New! View global litigation for patent families

US20090130037A1 - Method of Applying Makeup to a Surface and a Kit for Implementing such a Method - Google Patents

Method of Applying Makeup to a Surface and a Kit for Implementing such a Method Download PDF

Info

Publication number
US20090130037A1
US20090130037A1 US11663977 US66397705A US2009130037A1 US 20090130037 A1 US20090130037 A1 US 20090130037A1 US 11663977 US11663977 US 11663977 US 66397705 A US66397705 A US 66397705A US 2009130037 A1 US2009130037 A1 US 2009130037A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
polymer
particular
magnetic
amp
monomers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11663977
Inventor
Ludovic Thevenet
Xavier Blin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
L'Oreal SA
Original Assignee
L'Oreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Images

Classifications

    • AHUMAN NECESSITIES
    • A45HAND OR TRAVELLING ARTICLES
    • A45DHAIRDRESSING OR SHAVING EQUIPMENT; MANICURING OR OTHER COSMETIC TREATMENT
    • A45D34/00Containers or accessories specially adapted for handling liquid toilet or cosmetic substances, e.g. perfumes
    • AHUMAN NECESSITIES
    • A45HAND OR TRAVELLING ARTICLES
    • A45DHAIRDRESSING OR SHAVING EQUIPMENT; MANICURING OR OTHER COSMETIC TREATMENT
    • A45D33/00Containers or accessories specially adapted for handling toilet or cosmetic powder
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/04Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06Lipsticks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q3/00Manicure or pedicure preparations
    • A61Q3/02Nail coatings
    • AHUMAN NECESSITIES
    • A45HAND OR TRAVELLING ARTICLES
    • A45DHAIRDRESSING OR SHAVING EQUIPMENT; MANICURING OR OTHER COSMETIC TREATMENT
    • A45D29/00Manicuring or pedicuring implements
    • A45D29/004Masking devices for applying polish to the finger nails
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET 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
    • A61K2800/42Colour properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET 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
    • A61K2800/47Magnetic materials; Paramagnetic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88Two- or multipart kits

Abstract

The present invention relates to a method of making up keratinous substances, especially the skin, lips, hair, or nails, the method comprising the following steps:
    • a) applying to the keratinous substances at least one make-up composition comprising:
      • i) at least one volatile solvent;
      • ii) particles with non-zero magnetic susceptibility; and
    • b) applying a magnetic field to the deposit to modify the orientation and/or displace at least some of said particles with non-zero magnetic susceptibility.

Description

  • [0001]
    The present invention relates to applying makeup to keratinous substances, in particular the skin, the lips, the nails, or hair, e.g. the eyelashes.
  • [0002]
    The applicant company has internally developed makeup compositions, in particular for the lips, that include magnetic particles that are capable, in the presence of a magnetic field, of being oriented and/or displaced, and of causing new optical effects.
  • [0003]
    A problem posed with such compositions is long-term durability of the effect obtained.
  • [0004]
    The invention seeks to propose a composition for applying to keratinous substances, in particular the skin or the lips, that enables a durable result to be obtained.
  • Make-Up Method
  • [0005]
    In one aspect, the invention provides a method of making up keratinous substances, especially the skin and lips, comprising the following steps:
  • [0006]
    a) applying to the keratinous substances at least one make-up composition comprising:
      • i) at least one volatile solvent, especially a volatile oil; and
      • ii) particles with non-zero magnetic susceptibility; and
  • [0009]
    b) applying a magnetic field to the deposit to modify the orientation and/or displace at least some of said particles with non-zero magnetic susceptibility.
  • [0010]
    The presence of at least one volatile solvent, especially a volatile oil, is advantageous since immediately after application it endows the magnetic particles with a certain mobility under the effect of a magnetic field, and following a certain drying period, it also immobilizes those particles in the orientation imposed upon them.
  • [0011]
    Advantageously, the composition includes at least one film-forming polymer, which can further enhance immobilization of the particles after drying.
  • [0012]
    The magnetic field may be applied to form at least one pattern on the composition, the pattern being linked to the shape of the field lines, for example.
  • [0013]
    If appropriate, a layer of a second cosmetic composition may be applied to the layer containing the magnetic bodies, for example to obtain an effect of depth, gloss, smoothness, or otherwise. Said second composition may be transparent, colored or not colored. The second composition may also be applied to the surface before the first composition, for example to create a colored background or to improve the hold of the first composition and/or for comfort.
  • [0014]
    The magnetic field may be applied until the composition containing the magnetic bodies obtains a fixed appearance, i.e. the appearance of said composition ceases to vary even if the magnetic field continues to exist. In a variant, the magnetic field may be applied for a period of time that is shorter than the period of time that causes all of the magnetic bodies in the exposed region to be permanently displaced and/or oriented. Since the clarity and/or the color of the composition change progressively under the effect of the magnetic field, the user can stop subjecting the magnetic bodies to the field when the first composition presents the desired appearance.
  • [0015]
    The magnetic field may be exerted successively on different regions of the surface that are coated with the composition.
  • [0016]
    The magnetic field may be exerted on regions of the surface that are disjoint, so as to create separate patterns, for example.
  • [0017]
    A region of the surface coated with the composition need not be exposed to the magnetic field, so as not to modify the appearance of the composition in said region after it has been deposited.
  • [0018]
    Two regions of the surface may be exposed unequally to the magnetic field.
  • [0019]
    The composition may be applied in various ways, e.g. by means of a cosmetics applicator that is preferably non-magnetic and that is selected from brushes, flocked endpieces, foams, woven fabrics, non-woven fabrics, brushes, or combs, for example, or it may be applied without using an applicator, with the composition being spread on with the fingers, or sprayed on, for example.
  • [0020]
    The invention also provides a kit for implementing the method described above.
  • [0021]
    Said kit may comprise:
      • a makeup composition comprising:
      • i) at least one volatile solvent, especially a volatile oil; and
      • ii) particles with non-zero magnetic susceptibility; and
      • a magnetic device.
  • [0026]
    Advantageously, the composition further comprises at least one film-forming polymer.
  • [0027]
    The magnetic device may comprise at least one permanent magnet or an electromagnet powered, for example, by a battery, in which case the magnetic device may include a switch so that the electromagnet can be powered selectively with electricity.
  • [0028]
    The magnetic device of the kit may be arranged to create a magnetic field of orientation that varies with time. When the magnetic device comprises a magnet, the device may, for example, include a motor to rotate the magnet. In a variation, the magnetic device may include a plurality of solenoids disposed so that, when sequentially powered with electricity, a rotating magnetic field is generated.
  • [0029]
    A rotary magnetic field may, for example, produce a pattern with symmetry of revolution, for example a pattern giving the impression of a sphere in relief.
  • [0030]
    The electromagnet or electromagnets may be powered permanently or intermittently, as dictated by the user. In particular, the magnetic device of the kit may be arranged so that the electromagnet or electromagnets are not powered while the magnetic device is not correctly positioned close to the surface coated with composition.
  • [0031]
    The magnetic field is, for example, at least 50 mT [megaTorr], or even at least 0.2 T or 1 T.
  • [0032]
    In order to render application of the magnetic field easier, the magnetic device of the kit may include a member that allows it to be positioned relative to the surface on which the composition has been deposited. This may, for example, prevent the magnetic device from accidentally coming into contact with the composition and/or to allow the pattern produced to be centered on the region concerned.
  • [0033]
    The magnetic device of the kit may be attached to an applicator allowing the cosmetic composition to be applied. This reduces the number of articles that are manipulated by the user and facilitates making up.
  • [0034]
    The magnetic device of the kit may include a magnet mounted at one end of a rod having its other end connected to a grip member of an applicator serving to apply the cosmetic composition.
  • [0035]
    The magnetic field may also be exerted by means of a magnetic structure, especially a flexible structure, comprising alternating N and S poles. Such a structure may, for example, produce repeating patterns on the composition, for example stripes.
  • [0036]
    The kit may include a casing housing the cosmetic composition and the magnetic device. By way of example, the casing may then include a plurality of magnets of different shapes to produce different patterns.
  • [0037]
    In a further aspect, the invention provides a cosmetic composition comprising:
      • at least one volatile solvent, especially a volatile oil; and
      • magnetic bodies comprising metallic iron, optionally coated, especially soft iron.
  • [0040]
    Advantageously, the composition includes at least one film-forming polymer.
  • [0041]
    The presence of metallic iron ensures that the magnetic bodies are highly sensitive to the magnetic field.
  • [0042]
    The invention can be better understood from the following detailed description of non-limiting examples, and from an examination of the accompanying drawings, in which:
  • [0043]
    FIG. 1 diagrammatically shows an example of a kit for carrying out the method;
  • [0044]
    FIG. 2 shows the composition being applied to the lips; and
  • [0045]
    FIG. 3 shows exposure of the composition to a magnetic field.
  • [0046]
    The kit 1 shown in FIG. 1 comprises a receptacle 2 containing a fluid composition C for application to the lips, and an applicator 3 comprising an application member 4 mounted at one end of a rod 5 having its other end connected to a grip member 6 that also constitutes a closure for the receptacle 2.
  • [0047]
    The receptacle 2 is provided with a wiper member 7 for the rod 5 and the application member 4, in conventional manner.
  • [0048]
    The kit 1 also comprises a magnetic device 10 which is constituted by a permanent magnet, for example, but which in a variation (not shown) may comprise at least one electromagnet, or a magnet that is attached to a mechanical or electromechanical system causing it to move in a predetermined manner to create a pattern with the desired shape on the deposit of the composition to be produced.
  • [0049]
    The kit 1 is used by firstly applying the composition C using the applicator 3, as shown in FIG. 2, for example in the form of one or more thin layers then, as shown in FIG. 3, by exposing the composition that has been deposited to a magnetic field before it dries, to enable the desired pattern to be formed.
  • [0050]
    In one aspect of the invention, the composition contains at least one volatile solvent.
  • Volatile Solvents
  • [0051]
    The term “volatile solvent” as used in the context of the present invention means a solvent that is liquid at ambient temperature, having a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular a vapor pressure in the range 0.13 pascals (Pa) to 40000 Pa (10−3 millimeters of mercury (mm Hg) to 300 mm Hg), and preferably in the range 1.3 Pa to 13000 Pa (0.01 mm Hg to 100 mm Hg), and preferably in the range 1.3 Pa to 1300 Pa (0.01 mm Hg to 10 mm Hg).
  • [0052]
    In general, the quantity of solvent(s) depends on the nature of the surface to which the composition is intended to be applied.
  • [0053]
    The solvent may be selected from water, organic solvents, and oils.
  • [0054]
    The oil may be a silicone oil or a hydrocarbon oil, or may include a mixture of such oils.
  • [0055]
    The term “silicone oil” as used in the context of the present invention means an oil including at least one silicon atom, and in particular at least one Si—O group.
  • [0056]
    The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur, and/or phosphorus atoms.
  • [0057]
    The volatile hydrocarbon oils may be selected from hydrocarbon oils having 8 to 16 carbon atoms, and in particular C8-C16 branched alkanes (also termed isoparaffins) such as isododecane (also termed 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and oils sold under the trade names Isopars® or Permethyls®, for example.
  • [0058]
    Volatile oils that may also be used are volatile silicones, such as volatile linear or cyclic silicone oils, for example, in particular oils having a viscosity ≦8 centistokes (cSt) (8×10−6 square meters per second (m2/s)), and having in particular 2 to 10 silicon atoms, and in particular 2 to 7 silicon atoms, the silicones possibly including alkyl or alkoxy groups having 1 to 10 carbon atoms. In the invention, suitable volatile silicone oils that may be mentioned are in particular dimethicones having a viscosity of 5 cSt to 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.
  • [0059]
    It is also possible to use fluorinated volatile oils such as nonafluoromethoxybutane or perfluoromethylcyclopentane, and mixtures thereof.
  • [0060]
    A composition of the invention may contain 0.01% to 95% by weight of volatile oil relative to the total weight of the composition, and preferably 1% to 75% by weight.
  • [0061]
    The composition may comprise at least one organic solvent selected from the following list:
      • ketones that are liquid at ambient temperature, such as methylethylketone, methylisobutylketone, diisobutylketone, isophorone, cyclohexanone, or acetone;
      • alcohols that are liquid at ambient temperature, such as ethanol, isopropanol, diacetone alcohol, 2-butoxyethanol, or cyclohexanol;
      • glycols that are liquid at ambient temperature, such as ethylene glycol, propylene glycol, pentylene glycol, or glycerol;
      • propylene glycol ethers that are liquid at ambient temperature, such as propylene glycol monomethyl ether, the acetate of propylene glycol monomethyl ether, or dipropylene glycol mono n-butyl ether; and
      • short-chain esters (containing a total of 3 to 8 carbon atoms), such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, or isopentyl acetate.
  • [0067]
    The composition may also comprise water or a mixture of water and hydrophilic organic solvents which are routinely used in cosmetics, such as alcohols, in particular linear or branched lower monoalcohols containing 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, polyols such as glycerine, diglycerine, propylene glycol, sorbitol, penthylene glycol, or polyethylene glycols, hydrophilic C2 ethers and C2-C4 aldehydes.
  • [0068]
    The water or mixture of water and hydrophilic organic solvents may be present in the composition in an amount in the range 0% to 90%, in particular 0.1% to 90% by weight, and preferably 0% to 60% by weight, more particularly 0.1% to 60% by weight relative to the total weight of the composition.
  • [0069]
    In accordance with an aspect of the invention, the composition applied contains at least one film-forming polymer.
  • Film-Forming Polymers
  • [0070]
    The term “film-forming polymer” means a polymer that can form, by itself or in the presence of an additional film-forming agent, a continuous film that adheres to a surface, in particular to keratinous substances, and preferably a cohesive film, and better still a film having cohesion and mechanical properties such that said film may be isolated from said surface.
  • [0071]
    Suitable film-forming polymers for use in the composition of the invention that may be mentioned include synthetic polymers, of the radical or polycondensate type, natural polymers, and mixtures thereof.
  • [0072]
    As film-forming polymers, mention may be made in particular of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, and cellulose/cellulosic polymers, such as nitrocellulose.
  • [0073]
    Said film-forming polymers may be separated into four categories depending on their solubility as regards an aqueous phase or a liquid oily phase.
  • [0074]
    In one example, the film-forming polymer is at least one polymer selected from the group comprising:
      • film-forming polymers that are soluble in the liquid oily phase of the composition, in particular liposoluble polymers;
      • film-forming polymers that are dispersible in the liquid oily phase of the composition, in particular polymers in the form of non-aqueous dispersions of polymer particles, in particular dispersions in silicone or hydrocarbon oils;
      • aqueous dispersions of particles of film-forming polymers, usually termed “latexes”; in this case, in addition to the liquid oily phase, the composition must include an aqueous phase;
      • hydrosoluble film-forming polymers; in this case also, the composition must include an aqueous phase in addition to the liquid oily phase.
  • [0079]
    In a further implementation of the invention, the film-forming polymer contains silicone and may be selected from polymers with a non-silicone organic backbone grafted with monomers containing a polysiloxane.
  • [0080]
    In a further implementation of the invention, the film-forming polymer contains silicone and is selected from silicone polymers grafted with non-silicone organic monomers. Said polymers may be liposoluble, lipodispersible, hydrosoluble, or dispersible in an aqueous medium, as appropriate.
  • [0081]
    For obvious reasons, the quantities of film-forming agent in the compositions of the invention can vary significantly, especially as a function of the nature of the film-forming agent under consideration and also of the desired qualities of the composition into which it is incorporated.
  • [0082]
    Thus, the cosmetic compositions of the invention may contain an amount of film-forming polymer(s) which can be from 0.01% to 65% by weight, especially 0.1% to 60% by weight, in particular 1% to 45% by weight relative to the total composition weight.
  • [0083]
    The composition may comprise, as a polymer, a dispersion of particles of a graft ethylenic polymer in a liquid oily phase.
  • [0084]
    The term “ethylenic” polymer means a polymer obtained by polymerizing monomers comprising an ethylenically unsaturated bond.
  • [0085]
    The dispersion of graft ethylenic polymer is exempt of stabilizing polymer which is distinct from said graft polymer, such as those described in EP-A-0 749 747 and described below, and the surfaces of the particles of graft ethylenic polymer are thus not stabilized by said additional stabilizing polymers. The graft polymer is thus dispersed in the liquid oily phase in the absence of additional stabilizer at the particle surface.
  • [0086]
    The term “graft” polymer means a polymer having a backbone comprising at least one pendant side chain or chain located at a chain end, preferably a pendant chain
  • [0087]
    Advantageously, the graft ethylenic polymer comprises an ethylenic backbone that is insoluble in the liquid oily phase, and side chains which are covalently bonded to said backbone and are soluble in the liquid oily phase.
  • [0088]
    In particular, the graft ethylenic polymer is a non cross-linked polymer. In particular, the polymer is obtained by polymerizing monomers comprising a single polymerizable group.
  • [0089]
    The graft ethylenic polymer is a graft acrylic polymer, for example.
  • [0090]
    The graft ethylenic polymer is capable of being obtained by radical polymerization, in an organic polymerization medium, of:
      • at least one ethylenic monomer, in particular at least one acrylic monomer and optionally at least one additional non-acrylic vinyl monomer, to form said insoluble backbone; and
      • at least one macromonomer comprising a terminal polymerizable group to form side chains, said macromonomer having a mass average molecular weight of 200 or more and the amount of polymerized macromonomer representing 0.05% to 20% by weight of polymer.
  • [0093]
    The liquid oily phase may contain the organic medium for polymerizing the graft ethylenic polymer.
  • [0094]
    The liquid organic dispersion medium, corresponding to the medium in which the graft polymer is supplied, may be identical to the polymerization medium.
  • [0095]
    However, the polymerization medium may be wholly or partially substituted by another liquid organic medium. After polymerization, said other liquid organic medium may be added, to the polymerization medium. The medium is then completely or partially evaporated off.
  • [0096]
    The liquid oily phase may contain liquid organic compounds other than those present in the dispersion medium. Said other compounds are selected so that the graft polymer remains in the dispersed state in the liquid oily phase.
  • [0097]
    The liquid organic dispersion medium may be present in the liquid oily phase of the composition of the invention because the graft polymer dispersion obtained is introduced into the composition.
  • [0098]
    The liquid oily phase preferably mainly comprises one or more liquid organic compounds (or oils) as defined below.
  • [0099]
    In particular, the liquid oily phase may be a non-aqueous liquid organic phase which is not miscible with water at ambient temperature (25° C.).
  • [0100]
    The term “liquid organic compound” means a non-aqueous compound which is in the liquid state at ambient temperature (25° C.) and which thus flows under its own weight.
  • [0101]
    Examples of liquid organic compounds or oils which may be present in the liquid organic dispersion medium that may be mentioned are:
      • liquid organic compounds, in particular non-silicone or silicone, having an overall solubility parameter in the Hansen solubility space of 18 (MPa)1/2 or less, preferably 17 (MPa)1/2 or less;
      • mono-alcohols having an overall solubility in the Hansen solubility space of 20 (mPa)1/2 or less; and
      • mixtures thereof.
  • [0105]
    The overall solubility parameter δ in the Hansen solubility space is defined in the article “Solubility parameter values” by Eric A Grulke in the “Polymer Handbook”, 3rd edition, Chapter VII, p 519-559 by the relationship:
  • [0000]

    δ=(δD 2P 2H 2)1/2
  • [0000]
    in which:
      • δdD characterizes the LONDON dispersion forces from the formation of dipoles induced during molecular impacts;
      • δP characterizes the DEBYE interaction forces between permanent dipoles; and
      • δH characterizes the specific interaction forces (hydrogen bonds, acid/base, donor/acceptor, etc).
  • [0109]
    The definition of solvents in the Hansen solubility space is described in the article by C M Hansen, “The three-dimensional solubility parameters”, J. Paint Technology, 39, 105 (1967).
  • [0110]
    Examples of organic liquid compounds, especially non-silicone or silicone, with an overall solubility parameter in the Hansen solubility space of 18 (MPa)1/2 or less that may be mentioned are liquid fats, especially oils, which may be selected from carbon-containing, hydrocarbon-containing, fluorinated, silicone, optionally branched natural or synthetic oils, used alone or as a mixture.
  • [0111]
    Of said oils, the following may be mentioned: vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides, such as sunflower seed oil, sesame seed oil or rapeseed oil, or esters derived from long chain alcohols or acids (i.e. containing 6 to 20 carbon atoms), especially esters with formula RCOOR′ in which R represents the residue of a higher fatty acid containing 7 to 19 carbon atoms and R′ represents a hydrocarbon chain containing 3 to 20 carbon atoms, such as palmitates, adipates, or benzoates, especially diisopropyl adipate.
  • [0112]
    Linear, branched, and/or cyclic alkanes, which may be volatile, may also be mentioned, in particular paraffin oil, Vaseline oil or hydrogenated polyisobutylene, isododecane or ISOPARS, which are volatile isoparaffins. Esters, ethers and ketones may also be mentioned.
  • [0113]
    It is also possible to mention silicone oils such as polydimethylsiloxanes and polymethylphenylsiloxanes, optionally substituted with aliphatic and/or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl groups, thiols and/or amines, and volatile silicone oils, in particular cyclic oils.
  • [0114]
    In particular, silicone oils, which may be branched, volatile, and/or non volatile, may be mentioned.
  • [0115]
    In particular, the following non-silicone liquid organic compounds with an overall solubility in the Hansen solubility space of 18 (MPa)1/2 or less may be mentioned:
      • linear, branched or cyclic esters containing at least 6 carbon atoms, especially 6 to 30 carbon atoms;
      • ethers containing at least 6 carbon atoms, especially 6 to 30 carbon atoms; and
      • ketones containing at least 6 carbon atoms, especially 6 to 30 carbon atoms.
  • [0119]
    The term “liquid mono-alcohols having an overall solubility parameter in the Hansen solubility space of 20 (MPa)1/2” means liquid aliphatic fatty mono-alcohols containing 6 to 30 carbon atoms, the hydrocarbon chain having no substitution group. Mono-alcohols in accordance with the invention that may be mentioned are oleic alcohol, decanol, octyldodecanol and linoleic alcohol.
  • [0120]
    When the liquid oily phase of the composition is a non-silicone liquid oily phase, the macromonomers present in the grafted polymer are advantageously carbon-containing macromonomers as described below.
  • [0121]
    In particular, when the liquid oily phase of the composition is a non-silicone liquid oily phase, the graft polymer present in the composition is advantageously a non-silicone graft polymer.
  • [0122]
    The term “non-silicone graft polymer” means a graft polymer containing a mainly carbon-containing macromonomer and optionally containing at most 7% by weight, preferably at most 5% by weight or even no silicone macromonomer.
  • [0123]
    When the liquid oily phase of the cosmetic composition of the invention is a silicone liquid oily phase, the macromonomers present in the graft polymer are advantageously silicone macromonomers as described below.
  • [0124]
    In particular, when the liquid oily phase is a silicone liquid oily phase, the graft polymer present in the composition is advantageously a silicone graft polymer.
  • [0125]
    The term “silicone graft polymer” means a graft polymer mainly containing a silicone macromonomer and optionally containing at most 7% by weight, preferably at most 5% by weight, or even no carbon-containing macromonomer.
  • a) Monomers
  • [0126]
    The choice of monomers constituting the backbone of the polymer, the macromonomers, the molecular weight of the polymer, and the proportion of monomers and macromonomers may be made as a function of the liquid organic dispersion medium to advantageously obtain a dispersion of particles of graft polymers, in particular a stable dispersion; this choice can be made by the skilled person.
  • [0127]
    The term “stable dispersion” means a dispersion which is not capable of forming a solid deposit or of liquid/solid phase separation, in particular after centrifuging, for example at 4000 rpm for 15 minutes.
  • [0128]
    The graft ethylenic polymer forming the particles in dispersion thus comprises a backbone that is insoluble in said dispersion medium and a portion that is soluble in said dispersion medium.
  • [0129]
    The graft ethylenic polymer may be a random polymer.
  • [0130]
    In accordance with the invention, the term “graft ethylenic polymer” means a polymer that can be obtained by radical polymerization:
      • of one or more ethylenic monomer(s);
      • with one or more macromonomer(s) in an organic polymerization medium.
  • [0133]
    According to the invention, the term “graft acrylic polymer” means a polymer that can be obtained by radical polymerization:
      • of one or more acrylic monomers, and optionally one or more additional non-acrylic vinyl monomer(s);
      • with one or more macromonomer(s) in an organic polymerization medium.
  • [0136]
    Advantageously, the acrylic monomers represent 50% to 100% by weight, preferably 55% to 100% by weight (in particular 5% to 95% by weight), preferably 60% to 100% by weight (in particular 60% to 90% by weight) of the (acrylic monomer+any non-acrylic vinyl monomer) mixture.
  • [0137]
    In particular, the acrylic monomers are selected from monomers, the homopolymer of which is insoluble in the dispersion medium under consideration, i.e. the homopolymer is in the solid (or undissolved) form at a concentration of 5% by weight or more at ambient temperature (20° C.) in said dispersion medium.
  • [0138]
    According to the invention, the term “macromonomer having a polymerizable terminal group” means any polymer having at only one of its ends a polymerizable terminal group that can react during the polymerization reaction with the acrylic monomers and the optional additional non-acrylic vinyl monomers constituting the backbone. The macromonomer can form side chains of graft acrylic polymer. The polymerizable group of the macromonomer may advantageously be a group with an ethylenically unsaturated bond that can polymerize by radical polymerization with the monomers constituting the backbone.
  • [0139]
    The term “carbon-containing macromonomer” means a non-silicone macromonomer, especially an oligomeric macromonomer obtained by polymerizing non-silicone monomer(s) with an ethylenically unsaturated bond, and principally by polymerizing acrylic and/or non-acrylic vinyl monomers.
  • [0140]
    The term “silicone macromonomer” means an organopolysiloxane macromonomer, in particular a polydimethylsiloxane macromonomer.
  • [0141]
    In particular, the macromonomer is selected from macromonomers the homopolymer of which is soluble in the dispersion medium under consideration, i.e. completely dissolved in a concentration which is 5% by weight or more and at ambient temperature in said dispersion medium.
  • [0142]
    Thus, the graft acrylic polymer includes a backbone (or principal chain) constituted by a concatenation of acrylic patterns especially resulting from polymerization of one or more acrylic monomers and side chains (or grafts) derived from reacting the macromonomers, said side chains being covalently bonded to said principal chain.
  • [0143]
    The backbone (or principal chain) is insoluble in the dispersion medium under consideration, while the side chains (or grafts) are soluble in said dispersion medium.
  • [0144]
    The term “acrylic monomer” as used in the present application means monomers selected from (meth)acrylic acid, esters of (meth)acrylic acid (also termed (meth)acrylates), and amides of (meth)acrylic acid (also termed (meth)acrylamides).
  • [0145]
    Examples that may be mentioned of acrylic monomers that can be used to form the insoluble polymer backbone when used alone or as a mixture are as follows, along with salts thereof:
  • [0146]
    i) (meth)acrylates with formula (VIII):
  • [0000]
    Figure US20090130037A1-20090521-C00001
  • [0000]
    in which:
      • R1 designates a hydrogen atom or a methyl group;
      • R2 represents a group selected from:
        • a linear or branched alkyl group containing 1 to 6 carbon atoms, said group possibly comprising one or more heteroatoms selected from O, N and S in its chain; and/or possibly comprising one or more substituents selected from —OH, halogen atoms (F, Cl, Br, I) and —NR′R″, where R′ and R″, which may be identical or different, are selected from linear or branched C1-C4 alkyls; and/or possibly substituted with at least one polyoxyalkylene group, in particular with C2-C4 alkylene, in particular polyoxyethylene and/or polyoxypropylene, said polyoxyalkylene being constituted by repeating 5 to 30 oxyalkylene patterns;
        • a cyclic alkyl group containing 3 to 6 carbon atoms, said group possibly comprising one or more heteroatoms selected from O, N and S in its chain, and/or possibly comprising one or more substituents selected from OH and halogen atoms (F, Cl, Br, I).
  • [0151]
    Examples of R2 that may be mentioned are methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl, methoxy-polyoxyethylene 350 OE, trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl and dimethylaminopropyl.
  • [0152]
    ii) (meth)acrylamides with formula (IX):
  • [0000]
    Figure US20090130037A1-20090521-C00002
  • [0000]
    in which:
      • R3 designates a hydrogen atom or a methyl group;
      • R4 and R5, which may be identical or different, represent a hydrogen atom or a linear or branched alkyl group containing 1 to 6 carbon atoms, possibly comprising one or more substituents selected from —OH, halogen atoms (F, Cl, Br, I) and —NR′R″ where R′ and R″, which may be identical or different, are selected from linear or branched alkyls C1-C4; or
      • R4 represents a hydrogen atom and R5 represents a 1,1-dimethyl-3-oxobutyl group.
  • [0156]
    Examples of alkyl groups which may constitute R4 and R5, that may be mentioned are n-butyl, t-butyl, n-propyl, dimethylaminoethyl, diethylaminoethyl and dimethylaminopropyl:
  • [0157]
    iii) (meth)acrylic monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as acrylic acid, methacrylic acid or acrylamidopropanesulfonic acid.
  • [0158]
    Particular acrylic monomers that may be mentioned are methyl, ethyl, propyl, butyl and isobutyl (meth)acrylates; methoxyethyl or ethoxyethyl (meth)acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate; dimethylaminopropyl methacrylamide; salts thereof; and mixtures thereof.
  • [0159]
    In particular, the acrylic monomers are selected from methyl acrylate, methoxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, dimethylaminoethyl methacrylate, and mixtures thereof.
  • [0160]
    Additional non-acrylic vinyl monomers that may be mentioned include:
      • vinyl esters with the following formula:
  • [0000]

