic or cycloaliphatic carboxylic diacids containing in particular 3 to 50 carbon atoms, preferably 3 to 20 and more preferably 3 to 10 carbon atoms, such as adipic acid or sebacic acid, aromatic carboxylic diacids having in particular 8 to 50 carbon atoms, preferably 8 to 20 and more preferably 8 to 14 carbon atoms, such as phthalic acids, more particularly terephthalic acid, and/or carboxylic diacids obtained from dimers of ethylenically unsaturated fatty acids, such as the dimers of oleic or linoleic acids that are described in patent application EP-A-959 066 (paragraph [0021]) and are sold under the name Pripol ® by Unichema or Empol by Henkel, all of these diacids necessarily being devoid of polymerizable ethylenic double bonds
  • Polyesters having side and/or terminal (meth) acrylate groups this is a group of polymers of polyester type which are obtained by polycondensation of a mixture : of linear or branched aliphatic or cycloaliphatic carboxylic diacids containing in particular 3 to 50 carbon atoms, preferably 3 to 20 and more preferably 3 to 10 carbon atoms, such as adipic acid or sebacic acid, aromatic carboxylic diacids having in particular 8 to 50 carbon atoms, preferably 8 to 20 and more preferably 8 to 14 carbon atoms, such as phthalic acids, more particularly terephthalic acid, and/or carboxylic diacids obtained from dimers of ethylenically unsaturated fatty acids, such as the dimers of oleic or linoleic acids that are described in patent application EP-A-959 066 (paragraph [0021]) and are sold under the name Pripol by Unichema or Empol ® by Henkel, all of these
  • polyesters are different from those described above in section a) in that the ethylenic double bonds are situated not in the main chain but on side groups or at the end of the chains. These ethylenic double bonds are those of the (meth) acrylate groups present in the polymer.
  • Polyesters of this kind are sold for example by UCB under the name Ebecryl ® (Ebecryl ® 450: molar mass 1600, on average 6 acrylate functions per molecule, Ebecryl ® 652: molar mass 1500, on average 6 acrylate functions per molecule, Ebecryl ® 800: molar mass 780, on average 4 acrylate functions per molecule, Ebecryl 810: molar mass 1000, on average 4 acrylate functions per molecule, Ebecryl 50 000: molar mass 1500, on average 6 acrylate functions per molecule) .
  • Ebecryl ® 450 molar mass 1600, on average 6 acrylate functions per molecule
  • Ebecryl ® 652 molar mass 1500, on average 6 acrylate functions per molecule
  • Ebecryl ® 800 molar mass 780, on average 4 acrylate functions per molecule
  • Ebecryl 810 molar mass 1000, on average 4 acrylate functions per molecule
  • aliphatic, cycloaliphatic and/or aromatic diisocyanates, triisocyanates and/or polyisocyanates having in particular 4 to 50, preferably 4 to 30, carbon atoms, such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or the isocyanurates of formula :
  • polyols more particularly of diols, which are devoid of polymerizable ethylenic unsaturations, such as 1, 4-butanediol, ethylene glycol or trimethylolpropane, and/or from polyamines, more particularly diamines, which are aliphatic, cycloaliphatic and/or aromatic and have more particularly 3 to 50 carbon atoms, such as ethylenediamine or hexamethylene- diamine, and
  • Polyurethanes/polyureas of these kinds containing acrylate groups are sold for example under the name SR 368 (tris (2-hydroxyethyl) isocyanurate triacrylate) or Craynor 435 by Cray Valley, or under the name Ebecryl ® by UCB
  • Ebecryl ® 270 molar mass 1500, 2 acrylate functions per molecule
  • Ebecryl 8402 molar mass 1000, 2 acrylate functions per molecule
  • Ebecryl ® 8804 molar mass 1300, 2 acrylate functions per molecule
  • Ebecryl ® 220 molar mass 1000, 6 acrylate functions per molecule
  • Ebecryl ® 2220 molar mass 1200, 6 acrylate functions per molecule
  • Ebecryl 1290 molar mass 1000, 6 acrylate functions per molecule
  • Ebecryl" 800 molar mass 800, 6 acrylate functions per molecule
  • Polyoxyethylene di (meth) acrylates of appropriate molar mass are sold for example under the names SR 259, SR 344, SR 610, SR 210,
  • At least one diepoxide selected for example from: (i) bisphenol A diglycidyl ether,
  • carboxylic acids or polycarboxylic acids containing at least one ethylenic double bond positioned ⁇ , ⁇ to the carboxyl group such as (meth) acrylic acid or crotonic acid, or the esters of (meth) acrylic acid and a diol or polyol having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, such as 2-hydroxyethyl (meth) acrylate .
  • Polymers of this kind are sold for example under the names SR 349, SR 601, CD 541, SR 602, SR 9036, SR 348, CD 540, SR 480 and CD 9038 by Cray Valley, under the names Ebecryl ® 600 and Ebecryl ® 609, Ebecryl ® 150, Ebecryl ® 860 and Ebecryl ® 3702 by UCB, and under the names Photomer ® 3005 and Photomer ® 3082 by Henkel.
  • Copolymers of this kind are sold for example under the names IRR ® 375, OTA ® 480 and Ebecryl ® 2047 by
  • Polyolefins such as polybutene and polyiso- butylene .
  • ⁇ , ⁇ -Diol perfluoropolyethers of this kind are described in particular in EP-A-1057849 and are sold by Ausimont under the name Fomblin ® Z DIOL.
  • Dendrimers and hyperbranched polymers which carry terminal (meth) acrylate or (meth) - acrylamide groups obtained respectively by esterification or amidification of dendrimers and hyperbranched polymers having terminal hydroxyl or amino functions with (meth) acrylic acid.
  • Engl. Ed., vol. 29, no. 2, pages 138-175) They are structures constructed around a generally polyfunctional central unit. Arrayed in chains around this central unit, in accordance with a well-defined structure, are branched chain- extension units, hence giving rise to monodisperse symmetrical macromolecules which have a well- defined chemical and stereochemical structure. Polyamidoamine dendrimers are sold for example under the name Starburst ® by Dendritech.
  • Hyperbranched polymers are polycondensates, generally of polyester, polyamide or polyethyleneamine type, which are obtained from polyfunctional monomers, which have an arborescent structure similar to that of the dendrimers but much less regular than them (see, for example, WO- A-93/17060 and WO 96/12754) .
  • Hyperbranched polyesters are found under the name Comburst from the company Dendritech. Hyperbranched poly (esteramides) having hydroxyl eennddss aarre sold by the company DSM under the name Hybrane ⁇ ®
  • dendrimers and hyperbranched polymers esterified or amidified by acrylic and/or methacrylic acid differ from the polymers described in sections a) to h) above in the very large number of ethylenic double bonds present.
  • This high functionality most often greater than 5, makes them particularly useful, allowing them to act as a "crosslinking node", in other words as a site of multiple crosslinking. It is therefore possible to use these dendritic and hyperbranched polymers in combination with one or more of the polymers and/or oligomers a) to h) above .
  • compositions comprising the compound X and/or Y may further comprise at least one additional reactive compound such as: organic or inorganic particles comprising on their surface at least 2 unsaturated aliphatic groups, examples including silicas surface- treated with, for example, silicone compounds having vinyl groups, such as, for example, cyclotetramethyltetravinylsiloxane-treated silica; silazane compounds such as hexamethyldi- silazane .
  • additional reactive compound such as: organic or inorganic particles comprising on their surface at least 2 unsaturated aliphatic groups, examples including silicas surface- treated with, for example, silicone compounds having vinyl groups, such as, for example, cyclotetramethyltetravinylsiloxane-treated silica; silazane compounds such as hexamethyldi- silazane .
  • the hydrosilylation reaction takes place advantageously in the presence of a catalyst which may be present in one or other of the compositions comprising the compound X and/or the compound Y or in a separate composition, the catalyst being preferably based on platinum or on tin.
  • Examples include catalysts based on platinum deposited on a silica gel support or on a charcoal powder
  • platinum complexes such as those based on chloroplatinic acid hexahydrate and divinyltetramethyldisiloxane .
  • the catalyst may be present in one or other of the compositions useful in the present invention in an amount of from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.
  • compositions of the invention it is also possible to introduce polymerization inhibitors or retardants, and more particularly catalyst inhibitors, for the purpose of increasing the stability of the composition over time or of retarding the polymerization.
  • polymerization inhibitors or retardants and more particularly catalyst inhibitors
  • cyclic polymethylvinylsiloxanes and especially tetravinyltetramethylcyclotetrasiloxane
  • acetylenic alcohols preferably volatile acetylenic alcohols, such as methylisobutynol .
  • ionic salts such as sodium acetate
  • the presence of ionic salts, such as sodium acetate, in one and/or the other of the first and second compositions may influence the rate of polymerization of the compounds.
  • the compounds X and Y are selected from silicone compounds able to react by hydrosilylation; in particular, the compound X is selected from polyorganosiloxanes containing units of formula (I) described above, and the compound Y is selected from organosiloxanes containing alkylhydrogenosiloxane units of formula (III) described above.
  • the compound X is a polydimethylsiloxane having terminal vinyl groups, and the compound Y is methylhydrogenosiloxane .
  • the compound X carries at least one polar group.
  • the compounds X and Y are able to react by condensation, either in the presence of water (hydrolysis), by reaction of 2 compounds which carry alkoxysilane groups, or by so-called direct condensation, by reaction of a compound which carries one or more alkoxysilane groups and a compound which carries one or more silanol groups, or by reaction of 2 compounds which carry one or more silanol groups.
  • the water may be in particular ambient moisture, residual water on the lashes, or water provided by an external source, for example by wetting of the lashes beforehand (for example by means of an atomizer, natural or artificial tears) .
  • the compounds X and Y which are identical or different, may therefore be selected from silicone compounds whose main chain comprises at least two alkoxysilane groups and/or at least two silanol (Si-OH) groups, which are side groups and/or chain-end groups.
  • the compound X and/or the compound Y carries at least one polar group, as described above, capable of forming at least one hydrogen bond with the lashes .
  • the compounds X and/or Y are selected from polyorganosiloxanes comprising at least two alkoxysilane groups.
  • An alkoxysilane group is a group comprising at least one moiety -Si-OR, R being an alkyl group containing 1 to 6 carbon atoms.
  • the compounds X and Y are more particularly selected from polyorganosiloxanes comprising terminal alkoxysilane groups, more specifically those which comprise at least 2 terminal alkoxysilane groups, preferably terminal trialkoxysilane groups.
  • R 9 independently represents a radical selected from alkyl groups containing 1 to 6 carbon atoms, phenyl, and fluoroalkyl groups, and s is 0, 1, 2 or 3.
  • R 9 independently represents an alkyl group containing 1 to 6 carbon atoms.
  • the alkyl group mention may be made in particular of methyl, propyl, butyl, hexyl and mixtures thereof, preferably methyl or ethyl.
  • a fluoroalkyl group mention may be made of 3,3, 3-trifluoropropyl .
  • the compounds X and Y which are identical or different, are polyorganosiloxanes comprising units of formula
  • R 9 is as described above, R 9 preferably being a methyl radical, and f is more particularly such that the polymer has a viscosity at 25°C of from 0.5 to 3000 Pa. s, preferably of from 5 to 150 Pa. s; for example, f may be from 2 to 5000, preferably from 3 to 3000, more preferably from 5 to 1000.
  • These polyorganosiloxane compounds X and Y comprise at least two terminal trialkoxysilane groups per polymer molecule, the said groups having the formula
  • radicals R represent independently a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl group, preferably a methyl or ethyl group
  • R 1 is a methyl or ethyl group
  • x is 0 or 1, preferably 0 and
  • Z is selected from the following: divalent hydrocarbon groups containing no ethylenic unsaturation and containing 1 to 18 carbon atoms, preferably 2 to 18 carbon atoms (alkylene groups) , the combinations of divalent hydrocarbon radicals and of siloxane segments of formula (IX) :
  • G is a divalent hydrocarbon radical containing no ethylenic unsaturation and containing 1 to 18 carbon atoms, preferably 2 to 18 carbon atoms, and c is an integer of from 1 to 6.
  • Z and G may more particularly be selected from alkylene groups such as methylene, ethylene, propylene, butylene, pentylene and hexylene, and arylene groups such as phenylene.
  • Z is an alkylene group, and more preferably ethylene .
  • These polymers may have on average at least 1.2 trialkoxysilane end groups or terminal trialkoxysilane chains per molecule, and preferably on average at least 1.5 trialkoxysilane end groups per molecule.
  • Possible examples of such end groups include trimethoxysilane, triethoxysilane, vinyldimethoxysilane and vinylmethyl- oxyphenylsilane groups.
  • the compounds X and/or Y may further comprise a mixture of polymer of formula (VII) above with polymers of formula (VI I I ) :
  • the polyorganosiloxane compound X and/or Y having one or more alkoxysilane groups comprises such a mixture
  • the different polyorganosiloxanes are present in amounts such that the terminal organosilyl chains represent less than 40%, preferably less than 25%, by number of the terminal chains.
  • the particularly preferred polyorganosiloxane compounds X and/or Y are those of formula (VII) that were described above. Compounds X and/or Y of this kind are described for example in document WO 01/96450.
  • the compounds X and Y represent a mixture of polydimethylsiloxanes having methoxysilane groups.
  • the compounds X and Y may be identical or different.
  • one of the two reactive compounds, X or Y is of silicone type and the other is of organic type.
  • the compound X is selected from organic oligomers or polymers or organic/silicone hybrid oligomers or polymers, the said polymers or oligomers comprising at least two alkoxysilane groups, and Y is selected from silicone compounds such as the polyorganosiloxanes described above.
  • the organic oligomers or polymers are selected from vinyl and (meth) acrylic oligomers or polymers, polyesters, polyamides, polyurethanes and/or polyureas, polyethers, polyolefins, perfluoropolyethers, organic dendrimers and hyperbranched polymers, and mixtures thereof.
  • the organic or organic/silicone hybrid compound X carries at least one polar group, as described above, which is able to form at least one hydrogen bond with the lashes.
  • the organic polymers of vinyl or (meth) acrylic kind which carry alkoxysilane side groups may in particular be obtained by copolymerizing at least one vinyl or (meth) acrylic organic monomer with a (meth) acryloyloxy- propyltrimethoxysilane, a vinyltrimethoxysilane, a vinyltriethoxysilane, an allyltrimethoxysilane, etc. Mention may be made for example of the (meth) acrylic polymers described in the document of Kusabe.
  • the organic polymers which result from a polycondensation or from a polyaddition such as polyesters, polyamides, polyurethanes and/or polyureas, and polyethers, and which carry alkoxysilane side and/or end groups, may result, for example, from the reaction of an oligomeric prepolymer as described above with one of the following silane coreactants which carry at least one alkoxysilane group: aminopropyltri- methoxysilane, aminopropyltriethoxysilane, aminoethyl- aminopropyltrimethoxysilane, glycidyloxypropyltri- methoxysilane, glycidyloxypropyltriethoxysilane, epoxy- cyclohexylethyltrimethoxysilane, mercaptopropyltri- methoxysilane .
  • polyethers and of polyisobutylenes having alkoxysilane groups are described in the publication of Kusabe, M., Pitture e Vernici - European Coating; 12-B, pages 43-49, 2005.
  • Possible examples of polyurethanes having alkoxysilane end groups are those described in the document of Probster, M., Adhesion-Kleben & Dichten, 2004, 481 (1-2), pages 12-14 or else those described in the document of Landon, S., Pitture e Vernici vol. 73, No. 11, pages 18-24, 1997 or in the document of Huang, Mowo, Pitture e Vernici vol. 5, 2000, pages 61-67; mention may be made in particular of the polyurethanes having alkoxysilane groups from OSI-WITCO-GE.
  • polyorganosiloxane compounds X and/or Y mention may be made of the resins of type MQ or MT which themselves carry alkoxysilane and/or silanol ends, such as, for example, the poly (isobutylsilsesquioxane) resins functionalized with silanol groups that are provided under the name SST-S7C41 (3 Si-OH groups) by Gelest.
  • SST-S7C41 3 Si-OH groups
  • compositions useful in the present invention may further comprise an additional reactive compound comprising at least two alkoxysilane or silanol groups.
  • additional reactive compound comprising at least two alkoxysilane or silanol groups.
  • Possible examples include organic or inorganic particles comprising on their surface alkoxysilane and/or silanol groups, for example fillers surface- treated with such groups.
  • the condensation reaction may take place in the presence of a metal-based catalyst, which may be present in one or the other of the compositions comprising X and/or Y or in a separate composition.
  • a metal-based catalyst which may be present in one or the other of the compositions comprising X and/or Y or in a separate composition.
  • the catalyst useful in this type of reaction is preferably a catalyst based on titanium.
  • R 2 is selected from tertiary alkyl radicals such as tert-butyl, tert-amyl and 2, 4-dimethyl- 3-pentyl;
  • R represents an alkyl radical containing 1 to 6 carbon atoms, preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or hexyl group; and
  • y is a number of from 3 to 4, more preferably from 3.4 to 4.
  • the catalyst may be present in the one or the other of the compositions useful in the present invention, in an amount of from 0.0001% to 20% by weight relative to the total weight of the composition or compositions containing it.
  • the useful compositions comprising X and/or Y may further comprise a volatile silicone oil (or diluent) intended for lowering the viscosity of the composition.
  • This oil may be selected from short-chain linear silicones such as hexamethyldisiloxane and octamethyl- trisiloxane and from cyclic silicones such as octa- methylcyclotetrasiloxane and decamethylcyclopenta- siloxane, and mixtures thereof.
  • This silicone oil may represent from 5% to 95%, preferably from 10% to 80%, by weight relative to the weight of each composition.
  • the invention provides a lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately, the kit comprising at least one compound (X) , at least one compound (Y) , and at least one peroxide, at least one of the compounds, X or Y, being a silicone compound, - with the proviso that the compounds X and Y and the peroxide are not present simultaneously in the same composition, the said compounds X and Y reacting together by a crosslinking reaction when they are contacted with one another in the presence of peroxide, and fibres, and preferably at least one phenyl silicone oil .
  • the compounds X and Y which are identical or different, comprise at least two -CH 3 side groups and/or at least two side chains which carry a -CH 3 group .
  • the compounds X and Y are preferably silicone compounds and may be selected, for example, from non-volatile linear polydimethylsiloxanes of high molecular weight, having a degree of polymerization of more than 6, which have at least two -CH 3 side groups joined to the silicon atom and/or at least two side chains which carry a -CH 3 group.
  • Examples include the polymers described in the "Reactive Silicones" catalogue of the company Gelest Inc., 2004 edition, page 6, and more particularly the vinylmethylsiloxane-dimethylsiloxane copolymers (also called rubbers) of molecular weights of from 500 000 to 900 000 and in particular of a viscosity greater than 2 000 000 cSt.
  • peroxides which can be used in the context of the invention, mention may be made of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide and mixtures thereof.
  • the hydrosilylation reaction or the condensation reaction or else the crosslinking reaction in the presence of a peroxide between the compounds X and Y is accelerated by provision of heat, with the temperature of the system being raised, for example, to between 25°C and 180 0 C.
  • the system will react more particularly on the lashes.
  • the molar percentage of X relative to the entirety of the compounds X and Y i.e. the ratio X/ (X+Y) x 100, may range from 5% to 95%, preferably from 10% to 90%, more preferably still from 20% to 80%.
  • the molar percentage of Y relative to the entirety of the compounds X and Y i.e. the ratio Y/ (X+Y) x 100, may range from 5% to 95%, preferably from 10% to 90%, more preferably still from 20% to 80%.
  • the compound X may have a weight-average molecular mass (Mw) of from 150 to 1 000 000, preferably from 200 to 800 000, more preferably from 200 to 250 000.
  • the compound Y may have a weight-average molecular mass (Mw) of from 200 to 1 000 000, preferably from 300 to 800 000, more preferably from 500 to 250 000.
  • the compound X may represent from 0.5% to 95% by weight relative to the total weight of the compositions containing it, in particular relative to the total weight of each first and second composition, preferably from 1% to 90% by weight, and more preferably from 5% to 80% by weight.
  • the compound Y may represent from 0.05% to 95% by weight relative to the total weight of the compositions containing it, in particular relative to the total weight of each first and second composition, preferably from 1% to 90% by weight, and more preferably from 5% to 80% by weight.
  • the ratio between the compounds X and Y may be changed so as to modify the rate of reaction and hence the rate at which the film is formed, or else so as to adapt the properties of the resulting film (for example its adhesive properties) in accordance with the desired application .
  • the compounds X and Y may be present in a molar X/Y ratio of from 0.05 to 20 and more preferably from 0.1 to 10.
  • one at least of the compositions may comprise at least one silica, in particular a synthetic silica surface-treated with a hydrophobic agent (preferably a silicone agent) , in particular a surface- treated fumed silica, such as, for example, the silicas described below in the fillers or the gelling agents.
  • a hydrophobic agent preferably a silicone agent
  • fumed silica such as, for example, the silicas described below in the fillers or the gelling agents.
  • Possible examples include the treated fillers Cab-O- Sil ® TS-530, Aerosil ® R8200 and Wacker HDX H2000.
  • One at least of the first and second compositions comprises fibres.
  • fibre is meant an object of length L and diameter D such that L is greater than D, and preferably very much greater than D, D being the diameter of the circle within which the cross section of the fibre is inscribed.
  • L/D or form factor
  • the ratio L/D is selected from the range from 3.5 to 2500, preferably from 5 to 500, and more preferably from 5 to 150.
  • the fibres which can be used in the composition or compositions of the invention may be organic or inorganic fibres of synthetic or natural origin. They may be short or long, unitary or organized, for example braided, and hollow or solid. They may have any shape, and may more particularly have a circular or polygonal
  • the fibres have a length of from 1 ⁇ m to 10 mm, preferably from 0.1 mm to 5 mm and more preferably from 0.3 mm to 3 mm.
  • Their cross section may be included within a circle whose diameter is from 2 nm to 500 ⁇ m, preferably from 100 nm to 100 ⁇ m and more preferably from 1 ⁇ m to 50 ⁇ m.
  • the weight or linear density of the fibres is often given in denier or decitex, and represents the weight in grams per 9 km of yarn.
  • the fibres according to the invention preferably have a linear density selected from the range from 0.01 to 10 denier, preferably from 0.1 to 2 denier and more preferably from 0.3 to 0.7 denier.
  • the fibres may be those which are used in the manufacture of textiles, and more particularly fibres of silk, cotton, wool, flax, fibres of cellulose particularly those extracted more particularly from wood, from vegetables or from algae, or fibres of rayon, polyamide (Nylon ® ) , viscose, acetate, especially rayon acetate, or fibres of acrylic polymer, more particularly of polymethyl methacrylate or of poly-2- hydroxyethyl methacrylate, of polyolefin and more particularly of polyethylene or of polypropylene, or fibres of glass, silica, carbon, more particularly in graphite form, or fibres of polytetrafluoroethylene
  • fibres of insoluble collagen such as Teflon ®
  • polyesters such as Teflon ®
  • polyvinyl chloride or polyvinylidene chloride such as polyvinyl alcohol
  • polyacrylonitrile such as polyacrylonitrile
  • chitosan such as polyurethane
  • polyethylene phthalate such as polyamide/polyester fibres.
  • the fibres are preferably polyamide fibres (Nylon ® ) .
  • the fibres that are used in surgery such as the absorbable synthetic fibres prepared from glycolic acid and caprolactone
  • the fibres may be surface-treated or not and may be uncoated or coated with a protective coat.
  • Coated fibres which can be used in the invention include polyamide fibres coated with copper sulphide for an antistatic effect (for example "R-STAT” from Rhodia) or another polymer allowing a particular organization of the fibres (specific surface treatment) . Mention may also be made of the fibres coated with organic or inorganic pigments, such as the pigments cited later on below in the application.
  • the fibres which can be used in the composition or compositions according to the invention are preferably polyamide, cellulose or polyethylene fibres.
  • Their length (L) may be from 0.1 mm to 5 mm, preferably from 0.25 mm to 1.6 mm, and their mean diameter may be from 1 ⁇ m to 50 ⁇ m.
  • cellulose fibres or rayon fibres having a mean diameter of 50 ⁇ m and a length of from 0.5 mm to 6 mm, such as those sold under the name "Natural rayon flock fiber RClBE - N003 - M04" by the company Claremont Flock. It is also possible to use polyethylene fibres such as those sold under the name “Shurt Stuff 13 099 F” by the company Mini Fibers.
  • composition or compositions according to the invention comprises or comprise fibres referred to as "rigid" fibres, in contrast to the aforementioned fibres, which are not rigid fibres.
  • the rigid fibres which initially are substantially straight, when placed in a dispersing medium, do not undergo a substantial change in shape, a fact which is reflected in the angular condition defined below, which reflects a shape that may be described as still substantially straight and linear.
  • This angle condition reflects the stiffness of the fibres, which it is difficult to express by any other parameter for objects that are as small as the rigid fibres.
  • the stiffness of the fibres is manifested in the following angular condition: advantageously at least 50%, preferably at least 75% and more preferably at least 90% of the fibres, in numerical terms, are such that the angle formed between the tangent to the longitudinal central axis of the fibre and the straight line joining the said end to the point on the longitudinal central axis of the fibre corresponding to half the length of the fibre is less than 15°, and the angle formed between the tangent of the longitudinal central axis of the fibre at a point half-way along the fibre, and the straight line connecting one of the ends to the point on the longitudinal central axis of the fibre that corresponds to half the length of the fibre, is less than or equal to 15°, for a given fibre length of from 0.8 mm to 5 mm, preferably from 1 mm to 4 mm, preferably from 1 mm to 3 mm, and more preferably of 2 mm.
  • the abovementioned angle is measured at the two ends of the fibre and at a point half-way along the fibre; in other words, three measurements are taken in this case, and the average of the angles measured is less than or equal to 15°.
  • the tangent at any point on the fibre, forms an angle of less than 15°.
  • the angle formed by the tangent at a point on the fibre is the angle formed between the tangent to the longitudinal central axis of the fibre at the said point on the fibre, and the straight line connecting the end of the fibre that is closest to the said point to the point on the longitudinal central axis of the fibre that corresponds to half the length of the fibre.
  • the rigid fibres which can be used in the composition or compositions according to the invention have the same fibre length or a substantially identical length.
  • a numerical majority of rigid fibres in other words at least 50% of the rigid fibres, preferably at least 75% of the rigid fibres and more preferably at least 90% of the rigid fibres, in numerical terms, are required to satisfy the angular condition defined above.
  • the measurement which leads to the value of the angle is carried out for a given length of fibres; this length is included in the range from 0.8 mm to 5 mm, preferably from 1 to 4 mm, preferably from 1 to 3 mm, and more preferably 2 mm.
  • the medium in which the observation is made is a dispersing medium that ensures the effective dispersion of the rigid fibres - for example, water or an aqueous gel of clay or of associative polyurethane . It is even possible to make a direct observation of the composition containing the rigid fibres. A sample of the composition or of the prepared dispersion is placed between a slide and cover slip for observation under the microscope with a lens allowing a magnification of 2.5 and with full-field vision. Full-field vision allows the fibres to be viewed in their entirety.
  • the rigid fibres may be selected from fibres of a synthetic polymer selected from polyesters, polyurethanes, acrylic polymers, polyolefins, polyamides, in particular non-aromatic polyamides and aromatic polyimide-amides .
  • a synthetic polymer selected from polyesters, polyurethanes, acrylic polymers, polyolefins, polyamides, in particular non-aromatic polyamides and aromatic polyimide-amides .
  • Possible examples of rigid fibres include the following fibres :
  • Taille 3 mm (eight-lobed cross section), Fibre 265-34- R11-56T Taille 3 mm (round cross section) , Fibre Coolmax 50-34-591 Taille 3 mm (four-lobed cross section) by DuPont de Nemours;
  • polyamide fibres such as those sold under the names Trilobal Nylon 0.120-1.8 DPF, Trilobal Nylon 0.120-18 DPF and Nylon 0.120-6 DPF by Cellusuede products; or fibres obtained by chopping yarns sold under the name Fibre Nomex Brand 430 Taille 3 mm by DuPont de Nemours;
  • - fibres with a multi-layer structure comprising alternate layers of polymers selected from polyesters, acrylic polymers and polyamides, such as those described in documents EP-A-6921217, EP-A-686858 and
  • Particularly preferred rigid fibres are the aromatic polyimide-amide fibres.
  • Polyimide-amide yarns or fibres which can be used for the compositions of the invention are described, for example, in the document by R. Pigeon and P. Allard, Chimie Macromole Diagram Appliquee, 40/41 (1974), pages 139-158 (No. 600), or else in the documents US-A- 3 802 841, FR-A-2 079 785, EP-Al-O 360 728, EP-A-O 549 494, to which reference may be made.
  • Preferred aromatic polyimide-amide fibres are polyimide-amide fibres comprising repeating units of formula :
  • the fibres may be present in an amount of from 0.01% to 10% by weight, relative to the total weight of each composition comprising them, in particular relative to the total weight of each first or second composition, preferably from 0.1% to 5% by weight and more preferably from 0.5% to 3% by weight.
  • fibres may differ in their nature and/or in their dimensions, more particularly in their lengths. In this way it is possible to alter the features of the makeup obtained and/or the application properties of the mascara.
  • At least one of the first and second compositions used in the invention advantageously comprises a liquid fatty phase.
  • a liquid fatty phase in the sense of the patent application is a fatty phase which is liquid at ambient temperature (25°C) and atmospheric pressure (760 mmHg) and is composed of one or more non-aqueous fatty substances which are liquid at ambient temperature, also referred to as organic solvents or oils.
  • the oil may be selected from volatile oils and/or nonvolatile oils, and mixtures thereof.
  • the oil or oils may be present in an amount of from 0.5% to 90% by weight, preferably from 5% to 80% by weight, more preferably from 10% to 60% by weight and more preferably still from 20% to 55% by weight relative to the total weight of each composition comprising them, in particular relative to the total weight of each first and second composition.
  • a "volatile oil” for the purposes of the invention is an oil which is able to evaporate on contact with the lashes in less than one hour at ambient temperature and atmospheric pressure.
  • the volatile organic solvent or solvents and the volatile oils of the invention are organic solvents and volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapour pressure at ambient temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10 ⁇ to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg) .
  • the volatile oils are selected from oils possessing an evaporation rate greater than or equal to 0.002 mg/cm 2 /min.
  • the evaporation rate is measured as follow: 15 g of oil or of the mixture of oils to be tested are introduced into a crystallizing basin (diameter 7 cm) placed on a balance which is located within a chamber of approximately 0.3 m 3 and whose temperature (25°C) and hygrometry (relative humidity 50%) are regulated.
  • the liquid is left to evaporate freely, without agitation, with ventilation provided by a fan (rotary speed 2700 revolutions/minute and size 80> ⁇ 80 ⁇ 42 mm, for example the reference 8550 N from Papst-Motoren, the output corresponding to approximately 50 m 3 /hour) which is placed vertically above the crystallizing basin containing the solvent, the vanes being directed towards the crystallizing basin and at a distance of 20 cm from the base of the crystallizing basin.
  • the mass of oil remaining in the crystallizing basin is measured at regular intervals.
  • the evaporation rates are expressed in mg of oil evaporated per unit surface area (cm 2 ) and per unit time (minute) .
  • non-volatile oil is an oil which remains on the lashes at ambient temperature and atmospheric pressure for at least a number of hours and which has more particularly a vapour pressure of less than 10 ⁇ 3 mmHg
  • oils may be hydrocarbon oils, silicone oils, fluoro oils, or mixtures thereof.
  • a “hydrocarbon oil” is an oil containing principally hydrogen and carbon atoms and optionally oxygen, nitrogen, sulphur and/or phosphorus atoms.
  • the volatile hydrocarbon oils may be selected from hydrocarbon oils having 8 to 16 carbon atoms, and more particularly C8-C16 branched alkanes such as the C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2, 2, 4, 4, 6-pentamethylheptane) , isodecane and isohexadecane, and, for example, the oils sold under the trade names Isopars or Permetyls, branched C8-C16 esters such as isohexyl neopentanoate, and mixtures thereof.
  • Other volatile hydrocarbon oils may also be used, such as the petroleum distillates, more particularly those sold under the name Shell SoIt by Shell.
  • the volatile solvent is preferably selected from volatile hydrocarbon oils having 8 to
  • volatile oils which can be used are the volatile silicones, such as, for example, volatile linear or cyclic silicone oils, more particularly those having a viscosity ⁇ 8 centistokes (8 ⁇ lO ⁇ 6 m 2 /s) , and have more particularly 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having 1 to 10 carbon atoms.
  • Possible volatile silicone oils which can be used in the invention include, more particularly, octamethylcyclotetrasiloxane, decamethyl- cyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltri- siloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.
  • oils of general formula (I) include: 3-butyl-l, 1,1,3,5,5, 5-heptamethyltrisiloxane, 3-propyl-l, 1,1,3,5,5, 5-heptamethyltrisiloxane, and 3-ethyl-l, 1,1,3,5,5, 5-heptamethyltrisiloxane, corresponding to the oils of formula (I) for which R is a butyl group, a propyl group or an ethyl group, respectively.
  • volatile fluorine-containing solvents such as nonafluoromethoxybutane or perfluoro- methylcyclopentane .
  • composition or compositions may further comprise at least one non-volatile oil, selected more particularly from non-volatile hydrocarbon oils and/or silicone oils and/or fluoro oils.
  • non-volatile hydrocarbon oils include more particularly:
  • oils of plant origin such as the triesters of fatty acids and glycerol, in which the fatty acids may have varied chain lengths from C4 to C24, these chains being linear or branched and saturated or unsaturated; these oils are more particularly wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, maize oil, apricot oil, castor oil, karite oil, avocado oil, olive oil, soya oil, sweet almond oil, palm oil, rapeseed oil, cotton oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil or musk rose oil; or else caprylic/capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the
  • Rl represents the residue of a linear or branched fatty acid containing 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, more particularly a branched hydrocarbon chain, containing 1 to 40 carbon atoms, with the proviso that Rl + R2 is ⁇ 10, such as, for example, Purcellin oil (cetostearyl octanoate) , isopropyl myristate, isopropyl palmitate, C12 to C15 alcohol benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, octano
  • composition or compositions according to the invention comprise at least one non-volatile hydrocarbon oil having a molecular mass of more than 500 g/mol, preferably more than 600 g/mol and more preferably more than 650 g/mol, but not exceeding 15 000 g/mol, preferably not exceeding 10 000 g/mol and more preferably not exceeding 7500 g/mol.
  • the refractive index is preferably greater than 1.440 at 20 0 C (the refractive index being measured using a refractometer) and advantageously is greater than 1.450 and more preferably greater than 1.460.
  • a “hydrocarbon” compound is a compound containing principally carbon and hydrogen atoms and optionally one or more functions selected from hydroxyl, ester, ether and carboxyl functions. In particular these compounds are devoid of -Si-O- groups.
  • This non-volatile hydrocarbon oil may be selected from:
  • the non-volatile hydrocarbon oil is preferably selected from polybutenes.
  • the non-volatile hydrocarbon oil may represent from 0.5% to 40% by weight, preferably from 1% to 30% and more preferably from 5% to 20% by weight relative to the total weight of the composition comprising it, in particular relative to the total weight of each first and second composition.
  • the non-volatile silicone oils which can be used in the composition according to the invention may be nonvolatile polydimethylsiloxanes (PDMS) , polydimethyl- siloxanes containing alkyl or alkoxy groups pendantly and/or at the end of the silicone chain, these groups each having 2 to 24 carbon atoms, or phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldi- methicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates .
  • PDMS nonvolatile polydimethylsiloxanes
  • phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldi- meth
  • the fluoro oils which can be used in the invention are more particularly fluorosilicone oils, fluorine- containing polyethers and fluorosilicones as described in document EP-A-847752.
  • composition or compositions comprises or comprise at least one nonvolatile silicone oil and preferably a phenyl silicone oil .
  • the phenyl silicone oils which can be used in the present invention have a viscosity as measured at 25°C and atmospheric pressure of 5 to 100 000 cSt, and preferably of 5 to 10 000 cSt.
  • the silicone oil may be, for example, a phenyltrimethicone, a phenyldimethicone, a phenyltri- methylsiloxydiphenylsiloxane, a diphenyldimethicone, a diphenylmethyldiphenyltrisiloxane or a mixture of different phenyl silicone oils, and in particular may correspond to the following formula (A) :
  • R 9 and R 12 each independently are a Ci-C 30 alkyl radical, an aryl radical or an aralkyl radical,
  • - Rio and Rn each independently are a Ci-C 30 alkyl radical or an aralkyl radical
  • - u, v, w and x each independently are integers from 0 to 900, with the provisos that the sum v+w+x is different from 0 and that the sum u+v+w+x is from 1 to 900, in particular from 1 to 800.
  • R 9 is a Ci-C 2 O alkyl radical, a phenyl radical or an aralkyl radical of type R' -CeH 5 , R' being a Ci-C 5 alkyl, Ri 0 and Rn each independently are a Ci-C 2 O alkyl radical or an aralkyl radical of type R'-C ⁇ H 5 , R' being a Ci-C 5 alkyl, and R 12 is a Ci-C 20 alkyl radical.
  • R 9 is a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or else a phenyl, tolyl, benzyl or phenethyl radical
  • Ri 0 and Rn each independently are a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or else a tolyl, benzyl or phenethyl radical
  • Ri 2 is a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical.
  • the composition or compositions contains or contain a phenyl silicone oil having a viscosity of less than 500 cSt at 25°C, referred to as "low- viscosity phenyl silicone oil", and a phenyl silicone oil having a viscosity of at least 500 cSt at 25°C, referred to as "high-viscosity phenyl silicone oil”.
  • the low-viscosity phenyl silicone oil has a viscosity at 25°C of for example from 5 to 499 cSt, preferably from 5 to 300 cSt and more preferably from 5 to 100 cSt
  • the high-viscosity phenyl silicone oil has a viscosity at 25°C of, for example, from 500 to 10 000 cSt, preferably from 600 to 5000 cSt and more preferably from 600 to 3000 cSt.
  • phenyl silicone oils of low and high viscosity as defined above makes it possible to obtain, following deposition on the lashes, a film of composition which is particularly glossy, homogeneous and tenacious.
  • low-viscosity and high-viscosity phenyl silicone oils preferably conform to the formula (A) .
  • the first, low-viscosity phenyl silicone oil conforms to the formula (A) with the sum u+v+w+x being from 1 to 150 and more preferably from 1 to 100, or even from 1 to 50
  • the second, high-viscosity phenyl silicone oil conforms to the formula (A) with the sum u+v+w+x being from 151 to 900, more preferably from 160 to 800, or even from 160 to 500.
  • Re is a C1-C30 alkyl radical, an aryl radical or an aralkyl radical,
  • n is an integer from 0 to 100 and more preferably less than 100
  • m is an integer from 0 to 100, with the proviso that the sum m+n is from 1 to 100 and more preferably is less than 100.
  • Rs is a C1-C20 alkyl radical, a phenyl radical or an aralkyl radical of type R' -CeH 5 , R' being a Ci-C 5 alkyl.
  • Rs is a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or else a phenyl, tolyl, benzyl or phenethyl radical.
  • Rs is a methyl radical.
  • the low-viscosity phenyl silicone oils which can be used in the invention include the oils DC556
  • Silbione 70 633 V 30 (28 cSt) from Rhone Poulenc, the oils 15 M 40 (50 to 100 cSt) , 15 M 50 (20 to 25 cSt) from PCR, the oils SF 1550 (25 cSt) and PK 20 (20 cSt) from Bayer , the oil Belsil PDM 200 (200 cSt) from
  • the high-viscosity phenyl silicone oils which can be used in the invention include the oils 15 M 30 from PCR (500 cSt) and Belsil PDM 1000 (1000 cSt) from Wacker. The values in brackets represent the viscosities at 25°C.
  • each composition, and in particular each of the first and second compositions comprises at least one low-viscosity phenyl silicone oil and at least one high-viscosity phenyl silicone oil.
  • the non-volatile silicone oils may represent from 1% to 90%, preferably from 5% to 60%, more preferably from 10% to 50% and more preferably still from 30% to 50% of the total weight of the composition comprising them, in particular of the total weight of each first and second composition .
  • first and second compositions employed in the method according to the invention are anhydrous.
  • an “anhydrous” composition is one comprising less than 5% by weight of water, preferably less than 3% by weight of water, relative to the total weight of the composition, and more preferably devoid of water.
  • At least one of the first and second compositions may comprise an aqueous phase.
  • the aqueous phase may be composed essentially of water; it may also comprise a mixture of water and water- miscible solvent (with a miscibility in water of more than 50% by weight at 25°C), such as lower monoalcohols having 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol and dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes and mixtures thereof.
  • water- miscible solvent with a miscibility in water of more than 50% by weight at 25°C
  • lower monoalcohols having 1 to 5 carbon atoms, such as ethanol and isopropanol
  • glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol and dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes
  • the aqueous phase (water and, where appropriate, the water-miscible solvent) may be present in an amount of from 5% to 95% by weight, relative to the total weight of each composition, preferably from 10% to 85% by weight and more preferably from 2% to 80% by weight.
  • At least one of the first and second compositions may further comprise at least one wax, which may be animal, plant, mineral or synthetic in origin.
  • the wax considered in the context of the present invention is, generally speaking, a lipophilic compound which is solid at ambient temperature (25°C) and exhibits a reversible solid/liquid state change, having a melting point greater than or equal to 30 0 C and possibly up to 120 0 C.
  • a lipophilic compound which is solid at ambient temperature (25°C) and exhibits a reversible solid/liquid state change, having a melting point greater than or equal to 30 0 C and possibly up to 120 0 C.
  • the waxes suitable for the invention may have a melting point greater than approximately 45°, and in particular greater than 55°C.
  • the melting point of the wax can be measured using a differential scanning calorimeter (DSC) , an example being the calorimeter sold under the name DSC 30 by Mettler.
  • DSC differential scanning calorimeter
  • the measurement protocol is as follows: A 15 mg sample of product in a crucible is subjected to a first temperature rise from 0 0 C to 120 0 C, at a heating rate of 10°C/minute, and is cooled from 120 0 C to 0 0 C at a cooling rate of 10°C/minute, and finally is subjected to a second temperature rise from 0 0 C to 120 0 C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the power difference absorbed by the empty crucible and by the crucible containing the sample of product is measured as a function of the temperature.
  • the melting point of the compound is the temperature value 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 waxes which can be used in the first and second compositions according to the invention are selected from solid waxes which are deformable or non-deformable at ambient temperature and are of animal, plant, mineral or synthetic origin, and mixtures thereof.
  • the wax may also have a hardness of from 0.05 MPa to 30 MPa, and preferably from 6 MPa to 15 MPa. The hardness is determined by measuring the compression force measured at 20 0 C with the aid of the texturometer sold under the name TA-TX2i by Rheo, equipped with a stainless steel cylinder with a diameter of 2 mm which moves at a measuring speed of 0.1 mm/s and penetrates the wax to a depth of 0.3 mm.
  • the measurement protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 20 0 C. The melted wax is poured into a container with a diameter of 30 mm and a depth of 20 mm. The wax is recrystallized at ambient temperature (25°C) for 24 hours and then the wax is kept at 20 0 C for at least 1 hour before the hardness measurement is performed. The value of the hardness is the maximum compression force measured, divided by the surface area of the cylinder of the texturometer that is in contact with the wax.
  • hydrocarbon waxes such as beeswax, lanolin wax and Chinese insect waxes
  • montan wax, microcrystalline waxes, paraffins and ozokerite polyethylene waxes, waxes obtained by Fischer-Tropsch synthesis, and waxy copolymers, and also their esters.
  • waxes obtained by catalytic hydrogenation of animal or plant oils having C8-C32 linear or branched fatty chains Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils having C8-C32 linear or branched fatty chains.
  • hydrogenated jojoba oil isomerized jojoba oil, such as the trans isomerized partially hydrogenated jojoba oil manufactured and sold by Desert Whale under the commercial reference ISO-JOJOBA-50 ® , hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin oil, the di (1,1,1- trimethylolpropane) tetrastearate sold under the name Hest 2T-4S by Heterene and the di (1,1,1- trimethylolpropane) tetrabehenate sold under the name Hest 2T-4B by Heterene.
  • waxes obtained by transesterification and hydrogenation of vegetable oils such as castor oil or olive oil, such as the waxes sold under the names Phytowax ricin 16L64 ® and 22L73 ® and Phytowax Olive 18L57 by Sophim. Waxes of this kind are described in Patent Application FR-A- 2792190.
  • silicone waxes which may advantageously be substituted polysiloxanes, preferably having a low melting point.
  • substituted linear polysiloxanes composed essentially (with the exception of the end groups) of units of formulae II and III, in the respective molar proportions m and n:
  • each R' independently represents an optionally unsaturated (linear or branched) alkyl having 6-30 carbon atoms, or else a group -X-R", each X independently representing:
  • each R" independently represents an optionally unsaturated alkyl group having 6 to 30 carbon atoms
  • - m is a number from 0 to 400, and in particular from 0 to 100,
  • - n is a number from 1 to 200, and in particular from 1 to 100, the sum (m+n) being less than 400, and in particular less than or equal to 100.
  • silicone waxes are known or can be prepared in accordance with known processes.
  • the commercial silicone waxes of this type include, more particularly, those sold under the names Abilwax 9800, 9801 or 9810 (Goldschmidt) , KF910 and KF7002 (Shin Etsu) , or 176-1118-3 and 176-11481 (General Electric) .
  • silicone waxes which can be used may also be selected from the compounds of formula:
  • Ri represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 6 to 30 carbon atoms, or a group of formula: o o
  • R 2 represents an alkyl group of 6 to 30 C, an alkoxy group having 6 to 30 C or a group of formula :
  • R" being an alkyl having 6 to 30 carbon atoms
  • z is a number from 1 to 100.
  • the silicone waxes of formula (IV) include more particularly the alkyldimethicones or alkoxy- dimethicones such as the following commercial products: Abilwax 2428, 2434 and 2440 (Goldschmidt) , or VP 1622 and VP 1621 (Wacker) , and also (C20-C60)- alkyldimethicones, in particular (C30-C45) alkyldimethicones, such as the silicone wax sold under the name SF-1642 by GE-Bayer Silicones.
  • alkyldimethicones or alkoxy- dimethicones such as the following commercial products: Abilwax 2428, 2434 and 2440 (Goldschmidt) , or VP 1622 and VP 1621 (Wacker)
  • C20-C60 alkyldimethicones
  • C30-C45 alkyldimethicones
  • hydrocarbon waxes which are modified with silicone or fluoro groups such as, for example, the following: siliconyl candelilla, siliconyl beeswax and Fluorobeeswax from Koster Keunen.
  • the waxes may also be selected from fluorowaxes.
  • the first and second compositions according to the invention may comprise at least one wax referred to as a tacky wax and hence possessing a tack of greater than or equal to 0.7 N. s and a hardness of less than or equal to 3.5 MPa.
  • the tacky wax used may more particularly possess a tack of from 0.7 N. s to 30 N.s, in particular greater than or equal to 1 N.s, more particularly from 1 N.s to 20 N.s, in particular greater than or equal to 2 N.s, more particularly from 2 N.s to 10 N.s, and in particular from 2 N.s to 5 N.s.
  • the tack of the wax is determined by measuring the change in force (compression force or drawing force) as a function of time, at 20 0 C, using the texturometer sold under the name TA-TX2i ® by Rheo, equipped with a conical acrylic polymer spindle forming an angle of 45°.
  • the measurement protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 10 0 C. The melted wax is poured into a container with a diameter of 25 mm and a depth of 20 mm. The wax is recrystallized at ambient temperature (25°C) for 24 hours such that the surface of the wax is flat and smooth, and then the wax is kept at 20 0 C for at least 1 hour before the tack is measured.
  • the texturometer spindle is moved at a speed of 0.5 mm/s and then penetrates the wax to a depth of 2 mm.
  • the spindle is held still for 1 second (corresponding to the relaxation time) and then is withdrawn at a speed of 0.5 mm/s.
  • the tack corresponds to the integral of the curve of the force as a function of time for the part of the curve that corresponds to negative values of the force (drawing force) .
  • the tack value is expressed in N.s.
  • the tacky wax which can be used generally has a hardness of less than or equal to 3.5 MPa, in particular from 0.01 MPa to 3.5 MPa, more particularly from 0.05 MPa to 3 MPa, and even from 0.1 MPa to 2 . 5 MPa .
  • the hardness is measured according to the protocol described above.
  • a tacky wax it is possible to use a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group containing 20 to 40 carbon atoms), alone or in a mixture, in particular a C20-C40 alkyl 12- (12' -hydroxystearyloxy) - stearate .
  • a wax of this kind is sold more particularly under the names Kester Wax K 82 P ® and Kester Wax K 80 P ® by Koster Keunen.
  • the aforementioned waxes generally have a melting point commencing at below 45°C.
  • the wax or waxes may be present in the form of an aqueous wax microdispersion .
  • An aqueous wax microdispersion is an aqueous dispersion of wax particles in which the size, expressed as the volume- average "effective" diameter D [4, 3], of the said wax particles is less than or equal to approximately 1 ⁇ m.
  • the wax microdispersions are stable dispersions of colloidal wax particles and are described more particularly in "Microemulsions Theory and Practice", L. M. Prince Ed., Academic Press (1977) pages 21-32.
  • wax microdispersions may be obtained by melting the wax in the presence of a surfactant, and optionally part of the water, and then progressively adding hot water with stirring. The intermediate formation of a water-in-oil emulsion is observed, followed by a phase inversion, leading finally to an oil-in-water microemulsion . On cooling, a stable microdispersion of solid colloidal wax particles is obtained.
  • the wax microdispersions may also be obtained by stirring the mixture of wax, surfactant and water using stirrer means such as ultrasound, a high-pressure homogenizer or turbines.
  • the particles of the wax microdispersion preferably have average dimensions of less than 1 ⁇ m (more particularly from 0.02 ⁇ m to 0.99 ⁇ m) , preferably less than 0.5 ⁇ m (more particularly from 0.06 ⁇ m to 0.5 ⁇ m) .
  • These particles are composed essentially of a wax or of a mixture of waxes. They may, however, comprise, to a minor extent, oily and/or pasty fatty additives, a surfactant and/or a customary fat-soluble additive/active.
  • the waxes may represent from 0.1 to 70% by weight, relative to the total weight of each composition, in particular relative to the total weight of each first and second composition, more preferably from 1% to 40% and more preferably still from 2% to 30% by weight.
  • At least one of the first and second compositions may comprise a film-forming polymer.
  • film-forming polymer means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, of forming a continuous film that adheres to a support and especially to the lashes.
  • the film-forming polymer may be present in a solids content (or active material content) ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1% to 15% by weight relative to the total weight of each composition.
  • 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.
  • free-radical film-forming polymer means a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopoly- merizing (unlike polycondensates) .
  • the film-forming polymers of free-radical type may be, in particular, vinyl polymers or copolymers, in particular acrylic polymers.
  • the vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acidic group and/or esters of these acidic monomers and/or amides of these acidic monomers .
  • Monomers bearing an acidic group which may be used are ⁇ , ⁇ -ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth) acrylic acid and crotonic acid are preferably used, and more preferably (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 C1-C30 and preferably C1-C20 alkyl, (meth) acrylates of an aryl, in particular of a C ⁇ -Cio aryl, and (meth) acrylates of a hydroxyalkyl, in particular of a C2-C6 hydroxyalkyl.