    R6—COO—CH═CH2
  • [0000]
    in which:
      • R6 represents a linear or branched alkyl group containing 1 to 6 atoms, or a cyclic alkyl group containing 3 to 6 carbon atoms and/or an aromatic group, for example of the benzene, anthracene or naphthalene type;
      • non-acrylic vinyl monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid or vinylphosphoric acid, and salts thereof;
      • non-acrylic vinyl monomers comprising at least one tertiary amine function, such as 2-vinylpyridine or 4-vinylpyridine; and
      • mixtures thereof.
  • [0166]
    Advantageously, acrylic monomers present in the graft polymer comprise at least one (meth)acrylic acid and at least one monomer selected from the (meth)acrylates and (meth)acrylamides described above under points i) and ii). Preferably, the acrylic monomers comprise at least one (meth)acrylic acid and at least one monomer selected from C1-C3 alkyl (meth)acrylates. The (meth)acrylic acid may be present in an amount of at least 5% by weight relative to the total polymer weight, especially from 5% to 80% by weight, preferably at least 10% by weight, in particular from 10% by weight to 70% by weight, preferably at least 15% by weight, in particular 15% to 60% by weight.
  • [0167]
    Salts that may be mentioned include those obtained by neutralizing acid groups using inorganic bases such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide or alkanolamine type organic bases such as monoethanolamine, diethanolamine, triethanolamine or 2-methyl-2-amino-1-propanol.
  • [0168]
    Salts formed by neutralizing tertiary amine moieties, for example using a mineral or organic acid, may also be mentioned. Mineral acids that may be mentioned include sulfuric acid and hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and boric acid. Organic acids that may be mentioned include acids comprising one or more carboxylic, sulfonic or phosphonic groups. It may concern linear, branched or cyclic aliphatic acids, or aromatic acids. Said acids may also include one or more heteroatoms selected from O and N, for example in the form of hydroxyl groups. In particular, acetic acid and propionic acid, terephthalic acid and citric and tartaric acid may be mentioned.
  • [0169]
    In one implementation of the invention, the graft ethylenic polymer contains no additional non-acrylic vinyl monomers as described above. In this implementation, the insoluble backbone of the graft ethylenic polymer is formed solely of acrylic monomers as described above.
  • [0170]
    It should be understood that these non-polymerized acrylic monomers may be soluble in the dispersion medium under consideration, but the polymer formed with said monomers is insoluble in the dispersion medium.
  • [0171]
    In a particular implementation of the invention, the ethylenic graft polymer may be obtained by radical polymerization in an organic polymerization medium:
      • of a principal acrylic monomer selected from C1-C3 alkyl (meth)acrylates, used alone or as a mixture, and optionally one or more additional acrylic monomers selected from (meth)acrylic acid, methacrylic acid and alkyl (meth)acrylates with formula (X) defined below, and salts thereof, to form said insoluble backbone; and
      • of at least one silicone macromonomer comprising a polymerizable terminal group as defined above.
  • [0174]
    The principal acrylic monomer may be methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate or isopropyl methacrylate, and mixtures thereof.
  • [0175]
    More particularly, methyl acrylate, methyl methacrylate and ethyl methacrylate may be mentioned.
  • [0176]
    The additional acrylic monomers may be selected from:
  • [0177]
    (meth)acrylic acid and salts thereof;
  • [0178]
    (meth)acrylates with formula (X) and salts thereof:
  • [0000]
    Figure US20090130037A1-20090521-C00003
  • [0000]
    in which:
      • R′1 designates a hydrogen atom or a methyl group;
      • R′2 represents:
        • a linear or branched alkyl group containing 1 a 6 carbon atoms, said group comprising one or more oxygen atoms in its chain and/or comprising one or more substituents selected from —OH, halogen atoms (F, Cl, Br, I) and —NR′R″ where R′ and R″, which may be identical or different, are selected from linear or branched C1-C3 alkyls;
        • a cyclic alkyl group containing 3 to 6 carbon atoms, said group possibly comprising in its chain one or more oxygen atoms and/or possibly comprising one or more substituents selected from OH and halogen atoms (F, Cl, Br, I); and
        • mixtures thereof.
  • [0184]
    Examples of R′2, that may be mentioned include methoxyethyl, ethoxyethyl, trifluoroethyl; 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl and dimethylaminopropyl.
  • [0185]
    More particular additional acrylic monomers that may be mentioned include (meth)acrylic acid, methoxyethyl or ethoxyethyl (meth)acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, salts and mixtures thereof.
  • [0186]
    More particularly, acrylic acid and methylacrylic acid may be mentioned.
  • b) Macromonomers
  • [0187]
    Macromonomers include a polymerizable terminal group at one end of the chain which can react during polymerization with acrylic monomers, and optional additional vinyl monomers, to form the side chains of the graft ethylenic polymer. Said polymerizable terminal group may in particular be a vinyl group or a (meth)acrylate (or (meth)acryloxy) group, preferably a (meth)acrylate group.
  • [0188]
    The macromonomers are preferably selected from macromonomers wherein the homopolymer has a glass transition temperature (Tg) of 25° C. or less, especially from −100° C. at 25° C., preferably from −80° C. to 0° C.
  • [0189]
    The macromonomers have a mass average molecular mass of 200 or more, preferably 300 or more, more preferably 500 or more, and still more preferably more than 600.
  • [0190]
    Preferably, the macromonomers have a mass average molecular mass (Mw) of 200 to 100000, preferably 500 to 50000, more preferably 800 to 20000, still more preferably 800 to 10000 and still more preferably 800 to 6000.
  • [0191]
    In the present application, the mass average molecular masses (Mw) and number average molecular masses (Mn) were determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene specimens, refractometric detector).
  • [0192]
    Particular carbon-containing macromonomers that may be mentioned are:
  • [0193]
    i) linear or branched C8 to C22 alkyl (meth)acrylate homopolymers and copolymers having a polymerizable terminal group selected from vinyl or (meth)acrylate groups, in particular: macromonomers of poly(ethyl-2 hexyl acrylate) with a mono(meth)acrylate end; macromonomers of poly(dodecyl acrylate) or poly(dodecyl methacrylate) with a mono(meth)acrylate end; macromonomers of poly(stearyl acrylate) or poly(stearyl methacrylate) with a mono(meth)acrylate end.
  • [0194]
    Such macromonomers have in particular been described in patents EP-A-0 895 467 and EP-A-0 096 459 and in the article by Gillman K. F., Polymer Letters, Vol 5, page 477-481 (1967).
  • [0195]
    In particular, macromonomers based on poly(2-ethylhexyl acrylate) or poly(dodecyl acrylate) with a mono(meth)acrylate end may be mentioned.
  • [0196]
    ii) polyolefins having a terminal group with an ethylenically unsaturated bond, in particular a (meth)acrylate terminal group. Particular examples of said polyolefins that may be mentioned are the following macromonomers, it being understood that they have a (meth)acrylate terminal group: polyethylene macromonomers, polypropylene macromonomers, polyethylene/polypropylene copolymer macromonomers, polyethylene/polybutylene copolymer macromonomers, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; and poly(ethylene/butylene)-polyisoprene macromonomers.
  • [0197]
    Such macromonomers have in particular been described in U.S. Pat. No. 5,625,005 which mentions ethylene/butylene macromonomers and ethylene/propylene macromonomers with a reactive (meth)acrylate terminal group.
  • [0198]
    In particular, poly(ethylene/butylenes) methacrylate may be mentioned, such as that sold under the trade name KRATON LIQUID L-1253 by KRATON POLYMERS.
  • [0199]
    Examples of silicone macromonomers that may be mentioned are polydimethylsiloxanes with a mono (meth)acrylate terminal group, in particular those with the following formula (XI):
  • [0000]
    Figure US20090130037A1-20090521-C00004
  • [0000]
    in which:
      • R8 designates a hydrogen atom or a methyl group;
      • R9 designates a divalent hydrocarbon group containing 1 to 10 carbon atoms and optionally containing one or two ether bonds, —O—;
      • R10 designates an alkyl group containing 1 to 10 carbon atoms, especially 2 to 8 carbon atoms; and
      • n designates a whole number from 1 to 300, preferably 3 to 200, and preferably 5 to 100.
  • [0204]
    Examples of silicone macromonomers which may be used are monomethacryloxypropyl polydimethylsiloxanes such as those sold under the trade name PS560-K6 by UNITED CHEMICAL TECHNOLOGIES INC. (UCT) or under the trade name MCR-M17 by GELEST INC.
  • [0205]
    More particularly, the polymerized macromonomer (constituting the side chains of the graft polymer) represents 0.1% to 15% by weight of the total polymer weight, preferably 0.2% to 10% by weight, and more preferably 0.3% to 8% by weight.
  • [0206]
    Particularly advantageous graft ethylenic polymers dispersed in a non-silicone liquid oily phase which may be used are those obtained by polymerizing:
      • methyl acrylate and polyethylene/polybutylene macromonomer with a methacrylate terminal group (in particular KRATON L-1253), in particular in a solvent selected from isododecane, isononyl isononanoate, octyldodecanol, diisostearyl malate, and a C12-C15 alkyl benzoate (such as Finsolv TN);
      • methoxyethyl acrylate and polyethylene/|polybutylene macromonomer with a methacrylate terminal group (especially KRATON L-1253), in particular in isododecane;
      • methyl acrylate/methyl methacrylate monomers and polyethylene/polybutylene macromonomer with a methacrylate terminal group (especially KRATON L-1253), in particular in isododecane;
      • methyl acrylate/acrylic acid monomers and polyethylene/polybutylene macromonomer with a methacrylate terminal group (in particular KRATON L-1253), in particular in isododecane;
      • methyl acrylate/dimethylaminoethyl methacrylate monomers and polyethylene/polybutylene macromonomer with a methacrylate terminal group (especially KRATON L-1253), in particular in isododecane;
      • methyl acrylate/2-hydroxyethyl methacrylate monomers and polyethylene/polybutylene macromonomer with a methacrylate terminal group (especially KRATON L-1253), in particular in isododecane.
  • [0213]
    In particular, the graft acrylic polymer dispersed in a silicone liquid oily phase may be selected from those obtained by polymerizing:
      • methyl acrylate and monomethacryloxypropylpolydimethylsiloxane macromonomer with a mass average molecular mass of 800 to 6000, in particular in decamethylcyclopentasiloxane or phenyltrimethicone;
      • methyl acrylate, acrylic acid and monomethacryloxypropylpolydimethylsiloxane macromonomer with a mass average molecular mass of 800 to 6000, in particular in decamethylcyclopentasiloxane or phenyltrimethicone.
  • [0216]
    In particular, the graft polymer has a mass average molecular mass (Mw) in the range 10000 to 300000, especially in the range 20000 to 200000, more preferably in the range 25000 to 150000.
  • [0217]
    Because of the above characteristics, in a given organic medium, the polymers have the ability to fold upon themselves thereby forming particles which are substantially spherical in shape, with the deployed side chains on the circumference of said particles, stabilizing the particles. Said particles resulting from the graft polymer characteristics do not agglomerate in said medium and thus self-stabilize and form a dispersion of particles of polymer which is particularly stable.
  • [0218]
    In particular, the graft ethylenic polymers of the dispersion may form nanometric particles with a mean size of 10 nm [nanometer] to 400 nm, preferably 20 nm to 200 nm.
  • [0219]
    Because of this very small size, the particles of graft polymer in dispersion are particularly stable and thus less likely to form agglomerates.
  • [0220]
    The graft polymer dispersion may thus be a stable dispersion and not form sediments when placed for a prolonged period (for example 24 hours) at ambient temperature (25° C.).
  • [0221]
    In particular, the dispersion of graft polymer particles has a dry matter content (dry extract) of polymer which may be from 40% to 70% by weight of dry matter, especially 45% to 65% by weight.
  • c) Production Method
  • [0222]
    The graft polymer particle dispersion may be prepared by a method comprising a radical copolymerization step, in an organic polymerization medium, of one or more acrylic monomers as defined above with one or more macromonomers as defined above.
  • [0223]
    As indicated above, the liquid organic dispersion medium may be identical to or different from the polymerization medium.
  • [0224]
    In conventional manner, copolymerization is carried out in the presence of a polymerization initiator. The polymerization initiators may be radical initiators. In general, such a polymerization initiator may be selected from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide, tert-butyl 2-peroxyethylhexanoate; and from diazo compounds such as azobisisobutyronitrile or azobisdimethylvaleronitrile.
  • [0225]
    The reaction may also be initiated using photoinitiators or radiation such as UV, neutrons or a plasma.
  • [0226]
    In general, to carry out said method, at least part of the organic polymerization medium, part of the acrylic monomers and/or additional vinyl monomers which, after polymerization, constitute the insoluble backbone, all of the macromonomer (which constitutes the side chains of the polymer) and a portion of the polymerization initiator are introduced into a reactor of suitable size for the quantity of polymer to be produced. At this stage of the introduction, the reaction medium forms a relatively homogeneous medium.
  • [0227]
    The reaction medium is then stirred and heated to a temperature to obtain polymerization of the monomers and macromonomers. After a certain period, the initially homogeneous and clear medium takes on a milky appearance. A mixture constituted by the remaining portion of the monomers and the polymerization initiator is then added. After a suitable period during which the mixture is heated with stirring, the medium stabilizes into the form of a milky dispersion, the dispersion comprising polymer particles stabilized in the medium in which they were created, said stabilization being due to the presence, in the polymer, of side chains which are soluble in said dispersion medium.
  • [0228]
    The graft polymer may be present in the composition of the invention in a dry matter content (active substance) of 1% to 70% by weight relative to the total composition weight, preferably 5% to 60%, more preferably 6% to 45% and still more preferably 8% to 40% by weight.
  • [0229]
    In one implementation, the film-forming polymer is an organic film-forming polymer which is soluble in the liquid oily phase of the composition, especially in the oil or oils of the composition.
  • [0230]
    In this case, we speak of a liposoluble polymer. The liposoluble polymer may be of any chemical type and may in particular be selected from:
  • [0231]
    a) Liposoluble and amorphous homopolymers and copolymers of olefins, cycloolefins, butadiene, isoprene, styrene, ethers, esters or vinyl amides, ester or amides of (meth)acrylate acid containing a linear, branched or cyclic C4-C50 alkyl group, in particular amorphous. Preferred liposoluble homopolymers and copolymers are obtained from monomers selected from the group constituted by isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, methyl (meth)acrylate, tertio-butyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, or mixtures thereof. Examples that may be mentioned are the alkyl acrylate/cycloalkyl acrylate copolymer sold by PHOENIX CHEM. under the trade name GIOVAREZ AC-5099 ML, and vinylpyrrolidone copolymers such as copolymers of a C2 to C30 alkene, such as C3 to C22, and associations thereof. Examples of VP copolymers which may be used in the invention that may be mentioned are VP/vinyl laurate copolymer, VP/vinyl stearate copolymer, butylated polyvinylpyrrolidone (PVP), VP/hexadecene, VP/triacontene or VP/acrylic acid/lauryl methacrylate.
  • [0232]
    Particular liposoluble copolymers that may be mentioned are:
  • [0233]
    i) silicone graft acrylic polymers having a silicone backbone, and acrylic grafts or an acrylic backbone and silicone grafts, such as the product sold under the trade name SA 70.5 by 3M and described in U.S. Pat. No. 5,725,882, U.S. Pat. No. 5,209,924, U.S. Pat. No. 4,972,037, U.S. Pat. No. 4,981,903, U.S. Pat. No. 4,981,902, U.S. Pat. No. 5,468,477, and in U.S. Pat. No. 5,219,560 and EP 0 388 582;
  • [0234]
    ii) liposoluble polymers carrying fluorinated groups belonging to one of the categories described in the text above, in particular FOMBLIN and those described U.S. Pat. No. 5,948,393 and copolymers of alkyl (meth)acrylate/|perfluoroalkyl (meth)acrylate described in EP 0 815 836 and U.S. Pat. No. 5,849,318;
  • [0235]
    iii) polymers or copolymers resulting from polymerization or copolymerization of an ethylenic monomer comprising one or more ethylenic bonds, preferably conjugated (or dienes). Polymers or copolymers resulting from polymerization or copolymerization of an ethylenic monomer which may be used include vinyl, acrylic and methacrylic copolymers.
  • [0236]
    In one implementation, the film-forming polymer is a block copolymer comprising at least one block constituted by styrene moieties or styrene derivatives (for example methylstyrene, chlorostyrene or chloromethylstyrene). The copolymer comprising at least one styrene block may be a two- or three-block copolymer, or even a multi-block copolymer, or a star or radial copolymer. The copolymer comprising at least one styrene block may further comprise, for example, an alkyl styrene block (AS), an ethylene/butylene block (EB), an ethylene/propylene block (EP), a butadiene block (B), an isoprene block (I), an acrylate block (A), a methacrylate block (MA) or an association of these blocks. The copolymer comprising at least one block constituted by styrene moieties or styrene derivatives may be a two- or three-block copolymer, in particular of the polystyrene/polyisoprene or polystyrene/poly butadiene type, such as those sold or manufactured under the trade name “LUVITOL HSB” by BASF and those of the polystyrene/copoly(ethylene-propylene) type or, alternatively, of the polystyrene/copoly(ethylene/butylene) type, such as those sold or manufactured under the trade name “KRATON” by SHELL CHEMICAL CO. or GELLED PERMETHYL 99A by PENRECO, may be used.
  • [0237]
    The following may, for example, be mentioned: KRATON G1650 (SEBS), KRATON G1651 (SEBS), KRATON G1652 (SEBS), KRATON G1657X (SEBS), KRATON G1701X (SEP), KRATON G1702X (SEP), KRATON G1726X (SEB), KRATON D-1101 (SBS), KRATON D-1102 (SBS), KRATON D-1107 (SIS), GELLED PERMETHYL 99A-750, GELLED PERMETHYL 99A-753-58 (mixture of star block copolymer and three-block polymer), GELLED PERMETHYL 99A-753-59 (mixture of star block copolymer and three-block polymer), VERSAGEL 5970 and VERSAGEL 5960 from PENRECO (mixture of star block copolymer and three-block polymer in isododecane).
  • [0238]
    Styrene-methacrylate copolymers may also be used, such as polymers sold under the trade name OS 129880, OS 129881 and OS 84383 from LUBRIZOL (styrene-methacrylate copolymer).
  • [0239]
    In one implementation, the film-forming polymer is selected from copolymers of a vinyl ester (the vinyl group being directly bonded to the oxygen atom of the ester group and the vinyl ester having a saturated, linear or branched hydrocarbon radical containing 1 to 19 carbon atoms, bonded to the carbonyl of the ester group) and at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (containing 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a saturated, linear or branched hydrocarbon radical containing 1 to 19 carbon atoms bonded to the carbonyl of the ester group).
  • [0240]
    Said copolymers may be partially cross-linked using cross-linking agents which may be either vinyl in type or allyl or methallyl in type, such as tetra-allylocyethane, divinylbenzene, divinyloctanedioate, divinyldodecanedioate and divinyloctadecanedioate.
  • [0241]
    Examples of said copolymers that may be mentioned are as follows: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/|octadecylvinylether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/|octadecene-1, vinyl acetate/dodecene-1, vinyl stearate/|ethylvinylther, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2,2-dimethyloctanoate/|vinyl laurate, allyl 2,2-dimethylpentanoate/vinyl laurate, vinyl dimethyl propionate/vinyl stearate, allyl dimethyl propionate/vinyl stearate, vinyl propionate/|vinyl stearate cross-linked with 0.2% of divinyl benzene, vinyl dimethyl propionate/vinyl laurate cross-linked with 0.2% of divinyl benzene, vinyl acetate/octadecyl vinyl ether cross-linked with 0.2% of tetraallyloxyethane, vinyl acetate/allyl stearate, cross-linked with 0.2% of divinyl benzene, vinyl acetate/octadecene-1 cross-linked with 0.2% of divinyl benzene and allyl propionate/allyl stearate cross-linked with 0.2% of divinyl benzene.
  • [0242]
    Further liposoluble film-forming polymers that may be mentioned are liposoluble copolymers, in particular those resulting from copolymerizing vinyl esters containing 9 to 22 carbon atoms or alkyl acrylates or methacrylates, the alkyl radicals containing 10 to 20 carbon atoms.
  • [0243]
    Said liposoluble copolymers may be selected from copolymers of vinyl polystearate, vinyl polystearate cross-linked with divinyl benzene, diallyl ether or diallyl phthalate, copolymers of stearyl poly (meth)acrylate, vinyl polylaurate, lauryl poly (meth)acrylate, said poly (meth)acrylates possibly being cross-linked using ethylene glycol dimethacrylate or tetraethylene glycol.
  • [0244]
    The liposoluble copolymers defined above are known and have been described in FR-A-2 232 303; they may have a mass average molecular mass of 2000 to 500000, in particular 4000 to 200000.
  • [0245]
    Examples of liposoluble polymers which may be used in the context of the invention and that may be mentioned are polyalkylenes, copolymers of C2-C20 alkenes, in particular polybutene.
  • [0246]
    Examples of liposoluble polymers which may be used in the context of the invention that may be mentioned are poly alkylenes, copolymers of C2-C20 alkenes, in particular polybutene.
  • [0247]
    b) Amorphous and liposoluble polycondensates, in particular containing no hydrogen interaction donor groups, in particular aliphatic polyesters containing C4-C50 alkyl side chains or polyesters resulting from the condensation of fatty acid dimers, or even polyesters comprising a silicone segment in the form of a sequence, graft or terminal group, as defined in patent FR 0 113 920; and
  • [0248]
    c) Amorphous and liposoluble polysaccharides comprising alkyl side chains (ether or ester), in particular alkyl celluloses containing a saturated or unsaturated, linear or branched C1 to C8 alkyl radical such as ethyl cellulose or propyl cellulose.
  • [0249]
    The film-forming polymer may in particular be selected from cellulose polymers such as nitro cellulose, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, ethyl cellulose, or from polyurethanes, acrylic polymers, vinyl polymers, polyvinylbutyrals, alkyd resins, resins derived from the condensation products of aldehydes such as arylsulfonamide formaldehyde resins, such as the toluene sulfonamide formaldehyde resin, and aryl-sulfonamide epoxy resins.
  • [0250]
    The film-forming polymer used may in particular be nitrocellulose RS ⅛ sec; RS ¼ sec.; ½ sec.; RS 5 sec.; RS 15 sec.; RS 35 sec.; RS 75 sec.; RS 150 sec; AS ¼ sec.; AS ½ sec.; SS ¼ sec.; SS 5 sec.; SS 5 sec., especially those sold by HERCULES; “KETJENTFLEX MS80” toluene sulfonamide formaldehyde resin from AKZO or “SANTOLITE MHP”, “SANTOLITE MS 80” from FACONNIER or “RESIMPOL 80” from PAN AMERICANA, the alkyd resin “BECKOSOL ODE 230-70-E” from DAINIPPON, the acrylic resin “ACRYLOID B66”, from ROHM & HAAS, and the polyurethane resin “TRIXENE PR 4127” from BAXENDEN.
  • [0251]
    d) Silicone resins, generally soluble or swellable in silicone oils. These resins are cross-linked polyorganosiloxane polymers.
  • [0252]
    The term “resin” means a three-dimensional structure.
  • [0253]
    In one implementation, the silicone resin is selected from silsesquioxanes and siloxysilicates.
  • [0254]
    In one implementation, the silicone resin is selected from siloxysilicates such as trimethylsiloxysilicates represented by the following formula:
  • [0000]

    [R3SiO1/2]x—(SiO4/2)y (M and Q moieties)
  • [0000]
    in which x and y may have values of 50 to 80, and R represents an alkyl, such as a methyl or an alkyl with two or more carbon atoms.
  • [0255]
    The ratio of moieties M to moieties Q may, for example, be about 0.7:1. The film-forming silicone resin may, for example, be selected from WACKER 803 and 804 resins available from WACKER SILICONE CORPORATION, and G.E. 1 170-002, available from GENERAL ELECTRIC.
  • [0256]
    In a further implementation, the silicone resin is selected from silsesquioxanes comprising T moieties:
  • [0000]