  • acrylic acid esters also known as (meth) acrylates
  • alkyl in particular of a C1-C30 and preferably C1-C20 alkyl
  • aryl in particular of a C ⁇ -Cio aryl
  • hydroxyalkyl in particular of a C2-C6 hydroxyalkyl
  • alkyl (meth) acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl 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 that are particularly preferred are the 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 that may be mentioned are (meth) acrylamides, and especially N- alkyl (meth) acrylamides, in particular of a C2-C12 alkyl.
  • N-alkyl (meth) acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide .
  • 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 above.
  • vinyl esters examples include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate .
  • Styrene monomers that may be mentioned are styrene and ⁇ -methylstyrene .
  • polyurethanes examples include polyurethanes, polyesters, polyester- amides, polyamides, epoxyester resins and polyureas.
  • the polyurethanes may be chosen from anionic, cationic, nonionic and amphoteric polyurethanes, polyurethane- acrylics, polyurethane-polyvinylpyrrolidones, poly- ester-polyurethanes, polyether-polyurethanes, polyureas and polyurea/polyurethanes, and mixtures thereof.
  • the polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols.
  • the dicarboxylic acid may be aliphatic, alicyclic or aromatic.
  • acids that may be mentioned are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2, 2-dimethylglutaric acid, azeleic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclo- hexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2, 5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2, 5-naphthalenedicarboxylic acid or 2, 6-naphthalenedicarboxylic acid.
  • dicarboxylic acid monomers may be used alone or as a combination of at least two dicarboxylic acid monomers.
  • the ones preferentially chosen are phthalic acid, isophthalic acid and terephthalic acid.
  • the diol may be chosen from aliphatic, alicyclic and aromatic diols.
  • the diol used is preferably chosen 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 trimethylol- propane .
  • the polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycon- densation of diacids with diamines or amino alcohols.
  • Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para-phenylenedi- amine.
  • An amino alcohol that may be used is monoethanolamine .
  • the polyester may also comprise at least one monomer bearing at least one group -SO 3 M, with M representing a hydrogen atom, an ammonium ion NH 4 + or a metal ion such as, for example, an Na + , Li + , K + , Mg 2+ , Ca 2+ , Cu 2+ , Fe 2+ or Fe 3+ ion.
  • a difunctional aromatic monomer comprising such a group -SO 3 M may be used in particular.
  • the aromatic nucleus of the difunctional aromatic monomer also bearing a group -SO3M as described above may be chosen, for example, from benzene, naphthalene, anthracene, biphenyl, oxybiphenyl, sulphonylbiphenyl and methylenebiphenyl nuclei.
  • difunctional aromatic monomers also bearing a group -SO3M mention may be made of: sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid, 4-sulphonaphthalene-2 , 7-dicarboxylic acid.
  • the copolymers preferably used are those based on isophthalate/sulphoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexanedimethanol, isophthalic acid and sulphoisophthalic acid.
  • the polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac gum, dammar resins, elemi gums, copal resins and cellulose polymers, and mixtures thereof.
  • the film-forming polymer may be a water-soluble polymer and may be present in an aqueous phase of the first and/or second composition; the polymer is thus solubilized in the aqueous phase of the composition.
  • the film-forming polymer may be a polymer dissolved in a liquid fatty phase comprising organic solvents or oils such as those described above (the film-forming polymer is thus the said to be a liposoluble polymer) .
  • the liquid fatty phase preferably comprises a volatile oil, optionally mixed with a non-volatile oil, the oils possibly being chosen from those mentioned above.
  • liposoluble polymers examples include copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present) , an ⁇ -olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group comprises from 2 to 18 carbon atoms) or an allylic or methallylic ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) .
  • copolymers may be crosslinked with the aid of crosslinking agents, which may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octane- dioate, divinyl dodecanedioate and divinyl octadecane- dioate .
  • crosslinking agents may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octane- dioate, divinyl dodecanedioate and divinyl octadecane- dioate .
  • copolymers examples include the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/ octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/ 1-octadecene, vinyl acetate/1-dodecene, vinyl stearate/ ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2, 2-dimethyloctan- oate/vinyl laurate, allyl 2, 2-dimethylpentanoate/vinyl laurate, vinyl dimethylpropionate/vinyl stearate, allyl dimethylpropionate/vinyl stearate, vinyl vinyl dimethylpropionat
  • liposoluble film-forming polymers examples include liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, and alkyl radicals containing from 10 to 20 carbon atoms.
  • Such liposoluble copolymers may be chosen from polyvinyl stearate, polyvinyl stearate crosslinked with the aid of divinylbenzene, of diallyl ether or of diallyl phthalate, polystearyl (meth) acrylate, poly- vinyl laurate and polylauryl (meth) acrylate copolymers, it being possible for these poly (meth) acrylates to be crosslinked with the aid of ethylene glycol dimeth- acrylate or tetraethylene glycol dimethacrylate .
  • the liposoluble copolymers defined above are known and are described in particular in patent application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000. Mention may also be made of liposoluble homopolymers, and in particular those resulting from the homopolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals containing from 2 to 24 carbon atoms.
  • liposoluble homopolymers examples include: polyvinyl laurate and polylauryl (meth) acrylates, these poly (meth) acrylates possibly being crosslinked using ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate .
  • the first and/or second composition of the method according to the invention comprises at least one polyvinyl laurate film-forming polymer.
  • liposoluble film-forming polymers which may be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched, saturated or unsaturated Ci-Cs alkyl radical, for instance ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still C3 to C20 alkene.
  • polyalkylenes and in particular copolymers of C2-C20 alkenes such as polybutene, alkylcelluloses with a linear or branched, saturated or unsaturated Ci-Cs alkyl radical, for instance ethylcellulose and propylcellulose
  • VP vinylpyrrolidone
  • VP copolymers which may be used in the invention, mention may be made of the copolymers of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP) , VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate.
  • PVP polyvinylpyrrolidone
  • silicone resins which are generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers.
  • the nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters "MDTQ” characterizing a type of unit.
  • MDTQ polymethylsilsesqui- oxane resins
  • Examples of commercially available polymethylsilsesqui- oxane resins that may be mentioned include those sold: by the company Wacker under the reference Resin MK, such as Belsil PMS MK; by the company Shin-Etsu under the reference KR-220L.
  • Siloxysilicate resins that may be mentioned include trimethyl siloxysilicate (TMS) resins such as those sold under the reference SR 1000 by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of the trimethyl siloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name KF-7312J by the company Shin-Etsu, and DC 749 and DC 593 by the company Dow Corning.
  • TMS trimethyl siloxysilicate
  • silicone resin copolymers such as those mentioned above with polydimethyl- siloxanes, for instance the pressure-sensitive adhesive copolymers sold by the company Dow Corning under the reference Bio-PSA and described in document US 5 162 410, or the silicone copolymers derived from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane, as described in document WO 2004/073626.
  • silicone polyamides of the polyorganosiloxane type such as those described in documents US-A-5 874 069, US-A-5 919 441,
  • the film- forming polymer is a film-forming linear block ethylenic polymer, which preferably comprises at least a first block and at least a second block with different glass transition temperatures (Tg) , the said first and second blocks being linked together via an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
  • Tg glass transition temperatures
  • the first and second blocks of the block polymer are mutually incompatible.
  • Such polymers are described, for example, in document EP 1 411 069 or WO 04/028488.
  • the film-forming polymer may also be present in the first and/or second composition in the form of particles dispersed in an aqueous phase or in a nonaqueous solvent phase, which is generally known as a latex or pseudolatex.
  • a latex or pseudolatex The techniques for preparing these dispersions are well known to those skilled in the art .
  • Aqueous dispersions of film-forming polymers that may be used include the acrylic dispersions sold under the names Neocryl XK-90 ® , Neocryl A-1070 ® , Neocryl A-1090 ® , Neocryl BT-62 ® , Neocryl A-1079 ® and Neocryl A-523 ® by the company Avecia-Neoresins, Dow Latex 432 ® by the company Dow Chemical, Daitosol 5000 AD ® or Daitosol 5000 SJ ® by the company Daito Kasey Kogyo; Syntran 5760 ® by the company Interpolymer, Allianz OPT by the company Rohm & Haas, aqueous dispersions of acrylic or styrene/acrylic polymers sold under the brand name Joncryl ® by the company Johnson Polymer, or the aqueous dispersions of polyurethane sold under the names Neorez R-981 ® and Neorez R-974 ® by the company Avecia-Ne
  • non-aqueous film-forming polymer dispersions examples include acrylic dispersions in isododecane, for instance Mexomer PAP ® from the company Chimex, and dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described especially in document WO 04/055081.
  • the compositions according to the invention may comprise a plasticizer that promotes the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from any compound known to those skilled in the art as being capable of fulfilling the desired function.
  • At least one of the first and second compositions used in the process according to the invention may comprise at least one colorant chosen, for example, from pigments, nacres, dyes and materials with an effect, and mixtures thereof.
  • colorants may be present in a content ranging from 0.01% to 50% by weight and preferably from 0.01% to 30% by weight relative to the weight of each first and second composition or relative to the total weight of the composition when A and B are present in the same composition .
  • the pigments that are useful in the present invention may be in the form of powder or of pigmentary paste.
  • dyes should be understood as meaning compounds, generally organic, which are soluble in at least one oil or in an aqueous-alcoholic phase.
  • pigments should be understood as meaning white or coloured, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify the resulting film.
  • nacres or nacreous pigments should be understood as meaning coloured particles of any form, which may or may not be iridescent, especially produced by certain molluscs in their shell or else synthesized, and which have a colour effect via optical interference .
  • the pigment may be an organic pigment.
  • organic pigment means any pigment that satisfies the definition in Ullmann' s encyclopaedia in the chapter on organic pigments.
  • the organic pigment may especially be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.
  • the organic pigment (s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanin blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17
  • These pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be composed especially of particles comprising an inorganic nucleus at least partially coated with an organic pigment and at least one binder to fix the organic pigments to the nucleus. Examples that may also be mentioned include pigmentary pastes of organic pigments such as the products sold by the company Hoechst under the names:
  • Cosmenyl FB Pigment Red 5 (CI 12490);
  • the pigment may also be a lake.
  • the term "lake” means insolubilized dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use .
  • the inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.
  • D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).
  • An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850 : 1 ) .
  • the pigment may also be a pigment with special effects.
  • pigments with special effects means pigments that generally create a non-uniform coloured appearance (characterized by a certain shade, a certain vivacity and a certain lightness) that changes as a function of the conditions of observation (light, temperature, observation angles, etc.). They thus contrast with white or coloured pigments that afford a standard uniform opaque, semi-transparent or transparent shade.
  • pigment with special effects Two types of pigment with special effects exist: those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a high refractive index, such as nacres or flakes.
  • Pigments with special effects include nacreous pigments such as 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 especially with ferric blue or with chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.
  • Pigments with an interference effect may also be made of pigments with an interference effect that are not fixed onto a substrate, for instance liquid crystals (Helicones HC from Wacker) , holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek) .
  • Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
  • Quantum dots are luminescent semiconductive nanoparticles capable of emitting, under light excitation, irradiation with a wavelength of between 400 nm and 700 nm. These nanoparticles are known from - li ⁇ the literature. They may be manufactured in particular according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications cited therein, and also in the following publications: Dabboussi B. O. et al . "(CdSe)ZnS core-shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites" Journal of Physical Chemistry B, vol. 101, 1997, pp.
  • Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments and thermochromic pigments.
  • the pigment may be a mineral pigment.
  • mineral pigment means any pigment that satisfies the definition in Ullmann' s encyclopaedia in the chapter on inorganic pigments.
  • mineral pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also iron oxide or chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium dioxide.
  • the following mineral pigments may also be used: Ta2 ⁇ 0 5 , Ti 3 O 5 , Ti 2 O 3 , TiO, ZrO 2 as a mixture with TiO 2 , ZrO 2 , Nb 2 O 5 , CeO 2 , ZnS.
  • the pigment may also be a nacreous pigment such as white nacreous pigments, for example mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica coated with titanium and with iron oxides, mica coated with titanium and especially with ferric blue or chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also nacreous pigments based on bismuth oxychloride.
  • nacreous pigments such as white nacreous pigments, for example mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica coated with titanium and with iron oxides, mica coated with titanium and especially with ferric blue or chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also nacreous pigments based on bismuth oxychloride.
  • examples that may be mentioned include the Cellini pigments sold by Engelhard (Mica-TiO 2 -lake) , Prestige sold by Eckart (Mica
  • multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicates, and aluminium, may be envisaged.
  • the size of the pigment that is useful in the context of the present invention is generally between 10 nm and 200 ⁇ m, preferably between 20 nm and 80 ⁇ m and more preferentially between 30 nm and 50 ⁇ m.
  • the pigments may be dispersed in the product by means of a dispersant.
  • the dispersant serves to protect the dispersed particles against agglomeration or flocculation .
  • This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they can physically or chemically attach to the surface of the pigments.
  • These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium.
  • 12-hydroxystearic acid esters and Cs to C 2 o fatty acid esters of polyols such as glycerol or diglycerol are used, such as poly (12-hydroxystearic acid) stearate with a molecular weight of about 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel PlOO by the company Uniqema, and mixtures thereof.
  • poly (12-hydroxystearic acid) stearate with a molecular weight of about 750 g/mol such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or poly
  • dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.
  • the polydihydroxystearic acid and the 12-hydroxystearic acid esters are preferably intended for a hydrocarbon- based or fluorinated medium, whereas the mixtures of oxyethylene/oxypropylenated dimethylsiloxane are preferably intended for a silicone medium.
  • compositions according to the invention may comprise at least one filler, especially in a content ranging from 0.01% to 50% by weight and preferably ranging from 0.01% to 30% by weight relative to the total weight of each first and second composition or relative to the total weight of the composition when A and B are present in the same composition.
  • the fillers may be mineral or organic and of any form, platelet- shaped, spherical or oblong, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.).
  • talc Mention may be made of talc, mica, silica, silica surface-treated with a hydrophobic agent, kaolin, polyamide powder, for instance Nylon ® (Orgasol ® from Atochem) , poly- ⁇ -alanine powder and polyethylene powder, tetrafluoroethylene polymer powders, (Teflon ® ) , lauroyllysine, starch, boron nitride, expanded hollow polymer microspheres such as those made of polyvinylidene chloride/acrylonitrile, for instance Expancel ® (Nobel Industrie), acrylic acid copolymers (Polytrap ® from Dow Corning) and silicone resin microbeads (for example Tospearls ® from Toshiba) , elastomeric polyorgano- siloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads ® from
  • compositions according to the invention may also contain ingredients commonly used in cosmetology, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, fragrances, acidifying or basifying agents, preserving agents, sunscreens, surfactants, antioxidants, fibres and care agents, or mixtures thereof.
  • ingredients commonly used in cosmetology such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, fragrances, acidifying or basifying agents, preserving agents, sunscreens, surfactants, antioxidants, fibres and care agents, or mixtures thereof.
  • the gelling agents that may be used in the compositions according to the invention may be organic or mineral, and polymeric or molecular, hydrophilic or lipophilic gelling agents.
  • Mineral lipophilic gelling agents that may be mentioned include optionally modified clays, for instance hectorites modified with a Cio to C22 fatty acid ammonium chloride, for instance hectorite modified with distearyldimethylammonium chloride, for instance the product sold under the name "Bentone 38V ® " by the company Elementis.
  • fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 ⁇ m.
  • a hydrophobic silica is then obtained.
  • the hydrophobic groups may be: trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane .
  • Silicas thus treated are known as "silica silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R812 ® by the company Degussa, and Cab-O-Sil TS- 530 ® by the company Cabot;
  • silica thus treated are known as "silica dimethyl silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R972 ® and Aerosil R974 ® by the company Degussa, and Cab-O-Sil TS-610 ® and Cab-O-Sil TS-720 ® by the company Cabot.
  • the hydrophobic fumed silica particularly has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.
  • the polymeric organic lipophilic gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6 ® , KSG16 ® and KSG18 ® from Shin-Etsu, Trefil E-505C ® or Trefil E-506C ® from Dow Corning, Gransil SR-CYC ® , SR DMF 10 ® , SR-DC556 ® , SR 5CYC gel ® , SR DMF 10 gel ® and SR DC 556 gel ® from Grant Industries and SF 1204 ® and JK 113 ® from General Electric; ethylcellulose, for instance the product sold under the name Ethocel by Dow Chemical; polycondensates of polyamide type resulting from condensation between ( ⁇ ) at least one acid chosen from dicarboxylic acids containing at least 32 carbon atoms, such as fatty acid dimers, and ( ⁇ ) an alkylenedi
  • fatty acid esters of dextrin such as dextrin palmitates, especially the products sold under the name Rheopearl Tl/ or Rheopearl Kl/ by the company Chiba Flour.
  • the lipophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 40% by weight, preferably from 0.5% to 20% and better still from 1% to 15% by weight relative to the total weight of the composition comprising them, in particular to the weight of each first and second composition.
  • Hydrophilic or water-soluble gelling agents that may be mentioned include: - homopolymers or copolymers of acrylic or methacrylic acid or the salts 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 the polyacrylic acids of Synthalen K type;
  • water-soluble gelling polymers As other examples of water-soluble gelling polymers, mention may be made of:
  • proteins of plant origin such as wheat or soybean proteins
  • proteins of animal origin such as keratins, for example keratin hydrolysates and sulphonic keratins
  • cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, 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;
  • - associative polyurethanes such as the C16-OE120-C16 polymer from the company Servo Delden (sold under the name Ser Ad FXIlOO, which is a molecule containing urethane functions and having a weight-average molecular weight of 1300), OE being an oxyethylene unit, Rheolate 205 containing urea functions, sold by the company Rheox, or Rheolate 208 or 204 (these polymers being sold in pure form) or DW 1206B from Rohm & Haas, containing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% in water.
  • Ser Ad FXIlOO which is a molecule containing urethane functions and having a weight-average molecular weight of 1300
  • OE being an oxyethylene unit
  • Rheolate 205 containing urea functions sold by the company Rheox
  • Rheolate 208 or 204 these polymers being sold
  • solutions or dispersions of these associative polyurethanes especially in water or in aqueous-alcoholic medium.
  • examples of such polymers include Ser Ad FXlOlO, Ser Ad FX1035 and Ser Ad 1070 from the company Servo Delden, and Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Rheox.
  • Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Rheox.
  • - mucopolysaccharides such as hyaluronic acid and chondroitin sulphates, and mixtures thereof.
  • the hydrophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 20% by weight, preferably from 0.5% to 10% and better still from 0.8% to 5% by weight relative to the total weight of each first and second composition .
  • compositions according to the invention may contain emulsifying surfactants, which are especially present in a proportion ranging from 0.1% to 30% by weight, better still from 1% to 15% and even better still from 2% to 10% relative to the total weight of each composition.
  • These surfactants may be chosen from anionic, nonionic, amphoteric and zwitterionic surfactants.
  • the surfactants preferentially used in the first and second compositions according to the invention are chosen from: a) nonionic surfactants with an HLB of greater than or equal to 8 at 25°C, used alone or as a mixture; mention may be made especially of:
  • ethers which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups of glycerol;
  • - oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) of fatty alcohols (especially of C8-C24 and preferably C12-C18 alcohol) , such as oxyethylenated cetearyl alcohol ether containing 30 oxyethylene groups (CTFA name Ceteareth-30) and the oxyethylenated ether of the mixture of C12-C15 fatty alcohols comprising 7 oxyethylene groups (CTFA name C12-15 Pareth-7 sold under the name Neodol 25-7 ® by Shell Chemicals) ;
  • CTFA name Ceteareth-30 oxyethylenated cetearyl alcohol ether containing 30 oxyethylene groups
  • CTFA name C12-15 Pareth-7 sold under the name Neodol 25-7 ® by Shell Chemicals
  • - fatty acid esters (especially of a C8-C24 and preferably C16-C22 acid) of polyethylene glycol (which may comprise from 1 to 150 ethylene glycol units), such as PEG-50 stearate and PEG-40 monostearate sold under the name Myrj 52P by the company ICI Uniqema;
  • glyceryl stearate polyethoxylated with 30 ethylene oxide groups for instance the product Tagat S sold by the company Goldschmidt, glyceryl oleate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat O sold by the company Goldschmidt, glyceryl cocoate polyethoxylated with 30 ethylene oxide groups, for instance the product Varionic LI 13 sold by the company Sherex, glyceryl isostearate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat L sold by the company
  • nonionic surfactants with an HLB of less than 8 at 25°C optionally combined with one or more nonionic surfactants with an HLB of greater than 8 at 25°C, as mentioned above, such as:
  • sucrose stearate sucrose cocoate and sorbitan stearate, and mixtures thereof, for instance Arlatone 2121 sold by the company ICI;
  • fatty acid esters (especially of a C8-C24 and preferably C16-C22 acid) of polyols, especially of glycerol or of sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name Tegin M by the company Goldschmidt, glyceryl laurate such as the product sold under the name Imwitor 312 by the company HuIs, polyglyceryl-2 stearate, sorbitan tristearate or glyceryl ricinoleate; - the mixture of cyclomethicone/dimethicone copolyol sold under the name Q2-3225C by the company Dow Corning.
  • anionic surfactants such as:
  • - C16-C30 fatty acid salts especially those derived from amines, for instance triethanolamine stearate;
  • Croda and cetyl phosphate (Amphisol K from the company DSM Nutritional Products) ;
  • sulphosuccinates such as Disodium PEG-5 citrate lauryl sulphosuccinate and Disodium ricinoleamido MEA sulphosuccinate;
  • alkyl ether sulphates such as sodium lauryl ether sulphate
  • Triethanolamine stearate is most particularly suitable for the invention. It is generally obtained by simple mixing of stearic acid and triethanolamine. Surfactants that allow an oil-in-water or wax-in-water emulsion to be obtained are preferably used.
  • compositions according to the invention may comprise any cosmetic active agent, such as active agents chosen from antioxidants, preserving agents, fragrances, bactericidal or antiperspirant active agents, neutralizers, emollients, moisturizers, vitamins and screening agents, in particular sunscreens .
  • active agents chosen from antioxidants, preserving agents, fragrances, bactericidal or antiperspirant active agents, neutralizers, emollients, moisturizers, vitamins and screening agents, in particular sunscreens .
  • sunscreens a person skilled in the art will take care to select this or these optional additional compound (s), and/or the amount thereof, such that the advantageous properties of the corresponding composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition, especially so as not to interfere with the reaction between compounds A and B.
  • compositions according to the invention may be, independently, in the form of a suspension, a dispersion, a solution, a gel, an emulsion, especially an oil-in-water (O/W) emulsion, a wax-in-water or water-in-oil (W/O) emulsion or a multiple emulsion
  • W/O/W or polyol/O/W or 0/W/O or in the form of a cream, a paste, a mousse, a vesicular dispersion, especially of ionic or nonionic lipids, a two-phase or multiphase lotion, a powder or a paste, especially a soft paste.
  • a person skilled in the art may select the appropriate formulation, and also the method for preparing it, on the basis of his or her general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the vehicle, and secondly the intended use of each composition.
  • Example 1 Mascara
  • the black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring.
  • the other compounds are mixed in a beaker with gentle turbine stirring.
  • the premix of phenyltrimethicone and pigments is then added, with gentle stirring continued. The whole of the procedure is carried out at ambient temperature.
  • the black iron oxide is dispersed in the phenyl- trimethicone DC556 with gentle magnetic stirring.
  • the other compounds are mixed in a beaker with gentle turbine stirring.
  • the premix of phenyltrimethicone and pigments is then added, with gentle stirring continued.
  • the whole of the procedure is carried out at ambient temperature.
  • a layer of the first composition is applied to 6 specimens of Caucasian hair (30 hairs 1 cm long distributed over a distance of 1 cm) , and then a layer of the composition 2 is applied. The coated hair is left to dry for several minutes.
  • each test specimen is wiped with a cotton swab and then the amount of mascara on the cotton and on the lashes is evaluated. After 1 week of immersion in water or in sebum, no transfer of mascara was observed on the swab.
  • compositions of Examples 1 and 2 can also be applied by mixing the first and second compositions at the time of use.
  • the black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. This dispersion and the fibres are added under Rayneri stirring in the polyethylene wax already melted, and stirring is maintained during cooling of the mixture. When the mixture is thickening but is still melted, mixture A (non heated) is added, with gentle stirring continued until recovering at ambient temperature.
  • the black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. This dispersion and the fibres are added under Rayneri stirring in the silicone wax already melted, and stirring is maintained during cooling of the mixture. When the mixture is thickening but is still melted, mixture A (non heated) is added, with gentle stirring continued until recovering at ambient temperature.
  • Example 5 Mascara
  • the black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring.
  • the mixture C is placed in a beaker with gentle turbine stirring.
  • the premix of phenyltrimethicone and pigments is added, still with gentle stirring.
  • the totality of the procedure is carried out at ambient temperature.
  • Composition 1 is mixed with composition 2 in a 10/1 ratio .
  • the black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring.
  • the other compounds are mixed in a beaker with gentle turbine stirring.
  • the premix of phenyltrimethicone and pigments is added, still with gentle stirring.
  • the totality of the procedure is carried out at ambient temperature.
  • composition 1 is mixed with composition 2 in a 4/1 ratio .
  • Example 7 Mascara
  • the black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring.
  • the other compounds are mixed in a beaker with gentle turbine stirring.
  • the premix of phenyltrimethicone and pigments is added, still with gentle stirring.
  • the totality of the procedure is carried out at ambient temperature.
  • composition 1 is mixed with composition 2 in 60/40 ratio .