    [RSiO3/2]t (T moieties)
  • [0000]
    in which t has a value which may be up to several thousand and R represents an alkyl, such as a methyl or an alkyl with two or more carbon atoms. In one implementation, the silsesquioxane is selected from polymethyl silsesquioxanes which are silsesquioxanes in which R is a methyl group.
  • [0257]
    The polymethyl silsesquioxanes may, for example, comprise less than about 500 T moieties, preferably from about 50 to about 500 T moieties.
  • [0258]
    Not all polymethylsilsesquioxanes are film-forming. As an example, polymethylsilsesquioxanes such as TOSPEARL™ from TOSHIBA or KMP590 from SHIN-ETSU are highly insoluble in oils and thus are ineffective film-forming agents. The molecular mass of those polymethylsilsesquioxanes is difficult to determine as they generally contain a thousand or more T moieties.
  • [0259]
    One example of a polymethylsilsesquioxane which may be used in the invention is BELSIL PMS MK (also known as MK resin), available from WACKER CHEMIE. The polymethylsilsesquioxane is a polymer principally constituted by CH3SiO3/2 (T moieties) repeat moieties and may also contain up to about 1% (by weight or in moles) of (CH3)2SiO2/2 (D moieties).
  • [0260]
    Suitable polymethylsilsesquioxanes for use in the present invention include KR-220L available from SHIN-ETSU. The structure of KR-220L is essentially constituted by T silicone moieties (CH3SiO3/2) with terminal Si—OH or silanol moieties; both are available from SHIN-ETSU.
  • [0261]
    The polymethylsilsesquioxane KR-242A has a structure having about 98% T methyl moieties and about 2% dimethyl D moieties, with Si—OH or silanol terminal moieties, and KR-251, which has a structure having about 88% T methyl moieties and about 12% dimethyl D moieties, with SiOH or silanol terminal moieties; both are available from SHIN-ETSU.
  • [0262]
    In one implementation of the invention, the silicone resin is soluble or dispersible in silicone oils or volatile organic liquids. In one implementation, the silicone resin is solid at 25° C.
  • [0263]
    In one implementation, the silicone resin may have a molecular mass of 1000 grams/mole to 10000 grams/mol. In another implementation, the resin is present in the composition in a quantity of 0.5% to 20% by weight relative to the total composition weight, preferably in a quantity of 1% to 10%.
  • [0264]
    In one implementation of the invention, the silicone resin is selected from combinations of M, D, T and Q moieties containing at least two moieties selected from M, D, T and Q satisfying the relationship RnSiO(4-n), in which n has a value of 1.0 to 1.50. Certain resins of that type are described in U.S. Pat. No. 6,074,654.
  • [0265]
    In a further implementation, the film-forming silicone resin is a copolymer in which at least one moiety of the copolymer is selected from the silicone moieties M, D, T and Q, and in which at least one additional moiety of the copolymer is selected from esters. The film-forming silicone resin may, for example, be selected from diisostearoyltrimethylolpropane siloxysilicates such as SF 1 318 available from GE SILICONES.
  • [0266]
    e) Polyamide-silicone copolymers of the polyorganosiloxane type, such as those described in documents U.S. Pat. No. 5,874,069, U.S. Pat. No. 5,919,441, U.S. Pat. No. 6,051,216 and U.S. Pat. No. 5,981,680.
  • [0267]
    In accordance with the invention, said silicone polymers may belong to the following two categories:
  • [0268]
    1) polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, said two groups being located in the chain of the polymer; and/or
  • [0269]
    2) polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, said two groups being located on the grafts or branches.
  • [0270]
    The polymers comprising two groups capable of establishing hydrogen interactions in the chain of the polymer may be polymers comprising at least one moiety having formula (XXII):
  • [0000]
    Figure US20090130037A1-20090521-C00005
  • [0000]
    in which:
  • [0271]
    1) R4, R5, R6 and R7, which may be identical or different, represent a group selected from:
      • linear, branched or cyclic, saturated or unsaturated C1 to C40 hydrocarbon groups which may contain one or more atoms of oxygen, sulfur and/or nitrogen in their chain, and which may be partially or completely substituted with fluorine atoms;
      • C6 to C10 aryl groups, optionally substituted with one or more C1 to C4 alkyl groups;
      • polyorganosiloxane chains containing or not containing one or more oxygen, sulfur and/or nitrogen atoms;
  • [0275]
    2) the Xs, which may be identical or different, represent a linear or branched C1 to C30 alkylene diyl group which may contain one or more oxygen and/or nitrogen atoms in its chain;
  • [0276]
    3) Y is a saturated or unsaturated C1-C50 divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene group, which may comprise one or more oxygen, sulfur and/or nitrogen atoms and/or carry one of the following atoms or groups of atoms as a substituent: fluorine, hydroxyl, C3 to C8 cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted with 1 to 3 C1 to C3 alkyl groups, C1 to C3 hydroxyalkyl or C1 to C6 aminoalkyl; or
  • [0277]
    4) Y represents a group with formula (XXIII):
  • [0000]
    Figure US20090130037A1-20090521-C00006
  • [0000]
    in which:
      • T represents a trivalent or tetravalent, linear or branched, saturated or unsaturated C3 to C24 hydrocarbon group optionally substituted with a polyorganosiloxane chain, and which may contain one or more atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and Al; and
      • R8 represents a linear or branched C1 to C50 alkyl group or a polyorganosiloxane chain which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups which may optionally be bonded to another chain of the polymer
  • [0280]
    5) the Gs, which may be identical or different, represent divalent groups selected from:
  • [0000]
    Figure US20090130037A1-20090521-C00007
  • [0000]
    where R9 represents a hydrogen atom or a linear or branched C1 to C20 alkyl group, provided that at least 50% of the radicals R9 of the polymer represents a hydrogen atom and at least two of the G groups of the polymer are a group other than:
  • [0000]
    Figure US20090130037A1-20090521-C00008
  • [0281]
    6) n is a whole number from 2 to 500, in particular 2 to 200, and m is a whole number from 1 to 1000, in particular 1 to 700 and more preferably 6 to 200.
  • [0282]
    In accordance with the invention, 80% of the R4, R5, R6 and R7 groups of the polymer are preferably selected from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups.
  • [0283]
    In accordance with the invention, Y may represent various divalent groups, optionally further comprising one or more free valencies in order to establish bonds with other moieties of the polymer or copolymer. In particular, Y represents a group selected from:
  • [0284]
    a) linear C1 to C20 alkylene groups, preferably C1 to C10;
  • [0285]
    b) branched C30 to C56 alkylene groups which may include cycles and non conjugated unsaturated bonds;
  • [0286]
    c) C5-C6 cycloalkylene groups;
  • [0287]
    d) phenylene groups, optionally substituted with one or more C1 to C40 alkyl groups;
  • [0288]
    e) C1 to C20 alkylene groups comprising 1 to 5 amide groups;
  • [0289]
    f) C1 to C20 alkylene groups comprising one or more substituents selected from hydroxyl, C3 to C8 cycloalkane groups, C1 to C3 hydroxyalkyl and C1 to C6 alkylamines;
  • [0290]
    g) Polyorganosiloxane chains with formula (XXIV):
  • [0000]
    Figure US20090130037A1-20090521-C00009
  • [0000]
    in which R4, R5, R6, R7, T and m are as defined above; and
  • [0291]
    h) polyorganosiloxane chains with formula (XXV):
  • [0000]
    Figure US20090130037A1-20090521-C00010
  • [0292]
    The polyorganosiloxanes of the second category may be polymers comprising at least one moiety having formula (XXVI):
  • [0000]
    Figure US20090130037A1-20090521-C00011
  • [0000]
    in which:
      • R4 and R6, which may be identical or different, are as defined above for formula (XXII);
      • R10 represents a group as defined above for R4 and
  • [0295]
    R6, or represents the group with formula —X-G-R12 in which X and G are as defined above for formula (XXII) and R12 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated C1 to C50 hydrocarbon group optionally comprising one or more atoms selected from O, S and N in its chain, optionally substituted with one or more fluorine atoms and/or one or more hydroxyl groups, or a phenyl group optionally substituted with one or more C1 to C4 alkyl groups;
      • R11 represents the group with formula —X-G-R9 in which X, G and R12 are as defined above;
      • m1 is a whole number from 1 to 998; and
      • m2 is a whole number from 2 to 500.
  • [0299]
    According to the invention, the polymer used may be a homopolymer, i.e. a polymer comprising several identical moieties, in particular moieties with formula (XXII) or formula (XXVI).
  • [0300]
    According to the invention, it is also possible to use a polymer constituted by a copolymer comprising several different moieties with formula (XXII), i.e. a polymer in which at least one of R4, R5, R6, R7, X, G, Y, m and n is different in one of the moieties. The copolymer may also be formed by several moieties with formula (XXVI) in which at least one of R4, R6, R10, R11, m1 and m2 is different in at least one of the moieties.
  • [0301]
    It is also possible to use a copolymer comprising at least one moiety with formula (XXII) and at least one moiety with formula (XXVI), the moieties with formula (XXII) and moieties with formula (XXVI) possibly being identical or different from each other.
  • [0302]
    In a variation, it is also possible to use a copolymer comprising, in addition, at least one hydrocarbon moiety comprising two groups capable of establishing hydrogen bonds, selected from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidine and biguanidino groups and combinations thereof.
  • [0303]
    Said copolymers may be block copolymers, sequenced copolymers or graft copolymers.
  • [0304]
    f) Linear Ethylenic Sequenced Polymers
  • [0305]
    The composition of the invention may contain, as a film-forming agent, a linear sequenced ethylenic polymer below termed a “sequenced polymer” with a particular structure that is described below.
  • [0306]
    The term “sequenced” polymer means a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences.
  • [0307]
    The polymer is a polymer with a linear structure.
  • [0308]
    In contrast, an example of a non-linear structured polymer is a polymer with a branched, star, graft or other structure.
  • [0309]
    Advantageously, the sequenced polymer is free of styrene. The term “polymer free of styrene” means a polymer containing less than 10% by weight, relative to the total polymer weight, preferably less than 5% by weight, more preferably less than 2% by weight and still more preferably less than 1% by weight or contains no styrene-like monomer such as styrene, styrene derivatives such as methylstyrene, chlorostyrene or chloromethylstyrene.
  • [0310]
    In particular, the sequenced polymer comprises at least one first sequence and at least one second sequence having different glass transition temperatures (Tg), said first and second sequences being connected together by an intermediate sequence comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence.
  • [0311]
    The term “at least” one sequence means one or more sequences.
  • [0312]
    The intermediate sequence is a sequence comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence of the polymer in order to “compatibilize” these sequences.
  • [0313]
    More precisely, in the above and below, the terms “first” and “second” sequences do not in any way dictate the order of said sequences (or blocks) in the structure of the sequenced polymer.
  • [0314]
    Advantageously, the first and second sequences and the sequenced polymer are incompatible with each other.
  • [0315]
    The term “sequences which are incompatible with each other” means that the mixture formed by the polymer corresponding to the first sequence and the polymer corresponding to the second sequence is not miscible in the organic liquid which is in the mass majority of the liquid oily phase at ambient temperature (25° C.) and at atmospheric pressure (105 Pa [Pascal]), for an amount of the polymer mixture of 5% by weight or more relative to the total weight of the mixture (polymers and solvent), it being understood that:
  • [0316]
    i) said polymers are present in the mixture in an amount such that the respective weight ratio is from 10/90 to 90/10; and
  • [0317]
    ii) each of the polymers corresponding to the first and second sequences has a (mass or number) average molecular mass equal to that of the sequenced polymer ±15%.
  • [0318]
    When the composition comprises a liquid oily phase comprising a mixture of organic liquids, assuming that two or more organic liquids are present in identical proportions by weight, said mixture of polymers is not miscible in at least one of them.
  • [0319]
    Clearly, when the liquid oily phase comprises a single organic liquid, the organic liquid is the major organic liquid.
  • [0320]
    In particular, the sequenced polymer does not include silicon atoms in its backbone. The term “backbone” means the principal chain of the polymer, in contrast to the pendant side chains.
  • [0321]
    In particular, the sequenced polymer is not soluble in water or in a mixture of water and linear or branched lower mono-alcohols containing 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without modifying the pH, at an active material content of at least 1% by weight, at ambient temperature (25° C.).
  • [0322]
    In particular, the sequenced polymer is not an elastomer.
  • [0323]
    The term “non-elastomeric polymer” means a polymer which, when it is subjected to a force intended to extend it (for example by 30% relative to its initial length), does not return to a length substantially identical to its initial length when the force ceases.
  • [0324]
    More specifically, the term “non-elastomeric polymer” means a polymer with an instantaneous recovery, Ri, of <50% and a delayed recovery, R2h, of <70% after undergoing an extension of 30%. Preferably, Ri is <30% and R2h is <50%.
  • i) Recovery Test
  • [0325]
    More precisely, the non-elastomeric character of the polymer is determined using the following protocol:
  • [0326]
    A film of polymer is prepared by pouring a solution of polymer into a Teflon lined matrix then drying for 7 days under a controlled atmosphere at 23±5° C. and 50±10% relative humidity.
  • [0327]
    A film about 100 μm [micrometer] thick is obtained from which rectangular specimens are cut (for example using a punch) with a width of 15 mm [millimeter] and a length of 80 mm.
  • [0328]
    A tension is applied to said specimen using a Zwick apparatus, applying the temperature and humidity conditions used for drying.
  • [0329]
    The specimens are drawn at a rate of 50 mm/min and the distance between the jaws is 50 mm, corresponding to the initial length (I0) of the specimen.
  • [0330]
    The instantaneous recovery Ri is determined as follows:
      • the specimen is extended by 30% (εmax), i.e. about 0.3 times its initial length (I0);
      • the force is relaxed, imposing a return rate equal to the draw rate, i.e. 50 mm/min, and the residual extension of the sample is measured as a percentage after returning to the zero stress (ε1).
  • [0333]
    The instantaneous recovery, as a % (Ri), is given by the following formula:
  • [0000]

    R i=(εmax−ε1)/εmax)×100
  • [0334]
    To determine the delayed recovery, the residual lengthening of the specimen is measured as a percentage (ε2h), 2 hours after returning to zero stress.
  • [0335]
    The delayed recovery, as a % (R2h), is given by the following formula:
  • [0000]

    R 2h=(εmax−ε2h)/εmax)×100
  • [0336]
    Purely by way of indication, a polymer in one implementation of the invention has an instantaneous recovery Ri of 10% and a delayed recovery R2h of 30%.
  • [0337]
    Advantageously, the sequenced polymer has a polydispersity I of more than 2, for example 2 to 9, in particular 2.5 or more, for example from 2.5 to 8, and more particularly 2.8 or more, especially 2.8 to 6.
  • [0338]
    The polydispersity index I of the sequenced polymer is equal to the ratio of the mass average molecular mass Mw to the number average molecular mass Mn.
  • [0339]
    The mass average molecular mass (Mw) and number average molecular mass (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene specimens, refractometric detector).
  • [0340]
    The mass average molecular weight (Mw) of the sequenced polymer is in particular 300000 or less, for example 35000 to 200000, more particularly 45000 to 150000.
  • [0341]
    The mass average molecular mass (Mn) of the sequenced polymer is, in particular, 70000 or less, for example 10000 to 60000, more particularly 12000 to 50000.
  • [0342]
    Each sequence or block of the sequenced polymer is derived from a type of monomer or several different types of monomers.
  • [0343]
    This means that each sequence may be constituted by a homopolymer or a copolymer; said copolymer constituting the sequence which may in turn be random or alternating.
  • [0344]
    Advantageously, the intermediate sequence comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence of the sequenced polymer is a random polymer.
  • [0345]
    In particular, the intermediate sequence is essentially derived from the constituent monomers of the first sequence and the second sequence.
  • [0346]
    The term “essentially” means at least 85%, in particular at least 90%, more particularly 95% and more particularly 100%.
  • [0347]
    Advantageously, the intermediate sequence has a glass transition temperature Tg in the range between the glass transition temperatures of the first and second sequences.
  • [0348]
    The glass transition temperatures indicated for the first and second sequences may be the theoretical Tgs determined from the theoretical Tgs of the constituents monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 3rd edition, John Wiley, using the following relationship known as Fox's Law:
  • [0000]
    1 / Tg = ( ω i / Tg i ) i
  • [0349]
    {acute over (ω)}i being the mass fraction of monomer i in the sequence under consideration and Tgi being the glass transition temperature of the homopolymer of monomer i.
  • [0350]
    Unless otherwise indicated, the Tgs indicated for the first and second sequences in the present application are theoretical Tgs.
  • [0351]
    The difference between the glass transition temperatures of the first and second sequences is generally more than 10° C., in particular more than 20° C., and more particularly more than 30° C.
  • ii) Polymer Sequences
  • [0352]
    In particular, the first sequence of the sequenced polymer may be selected from:
  • [0353]
    a) a sequence having a Tg of 40° C. or more;
  • [0354]
    b) a sequence having a Tg of 20° C. or less;
  • [0355]
    c) a sequence having a Tg between 20° C. and 40° C.; and
  • [0356]
    the second sequence is selected from a category a),
  • [0357]
    b) or c) which is different from that of the first sequence.
  • [0358]
    The term “between . . . and . . . ” as used in the present invention means a range of values from which the limits mentioned are excluded, and “ . . . to . . . ” and “from . . . to . . . ” means a range of values the limits of which are included.
  • a) Sequence Having a Tg of 40° C. or More
  • [0359]
    The sequence with a Tg of 40° C. or more has, for example, a Tg of 40° C. to 150° C., in particular 50° C. or more, for example from 50° C. to 120° C., in particular 60° C. or more, for example from 60° C. to 120° C.
  • [0360]
    The sequence with a Tg of 40° C. or more may be a homopolymer or a copolymer.
  • [0361]
    When said sequence is a homopolymer, it is derived from monomers that are such that the homopolymers prepared from said monomers have glass transition temperatures or 40° C. or more. This first sequence may be a homopolymer constituted by a single type of monomer (where the Tg of the corresponding homopolymer is 40° C. or more).
  • [0362]
    When the first sequence is a copolymer, it may be completely or partially derived from one or more monomers, the nature of which and the concentration of which are selected so that the Tg of the resulting copolymer is 40° C. or more. As an example, the copolymer may comprise:
      • monomers that are such that homopolymers prepared from said monomers have a Tg of 40° C. or more, for example a Tg of 40° C. to 150° C., in particular 50° C. or more, for example from 50° C. to 120° C., in particular 60° C. or more, for example from 60° C. to 120° C.; and
      • monomers that are such that homopolymers prepared from said monomers have a Tg of 40° C. or less, selected from monomers having a Tg between 20° C. and 40° C. and/or monomers having a Tg of 20° C. or less, for example a Tg of −100° C. to 20° C., in particular less than 15° C., especially from −80° C. to 15° C. and in particular less than 10° C., for example −50° C. to 0° C. as described below.
  • [0365]
    Monomers the homopolymers of which have a glass transition temperature of 40° C. or more are preferably selected from the following monomers, also termed principal monomers:
      • methacrylates with formula (XII):
  • [0000]

    CH2═C(CH3)—COOR1  (XII)
  • [0000]
    in which R1 represents an unsubstituted linear or branched alkyl group containing 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R1 represents a C4 to C12 cycloalkyl group;
      • acrylates with formula (XIII):
  • [0000]

    CH2═CH—COOR2  (XIII)
  • [0000]
    in which R2 represents a C4 to C12 cycloalkyl group such as isobornyl acrylate or a tertiobutyl group;
  • [0368]
    (meth)acrylamides with formula (XIV):
  • [0000]
    Figure US20090130037A1-20090521-C00012
  • [0000]
    where:
      • R7 and R8, which may be identical or different, each represent a hydrogen atom or a linear or branched C1 to C12 alkyl group such as a n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl group; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group; and
      • R′ designates H or methyl; and
      • mixtures thereof.
  • [0372]
    Examples of monomers that may be mentioned are N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide.
  • [0373]
    Particularly advantageous principal monomers are methyl methacrylate, isobutyl (meth)acrylate, isobornyl (meth)acrylate and mixtures thereof.
  • b) Sequence Having a Tg of 20° C. or Less
  • [0374]
    The sequence having a Tg of 20° C. or less has, for example, a Tg of −100° C. to 20° C., preferably 15° C. or less, especially from −80° C. to 15° C. and more preferably 10° C. or less, for example from −50° C. to 0° C.
  • [0375]
    The sequence with a Tg of 20° C. or less may be a homopolymer or a copolymer.
  • [0376]
    When said sequence is a homopolymer, it is derived from monomers, which are such that homopolymers prepared from said monomers have glass transition temperatures of 20° C. or less. Said second sequence may be a homopolymer constituted by a single type of monomer (wherein the Tg of the corresponding homopolymer is 20° C. or less).
  • [0377]
    When the sequence with a Tg of 20° C. or less is a copolymer, it may be wholly or partially derived from one or more monomers, the nature and concentration of which are selected so that the Tg of the resulting copolymer is 20° C. or less.
  • [0378]
    As an example, it may comprise:
      • one or more monomers wherein the corresponding homopolymer has a Tg of 20° C. or less, for example a Tg of −100° C. to 20° C., in particular less than 15° C., especially −80° C. to 15° C. and in particular less than 10° C., for example from −50° C. to 0° C.; and
      • one or more monomers wherein the corresponding homopolymer has a Tg of more than 20° C., such as monomers having a Tg of 40° C. or more, for example a Tg of 40° C. to 150° C., in particular 50° C. or more, for example from 50° C. to 120° C., and in particular 60° C. or more, for example from 60° C. to 120° C. and/or monomers having a Tg between 20° C. and 40° C., as described above.
  • [0381]
    In particular, the sequence with a Tg of 20° C. or less is a homopolymer.
  • [0382]
    Monomers the homopolymer of which has a Tg of 20° C. or less are preferably selected from the following monomers or principal monomers:
      • acrylates with formula (XV):
  • [0000]

    CH2═CHCOOR3  (XV)
  • [0384]
    R3 representing an unsubstituted linear or branched C1 to C12 alkyl group in which one or more heteroatoms selected from O, N and S are interposed;
      • methacrylates with formula (XVI):
  • [0000]

    CH2═C(CH3)—COOR4  (XVI)
  • [0386]
    R4 represents an unsubstituted linear or branched alkyl C6 to C12 group in which one or more heteroatoms selected from O, N and S are optionally interposed;
      • vinyl esters with formula (XVII):
  • [0000]

    R5—CO—O—CH═CH2  (XVII)
  • [0000]
    where R5 represents a linear or branched C4 to C12 alkyl group;
      • ethers of vinyl alcohol and C4 to C12 alcohol;
      • C4 to C12 alkyl N-alkylated acrylamides, such as N-octylacrylamide; and
      • mixtures thereof.
  • [0391]
    Particularly preferred principal monomers for the sequence with a Tg of 20° C. or less are alkyl acrylates the alkyl chain of which contains 1 to 10 carbon atoms, such as methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.
  • c) Sequence Having a Tg Between 20° C. and 40° C.
  • [0392]
    The sequence with a Tg between 20° C. and 40° C. may be a homopolymer or a copolymer.
  • [0393]
    When said sequence is a homopolymer, it is derived from monomers (or principal monomers) which are such that homopolymers prepared from said monomers have glass transition temperatures between 20° C. and 40° C. Said first sequence may be a homopolymer, constituted by a single type of monomer (wherein the Tg of the corresponding homopolymer is from 20° C. to 40° C.).
  • [0394]
    Monomers with a homopolymer with a glass transition temperature between 20° C. and 40° C. are preferably selected from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate, isodecylacrylamide and mixtures thereof.
  • [0395]
    When the sequence with a Tg between 20° C. and 40° C. is a copolymer, it is completely or partially derived from one or more monomers (or a principal monomer) the nature and concentration of which are selected so that the Tg of the resulting copolymer is between 20° C. and 40° C.
  • [0396]
    Advantageously, the sequence with a Tg between 20° C. and 40° C. is a copolymer wholly or partially derived from:
      • principal monomers the corresponding homopolymer of which has a Tg of 40° C. or more, for example a Tg of 40° C. to 150° C., in particular 50° C. or more, for example 50° C. to 120° C., and preferably 60° C. or more, for example 60° C. to 120° C., as described above; and/or
      • principal monomers the corresponding homopolymer of which has a Tg of 20° C. or less, for example a Tg from −100° C. to 20° C., in pa 15° C. or less, especially −80° C. to 15° C. and in particular 10° C. or less, for example −50° C. to 0° C., as described above;
        said monomers being selected so that the Tg of the copolymer forming the first sequence is between 20° C. and 40° C.
  • [0399]
    Said principal monomers are, for example, selected from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.
  • [0400]
    More particularly, the proportion of the second sequence with a Tg of 20° C. or less is from 10% to 85% by weight of polymer, preferably 20% to 70% and more preferably 20% to 50%.
  • [0401]
    Each sequence may nevertheless contain a minor proportion of at least one constituent monomer of the other sequence.
  • [0402]
    Hence, the first sequence may contain at least one constituent monomer of the second sequence, and conversely.
  • [0403]
    In addition to the monomers indicated above, each of the first and/or second sequences of the sequenced polymer may comprise one or more monomers termed additional monomers, which differ from the principal monomers mentioned above.
  • [0404]
    The nature and quantity of these additional monomer or monomers are selected so that the sequence in which they are formed has the desired glass transition temperature.
  • [0000]
    iii) Additional Monomer
  • [0405]
    This additional monomer is, for example, selected from:
      • hydrophilic monomers such as:
        • monomers with an ethylenically unsaturated bond comprising at least one carboxylic or sulfonic acid function, such as:
          • acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and salts thereof;
        • monomers with an ethylenically unsaturated bond comprising at least one tertiary amine function such as:
          • 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and salts thereof;
          • methacrylates with formula (XVIII):
  • [0000]

    CH2═C(CH3)—COOR6  (XVIII)
  • [0000]
    in which R6 represents a linear or branched alkyl group containing 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted with one or more substituents selected from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate;
      • methacrylates with formula (XIX):
  • [0000]

    CH2═C(CH3)—COOR9  (XIX)
  • [0000]
    in which R9 represents a linear or branched C6 to C12 alkyl group, in which one or more heteroatoms selected from O, N and S are optionally interposed, said alkyl group being substituted with one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I, F);
      • acrylates with formula (XX):
  • [0000]