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Abstract

The present invention provides a lash coating kit comprising at least one first composition and at least one second composition, which are packaged separately, the kit comprising at least one compound (X), at least one compound (Y) and optionally at least one catalyst or one peroxide, at least one of the compounds, X or Y, being a silicone compound, with the proviso that the compounds X and Y and the catalyst, when present, or the peroxide are not present simultaneously in the same composition, the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide, when they are brought into contact with one another, and fibres.

Description

Lash coating kit comprising silicone compounds X and Y and fibres .
The present invention relates to a lash coating composition or mascara, in particular a non-therapeutic eyelash makeup or care composition, comprising at least two compounds X and Y that are capable of reacting together, one at least of the compounds being a silicone compound, and fibres. The invention also relates to a cosmetic kit comprising the said compounds X and Y.
The composition may be a lash makeup composition, a lash makeup base, a composition for application over a mascara, also known as top-coat, or else a cosmetic lash treatment composition. The mascara is intended more particularly for the lashes of human beings, but also for false eyelashes.
In the case of the lash coating compositions or mascaras, anhydrous mascaras or mascaras with a low level of water and/or water-soluble solvents are known in particular, being known as "waterproof" mascaras, which are formulated as a dispersion of waxes in nonaqueous solvents and which exhibit effective resistance to water and/or sebum.
However, the makeup film obtained after these compositions have been applied is not sufficiently water-resistant, on bathing or showering, for example, to tears or perspiration, or else to sebum. The mascara thus tends to disintegrate over time: grains are deposited, and unattractive lines appear around the eyes. Moreover, the use of fibres to produce a lash- lengthening effect is not beneficial to a smooth, homogeneous deposit on the lashes, thereby giving rise to poor hold on the part of the fibres, which have a tendency to become detached more easily.
This is manifested not only in a deterioration in the deposit and hence in the overall makeup result, but also in discomfort for the user. The invention allows another formulation pathway to be proposed for a lash coating composition, allowing the lashes to receive a makeup which exhibits very good hold, which leads to lengthening and which leads to a continuous smooth, intense black and glossy film. The compositions lead to lash makeup which exhibits good hold both of the fibres and of the overall makeup film.
Moreover, the compositions according to the invention permit smooth and homogeneous application.
The mascaras according to the invention allow a makeup result which holds for more than 1 day, more preferably for more than 3 days, and more preferably still for more than a week.
The inventors have found that it is possible to obtain such properties by using compositions comprising fibres and compounds, preferably silicone compounds, which polymerize and/or crosslink in situ so as to adhere more effectively to the lashes. These compounds additionally exhibit a high level of biocompatibility .
These compounds are able to react together on the lashes or on a substrate so as to form an adherent film with good hold on the lashes.
Accordingly, in a first aspect, the present invention provides a lash coating kit comprising: - at least one first composition and at least one second composition, which are packaged separately,
- the kit comprising at least one compound (X) , at least one compound (Y) and optionally at least one catalyst or one peroxide, at least one of the compounds, X or Y, being a silicone compound,
- with the proviso that the compounds X and Y and the catalyst, when present, or the peroxide are not present simultaneously in the same composition,
- the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide, when they are brought into contact with one another, and fibres.
Preferably, in a first aspect, the present invention provides a lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately,
- the kit comprising at least one compound (X) , at least one compound (Y) and at least one catalyst, at least one of the compounds, X or Y, being a silicone compound, - with the proviso that the compounds X and Y and the catalyst are not present simultaneously in the same composition,
- the said compounds X and Y being able to react together by a hydrosilylation reaction, when they are brought into contact with one another in the presence of a catalyst, fibres, and at least one phenyl silicone oil.
The present invention likewise provides a lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately, - the kit comprising at least one compound (X) , at least one compound (Y) and optionally at least one catalyst, at least one of the compounds, X or Y, being a silicone compound,
- with the proviso that the compounds X and Y - A - and the catalyst, when it is present, are not present simultaneously in the same composition,
- the said compounds X and Y reacting together by a condensation reaction when they are brought into contact with one another, fibres, and at least one phenyl silicone oil.
The compound or compounds X and the compound or compounds Y may be applied to the lashes from two or more compositions containing the compound or compounds X, the compound or compounds Y and the fibres, alone or in a mixture, or from a single composition containing the compound or compounds X, the compound or compounds Y and the fibres.
The compound or compounds X and the compound or compounds Y may in particular be present in the first and/or in the second composition.
The fibres may in particular be present in the first and/or in the second composition.
In one particular embodiment of the invention a first composition comprising the compound or compounds X, the compound or compounds Y and the fibres is applied to the lashes.
In another particular embodiment of the invention a first composition comprising the fibres and a second composition comprising the compound or compounds X and the compound or compounds Y are applied to the lashes, the order in which the first and second compositions are applied being arbitrary.
In another particular embodiment of the invention, a first composition comprising the fibres, a second composition comprising the compound or compounds X and a third composition comprising the compound or compounds Y are applied to the lashes, the order in which the said compositions are applied being arbitrary.
In another particular embodiment of the invention a first composition comprising the compound or compounds X and fibres and a second composition comprising the compound or compounds Y are applied to the lashes, the order in which the said compositions are applied being arbitrary. In another particular embodiment of the invention a first composition comprising the compound or compounds X and a second composition comprising the compound or compounds Y and the fibres are applied to the lashes, the order in which the said compositions are applied being arbitrary.
In one particular embodiment of the invention at least one catalyst as defined below is applied to the lashes in order to activate the reaction between the compound or compounds X and the compound or compounds Y.
For example the catalyst or catalysts may be present in one or other or in each of the first and second compositions that are applied to the lashes, or in an additional composition, in which case the order in which the various compositions are applied to the lashes is arbitrary.
The catalysts advantageously selected are those described hereinbelow.
In one preferred embodiment the first composition comprises at least one compound X and at least one compound Y, the second composition comprises at least one compound X and a catalyst, and one at least of the first and second compositions comprises fibres.
In another particular embodiment of the invention at least one additional reactive compound as defined hereinbelow is applied to the lashes. For example the additional reactive compound or compounds may be present in one or the other or in each of the first and second compositions applied to the lashes, or in an additional composition, in which case the order in which the various compositions are applied to the lashes is arbitrary.
The additional reactive compounds advantageously selected are those described hereinbelow.
In one embodiment the kit further comprises a supplementary composition intended to remove the coating obtained on the lashes by reaction of the compounds X and Y, the said composition preferably comprising at least one organic solvent or oil selected from the organic solvents or oils described later on.
Each composition of the kit may be packaged separately in a single pack, as for example in a twin-compartment pen, the base composition being delivered by one end of the pen and the top composition being delivered by the other end of the pen, with each end being closed, more particularly closed tightly, by a cap. Each composition may also be packaged in a compartment within a single pack, the mixing of the two compositions taking place at the end or ends of the pack at the time of delivery of each composition.
Alternatively, each composition may be packaged in a different pack.
The invention further provides for the use of a kit or of a composition as described above to give a film deposited on the lashes that exhibits enhanced properties of hold, gloss and/or comfort and also a lengthening effect.
According to another aspect the present invention provides a cosmetic lash coating method comprising applying to the said lashes at least one layer of a mixture of a first composition and a second composition, each of the first and second compositions comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide; one at least of the compounds X and Y being a silicone compound, the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide when they are brought into contact with one another, the compounds X and Y and the catalyst, when present, or the peroxide not being present simultaneously in the same composition, the said mixture being obtained either at the time of use, before application to the lashes, or simultaneously with its application to the lashes, and one at least of the said first and second compositions comprising fibres.
In one embodiment the compounds X and Y are mixed at the time of use and then the mixture is applied to the lashes .
Accordingly the invention provides a cosmetic lash coating method comprising: a. mixing, at the time of use, at least one first composition and at least one second composition, each of the first and second compositions comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide, one at least of the compounds X and Y being a silicone compound, the compounds X and Y and the catalyst, when present, or the peroxide not being present simultaneously in the same composition, the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide when they are brought into contact with one another, and one at least of the said first and second compositions comprising fibres, and then b. applying at least one layer of the said mixture to the said lashes.
In one version at least two separate compositions are applied to the lashes, each composition comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide.
Accordingly, the present invention provides a cosmetic lash coating method comprising applying to the lashes: a. at least one layer of a first composition, b. at least one layer of a second composition, each of the first and second compositions comprising at least one compound X and/or at least one compound Y, and optionally at least one catalyst or a peroxide, one at least of the compounds X and Y being a silicone compound, the compounds X and Y and the catalyst, when present, or the peroxide not being present simultaneously in the same composition, the said compounds X and Y being able to react together by a hydrosilylation reaction, or by a condensation reaction or by a crosslinking reaction in the presence of a peroxide when they are brought into contact with one another, and one at least of the said first and second compositions comprising fibres.
The order in which the first and second compositions are applied is arbitrary. It is also possible to apply a plurality of layers of each of the first and second compositions in alternation to the lashes.
In one particular embodiment of the invention at least one catalyst as defined later on is applied to the lashes in order to activate the reaction between the compound or compounds X and the compound or compounds Y. For example the catalyst or catalysts may be present in one or the other or in each of the first and second compositions applied to the lashes, or in an additional composition, in which case the order in which the various compositions are applied to the lashes is arbitrary.
The catalysts advantageously selected are those described hereinbelow.
In another embodiment at least one additional layer of at least one composition comprising a cosmetically acceptable medium and preferably at least one film- forming polymer and at least one organic (or oily) or aqueous solvent medium is applied to the layer or layers of the composition or compositions comprising the compounds X and/or Y for the purpose, for example, of enhancing its or their hold, gloss and/or comfort.
The invention additionally provides a lash coating composition comprising: - at least one compound X and at least one compound Y, one at least of the compounds X and Y being a silicone compound, and optionally at least one catalyst or a peroxide, the said compounds X and Y being able to react together by a hydrosilylation reaction, a condensation reaction or a crosslinking reaction in the presence of the catalyst or the peroxide when they are brought into contact with one another, and fibres.
In this embodiment one at least of the compounds X and Y may be present in an encapsulated form. In one version the two compounds X and Y are both present in separate encapsulated forms.
More particularly the compounds X and/or Y may be present in the form of microcapsules, and more particularly of core/shell nanocapsules, the lipophilic core containing the compound X or the compound Y.
Each composition, of course, comprises a cosmetically acceptable medium, in other words a medium which is not toxic and can be applied to the lashes of human beings, and with a pleasant appearance, odour and feel.
I/ Compounds X and Y
A silicone compound is a compound comprising at least two organosiloxane units. In one particular embodiment the compounds X and the compounds Y are silicone compounds . The compounds X and the compounds Y may be aminated or non-aminated.
In another embodiment at least one of the compounds X and Y is a polymer whose main chain is formed predominantly of organosiloxane units.
Some of the silicone compounds mentioned below may have both film-forming properties and adhesive properties, depending, for example, on their proportion of silicone or on whether they are used in a mixture with a specific additive. It is possible, consequently, to modify the film-forming properties or the adhesive properties of such compounds in accordance with the intended use; this is the case in particular for the reactive elastomeric silicones known as "room temperature vulcanization" silicones.
The compounds X and Y may react together at a temperature varying between ambient temperature and 1800C. Advantageously the compounds X and Y are able to react together at ambient temperature (20 ± 50C) and atmospheric pressure, alone or advantageously in the presence of a catalyst, by a hydrosilylation reaction or a condensation reaction, or a crosslinking reaction in the presence of a peroxide.
Polar groups
In one particular embodiment one at least of the compounds X and Y carries at least one polar group able to form at least one hydrogen bond with the lashes. A polar group is a group which contains carbon atoms and hydrogen atoms in its chemical structure and also at least one heteroatom (such as O, N, S and P) such that the said group is capable of establishing at least one hydrogen bond with the lashes.
Compounds which carry at least one group capable of establishing a hydrogen bond are particularly advantageous, since they provide the compositions containing them with improved adhesion to the lashes, owing to the capacity of these groups to establish a hydrogen bond with the lashes.
The polar group or groups carried by at least one of the compounds X and Y is or are capable of establishing a hydrogen bond, and include or includes either a hydrogen atom bonded to an electronegative atom, or an electronegative atom such as, for example, O, N or S .
When the group contains a hydrogen atom bonded to an electronegative atom, the hydrogen atom can interact with another electronegative atom carried, for example, by another molecule, such as keratin, to form a hydrogen bond. When the group contains an electronegative atom, the electronegative atom can interact with a hydrogen atom bonded to an electronegative atom carried, for example, by another molecule, such as keratin, to form a hydrogen bond. Advantageously these polar groups may be selected from the following groups: carboxylic acids -COOH, alcohols, such as -CH2OH or -CH(R)OH, R being an alkyl radical containing 1 to 6 carbon atoms, amino of formula -NRiR2, in which the radicals
Ri and R2, which are identical or different, represent an alkyl radical containing 1 to 6 carbon atoms, or one of the radicals, Ri or R2, denotes a hydrogen atom, pyridino, amido of formula -NH-COR' or -CO-NH-R' in which
R' represents a hydrogen atom or an alkyl radical containing 1 to 6 carbon atoms, pyrrolidino selected preferably from the groups of formula:
Figure imgf000013_0001
Ri being an alkyl radical containing 1 to 6 carbon atoms, carbamoyl of formula -O-CO-NH-R' or -NH-CO-OR' , R' being as defined above, thiocarbamoyl, such as -O-CS-NH-R' or -NH-CS-O-R' , R' being as defined above, ureyl such as -NR' -CO-N (R' ) 2, the identical or different radicals R' being as defined above, sulphonamido such as -NR' -S (=0) 2-R' , R' corresponding to the definition above.
Preferably these polar groups are present in an amount of less than or equal to 10% by weight relative to the weight of each compound X or Y, preferably less than or equal to 5% by weight, for example in an amount of from 1 to 3% by weight. The polar group or groups may be situated in the main chain of the compound X and/or Y or are pendant to the main chain or are situated at the ends of the main chain of the compound X and/or Y.
1- Compounds X and Y able to react by hydrosilylation
In one embodiment the compounds X and Y are able to react by hydrosilylation, a reaction which can be depicted in a simplified way as follows:
Figure imgf000014_0001
where W represents a carbon and/or silicone chain containing one or more unsaturated aliphatic groups.
In this case the compound X may be selected from silicone compounds comprising at least two unsaturated aliphatic groups. By way of example, the compound X may comprise a main silicone chain whose unsaturated aliphatic groups are pendant to the main chain (side group) or are situated at the ends of the main chain of the compound (terminal group) . In the remainder of the description, these specific compounds will be referred to as polyorganosiloxanes having unsaturated aliphatic groups.
In one embodiment the compound X and/or the compound Y carries at least one polar group, as described above, able to form at least one hydrogen bond with the lashes. This polar group is advantageously carried by the compound X which comprises at least two unsaturated aliphatic groups.
In one embodiment the compound X is selected from polyorganosiloxanes comprising at least two unsaturated aliphatic groups, for example two or three vinyl or allyl groups, each bonded to a silicon atom. In one advantageous embodiment the compound X is selected from polyorganosiloxanes containing siloxane units of formula:
" (I)
in which:
R represents a monovalent linear or cyclic hydrocarbon group containing 1 to 30 carbon atoms, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as, for example, a short-chain alkyl radical, containing for example 1 to 10 carbon atoms, in particular a methyl radical or else a phenyl group, preferably a methyl radical, - m is 1 or 2, and R' represents: o an unsaturated aliphatic hydrocarbon group containing 2 to 10, preferably 2 to 5, carbon atoms such as, for example, a vinyl group or a group -R"-CH=CHR"' in which R" is a divalent aliphatic hydrocarbon chain containing 1 to 8 carbon atoms which is bonded to the silicon atom, and R"' is a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, preferably a hydrogen atom; possibilities for group R' include vinyl groups, allyl groups and mixtures thereof; or o an unsaturated cyclic hydrocarbon group containing 5 to 8 carbon atoms, such as, for example, a cyclohexenyl group. Preferably, R' is an unsaturated aliphatic hydrocarbon group, preferably a vinyl group.
In one particular embodiment the polyorganosiloxane further comprises units of formula R SiO , ,
F
(Ii) in which R is a group as defined above and n is 1, 2 or 3.
In one version the compound X may be a silicone resin containing at least two ethylenic unsaturations, the said resin being capable of reacting with the compound Y by hydrosilylation . Possible examples include the resins of type MQ or MT which themselves carry unsaturated reactive end groups -CH=CH2.
These resins are crosslinked organosiloxane polymers. The nomenclature of silicone resins is known by the name of "MDTQ", the resin being described as a function of the different monomeric siloxane units it comprises, with each of the letters MDTQ characterizing one type of unit.
The letter M represents the monofunctional unit of formula (CH3) 3Si0i/2, the silicon atom being joined to a single oxygen atom in the polymer comprising this unit. The letter D signifies a difunctional unit (CH3) 2Siθ2/2 in which the silicon atom is joined to two oxygen atoms .
The letter T represents a trifunctional unit of formula (CH3)SiO372. In the units M, D and T defined above, at least one of the methyl groups may be substituted by a group R other than the methyl group, such as a hydrocarbon radical (more particularly alkyl) having 2 to 10 carbon atoms, or a phenyl group, or else a hydroxyl group. Finally, the letter Q signifies a tetrafunctional unit Siθ4/2 in which the silicon atom is bonded to four hydrogen atoms which are themselves bonded to the remainder of the polymer. Possible examples of such resins include the MT silicone resins such as the poly (phenylvinylsilsesquioxanes) like those sold under the name SST-3PV1 by Gelest. The compounds X preferably contain from 0.01% to 1% by weight of unsaturated aliphatic groups.
Advantageously the compound X is selected from polyorganopolysiloxanes, more particularly those comprising the siloxane units (I) and optionally (II) described above.
The compound Y preferably comprises at least two free Si-H groups (hydrogenosilane groups) .
The compound Y may advantageously be selected from organosiloxanes comprising at least one alkylhydrogeno- siloxane unit of formula:
2 (ιu) in which:
R represents a monovalent linear or cyclic hydrocarbon group containing 1 to 30 carbon atoms, such as, for example, an alkyl radical having 1 to 30 carbon atoms, preferably 1 to 20 and more preferably 1 to 10 carbon atoms, in particular a methyl radical, or else a phenyl group, and p is 1 or 2. Preferably R is a hydrocarbon group, preferably methyl.
These organosiloxane compounds Y having alkylhydrogeno- siloxane units may further comprise units of formula:
2
(M) as defined above.
The compound Y may be a silicone resin comprising at least one unit selected from the M, D, T and Q units as defined above and comprising at least one Si-H group, such as the poly (methylhydridosilsesquioxanes) sold under the name SST-3MH1.1 by Gelest.
Preferably these organosiloxane compounds Y contain from 0.5% to 2.5% by weight of Si-H groups. Advantageously the radicals R represent a methyl group in the formulae (I), (II) and (III) above. Preferably these organosiloxanes Y comprise terminal groups of formula (CH3) 3Si0i/2. Advantageously the organosiloxanes Y comprise at least two alkylhydrogenosiloxane units of formula (H2C) (H) SiO and optionally comprise units (H3C) 2SiO.
Organosiloxane compounds Y of this kind containing hydrogenosilane groups are described for example in document EP 0465744.
In one version the compound X is selected from organic oligomers or polymers (organic compounds are those whose main chain is not a silicone chain, preference being given to compounds containing no silicon atoms) or from hybrid organic/silicone polymers or oligomers, the said oligomers or polymers carrying at least two reactive unsaturated aliphatic groups, and the compound Y being selected from the aforementioned hydrogenosiloxanes .
In one embodiment the organic or organic/silicone hybrid compounds X carrying at least two reactive unsaturated aliphatic groups carry at least one polar group as described above.
The compound X, which is organic in nature, may then be selected from vinyl and (meth) acrylic oligomers or polymers, polyesters, polyurethanes and/or polyureas, polyethers, perfluoropolyethers, polyolefins such as polybutene and polyisobutylene, dendrimers or hyperbranched organic polymers, or mixtures thereof.
In particular the organic polymer or the organic part of the hybrid polymer may be selected from the following polymers: a) ethylenically unsaturated polyesters: this is a group of polymers of polyester type having at least 2 ethylenic double bonds distributed anywhere in the main chain of the polymer. These unsaturated polyesters are obtained by polycondensation of a mixture: - of linear or branched aliphatic or cycloaliphatic carboxylic diacids containing in particular 3 to 50 carbon atoms, preferably 3 to 20 and more preferably 3 to 10 carbon atoms, such as adipic acid or sebacic acid, aromatic carboxylic diacids having in particular 8 to 50 carbon atoms, preferably 8 to 20 and more preferably 8 to 14 carbon atoms, such as phthalic acids, more particularly terephthalic acid, and/or carboxylic diacids obtained from dimers of ethylenically unsaturated fatty acids, such as the dimers of oleic or linoleic acids that are described in patent application EP-A-959 066 (paragraph [0021]) and are sold under the name Pripol® by Unichema or Empol by Henkel, all of these diacids necessarily being devoid of polymerizable ethylenic double bonds, - of linear or branched aliphatic or cycloaliphatic diols containing in particular 2 to 50 carbon atoms, preferably 2 to 20 and more preferably 2 to 10 carbon atoms, such as ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol or cyclohexanedimethanol, aromatic diols having 6 to 50 carbon atoms, preferably 6 to 20 and more preferably 6 to 15 carbon atoms, such as bisphenol A and bisphenol B, and/or diol dimers obtained from the reduction of dimers of fatty acids as defined above, and of one or more carboxylic diacids or their anhydrides containing at least one polymerizable ethylenic double bond and having 3 to 50 carbon atoms, preferably 3 to 20 and more preferably 3 to 10 carbon atoms, such as maleic acid, fumaric acid or itaconic acid.
Polyesters having side and/or terminal (meth) acrylate groups: this is a group of polymers of polyester type which are obtained by polycondensation of a mixture : of linear or branched aliphatic or cycloaliphatic carboxylic diacids containing in particular 3 to 50 carbon atoms, preferably 3 to 20 and more preferably 3 to 10 carbon atoms, such as adipic acid or sebacic acid, aromatic carboxylic diacids having in particular 8 to 50 carbon atoms, preferably 8 to 20 and more preferably 8 to 14 carbon atoms, such as phthalic acids, more particularly terephthalic acid, and/or carboxylic diacids obtained from dimers of ethylenically unsaturated fatty acids, such as the dimers of oleic or linoleic acids that are described in patent application EP-A-959 066 (paragraph [0021]) and are sold under the name Pripol by Unichema or Empol® by Henkel, all of these diacids necessarily being devoid of polymerizable ethylenic double bonds, of linear or branched aliphatic or cycloaliphatic diols containing in particular 2 to 50 carbon atoms, preferably 2 to 20 and more preferably 2 to 10 carbon atoms, such as ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol or cyclohexanedimethanol, aromatic diols having 6 to 50 carbon atoms, preferably 6 to 20 and more preferably 6 to 15 carbon atoms, such as bisphenol A and bisphenol B, and
- of at least one ester of (meth) acrylic acid and a diol or polyol having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and glycerol methacrylate . These polyesters are different from those described above in section a) in that the ethylenic double bonds are situated not in the main chain but on side groups or at the end of the chains. These ethylenic double bonds are those of the (meth) acrylate groups present in the polymer.
Polyesters of this kind are sold for example by UCB under the name Ebecryl® (Ebecryl® 450: molar mass 1600, on average 6 acrylate functions per molecule, Ebecryl® 652: molar mass 1500, on average 6 acrylate functions per molecule, Ebecryl® 800: molar mass 780, on average 4 acrylate functions per molecule, Ebecryl 810: molar mass 1000, on average 4 acrylate functions per molecule, Ebecryl 50 000: molar mass 1500, on average 6 acrylate functions per molecule) .
Polyurethanes and/or polyureas having (meth) acrylate groups, obtained by polycondensation :
- of aliphatic, cycloaliphatic and/or aromatic diisocyanates, triisocyanates and/or polyisocyanates, having in particular 4 to 50, preferably 4 to 30, carbon atoms, such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or the isocyanurates of formula :
Figure imgf000022_0001
resulting from the trimerization of 3 molecules of diisocyanates OCN-R-CNO, where R is a linear, branched or cyclic hydrocarbon radical containing 2 to 30 carbon atoms,
- of polyols, more particularly of diols, which are devoid of polymerizable ethylenic unsaturations, such as 1, 4-butanediol, ethylene glycol or trimethylolpropane, and/or from polyamines, more particularly diamines, which are aliphatic, cycloaliphatic and/or aromatic and have more particularly 3 to 50 carbon atoms, such as ethylenediamine or hexamethylene- diamine, and
- from at least one ester of (meth) acrylic acid and a diol or polyol having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, such as 2-hydroxyethyl (meth) - acrylate, 2-hydroxypropyl (meth) acrylate and glycerol methacrylate .
Polyurethanes/polyureas of these kinds containing acrylate groups are sold for example under the name SR 368 (tris (2-hydroxyethyl) isocyanurate triacrylate) or Craynor 435 by Cray Valley, or under the name Ebecryl® by UCB
(Ebecryl® 210: molar mass 1500, 2 acrylate functions per molecule, Ebecryl® 230: molar mass 5000, 2 acrylate functions per molecule,
Ebecryl® 270: molar mass 1500, 2 acrylate functions per molecule, Ebecryl 8402: molar mass 1000, 2 acrylate functions per molecule, Ebecryl® 8804: molar mass 1300, 2 acrylate functions per molecule, Ebecryl® 220: molar mass 1000, 6 acrylate functions per molecule, Ebecryl® 2220: molar mass 1200, 6 acrylate functions per molecule, Ebecryl 1290: molar mass 1000, 6 acrylate functions per molecule, Ebecryl" 800: molar mass 800, 6 acrylate functions per molecule) . Mention may also be made of the water-soluble aliphatic polyurethane diacrylates sold under the names Ebecryl® 2000, Ebecryl® 2001 and Ebecryl® 2002, and of the polyurethane diacrylates in aqueous dispersion that are sold under the trade names IRR® 390, IRR® 400, IRR®
422 and IRR® 424 by UCB.
Polyethers having (meth) acrylate groups which are obtained by esterification, by (meth) - acrylic acid, of terminal hydroxyl groups of homopolymers or copolymers of Ci_4 alkylene glycols, such as polyethylene glycol, polypropylene glycol, the copolymers of ethylene oxide and propylene oxide having preferably a weight-average molecular mass of less than 10 000, and polyethoxylated or polypropoxylated trimethylolpropane . Polyoxyethylene di (meth) acrylates of appropriate molar mass are sold for example under the names SR 259, SR 344, SR 610, SR 210,
SR 603 and SR 252 by Cray Valley or under the name Ebecryl (R) 11 by UCB. Polyethoxylated trimethylolpropane triacrylates are sold for example under the names SR 454, SR 498, SR 502, SR 9035 and SR 415 by Cray Valley or under the name Ebecryl (R) 160 by UCB. Polypropoxylated trimethylolpropane triacrylates are sold for example under the names SR 492 and SR 501 by Cray Valley. e) Epoxy acrylates obtained by reacting
- at least one diepoxide selected for example from: (i) bisphenol A diglycidyl ether,
(ii) a diepoxy resin resulting from the reaction of bisphenol A diglycidyl ether and epichlorohydrin,
(iii)an epoxy ester resin having α,ω-diepoxy ends, resulting from the condensation of a dicarboxylic acid having 3 to 50 carbon atoms with a stoichiometric excess of (i) and/or (ii) ,
(iv) an epoxy ether resin having α,ω-diepoxy ends, resulting from the condensation of a diol having 3 to 50 carbon atoms with a stoichiometric excess of (i) and/or (ϋ),
(v) natural or synthetic oils carrying at least 2 epoxide groups, such as epoxidized soya oil, epoxidized linseed oil and epoxidized vernonia oil, (vi) a phenol-formaldehyde polycondensate (Novolac resin) whose ends and/or side groups have been epoxidized,
and
- one or more carboxylic acids or polycarboxylic acids containing at least one ethylenic double bond positioned α, β to the carboxyl group, such as (meth) acrylic acid or crotonic acid, or the esters of (meth) acrylic acid and a diol or polyol having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, such as 2-hydroxyethyl (meth) acrylate .
Polymers of this kind are sold for example under the names SR 349, SR 601, CD 541, SR 602, SR 9036, SR 348, CD 540, SR 480 and CD 9038 by Cray Valley, under the names Ebecryl® 600 and Ebecryl® 609, Ebecryl® 150, Ebecryl® 860 and Ebecryl® 3702 by UCB, and under the names Photomer® 3005 and Photomer® 3082 by Henkel.
f) Poly-Ci-50 alkyl (meth) acrylates, the said alkyl being linear, branched or cyclic, containing at least two functions having an ethylenic double bond, which are carried by the terminal and/or side hydrocarbon chains.
Copolymers of this kind are sold for example under the names IRR® 375, OTA® 480 and Ebecryl® 2047 by
UCB.
g) Polyolefins such as polybutene and polyiso- butylene .
h) Perfluoropolyethers having acrylate groups which are obtained by esterification, for example with (meth) acrylic acid, of perfluoropolyethers which carry terminal and/or side hydroxyl groups. α,ω-Diol perfluoropolyethers of this kind are described in particular in EP-A-1057849 and are sold by Ausimont under the name Fomblin® Z DIOL.
i) Dendrimers and hyperbranched polymers which carry terminal (meth) acrylate or (meth) - acrylamide groups obtained respectively by esterification or amidification of dendrimers and hyperbranched polymers having terminal hydroxyl or amino functions with (meth) acrylic acid.
Dendrimers (from the Greek dendron = tree) are "arborescent", in other words highly branched, polymer molecules invented by D. A. Tomalia and his team at the beginning of the 1990s
(Donald A. Tomalia et al . , Angewandte Chemie, Int.
Engl. Ed., vol. 29, no. 2, pages 138-175). They are structures constructed around a generally polyfunctional central unit. Arrayed in chains around this central unit, in accordance with a well-defined structure, are branched chain- extension units, hence giving rise to monodisperse symmetrical macromolecules which have a well- defined chemical and stereochemical structure. Polyamidoamine dendrimers are sold for example under the name Starburst® by Dendritech. Hyperbranched polymers are polycondensates, generally of polyester, polyamide or polyethyleneamine type, which are obtained from polyfunctional monomers, which have an arborescent structure similar to that of the dendrimers but much less regular than them (see, for example, WO- A-93/17060 and WO 96/12754) .
Under the name Boltorn®, the company Perstorp sells hyperbranched polyesters. Hyperbranched polyethylene amines are found under the name Comburst from the company Dendritech. Hyperbranched poly (esteramides) having hydroxyl eennddss aarre sold by the company DSM under the name Hybrane^ ®
These dendrimers and hyperbranched polymers esterified or amidified by acrylic and/or methacrylic acid differ from the polymers described in sections a) to h) above in the very large number of ethylenic double bonds present. This high functionality, most often greater than 5, makes them particularly useful, allowing them to act as a "crosslinking node", in other words as a site of multiple crosslinking. It is therefore possible to use these dendritic and hyperbranched polymers in combination with one or more of the polymers and/or oligomers a) to h) above . Ia Additional reactive compounds
In one embodiment the compositions comprising the compound X and/or Y may further comprise at least one additional reactive compound such as: organic or inorganic particles comprising on their surface at least 2 unsaturated aliphatic groups, examples including silicas surface- treated with, for example, silicone compounds having vinyl groups, such as, for example, cyclotetramethyltetravinylsiloxane-treated silica; silazane compounds such as hexamethyldi- silazane .
Ib Catalyst
The hydrosilylation reaction takes place advantageously in the presence of a catalyst which may be present in one or other of the compositions comprising the compound X and/or the compound Y or in a separate composition, the catalyst being preferably based on platinum or on tin.
Examples include catalysts based on platinum deposited on a silica gel support or on a charcoal powder
(carbon) support, platinum chloride, platinum salts and chloroplatinic acids.
Preference is given to using chloroplatinic acids in hexahydrate or anhydrous form, which are readily dispersible in organosilicone media.
Mention may also be made of platinum complexes such as those based on chloroplatinic acid hexahydrate and divinyltetramethyldisiloxane .
The catalyst may be present in one or other of the compositions useful in the present invention in an amount of from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.
In the compositions of the invention it is also possible to introduce polymerization inhibitors or retardants, and more particularly catalyst inhibitors, for the purpose of increasing the stability of the composition over time or of retarding the polymerization. Without limitation mention may be made of cyclic polymethylvinylsiloxanes, and especially tetravinyltetramethylcyclotetrasiloxane, and acetylenic alcohols, preferably volatile acetylenic alcohols, such as methylisobutynol .
The presence of ionic salts, such as sodium acetate, in one and/or the other of the first and second compositions may influence the rate of polymerization of the compounds.
An example of a combination of compounds X and Y which react by hydrosilylation includes the following references provided by Dow Corning: DC 7-9800 Soft Skin Adhesive Parts A & B, and also the following mixtures A and B prepared by Dow Corning:
MIXTURE A:
Figure imgf000028_0001
MIXTURE B
Figure imgf000029_0001
Advantageously the compounds X and Y are selected from silicone compounds able to react by hydrosilylation; in particular, the compound X is selected from polyorganosiloxanes containing units of formula (I) described above, and the compound Y is selected from organosiloxanes containing alkylhydrogenosiloxane units of formula (III) described above. In one particular embodiment the compound X is a polydimethylsiloxane having terminal vinyl groups, and the compound Y is methylhydrogenosiloxane .
More preferably the compound X carries at least one polar group.
2/ Compounds X and Y able to react by condensation
In this embodiment the compounds X and Y are able to react by condensation, either in the presence of water (hydrolysis), by reaction of 2 compounds which carry alkoxysilane groups, or by so-called direct condensation, by reaction of a compound which carries one or more alkoxysilane groups and a compound which carries one or more silanol groups, or by reaction of 2 compounds which carry one or more silanol groups.
When the condensation takes place in the presence of water, the water may be in particular ambient moisture, residual water on the lashes, or water provided by an external source, for example by wetting of the lashes beforehand (for example by means of an atomizer, natural or artificial tears) .
In this mode of condensation reaction, the compounds X and Y, which are identical or different, may therefore be selected from silicone compounds whose main chain comprises at least two alkoxysilane groups and/or at least two silanol (Si-OH) groups, which are side groups and/or chain-end groups.
In one embodiment, the compound X and/or the compound Y carries at least one polar group, as described above, capable of forming at least one hydrogen bond with the lashes .
In one advantageous embodiment the compounds X and/or Y are selected from polyorganosiloxanes comprising at least two alkoxysilane groups. An alkoxysilane group is a group comprising at least one moiety -Si-OR, R being an alkyl group containing 1 to 6 carbon atoms. The compounds X and Y are more particularly selected from polyorganosiloxanes comprising terminal alkoxysilane groups, more specifically those which comprise at least 2 terminal alkoxysilane groups, preferably terminal trialkoxysilane groups.
These compounds X and/or Y preferably comprise predominantly units of formula
'■ ' (IV) in which R9 independently represents a radical selected from alkyl groups containing 1 to 6 carbon atoms, phenyl, and fluoroalkyl groups, and s is 0, 1, 2 or 3. Preferably R9 independently represents an alkyl group containing 1 to 6 carbon atoms. As the alkyl group, mention may be made in particular of methyl, propyl, butyl, hexyl and mixtures thereof, preferably methyl or ethyl. As a fluoroalkyl group, mention may be made of 3,3, 3-trifluoropropyl .
In one particular embodiment the compounds X and Y, which are identical or different, are polyorganosiloxanes comprising units of formula
(R'jSiCtfr - (V) in which R9 is as described above, R9 preferably being a methyl radical, and f is more particularly such that the polymer has a viscosity at 25°C of from 0.5 to 3000 Pa. s, preferably of from 5 to 150 Pa. s; for example, f may be from 2 to 5000, preferably from 3 to 3000, more preferably from 5 to 1000.
These polyorganosiloxane compounds X and Y comprise at least two terminal trialkoxysilane groups per polymer molecule, the said groups having the formula
- --A~(vi) in which the radicals R represent independently a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl group, preferably a methyl or ethyl group, R1 is a methyl or ethyl group, x is 0 or 1, preferably 0 and
Z is selected from the following: divalent hydrocarbon groups containing no ethylenic unsaturation and containing 1 to 18 carbon atoms, preferably 2 to 18 carbon atoms (alkylene groups) , the combinations of divalent hydrocarbon radicals and of siloxane segments of formula (IX) :
I -G-(SiOk-Si-O-
(IX) R9 being as described above, G is a divalent hydrocarbon radical containing no ethylenic unsaturation and containing 1 to 18 carbon atoms, preferably 2 to 18 carbon atoms, and c is an integer of from 1 to 6.
Z and G may more particularly be selected from alkylene groups such as methylene, ethylene, propylene, butylene, pentylene and hexylene, and arylene groups such as phenylene. Preferably Z is an alkylene group, and more preferably ethylene .
These polymers may have on average at least 1.2 trialkoxysilane end groups or terminal trialkoxysilane chains per molecule, and preferably on average at least 1.5 trialkoxysilane end groups per molecule. These polymers may have at least 1.2 trialkoxysilane end groups per molecule, and some may comprise other types of end groups, such as end groups of formula CH2=CH-SiR9 2- or of formula R6 3-Si-, in which R9 is as defined above and each group R6 is selected independently from groups R9 or vinyl. Possible examples of such end groups include trimethoxysilane, triethoxysilane, vinyldimethoxysilane and vinylmethyl- oxyphenylsilane groups.
Polymers of this kind are described more particularly in documents US 3 175 993, US 4 772 675, US 4 871 827, US 4 888 380, US 4 898 910, US 4 906 719 and US 4 962 174, whose content is incorporated by reference into the present patent application.
As compound X and/or Y it is possible in particular to mention the polymer of formula
(RO)3_xKi -Z -(SϊO)fSi-2-Si(ORh→:
[ R9 RQ
(V!!) in which R, R1, R9, Z, x and f are as described above. The compounds X and/or Y may further comprise a mixture of polymer of formula (VII) above with polymers of formula (VI I I ) :
S9 Ii11 K? Rl
. . I
CH2=Cϊi-SiOfXiO)^-k^Sn(f)R)3.λ
R9 R1J RV (ViIi) in which R, R1, R9, Z, x and f are as described above. When the polyorganosiloxane compound X and/or Y having one or more alkoxysilane groups comprises such a mixture, the different polyorganosiloxanes are present in amounts such that the terminal organosilyl chains represent less than 40%, preferably less than 25%, by number of the terminal chains.
The particularly preferred polyorganosiloxane compounds X and/or Y are those of formula (VII) that were described above. Compounds X and/or Y of this kind are described for example in document WO 01/96450.
In one preferred embodiment the compounds X and Y represent a mixture of polydimethylsiloxanes having methoxysilane groups.
As indicated above, the compounds X and Y may be identical or different.
In one version one of the two reactive compounds, X or Y, is of silicone type and the other is of organic type. For example, the compound X is selected from organic oligomers or polymers or organic/silicone hybrid oligomers or polymers, the said polymers or oligomers comprising at least two alkoxysilane groups, and Y is selected from silicone compounds such as the polyorganosiloxanes described above. In particular the organic oligomers or polymers are selected from vinyl and (meth) acrylic oligomers or polymers, polyesters, polyamides, polyurethanes and/or polyureas, polyethers, polyolefins, perfluoropolyethers, organic dendrimers and hyperbranched polymers, and mixtures thereof.
In one embodiment the organic or organic/silicone hybrid compound X carries at least one polar group, as described above, which is able to form at least one hydrogen bond with the lashes.
The organic polymers of vinyl or (meth) acrylic kind which carry alkoxysilane side groups may in particular be obtained by copolymerizing at least one vinyl or (meth) acrylic organic monomer with a (meth) acryloyloxy- propyltrimethoxysilane, a vinyltrimethoxysilane, a vinyltriethoxysilane, an allyltrimethoxysilane, etc. Mention may be made for example of the (meth) acrylic polymers described in the document of Kusabe. M, Pitture e Vernici - European Coating; 12-B, pages 43-49, 2005, and more particularly the polyacrylates having alkoxysilane groups that are called MAX, from Kaneka, or those described in the publication of Probster, M, Adhesion-Kleben & Dichten, 2004, 481 (1-2) , pages 12-14.
The organic polymers which result from a polycondensation or from a polyaddition, such as polyesters, polyamides, polyurethanes and/or polyureas, and polyethers, and which carry alkoxysilane side and/or end groups, may result, for example, from the reaction of an oligomeric prepolymer as described above with one of the following silane coreactants which carry at least one alkoxysilane group: aminopropyltri- methoxysilane, aminopropyltriethoxysilane, aminoethyl- aminopropyltrimethoxysilane, glycidyloxypropyltri- methoxysilane, glycidyloxypropyltriethoxysilane, epoxy- cyclohexylethyltrimethoxysilane, mercaptopropyltri- methoxysilane .
Examples of polyethers and of polyisobutylenes having alkoxysilane groups are described in the publication of Kusabe, M., Pitture e Vernici - European Coating; 12-B, pages 43-49, 2005. Possible examples of polyurethanes having alkoxysilane end groups are those described in the document of Probster, M., Adhesion-Kleben & Dichten, 2004, 481 (1-2), pages 12-14 or else those described in the document of Landon, S., Pitture e Vernici vol. 73, No. 11, pages 18-24, 1997 or in the document of Huang, Mowo, Pitture e Vernici vol. 5, 2000, pages 61-67; mention may be made in particular of the polyurethanes having alkoxysilane groups from OSI-WITCO-GE.
As polyorganosiloxane compounds X and/or Y, mention may be made of the resins of type MQ or MT which themselves carry alkoxysilane and/or silanol ends, such as, for example, the poly (isobutylsilsesquioxane) resins functionalized with silanol groups that are provided under the name SST-S7C41 (3 Si-OH groups) by Gelest.
2a Additional reactive compound
One of the compositions useful in the present invention may further comprise an additional reactive compound comprising at least two alkoxysilane or silanol groups. Possible examples include organic or inorganic particles comprising on their surface alkoxysilane and/or silanol groups, for example fillers surface- treated with such groups.
2b Catalyst
The condensation reaction may take place in the presence of a metal-based catalyst, which may be present in one or the other of the compositions comprising X and/or Y or in a separate composition. The catalyst useful in this type of reaction is preferably a catalyst based on titanium.
Mention may be made in particular of the tetraalkoxytitanium-based catalysts of formula THOR2}y(OK%y;
in which R2 is selected from tertiary alkyl radicals such as tert-butyl, tert-amyl and 2, 4-dimethyl- 3-pentyl; R represents an alkyl radical containing 1 to 6 carbon atoms, preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or hexyl group; and y is a number of from 3 to 4, more preferably from 3.4 to 4.
The catalyst may be present in the one or the other of the compositions useful in the present invention, in an amount of from 0.0001% to 20% by weight relative to the total weight of the composition or compositions containing it.
2c Diluent
The useful compositions comprising X and/or Y may further comprise a volatile silicone oil (or diluent) intended for lowering the viscosity of the composition. This oil may be selected from short-chain linear silicones such as hexamethyldisiloxane and octamethyl- trisiloxane and from cyclic silicones such as octa- methylcyclotetrasiloxane and decamethylcyclopenta- siloxane, and mixtures thereof.
This silicone oil may represent from 5% to 95%, preferably from 10% to 80%, by weight relative to the weight of each composition.
As an example of a combination of compounds X and Y which carry alkoxysilane groups and react by condensation, mention may be made of the combination of the following mixtures A' and B' , prepared by Dow Corning : Mixture A'
Figure imgf000037_0001
Mixture B' :
Figure imgf000037_0002
It should also be noted that the identical compounds X and Y are brought together in the mixture A' .
3/ Crosslinking in the presence of peroxide
In one embodiment the invention provides a lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately, the kit comprising at least one compound (X) , at least one compound (Y) , and at least one peroxide, at least one of the compounds, X or Y, being a silicone compound, - with the proviso that the compounds X and Y and the peroxide are not present simultaneously in the same composition, the said compounds X and Y reacting together by a crosslinking reaction when they are contacted with one another in the presence of peroxide, and fibres, and preferably at least one phenyl silicone oil . This reaction takes place preferably by heating at a temperature greater than or equal to 500C, preferably greater than or equal to 800C, and of up to 1200C. In this case the compounds X and Y, which are identical or different, comprise at least two -CH3 side groups and/or at least two side chains which carry a -CH3 group . The compounds X and Y are preferably silicone compounds and may be selected, for example, from non-volatile linear polydimethylsiloxanes of high molecular weight, having a degree of polymerization of more than 6, which have at least two -CH3 side groups joined to the silicon atom and/or at least two side chains which carry a -CH3 group. Examples include the polymers described in the "Reactive Silicones" catalogue of the company Gelest Inc., 2004 edition, page 6, and more particularly the vinylmethylsiloxane-dimethylsiloxane copolymers (also called rubbers) of molecular weights of from 500 000 to 900 000 and in particular of a viscosity greater than 2 000 000 cSt.
As peroxides which can be used in the context of the invention, mention may be made of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide and mixtures thereof.
In one embodiment the hydrosilylation reaction or the condensation reaction or else the crosslinking reaction in the presence of a peroxide between the compounds X and Y is accelerated by provision of heat, with the temperature of the system being raised, for example, to between 25°C and 1800C. The system will react more particularly on the lashes.
Generally speaking, irrespective of the type of reaction by which the compounds X and Y react together, the molar percentage of X relative to the entirety of the compounds X and Y, i.e. the ratio X/ (X+Y) x 100, may range from 5% to 95%, preferably from 10% to 90%, more preferably still from 20% to 80%.
Similarly, the molar percentage of Y relative to the entirety of the compounds X and Y, i.e. the ratio Y/ (X+Y) x 100, may range from 5% to 95%, preferably from 10% to 90%, more preferably still from 20% to 80%.
The compound X may have a weight-average molecular mass (Mw) of from 150 to 1 000 000, preferably from 200 to 800 000, more preferably from 200 to 250 000. The compound Y may have a weight-average molecular mass (Mw) of from 200 to 1 000 000, preferably from 300 to 800 000, more preferably from 500 to 250 000.
The compound X may represent from 0.5% to 95% by weight relative to the total weight of the compositions containing it, in particular relative to the total weight of each first and second composition, preferably from 1% to 90% by weight, and more preferably from 5% to 80% by weight. The compound Y may represent from 0.05% to 95% by weight relative to the total weight of the compositions containing it, in particular relative to the total weight of each first and second composition, preferably from 1% to 90% by weight, and more preferably from 5% to 80% by weight.
The ratio between the compounds X and Y may be changed so as to modify the rate of reaction and hence the rate at which the film is formed, or else so as to adapt the properties of the resulting film (for example its adhesive properties) in accordance with the desired application .
In particular, the compounds X and Y may be present in a molar X/Y ratio of from 0.05 to 20 and more preferably from 0.1 to 10.
In one embodiment one at least of the compositions may comprise at least one silica, in particular a synthetic silica surface-treated with a hydrophobic agent (preferably a silicone agent) , in particular a surface- treated fumed silica, such as, for example, the silicas described below in the fillers or the gelling agents. Possible examples include the treated fillers Cab-O- Sil®TS-530, Aerosil®R8200 and Wacker HDX H2000.
11/ Fibres
One at least of the first and second compositions comprises fibres.
By "fibre" is meant an object of length L and diameter D such that L is greater than D, and preferably very much greater than D, D being the diameter of the circle within which the cross section of the fibre is inscribed. In particular the ratio L/D (or form factor) is selected from the range from 3.5 to 2500, preferably from 5 to 500, and more preferably from 5 to 150.
The fibres which can be used in the composition or compositions of the invention may be organic or inorganic fibres of synthetic or natural origin. They may be short or long, unitary or organized, for example braided, and hollow or solid. They may have any shape, and may more particularly have a circular or polygonal
(square, hexagonal or octagonal) cross section, depending on the specific application envisaged. In particular their ends are blunt and/or polished so as to avoid injury.
In particular the fibres have a length of from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and more preferably from 0.3 mm to 3 mm. Their cross section may be included within a circle whose diameter is from 2 nm to 500 μm, preferably from 100 nm to 100 μm and more preferably from 1 μm to 50 μm. The weight or linear density of the fibres is often given in denier or decitex, and represents the weight in grams per 9 km of yarn. The fibres according to the invention preferably have a linear density selected from the range from 0.01 to 10 denier, preferably from 0.1 to 2 denier and more preferably from 0.3 to 0.7 denier.
The fibres may be those which are used in the manufacture of textiles, and more particularly fibres of silk, cotton, wool, flax, fibres of cellulose particularly those extracted more particularly from wood, from vegetables or from algae, or fibres of rayon, polyamide (Nylon®) , viscose, acetate, especially rayon acetate, or fibres of acrylic polymer, more particularly of polymethyl methacrylate or of poly-2- hydroxyethyl methacrylate, of polyolefin and more particularly of polyethylene or of polypropylene, or fibres of glass, silica, carbon, more particularly in graphite form, or fibres of polytetrafluoroethylene
(such as Teflon®) , or fibres of insoluble collagen, polyesters, polyvinyl chloride or polyvinylidene chloride, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, or fibres formed from a blend of polymers such as those mentioned above, such as polyamide/polyester fibres. The fibres are preferably polyamide fibres (Nylon®) .
It is also possible to use the fibres that are used in surgery, such as the absorbable synthetic fibres prepared from glycolic acid and caprolactone
("Monocryl" from Johnson & Johnson) ; absorbable synthetic fibres of lactic acid and glycolic acid copolymer type ("Vicryl" from Johnson & Johnson) ; terephthalic polyester fibres ("Ethibond" from Johnson & Johnson) ; and stainless steel threads ("Acier" from Johnson & Johnson) .
Furthermore, the fibres may be surface-treated or not and may be uncoated or coated with a protective coat.
Coated fibres which can be used in the invention include polyamide fibres coated with copper sulphide for an antistatic effect (for example "R-STAT" from Rhodia) or another polymer allowing a particular organization of the fibres (specific surface treatment) . Mention may also be made of the fibres coated with organic or inorganic pigments, such as the pigments cited later on below in the application.
Preference is given to using fibres of synthetic origin, and especially organic fibres, such as those used in surgery.
The fibres which can be used in the composition or compositions according to the invention are preferably polyamide, cellulose or polyethylene fibres. Their length (L) may be from 0.1 mm to 5 mm, preferably from 0.25 mm to 1.6 mm, and their mean diameter may be from 1 μm to 50 μm. In particular it is possible to use the polyamide fibres sold by Etablissements P. Bonte under the name "Polyamide 0.9 Dtex 3 mm", having a mean diameter of 6 μm, a linear density of approximately 0.9 dtex and a length of from 0.3 mm to 5 mm, or else the polyamide fibres sold under the name Fiberlon 931 Dl-S by LCW, having a linear density of approximately 0.9 dtex and a length of approximately 0.3 mm.
It is also possible to use cellulose fibres (or rayon fibres) having a mean diameter of 50 μm and a length of from 0.5 mm to 6 mm, such as those sold under the name "Natural rayon flock fiber RClBE - N003 - M04" by the company Claremont Flock. It is also possible to use polyethylene fibres such as those sold under the name "Shurt Stuff 13 099 F" by the company Mini Fibers.