    CH2═CHCOOR10  (XX)
  • [0000]
    in which R10 represents a linear or branched C1 to C12 alkyl group substituted with one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R10 represents a C1 to C12—O—POE (polyoxyethylene) with 5 to 30 repetitions of the oxyethylene moiety, for example methoxy-POE, or R8 represents a polyoxyethylene group containing 5 to 30 ethylene oxide moieties;
      • monomers with an ethylenically unsaturated bond comprising one or more silicon atoms, such as methacryloxypropyl trimethoxy silane, methacryloxypropyl tris (trimethylsiloxy) silane; and
      • mixtures thereof.
  • [0416]
    Particularly preferred additional monomers are acrylic acid, methacrylic acid, trifluoroethyl methacrylate and mixtures thereof.
  • [0417]
    In a particular implementation, the sequenced polymer is a non-silicone polymer, i.e. a polymer free of silicon atoms.
  • [0418]
    Said additional monomers generally represent a quantity of 30% by weight or less, for example 1% to 30% by weight, preferably 5% to 20% by weight, more preferably 7% to 15% by weight of the total weight of the first and/or second sequences.
  • [0419]
    In particular, each of the first and second sequences comprises at least one monomer selected from (meth)acrylic acid esters, and optionally at least one monomer selected from (meth)acrylic acid and mixtures thereof.
  • [0420]
    Advantageously, each of the first and second sequences of the sequenced polymer is wholly derived from at least one monomer selected from acrylic acid, (meth)acrylate acid esters, and possibly at least one monomer selected from (meth)acrylate acid, and mixtures thereof.
  • iv) Production Method
  • [0421]
    The sequenced polymer may be obtained by radical polymerization in solution using the following preparation method:
      • introducing a portion of the polymerization solvent into a suitable reactor heated to a suitable temperature for polymerization (typically 60° C. to 120° C.);
      • once said temperature has been reached, introducing the constituent monomers of the first sequence in the presence of a portion of the polymerization initiator;
      • at the end of a time T corresponding to a maximum degree of conversion of 90%, introducing the constituent monomers of the second sequence and the other portion of the initiator;
      • reacting the mixture for a time T′ (from 3 to 6 h), at the end of which the mixture is returned to ambient temperature;
      • obtaining the polymer in solution in the polymerization solvent.
  • [0427]
    The term “polymerization solvent” means a solvent or a mixture of solvents. In particular, the polymerization solvent may be selected from ethyl acetate, butyl acetate, alcohols such as isopropanol or ethanol, aliphatic alkanes such as isododecane, and mixtures thereof. In particular, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.
  • [0428]
    In a particular implementation, the sequenced polymer comprises a first sequence with a Tg of 40° C. as described above in a) and a second sequence with a Tg of 20° C. or less, as described above at b).
  • [0429]
    In particular, the first sequence with a Tg of 40° C. or more is a copolymer derived from monomers which are such that the homopolymer prepared from said monomers has a glass transition temperature of 40° C. or more, such as the monomers described above.
  • [0430]
    Advantageously, the second sequence with a Tg of 20° C. or less is a homopolymer derived from monomers which are such that the homopolymer prepared from said monomers has a glass transition temperature of 20° C. or less, such as the monomers described above.
  • [0431]
    In particular, the proportion of the sequence with a Tg of 40° C. or more is from 20% to 90% by weight of polymer, preferably 30% to 80% and more preferably 50% to 70%.
  • [0432]
    In particular, the proportion of the sequence with a Tg of 20° C. or less is from 5% to 75% by weight of polymer, preferably 15% to 50%, and more preferably 25% to 45%.
  • [0433]
    Advantageously, the sequenced polymer may comprise:
      • a first sequence with a Tg of 40° C. or more, for example 85° C. to 115° C., which is an isobornyl acrylate/isobutyl methacrylate copolymer;
      • a second sequence with a Tg of 20° C. or less, for example −85° C. to −55° C., which is a 2-ethylhexyl acrylate homopolymer; and
      • an intermediate sequence which is a random isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate copolymer.
  • [0437]
    In a further implementation, the sequenced polymer comprises a first sequence having a glass transition temperature (Tg) between 20° C. and 40° C., as described in c), and a second sequence with a glass transition temperature of 20° C. or less, as described above in b) or a glass transition temperature of 40° C. or more, as described above.
  • [0438]
    In particular, the proportion of the first sequence with a Tg between 20° C. and 40° C. is from 10% to 85% by weight of polymer, in particular 30% to 80% by weight and more preferably 50% to 70%.
  • [0439]
    When the second sequence is a sequence having a Tg of 40° C. or more, in particular it is present in a proportion of 10% to 85% by weight of polymer, in particular 20% to 70% and more particularly 30% to 70%.
  • [0440]
    When the second sequence is a sequence with a Tg of 20° C. or less, in particular it is present in a proportion of 10% to 85% by weight of polymer, in particular 20% to 70% and more particularly 20% to 50%.
  • [0441]
    In particular, the first sequence with a Tg between 20° C. and 40° C. is a copolymer derived from monomers which are such that the corresponding homopolymer has a Tg of 40° C. or more, and monomers which are such that the corresponding homopolymer has a Tg of 20° C. or less.
  • [0442]
    Advantageously, the second sequence with a Tg of 20° C. or less or with a Tg of 40° C. or more is a homopolymer.
  • [0443]
    In a first variation, the sequenced polymer comprises:
      • a first sequence with a Tg between 20° C. and 40° C., for example with a Tg of 21° C. to 39° C., which is a copolymer comprising isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate;
      • a second sequence with a Tg of 20° C. or less, for example −65° C. to −35° C., which is a methyl methacrylate homopolymer; and
      • an intermediate sequence which is a random isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate copolymer.
  • [0447]
    In another variation, the sequenced polymer may comprise:
      • a first sequence with a Tg of 40° C. or more, for example from 85° C. to 115° C., which is an isobornyl acrylate/isobutyl methacrylate copolymer;
      • a second sequence with a Tg of 20° C. or less, for example −35° C. to −5° C., which is an isobutyl acrylate homopolymer; and
      • an intermediate sequence which is a random isobornyl methacrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
  • [0451]
    In a still further variation, the sequenced polymer may comprise:
      • a first sequence with a Tg of 40° C. or more, for example 60° C. to 90° C., which is an isobornyl acrylate/isobutyl methacrylate copolymer;
      • a second sequence with a Tg of 20° C. or more, for example from −35° C. to −5° C., which is an isobutyl acrylate homopolymer; and
      • an intermediate sequence which is a random isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate copolymer.
  • [0455]
    g) Products of reaction between a silica derivative and a polyorganosiloxane carrying terminal silanol groups, such as those described in U.S. Pat. No. 5,162,410, U.S. Pat. No. 0,330,747 and U.S. Pat. No. 5,451,610, the contents of shoulder are hereby incorporated by reference. Products of that type are sold under the trade name Bio-PSA by Dow Corning, for example the product of that range with reference number 7-4405.
  • [0456]
    In accordance with the invention, the film-forming polymer may be a solid which is insoluble in the oily phase of the composition at ambient temperature, for example about 25° C. The polymer is also insoluble in the oily phase at its softening temperature, in contrast to a wax of polymeric origin which is soluble in the liquid organic phase (or oily phase) at its melting temperature. In this respect, the polymer is not a wax.
  • 1) Polymers
  • [0457]
    The composition of the invention advantageously comprises at least one stable dispersion of essentially spherical polymer particles of one or more polymers in a physiologically acceptable oily phase.
  • [0458]
    Said dispersions may in particular be in the form of nano particles of polymers in stable dispersion in said liquid organic phase. The nano particles preferably have a mean size in the range 5 nm to 800 nm, and preferably in the range 50 nm to 500 nm. However, it is possible to obtain polymer particle sizes of up to 1 μm.
  • [0459]
    In particular, the polymer particles in dispersion are insoluble in hydrosoluble alcohols such as ethanol.
  • [0460]
    The polymers in dispersion which can be used in the composition of the invention preferably have a molecular weight of the order of 2000 to 10000000 g/mol, and a Tg of −100° C. to 300° C., preferably −50° C. to 100° C., more preferably −10° C. to 50° C.
  • [0461]
    It is possible to use polymers which can form films, preferably with a low Tg equal to or lower than the temperature of skin, and in particular 40° C. or less.
  • [0462]
    Examples of film-forming polymers that may be mentioned are acrylic or vinyl radical copolymers or homopolymers, preferably with a Tg of 40° C. or less and in particular from −10° C. to 30° C., used alone or as a mixture.
  • [0463]
    The term “radical type polymer” means a polymer obtained by polymerizing unsaturated monomers, in particular with ethylenically unsaturated bonds, each monomer being capable of self-polymerizing (in contrast to polycondensates). The radical type polymers may in particular be polymers or copolymers, vinyl, in particular acrylic polymers.
  • [0464]
    The acrylic polymers may result from polymerizing monomers with an ethylenically unsaturated bond containing at least one acid group and/or esters of said acid monomers and/or amides of said acids.
  • [0465]
    Monomers carrying an acid group which may be used include α,β-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid. In particular, (meth)acrylic acid, and crotonic acid may be used, more particularly (meth)acrylic acid.
  • [0466]
    The esters of acid monomers are advantageously selected from esters of (meth)acrylic acid (also known as (meth)acrylates), such as alkyl (meth)acrylates, in particular of C1-C20 alkyl, preferably C1-C8, aryl (meth)acrylates, in particular of C6-C10 aryl, and hydroxyalkyl (meth)acrylates, in particular C2-C6 hydroxyalkyl. Alkyl (meth)acrylates which may be mentioned include methyl, ethyl, butyl, isobutyl, 2-ethylhexyl, and lauryl methacrylate. Hydroxyalkyl (meth)acrylates which may be mentioned include hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Aryl (meth)acrylates which may be mentioned include benzyl acrylate and phenyl acrylate.
  • [0467]
    (Meth)acrylic acid esters that are particularly suited to cosmetic compositions of the invention are alkyl (meth)acrylates.
  • [0468]
    Particular radical polymers which may be used are (meth)acrylate acid and alkyl (meth)acrylate copolymers, in particular C1-C4 alkyl (meth)acrylate. More particularly, methyl acrylates optionally copolymerized with acrylic acid may be used.
  • [0469]
    Amides of acid monomers which may be mentioned are (meth)acrylamides, especially N-alkyl (meth)acrylamides, in particular C2-C12 alkyl (meth)acrylamides such as N-ethyl acrylamide, N-t-butyl acrylamide and N-t-octyl acrylamide; N-dialkyl C1-C4 alkyl (meth)acrylamides.
  • [0470]
    The acrylic polymers may also result from polymerizing monomers with an ethylenically unsaturated bond containing at least one amine group in free or partially or totally neutralized form, or indeed partially or totally quaternized. By way of example, such monomers may be dimethylaminoethyl (meth)acrylate, dimethylaminoethyl methacrylamide, vinylamine, vinylpyridine, and/or diallyldimethylammonium chloride.
  • [0471]
    The vinyl polymers may also result from homopolymerizing or copolymerizing at least one monomer selected from vinyl esters and styrene monomers. In particular, said monomers may be polymerized with acid monomers and/or their esters and/or their amides, such as those mentioned above. Examples of vinyl esters which may be mentioned are vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate, and vinyl t-butyl benzoate. An example of a styrene monomer which may be mentioned is alpha-methyl styrene.
  • [0472]
    The list of monomers given above is not limiting and it is possible to use any monomer which is known to the skilled person which falls into the categories of acrylic and vinyl monomers (including monomers modified by a silicone chain).
  • [0473]
    As other vinyl monomers that can used, mention can be made of:
      • N-vinylpyrrolidone, vinylcaprolactam, vinyl N-alkyl(C1-C6) pyrroles, vinyl-oxazoles, vinyl-thiazoles, vinylpyrimidines, vinylimidazoles;
      • olefins such ethylene, propylene, butylenes, isoprene, butadiene.
  • [0476]
    The vinyl polymer may be cross-linked using one or more di-functional monomers, in particular having at least two ethylenically unsaturated bonds, such as ethylene glycol dimethacrylate or diallyl phthalate.
  • [0477]
    In non-limiting manner, the polymers in dispersion of the invention may be selected from the following polymers or copolymers: polyurethanes, acrylic polyurethanes, polyureas, polyurea-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyesters, polyester amides, alkyds; acrylic and/or vinyl polymers or copolymers; acrylic-silicone copolymers; polyacrylamides; silicone polymers such as polyurethanes or silicone acrylics, fluorinated polymers, and mixtures thereof.
  • [0478]
    The polymer(s) in dispersion in the oily phase may represent 5% to 40% by weight of the dry matter of the composition, preferably 5% to 35%, better 8% to 30%.
  • 2) Stabilizer
  • [0479]
    In one implementation, the polymer particles in dispersion are surface stabilized by a stabilizer which is solid at ambient temperature. The dry matter content in the dispersion then represents the total quantity of polymer+stabilizer, given that the quantity of polymer cannot be less than 5%.
  • [0480]
    In particular, the polymer particles are surface stabilized using a stabilizer which may be a sequenced polymer, a graft polymer and/or a random polymer, used alone or as a mixture. Stabilization may be achieved by any known means, in particular by direct addition of stabilizing polymer during polymerization.
  • [0481]
    The stabilizer may also be present in the mixture before polymerizing the polymer. However, it is also possible to add it continuously, especially when the monomers are also added continuously.
  • [0482]
    2-30% by weight of stabilizer relative to the initial mixture of monomers, preferably 5-20% by weight, may be used.
  • [0483]
    When a graft and/or sequenced polymer is used as the stabilizer, the processing solvent is selected so that at least a portion of the grafts or sequences of said polymer-stabilizer is soluble in said solvent, the other portion of the grafts or sequences not being soluble therein. The polymer-stabilizer used during polymerization must be soluble or dispersible in the processing solvent. Further, it is preferable to select a stabilizer the insoluble sequences or grafts of which have a certain affinity for the polymer formed during polymerization.
  • [0484]
    Graft polymers that may be mentioned include silicone polymers grafted with a hydrocarbon chain; hydrocarbon polymers grafted with a silicone chain.
  • [0485]
    Thus, graft or sequenced block copolymers including at least one block of the polyorganosiloxane type and at least one block of a radical polymer may be used, such as graft copolymers of the acrylic/silicone type which may be used when the non aqueous medium is a silicone.
  • [0486]
    It is also possible to use graft or sequenced block copolymers comprising at least one block of the polyorganosiloxane type and at least one polyether. The polyorganosiloxane block may in particular be a polydimethylsiloxane or a polyalkyl(C2-C18)methylsiloxane; the polyether block may be a C2-C18 polyalkylene, in particular polyoxyethylene and/or polyoxypropylene. In particular, it is possible to use copolyol dimethicones or (C2-C18) alkyl dimethicone copolyols such as those sold under the trade name “DOW CORNING 3225C” by DOW CORNING, or lauryl methicones such as those sold by “DOW CORNING Q2-5200 by “DOW CORNING”.
  • [0487]
    Graft or sequenced block copolymers that may be mentioned include those comprising at least one block resulting from polymerizing at least one ethylenic monomer with one or more ethylenically unsaturated bonds which may be conjugated, such as ethylene or dienes such as butadiene or isoprene, and at least one block of a vinyl polymer and preferably styrene. When the ethylenic monomer comprises several ethylenically unsaturated bonds which may be conjugated, the residual ethylenically unsaturated bonds after polymerization are generally hydrogenated. In known manner, then, polymerization of the isoprene results in the formation of the ethylene-propylene block following hydrogenation, and butadiene polymerization results in the formation of the ethylene-butylene block after hydrogenation. Such polymers that may be mentioned include sequenced copolymers in particular of the two-block or three-block polystyrene/polyisoprene (SI), polystyrene/polybutadiene (SB) such as those sold under the trade name ‘LUVITOL HSB’ by BASF, of the polystyrene/copoly(ethylene-propylene) (SEP) type, such as those sold under the trade name “KRATON” by SHELL CHEMICAL Co or of the polystyrene/copoly(ethylene-butylene) (SEB) type. In particular, it is possible to use KRATON G1650 (SEBS), KRATON G1651 (SEBS), KRATON G1652 (SEBS), KRATON G1657X (SEBS), KRATON G1701X (SEP), KRATON G1702X (SEP), KRATON G1726X (SEB), KRATON D-1101 (SBS), KRATON D-1102 (SBS), or KRATON D-1107 (SIS). The polymers are generally termed copolymers of hydrogenated or non hydrogenated dienes.
  • [0488]
    It is also possible to use GELLED PERMETHYL 99A-750, 99A-753-59 and 99A-753-58 (mixture of three block and star polymer), VERSAGEL 5960 from PENRECO (three-block+star polymer); or OS129880, OS129881 and OS84383 from LUBRIZOL (styrene/methacrylate copolymer).
  • [0489]
    Graft or sequenced block copolymers comprising at least one block resulting from polymerizing at least one ethylenic monomer with one or more ethylenically unsaturated bonds and at least one block of an acrylic polymer that may be mentioned are two- or three-block poly(methyl methacrylate)/polyisobutene copolymers or graft copolymers with a poly(methyl methacrylate) backbone with polyisobutylene grafts.
  • [0490]
    Graft or sequenced block copolymers comprising at least one block resulting from polymerizing at least one ethylenic monomer with one or more ethylenically unsaturated bonds and at least one block of a polyether such as a C2-C18 polyalkylene (in particular polyethylene and/or polyoxypropylene) that may be mentioned are two- or three-block polyoxyethylene/polybutadiene or polyoxyethylene/polyisobutylene copolymers.
  • [0491]
    When a random polymer is used as the stabilizer, it is selected so that it has a sufficient quantity of groups to render it soluble in the envisaged processing solvent.
  • [0492]
    Thus, it is possible to use copolymers based on alkyl acrylates or methacrylates derived from C1-C4 alcohols, and alkyl acrylates or methacrylates derived from C8-C30 alcohols. In particular, stearyl methacrylate/methyl methacrylate copolymer may be mentioned.
  • [0493]
    When the polymer processing solvent is apolar, it is advantageous to select as the stabilizer a polymer which coats the particles in as complete a manner as possible, several polymer-stabilizer chains then becoming adsorbed on a particle of polymer obtained by polymerization.
  • [0494]
    It is then preferable to use as the stabilizer either a graft polymer or a sequenced polymer in order to have a better interfacial activity.
  • [0495]
    Sequences or grafts which are insoluble in the processing solvent produce a more voluminous coating on the particle surface.
  • [0496]
    When the processing solvent comprises at least one silicone oil, the stabilizing agent is preferably selected from the group constituted by graft or sequenced block copolymers comprising at least one polyorganosiloxane type block and at least one radical polymer block or polyether or polyester block, such as polyoxypropylene and/or oxyethylene blocks.
  • [0497]
    When the processing solvent includes silicone oil, the stabilizer agent is preferably selected from the group constituted by:
  • [0498]
    a) graft or sequenced block copolymers comprising at least one polyorganosiloxane type block and at least one block of a radical polymer or a polyether or a polyester;
  • [0499]
    b) copolymers of alkyl acrylates or methacrylates derived from C1-C4 alcohols, and alkyl acrylates or methacrylates derived from C8-C30 alcohols;
  • [0500]
    c) graft or sequenced block copolymers comprising at least one block resulting from polymerizing at least one ethylenically unsaturated monomer with conjugated ethylenically unsaturated bonds; and
  • [0000]
    at least one block of a vinyl or acrylic polymer or a polyether or a polyester, or mixtures thereof.
  • [0501]
    Preferably, two block polymers are used as the stabilizer agent.
  • [0502]
    The film-forming polymer which is liposoluble or dispersed in an oily phase may also be used in a quantity of 0.01% to 20% (active substance) relative to the total composition weight, such as 1% to 10%, as appropriate.
  • I. Film-Forming Agent Dispersible in an Aqueous Phase of the Composition
  • [0503]
    In a further implementation, the film-forming polymer may be selected from aqueous dispersions of polymer particles when the composition of the invention comprises an aqueous phase.
  • [0504]
    The aqueous dispersion comprising one or more film-forming polymers may be prepared by the skilled person on the basis of general knowledge, in particular by emulsion polymerization or by dispersing the polymer formed.
  • [0505]
    Film-forming polymers which may be used in the composition of the present invention that may be mentioned include synthetic polymers of the polycondensate or radical type, polymers of natural origin, and mixtures thereof.
  • 1) Polycondensates
  • [0506]
    Polycondensates that may also be mentioned are anionic, cationic, non ionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea/polyurethanes, and mixtures thereof.
  • [0507]
    The polyurethanes may, for example, be a polyurethane copolymer, which may be aliphatic, cycloaliphatic or aromatic, a polyurea/polyurethane copolymer, or a polyurea copolymer, comprising used alone or as a mixture:
      • at least one aliphatic and/or cycloaliphatic and/or aromatic sequence of linear or branched polyester origin; and/or
      • at least one aliphatic and/or cycloaliphatic and/or aromatic sequence of polyether origin; and/or
      • at least one silicone sequence, which may or may not be substituted and which may or may not be branched, for example polydimethylsiloxane or polymethylphenylsiloxane; and/or
      • at least one sequence comprising fluorinated groups.
  • [0512]
    The polyurethanes as defined in the invention may also be obtained from polyesters, which may or may not be branched, or from alkyds comprising mobile hydrogens which are modified by means of a polyaddition with a diisocyanate and an organic bifunctional co-reagent compound (for example dihydro, diamino or hydroxy-amino), comprising in addition either a carboxylate group or carboxylic acid, or a sulfonate group or sulfonic acid, or even a neutralizable tertiary amine group or a quaternary ammonium group.
  • [0513]
    The polyesters may be obtained in known manner by means of polycondensation of aliphatic or aromatic dibasic acids avec aliphatic or aromatic diols or with polyols. Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or sebacic acid may be used as aliphatic dibasic acids. Terephthalic acid or isophthalic acid, or even a derivative such as phthalic anhydride, may be used as aromatic dibasic acids. Glycol ethylene, glycol propylene, glycol diethylene, glycol neopentyl, cyclohexanedimethanol, and 4,4-N-(1-methylpropylidene)bisphenol, may be used as aliphatic diols. Glycerol, pentaerythritol, sorbitol, and trimethylolpropane may be used as polyols.
  • [0514]
    The polyesteramides may be obtained in a manner which is analogous to that used for polyesters, by means of polycondensation of dibasic acids with diamines or aminoalcohols. Ethylenediamine, hexamethylnediamine and meta- or para-phenylenediamine may be used as diamine. Monoethanolamine may be used as an aminoalcohol.
  • [0515]
    Examples of monomers carrying an anionic group which may be used during polycondensation that may be mentioned are dimethylolpropionic acid, trimellitic acid or a derivative such as trimellitic anhydride, the sodium salt of 3-sulfopentanediol and the sodium salt of 5-sulfo-1,3-benzenedicarboxylic acid. Polyesters with a fatty chain may be obtained using diols with a fatty chain during polycondensation. Epoxy ester resins may be obtained by polycondensating fatty acids with a condensate at the α,ω-diepoxy ends.
  • [0516]
    In particular, the radical polymers may be acrylic and/or vinyl polymers or copolymers. Polymers with an anionic radical are preferred. Examples of monomers carrying an anionic group which may be used during radical polymerization that may be mentioned are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid.
  • [0517]
    The acrylic polymers may result from copolymerizing monomers selected from esters and/or amides of acrylic acid or methacrylic acid. Examples of ester type monomers that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate. Examples of amide type monomers that may be mentioned are N-t-butylacrylamide and N-t-octylacrylamide.
  • [0518]
    In particular, acrylic polymers obtained by copolymerizing monomers with an ethylenically unsaturated bond containing hydrophilic groups, preferably non-ionic in nature are used, such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.
  • [0519]
    Vinyl polymers may result from homo polymerization or copolymerization of monomers selected from vinyl esters, styrene or butadiene. Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
  • [0520]
    It is also possible to use acrylic/silicone copolymers or even nitrocellulose/acrylic copolymers.
  • 2) Polymer Type Radical
  • [0521]
    It is also possible to mention polymers resulting from radical polymerization of one or more radical monomers, within and/or partially on the surface of pre-existing particles of at least one polymer selected from the group constituted by polyurethanes, polyureas, polyesters, polyester amides and/or alkyds. Said polymers are generally termed “hybrid polymers”.
  • [0522]
    When an aqueous dispersion of polymer particles is used, the dry matter content of said aqueous dispersion may be of the order of 3% to 60% by weight, preferably 10% to 50%.
  • [0523]
    The particle size of the polymers in aqueous dispersion may be in the range 10 nm to 500 nm, and it is preferably in the range 20 nm to 150 nm, allowing a film with a substantial gloss to be obtained. However, it is possible to employ particle sizes of up to one micron.
  • [0524]
    Examples of aqueous dispersions of film-forming polymers which may be used are acrylic dispersions sold under the trade names “NEOCRYL XK-90®”, “NEOCRYL A-1070 T, NEOCRYL A-1090®”, “NEOCRYL BT-62®”, “NEOCRYL A-1079®” and “NEOCRYL A-523®” from AVECIA-NEORESINS, “DOW LATEX 432®” from DOW CHEMICALS, “DAITOSOL 5000 AD®” or “DAITOSOL 5000 SJ” from DAITO KASEY KOGYO; “SYNTRAN 5760” from INTERPOLYMER or aqueous dispersions of polyurethane sold under the trade name “NEOREZ R-981®” and “NEOREZ R-974® from AVECIA-NEORESINS, “AVALURE UR-405®”, “AVALURE UR-410®”, “AVALURE UR-425®”, “AVALURE UR-450®”, SANCURE 875®”, “SANCURE 861®”, “SANCURE 878®” and “SANCURE 2060” from GOODRICH, “IMPRANIL 85®” from BAYER, “AQUAMERE H-1511®” from HYDROMER; sulfopolyesters sold under the trade name “EASTMAN AQ®” from EASTMAN CHEMICAL PRODUCTS, vinyl dispersions such as “MEXOMERE PAM”, aqueous dispersions of polyvinylacetate such as “VINYBRAN®” from NISSHIN CHEMICAL or those sold by UNION CARBIDE, aqueous dispersions of vinyl pyrrolidone terpolymer, dimethylaminopropyl methacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride, such as STYLEZE W from ISP, aqueous dispersions of polyurethane/polyacrylic polymers such as those sold under the trade name “HYBRIDUR®” by AIR PRODUCTS or “DUROMER®” from NATIONAL STARCH, core/shell type dispersions: for example those sold by ATOFINA with reference number KYNAR (core: fluoride; shell: acrylic) or those described in U.S. Pat. No. 5,188,899 (core: silica; shell: silicone) and mixtures thereof.
  • [0525]
    When the composition includes an aqueous phase, the film-forming polymer may be a hydrosoluble polymer. The hydrosoluble polymer is thus dissolved in the aqueous phase of the composition.
  • [0526]
    Examples of hydrosoluble film-forming polymers that may be mentioned include the following cationic polymers:
  • [0527]
    1) Acrylic polymers or copolymers, such as poly acrylates or poly methacrylates; copolymers of category (1) may further contain one or more moieties deriving from co-monomers which may be selected from the acrylamide, methacrylamide, diacetoneacrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls, acrylic or methacrylic acids or esters thereof, vinyllactames such as vinylpyrrolidone or vinylcaprolactame, and vinyl esters.
  • [0528]
    Thus, copolymers of family (1) that may be mentioned include:
      • copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized by dimethyl sulfate, or by a dimethyl halide such as that sold under the trade name HERCOFLOC by HERCULES;
      • the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in patent application EP-A-0 809 76 and sold under the trade name BINA QUAT P 100 by CIBA GEIGY;
      • the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the trade name RETEN by HERCULES;
      • vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate, quaternized or not quaternized, such as the products sold under the trade name “GAFQUAT” by ISP, such as “GAFQUAT 734” or “GAFQUAT 755”, or products denoted as “COPOLYMER 845, 958 and 937”. Those polymers are described in detail in French patents FR-A-2 077 143 and 2 393 573;
      • terpolymers of dimethylaminoethyl methacrylate/|vinylcaprolactame/vinylpyrrolidone such as the product sold under the trade name GAFFIX VC 713 by ISP; and
      • the vinylpyrrolidone/quaternized dimethylaminopropylmethacrylamide copolymer, such as the product sold under the trade name “GAFQUAT HS100” by ISP.
  • [0535]
    2) quaternized polysaccharides, described more particularly in U.S. Pat. No. 3,589,578 and U.S. Pat. No. 4,031,307, such as guar gums containing cationic trialkylammonium groups. Such products are in particular sold under the trade names JAGUAR C13 S, JAGUAR C 15 and JAGUAR C 17 by MEYHALL.
  • [0536]
    3) copolymers of quaternary vinylpyrrolidone and vinylimidazole;
  • [0537]
    4) chitosans or salts thereof;
  • [0538]
    5) cationic cellulose derivatives, such as copolymers of cellulose or cellulose derivatives grafted with a hydrosoluble monomer comprising a quaternary ammonium, described in particular in U.S. Pat. No. 4,131,576 such as hydroalkyl celluloses, such as hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses, in particular grafted with a methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. Particular commercial products corresponding to that definition are products sold under the trade name “CELQUAT L 200” and “CELQUAT H 100” by NATIONAL STARCH COMPANY.
  • [0539]
    Hydrosoluble film-forming polymers that may be mentioned include the following amphoteric polymers:
  • [0540]
    1) polymers resulting from copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group, more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid and a basic monomer derived from a substituted vinyl compound containing at least one base atom, more particularly a dialkylaminoalkyl methacrylate or acrylate and a dialkylaminoalkylmethacrylamide and acrylamide. Said compounds are described in U.S. Pat. No. 3,836,537;
  • [0541]
    2) polymers comprising the moieties deriving:
  • [0542]
    a) from at least one monomer selected from acrylamides or methacrylamides substituted on the nitrogen by an alkyl radical;
  • [0543]
    b) from at least one acid co-monomer containing one or more carboxylic reactive groups; and
  • [0544]
    c) from at least one basic co-monomer such as esters, containing primary, secondary, tertiary and quaternary amine substituents or acrylic and methacrylic acids, and the product of quaternizing dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate;
  • [0545]
    d) cross-linked alkoylpolyaminoamides completely or partially derived from polyaminoamide;
  • [0546]
    3) polymers comprising zwitterionic moieties;
  • [0547]
    4) the polymer derived from chitosan;
  • [0548]
    5) polymers derived from N-carboxyalkylation of chitosan, such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the trade name “EVALSAN” by JAN DEKKER;
  • [0549]
    6) (C1-C5)alkylvinylether/maleic anhydride copolymers partially modified by semi-amidification by a N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine or by semi-esterification by a N,N-dialkanolamine. Said copolymers may also comprise other vinyl co-monomers such as vinylcaprolactame.
  • [0550]
    The hydrosoluble film-forming polymers are preferably selected from the group constituted by:
      • proteins, such as proteins of vegetable origin, such as wheat or soya proteins; proteins of animal origin such as keratin, for example keratin hydrolysates or sulfonic keratins;
      • anionic, cationic, amphoteric or non-ionic polymers of chitin or chitosan;
      • cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, and quaternized derivatives of cellulose;
      • acrylic polymers or copolymers such as polyacrylates or polymethacrylates;
      • vinyl polymers such as polyvinylpyrrolidones, copolymers of methylvinylether and maleic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate;
      • copolymers of vinylpyrrolidone and caprolactame; polyvinyl alcohols;
      • optionally modified polymers of natural origin, such as:
        • gum arabic, guar gum, xanthan derivatives, karaya gum;
        • alginates and carragheens;
        • glycoaminoglycans, hyaluronic acid and its derivatives;
        • shellac, sanderac gum, dammar gums, gum elemi, copals;
        • deoxyribonucleic acid;
        • mucopolysaccharides such as hyaluronic acid, chondroitin sulfate, and mixtures thereof.
  • [0564]
    These polymers are used in particular if the film is to be largely eliminated with water.
  • [0565]
    To improve the film-forming nature of an oily or aqueous polymer, it is possible to add a coalescence agent to the polymer system, which agent is selected from known coalescence agents.
  • II. Silicone Film-Forming Agent
  • [0566]
    1) Polymer with a Grafted Non-Silicone Organic Backbone
  • [0567]
    Said polymers may be liposoluble, lipodispersible, hydrosoluble or dispersible in an aqueous medium, if appropriate.
  • [0568]
    Polymers with a non-silicone organic backbone grafted with monomers containing a polysiloxane are constituted by a principal organic chain formed by organic monomers comprising no silicone, onto which we graft, inside said chain and optionally on at least one of the ends thereof, at least one polysiloxane macromer.
  • [0569]
    In the following, it should be understood that the expression “polysiloxane macromer” designates, as is generally accepted, means any monomer containing a polymer chain of the polysiloxane type in its structure.
  • [0570]
    The non-silicone organic monomers constituting the principal chain of the graft silicone polymer may be selected from monomers with an ethylenically unsaturated bond which may be polymerized by the radical method, monomers polymerizable by polycondensation such as those forming polyamides, polyesters, polyurethanes, monomers with an opening cycle such as those of the oxazoline or caprolactone type.
  • [0571]
    Polymers having a non-silicone organic backbone grafted by monomers containing a polysiloxane of the present invention may be obtained using any method which is known to the skilled person, in particular by reaction between (i) a starting polysiloxane macromer correctly functionalized on the polysiloxane chain and (ii) one or more non-silicone organic compounds, themselves correctly functionalized by a function which is capable of reacting with the functional group or groups carried by said silicone, forming a covalent bond; a classic example of such a reaction is the radical reaction between a vinyl group carried at one end of the silicone with a double bond of a monomer with an ethylenically unsaturated bond of the principal chain.
  • [0572]
    Polymers having a non-silicone organic backbone grafted with monomers containing a polysiloxane of the invention are preferably selected from those described in U.S. Pat. No. 4,693,935, U.S. Pat. No. 4,728,571 and U.S. Pat. No. 4,972,037 and patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578. It concerns copolymers obtained by radical polymerization starting from monomers with an ethyleneically unsaturated bond and monomers having a terminal vinyl group, or copolymers obtained by reacting a polyolefin containing functionalized groups and a polysiloxane macromer having a terminal function which reacts with said functionalized groups.
  • [0573]
    A particular family of graft silicone polymers which is suitable for carrying out the present invention is constituted by graft silicone polymers containing:
  • [0574]
    a) 0 to 98% by weight of at least one lipophilic monomer (A) with a low lipophilic polarity with an ethylenically unsaturated bond, polymerizable by a radical method;
  • [0575]
    b) 0 to 98% by weight of at least one polar hydrophilic monomer (B) with an ethylenically unsaturated bond, copolymerizable with the monomer or monomers of type (A);
  • [0576]
    c) 0.01 to 50% by weight of at least one polysiloxane macromer (C) with general formula (XXVII):
  • [0000]

    X(Y)nSi(R)3-mZm  (XXVII)
  • [0000]
    in which:
      • X designates a vinyl group copolymerizable with monomers (A) and (B);
      • Y designates a group having a divalent bond;
      • R designates hydrogen, alkyl or C1-C6 alkoxy, C6-C12 aryl;
      • Z designates a monovalent polysiloxane having a number average molecular mass of at least 500;
      • n is 0 or 1 and m is a whole number from 1 to 3; the percentages are calculated relative to the total weight of monomers (A), (B), and (C).
  • [0582]
    Said polymers have a number average molecular mass from 10000 to 2000000 and preferably a glass transition temperature Tg or a crystal melting temperature Tm of at least −20° C.
  • [0583]
    Examples of lipophilic monomers (A) that may be mentioned are esters of C1-C18 alcohol and acrylic or methacrylic acid; esters of C12-C30 alcohol and methacrylic acid; styrene; polystyrene macromers; vinyl acetate; vinyl propionate; alpha-methylstyrene; tertio-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene, esters of acrylic or methacrylic acid and 1,1-dihydroperfluoroalkanols or homologues thereof; esters of acrylic or methacrylic acid and omega-hydrofluoroalkanols; esters of acrylic or methacrylic acid and fluoroalkylsulfonamidoalcohols; esters of acrylic or methacrylic acid and fluoroalkylalcohols; esters of acrylic or methacrylic acid and alcoholfluoroethers; or mixtures thereof. Preferred monomers (A) are selected from the group constituted by n-butyl methacrylate, isobutyl methacrylate, tertio-butyl acrylate, tertio-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, 2-(N-methylperfluorooctanesulfonamido)ethyl acrylate, 2-(N-butylperfluorooctanesulfonamido)ethyl acrylate, or mixtures thereof.
  • [0584]
    Examples of polar monomers (B) that may be mentioned are acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, (meth)acrylamide, N-t-butylacrylamide, maleic acid, maleic anhydride and hemi-esters thereof, hydroxyalkyl (meth)acrylates, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ethers, maleimides, vinylpyridine, vinylimidazole, polar vinyl and heterocyclic compounds, styrene sulfonate, allyl alcohol, vinyl alcohol, vinylcaprolactame or mixtures thereof. Preferably, monomers (B) are selected from the group constituted by acrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinylpyrrolidone, and mixtures thereof.
  • [0585]
    In particular, the product KP 561 or KP 562 sold by SHIN ETSU may be mentioned in which monomer (A) is selected from esters of C18-C22 alcohol and methacrylic acid.
  • [0586]
    The polysiloxane macromers (C) with formula (XXVII) are preferably selected from those corresponding to the following general formula (XXVII):
  • [0000]
    Figure US20090130037A1-20090521-C00013
  • [0000]
    in which:
      • R1 is hydrogen or —COOH (preferably hydrogen);
      • R2 is hydrogen, methyl or —CH2COOH (preferably methyl);
      • R3 is alkyl, alkoxy or C1-C6 alkylamino, C6-C12 aryl or hydroxyl (preferably methyl);
      • R4 is alkyl, alkoxy or C1-C6 alkylamino, C6-C12 aryl or hydroxyl (preferably methyl);
      • q is a whole number from 2 to 6 (preferably 3);
      • p is 0 or 1;
      • r is a whole number from 5 to 700;
      • m is a whole number from 1 to 3 (preferably 1).
  • [0595]
    Preferably, macromers of polysiloxane with formula (XXIX) are used:
  • [0000]
    Figure US20090130037A1-20090521-C00014
  • [0000]
    n being a number from 5 to 700 and I being a whole number in the range 0 to 3.
  • [0596]
    One implementation of the invention consists of using a copolymer which is capable of being obtained by radical polymerization starting from a mixture of monomers constituted by:
  • [0597]
    a) 60% by weight of tertio-butylacrylate;
  • [0598]
    b) 20% by weight of acrylic acid;
  • [0599]
    c) 20% by weight of silicone macromer with formula (XXX):
  • [0000]
    Figure US20090130037A1-20090521-C00015
  • [0000]
    n being a number from 5 to 700 and I being a whole number in the range 0 to 3, the percentages by weight being calculated relative to the total weight of monomers.
  • [0600]
    A further particular implementation of the invention consists of using a copolymer which is capable of being obtained by radical polymerization from a mixture of monomers constituted by:
  • [0601]
    a) 80% by weight of tertio-butyl acrylate;
  • [0602]
    b) 20% by weight of silicone macromer with formula (XXXI):
  • [0000]
    Figure US20090130037A1-20090521-C00016
  • [0000]
    n being a number from 5 to 700 and I being a whole number in the range 0 to 3, the percentages by weight being calculated relative to the total monomer weight.
  • [0603]
    A further particular family of graft silicone polymers with an organic non-silicone backbone suitable for the present invention is constituted by graft silicone copolymers capable of being obtained by reactive extrusion of a polysiloxane macromer with a reactive terminal function on a polymer of the polyolefin type comprising reactive groups which are capable of reacting with the terminal function of a polysiloxane macromer to form a covalent bond to allow the silicone to graft onto the principal chain of the polyolefin. Said polymers, and their preparation process, have been described in International patent application WO-A-95/00578.
  • [0604]
    The reactive polyolefins are preferably selected from polyethylenes or polymers of monomers derived from ethylene, such as propylene, styrene, alkylstyrene, butylene, butadiene, (meth)acrylates, vinyl esters or the like, comprising reactive functions which are capable of reacting with the terminal function of the polysiloxane macromer. More particularly, they are selected from copolymers of ethylene or ethylene derivatives and monomers selected from those comprising a carboxylic function such as (meth)acrylic acid; those comprising an acid anhydride function such as maleic acid anhydride; those comprising an acid chloride function such as (meth)acrylic acid chloride; those comprising an ester function such as esters of (meth)acrylic acid; and those comprising an isocyanate function.
  • [0605]
    The silicone macromers are preferably selected from polysiloxanes comprising a functionalized group, at the end of the polysiloxane chain or close to the end of said chain, selected from the group constituted by alcohols, thiols, epoxies, primary and secondary amines, and more particularly from those corresponding to general formula (XXXII):
  • [0000]