Advantageously the composition or compositions according to the invention comprises or comprise fibres referred to as "rigid" fibres, in contrast to the aforementioned fibres, which are not rigid fibres. The rigid fibres, which initially are substantially straight, when placed in a dispersing medium, do not undergo a substantial change in shape, a fact which is reflected in the angular condition defined below, which reflects a shape that may be described as still substantially straight and linear. This angle condition reflects the stiffness of the fibres, which it is difficult to express by any other parameter for objects that are as small as the rigid fibres.
The stiffness of the fibres is manifested in the following angular condition: advantageously at least 50%, preferably at least 75% and more preferably at least 90% of the fibres, in numerical terms, are such that the angle formed between the tangent to the longitudinal central axis of the fibre and the straight line joining the said end to the point on the longitudinal central axis of the fibre corresponding to half the length of the fibre is less than 15°, and the angle formed between the tangent of the longitudinal central axis of the fibre at a point half-way along the fibre, and the straight line connecting one of the ends to the point on the longitudinal central axis of the fibre that corresponds to half the length of the fibre, is less than or equal to 15°, for a given fibre length of from 0.8 mm to 5 mm, preferably from 1 mm to 4 mm, preferably from 1 mm to 3 mm, and more preferably of 2 mm.
Advantageously the abovementioned angle is measured at the two ends of the fibre and at a point half-way along the fibre; in other words, three measurements are taken in this case, and the average of the angles measured is less than or equal to 15°.
In particular the tangent, at any point on the fibre, forms an angle of less than 15°. In the present application, the angle formed by the tangent at a point on the fibre is the angle formed between the tangent to the longitudinal central axis of the fibre at the said point on the fibre, and the straight line connecting the end of the fibre that is closest to the said point to the point on the longitudinal central axis of the fibre that corresponds to half the length of the fibre.
Generally speaking, the rigid fibres which can be used in the composition or compositions according to the invention have the same fibre length or a substantially identical length.
More specifically, when a medium in which the rigid fibres are dispersed at a fibre concentration of 1% by weight is observed with a microscope, with a lens allowing a magnification of 2.5 and with full-field vision, a numerical majority of rigid fibres, in other words at least 50% of the rigid fibres, preferably at least 75% of the rigid fibres and more preferably at least 90% of the rigid fibres, in numerical terms, are required to satisfy the angular condition defined above. The measurement which leads to the value of the angle is carried out for a given length of fibres; this length is included in the range from 0.8 mm to 5 mm, preferably from 1 to 4 mm, preferably from 1 to 3 mm, and more preferably 2 mm.
The medium in which the observation is made is a dispersing medium that ensures the effective dispersion of the rigid fibres - for example, water or an aqueous gel of clay or of associative polyurethane . It is even possible to make a direct observation of the composition containing the rigid fibres. A sample of the composition or of the prepared dispersion is placed between a slide and cover slip for observation under the microscope with a lens allowing a magnification of 2.5 and with full-field vision. Full-field vision allows the fibres to be viewed in their entirety.
The rigid fibres may be selected from fibres of a synthetic polymer selected from polyesters, polyurethanes, acrylic polymers, polyolefins, polyamides, in particular non-aromatic polyamides and aromatic polyimide-amides . Possible examples of rigid fibres include the following fibres :
- polyester fibres, such as those obtained by chopping yarns sold under the names Fibre 255-100-R11-242T
Taille 3 mm (eight-lobed cross section), Fibre 265-34- R11-56T Taille 3 mm (round cross section) , Fibre Coolmax 50-34-591 Taille 3 mm (four-lobed cross section) by DuPont de Nemours;
- polyamide fibres, such as those sold under the names Trilobal Nylon 0.120-1.8 DPF, Trilobal Nylon 0.120-18 DPF and Nylon 0.120-6 DPF by Cellusuede products; or fibres obtained by chopping yarns sold under the name Fibre Nomex Brand 430 Taille 3 mm by DuPont de Nemours;
- polyimide-amide fibres such as those sold under the name "Kermel", "Kermel Tech" by Rhodia;
- poly (p-phenyleneterephthalamide) (or aramid) fibres, more particularly those sold under the name Kevlar® by DuPont de Nemours;
- fibres with a multi-layer structure comprising alternate layers of polymers selected from polyesters, acrylic polymers and polyamides, such as those described in documents EP-A-6921217, EP-A-686858 and
US-A-5472798. Fibres of this kind are sold under the names "Morphotex" and "Teijin Tetron Morphotex" by Teijin.
Particularly preferred rigid fibres are the aromatic polyimide-amide fibres.
Polyimide-amide yarns or fibres which can be used for the compositions of the invention are described, for example, in the document by R. Pigeon and P. Allard, Chimie Macromoleculaire Appliquee, 40/41 (1974), pages 139-158 (No. 600), or else in the documents US-A- 3 802 841, FR-A-2 079 785, EP-Al-O 360 728, EP-A-O 549 494, to which reference may be made.
Preferred aromatic polyimide-amide fibres are polyimide-amide fibres comprising repeating units of formula :
Figure imgf000046_0001
obtained by polycondensation of toluylene diisocyanate and trimellitic anhydride.
The fibres may be present in an amount of from 0.01% to 10% by weight, relative to the total weight of each composition comprising them, in particular relative to the total weight of each first or second composition, preferably from 0.1% to 5% by weight and more preferably from 0.5% to 3% by weight.
It is also possible to use a mixture of two or more different fibres in the composition or compositions according to the invention. Such fibres may differ in their nature and/or in their dimensions, more particularly in their lengths. In this way it is possible to alter the features of the makeup obtained and/or the application properties of the mascara.
Ill/ Liquid fatty phase
At least one of the first and second compositions used in the invention advantageously comprises a liquid fatty phase.
A liquid fatty phase in the sense of the patent application is a fatty phase which is liquid at ambient temperature (25°C) and atmospheric pressure (760 mmHg) and is composed of one or more non-aqueous fatty substances which are liquid at ambient temperature, also referred to as organic solvents or oils.
The oil may be selected from volatile oils and/or nonvolatile oils, and mixtures thereof.
The oil or oils may be present in an amount of from 0.5% to 90% by weight, preferably from 5% to 80% by weight, more preferably from 10% to 60% by weight and more preferably still from 20% to 55% by weight relative to the total weight of each composition comprising them, in particular relative to the total weight of each first and second composition.
A "volatile oil" for the purposes of the invention is an oil which is able to evaporate on contact with the lashes in less than one hour at ambient temperature and atmospheric pressure. The volatile organic solvent or solvents and the volatile oils of the invention are organic solvents and volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapour pressure at ambient temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10~ to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg) . In particular the volatile oils are selected from oils possessing an evaporation rate greater than or equal to 0.002 mg/cm2/min. The evaporation rate is measured as follow: 15 g of oil or of the mixture of oils to be tested are introduced into a crystallizing basin (diameter 7 cm) placed on a balance which is located within a chamber of approximately 0.3 m3 and whose temperature (25°C) and hygrometry (relative humidity 50%) are regulated. The liquid is left to evaporate freely, without agitation, with ventilation provided by a fan (rotary speed 2700 revolutions/minute and size 80><80χ42 mm, for example the reference 8550 N from Papst-Motoren, the output corresponding to approximately 50 m3/hour) which is placed vertically above the crystallizing basin containing the solvent, the vanes being directed towards the crystallizing basin and at a distance of 20 cm from the base of the crystallizing basin. The mass of oil remaining in the crystallizing basin is measured at regular intervals. The evaporation rates are expressed in mg of oil evaporated per unit surface area (cm2) and per unit time (minute) .
A "non-volatile oil" is an oil which remains on the lashes at ambient temperature and atmospheric pressure for at least a number of hours and which has more particularly a vapour pressure of less than 10~3 mmHg
(0.13 Pa) .
These oils may be hydrocarbon oils, silicone oils, fluoro oils, or mixtures thereof.
A "hydrocarbon oil" is an oil containing principally hydrogen and carbon atoms and optionally oxygen, nitrogen, sulphur and/or phosphorus atoms. The volatile hydrocarbon oils may be selected from hydrocarbon oils having 8 to 16 carbon atoms, and more particularly C8-C16 branched alkanes such as the C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2, 2, 4, 4, 6-pentamethylheptane) , isodecane and isohexadecane, and, for example, the oils sold under the trade names Isopars or Permetyls, branched C8-C16 esters such as isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon oils may also be used, such as the petroleum distillates, more particularly those sold under the name Shell SoIt by Shell. The volatile solvent is preferably selected from volatile hydrocarbon oils having 8 to 16 carbon atoms, and mixtures thereof.
Further volatile oils which can be used are the volatile silicones, such as, for example, volatile linear or cyclic silicone oils, more particularly those having a viscosity ≤ 8 centistokes (8χlO~6 m2/s) , and have more particularly 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having 1 to 10 carbon atoms. Possible volatile silicone oils which can be used in the invention include, more particularly, octamethylcyclotetrasiloxane, decamethyl- cyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltri- siloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.
Mention may also be made of the volatile linear alkyltrisiloxane oils of general formula (I):
Figure imgf000049_0001
where R represents an alkyl group containing 2 to 4 carbon atoms, and in which one or more hydrogen atoms may be substituted by a fluorine or chlorine atom. The oils of general formula (I) include: 3-butyl-l, 1,1,3,5,5, 5-heptamethyltrisiloxane, 3-propyl-l, 1,1,3,5,5, 5-heptamethyltrisiloxane, and 3-ethyl-l, 1,1,3,5,5, 5-heptamethyltrisiloxane, corresponding to the oils of formula (I) for which R is a butyl group, a propyl group or an ethyl group, respectively.
It is also possible to use volatile fluorine-containing solvents such as nonafluoromethoxybutane or perfluoro- methylcyclopentane .
The composition or compositions may further comprise at least one non-volatile oil, selected more particularly from non-volatile hydrocarbon oils and/or silicone oils and/or fluoro oils. Possible non-volatile hydrocarbon oils include more particularly:
- hydrocarbon oils of plant origin such as the triesters of fatty acids and glycerol, in which the fatty acids may have varied chain lengths from C4 to C24, these chains being linear or branched and saturated or unsaturated; these oils are more particularly wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, maize oil, apricot oil, castor oil, karite oil, avocado oil, olive oil, soya oil, sweet almond oil, palm oil, rapeseed oil, cotton oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil or musk rose oil; or else caprylic/capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel, - synthetic ethers having 10 to 14 carbon atoms;
- linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutenes such as Parleam, and squalane, and mixtures thereof; - synthetic esters such as the oils of formula R1COOR2 in which Rl represents the residue of a linear or branched fatty acid containing 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, more particularly a branched hydrocarbon chain, containing 1 to 40 carbon atoms, with the proviso that Rl + R2 is ≥ 10, such as, for example, Purcellin oil (cetostearyl octanoate) , isopropyl myristate, isopropyl palmitate, C12 to C15 alcohol benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols, such as propylene glycol dioctanoate; hydroxyl-containing esters such as isostearyl lactate and diisostearyl malate; and pentaerythritol esters; - fatty alcohols which are liquid at ambient temperature and have a branched and/or unsaturated carbon chain having 12 to 26 carbon atoms, such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpenta- decanol;
- higher fatty acids such as oleic acid, linoleic acid and linolenic acid;
- carbonates, - acetals,
- citrates,
- and mixtures thereof.
In one particular embodiment the composition or compositions according to the invention comprise at least one non-volatile hydrocarbon oil having a molecular mass of more than 500 g/mol, preferably more than 600 g/mol and more preferably more than 650 g/mol, but not exceeding 15 000 g/mol, preferably not exceeding 10 000 g/mol and more preferably not exceeding 7500 g/mol.
The refractive index is preferably greater than 1.440 at 200C (the refractive index being measured using a refractometer) and advantageously is greater than 1.450 and more preferably greater than 1.460.
A "hydrocarbon" compound is a compound containing principally carbon and hydrogen atoms and optionally one or more functions selected from hydroxyl, ester, ether and carboxyl functions. In particular these compounds are devoid of -Si-O- groups.
This non-volatile hydrocarbon oil may be selected from:
- lipophilic polymers such as: - polybutenes such as Indopol H-100 (of molar mass or MM=920 g/mol), Indopol H-300 (MM=1340 g/mol), Indopol H-1500 (MM=2160 g/mol), which are sold or manufactured by Innovene, - hydrogenated polyisobutylenes such as Panalane H-300 E, sold or manufactured by Amoco (M=1340 g/mol, refractive index of 1.498), Viseal
20000, sold or manufactured by Synteal (MM=6000 g/mol), Rewopal PIB 1000, sold or manufactured by Witco (MM=IOOO g/mol) ,
- polydecenes and hydrogenated polydecenes such as Puresyn 10 (MM=723 g/mol), Puresyn 150 (MM=9200 g/mol), sold or manufactured by Mobil
Chemicals, - esters such as
- esters of linear fatty acids having a total carbon number of from 30 to 70, such as penta- erythrityl tetrapelargonate (MM=697.05 g/mol),
- hydroxyl-containing esters such as diisostearyl malate (MM=639 g/mol, refractive index of 1.462),
- aromatic esters such as tridecyl trimellitate (MM=757.19 g/mol) ,
- esters of C24-C28 branched fatty acids or fatty alcohols, such as those described in patent application EP-A-O 955 039, and more particularly triisocetyl citrate (MM=865 g/mol), penta- erythrityl tetraisononanoate (MM=697.05 g/mol), glyceryl triisostearate (MM=891.51 g/mol), glyceryl tri-2-decyltetradecanoate (MM=1143.98 g/mol), pentaerythrityl tetraiso- stearate (MM=1202.02 g/mol), poly-2-glyceryl tetraisostearate (MM=1232.04 g/mol) or else pentaerythrityl tetra-2-decyltetradecanoate
(MM=1538.66 g/mol) , - oils of plant origin such as sesame oil (820.6 g/mol)
- and mixtures thereof.
The non-volatile hydrocarbon oil is preferably selected from polybutenes.
The non-volatile hydrocarbon oil may represent from 0.5% to 40% by weight, preferably from 1% to 30% and more preferably from 5% to 20% by weight relative to the total weight of the composition comprising it, in particular relative to the total weight of each first and second composition.
The non-volatile silicone oils which can be used in the composition according to the invention may be nonvolatile polydimethylsiloxanes (PDMS) , polydimethyl- siloxanes containing alkyl or alkoxy groups pendantly and/or at the end of the silicone chain, these groups each having 2 to 24 carbon atoms, or phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldi- methicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates .
The fluoro oils which can be used in the invention are more particularly fluorosilicone oils, fluorine- containing polyethers and fluorosilicones as described in document EP-A-847752.
In one advantageous embodiment the composition or compositions comprises or comprise at least one nonvolatile silicone oil and preferably a phenyl silicone oil .
The phenyl silicone oils which can be used in the present invention have a viscosity as measured at 25°C and atmospheric pressure of 5 to 100 000 cSt, and preferably of 5 to 10 000 cSt.
The silicone oil may be, for example, a phenyltrimethicone, a phenyldimethicone, a phenyltri- methylsiloxydiphenylsiloxane, a diphenyldimethicone, a diphenylmethyldiphenyltrisiloxane or a mixture of different phenyl silicone oils, and in particular may correspond to the following formula (A) :
Figure imgf000054_0001
in which
- R9 and R12 each independently are a Ci-C30 alkyl radical, an aryl radical or an aralkyl radical,
- Rio and Rn each independently are a Ci-C30 alkyl radical or an aralkyl radical,
- u, v, w and x each independently are integers from 0 to 900, with the provisos that the sum v+w+x is different from 0 and that the sum u+v+w+x is from 1 to 900, in particular from 1 to 800.
Advantageously R9 is a Ci-C2O alkyl radical, a phenyl radical or an aralkyl radical of type R' -CeH5, R' being a Ci-C5 alkyl, Ri0 and Rn each independently are a Ci-C2O alkyl radical or an aralkyl radical of type R'-CδH5, R' being a Ci-C5 alkyl, and R12 is a Ci-C20 alkyl radical.
Preferably R9 is a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or else a phenyl, tolyl, benzyl or phenethyl radical, Ri0 and Rn each independently are a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or else a tolyl, benzyl or phenethyl radical, and Ri2 is a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical.
In accordance with one particular embodiment of the invention the composition or compositions contains or contain a phenyl silicone oil having a viscosity of less than 500 cSt at 25°C, referred to as "low- viscosity phenyl silicone oil", and a phenyl silicone oil having a viscosity of at least 500 cSt at 25°C, referred to as "high-viscosity phenyl silicone oil". Advantageously the low-viscosity phenyl silicone oil has a viscosity at 25°C of for example from 5 to 499 cSt, preferably from 5 to 300 cSt and more preferably from 5 to 100 cSt, and the high-viscosity phenyl silicone oil has a viscosity at 25°C of, for example, from 500 to 10 000 cSt, preferably from 600 to 5000 cSt and more preferably from 600 to 3000 cSt.
The use of phenyl silicone oils of low and high viscosity as defined above makes it possible to obtain, following deposition on the lashes, a film of composition which is particularly glossy, homogeneous and tenacious.
These low-viscosity and high-viscosity phenyl silicone oils preferably conform to the formula (A) . Preferably the first, low-viscosity phenyl silicone oil conforms to the formula (A) with the sum u+v+w+x being from 1 to 150 and more preferably from 1 to 100, or even from 1 to 50, and the second, high-viscosity phenyl silicone oil conforms to the formula (A) with the sum u+v+w+x being from 151 to 900, more preferably from 160 to 800, or even from 160 to 500.
In particular the low-viscosity phenyl silicone oil conforms to the formula (III)
Figure imgf000055_0001
in which :
• Re is a C1-C30 alkyl radical, an aryl radical or an aralkyl radical,
• n is an integer from 0 to 100 and more preferably less than 100,
• m is an integer from 0 to 100, with the proviso that the sum m+n is from 1 to 100 and more preferably is less than 100.
Advantageously Rs is a C1-C20 alkyl radical, a phenyl radical or an aralkyl radical of type R' -CeH5, R' being a Ci-C5 alkyl.
Preferably Rs is a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or else a phenyl, tolyl, benzyl or phenethyl radical. Advantageously, Rs is a methyl radical.
The low-viscosity phenyl silicone oils which can be used in the invention include the oils DC556
(22.5 cSt) , SF558 (10-20 cSt) from Dow Corning, the oil
Abil AV8853 (4-6 cSt) from Goldschmidt, the oil
Silbione 70 633 V 30 (28 cSt) from Rhone Poulenc, the oils 15 M 40 (50 to 100 cSt) , 15 M 50 (20 to 25 cSt) from PCR, the oils SF 1550 (25 cSt) and PK 20 (20 cSt) from Bayer , the oil Belsil PDM 200 (200 cSt) from
Wacker, and the oils KF 53 (175 cSt) , KF 54 (400 cSt) and KF 56 (14 cSt) from Shin-Etsu.
The high-viscosity phenyl silicone oils which can be used in the invention include the oils 15 M 30 from PCR (500 cSt) and Belsil PDM 1000 (1000 cSt) from Wacker. The values in brackets represent the viscosities at 25°C.
The ratio by weight between the low-viscosity phenyl silicone oil and the high-viscosity phenyl silicone oil may be for example from 70/30 to 30/70 and more preferably from 60/40 to 40/60. Preferably each composition, and in particular each of the first and second compositions, comprises at least one low-viscosity phenyl silicone oil and at least one high-viscosity phenyl silicone oil.
The non-volatile silicone oils may represent from 1% to 90%, preferably from 5% to 60%, more preferably from 10% to 50% and more preferably still from 30% to 50% of the total weight of the composition comprising them, in particular of the total weight of each first and second composition .
In one embodiment the first and second compositions employed in the method according to the invention are anhydrous.
An "anhydrous" composition is one comprising less than 5% by weight of water, preferably less than 3% by weight of water, relative to the total weight of the composition, and more preferably devoid of water.
Aqueous phase
At least one of the first and second compositions may comprise an aqueous phase.
The aqueous phase may be composed essentially of water; it may also comprise a mixture of water and water- miscible solvent (with a miscibility in water of more than 50% by weight at 25°C), such as lower monoalcohols having 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol and dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes and mixtures thereof.
The aqueous phase (water and, where appropriate, the water-miscible solvent) may be present in an amount of from 5% to 95% by weight, relative to the total weight of each composition, preferably from 10% to 85% by weight and more preferably from 2% to 80% by weight.
Wax
At least one of the first and second compositions may further comprise at least one wax, which may be animal, plant, mineral or synthetic in origin.
The wax considered in the context of the present invention is, generally speaking, a lipophilic compound which is solid at ambient temperature (25°C) and exhibits a reversible solid/liquid state change, having a melting point greater than or equal to 300C and possibly up to 1200C. By taking the wax into the liquid state (melting) it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but by lowering the temperature of the mixture to ambient temperature the wax undergoes recrystallization in the oils of the mixture.
In particular the waxes suitable for the invention may have a melting point greater than approximately 45°, and in particular greater than 55°C. The melting point of the wax can be measured using a differential scanning calorimeter (DSC) , an example being the calorimeter sold under the name DSC 30 by Mettler.
The measurement protocol is as follows: A 15 mg sample of product in a crucible is subjected to a first temperature rise from 00C to 1200C, at a heating rate of 10°C/minute, and is cooled from 1200C to 00C at a cooling rate of 10°C/minute, and finally is subjected to a second temperature rise from 00C to 1200C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the power difference absorbed by the empty crucible and by the crucible containing the sample of product is measured as a function of the temperature. The melting point of the compound is the temperature value 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 waxes which can be used in the first and second compositions according to the invention are selected from solid waxes which are deformable or non-deformable at ambient temperature and are of animal, plant, mineral or synthetic origin, and mixtures thereof. The wax may also have a hardness of from 0.05 MPa to 30 MPa, and preferably from 6 MPa to 15 MPa. The hardness is determined by measuring the compression force measured at 200C with the aid of the texturometer sold under the name TA-TX2i by Rheo, equipped with a stainless steel cylinder with a diameter of 2 mm which moves at a measuring speed of 0.1 mm/s and penetrates the wax to a depth of 0.3 mm. The measurement protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 200C. The melted wax is poured into a container with a diameter of 30 mm and a depth of 20 mm. The wax is recrystallized at ambient temperature (25°C) for 24 hours and then the wax is kept at 200C for at least 1 hour before the hardness measurement is performed. The value of the hardness is the maximum compression force measured, divided by the surface area of the cylinder of the texturometer that is in contact with the wax.
Use may be made in particular of hydrocarbon waxes such as beeswax, lanolin wax and Chinese insect waxes; rice wax, carnauba wax, candelilla wax, ouricury wax, alfa wax, cork fibre wax, sugarcane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fischer-Tropsch synthesis, and waxy copolymers, and also their esters.
Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils having C8-C32 linear or branched fatty chains.
Among these, mention may be made more particularly of hydrogenated jojoba oil, isomerized jojoba oil, such as the trans isomerized partially hydrogenated jojoba oil manufactured and sold by Desert Whale under the commercial reference ISO-JOJOBA-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin oil, the di (1,1,1- trimethylolpropane) tetrastearate sold under the name Hest 2T-4S by Heterene and the di (1,1,1- trimethylolpropane) tetrabehenate sold under the name Hest 2T-4B by Heterene. It is also possible to use the waxes obtained by transesterification and hydrogenation of vegetable oils, such as castor oil or olive oil, such as the waxes sold under the names Phytowax ricin 16L64® and 22L73® and Phytowax Olive 18L57 by Sophim. Waxes of this kind are described in Patent Application FR-A- 2792190.
It is also possible to use silicone waxes, which may advantageously be substituted polysiloxanes, preferably having a low melting point. These are, more particularly, substituted linear polysiloxanes composed essentially (with the exception of the end groups) of units of formulae II and III, in the respective molar proportions m and n:
Figure imgf000060_0001
OO (ill)
in which
- each substituent R is defined as above,
- each R' independently represents an optionally unsaturated (linear or branched) alkyl having 6-30 carbon atoms, or else a group -X-R", each X independently representing:
-O-,
Figure imgf000061_0001
- (CH2)Io-CO-O-, a and b independently representing numbers from 0 to 6, and each R" independently represents an optionally unsaturated alkyl group having 6 to 30 carbon atoms,
- m is a number from 0 to 400, and in particular from 0 to 100,
- n is a number from 1 to 200, and in particular from 1 to 100, the sum (m+n) being less than 400, and in particular less than or equal to 100.
These silicone waxes are known or can be prepared in accordance with known processes. The commercial silicone waxes of this type include, more particularly, those sold under the names Abilwax 9800, 9801 or 9810 (Goldschmidt) , KF910 and KF7002 (Shin Etsu) , or 176-1118-3 and 176-11481 (General Electric) .
The silicone waxes which can be used may also be selected from the compounds of formula:
Ri-Si (CHs)2-O- [Si (R)2-O-] Z-Si (CH3) 2-R2
in which:
R is defined as above,
Ri represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 6 to 30 carbon atoms, or a group of formula: o o
cca^-αo-ir or —(CM^-O-C-R"
R2 represents an alkyl group of 6 to 30 C, an alkoxy group having 6 to 30 C or a group of formula :
A O
(Oy1-OCMl' or -(QI2VO-C-R"
a and b representing a number from 0 to 6, R" being an alkyl having 6 to 30 carbon atoms, and z is a number from 1 to 100.
The silicone waxes of formula (IV) include more particularly the alkyldimethicones or alkoxy- dimethicones such as the following commercial products: Abilwax 2428, 2434 and 2440 (Goldschmidt) , or VP 1622 and VP 1621 (Wacker) , and also (C20-C60)- alkyldimethicones, in particular (C30-C45) alkyldimethicones, such as the silicone wax sold under the name SF-1642 by GE-Bayer Silicones.
It is also possible to use hydrocarbon waxes which are modified with silicone or fluoro groups, such as, for example, the following: siliconyl candelilla, siliconyl beeswax and Fluorobeeswax from Koster Keunen.