    T-(CH2)6—Si—[—(OSiR5R6)t—R7]y  (XXXII)
  • [0000]
    in which T is selected from the group constituted by NH2, NHRN, an epoxy function, OH, SH; R5, R6, R7 and RN independently designate C1-C6 alkyl, phenyl, benzyl or C6-C12 alkylphenyl, hydrogen; s is a number from 2 to 00, t is a number from 0 to 1000 and y is a number from 1 to 3. They preferably have a number average molecular mass from 5000 to 300000, more preferably from 8000 to 200000, and more particularly from 9000 to 40000.
  • [0606]
    In a particular implementation, the film-forming polymer may be obtained from the MINNESOTA MINING AND MANUFACTURING COMPANY under the polymer trade names “SILICONE PLUS”. As an example, poly(isobutyl-co-FOSEA methyl methacrylate)-g-poly(dimethylsiloxane) is sold under the trade name SA 70-5 IBMMF.
  • [0000]
    2) Polymer with Silicone Backbone
  • [0607]
    Said graft silicone polymer or polymers has a polysiloxane backbone grafted with organic non-silicone monomers containing a principal silicone chain (or polysiloxane (/SiO—)n) on which is grafted, within said chain and optionally at one of its ends, at least one organic group comprising no silicone.
  • [0608]
    Polymers with a polysiloxane backbone grafted with organic non-silicone monomers of the invention may be existing commercially available products, or they may be obtained by any means known to the skilled person, in particular by a reaction between (i) a starting silicone correctly functionalized on one or more of its silicon atoms and (ii) an organic non-silicone compound itself correctly functionalized by a function which is capable of reacting with the functional group or groups carried by said silicone to form a coavalent bond; a classic example of said reaction is the hydrosilylation reaction between —Si—H groups and vinyl groups, CH2═CH—, or the reaction between thio-functional groups —SH and the same vinyl groups.
  • [0609]
    Examples of polymers having a polysiloxane backbone grafted with organic non-silicone monomers suitable for use in the present invention and their specific preparation methods are described in particular in patent applications EP-A-0 582 152, WO-A-93/23009 and WO-A-95/03776, the disclosures of which are included in their entirety in the present description by way of non-limiting reference.
  • [0610]
    In a particularly preferred implementation of the present invention, the silicone polymer with a polysiloxane backbone grafted with non-silicone organic monomers which is employed is constituted by the result of radical copolymerization between at least one non-silicone anionic organic monomer with an ethylenically unsaturated bond and/or a hydrophobic non-silicone organic monomer with an ethylenically unsaturated bond and a silicone having at least one functional group in its chain, and more preferably, capable of reacting with said ethylenically unsaturated bonds of said non-silicone monomers to form a covalent bond, in particular thiofunctional groups.
  • [0611]
    In accordance with the present invention, said anionic monomers with an ethylenically unsaturated bond are preferably selected, alone or as mixtures, from unsaturated linear or branched carboxylic acids which are optionally partially or completely neutralized into the salt form, said unsaturated carboxylic acid(s) more particularly possibly being acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid or crotonic acid. Particular suitable salts are alkali, alkaline-earth and ammonium salts. It should be noted that, similarly, in the final graft silicone polymer, the organic group with an anionic nature which is constituted by the result of radical (homo)polymerization of at least one unsaturated carboxylic acid type anionic monomer may, after reaction, be post-neutralized with a base (sodium hydroxide, ammonia, etc) to put it into its salt form.
  • [0612]
    In the present invention, the hydrophobic monomers with an ethylenically unsaturated bond are preferably selected, alone or as a mixture, from esters of acrylic acid and alkanols and/or esters of methacrylic acid and alkanols. The alkanols are preferably C1 to C30, more particularly C1 to C22. Preferred monomers are selected from the group constituted by isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, methyl (meth)acrylate, tertio-butyl (meth)acrylate, tridecyl (meth)acrylate and stearyl (meth)acrylate, or mixtures thereof.
  • [0613]
    One family of silicone polymers having a polysiloxane backbone grafted with organic non-silicone monomers which is particularly suitable to carrying out the present invention is constituted by silicone polymers comprising the moiety with the following formula (XXXIII) in their structure:
  • [0000]
    Figure US20090130037A1-20090521-C00017
  • [0000]
    in which radicals G1, which may be identical or different, represent hydrogen or a C1-C10 alkyl radical, or a phenyl radical; radicals G2, which may be identical or different, represent a C1-C10 alkylene group; G3 represents a polymer residue resulting from (homo)polymerization of at least one anionic monomer having an ethylenically unsaturated bond; G4 represents a polymer residue resulting from (homo)polymerization of at least one monomer of at least one hydrophobic [sic] monomer with an ethylenically unsaturated bond; m and n equal 0 or 1; a is a whole number from 0 to 50; b is a whole number which may be in the range 10 to 350, c is a whole number from 0 to 50; provided that one of parameters a and c is other than 0.
  • [0614]
    The moiety with formula (XXXIII) above preferably has at least one and more preferably all of the following characteristics:
      • radicals G1 designate an alkyl radical, preferably a methyl radical;
      • n is not zero, and radicals G2 represent a divalent C1-C3 radical, preferably a propylene radical;
      • G3 represents a polymer radical resulting from (homo)polymerization of at least one monomer of the carboxylic acid type with an ethylenically unsaturated bond, preferably acrylic acid and/or methacrylic acid;
      • G4 represents a polymer radical resulting from (homo)polymerization of at least one monomer of the C1-C10 alkyl (meth)acrylate type, preferably isobutyl or methyl (meth)acrylate.
  • [0619]
    Particular examples of silicone polymers corresponding to formula (XXXIII) are polydimethylsiloxanes (PDMS) onto which are grafted, via a secondary thiopropylene type bond, mixed polymer moieties of the poly (meth)acrylic acid type and of the alkyl poly (meth)acrylic type.
  • [0620]
    Other particular examples of silicone polymers corresponding to formula (XXXIII) are polydimethylsiloxanes (PDMS) onto which are grafted, via a secondary thiopropylene type bond, polymer moieties mixed of the isobutyl poly (meth)acrylate type.
  • [0621]
    Such polymers comprise polymers comprising at least one group with formula (XXXIV):
  • [0000]
    Figure US20090130037A1-20090521-C00018
  • [0000]
    in which:
    a, b and c, which may be identical or different, are each a number from 1 to 100000; and the terminal groups, which may be identical or different, are each selected from linear C1 to C20 alkyl groups, C3 to C20 alkyl groups with a branched chain, C3 to C20 aryl groups, linear C1 to C20 alkoxy groups and branched C3 to C20 alkoxy groups.
  • [0622]
    Such polymers are disclosed in the following patents: U.S. Pat. No. 4,972,037, U.S. Pat. No. 5,061,481, U.S. Pat. No. 5,209,924, U.S. Pat. No. 5 849 275 and U.S. Pat. No. 6,033,650, and WO 93/23446 and WO 95/06078.
  • [0623]
    Another family of silicone polymers having a polysiloxane backbone grafted by non-silicone organic monomers which is particularly suitable for implementation of the present invention is constituted by silicone polymers comprising the following moiety with formula (XXXV) in their structure:
  • [0000]
    Figure US20090130037A1-20090521-C00019
  • [0000]
    in which radicals G1 and G2 have the meanings given above; G5 represents a polymer residue resulting from (homo)polymerization of at least one hydrophobic monomer with an ethylenically unsaturated bond or from copolymerization of at least one anionic monomer with an ethylenically unsaturated bond and at least one hydrophobic monomer with an ethylenically unsaturated bond; n is equal to 0 or 1; a is a whole number from 0 to 50; b is a whole number which may be in the range 10 to 350; provided that a is other than 0.
  • [0624]
    The moiety with formula (XXXV) above preferably has at least one and more preferably all of the following characteristics:
      • radicals G1 designate an alkyl radical, preferably a methyl radical;
      • n is not zero, and radicals G2 represent a divalent C1-C3 radical, preferably a propylene radical.
  • [0627]
    The number average molecular mass of the silicone polymers having a polysiloxane backbone grafted by organic non-silicone monomers of the invention preferably varies from about 10000 to 1000000, more preferably from about 10000 to 100000.
  • [0628]
    In a particular implementation, a silicone film-forming polymer which is particularly suitable for the present invention may be a copolymer comprising carboxylate groups and polydimethylsiloxane groups.
  • [0629]
    The term “copolymer comprising carboxylate groups and polydimethylsiloxane groups” as used in the present invention means a copolymer obtained from a) one or more carboxylic monomers (acid or ester) and b) one or more polydimethylsiloxane chains (PDMS).
  • [0630]
    The term “carboxylic monomer” as used in the present application means both carboxylic acid monomers and carboxylic acid ester monomers. Thus, monomer a) may, for example, be selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, their esters and mixtures of said monomers. Ester monomers that may be mentioned: acrylate, methacrylate, maleate, fumarate, itaconoate and/or crotonoate. More particularly, monomers in the form of esters are selected from linear or branched alkyl acrylates and methacrylates, preferably C1-C24 and more preferably C1-C22, the alkyl radical preferably being selected from methyl, ethyl, stearyl, butyl, 2-ethylhexyl radicals, and mixtures thereof.
  • [0631]
    The copolymer may also comprise, as carboxylate groups, at least one group selected from acrylic acid, methacrylic acid, methyl, ethyl, stearyl, butyl, 2-ethylhexyl acrylates or methacrylates, and mixtures thereof.
  • [0632]
    The term “polydimethylsiloxanes” (also known as organopolysiloxanes, abbreviated to PDMS) as used here and conventionally, means any organosilicated oligomer or polymer with a linear structure, with various molecular weights, obtained by polymerization and/or polycondensation of appropriately functionalized silanes and essentially constituted by repeating the principal moieties in which the silicon atoms are connected together by oxygen atoms (siloxane bond ≡Si—O—Si≡), comprising trimethyl radicals directly connected via a carbon atom to said silicon atoms. The PDMS chains may be used to obtain the copolymer comprising at least one polymerizable radical group, preferably located on at least one of the chain ends, i.e. the PDMS may, for example, have a polymerizable radical on both ends of the chain or a polymerizable radical group on one end of the chain and a terminal trimethylsilyl group on the other end of the chain. The polymerizable radical group may in particular be an acrylic or methacrylic group, in particular a CH2═CR1—CO—O—R2 group, in which R1 represents a hydrogen or a methyl group, and R2 represents —CH2—, —(CH2)n—, in which n=3, 5, 8 or 10, —CH2—CH(CH3)—CH2—, —CH2—CH2—O—CH2—CH2—, —CH2—CH2—O—CH2—CH2—CH(CH3)—CH2—, or —CH2—CH2—O—CH2 CH2—O—CH2—CH2—CH2—.
  • [0633]
    The copolymers used are generally obtained using the usual polymerization and grafting methods, for example by radical polymerization (A) of a PDMS comprising at least one polymerizable radical (for example on one end of the chain or on both ends) and (B) of at least one carboxylic monomer as described, for example, in U.S. Pat. No. 5,061,481 and U.S. Pat. No. 5,219,560.
  • [0634]
    The copolymers obtained generally have a molecular weight from about 3000 to 200000 and preferably from about 5000 to 100000.
  • [0635]
    The copolymer may be as is, or in the dispersed form in a solvent such as lower alcohols containing 2 to 8 carbon atoms, such as isopropyl alcohol, or oils such as volatile silicone oils (for example cyclopentasiloxane).
  • [0636]
    Examples of copolymers which may be used that may be mentioned are copolymers of acrylic acid and stearyl acrylate with polydimethylsiloxane grafts, copolymers of stearyl methacrylate with polydimethylsiloxane grafts, copolymers of acrylic acid and stearyl methacrylate with polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. Particular suitable copolymers that may be mentioned are copolymers sold by SHIN-ETSU under the trade names KP-561 (CTFA: acrylates/dimethicone), KP-541 where the copolymer is dispersed at 60% by weight in isopropyl alcohol (CTFA name: acrylates/dimethicone and isopropyl alcohol), KP-545 where the copolymer is 30% dispersed in cyclopentasiloxane (CTFA name: acrylates/dimethicone and cyclopentasiloxane). In a preferred implementation of the invention, KP561 is used; that copolymer is not dispersed in a solvent, but is in a waxy form, its melting point being about 30° C.
  • [0637]
    More generally, the total quantity of polymer must be in a quantity sufficient to form a cohesive film on the skin and/or lips capable of following the movements of the skin and/or the lips without detaching or cracking.
  • [0638]
    When the polymer has too high a glass transition temperature for the desired use, a plasticizer may be associated with it to reduce that mixing temperature. The plasticizer may be selected from plasticizers which are normally used in the field of application, and especially from compounds which may be solvents for the polymer.
  • Particles Having Non-Zero Magnetic Susceptibility (Magnetic Particles)
  • [0639]
    The term “magnetic particles”, also termed as “magnetic bodies”, means particles presenting magnetic susceptibility, i.e. particles that are sensitive to the action of a magnetic field, and that tend to come into alignment with the field lines, for example.
  • [0640]
    The composition may contain both magnetic particles and non-magnetic particles.
  • [0641]
    The presence of magnetic particles and of non-magnetic particles in the composition makes it possible to create novel optical effects that can be modulated under the effect of a magnetic field, for example.
  • [0642]
    In the absence of a magnetic field, the magnetic particles used preferably do not present any remanent magnetism.
  • [0643]
    The magnetic particles may comprise any magnetic material that presents sensitivity to the lines of a magnetic field, regardless of whether the field is produced by a permanent magnet or is the result of induction, the material being selected from nickel, cobalt, iron, and alloys and oxides thereof, in particular Fe3O4, and also from gadolinium, terbium, dysprosium, erbium, and alloys and oxides thereof, for example. The magnetic material may be of the “soft” or of the “hard” type, and in particular may comprise metallic iron, in particular soft iron, which may optionally be coated.
  • [0644]
    The magnetic particles may optionally present a multilayer structure including at least one layer of a magnetic material such as iron, nickel, cobalt, and alloys and oxides thereof, in particular Fe3O4, for example.
  • [0645]
    The magnetic particles are preferably aspherical, presenting an elongate shape, for example. Thus, when the particles are subjected to the magnetic field, they tend to become oriented with their longitudinal axes in alignment with the field lines, and they are subjected to a change in orientation which results in the first composition changing in appearance.
  • [0646]
    When the magnetic particles are substantially spherical, their appearance is preferably non-uniform, so that a change in orientation results in a change in appearance.
  • [0647]
    The quantity of magnetic particles is sufficient to enable the appearance of the composition to depend on their orientation and/or on their positioning.
  • [0648]
    The concentration of magnetic particles may be in the range about 0.05% to about 97% by weight, for example, and in particular in the range about 0.1% to about 95% by weight, and preferably in the range about 0.1% to about 90% by weight, e.g. about 3% by weight. The size of the magnetic particles may be in the range 1 nanometer (nm) to 700 micrometers (μm), for example, preferably in the range 1 μm to 500 μm, and more preferably in the range 10 μm to 150 μm. The term “size” means the size given by the statistical grain size distribution at half the population, referred to as “D50”.
  • Magnetic Pigments
  • [0649]
    The magnetic particles of the first composition may comprise magnetic pigments. Particularly suitable pigments are nacres comprising iron oxide Fe3O4. By way of example, pigments presenting magnetic properties are those sold under the trade names COLORONA BLACKSTAR BLUE, COLORONA BLACKSTAR GREEN, COLORONA BLACKSTAR GOLD, COLORONA BLACKSTAR RED, CLOISONNE NU ANTIQUE SUPER GREEN, MICRONA MATTE BLACK (17437), MICA BLACK (17260), COLORONA PATINA SILVER (17289), and COLORONA PATINA GOLD (117288) by MERCK, or indeed FLAMENCO TWILIGHT RED, FLAMENCO TWILIGHT GREEN, FLAMENCO TWILIGHT GOLD, FLAMENCO TWILIGHT BLUE, TIMICA NU ANTIQUE SILVER 110 AB, TIMICA NU ANTIQUE GOLD 212 GB, TIMICA NU-ANTIQUE COPPER 340 AB, TIMICA NU ANTIQUE BRONZE 240 AB, CLOISONNE NU ANTIQUE GREEN 828 CB, CLOISONNE NU ANTIQUE BLUE 626 CB, GEMTONE MOONSTONE G 004, CLOISONNE NU ANTIQUE RED 424 CHROMA-LITE, BLACK (4498), CLOISONNE NU ANTIQUE ROUGE FLAMBE (code 440 XB), CLOISONNE NU ANTIQUE BRONZE (240 XB), CLOISONNE NU ANTIQUE GOLD (222 CB), and CLOISONNE NU ANTIQUE COPPER (340 XB) by ENGELHARD.
  • [0650]
    Black iron oxide particles, e.g. those sold under the trade name SICOVIT noir E172 by BASF, or soft-iron based particles proposed under the trade name STAPA® WM IRON VP 041040 by ECKART, may also be mentioned.
  • [0651]
    The magnetic particles may be fibers.
  • [0652]
    The term “fibers” means generally elongate bodies presenting, for example, a form factor in the range 3.5 to 2500 or 5 to 500, e.g. 5 to 150. The form factor is defined by the ratio L/D, where L is the length of the fiber and D is the diameter of the circle in which the widest cross-section of the fiber is inscribed.
  • [0653]
    By way of example, the cross-section of the fibers may be inscribed in a circle having a diameter in the range 2 nm to 500 μm, e.g. in the range 100 nm to 100 μm, or even 1 μm to 50 μm.
  • [0654]
    By way of example, the fibers may present a length in the range 1 μm to 10 millimeters (mm), e.g. 0.1 mm to 5 mm, or even 0.3 mm to 3.5 mm.
  • [0655]
    By way of example, the fibers may present a weight in the range 0.15 denier to 30 denier (weight in grams for 9 km of thread), e.g. 0.18 denier to 18 denier.
  • [0656]
    The cross-section of the fibers may be of any shape, e.g. circular, or polygonal, in particular square, hexagonal, or octagonal.
  • [0657]
    The composition may contain solid or hollow fibers that may be independent or interlinked, e.g. braided.
  • [0658]
    The composition may contain fibers having ends that are blunted and/or rounded, e.g. by polishing.
  • [0659]
    The shape of the fibers need not be significantly modified when they are inserted into the composition, with said fibers being initially rectilinear and sufficiently rigid to keep their shape. In a variant, the fibers may present flexibility that enables them to be substantially deformed within the composition.
  • [0660]
    The fibers may contain a non-zero amount, that may be as great as 100%, of a magnetic material selected from soft magnetic materials, hard magnetic materials, in particular based on iron, zinc, nickel, cobalt, or manganese, and alloys and oxides thereof, in particular Fe3O4, rare earths, barium sulfate, iron-silicon alloys, possibly containing molybdenum, Cu2MnAl, MnBi, or a mixture thereof, this list not being limiting.
  • [0661]
    When the composition contains fibers containing magnetic particles, said magnetic particles may be present at least at the surface of the fibers, or only at the surface of the fibers, or only inside the fibers, or they may even be dispersed within the fibers in substantially uniform manner, for example.
  • [0662]
    By way of example, each fiber may include a non-magnetic core with a plurality of magnetic particles on its surface.
  • [0663]
    Each fiber may also include a synthetic matrix containing a plurality of magnetic grains dispersed therein.
  • [0664]
    Where appropriate, a synthetic material filled with magnetic particles may itself be covered by a non-magnetic membrane. By way of example, such a membrane constitutes a barrier isolating the magnetic material(s) from the surrounding environment and/or it can provide color. Each fiber may comprise a one-piece magnetic core and be covered by a non-magnetic membrane, or it may comprise a one-piece non-magnetic core and be covered by a magnetic membrane.
  • [0665]
    The composition may contain fibers made by extruding or co-extruding one or more polymeric materials, in particular thermoplastics and/or elastomers. One of the extruded materials may contain a filler of dispersed magnetic particles.
  • [0666]
    Each fiber may comprise a synthetic material selected from polyamides; polyethylene terephthalate (PET); acetates; polyolefins, in particular polyethylene (PE) or polypropylene (PP); polyvinyl chloride (PVC); polyester block amide; plasticized Rilsan®; elastomers, in particular polyester elastomers, polyethylene (PE) elastomers, silicone elastomers, nitrile elastomers; or a mixture of these materials, this list not being limiting.
  • [0667]
    The composition may contain composite fibers each comprising a magnetic core that is covered, at least in part, by at least one non-magnetic, synthetic, or natural material. By way of example, the magnetic core may be covered by co-extruding a membrane made of a non-magnetic material around the core.
  • [0668]
    The core may alternatively be covered in some other way, e.g. by polymerization in situ.
  • [0669]
    The core may be a single piece or it may include a filler of magnetic grains dispersed in a matrix.
  • [0670]
    The composition may also contain composite fibers obtained by covering a non-magnetic, synthetic, or natural core, with a synthetic material filled with magnetic particles, the core being composed of a fiber made of wood; rayon; polyamide; plant matter; or polyolefin, in particular polyethylene, Nylon®, polyimide-amide, or aramid, this list not being limiting.
  • [0671]
    The composition may also contain magnetic composite particles, in particular a magnetic latex.
  • Magnetic Composite Particles
  • [0672]
    A magnetic composite particle is a composite material constituted by an organic or an inorganic matrix and by magnetic grains. At their surfaces and/or within themselves, the magnetic composite particles may thus include grains of a magnetic material. The composite particles may be constituted by a magnetic core covered by an organic or an inorganic matrix, or they may be constituted by an organic or an inorganic core covered by a magnetic matrix.
  • [0673]
    The magnetic composite particles include one of the above-mentioned magnetic materials, for example.
  • [0674]
    The size of the magnetic composite particles may be in the range 1 nm to 1 mm, for example, preferably in the range 100 nm to 500 μm, and more preferably in the range 500 nm to 100 μm. The term “size” means the size given by the statistical grain size distribution at half the population, referred to as “D50”.
  • [0675]
    The thesis by C. GOUBAULT, dated Mar. 23, 2004, and incorporated herein by reference, refers, in chapter 1, to the prior art on the subject of magnetic composite particles, and draws up a list of preparation methods that are suitable for being used to prepare magnetic composite particles, namely separately synthesizing the magnetic grains and the matrix, synthesizing the magnetic grains in contact with the matrix, or synthesizing the matrix in the presence of the magnetic grains.
  • [0676]
    KISKER markets inorganic-matrix magnetic composite particles composed of silica. DYNAL, SERADYN, ESTAPOR, and ADEMTECH propose organic-matrix magnetic composite particles that are also suitable for being used in the invention.
  • [0677]
    More particularly, under the reference M1-070/60, ESTAPOR markets magnetic latex constituted by grains of ferrite that are evenly distributed in a polystyrene matrix, said latex including 65% iron oxide, the mean diameter of the polystyrene particles being 890 nm, and the dry material mass content being 10%.
  • Ferrofluid
  • [0678]
    The composition may contain a ferrofluid, i.e. a stable colloidal suspension of magnetic particles, in particular of magnetic nanoparticles.
  • [0679]
    The particles, having a size of the order of several tens of nanometers, for example, are dispersed in a solvent (water, oil, organic solvent), either by means of a surfactant or a dispersant, or by electrostatic interactions.
  • [0680]
    By way of example, the ferrofluids can be prepared by grinding ferrites or other magnetic particles until nanoparticles are obtained, which particles are then dispersed in a fluid containing a surfactant which is absorbed by the particles and stabilizes them, or else they can be prepared by precipitating a metallic-ion solution in a basic medium.
  • [0681]
    Each particle of the ferrofluid presents a magnetic moment that is determined by the size of the particle, and by the nature of the magnetic material.
  • [0682]
    Under the action of a magnetic field, the magnetic moments of the particles tend to come into alignment with the field lines, with non-zero magnetization appearing in the liquid. If the field is removed, there is no hysteresis and magnetization drops to zero.
  • [0683]
    Beyond a field threshold value, it is also possible to cause macroscopic changes in the liquid, e.g. the appearance of peaks, or a change in Theological properties.
  • [0684]
    The term “ferrofluid” also encompasses an emulsion of ferrofluid droplets in a solvent. Each drop thus contains colloidal magnetic particles in stable suspension. This makes it possible to have a ferrofluid in any type of solvent. The size of the magnetic particles in suspension in the ferrofluid may be in the range 1 nm to 10 μm, for example, preferably in the range 1 nm to 1 μm, and more preferably in the range 1 nm to 100 nm. The term “size” means the size given by the statistical grain size distribution at half the population, referred to as “D50”.
  • [0685]
    Mention can be made in particular of ferrofluids sold by Liquids Research LTD under the references:
      • WHKS1S9 (A, B, or C), which is a water-based ferrofluid containing magnetite (Fe3O4), having particles of 10 nm in diameter.
      • WHJS1 (A, B, or C), which is an isoparaffin-based ferrofluid, containing magnetite (Fe3O4) particles that are 10 nm in diameter.
      • BKS25_dextran, which is a water-based ferrofluid stabilized by dextran, containing magnetite (Fe3O4) particles that are 9 nm in diameter.
        Chains of Particles and/or of Magnetic Fibers
  • [0689]
    The composition may also contain chains of particles and/or of magnetic fibers.
  • [0690]
    The composition may thus contain clumps of particles or fibers having a largest dimension, e.g. length, that may, for example, be in the range 1 nm to 10 mm, e.g. in the range 10 nm to 5 mm, or in the range 100 nm to 1 mm, or even in the range 0.5 μm to 3.5 mm, e.g. in the range 1 μm to 150 μm. The term “size” means the size given by the statistical grain size distribution at half the population, referred to as “D50”.
  • [0691]
    By way of example, chains of magnetic particles may be obtained by assembling colloidal magnetic particles, as described in the publications “Permanently linked monodisperse paramagnetic chains”, by E. M. Furst, C. Suzuki, M. Fermigier, A. P. Gast, Langmuir, 14, 7334-7336 (1998), “Suspensions of magnetic particles”, by M. Fermigier, Y. Grasselli, Bulletin of the SFP (105) July 1996, and “Flexible magnetic filaments as micromechanical sensors”, by C. Goubault, P. Jop, M. Fermigier, J. Baudry, E. Bertrand, J. Bibette, Phys. Rev. Lett., 91, 26, 260802-1 to 260802-4 (2003), the contents of which are incorporated herein by reference.
  • [0692]
    In particular, those articles describe how to proceed in order to obtain chains of magnetic-latex particles that include a polystyrene matrix containing grains of iron oxide with functions on the surface, and that are bonded together in permanent manner following a chemical reaction, in particular covalent bonds between the surfaces of adjacent particles; a method is also described of obtaining chains of ferrofluid-emulsion droplets that are bonded together by physical interactions. The length and the diameter of the permanent chains obtained in this way can be controlled. Such magnetic chains constitute anisotropic magnetic objects that can be oriented and displaced under the effect of a magnetic field.
  • [0693]
    The dimensions of the magnetic chains may satisfy the same conditions as for the magnetic fibers.
  • [0694]
    In general, the compounds of the invention advantageously contain an oily phase and/or an aqueous phase, in particular as defined above.
  • [0695]
    With regard to the oily phase, said phase may contain oils other than the above-mentioned volatile oils, in particular non-volatile hydrocarbon or silicone oils in association, where necessary, with solid fatty materials such as waxes and/or paste compounds.
  • Other Compounds
  • [0696]
    The composition may include reflective particles, in particular having metallic luster.
  • Reflective Particles
  • [0697]
    The particles may be in any form, e.g. flakes or globular, in particular spherical, possibly elongate, with a high form factor, where appropriate, and they may optionally present non-zero magnetic susceptibility, linked to the presence of a magnetic material.
  • [0698]
    When the reflective particles are magnetic, they preferably present a flat shape such that a change in their orientation within the composition leads to a change in appearance.
  • [0699]
    Regardless of their form, the reflective particles may optionally have a multilayer structure; for example, with a multilayer structure, they may have at least one layer preferably of uniform thickness, in particular of a reflective material, advantageously a metallic compound.
  • [0700]
    When the reflective particles do not have a multilayer structure, they may, for example., be composed of at least one metallic compound, e.g. a metal oxide, in particular an oxide of titanium or iron obtained by synthesis.
  • [0701]
    When the reflective particles have a multilayer structure they may, for example, comprise a natural or synthetic substrate, in particular a synthetic substrate which is at least partially coated with at least one, layer of a reflective material, in particular at least one layer of at least one metallic compound such as a metal or an alloy. The layer of the metallic compound is advantageously an outer layer of the structure.
  • [0702]
    The substrate may be a single material or multiple materials, and it may be organic and/or inorganic.
  • [0703]
    More particularly, the substrate may be selected from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica, and mixtures thereof, this list not being limiting.
  • [0704]
    Examples of reflective particles comprising a mineral substrate coated with a metal layer that may be mentioned are particles comprising a substrate of borosilicate coated with silver. Glass substrate particles coated with silver in the form of flakes are sold under the trade name MICROGLASS METASHINE REFSX 2025 PS by TOYAL. Glass substrate particles coated with nickel/chromium/molybdenum alloy are sold under the trade name CRYSTAL STAR GF 550, GF 2525 by the same company.
  • [0705]
    Reflective particles of any form may also be selected from particles of synthetic substrate at least partially coated with at least one layer of at least one metallic oxide selected, for example, from oxides of titanium, in particular TiO2, of iron, in particular Fe2O3, of tin, or of chromium, barium sulfate, and the following materials: MgF2, CrF3, ZnS, ZnSe, SiO2, Al2O3, MgO, Y2O3, SeO3, SiO, HfO2, ZrO2, CeO2, Nb2O5, Ta2O5, MoS2, and their mixtures.
  • [0706]
    Examples of such particles that may be mentioned are particles comprising a substrate of synthetic mica coated with titanium dioxide, or glass particles coated either with brown iron oxide, titanium oxide, tin oxide, or one of their mixtures such as those sold under the trade name REFLECKS® by ENGELHARD.
  • [0707]
    As other examples of reflective particles presenting, at their surface, a metallic compound or including at least one coated metallic compound, mention may be made of particles proposed under the trade names METASHINE® ME 2040 PS, METASHINE® MC5090 PS or METASHINE® MC280GP (2523) by NIPPON SHEET GLASS, SPHERICAL SILVER POWDER® DC 100, SILVER FLAKE® JV 6 or GOLD POWDER® A1570 by ENGELHARD, STARLIGHT REFLECTIONS FXM® by ENERGY STRATEGY ASSOCIATES INC, BRIGHT SILVER® 1 E 0.008X0.008 by MEADOWBROOK INVENTIONS, ULTRAMIN® (ALUMINIUM POUDRE FINE LIVING), and COSMETIC METALLIC POWDER VISIONNAIRE BRIGHT SILVER SEA®, COSMETIC METALLIC POWDER VISIONAIRE NATURAL GOLD® (60314) or COSMETIC METALLIC POWDER VISIONAIRE HONEY® (60316) by ECKART.
  • [0708]
    The reflective particles may optionally reflect the visible spectrum in substantially uniform manner, for example as occurs with particles coated with a metal such as silver or aluminum, which may, for example, thus lead to a metallic luster having a tone that is non-neutral, yellow, pink, red, bronze, orangey, brown, and/or coppery, depending on the nature of the metallic surface compound, for example.
  • [0709]
    The reflective particles may be present in the composition in an amount in the range 0.5% to 60% by weight relative to the total weight of the first composition, specifically 1% to 30% by weight, e.g. 3% to 10% by weight.
  • [0710]
    The composition may include at least one diffractive pigment.
  • Diffractive Pigment
  • [0711]
    The term “diffractive pigment” means a pigment that is capable of producing a variation in color depending on the angle of observation when lit by white light, because of the presence of a structure which diffracts the light. Such a pigment is also sometimes referred to as a holographic pigment.
  • [0712]
    A diffractive pigment may include a diffraction grating that is capable of diffracting an incident ray of monochromatic light in defined directions.
  • [0713]
    The diffraction grating may comprise a periodic pattern, in particular a line, with the distance between two adjacent patterns being the same as the wavelength of the incident light.
  • [0714]
    When the incident light is polychromatic, the diffraction grating separates the various spectral components of the light and produces a rainbow effect.
  • [0715]
    With regard to the structure of diffractive pigments, reference can usefully be made to the article “Pigments Exhibiting Diffractive Effects” by Alberto Argoitia and Matt Witzman, 2002, Society of Vacuum coaters, 45th Annual Technical Conference Proceedings 2002.
  • [0716]
    The diffractive pigment may be made with patterns having various profiles, in particular triangular, optionally symmetrical, notched, of optionally constant width, sinusoidal, or stepped.
  • [0717]
    The spatial frequency of the grating and the depth of the patterns are selected as a function of the degree of separation of the various desired orders. The frequency may be in the range 500 lines per mm to 3000 lines per mm, for example.
  • [0718]
    Each of the particles of the diffractive pigment preferably presents a flat shape, and in particular a wafer shape.
  • [0719]
    A single pigment particle may include two crossed diffraction gratings that are optionally perpendicular, and that optionally have the same ruling.
  • [0720]
    The diffractive pigment may present a multilayer structure comprising a layer of reflective material that is covered on at least one side by a layer of dielectric material. The dielectric material may make the diffractive pigment stiffer and longer lasting. For example, the dielectric material may thus be selected from the following materials: MgF2, SiO2, Al2O3, AlF3, CeF3, LaF3, NdF3, SmF2, BaF2, CaF2, LiF, and combinations thereof. For example, the reflective material may be selected from metals and alloys thereof, and also from non-metallic reflective materials: Metals that may be used include Al, Ag, Cu, Au, Pt, Sn, Ti, Pd, Ni, Co, Rd, Nb, Cr, and materials, combinations, or alloys thereof. Such a reflective material may, on its own, constitute the diffractive pigment which then comprises a single layer.
  • [0721]
    In a variant, the diffractive pigment may include a multilayer structure comprising a core of dielectric material with a reflective layer covering at least one side, or indeed completely encapsulating, the core. A layer of dielectric material may also cover the reflective layer(s). The dielectric material used is thus preferably inorganic, and may, for example, be selected from metal fluorides, metal oxides, metal sulfides, metal nitrides, metal carbides, and combinations thereof. The dielectric material may be in the crystalline, semi-crystalline, or amorphous state. In this configuration, the dielectric material may, for example, be selected from the following materials: MgF2, SiO, SiO2, Al2O3, TiO2, WO, AlN, BN, B4C, WC, TiC, TiN, N4Si3, ZnS, glass particles, diamond-type carbons, and combinations thereof.
  • [0722]
    In a variant, the diffractive pigment may be composed of a preformed dielectric or ceramic material such as a naturally lamellar mineral, e.g. mica peroskovite or talc; or synthetic platelets formed from glass, alumina, SiO2, carbon, an iron oxide/mica, mica covered in BN, BC, graphite, or bismuth oxychloride, and combinations thereof.
  • [0723]
    Instead of a layer of dielectric material, other materials that improve the mechanical properties may be suitable. Such materials may include silicone, metal silicides, semiconductor materials formed from elements of groups III, IV, and V, metals having a body centered cubic crystal structure, metal-ceramic compositions or materials, semiconductor glasses, and various combinations thereof.
  • [0724]
    In particular, the diffractive pigment used may be selected from those described in US patent application No. 2003/0031870 published on Feb. 13, 2003.
  • [0725]
    A diffractive pigment may, for example, have the following structure: MgF2/Al/MgF2, a diffractive pigment having this structure being sold by FLEX PRODUCTS under the trade names SPECTRAFLAIR 1400 Pigment Silver or SPECTRAFLAIR 1400 Pigment Silver FG. The proportion by weight of MgF2 may be in the range 80% to 95% of the total weight of the pigment.
  • [0726]
    Other diffractive pigments are sold under the trade names Metalure® Prismatic by ECKART®.
  • [0727]
    By way of example, the quantity of diffractive pigment may be in the range 0.1% to 5% by weight relative to the total weight of the first composition.
  • [0728]
    By way of example, the size of the diffractive pigment may be in the range 5 μm to 200 μm, and preferably in the range 5 μm to 100 μm, e.g. in the range 5 μm to 30 μm.
  • [0729]
    The thickness of the diffractive-pigment particles may be less than or equal to 3 μm, or preferably 2 μm, e.g. about 1 μm.
  • Other Coloring Agents
  • [0730]
    The composition may include at least one coloring agent producing light by absorbing at least a fraction of the visible spectrum.
  • [0731]
    Such a coloring agent, producing a color by an absorption phenomenon, may be constituted by a pigment that is an optionally magnetic, organic, or inorganic, or it may be a hybrid comprising both organic material and inorganic material.
  • [0732]
    The coloring agent may optionally be a particulate compound.
  • [0733]
    Where appropriate, the particles of a single magnetic pigment constitute both the coloring agent, producing the color by an absorption phenomenon, and the magnetic bodies.
  • [0734]
    When the coloring agent includes a colorant, said colorant may be selected from amongst liposoluble and hydrosoluble colorants.
  • [0735]
    Examples of liposoluble colorants are Sudan red, D&C Red No. 17, D&C Green No. 6, β-carotene, soybean oil, Sudan brown, D&C Yellow No. 11, D&C Violet No. 2, D&C orange No. 5, and quinoline yellow.
  • [0736]
    Examples of hydrosoluble colorants are beetroot juice and methylene blue.
  • [0737]
    By way of example, the colorants may represent 0.1% to 20% by weight of the first or second composition, or even 0.1% to 6%, when present.
  • [0738]
    The coloring agents may also be a lake or an organic pigment selected from the following materials and mixtures thereof:
      • cochineal carmine;
      • the organic pigments of azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane, or fluorane dyes;
      • organic lakes or insoluble salts of sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium, or of acid dyes such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane, or fluorine dyes, which dyes may comprise at least one carboxylic or sulfonic acid group.
  • [0742]
    Organic pigments that may be mentioned include those with the following denominations: D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange. No. 11, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6.
  • [0743]
    The coloring agent may be an organic lake supported by an organic support such as colophane or aluminum benzoate, for example.
  • [0744]
    Particular organic lakes that may be mentioned include those with the following denominations: D&C Red No. 2 Aluminum lake, D&C Red No. 3 Aluminum lake, D&C Red No. 4 Aluminum lake, D&C Red No. 6 Aluminum lake, D&C Red No. 6 Barium lake, D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6 Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7 Aluminum lake, D&C Red No. 7 Barium lake, D&C Red No. 7 Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red No. 9 Aluminum lake, D&C Red No. 9 Barium lake, D&C Red No. 9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C Red No. 10 Sodium lake, D&C Red No. 19 Aluminum lake, D&C Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C Red No. 21 Aluminum lake, D&C Red No. 21 Zirconium lake, D&C Red No. 22 Aluminum lake, D&C Red No. 27 Aluminum lake, D&C Red No. 27 Aluminum/Titanium/Zirconium lake, D&C Red No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red No. 27 Zirconium lake, D&C Red No. 28 Aluminum lake, D&C Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No. 33 Aluminum lake, D&C Red No. 34 Calcium lake, D&C Red No. 36 lake, D&C Red No. 40 Aluminum lake, D&C Blue No. 1 Aluminum lake, D&C Green No. 3 Aluminum lake, D&C Orange No. 4 Aluminum lake, D&C Orange No. 5 Aluminum lake, D&C Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminum lake, D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminum lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6 Aluminum lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow No. 10 Aluminum lake, FD&C Blue No. 1 Aluminum lake, FD&C Red No. 4 Aluminum lake, FD&C Red No. 40 Aluminum lake, FD&C Yellow No. 5 Aluminum lake, FD&C Yellow No. 6 Aluminum lake.
  • [0745]
    The chemical materials corresponding to each of the organic coloring substances listed above are mentioned in the work entitled “International Cosmetic Ingredient Dictionary and Handbook”, 1997 edition, pages 371 to 386 and 524 to 528, published by “The Cosmetic, Toiletry, and Fragrance Association”, the contents of which are incorporated herein by reference.
  • [0746]
    The composition may contain a composite pigment including a core that is coated at least in part by a membrane.
  • Composite Pigments
  • [0747]
    A composite pigment may be composed of particles comprising:
      • an inorganic core; and
      • at least one at least partial coating of at least one organic coloring substance.
  • [0750]
    At least one binder may advantageously contribute to fixing the organic coloring substance onto the inorganic core.
  • [0751]
    The particles of composite pigment may have a variety of forms. In particular, said particles may be in the form of flakes or they may be globular, in particular spherical, and may be hollow or solid. The term “in the form of flakes” means particles for which the ratio of the largest dimension to the thickness is 5 or more.
  • [0752]
    A composite pigment may, for example, have a specific surface area in the range 1 square meter per gram (m2/g) to 1000 m2/g, in particular in the range about 10 m2/g to about 600 m2/g, and in particular in the range about 20 m2/g to about 400 m2/g. The specific surface area is the value measured using the BET (Brunauer-Emmett-Teller) method.
  • [0753]
    The proportion by weight of the core may exceed 50% relative to the total weight of the composite pigment, for example lying in the range 50% to 70%, e.g. in the range 60% to 70%.
  • [0754]
    The composite pigment may be different from an interferential pigment as described in U.S. Pat. No. 6,428,773, for example. By way of example, an interferential pigment includes a plurality of layers of constant thickness of materials selected so as to be able to produce optical interferences.
  • [0755]
    The saturation C* of the composite pigment may be greater than or equal to 30, measured in accordance with the following protocol.
  • Protocol for Measuring the Saturation of the Composite Pigment
  • [0756]
    The values a* and b* in the CIE L*a*b* space of the composite pigment are measured as follows:
  • [0757]
    Pure composite pigment is compacted in a rectangular dish having dimensions of 2 centimeters (cm)×1.5 cm and a depth of 3 mm, by applying pressure of 100 bars.
  • [0758]
    The values a* and b* of the compacted pigment are measured with a MINOLTA 3700d spectrophotometer, in excluded specular mode, under D65 lighting, medium aperture. Saturation is given by C*=(a*2+b*2)1/2.
  • Inorganic Core
  • [0759]
    The inorganic core may have any form that is suitable for fixing particles of organic coloring substance, for example spherical, globular, granular, polyhedral, acicular, spindle-shaped, flattened in the form of a flake, a rice grain, or a scale, and a combination of these forms, this list not being limiting.
  • [0760]
    Preferably, the ratio of the largest dimension of the core to its smallest dimension may be in the range 1 to 50.
  • [0761]
    The inorganic core may have a mean size in the range about 1 nm to about 100 nm, or even in the range about 5 nm to about 75 nm, for example in the range about 10 nm to about 50 nm, in particular 20 nm or 25 nm.
  • [0762]
    The term “mean size” means the size given by the statistical grain size distribution at half the population, referred to as “D50”. The mean size may be a number mean size determined by image analysis (electron microscopy).
  • [0763]
    The inorganic core may present a refractive index that is greater than or equal to 2, or even greater than or equal to 2.1, e.g. greater than or equal to 2.2.
  • [0764]
    The inorganic core may be formed from an optionally-magnetic material selected from a non-limiting list comprising metallic salts and metal oxides, in particular oxides of titanium, zirconium, cerium, zinc, iron, iron blue, aluminum, and chromium, aluminas, glasses, ceramics, graphite, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica, and mixtures thereof.
  • [0765]
    Oxides of titanium, in particular TiO2, of iron, especially Fe2O3, of cerium, zinc, and aluminum, silicates, in particular aluminosilicates and borosilicates, are particularly suitable.
  • [0766]
    The inorganic core may have a specific surface area, measured using the BET method, in the range about 1 m2/g to about 1000 m2/g, preferably in the range about 10 m2/g to about 600 m2/g, for example in the range about 20 m2/g to about 400 m2/g.
  • [0767]
    The inorganic core may be colored if appropriate.
  • Organic Coloring Material
  • [0768]
    By way of example, the organic coloring material may comprise at least one organic pigment, e.g. at least one organic lake.
  • [0769]
    By way of example, the organic coloring material may be selected from the insoluble particulate compounds in the physiologically acceptable medium of the composition.
  • [0770]
    By way of example, the organic coloring material may comprise pigments, e.g. organic lakes or other organic coloring materials, that may be selected from the following compounds and mixtures thereof:
      • cochineal carmine;
      • the organic pigments of azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane, or fluorane dyes;
      • organic lakes or insoluble salts of sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium, or of acid dyes such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane, or fluorine dyes, which dyes may comprise at least one carboxylic or sulfonic acid group.
  • [0774]
    Organic pigments that may be mentioned include those with the following denominations: D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6.
  • [0775]
    The organic coloring substance may comprise an organic lake supported by an organic support such as colophane or aluminum benzoate, for example.
  • [0776]
    Particular organic lakes that may be mentioned include those with the following denominations: D&C Red No. 2 Aluminum lake, D&C Red No. 3 Aluminum lake, D&C Red No. 4 Aluminum lake, D&C Red No. 6 Aluminum lake, D&C Red No. 6 Barium lake, D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6 Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7 Aluminum lake, D&C Red No. 7 Barium lake, D&C Red No. 7 Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red No. 9 Aluminum lake, D&C Red No. 9 Barium lake, D&C Red No. 9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C Red No. 10 Sodium lake, D&C Red No. 19 Aluminum lake, D&C Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C Red No. 21 Aluminum lake, D&C Red No. 21 Zirconium lake, D&C Red No. 22 Aluminum lake, D&C Red No. 27 Aluminum lake, D&C Red No. 27 Aluminum/Titanium/Zirconium lake, D&C Red No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red No. 27 Zirconium lake, D&C Red No. 28 Aluminum lake, D&C Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No. 33 Aluminum lake, D&C Red No. 34 Calcium lake, D&C Red No. 36 lake, D&C Red No. 40 Aluminum lake, D&C Blue No. 1 Aluminum lake, D&C Green No. 3 Aluminum lake, D&C Orange No. 4 Aluminum lake, D&C Orange No. 5 Aluminum lake, D&C Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminum lake, D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminum lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6 Aluminum lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow No. 10 Aluminum lake, FD&C Blue No. 1 Aluminum lake, FD&C Red No. 4 Aluminum lake, FD&C Red No. 40 Aluminum lake, FD&C Yellow No. 5 Aluminum lake, FD&C Yellow No. 6 Aluminum lake.
  • [0777]
    The chemical compounds corresponding to each of the organic coloring substances listed above are mentioned in the work entitled “International Cosmetic Ingredient Dictionary and Handbook”, 1997 edition, pages 371 to 386 and 524 to 528, published by “The Cosmetic, Toiletry, and Fragrance Association”, the contents of which are incorporated herein by reference.
  • [0778]
    The proportion by weight of organic coloring material may lie in the range about 10 parts to about 500 parts by weight per 100 parts of inorganic core, or even in the range about 20 parts to about 250 parts by weight, e.g. in the range about 40 parts to about 125 parts by weight per 100 parts of inorganic core.
  • [0779]
    The total content of organic coloring material of the composition, coming from the composite pigment and from other possible pigments, may be less than 10%, for example, relative to the total weight of the composition.
  • [0780]
    The proportion of organic coloring material may exceed 30% relative to the total weight of the composite pigment, for example lying in the range 30% to 50%, e.g. in the range 30% to 40%.
  • Binder
  • [0781]
    The composite-pigment binder may be of any type provided that it allows the organic coloring substance to adhere to the surface of the inorganic core.
  • [0782]
    In particular, the binder may be selected from the following non-limiting list: silicone materials, polymeric, oligomeric or similar materials, in particular from organosilanes, fluoroalkylated organosilanes and polysiloxanes, for example polymethylhydrogen siloxane, as well as a variety of coupling agents such as coupling agents based on silanes, titanates, aluminates, zirconates, and mixtures thereof.
  • [0783]
    The silicone compound may be selected from the following non limiting list:
      • organosilanes (1) obtained from alkoxysilanes;
      • polysiloxanes (2) which may optionally be modified, selected from the following non limiting list:
        • modified polysiloxanes (2A) comprising at least one radical selected in particular from polyethers, polyesters and epoxy compounds (henceforth termed “modified polysiloxanes”);
        • polysiloxanes (2B) carrying, on one silicon atom located at the end of the polymer, at least one group selected from the following non-limiting list: carboxylic acids, alcohols, and hydroxyl groups; and
        • fluoroalkylated organosilane compounds (3) obtained from fluoroalkylsilanes.
  • [0789]
    The organosilane compounds (1) may be obtained from alkoxysilane compounds represented by formula (I):
  • [0000]

    R1 aSiX4-a  (I)
  • [0000]
    in which:
      • R1 represents C6H5—, (CH3)2CH—CH2— or a CbH2b+1-type radical (in which b lies in the range 1 to 18);
      • X represents CH3O— or C2H5O—; and
      • a lies in the range 0 to 3.
  • [0793]
    Specific examples of alkoxysilane compounds may include alkoxysilanes selected from: methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, and the like, in particular from methyltriethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, more preferably from methyltriethoxysilane, methyltrimethoxysilane, and phenyltriethoxysilane.
  • [0794]
    The polysiloxanes (2) may in particular have formula (II):
  • [0000]
    Figure US20090130037A1-20090521-C00020
  • [0000]
    in which R2 represents H— or CH3— and d lies in the range 15 to 450.
  • [0795]
    Polysiloxanes for which R2 represents H are preferred.
  • [0796]
    The modified polysiloxanes (2A) may in particular have the following formula (III):
      • (a1) modified polysiloxanes carrying polyethers, represented by formula (III):
  • [0000]
    Figure US20090130037A1-20090521-C00021
  • [0000]
    in which R3 represents —(CH2)h—; R4 represents —(CH2)i—CH3; R5 represents —OH, —COOH, —CH═CH2, —C(CH3)═CH2 or —(CH2)j—CH3; R6 represents —(CH2)k—CH3; g and h lie independently in the range 1 to 15; j and k lie independently in the range 0 to 15; e lies in the range 1 to 50, and f lies in the range 1 to 300;
      • (a 2) modified polysiloxanes carrying polyesters, represented by formula (IV):
  • [0000]
    Figure US20090130037A1-20090521-C00022
  • [0000]
    in which R7, R8, and R9 independently represent —(CH2)q—; R10 represents —OH, —COOH, —CH═CH2, —C(CH3)═CH2 or —(CH2)r—CH3; R11 represents —(CH2)s— CH3; n and q lie independently in the range 1 to 15, r and s lie independently in the range 0 to 15; e lies in the range 1 to 50, and f lies in the range 1 to 300,
      • (a3) modified polysiloxanes carrying epoxy radicals represented by formula (V):
  • [0000]
    Figure US20090130037A1-20090521-C00023
  • [0000]
    in which R12 represents —(CH2)v—; v lies in the range 1 to 15; t lies in the range 1 to 50, and u lies in the range 1 to 300; or mixtures thereof.
  • [0800]
    Preferred modified polysiloxanes (2A) are modified polysiloxanes carrying polyethers with formula (III).
  • [0801]
    Polysiloxanes modified at the terminal portion (2B) may have formula (VI):
  • [0000]
    Figure US20090130037A1-20090521-C00024
  • [0000]
    in which R13 and R14 may represent —OH, R16—OH, or R17—COOH, independently of each other; R15 represents —CH3 or —C6H5; R16 and R17 represent —(CH2)y—; y lies in the range 1 to 15; w lies in the range 1 to 200; and x lies in the range 0 to 100.
  • [0802]
    Preferred polysiloxanes modified on at least one end include those carrying at least a radical (R16 and/or R17) carrying a carboxylic acid group on at least one terminal silicon atom.
  • [0803]
    Fluoroalkylated organosilane compounds (3) may be obtained from fluoroalkylsilanes represented by formula (VII):
  • [0000]

    CF3(CF2)zCH2CH2 (R18)aSiX4-a  (VII)
  • [0000]
    in which:
      • R18 represents CH3—, C2H5—, CH3O— or C2H5O—;
      • X represents CH3O— or C2H5O—;
      • z lies in the range 0 to 15 and a lies in the range 0 to 3.
  • [0807]
    In particular, the fluoroalkylsilanes may be selected from the following non limiting list: trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecylmethyldiethoxysilane and the like, in particular trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane, and more preferably trifluoropropyl trimethoxysilane and tridecafluorooctyltrimethoxysilane.
  • [0808]
    The silane-based coupling agents may be selected from the following non limiting list: vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyl-triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, and the like.
  • [0809]
    The titanate-based coupling agents may be selected from the following list: isopropylstearoyl titanate, isopropyltris(dioctylpyrophosphate) titanate, isopropyltri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphate) titanate, tetra(2,2-diaryloxymethyl-1-butyl)bis(ditridecyl)phosphate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, and the like.
  • [0810]
    The aluminate-based coupling agents may be selected from acetoalkoxyaluminum diisopropylate, aluminum diisopropoxymonoethylacetoacetate, aluminum triethylacetoacetate, aluminum triacetylacetonate, and the like.
  • [0811]
    The zirconate-based coupling agents may be selected from the following list: zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tributoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate, and the like.
  • [0812]
    The compounds acting as a binder may have a molar mass in the range 300 to 100 000.
  • [0813]
    To obtain a layer which uniformly coats the inorganic cores, the binder is preferably in the liquid state or is soluble in water or other solvents.
  • [0814]
    The quantity of binder may lie in the range 0.01% to 15%, in particular from 0.02% to 12.5%, and more particularly from 0.03% to 10% by weight (calculated with respect to C or Si) relative to the weight of particles comprising the core and the binder. Further details regarding the calculation of the relative quantity of binder can be found in patent application EP 1 184 426 A2. The relative proportion of binder may be less than or equal to 5%, e.g. less than or equal to 3%, relative to the total weight of the composite pigment.
  • Preparation of Composite Pigment
  • [0815]
    The composite pigment may be prepared using any appropriate method, e.g. a mechanical/chemical method or a method of precipitation in solution, with the organic coloring material being dissolved, then precipitated onto the surface of the core.
  • [0816]
    A binder may optionally be used.
  • [0817]
    A method comprising mechanically mixing an organic pigment and the inorganic core is preferred.
  • [0818]
    A binder may be added or mixed to the inorganic core before the organic coloring material is introduced.
  • [0819]
    The composite pigment may, for example, be produced using one of the processes described in European patent applications EP 1 184 426 and EP 1 217 046, the contents of which are hereby incorporated by reference, and advantageously by the process described in EP 1 184 426.
  • [0820]
    In one implementation, the particles intended to constitute the inorganic core are first mixed with the binder.
  • [0821]
    So that the binder can adhere uniformly to the surface of the inorganic core, it is preferable to pass said particles initially through a mill to disaggregate them.
  • [0822]
    The mixing and agitation conditions are selected so that the core is uniformly coated with binder. Such conditions may be controlled so that the linear load is in the range 19.6 N/cm (newtons/centimeter) to 19160 N/cm, in particular in the range 98 N/cm to 14170 N/cm and preferably in the range 147 N/cm to 980 N/cm; the treatment time is in the range 5 minutes to 24 hours, preferably in the range 10 minutes to 20 hours; the rotation rate may be in the range 2 rpm (revolutions per minute) to 1000 rpm, in particular in the range 5 rpm to 1000 rpm, and more preferably in the range 10 rpm to 800 rpm.
  • [0823]
    After coating the inorganic core with binder, the organic coloring substance is added and mixed with agitation so that it adheres to the layer of binder.
  • [0824]
    Examples of addition methods are continuous addition in large quantities, or in small quantities.
  • [0825]
    Mixing and agitation, whether of the inorganic cores with the binder or of the organic coloring substance with the inorganic cores coated with binder, may be carried out using an apparatus which can apply a sharp shearing and/or compressive force to the mixture of powders. Examples of apparatus of that type are roller mixers, blade mixers, and the like. Roller mixers are particularly suitable. A list of suitable apparatus is given in EP 1 184 426 A2.
  • [0826]
    A further method for manufacturing a composite pigment has been described in Japanese patent JP 3286463, which discloses a solution precipitation process.
  • [0827]
    The organic coloring substance is dissolved in ethanol and the inorganic cores are then dispersed in said ethanolic solution.
  • [0828]
    An aqueous alkaline solution of sodium or potassium carbonate is then slowly added to these mixtures and finally, an ethanolic calcium chloride solution is slowly added, with constant agitation.
  • [0829]
    In addition to a coloring agent absorbing light by an absorption phenomenon, the composition may include at least one interferential or diffractive pigment and/or reflective particles.
  • [0830]
    In an implementation of the invention, the first composition contains at least one goniochromatic coloring agent in which a color change can be observed as a function of the angle of observation. The goniochromatic coloring agent may optionally be magnetic.
  • [0831]
    When the first composition contains magnetic particles of a certain color and a non-magnetic goniochromatic coloring agent, said coloring agent may be selected so that its range of colors passes substantially through the color of the magnetic particles.
  • [0832]
    By way of example, this can make the magnetic particles more difficult to detect so long as they are not oriented under the effect of a magnetic field.
  • [0833]
    This can also allow the pattern induced by orienting the magnetic particles to appear only when the made-up surface is under certain observation and/or lighting conditions, thereby making it possible to create pattern disposition and appearance effects that are particularly attractive.
  • Goniochromatic Coloring Agents
  • [0834]
    The composition may contain at least one goniochromatic coloring agent which may present magnetic properties, where appropriate.
  • [0835]
    The term “goniochromatic coloring agent” as used in the context of the present invention means a coloring agent that makes it possible, when the composition is spread on a surface, to obtain a color path in the a*b* plane of the 1976 CIE color space which corresponds to a variation Dh° of the hue angle h° of at least 200 when the angle of observation is varied relative to the normal in the range 0° to 80° for light at an angle of incidence of 45°.
  • [0836]
    By way of example, the color path may be measured by means of a spectrogonioreflectometer, from INSTRUMENT SYSTEMS and referenced GON 360 GONIOMETER, after the first composition has been spread in the fluid state to a thickness of 300 μm by means of an automatic spreader on a contrast card from ERICHSEN and referenced Typ 24/5, the measurements being performed on the black background of the card.
  • [0837]
    By way of example, the goniochromatic coloring agent may be selected from multilayer interference structures and liquid crystal coloring agents.
  • [0838]
    By way of example, a multilayer structure may comprise at least two layers, each layer being produced, for example, from at least one material selected from the group constituted by the following materials: MgF2, CeF3, ZnS, ZnSe, Si, SiO2, Ge, Te, Fe2O3, Pt, Va, Al2O3, MgO, Y2O3, S2O3, SiO, HfO2, ZrO2, CeO2, Nb2O5, Ta2O5, TiO2, Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn, MoS2, cryolite, alloys, polymers, and combinations thereof.
  • [0839]
    The multilayer structure may optionally be symmetrical with respect to a central layer as regards the chemical nature of the stacked layers. Depending on the thickness and nature of the various layers, different effects are obtained.
  • [0840]
    Examples of symmetrical multilayer interference structures are as follows: Fe2O3/SiO2/Fe2O3/SiO2/Fe2O3, a pigment having this structure being sold under the trade name SICOPEARL by BASF; MoS2/SiO2/mica-oxide/SiO2/MoS2; Fe2O3/SiO2/mica-oxide/SiO2/Fe2O3; TiO2/SiO2/TiO2 and TiO2/Al2O3/TiO2, pigments with these structures being sold under the trade name XIRONA by MERCK (Darmstadt).
  • [0841]
    By way of example, liquid crystal coloring agents comprise silicones, or cellulose ethers onto which mesomorphic groups have been grafted. Examples of suitable liquid crystal goniochromatic particles are those sold by CHENIX, and those sold under the trade name HELICONE® HC by WACKER.
  • [0842]
    Suitable goniochromatic coloring agents are some nacres; pigments having effects on synthetic substrates, in particular alumina, silica, borosilicate, iron oxide, or aluminum type substrates; or holographic interference flakes coming from a polyterephthalate film.
  • Nacres
  • [0843]
    The term “nacre” means colored particles of any form, which may optionally be iridescent, as produced in the shells of certain mollusks, or which are synthesized, and which exhibit a “pearlescent” coloring effect by optical interference.
  • [0844]
    Nacres may be selected from nacre pigments such as mica titanium coated with iron oxide, mica coated with bismuth oxychloride, mica titanium coated with chromium oxide, mica titanium coated with an organic colorant, in particular of the type mentioned above, and nacre pigments based on bismuth oxychloride. They may also be particles of mica on the surface of which at least two successive layers of metal oxides and/or organic coloring substances have been superimposed.
  • [0845]
    More particularly, the nacres may have a yellow, pink, red, bronze, orangey, brown, gold, and/or coppery color or glint.
  • [0846]
    Illustrative examples of nacres suitable for being introduced into the first composition and that may be mentioned are gold color nacres, in particular those sold by ENGELHARD under the trade names Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite), and Monarch gold 233×(Cloisonne); bronze nacres, in particular those sold by MERCK under the trade names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona), and by ENGELHARD under the trade name Super bronze (Cloisonne); orange nacres especially those sold by ENGELHARD under the trade names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica), and by MERCK under the trade names Passion orange (Colorona) and Matte orange (17449) (Microna); brown-tinted nacres sold by ENGELHARD under the trade names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacres with a copper glint sold by ENGELHARD under the trade name Copper 340A (Timica); nacres with a red glint, especially those sold by MERCK under the trade name Sienna fine (17386) (Colorona); nacres with a yellow glint, especially those sold by ENGELHARD under the trade name Yellow (4502) (Chromalite); red-tinted nacres with gold glints, especially those sold by ENGELHARD under the trade name Sunstone G012 (Gemtone); pink nacres, especially those sold by ENGELHARD under the trade name Tan opale G005 (Gemtone); black nacres with a glint, especially those sold by ENGELHARD under the trade name Nu antique bronze 240 AB (Timica); blue nacres, especially those sold by MERCK under the trade name Matte blue (17433) (Microna); white nacres with silvery glints, especially those sold by MERCK under the trade name Xirona Silver; and orange-pink green-gold highlight nacres sold by MERCK under the trade names Indian summer (Xirona) and mixtures thereof.
  • [0847]
    The composition may contain at least one optionally-magnetic filler.
  • Fillers
  • [0848]
    The term “filler” means particles of any form which are insoluble in the composition medium regardless of the temperature at which the composition is manufactured. A filler primarily acts to modify the rheology or texture of the composition. The nature and quantity of the particles could depend on the desired mechanical properties and textures.
  • [0849]
    Examples of fillers that may be mentioned include amongst others talc, mica, silica, kaolin, and sericite, and powders of polyamide, polyolefin, e.g. polyethylene, polytetrafluoroethylene, polymethylmethacrylate, or polyurethane, powdered starch, and silicone resin beads.
  • Active Ingredients
  • [0850]
    The composition may include at least one cosmetically or dermatologically active ingredient.
  • [0851]
    Suitable cosmetically, dermatologically, hygienically, or pharmaceutically active ingredients for use in the compositions of the invention that may be mentioned are moisturizing agents (polyols such as glycerine), vitamins (C, A, E, F, B, or PP), essential fatty acids, essential oils, ceramides, sphingolipids, liposoluble or nanoparticle sun screens, and specific skin treatment active ingredients (protective agents, antibacterials, anti-wrinkle agents, etc), self-tanning agents. Said active ingredients may be used in concentrations in the range 0 to 20%, for example, in particular in the range 0.001% to 15% relative to the total weight of the composition.
  • [0852]
    The composition may also contain ingredients that are routinely used in cosmetics, such as thickeners, surfactants, oligo-elements, moisturizing agents, softeners, sequestrating agents, fragrances, alkalinizing or acidifying agents, preservatives, antioxidants, UV filters, colorants, or mixtures thereof.
  • [0853]
    Depending on the envisaged application, the composition of the invention may include constituents which are conventionally used in the fields under consideration, and which are present in quantities appropriate to the desired dosage form.
  • Dosage Forms
  • [0854]
    The composition may be in a variety of forms, depending on its purpose. The composition may thus be in any dosage form that is normally used for topical application, in particular in the anhydrous form, in the form of an oily or aqueous solution, an oily or aqueous gel, an oil-in-water or a water-in-oil emulsion, a wax-in-water or a water-in-wax emulsion, a multiple emulsion or a dispersion of oil in water due to vesicles located on the oil/water interface.
  • EXAMPLES
  • [0855]
    The proportions indicated are given by weight unless otherwise specified.
  • Example A Lipstick
  • [0856]
  • [0000]
    Film-forming polymer** 65.24
    Sucrose acetate isobutyrate 9.52
    Octyldodecanol 6
    Isododecane 14.1
    Magnetic pigment* 4.76
    Fragrance 0.38
    *STAPA ® VM VP 041040 soft iron based pigment from ECKART.
    **poly(isobornyl acrylate/isobornyl methacrylate/|isobutyl acrylate) block polymer, obtained as follows; 100 g of isododecane were introduced into a 1 litre reactor then the temperature was increased to heat it from ambient temperature (25° C.) to 90° C. in 1 hour.
  • [0857]
    Next, at 90° C. over one hour, 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 d'Akzo Nobel) were added.
  • [0858]
    The mixture was kept at 1 h 30 at 90° C.
  • [0859]
    Next, 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were introduced into the previous mixture, still at 90° C. and over 30 minutes.
  • [0860]
    The mixture was kept at 90° C. for 3 hours then cooled.
  • [0861]
    A solution was obtained with 50% of the active polymer substance in isododecane.
  • [0862]
    A polymer was obtained comprising a first sequence or poly(isobornyl acrylate/isobornyl methacrylate) block with a Tg of 110° C., a second isobutyl polyacrylate sequence with a Tg of −20° C. and an intermediate sequence which was a random isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate polymer.
  • [0863]
    Said polymer had a mass average molecular mass of 100300 g/mol and a number average molecular mass of 22800 g/mol, i.e. a polydispersity index I of 4.40. The lipstick composition was prepared by heating the non volatile oils to 60° C., with magnetic stirring. The sequenced polymer was introduced into a beaker along with the isododecane, and the whole was stirred with a Rayneri stirrer. When a transparent liquid was observed, the magnetic pigment was introduced and stirring was continued for 20 minutes with Rayneri stirring.
  • [0864]
    Said composition could be applied using an applicator as shown in FIG. 2.
  • [0865]
    Drying of the composition was sufficiently slow to allow the formation of a pattern by exposure to the magnetic field, which modified the orientation of the magnetic pigment particles. However, the composition set quickly enough for the pattern not to have time to be destroyed after the field was removed.
  • Example B Nail Varnish
  • [0866]
  • [0000]
    Nitrocellulose 11
    N-ethyl o,p-toluenesulfonamide 5
    Alkyde resin 10
    Isopropanol 4
    Magnetic pigments* 0.5
    Butyl acetate/ethyl acetate 50/50 Qsp 100
    *Nacres containing at least 14% of Fe3O4, referenced COLORONA PATINA GOLD (117288), and sold by MERCK.
  • [0867]
    The appearance of such a nail varnish can be changed by applying a magnetic field before the varnish has had time to dry.
  • [0868]
    The expression “in the range” should be understood as including the limits of the range, and “comprising a” should be understood as signifying “comprising at least one”.

Claims (30)

  1. 1. A method of making up keratinous substances, especially the skin, lips, hair, or nails, the method comprising:
    a) applying to the keratinous substances at least one make-up composition comprising:
    i) at least one volatile solvent; and
    ii) particles with non-zero magnetic susceptibility; and
    b) applying a magnetic field to the deposit to modify the orientation and/or displace at least some of said particles with non-zero magnetic susceptibility.
  2. 2. A method according to claim 1, in which the composition comprises at least one film-forming polymer.
  3. 3. A method according to claim 2, in which the film-forming polymer is a sequenced polymer.
  4. 4. A method according to claim 3, in which the sequenced polymer comprises at least three distinct sequences.
  5. 5. A method according to claim 1, in which the volatile solvent is an organic solvent.
  6. 6. A method according to claim 5, in which the volatile solvent comprises at least one volatile oil.
  7. 7. A method according to claim 6, in which the volatile oil is a hydrocarbon oil.
  8. 8. A method according to claim 6, in which the volatile oil is a silicone oil.
  9. 9. A method according to claim 7, in which the volatile oil comprises isododecane.
  10. 10. A method according to claim 1, in which the particles with non-zero magnetic susceptibility are pigments.
  11. 11. A method according to claim 1, in which the magnetic particles comprise metallic iron, in particular soft iron.
  12. 12. A method according to claim 1, in which the magnetic field is applied to form at least one pattern on the composition.
  13. 13. A method according to claim 1, in which the magnetic field is exerted by a permanent magnet.
  14. 14. A method according to claim 1, in which the magnetic field is exerted by an electromagnet.
  15. 15. A method according to claim 13, in which the magnetic field is a rotary field.
  16. 16. A method according to claim 1, in which at least one region of the surface coated with the composition is not exposed to the magnetic field.
  17. 17. A method according to claim 1, in which the composition is applied using a cosmetic applicator.
  18. 18. A method according to claim 1, in which the deposit is allowed to dry after application of the magnetic field.
  19. 19. A method according to claim 1, in which the deposit is formed on the lips.
  20. 20. A method according to claim 1, in which the deposit is formed on the nails.
  21. 21. A kit for making up keratinous substances, comprising:
    a make-up composition comprising:
    i) at least one volatile solvent; and
    ii) particles with non-zero magnetic susceptibility; and
    a magnetic device.
  22. 22. A kit according to claim 21, in which the make-up composition further comprises at least one film-forming polymer.
  23. 23. A kit according to claim 21, in which the magnetic device includes a permanent magnet.
  24. 24. A kit according to claim 21, in which the composition is for application to the lips.
  25. 25. A kit according to claim 21, in which the composition is contained in a packaging and application device comprising a receptacle and an applicator.
  26. 26. A kit according to claim 25, in which the applicator comprises a rod provided at one end with an application member and at the other end with a grip member.
  27. 27. A kit according to claim 20, in which the volatile solvent comprises at least one volatile oil.
  28. 28. A cosmetic composition comprising:
    at least one volatile solvent; and
    magnetic bodies comprising metallic iron.
  29. 29. A composition according to claim 28, in which the volatile solvent is a volatile oil.
  30. 30. A composition according to claim 28, comprising at least one film-forming polymer.
US11663977 2004-10-05 2005-07-08 Method of Applying Makeup to a Surface and a Kit for Implementing such a Method Abandoned US20090130037A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
FR0410501A FR2876011B1 (en) 2004-10-05 2004-10-05 Method makeup of a support and kit for the implementation of such process
FR0410501 2004-10-05
US61992804 true 2004-10-20 2004-10-20
US11663977 US20090130037A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup to a Surface and a Kit for Implementing such a Method
PCT/FR2005/050563 WO2006037905A1 (en) 2004-10-05 2005-07-08 Method for making up keratinous materials and kit therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11663977 US20090130037A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup to a Surface and a Kit for Implementing such a Method

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2005/050563 A-371-Of-International WO2006037905A1 (en) 2004-10-05 2005-07-08 Method for making up keratinous materials and kit therefor

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11242900 Continuation-In-Part US20060088483A1 (en) 2004-10-05 2005-10-05 Kit and method of applying makeup

Publications (1)

Publication Number Publication Date
US20090130037A1 true true US20090130037A1 (en) 2009-05-21

Family

ID=34949907

Family Applications (7)

Application Number Title Priority Date Filing Date
US11664003 Abandoned US20080124288A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup by Means of a Magnetic Composition Incorporating at Least one Coloring Agent Having Optical Properties that are Sensitive to an External Stimulus
US11663975 Abandoned US20080127990A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup to a Surface by Means of a Magnetic Composition Including Reflective Particles Having Metallic Luster
US11663772 Active 2030-10-20 US9609934B2 (en) 2004-10-05 2005-07-08 Method of applying makeup by means of a magnetic composition including at least one interferential pigment
US11663977 Abandoned US20090130037A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup to a Surface and a Kit for Implementing such a Method
US11663978 Abandoned US20080050324A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Differactive Pigment
US11663776 Abandoned US20080044443A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Coloring Agent Producing a Color by Absorbing at Least a Fraction of the Visible Spectrum
US11242901 Abandoned US20060088484A1 (en) 2004-10-05 2005-10-05 Method of applying makeup to a surface and a kit for implementing such a method

Family Applications Before (3)

Application Number Title Priority Date Filing Date
US11664003 Abandoned US20080124288A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup by Means of a Magnetic Composition Incorporating at Least one Coloring Agent Having Optical Properties that are Sensitive to an External Stimulus
US11663975 Abandoned US20080127990A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup to a Surface by Means of a Magnetic Composition Including Reflective Particles Having Metallic Luster
US11663772 Active 2030-10-20 US9609934B2 (en) 2004-10-05 2005-07-08 Method of applying makeup by means of a magnetic composition including at least one interferential pigment

Family Applications After (3)

Application Number Title Priority Date Filing Date
US11663978 Abandoned US20080050324A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Differactive Pigment
US11663776 Abandoned US20080044443A1 (en) 2004-10-05 2005-07-08 Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Coloring Agent Producing a Color by Absorbing at Least a Fraction of the Visible Spectrum
US11242901 Abandoned US20060088484A1 (en) 2004-10-05 2005-10-05 Method of applying makeup to a surface and a kit for implementing such a method

Country Status (6)