The waxes may also be selected from fluorowaxes.
In one particular embodiment the first and second compositions according to the invention may comprise at least one wax referred to as a tacky wax and hence possessing a tack of greater than or equal to 0.7 N. s and a hardness of less than or equal to 3.5 MPa. The tacky wax used may more particularly possess a tack of from 0.7 N. s to 30 N.s, in particular greater than or equal to 1 N.s, more particularly from 1 N.s to 20 N.s, in particular greater than or equal to 2 N.s, more particularly from 2 N.s to 10 N.s, and in particular from 2 N.s to 5 N.s.
The tack of the wax is determined by measuring the change in force (compression force or drawing force) as a function of time, at 200C, using the texturometer sold under the name TA-TX2i® by Rheo, equipped with a conical acrylic polymer spindle forming an angle of 45°.
The measurement protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 100C. The melted wax is poured into a container with a diameter of 25 mm and a depth of 20 mm. The wax is recrystallized at ambient temperature (25°C) for 24 hours such that the surface of the wax is flat and smooth, and then the wax is kept at 200C for at least 1 hour before the tack is measured.
The texturometer spindle is moved at a speed of 0.5 mm/s and then penetrates the wax to a depth of 2 mm. When the spindle has penetrated the wax to the depth of 2 mm, the spindle is held still for 1 second (corresponding to the relaxation time) and then is withdrawn at a speed of 0.5 mm/s.
During the relaxation time, the force (compression force) decreases greatly until it becomes zero, and then, when the spindle is withdrawn, the force (drawing force) becomes negative and then rises again to the value 0. The tack corresponds to the integral of the curve of the force as a function of time for the part of the curve that corresponds to negative values of the force (drawing force) . The tack value is expressed in N.s.
The tacky wax which can be used generally has a hardness of less than or equal to 3.5 MPa, in particular from 0.01 MPa to 3.5 MPa, more particularly from 0.05 MPa to 3 MPa, and even from 0.1 MPa to 2 . 5 MPa .
The hardness is measured according to the protocol described above.
As a tacky wax it is possible to use a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group containing 20 to 40 carbon atoms), alone or in a mixture, in particular a C20-C40 alkyl 12- (12' -hydroxystearyloxy) - stearate .
A wax of this kind is sold more particularly under the names Kester Wax K 82 P® and Kester Wax K 80 P® by Koster Keunen.
The aforementioned waxes generally have a melting point commencing at below 45°C.
The wax or waxes may be present in the form of an aqueous wax microdispersion . An aqueous wax microdispersion is an aqueous dispersion of wax particles in which the size, expressed as the volume- average "effective" diameter D [4, 3], of the said wax particles is less than or equal to approximately 1 μm.
The wax microdispersions are stable dispersions of colloidal wax particles and are described more particularly in "Microemulsions Theory and Practice", L. M. Prince Ed., Academic Press (1977) pages 21-32.
In particular these wax microdispersions may be obtained by melting the wax in the presence of a surfactant, and optionally part of the water, and then progressively adding hot water with stirring. The intermediate formation of a water-in-oil emulsion is observed, followed by a phase inversion, leading finally to an oil-in-water microemulsion . On cooling, a stable microdispersion of solid colloidal wax particles is obtained. The wax microdispersions may also be obtained by stirring the mixture of wax, surfactant and water using stirrer means such as ultrasound, a high-pressure homogenizer or turbines. The particles of the wax microdispersion preferably have average dimensions of less than 1 μm (more particularly from 0.02 μm to 0.99 μm) , preferably less than 0.5 μm (more particularly from 0.06 μm to 0.5 μm) .
These particles are composed essentially of a wax or of a mixture of waxes. They may, however, comprise, to a minor extent, oily and/or pasty fatty additives, a surfactant and/or a customary fat-soluble additive/active.
The waxes may represent from 0.1 to 70% by weight, relative to the total weight of each composition, in particular relative to the total weight of each first and second composition, more preferably from 1% to 40% and more preferably still from 2% to 30% by weight.
Film-forming polymer
At least one of the first and second compositions may comprise a film-forming polymer. According to the present invention, the term "film-forming polymer" means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, of forming a continuous film that adheres to a support and especially to the lashes.
The film-forming polymer may be present in a solids content (or active material content) ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1% to 15% by weight relative to the total weight of each composition.
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. The expression "free-radical film-forming polymer" means a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopoly- merizing (unlike polycondensates) .
The film-forming polymers of free-radical type may be, in particular, vinyl polymers or copolymers, in particular acrylic polymers. The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acidic group and/or esters of these acidic monomers and/or amides of these acidic monomers . Monomers bearing an acidic group which may be used are 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 preferably used, and more preferably (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 C1-C30 and preferably C1-C20 alkyl, (meth) acrylates of an aryl, in particular of a Cδ-Cio 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, lauryl methacrylate and cyclohexyl 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 that are particularly preferred are the 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. Examples of amides of the acid monomers that may be mentioned are (meth) acrylamides, and especially N- alkyl (meth) acrylamides, in particular of a C2-C12 alkyl. Among the N-alkyl (meth) acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide .
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 above.
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 are styrene and α-methylstyrene .
Among the film-forming polycondensates that may be mentioned are polyurethanes, polyesters, polyester- amides, polyamides, epoxyester resins and polyureas. The polyurethanes may be chosen from anionic, cationic, nonionic and amphoteric polyurethanes, polyurethane- acrylics, polyurethane-polyvinylpyrrolidones, poly- ester-polyurethanes, polyether-polyurethanes, polyureas and polyurea/polyurethanes, and mixtures thereof. The polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols.
The dicarboxylic acid may be aliphatic, alicyclic or aromatic. Examples of such acids that may be mentioned are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2, 2-dimethylglutaric acid, azeleic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclo- hexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2, 5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2, 5-naphthalenedicarboxylic acid or 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 preferentially chosen are phthalic acid, isophthalic acid and terephthalic acid. The diol may be chosen from aliphatic, alicyclic and aromatic diols. The diol used is preferably chosen 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 trimethylol- propane .
The polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycon- densation of diacids with diamines or amino alcohols. Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para-phenylenedi- amine. An amino alcohol that may be used is monoethanolamine . The polyester may also comprise at least one monomer bearing at least one group -SO3M, with M representing a hydrogen atom, an ammonium ion NH4 + or a metal ion such as, for example, an Na+, Li+, K+, Mg2+, Ca2+, Cu2+, Fe2+ or Fe3+ ion. A difunctional aromatic monomer comprising such a group -SO3M may be used in particular. The aromatic nucleus of the difunctional aromatic monomer also bearing a group -SO3M as described above may be chosen, for example, from benzene, naphthalene, anthracene, biphenyl, oxybiphenyl, sulphonylbiphenyl and methylenebiphenyl nuclei. As examples of difunctional aromatic monomers also bearing a group -SO3M, mention may be made of: sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid, 4-sulphonaphthalene-2 , 7-dicarboxylic acid. The copolymers preferably used are those based on isophthalate/sulphoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexanedimethanol, isophthalic acid and sulphoisophthalic acid. The polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac gum, dammar resins, elemi gums, copal resins and cellulose polymers, and mixtures thereof.
According to a first embodiment of the invention, the film-forming polymer may be a water-soluble polymer and may be present in an aqueous phase of the first and/or second composition; the polymer is thus solubilized in the aqueous phase of the composition.
According to another variant, the film-forming polymer may be a polymer dissolved in a liquid fatty phase comprising organic solvents or oils such as those described above (the film-forming polymer is thus the said to be a liposoluble polymer) . The liquid fatty phase preferably comprises a volatile oil, optionally mixed with a non-volatile oil, the oils possibly being chosen from those mentioned above. Examples of liposoluble polymers that may be mentioned are copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present) , an α-olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group comprises from 2 to 18 carbon atoms) or an allylic or methallylic ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) . These copolymers may be crosslinked with the aid of crosslinking agents, which may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octane- dioate, divinyl dodecanedioate and divinyl octadecane- dioate . Examples of these copolymers that may be mentioned are the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/ octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/ 1-octadecene, vinyl acetate/1-dodecene, vinyl stearate/ ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2, 2-dimethyloctan- oate/vinyl laurate, allyl 2, 2-dimethylpentanoate/vinyl laurate, vinyl dimethylpropionate/vinyl stearate, allyl dimethylpropionate/vinyl stearate, vinyl propionate/ vinyl stearate, crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate/vinyl laurate, crosslinked with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl stearate, crosslinked with 0.2% divinylbenzene, vinyl acetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and allyl propionate/allyl stearate, crosslinked with 0.2% divinylbenzene. Examples of liposoluble film-forming polymers that may also be mentioned are liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, and alkyl radicals containing from 10 to 20 carbon atoms.
Such liposoluble copolymers may be chosen from polyvinyl stearate, polyvinyl stearate crosslinked with the aid of divinylbenzene, of diallyl ether or of diallyl phthalate, polystearyl (meth) acrylate, poly- vinyl laurate and polylauryl (meth) acrylate copolymers, it being possible for these poly (meth) acrylates to be crosslinked with the aid of ethylene glycol dimeth- acrylate or tetraethylene glycol dimethacrylate . The liposoluble copolymers defined above are known and are described in particular in patent application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000. Mention may also be made of liposoluble homopolymers, and in particular those resulting from the homopolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals containing from 2 to 24 carbon atoms.
Examples of liposoluble homopolymers that may especially be mentioned include: polyvinyl laurate and polylauryl (meth) acrylates, these poly (meth) acrylates possibly being crosslinked using ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate .
According to one advantageous embodiment, the first and/or second composition of the method according to the invention comprises at least one polyvinyl laurate film-forming polymer.
As liposoluble film-forming polymers which may be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched, saturated or unsaturated Ci-Cs alkyl radical, for instance ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still C3 to C20 alkene. As examples of VP copolymers which may be used in the invention, mention may be made of the copolymers of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP) , VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate.
Mention may also be made of silicone resins, which are generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers. The nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters "MDTQ" characterizing a type of unit. Examples of commercially available polymethylsilsesqui- oxane resins that may be mentioned include those sold: by the company Wacker under the reference Resin MK, such as Belsil PMS MK; by the company Shin-Etsu under the reference KR-220L. Siloxysilicate resins that may be mentioned include trimethyl siloxysilicate (TMS) resins such as those sold under the reference SR 1000 by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of the trimethyl siloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name KF-7312J by the company Shin-Etsu, and DC 749 and DC 593 by the company Dow Corning. Mention may also be made of silicone resin copolymers such as those mentioned above with polydimethyl- siloxanes, for instance the pressure-sensitive adhesive copolymers sold by the company Dow Corning under the reference Bio-PSA and described in document US 5 162 410, or the silicone copolymers derived from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane, as described in document WO 2004/073626.
It is also possible to use 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.
These silicone polymers may belong to the following two families : polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and/or polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches. According to one embodiment of the invention, the film- forming polymer is a film-forming linear block ethylenic polymer, which preferably comprises at least a first block and at least a second block with different glass transition temperatures (Tg) , the said first and second blocks being linked together via an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
Advantageously, the first and second blocks of the block polymer are mutually incompatible.
Such polymers are described, for example, in document EP 1 411 069 or WO 04/028488.
The film-forming polymer may also be present in the first and/or second composition in the form of particles dispersed in an aqueous phase or in a nonaqueous solvent phase, which is generally known as a latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art .
Aqueous dispersions of film-forming polymers that may be used include the acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the company Avecia-Neoresins, Dow Latex 432® by the company Dow Chemical, Daitosol 5000 AD® or Daitosol 5000 SJ® by the company Daito Kasey Kogyo; Syntran 5760® by the company Interpolymer, Allianz OPT by the company Rohm & Haas, aqueous dispersions of acrylic or styrene/acrylic polymers sold under the brand name Joncryl® by the company Johnson Polymer, or the aqueous dispersions of polyurethane sold under the names Neorez R-981® and Neorez R-974® by the company Avecia-Neoresins, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Sancure 861®, Sancure 878® and Sancure 2060® by the company Goodrich, Impranil 85® by the company Bayer and Aquamere H-1511® by the company Hydromer; the sulphopolyesters sold under the brand name Eastman AQ® by the company Eastman Chemical Products, and vinyl dispersions, for instance Mexomer PAM® from the company Chimex, and mixtures thereof.
Examples of non-aqueous film-forming polymer dispersions that may also be mentioned include acrylic dispersions in isododecane, for instance Mexomer PAP® from the company Chimex, and dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described especially in document WO 04/055081. The compositions according to the invention may comprise a plasticizer that promotes the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from any compound known to those skilled in the art as being capable of fulfilling the desired function.
Colorants
At least one of the first and second compositions used in the process according to the invention may comprise at least one colorant chosen, for example, from pigments, nacres, dyes and materials with an effect, and mixtures thereof.
These colorants may be present in a content ranging from 0.01% to 50% by weight and preferably from 0.01% to 30% by weight relative to the weight of each first and second composition or relative to the total weight of the composition when A and B are present in the same composition .
The pigments that are useful in the present invention may be in the form of powder or of pigmentary paste.
The term "dyes" should be understood as meaning compounds, generally organic, which are soluble in at least one oil or in an aqueous-alcoholic phase. The term "pigments" should be understood as meaning white or coloured, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify the resulting film. The term "nacres" or nacreous pigments should be understood as meaning coloured particles of any form, which may or may not be iridescent, especially produced by certain molluscs in their shell or else synthesized, and which have a colour effect via optical interference .
The pigment may be an organic pigment. The term "organic pigment" means any pigment that satisfies the definition in Ullmann' s encyclopaedia in the chapter on organic pigments. The organic pigment may especially be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds. The organic pigment (s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanin blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and the pigments obtained by oxidative polymerization of indole or phenolic derivatives as described in patent FR 2 679 771.
These pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be composed especially of particles comprising an inorganic nucleus at least partially coated with an organic pigment and at least one binder to fix the organic pigments to the nucleus. Examples that may also be mentioned include pigmentary pastes of organic pigments such as the products sold by the company Hoechst under the names:
- Jaune Cosmenyl IOG: Pigment Yellow 3 (CI 11710);
- Jaune Cosmenyl G: Pigment Yellow 1 (CI 11680);
- Orange Cosmenyl GR: Pigment Orange 43 (CI 71105) ; - Rouge Cosmenyl R": Pigment Red 4 (CI 12085);
- Carmine Cosmenyl FB: Pigment Red 5 (CI 12490);
- Violet Cosmenyl RL: Pigment Violet 23 (CI 51319);
- Bleu Cosmenyl A2R: Pigment Blue 15.1 (CI 74160);
- Vert Cosmenyl GG: Pigment Green 7 (CI 74260); - Noir Cosmenyl R: Pigment Black 7 (CI 77266) .
The pigment may also be a lake. The term "lake" means insolubilized dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use . The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium. Among the organic dyes, mention may be made of cochineal carmine. Mention may also be made of the products known under the following names: D&C Red 21
(CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI
45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI
45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090). An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850 : 1 ) .
The pigment may also be a pigment with special effects. The term "pigments with special effects" means pigments that generally create a non-uniform coloured appearance (characterized by a certain shade, a certain vivacity and a certain lightness) that changes as a function of the conditions of observation (light, temperature, observation angles, etc.). They thus contrast with white or coloured pigments that afford a standard uniform opaque, semi-transparent or transparent shade.
Two types of pigment with special effects exist: those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a high refractive index, such as nacres or flakes. Pigments with special effects that may be mentioned include nacreous pigments such as 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 especially with ferric blue or with chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. Mention may also be made of pigments with an interference effect that are not fixed onto a substrate, for instance liquid crystals (Helicones HC from Wacker) , holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek) . Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
Quantum dots are luminescent semiconductive nanoparticles capable of emitting, under light excitation, irradiation with a wavelength of between 400 nm and 700 nm. These nanoparticles are known from - li ¬ the literature. They may be manufactured in particular according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications cited therein, and also in the following publications: Dabboussi B. O. et al . "(CdSe)ZnS core-shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites" Journal of Physical Chemistry B, vol. 101, 1997, pp. 9463-9475 and Peng, Xiaogang et al . "Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility", Journal of the American Chemical Society, vol. 119, No. 30, pp. 7019-7029. Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments and thermochromic pigments. The pigment may be a mineral pigment. The term "mineral pigment" means any pigment that satisfies the definition in Ullmann' s encyclopaedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also iron oxide or chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium dioxide. The following mineral pigments may also be used: Ta2<05, Ti3O5, Ti2O3, TiO, ZrO2 as a mixture with TiO2, ZrO2, Nb2O5, CeO2, ZnS. The pigment may also be a nacreous pigment such as white nacreous pigments, for example mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica coated with titanium and with iron oxides, mica coated with titanium and especially with ferric blue or chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also nacreous pigments based on bismuth oxychloride. Examples that may be mentioned include the Cellini pigments sold by Engelhard (Mica-TiO2-lake) , Prestige sold by Eckart (Mica-TiO2) or Colorona sold by Merck (MiCa-TiO2-Fe2O3) .
In addition to nacres on a mica support, multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicates, and aluminium, may be envisaged.
The size of the pigment that is useful in the context of the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm and more preferentially between 30 nm and 50 μm.
The pigments may be dispersed in the product by means of a dispersant. The dispersant serves to protect the dispersed particles against agglomeration or flocculation . This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they can physically or chemically attach to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, 12-hydroxystearic acid esters and Cs to C2o fatty acid esters of polyols such as glycerol or diglycerol are used, such as poly (12-hydroxystearic acid) stearate with a molecular weight of about 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel PlOO by the company Uniqema, and mixtures thereof. As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C. The polydihydroxystearic acid and the 12-hydroxystearic acid esters are preferably intended for a hydrocarbon- based or fluorinated medium, whereas the mixtures of oxyethylene/oxypropylenated dimethylsiloxane are preferably intended for a silicone medium.
The compositions according to the invention may comprise at least one filler, especially in a content ranging from 0.01% to 50% by weight and preferably ranging from 0.01% to 30% by weight relative to the total weight of each first and second composition or relative to the total weight of the composition when A and B are present in the same composition. The fillers may be mineral or organic and of any form, platelet- shaped, spherical or oblong, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, silica surface-treated with a hydrophobic agent, kaolin, polyamide powder, for instance Nylon® (Orgasol® from Atochem) , poly-β-alanine powder and polyethylene powder, tetrafluoroethylene polymer powders, (Teflon®) , lauroyllysine, starch, boron nitride, expanded hollow polymer microspheres such as those made of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® from Dow Corning) and silicone resin microbeads (for example Tospearls® from Toshiba) , elastomeric polyorgano- siloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos) , glass or ceramic microcapsules, and metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate or magnesium myristate . The compositions according to the invention may also contain ingredients commonly used in cosmetology, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, fragrances, acidifying or basifying agents, preserving agents, sunscreens, surfactants, antioxidants, fibres and care agents, or mixtures thereof.
The gelling agents that may be used in the compositions according to the invention may be organic or mineral, and polymeric or molecular, hydrophilic or lipophilic gelling agents.
Mineral lipophilic gelling agents that may be mentioned include optionally modified clays, for instance hectorites modified with a Cio to C22 fatty acid ammonium chloride, for instance hectorite modified with distearyldimethylammonium chloride, for instance the product sold under the name "Bentone 38V®" by the company Elementis.
Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 μm. Specifically, it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane . Silicas thus treated are known as "silica silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS- 530® by the company Cabot;
- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained especially by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane . Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.
The hydrophobic fumed silica particularly has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.
The polymeric organic lipophilic gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6®, KSG16® and KSG18® from Shin-Etsu, Trefil E-505C® or Trefil E-506C® from Dow Corning, Gransil SR-CYC®, SR DMF 10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® from Grant Industries and SF 1204® and JK 113® from General Electric; ethylcellulose, for instance the product sold under the name Ethocel by Dow Chemical; polycondensates of polyamide type resulting from condensation between (α) 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 one saturated and linear 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; galactomannans comprising from one to six and in particular from two to four hydroxyl groups per saccharide, substituted with a saturated or unsaturated alkyl chain, for instance guar gum alkylated with Ci to Ce, and in particular Ci to C3, alkyl chains, and mixtures thereof; block copolymers of "diblock" or "triblock" 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 .
Among the gelling agents that may be used in the compositions according to the invention, mention may also be made of fatty acid esters of dextrin, such as dextrin palmitates, especially the products sold under the name Rheopearl Tl/ or Rheopearl Kl/ by the company Chiba Flour.
The lipophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 40% by weight, preferably from 0.5% to 20% and better still from 1% to 15% by weight relative to the total weight of the composition comprising them, in particular to the weight of each first and second composition.
Hydrophilic or water-soluble gelling agents that may be mentioned include: - homopolymers or copolymers of acrylic or methacrylic acid or the salts 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 the 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, sodium polymethacrylate sold under the name Darvan No. 7 by the company Vanderbilt, and the sodium salts of polyhydroxycarboxylic acids sold under the name Hydagen F by the company Henkel;
- polyacrylic acid/alkyl acrylate copolymers of the Pemulen type; - AMPS (polyacrylamidomethylpropanesulphonic acid partially neutralized with ammonia and highly crosslinked) sold by the company Clariant;
- AMPS/acrylamide copolymers of the Sepigel or Simulgel type, sold by the company SEPPIC, and
- AMPS/polyoxyethylenated alkyl methacrylate copolymers (crosslinked or non-crosslinked) ; and mixtures thereof.
As other examples of water-soluble gelling polymers, mention may be made of:
- proteins, for instance proteins of plant origin, such as wheat or soybean proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and sulphonic keratins;
- anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;
- cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, 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;
- associative polyurethanes such as the C16-OE120-C16 polymer from the company Servo Delden (sold under the name Ser Ad FXIlOO, which is a molecule containing urethane functions and having a weight-average molecular weight of 1300), OE being an oxyethylene unit, Rheolate 205 containing urea functions, sold by the company Rheox, or Rheolate 208 or 204 (these polymers being sold in pure form) or DW 1206B from Rohm & Haas, containing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% 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 Ser Ad FXlOlO, Ser Ad FX1035 and Ser Ad 1070 from the company Servo Delden, and Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Rheox. It is also possible to use the product DW 1206F and DW 1206J, and also Acrysol RM 184 or Acrysol 44 from the company Rohm & Haas, or Borchigel LW 44 from the company Borchers;
- optionally modified polymers of natural origin, such as:
- gum arabics, guar gum, xanthan derivatives and karaya gum;
- alginates and carrageenans; glycoaminoglycans, and hyaluronic acid and its derivatives;
- shellac resin, sandarac gum, dammar resins, elemi gums and copal resins;
- deoxyribonucleic acid;
- mucopolysaccharides such as hyaluronic acid and chondroitin sulphates, and mixtures thereof.
The hydrophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 20% by weight, preferably from 0.5% to 10% and better still from 0.8% to 5% by weight relative to the total weight of each first and second composition .
The compositions according to the invention may contain emulsifying surfactants, which are especially present in a proportion ranging from 0.1% to 30% by weight, better still from 1% to 15% and even better still from 2% to 10% relative to the total weight of each composition. These surfactants may be chosen from anionic, nonionic, amphoteric and zwitterionic surfactants. Reference may be made to the document "Encyclopedia of Chemical Technology, Kirk-Othmer", Volume 22, pp. 333-432, 3rd Edition, 1979, Wiley, for the definition of the properties and functions (emulsifying) of surfactants, in particular pp. 347-377 of this reference, for the anionic and nonionic surfactants .
The surfactants preferentially used in the first and second compositions according to the invention are chosen from: a) nonionic surfactants with an HLB of greater than or equal to 8 at 25°C, used alone or as a mixture; mention may be made especially of:
- oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) of glycerol;
- oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) of fatty alcohols (especially of C8-C24 and preferably C12-C18 alcohol) , such as oxyethylenated cetearyl alcohol ether containing 30 oxyethylene groups (CTFA name Ceteareth-30) and the oxyethylenated ether of the mixture of C12-C15 fatty alcohols comprising 7 oxyethylene groups (CTFA name C12-15 Pareth-7 sold under the name Neodol 25-7® by Shell Chemicals) ;
- fatty acid esters (especially of a C8-C24 and preferably C16-C22 acid) of polyethylene glycol (which may comprise from 1 to 150 ethylene glycol units), such as PEG-50 stearate and PEG-40 monostearate sold under the name Myrj 52P by the company ICI Uniqema;
- fatty acid esters (especially of a C8-C24 and preferably C16-C22 acid) of oxyethylenated and/or oxypropylenated glyceryl ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) , for instance PEG-200 glyceryl monostearate sold under the name Simulsol 220 TM by the company SEPPIC; glyceryl stearate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat S sold by the company Goldschmidt, glyceryl oleate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat O sold by the company Goldschmidt, glyceryl cocoate polyethoxylated with 30 ethylene oxide groups, for instance the product Varionic LI 13 sold by the company Sherex, glyceryl isostearate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat L sold by the company Goldschmidt, and glyceryl laurate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat I from the company Goldschmidt; - fatty acid esters (especially of a C8-C24 and preferably C16-C22 acid) of oxyethylenated and/or oxypropylenated sorbitol ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) , for instance polysorbate 60 sold under the name Tween 60 by the company Uniqema;
- dimethicone copolyol, such as the product sold under the name Q2-5220 by the company Dow Corning;
- dimethicone copolyol benzoate (Finsolv SLB 101 and 201 by the company Fintex) ; - copolymers of propylene oxide and of ethylene oxide, also known as EO/PO polycondensates, for instance the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the name Synperonic, for instance Synperonic PE/L44 and Synperonic PE/F127, by the company ICI, and mixtures thereof;
- and mixtures thereof. b) nonionic surfactants with an HLB of less than 8 at 25°C, optionally combined with one or more nonionic surfactants with an HLB of greater than 8 at 25°C, as mentioned above, such as:
- saccharide esters and ethers, such as sucrose stearate, sucrose cocoate and sorbitan stearate, and mixtures thereof, for instance Arlatone 2121 sold by the company ICI;
- fatty acid esters (especially of a C8-C24 and preferably C16-C22 acid) of polyols, especially of glycerol or of sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name Tegin M by the company Goldschmidt, glyceryl laurate such as the product sold under the name Imwitor 312 by the company HuIs, polyglyceryl-2 stearate, sorbitan tristearate or glyceryl ricinoleate; - the mixture of cyclomethicone/dimethicone copolyol sold under the name Q2-3225C by the company Dow Corning. c) anionic surfactants such as:
- C16-C30 fatty acid salts, especially those derived from amines, for instance triethanolamine stearate;
- polyoxyethylenated fatty acid salts, especially those derived from amines or alkali metal salts, and mixtures thereof;
- phosphoric esters and salts thereof, such as DEA oleth-10 phosphate (Crodafos N ION from the company
Croda) and cetyl phosphate (Amphisol K from the company DSM Nutritional Products) ;
- sulphosuccinates such as Disodium PEG-5 citrate lauryl sulphosuccinate and Disodium ricinoleamido MEA sulphosuccinate;
- alkyl ether sulphates, such as sodium lauryl ether sulphate;
- isethionates;
- acylglutamates such as Disodium hydrogenated tallow glutamate (Amisoft HS-21 R sold by the company
Ajinomoto), and mixtures thereof.
Triethanolamine stearate is most particularly suitable for the invention. It is generally obtained by simple mixing of stearic acid and triethanolamine. Surfactants that allow an oil-in-water or wax-in-water emulsion to be obtained are preferably used.
The compositions according to the invention may comprise any cosmetic active agent, such as active agents chosen from antioxidants, preserving agents, fragrances, bactericidal or antiperspirant active agents, neutralizers, emollients, moisturizers, vitamins and screening agents, in particular sunscreens . Of course, a person skilled in the art will take care to select this or these optional additional compound (s), and/or the amount thereof, such that the advantageous properties of the corresponding composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition, especially so as not to interfere with the reaction between compounds A and B.
The first and second, and where appropriate third, compositions according to the invention may be, independently, in the form of a suspension, a dispersion, a solution, a gel, an emulsion, especially an oil-in-water (O/W) emulsion, a wax-in-water or water-in-oil (W/O) emulsion or a multiple emulsion
(W/O/W or polyol/O/W or 0/W/O) or in the form of a cream, a paste, a mousse, a vesicular dispersion, especially of ionic or nonionic lipids, a two-phase or multiphase lotion, a powder or a paste, especially a soft paste.
A person skilled in the art may select the appropriate formulation, and also the method for preparing it, on the basis of his or her general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the vehicle, and secondly the intended use of each composition.
The invention is illustrated in greater detail by the examples described below. Unless otherwise mentioned, the amounts indicated are expressed as mass percentages .
EXAMPLES
In the composition examples described below the combination of the following mixtures A and B, which are prepared by Dow Corning, is used: MIXTURE A:
Figure imgf000090_0001
MIXTURE B:
Figure imgf000090_0002
Example 1 : Mascara
Composition 1
Figure imgf000090_0003
At ambient temperature the various compounds are mixed in a beaker with gentle turbine stirring.
Composition 2
Figure imgf000091_0001
Procedure
The black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. In parallel, the other compounds are mixed in a beaker with gentle turbine stirring. The premix of phenyltrimethicone and pigments is then added, with gentle stirring continued. The whole of the procedure is carried out at ambient temperature.
Example 2 : Mascara
Composition 1
Figure imgf000091_0002
At ambient temperature the various compounds are mixed in a beaker with gentle turbine stirring.
Composition 2
Figure imgf000092_0001
Procedure
The black iron oxide is dispersed in the phenyl- trimethicone DC556 with gentle magnetic stirring.
In parallel, the other compounds are mixed in a beaker with gentle turbine stirring. The premix of phenyltrimethicone and pigments is then added, with gentle stirring continued. The whole of the procedure is carried out at ambient temperature.
For each example, a layer of the first composition is applied to 6 specimens of Caucasian hair (30 hairs 1 cm long distributed over a distance of 1 cm) , and then a layer of the composition 2 is applied. The coated hair is left to dry for several minutes.
Three of the 6 specimens of false eyelashes made-up with the compositions of Example 2 were immersed for 1 week in a crystallizer basin containing water, and 3 specimens of false eyelashes in a crystallizing basin containing artificial sebum (formulated on the basis of the known composition of sebum) .
After one week of immersion, each test specimen is wiped with a cotton swab and then the amount of mascara on the cotton and on the lashes is evaluated. After 1 week of immersion in water or in sebum, no transfer of mascara was observed on the swab.
The compositions of Examples 1 and 2 can also be applied by mixing the first and second compositions at the time of use.
Example 3 : Mascara
Composition 1
Figure imgf000093_0001
Procedure
The black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. This dispersion and the fibres are added under Rayneri stirring in the polyethylene wax already melted, and stirring is maintained during cooling of the mixture. When the mixture is thickening but is still melted, mixture A (non heated) is added, with gentle stirring continued until recovering at ambient temperature.
Composition 2
Figure imgf000093_0002
Example 4 Mascara
Composition 1
Figure imgf000094_0001
Composition 2
Figure imgf000094_0002
Procedure
The black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. This dispersion and the fibres are added under Rayneri stirring in the silicone wax already melted, and stirring is maintained during cooling of the mixture. When the mixture is thickening but is still melted, mixture A (non heated) is added, with gentle stirring continued until recovering at ambient temperature.
Example 5 : Mascara In the composition examples described below the combination of the following mixtures C and D, which are prepared by Dow Corning, is used:
MIXTUREC :
Figure imgf000095_0001
MIXTURE D :
Figure imgf000095_0002
Composition 1
Figure imgf000095_0003
The black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. In parallel the mixture C is placed in a beaker with gentle turbine stirring. Subsequently the premix of phenyltrimethicone and pigments is added, still with gentle stirring. The totality of the procedure is carried out at ambient temperature.
Composition 2
Figure imgf000096_0001
Procedure
Composition 1 is mixed with composition 2 in a 10/1 ratio .
Example 6 : Mascara
Composition 1
Figure imgf000096_0002
The black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. In parallel the other compounds are mixed in a beaker with gentle turbine stirring. Subsequently the premix of phenyltrimethicone and pigments is added, still with gentle stirring. The totality of the procedure is carried out at ambient temperature.
Composition 2
Figure imgf000096_0003
Procedure Composition 1 is mixed with composition 2 in a 4/1 ratio .
Example 7 : Mascara
Composition 1
Figure imgf000097_0001
The black iron oxide is dispersed in the phenyltrimethicone DC556 with gentle magnetic stirring. In parallel the other compounds are mixed in a beaker with gentle turbine stirring. Subsequently the premix of phenyltrimethicone and pigments is added, still with gentle stirring. The totality of the procedure is carried out at ambient temperature.
Composition 2
Figure imgf000097_0002
Procedure
Composition 1 is mixed with composition 2 in 60/40 ratio .

Claims

1. Lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately,
- the kit comprising at least one compound (X) , at least one compound (Y) and at least one catalyst, at least one of the compounds, X or Y, being a silicone compound,
- with the proviso that the compounds X and Y and the catalyst are not present simultaneously in the same composition,
- the said compounds X and Y reacting together by a hydrosilylation reaction, when they are brought into contact with one another in the presence of the catalyst, fibres; and at least one phenyl silicone oil.
2. Lash coating kit comprising: at least one first composition and at least one second composition, which are packaged separately, - the kit comprising at least one compound (X) at least one compound (Y) , at least one of the compounds, X or Y, being a silicone compound,
- with the proviso that the compounds X and Y are not present simultaneously in the same composition,
- the said compounds X and Y reacting together by a condensation reaction when they are brought into contact with one another, - fibres; and at least one phenyl silicone oil.
3. Kit according to Claim 1 or 2, characterized in that one at least of the compounds X and Y carries at least one polar group able to form at least one hydrogen bond with the lashes.
4. Kit according to Claim 2 or 3, characterized in that it comprises a catalyst.
5. Kit according to Claim 1 or 3, characterized in that the compound X is selected from silicone compounds comprising at least two unsaturated aliphatic groups.
6. Kit according to Claim 1, 3 or 5, wherein the compound X is a polyorganosiloxane comprising a silicone main chain whose unsaturated aliphatic groups are pendant to the main chain (side group) or are situated at the ends of the main chain of the compound (end group) .
7. Kit according to one of Claims 1, 3, 5 and 6, characterized in that the compound X carries at least one polar group able to form at least one hydrogen bond with the lashes.
8. Kit according to one of Claims 1, 3 and 5 to 7, characterized in that the compound X is selected from polyorganosiloxanes comprising at least two unsaturated aliphatic groups each bonded to a silicon atom.
9. Kit according to one of Claims 1, 3 and 5 to 8, characterized in that the compound X is selected from polyorganosiloxanes comprising siloxane units of formula:
Figure imgf000099_0001
in which:
R represents a monovalent linear or cyclic hydrocarbon group containing 1 to 30 carbon atoms, m is 1 or 2 and
R' represents: an unsaturated aliphatic hydrocarbon group containing 2 to 10, preferably 3 to 5, carbon atoms or an unsaturated cyclic hydrocarbon group containing 5 to 8 carbon atoms .
10. Kit according to Claim 9, wherein the polyorgano- siloxane of formula (I) is such that R' represents a vinyl group or a group -R"-CH=CHRD in which R" is a divalent aliphatic hydrocarbon chain containing 1 to 8 carbon atoms which is bonded to the silicon atom and RD is a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, preferably a hydrogen atom.
11. Kit according to Claim 9 or 10, characterized in that R represents an alkyl radical containing 1 to 10 carbon atoms or else a phenyl group and R' is selected from vinyl groups.
12. Kit according to one of Claims 1, 3 and 5 to 11, characterized in that the polyorganosiloxanes further comprise units of formula
K SiO,. v r (H) in which R is a group as defined in Claim 10 and n is 1, 2 or 3.
13. Kit according to one of Claims 1 to 4, characterized in that the compound X is selected from organic oligomers or polymers, organic/silicone hybrid oligomers or polymers, the said oligomers or polymers carrying at least two reactive unsaturated aliphatic groups, and mixtures thereof.
14. Kit according to one of Claims 1, 3 and 5 to 13, characterized in that the compound Y is selected from organosiloxanes comprising at least two free Si-H groups.
15. Kit according to one of Claims 1, 3 and 5 to 14, characterized in that the compound Y is selected from organosiloxanes comprising at least one alkylhydrogenosiloxane unit of formula:
Figure imgf000101_0001
in which:
R represents a monovalent linear or cyclic hydrocarbon group containing 1 to 30 carbon atoms or a phenyl group and p is 1 or 2.
16. Kit according to Claim 15, wherein the compound Y is such that the radicals R represent a Cl-ClO alkyl group, preferably methyl.
17. Kit according to one of Claims 14 to 16, wherein the organosiloxanes Y comprise at least two alkylhydrogenosiloxane units of formula HsCHSiO and optionally comprise (H3C) 2SiO units.
18. Kit according to one of Claims 1 and 4 to 17, characterized in that the catalyst is a catalyst based on platinum or on tin and is present in one or the other of the compositions comprising X and/or Y or in a separate composition.
19. Kit according to the preceding claim, characterized in that the catalyst represents from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.
20. Kit according to any one of Claims 1, 3 and 5 to 19, characterized in that the compound X is a polydimethylsiloxane having vinyl end groups and the compound Y is a methylhydrogenosiloxane .
21. Kit according to one of Claims 1, 3 and 5 to 20, wherein the compositions comprising the compound X and/or Y further comprise an additional reactive compound such as - organic or inorganic particles comprising on their surface at least 2 unsaturated aliphatic groups, examples including silicas surface- treated with, for example, silicone compounds having vinyl groups, such as, for example, cyclotetramethyltetravinylsiloxane-treated silica, silazane compounds such as hexamethyl- disilazane .
22. Kit according to one of Claims 2 to 4, wherein the compounds X and/or Y, which are identical or different, are silicone compounds whose main chain comprises at least two alkoxysilane groups and/or at least two silanol (Si-OH) groups, the said groups being side groups and/or chain-end groups.
23. Kit according to one of Claims 2 to 4 and 22, characterized in that the compounds X and/or Y, which are identical or different, predominantly comprise units of the formula
(IV) in which the R9 S independently represent a radical selected from alkyl groups containing 1 to 6 carbon atoms, phenyl, and fluoroalkyl groups, and s is 0, 1, 2 or 3.
24. Kit according to one of Claims 2 to 4, 22 and 23, characterized in that the compounds X and/or Y, which are identical or different, comprise units of formula
Figure imgf000103_0001
in which R9 is as defined in Claim 23, and f is more particularly such that the polymer has a viscosity at 25°C of from 0.5 to 3000 Pa. s, preferably from 5 to 150 Pa. s, and/or f is more particularly a number from 2 to 5000, preferably from 3 to 3000, more preferably from 5 to 1000.
25. Kit according to one of Claims 2 to 4 and 22 to
24, characterized in that the polyorganosiloxanes comprise at least 2 trialkoxysilane end groups per polymer molecule, the said groups having the formula
XV ,3-\ (V|) in which the radicals R independently represent a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl group,
R1 is a methyl or ethyl group, x is 0 or 1, preferably 0, and Z is selected from the following: divalent hydrocarbon groups containing no ethylenic unsaturation and containing 1 to 18 carbon atoms, the combinations of divalent hydrocarbon radicals and siloxane segments of formula (IX) :
R* R*
Figure imgf000103_0002
. ' R^ R9 (IX)
R9 being as defined in Claim 23, G is a divalent hydrocarbon radical containing no ethylenic unsaturation and containing 1 to 18 carbon atoms, and c is an integer from 1 to 6.
26. Kit according to one of Claims 2 to 4 and 22 to 25, characterized in that the polyorganosiloxanes are selected from the polymers of formula (VII) :
(R0)3_xSi - Z -(StO)fSi-Z-SUOR)3.x
I I
(VII) in which R, R1, R9, Z, x and f are as defined in Claims 23 and 25.
27. Kit according to one of the preceding claims, characterized in that at least one of the compositions comprises a catalyst based on titanium.
28. Kit according to one of the preceding claims, characterized in that the catalyst is present in an amount of from 0.0001% to 20% by weight relative to the total weight of the composition which comprises it.
29. Kit according to any one of Claims 2 to 4 and 22 to 28, wherein the compounds X and Y represent a mixture of polydimethylsiloxanes having methoxysilane groups.
30. Kit according to any one of the preceding claims, characterized in that it comprises in at least one of the compositions a filler selected from silica or surface-treated silica.
31. Kit according to either of Claims 3 and 7, characterized in that the polar group or groups able to form at least one hydrogen bond with the lashes are selected from the following groups: carboxylic acids -COOH, alcohols, such as -CH2OH or -CH(R)OH, R being an alkyl radical containing 1 to 6 carbon atoms, amino of formula -NRiR2, in which the radicals
Ri and R2, which are identical or different, represent an alkyl radical containing 1 to 6 carbon atoms, or one of the radicals, Ri or R2, denotes a hydrogen atom, pyridino, amido of formula -NH-COR' or -CO-NH-R' in which
R' represents a hydrogen atom or an alkyl radical containing 1 to 6 carbon atoms, pyrrolidino selected preferably from the groups of formula :
Figure imgf000105_0001
Ri being an alkyl radical containing 1 to 6 carbon atoms, carbamoyl of formula -O-CO-NH-R or -NH-CO-OR'
R' being as defined above, thiocarbamoyl, such as -O-CS-NH-R' or
-NH-CS-O-R', R' being as defined above, ureyl such as -NR' -CO-N (R' ) 2, the identical or different radicals R' being as defined above, sulphonamido such as -NR' -S (=0) 2-R' , R' corresponding to the definition above.
32. Kit according to one of Claims 3, 7 and 31, characterized in that the polar group or groups are present in an amount less than or equal to 10% by weight relative to the weight of each compound
X or Y, preferably less than or equal to 5% by weight, for example in an amount of from 1% to 3% by weight relative to the weight of each compound X or Y .
33. Kit according to one of Claims 3, 7, 31 and 32, characterized in that the polar group or groups are situated in the main chain of the compound X and/or Y or are pendant to the main chain or are situated at the ends of the main chain of the compound X and/or Y.
34. Kit according to one of the preceding claims, characterized in that the compound X has a weight- average molecular mass (Mw) of from 150 to 1 000 000, preferably from 200 to 800 000, more preferably from 200 to 250 000.
35. Kit according to one of the preceding claims, characterized in that the compound Y has a weight- average molecular mass (Mw) of from 200 to 1 000 000, preferably from 300 to 800 000, more preferably from 500 to 250 000.
36. Kit according to one of the preceding claims, characterized in that the compound X represents from 0.5% to 95% by weight relative to the total weight of the composition comprising it, preferably from 1% to 90% and more preferably from 5% to 80%.
37. Kit according to one of the preceding claims, characterized in that the compound Y represents from 0.5% to 95% by weight relative to the total weight of the composition comprising it, preferably from 1% to 90% and more preferably from 5% to 80%.
38. Kit according to one of the preceding claims, characterized in that the compounds X and Y are present in the compositions in a molar ratio X/Y of from 0.05 to 20 and more preferably from 0.1 to
10 .
39. Kit according to one of the preceding claims, characterized in that the fibres have a length of from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and more preferably from 0.3 to 3 mm.
40. Kit according to one of the preceding claims, characterized in that the fibres have a cross section included in a circle whose diameter is from 2 nm to 500 μm, preferably from 100 nm to 100 μm.
41. Kit according to one of the preceding claims, characterized in that the fibres are present in an amount of from 0.01% to 10% by weight relative to the total weight of the composition comprising them, preferably from 0.1% to 5% and more preferably from 0.5% to 3% by weight.
42. Kit according to one of the preceding claims, characterized in that the fibres are selected from fibres of silk, cotton, wool, flax, fibres of cellulose, rayon, polyamide, viscose, acetate, acrylic polymer, polyolefin, glass, silica, carbon, polytetrafluoroethylene, insoluble collagen, polyesters, polyvinyl chloride or polyvinylidene chloride, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, fibres formed from a blend of polymers, and mixtures thereof.
43. Kit according to one of the preceding claims, characterized in that the fibres are substantially rectilinear rigid fibres.
44. Kit according to the preceding claim, characterized in that the substantially rectilinear rigid fibres are fibres of a synthetic polymer selected from polyesters, polyurethanes, acrylic polymers, polyolefins and polyamides.
45. Kit according to Claim 43 or 44, characterized in that the substantially rectilinear rigid fibres are aromatic polyimide-amide fibres.
46. Kit according to Claim 45, characterized in that the polyimide-amide is obtained by polymerizing tolylene diisocyanate and trimellitic anhydride and comprises repeating units of formula:
Figure imgf000108_0001
obtained by polycondensation of tolylene diisocyanate and trimellitic anhydride.
47. Kit according to one of the preceding claims, characterized in that it comprises a first composition comprising at least one compound X and at least one compound Y, a second composition comprising at least one compound X and a catalyst, one at least of the first and second compositions comprising fibres and at least one liquid fatty phase comprising at least one phenyl silicone oil.
48. Kit according to Claim 47, characterized in that the liquid fatty phase further comprises at least one organic solvent or oil selected from volatile oils, non-volatile oils and mixtures thereof.
49. Kit according to Claim 48, characterized in that the oil or oils are present in an amount of from 0.5% to 90% by weight, preferably from 5% to 80% by weight, more preferably from 10% to 60% by weight and more preferably still from 20% to 55% by weight relative to the total weight of each composition comprising them.
50 Kit according to one of the preceding claims, characterized in that one at least of the first and second compositions comprises at least one low-viscosity phenyl silicone oil having a viscosity at 25°C of from 5 to 499 cSt and at least one high-viscosity phenyl silicone oil having a viscosity at 25°C of from 500 to 10 000 cSt.
51. Kit according to one of the preceding claims, characterized in that the first and second compositions each comprise a phenyl silicone oil.
52. Kit according to one of the preceding claims, characterized in that the first and second compositions each comprise at least one low- viscosity phenyl silicone oil having a viscosity at 25°C of from 5 to 499 cSt and a high-viscosity phenyl silicone oil having a viscosity at 25°C of from 500 to 10 000 cSt.
53. Kit according to one of the preceding claims, characterized in that the phenyl silicone oil is selected from the compounds of formula (A) :
Figure imgf000109_0001
in which
R9 and R12 are each independently a C1-C30 alkyl radical, an aryl radical or an aralkyl radical,
Rio and Rn are each independently a C1-C30 al kyl radical or an aralkyl radical, u, v, w and x are each independently integers from 0 to 900, with the provisos that the sum v+w+x is different from 0 and that the sum u+v+w+x is from 1 to 900, in particular from 1 to 800.
54. Kit according to one of Claims 49 to 53, characterized in that the phenyl silicone oils represent from 1% to 90%, preferably from 5% to 60%, more preferably from 10% to 50% and more preferably still from 30% to 50% of the total weight of the composition comprising them.
55. Kit according to one of the preceding claims, characterized in that at least one of the first and second compositions comprises at least one non-volatile hydrocarbon oil having a molecular mass of more than 500 g/mol.
56. Kit according to the preceding claim, characterized in that the non-volatile hydrocarbon oil is selected from polybutenes.
57. Kit according to Claim 55 or 56, characterized in that the non-volatile hydrocarbon oil represents from 0.5% to 40% by weight, preferably from 1% to 30% and more preferably from 5% to 20% by weight relative to the total weight of the composition comprising it.
58. Kit according to any one of the preceding claims, characterized in that the first and second compositions are anhydrous.
59. Kit according to any one of the preceding claims, characterized in that the first and second compositions are packaged separately in a single pack .
60. Cosmetic lash coating method comprising applying to the said lashes at least one layer of a mixture of a first composition and a second composition, each of the first and second compositions being as defined in Claims 1, 3, 5 to 21 or 30 to 59, the said mixture being obtained either at the time of use, before application to the lashes, or simultaneously with its application to the lashes.
61. Cosmetic lash coating method comprising applying to the said lashes at least one layer of a mixture of a first composition and a second composition, each of the first and second compositions being as defined in Claims 2 to 4 or 22 to 59, said mixture being obtained either at the time of use, before application to the lashes, or simultaneously with its application to the lashes.
62. Cosmetic lash coating method comprising: a. mixing, at the time of use, at least one first composition and at least one second composition, each of the first and second compositions being as defined in Claims 1, 3, 5 to 21 or 30 to 59, and then b. applying at least one layer of the said mixture to the said lashes.
63. Cosmetic lash coating method comprising: a. mixing, at the time of use, at least one first composition and at least one second composition, each of the first and second compositions being defined in Claims 2 to 4 or 22 to 59, and then b. applying at least one layer of the said mixture to the said lashes.
64. Cosmetic lash coating method comprising applying - Ill - to the lashes: a. at least one layer of a first composition, b. at least one layer of a second composition, each of the first and second compositions being as defined in Claims 1, 3, 5 to 21 or 30 to 59.
65. Cosmetic lash coating method, comprising applying to the lashes: a. at least one layer of a first composition; b. at least one layer of a second composition, each of the first and second compositions being as defined in Claims 2 to 4 or 22 to 59.
66. Method according to one of Claims 60 to 65, characterized in that the first composition comprises at least one compound X and at least one compound Y, the second composition comprises at least one compound X and a catalyst, and one at least of the first and second compositions comprises fibres and at least one phenyl silicone oil .
67. Method according to Claim 66, characterized in that the compounds X and Y are selected from silicone compounds able to react by hydrosilylation .
68. Method according to Claim 66 or 67, characterized in that the compound X is a polydimethylsiloxane having vinyl end groups and the compound Y is methylhydrogenosiloxane .
69. Method according to one of Claims 60 to 68, characterized in that one at least of the first and second compositions comprises at least one low-viscosity phenyl silicone oil having a viscosity at 25°C of from 5 to 499 cSt and a high- viscosity phenyl silicone oil having a viscosity at 25°C of from 500 to 10 000 cSt.
70. Method according to one of Claims 60 to 69, characterized in that it comprises an additional step comprising depositing on the layer or layers of compositions comprising X and Y at least one layer of a third composition comprising a film- forming polymer and an organic or aqueous solvent medium.
71. Lash coating composition comprising: at least one compound X and at least one compound Y, one at least of the compounds X and Y being a silicone compound, and at least one catalyst, the said compounds X and Y reacting together by a hydrosilylation reaction, when they are brought into contact with one another in the presence of the catalyst, and fibres, - and at least one phenyl silicone oil.
72. Lash coating composition comprising: at least one compound X and at least one compound Y, one at least of the compounds X and Y being a silicone compound, the said compounds X and Y reacting together by a condensation reaction, when they are brought into contact with one another, and fibres, - and at least one phenyl silicone oil.
73. Composition according to Claim 71 or 72, characterized in that the compounds X and Y are selected from silicone compounds able to react by hydrosilylation.
74. Method according to one of Claims 71 to 73, characterized in that the compound X is a polydimethylsiloxane having vinyl end groups and the compound Y is methylhydrogenosiloxane .
PCT/EP2007/064348 2006-12-20 2007-12-20 Lash coating kit comprising silicone compounds x and y and fibres WO2008074870A2 (en)

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FR0655741A FR2910305B1 (en) 2006-12-20 2006-12-20 KIT FOR COATING LILIES COMPRISING X AND SILICONE COMPOUNDS AND FIBERS
FR0655741 2006-12-20
US87845507P 2007-01-04 2007-01-04
US60/878,455 2007-01-04

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