Country Link
US (7) US20080124288A1 (en)
EP (7) EP1799069A1 (en)
JP (7) JP4841555B2 (en)
ES (6) ES2602182T3 (en)
FR (1) FR2876011B1 (en)
WO (8) WO2006037907A1 (en)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050238979A1 (en) * 2004-04-08 2005-10-27 Christophe Dumousseaux Compositions for application to the skin, to the lips, to the nails, and/or to hair
US20050257335A1 (en) * 2004-04-08 2005-11-24 Christophe Dumousseaux Composition for application to the skin, to the lips, to the nails, and/or to hair
US20060039876A1 (en) * 2002-10-02 2006-02-23 Christophe Dumousseaux Compositions to be applied to the skin and the integuments
US20060041054A1 (en) * 2002-10-02 2006-02-23 Christophe Dumousseaux Compositions to be applied to the skin and the integuments
US20060088483A1 (en) * 2004-10-05 2006-04-27 Ludovic Thevenet Kit and method of applying makeup
US20080044366A1 (en) * 2004-04-08 2008-02-21 L'oreal S.A. Compositions for application to the skin, to the lips, to the nails, and/or to hair
US20080044443A1 (en) * 2004-10-05 2008-02-21 L'oreal Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Coloring Agent Producing a Color by Absorbing at Least a Fraction of the Visible Spectrum
US20090081261A1 (en) * 2005-07-08 2009-03-26 L'oreal Liquid foundation, a makeup method, and a kit for implementing such a method
US20100310489A1 (en) * 2007-12-05 2010-12-09 L'oreal Cosmetic makeup and/or care process using a siloxane resin and a film-forming polymer
US20110020261A1 (en) * 2009-06-29 2011-01-27 L'ORéAL S.A. Long wear, waterproof mascara composition with water washability
US20110020257A1 (en) * 2009-06-29 2011-01-27 L'oreal S.A. Composition comprising a polyol, a sugar silicone surfactant and a oil-soluble polar modified polymer
US20110020263A1 (en) * 2009-06-01 2011-01-27 L'oreal Composition containing a block polymer and a nonvolatile ester oil
US20110038819A1 (en) * 2009-06-29 2011-02-17 L'ORéAL S.A. Composition comprising a sugar silicone surfactant and a oil-soluble polar modified polymer
US20120156270A1 (en) * 2009-07-07 2012-06-21 L'oreal Method for smoothing out the skin by filling in recessed portions
US8544475B2 (en) 2005-08-30 2013-10-01 L'oreal Packaging and applicator assembly including a magnetic device, a magnetic device, a method of forming a pattern on a nail using a magnetic device and a method of manufacturing a magnetic device
US8647611B2 (en) 2009-06-29 2014-02-11 L'oréal Composition containing a polyol and a reaction product
US8663667B2 (en) 2009-06-29 2014-03-04 L'oreal Refreshing cream foundation in gel form
US8747868B2 (en) 2010-12-30 2014-06-10 L'oreal Reaction product of a polar modified polymer and an alkoxysilane and a composition containing the reaction product
US8828366B2 (en) 2009-06-29 2014-09-09 L'oreal Hydrating cream foundation in emulsion form
US8932566B2 (en) 2009-06-29 2015-01-13 L'oreal Composition comprising a polyol and a oil-soluble polar modified polymer
US8992903B2 (en) 2002-09-26 2015-03-31 L'oreal Composition comprising at least one block polymer and at least one gelling agent
US9023387B2 (en) 2008-12-09 2015-05-05 L'oreal Transfer-resistant emulsion containing a surfactant
US9040593B2 (en) 2008-12-16 2015-05-26 L'oreal Water-insoluble reaction product of a polyamine and an oil-soluble high carbon polar modified polymer
US9073804B2 (en) 2010-12-21 2015-07-07 Dow Global Technologies Llc Enhanced conversion of syngas to propylene
US9192561B2 (en) 2010-05-14 2015-11-24 L'oreal Compositions containing hyperbranched polyol and acrylic film former
US9226888B2 (en) 2011-12-30 2016-01-05 L'oreal Compositions containing an acrylic film former, a tackifier and an ester
US20160068004A1 (en) * 2010-03-03 2016-03-10 Sicpa Holding Sa Security thread or stripe, magnetic orienting cylinder, and methods of making and using magnetic orienting cylinder
US20160074303A1 (en) * 2014-09-17 2016-03-17 The Procter & Gamble Company Method of making a skin care product
US9308396B2 (en) 2008-12-16 2016-04-12 L'oreal Transfer-resistant and long wear foundation in emulsion form containing oil absorbing powders
US9345657B2 (en) 2011-12-30 2016-05-24 L'oreal Compositions containing a silicon resin and a tackifying agent
US9351919B2 (en) 2011-12-30 2016-05-31 L'oreal Compositions containing silicon resin, oil and gelling agent
US9649261B2 (en) 2004-10-05 2017-05-16 L'oreal Method of applying makeup to a surface and a kit for implementing such a method

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8734421B2 (en) 2003-06-30 2014-05-27 Johnson & Johnson Consumer Companies, Inc. Methods of treating pores on the skin with electricity
US20050260146A1 (en) * 2004-04-08 2005-11-24 Xavier Blin Set of at least two solid compositions for application to the skin, to the lips, to the nails, and/or to hair
US20070149091A1 (en) * 2005-11-03 2007-06-28 Evelyn Viohl Interactive doll
US20070148105A1 (en) * 2005-12-22 2007-06-28 Donald Spector Compositions and methods comprising magnetic particles for health use
US20070292463A1 (en) * 2005-12-22 2007-12-20 Donald Spector Compositions and methods comprising energizable particles for health use
US20070183998A1 (en) * 2005-12-28 2007-08-09 L'oreal Cosmetic composition
US20110028776A1 (en) * 2006-02-06 2011-02-03 Donald Spector Packaged Magnetic Therapeutic Topical Preparation
FR2901476B1 (en) * 2006-05-29 2011-12-23 Oreal Method for coloring dark skin
WO2008007334A3 (en) * 2006-07-10 2008-04-03 Sylvie Epinette A makeup composition
FR2903304A1 (en) * 2006-07-10 2008-01-11 Oreal Fluid cosmetic composition e.g. for lips, comprises organic volatile solvents and color-effect particles contained in medium that enables color effect to develop progressively after composition is being applied
FR2903897B1 (en) * 2006-07-21 2012-01-13 Oreal Cosmetic composition comprising an interference pigment and a coloring agent generating a color by an absorption phenomenon
FR2903891B1 (en) * 2006-07-21 2011-03-04 Oreal Variety of cosmetic compositions comprising at least red interference pigment
EP1897529A1 (en) * 2006-07-21 2008-03-12 L'oreal Cosmetic composition
FR2903893B1 (en) * 2006-07-21 2012-11-16 Oreal cosmetic composition comprising at least one interference pigment and at least one coloring agent sensitive to an external stimulus
FR2903890B1 (en) * 2006-07-21 2012-12-28 Oreal cosmetic composition comprising at least one INTERFERENTIAL gigments and Magnetic body
US20080095723A1 (en) 2006-07-21 2008-04-24 L'oreal Cosmetic composition
EP1889599A1 (en) * 2006-07-21 2008-02-20 L'oreal Make-up composition and process for dark skin
FR2903892B1 (en) * 2006-07-21 2012-08-10 Oreal Cosmetic assembly comprising two compositions to be applied successively.
US20080268003A1 (en) * 2006-11-17 2008-10-30 L'oreal Covering cosmetic composition
US20080226574A1 (en) * 2006-11-17 2008-09-18 L'oreal Line of cosmetic compositions
FR2908642A1 (en) * 2006-11-17 2008-05-23 Oreal Cosmetic composition, useful for make-up of keratinous matter, comprises multilayer interference pigment, coloring agent, reflective pigment and diffractive pigment
FR2908638A1 (en) * 2006-11-17 2008-05-23 Oreal Cosmetic composition, useful for make-up of keratinous matter, comprises multilayer interference pigment, coloring agent, reflective pigment and diffractive pigment
FR2908636A1 (en) * 2006-11-17 2008-05-23 Oreal Cosmetic composition, useful for make-up of keratinous matter, comprises multilayer interference pigment, coloring agent, reflective pigment and diffractive pigment
FR2908643A1 (en) * 2006-11-17 2008-05-23 Oreal Cosmetic composition, useful for make-up of keratinous matter, comprises multilayer interference pigment, coloring agent, reflective pigment and diffractive pigment
FR2910295B3 (en) * 2006-12-20 2009-09-18 Oreal Method for making up keratin materials and kit for the implementation of such a process
FR2912041B1 (en) 2007-02-06 2011-03-11 Oreal Set for making up the eyelashes, having an application device comprising a heater
DE102007007610A1 (en) * 2007-02-13 2008-08-14 Beiersdorf Ag A method for increasing skin elasticity and / or strengthening the elasticity of the skin
CA2693598C (en) 2007-08-01 2016-11-08 Avon Products, Inc. Cosmetic applicator and method of making
FR2925320B1 (en) * 2007-12-20 2012-06-08 Oreal Method makeup lips.
EP2157138B1 (en) 2008-05-26 2010-11-24 Eckart GmbH Thin, platy iron pigments, method for their manufacture and use
FR2940181B1 (en) * 2008-12-23 2011-05-13 Oreal Packaging assembly comprising a magnetization device module.
US20120089232A1 (en) 2009-03-27 2012-04-12 Jennifer Hagyoung Kang Choi Medical devices with galvanic particulates
US8017038B2 (en) * 2009-09-04 2011-09-13 Samsung Sdi Co., Ltd. Green phosphor and plasma display panel including the same
JPWO2011052224A1 (en) 2009-11-02 2013-03-14 株式会社福元技研 Skin cosmetic kneaded compositions and methods for their preparation, use of skin cosmetic kneaded composition
DE102009054428B3 (en) * 2009-11-25 2010-12-30 Barthel, Hans-Jürgen Device for designing surface of fingernail, comprises a decorative mass containing magnetic particle, magnets, which align the magnetic particle inside the mass, and a magnet holder, which holds the magnets in defined distance to the mass
KR20110091461A (en) * 2010-02-05 2011-08-11 존슨 앤드 존슨 컨수머 캄파니즈, 인코포레이티드 Lip compositions comprising galvanic particulates
WO2011121510A3 (en) 2010-03-29 2011-12-15 L'oreal Device for the application of fibers to human keratinous fibers
US9192550B2 (en) * 2010-06-22 2015-11-24 Avon Products, Inc. Magnetically-oriented cosmetic fibers
CA2804272A1 (en) * 2010-07-08 2012-01-12 Johnson & Johnson Consumer Companies, Inc. Skin care emulsion composition
FR2968520B1 (en) 2010-12-14 2013-08-30 Oreal Element for applying fibers on human keratin fibers
DE202012005980U1 (en) * 2011-06-28 2012-10-17 Capardoni & C. S.R.L. Bottle system for magnetic nail polish
US9390676B2 (en) 2011-09-21 2016-07-12 International Business Machines Corporation Tactile presentation of information
CN102512332A (en) * 2011-12-19 2012-06-27 袁永欢 Preparation method for three-dimensional magnetic nail polish and product
FR2984727B1 (en) * 2011-12-23 2014-01-03 Oreal Skin makeup Method
FR2984728B1 (en) * 2011-12-23 2014-07-18 Oreal Makeup Skin
WO2013093890A3 (en) * 2011-12-23 2013-09-19 L'oreal Method for making up the skin
JP5916438B2 (en) * 2012-03-01 2016-05-11 三菱鉛筆株式会社 Liquid cosmetic
WO2013180391A1 (en) * 2012-05-31 2013-12-05 (주)아모레퍼시픽 Nail art device, system, and method using magnetism
US9125471B2 (en) * 2012-06-06 2015-09-08 Tair Jiuh Enterprise Co., Ltd. Cosmetic container
US9168209B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US9168393B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US9320687B2 (en) 2013-03-13 2016-04-26 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US9168394B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
FR3014299B1 (en) * 2013-12-09 2015-12-18 Oreal Necessary to cosmetic product comprising at least one batch of cosmetic product and an applicator
FR3015868B1 (en) 2013-12-30 2017-04-28 Lvmh Rech Device for packaging and applying a liquid composition
US9289046B1 (en) * 2014-12-22 2016-03-22 Jamberry Nails, LLC Nail stud application tool
US20180002493A1 (en) * 2015-01-06 2018-01-04 Lvmh Recherche Poly(ethylene glycol) methacrylate microgels, preparation method and uses

Citations (93)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030967A (en) * 1959-10-06 1962-04-24 Peyron Antoine Francois Process for applying cosmetic material to the skin
US3461885A (en) * 1967-05-09 1969-08-19 Howard W Coveney Cosmetic fingernail mask assembly
US3516422A (en) * 1967-06-26 1970-06-23 Chemway Corp Magnetic false eyelashes and method of affixing to the eyelids
US3836537A (en) * 1970-10-07 1974-09-17 Minnesota Mining & Mfg Zwitterionic polymer hairsetting compositions and method of using same
US3910862A (en) * 1970-01-30 1975-10-07 Gaf Corp Copolymers of vinyl pyrrolidone containing quarternary ammonium groups
US4055377A (en) * 1976-08-03 1977-10-25 Minnesota Mining And Manufacturing Company Magnetically orientable retroreflectorization particles
US4318844A (en) * 1979-06-20 1982-03-09 Bayer Aktiengesellschaft Inorganic pigments with improved gloss and distribution in lacquer binders
US4470715A (en) * 1979-10-26 1984-09-11 Reuchlin Johan George Dispenser/applicator for nail polish and the like
US5000688A (en) * 1987-12-22 1991-03-19 Clamp Esther L Magnetic stencil letters
US5030669A (en) * 1988-05-27 1991-07-09 Minnesota Mining And Manufacturing Company Pigment dispersions
US5040914A (en) * 1989-02-23 1991-08-20 Georg Karl Geka-Brush Gmbh Device for the application of cosmetic materials
US5122418A (en) * 1985-12-09 1992-06-16 Shiseido Company Ltd. Composite powder and production process
US5127952A (en) * 1986-10-10 1992-07-07 Rohne-Poulenc Chimie Core/oxide/dye pigmentary colorants
US5133805A (en) * 1987-08-28 1992-07-28 Toda Kogyo Corp. Plate-like hematite particles, a pigment comprising the same and showing a golden color, and a process for producing the same
US5188815A (en) * 1988-08-31 1993-02-23 Merck Patent Gesellschaft Mit Beschrankter Haftung Thermochromic mixtures
US5199808A (en) * 1989-11-30 1993-04-06 L'oreal Device for application of a liquid or pasty product to a surface
US5206011A (en) * 1989-02-16 1993-04-27 Amalia Inc. Quick-drying nail enamel compositions
US5291345A (en) * 1990-07-20 1994-03-01 Mitsubishi Electric Corp. Apparatus for applying magnetic field and magneto-optical disk storage having such apparatus
US5316026A (en) * 1992-01-31 1994-05-31 Fashion Nails, Inc. Method and apparatus for applying decoration to nails
US5356617A (en) * 1990-05-14 1994-10-18 Kobo Products, Inc. Pigment-material-microsphere complexes and their production
US5380359A (en) * 1992-03-31 1995-01-10 Kyowa Hakko Kogyo Co., Ltd. Cosmetics based on naturally derived melanin-coated pigments
US5486354A (en) * 1992-01-31 1996-01-23 L'oreal Cosmetic make-up composition containing a transparent titanium oxide and silicon oxide pigment
US5512273A (en) * 1994-10-31 1996-04-30 Almell, Ltd. Top nail coat composition
US5562706A (en) * 1995-01-11 1996-10-08 Electro Anti Age, Inc. Device for cosmetic and relaxation treatment
US5643672A (en) * 1992-09-11 1997-07-01 L'oreal Cosmetic composition containing solid particles coated with an amphoteric polymer
US5705093A (en) * 1993-08-06 1998-01-06 Merck Patent Gesellschaft Mit Beschrankter Haftung Thermochromic media
US5725483A (en) * 1994-02-22 1998-03-10 Podolsky; Grigory Massaging device
US5856653A (en) * 1996-06-13 1999-01-05 Boudreaux; Nona Mascara extender
US5873375A (en) * 1998-02-26 1999-02-23 Johnson; James Fingernail stencil system using precut design masks
US5913631A (en) * 1998-01-30 1999-06-22 Landry; Tina M. Cosmetic applicator
US5931166A (en) * 1998-12-22 1999-08-03 Weber; Paul J. Fingernail decorating
US5954871A (en) * 1996-12-16 1999-09-21 L'oreal Composite melanin pigment in the form of particles comprising a wax-based spherical core, preparation processes and cosmetic uses
US6033648A (en) * 1998-06-26 2000-03-07 Societe L'oreal S.A. Artificial tanning compositions comprising iron oxide nanopigments
US6033655A (en) * 1996-10-01 2000-03-07 E-L Management Corp. Magnetic cosmetic compositions
US6117435A (en) * 1998-06-24 2000-09-12 Color Access, Inc. Natural look cosmetic compositions
US6136907A (en) * 1997-08-29 2000-10-24 Taisei Chemical Industries, Ltd. Process for producing dispersion of functional compound
US6177093B1 (en) * 1999-03-17 2001-01-23 Color Access, Inc. Method and system for color customizing cosmetic mass products
US6203909B1 (en) * 1997-01-09 2001-03-20 Ciba Specialty Chemicals Corporation Composite pigment
US6209548B1 (en) * 1999-03-08 2001-04-03 Beauty Innovations Method and apparatus for nail coloring
US6213131B1 (en) * 1999-12-23 2001-04-10 Larry Vien Fingernail stenciling system
US6254876B1 (en) * 1997-12-22 2001-07-03 L'oreal Transfer-resistant cosmetic composition comprising a dispersion of polymer particles in a liquid fatty phase
US20010022025A1 (en) * 1999-09-01 2001-09-20 Skipper Adam M. Magnetic shaving system
US6299979B1 (en) * 1999-12-17 2001-10-09 Ppg Industries Ohio, Inc. Color effect coating compositions having reflective organic pigments
US20010033766A1 (en) * 2000-03-03 2001-10-25 Jean-Louis Gueret Device having a magnetic applicator and/or wiper member
US20020012683A1 (en) * 2000-03-17 2002-01-31 Jean-Christophe Henrion Cosmetic composition comprising at least one ingredient chosen from compounds of formula (1) and salts thereof, use thereof as colouring agent, and novel compounds of formulae (IIa), (IIIa), (IVa), (Va), and (VIa), and salts thereof
US20020015965A1 (en) * 2000-07-27 2002-02-07 Sweeting Linda Marie Efficient synthesis of triboluminescent lanthanide complexes
US20020031870A1 (en) * 1993-11-30 2002-03-14 Bryant Frank Randolph Transistor structure and method for making same
US6358495B1 (en) * 1999-03-26 2002-03-19 Shiseido Co., Ltd. Titanium-silica complex and cosmetic preparation compounding the same
US20020039562A1 (en) * 1998-10-02 2002-04-04 Masaru Kobayashi Pigments and extender pigments with enhanced skin adhesion for cosmetic preparations
US20020041853A1 (en) * 2000-06-05 2002-04-11 Showa Denko K.K. Cosmetic composition
US6387498B1 (en) * 1998-12-07 2002-05-14 Flex Products, Inc. Bright metal flake based pigments
US20020064509A1 (en) * 2000-10-03 2002-05-30 Sabine Grimm Method for producing a goniochromatic effect comprising applying to skin a cosmetic composition comprising at least one continuous lipophilic phase and at least one goniochromatic pigment
US20020070121A1 (en) * 1999-10-22 2002-06-13 The Board Of Trustees Of The University Of Illinois Family of discretely sized slicon nanoparticles and method for producing the same
US6432423B1 (en) * 1997-12-19 2002-08-13 L'oreal Use of hyperbranched polymers and dendrimers comprising a particular group as film-forming agent, film-forming compositions comprising same and use particularly in cosmetics and pharmaceutics
US6432386B1 (en) * 1999-11-19 2002-08-13 L'oreal, S.A. Cosmetic compositions comprising at least one polymer with specific characteristics and at least one thickening polymer
US20020117084A1 (en) * 2000-12-19 2002-08-29 Kazuyuki Hayashi Black composite iron oxide pigment, and paint and resin composition using the same
US20020134282A1 (en) * 2001-03-23 2002-09-26 Eckart Gmbh & Co. Kg Soft iron pigments
US6477398B1 (en) * 1997-11-13 2002-11-05 Randell L. Mills Resonant magnetic susceptibility imaging (ReMSI)
US20020182383A1 (en) * 2001-05-07 2002-12-05 Flex Products, Inc. Methods for producing imaged coated articles by using magnetic pigments
US6503761B1 (en) * 1999-10-19 2003-01-07 Kimberly-Clark Worldwide, Inc. Selective removal of contaminants from a surface using articles having magnets
US20030007942A1 (en) * 1999-10-19 2003-01-09 Koenig David W. Selective removal of contaminants from a surface using colored particles and articles having magnets
US20030012752A1 (en) * 2000-12-12 2003-01-16 Isabelle Bara Transparent or translucent cosmetic compositions colored by pigments
US6517818B1 (en) * 1998-01-04 2003-02-11 Coty B.V. Lip or care stick which contains vitamins
US6517628B1 (en) * 1999-04-16 2003-02-11 Merck Patent Gmbh Pigment mixture
US20030031870A1 (en) * 2001-07-31 2003-02-13 Flex Products, Inc. Diffractive pigment flakes and compositions
US20030039621A1 (en) * 2001-04-10 2003-02-27 L'oreal Two-coat make-up product, its use and a kit containing the make-up product
US20030064086A1 (en) * 2001-08-31 2003-04-03 Danuvio Carrion Cosmetic compositions comprising nanoparticles and processes for using the same
US6545809B1 (en) * 1999-10-20 2003-04-08 Flex Products, Inc. Color shifting carbon-containing interference pigments
US20030072602A1 (en) * 2001-04-13 2003-04-17 L'oreal Device comprising magnetizable particles
US6582684B1 (en) * 1999-03-23 2003-06-24 Xsight International Body coating composition
US20030118531A1 (en) * 2000-10-31 2003-06-26 Richard Kolodziej Cosmetic composition containing a photochromic colouring agent and its use for skin and/or skin appendage make-up and/or care
US20030134761A1 (en) * 2001-07-20 2003-07-17 L'oreal Foaming composition based on silica and on cationic polymer
US20030180535A1 (en) * 2000-08-31 2003-09-25 Masaakira Horino Novel composite powders and cosmetics containing the same
US20030180232A1 (en) * 2000-09-11 2003-09-25 Nobuaki Ishii Cosmetic composition
US20040001869A1 (en) * 2002-04-10 2004-01-01 Yuko Yago Cosmetic composition
US20040009309A1 (en) * 2002-07-15 2004-01-15 Flex Products, Inc., A Jds Uniphase Company Magnetic planarization of pigment flakes
US6679825B2 (en) * 2002-02-05 2004-01-20 Pedro J. Alicea Pain eliminator
US20040012683A1 (en) * 2001-01-23 2004-01-22 Masafumi Yamasaki Shake compensating device for optical devices
WO2004028490A2 (en) * 2002-09-26 2004-04-08 L'oréal Cosmetic composition comprising a sequenced polymer and a plasticizer
US20040109837A1 (en) * 1995-01-30 2004-06-10 L'oreal Cosmetic composition comprising a silicone-containing compound and a fatty acid ester
US20040175338A1 (en) * 2003-03-06 2004-09-09 L'oreal Cosmetic composition containing an ester and a pasty compound
US20050025728A1 (en) * 2002-12-24 2005-02-03 L'oreal Cosmetic compositions and contrast cards for characterizing them
US20050036964A1 (en) * 2002-12-24 2005-02-17 L'oreal Makeup compositions for dark skins
US20050118122A1 (en) * 2002-07-19 2005-06-02 Societe L'oreal S.A. Goniochromatic/light reflective cosmetic makeup compositions
US20050191337A1 (en) * 1999-03-31 2005-09-01 L'oreal S.A. Patch with a magnetic field effect
US20050238979A1 (en) * 2004-04-08 2005-10-27 Christophe Dumousseaux Compositions for application to the skin, to the lips, to the nails, and/or to hair
US20060018854A1 (en) * 2002-10-02 2006-01-26 Christophe Dumousseaux Cosmetic compositions
US20060041054A1 (en) * 2002-10-02 2006-02-23 Christophe Dumousseaux Compositions to be applied to the skin and the integuments
US20060051382A1 (en) * 2004-09-07 2006-03-09 Richard Vidal Compositions for body hairs and/or head hair
US20060088484A1 (en) * 2004-10-05 2006-04-27 Ludovic Thevenet Method of applying makeup to a surface and a kit for implementing such a method
US20060099160A1 (en) * 2002-10-02 2006-05-11 Christophe Dumousseaux Composition intended to be applied to the skin and the integuments
US20060118663A1 (en) * 2002-08-20 2006-06-08 Steiner Gmbh & Co. Kg Copper-based metal flakes, in particular comprising aluminum, and method for production thereof
US20070009454A1 (en) * 2005-07-08 2007-01-11 L'oreal Make-up method involving a magnetic interaction

Family Cites Families (185)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3623732A (en) * 1969-12-15 1971-11-30 Maurice E Peeples Golf putting cup with random-direction ball ejection means
DE2103898C2 (en) 1970-01-30 1983-07-28 Gaf Corp
DE2054934A1 (en) 1970-11-07 1972-08-24
US3791386A (en) 1971-09-27 1974-02-12 Mc Donald Medical Lab Instr Co Tracheotomy method and means
DE2313331C2 (en) * 1973-03-17 1986-11-13 Merck Patent Gmbh, 6100 Darmstadt, De
LU67772A1 (en) 1973-06-08 1975-03-06
FR2268512B1 (en) 1974-04-23 1978-01-20 Laguerre Rene
CA1051737A (en) 1974-04-23 1979-04-03 Rene Laguerre Method, product and apparatus for cleaning the cuticle
JPS5711008B2 (en) 1974-07-16 1982-03-02
JPS51137733A (en) * 1975-05-26 1976-11-27 Toyota Motor Corp Method to form a pattern coating with pictures or letters
US4031307A (en) 1976-05-03 1977-06-21 Celanese Corporation Cationic polygalactomannan compositions
US4223009A (en) * 1977-06-10 1980-09-16 Gaf Corporation Hair preparation containing vinyl pyrrolidone copolymer
CA1091160A (en) 1977-06-10 1980-12-09 Paritosh M. Chakrabarti Hair preparation containing vinyl pyrrolidone copolymer
US4131576A (en) * 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
JPS5581809A (en) * 1978-12-18 1980-06-20 Inoue Japax Res Inc Use of toiletry with magnetic substance
FR2478998B1 (en) * 1980-04-01 1983-02-18 Oreal
DE3273489D1 (en) 1981-11-30 1986-10-30 Ciba Geigy Ag Mixtures of quaternary polymeric acrylic ammonium salts, quaternary mono- or oligomeric ammonium salts and surfactants, their preparation and their use in cosmetic compositions
EP0096459A3 (en) 1982-05-14 1985-12-18 Imperial Chemical Industries Plc Polymerisation process
DE3301024A1 (en) 1983-01-14 1984-07-19 Bayer Ag Process for production of stable loesungen cationic methine dyes and their use for spinnfaerben
US4614366A (en) 1983-11-18 1986-09-30 Exactident, Inc. Nail identification wafer
JPS61112008A (en) 1984-11-05 1986-05-30 Hida Seisakusho:Kk Production of multi-colored lipstick
US4728571A (en) 1985-07-19 1988-03-01 Minnesota Mining And Manufacturing Company Polysiloxane-grafted copolymer release coating sheets and adhesive tapes
FR2588759B3 (en) * 1985-10-23 1988-01-15 Morel Charles Means for applying magnetic fields to the body care
FR2594130B1 (en) 1985-12-09 1991-09-27 Shiseido Co Ltd composite powder, process for its preparation and its cosmetic use
US4693935A (en) 1986-05-19 1987-09-15 Minnesota Mining And Manufacturing Company Polysiloxane-grafted copolymer pressure sensitive adhesive composition and sheet materials coated therewith
JPS63175670A (en) 1987-01-13 1988-07-20 Kansai Paint Co Ltd Forming method for coating film with pattern
US5066485A (en) 1987-02-06 1991-11-19 Revlon, Inc. Cosmetic compositions comprising oil-in-water emulsion containing pigment
JPH01242513A (en) 1988-03-25 1989-09-27 Shiseido Co Ltd Make-up cosmetic
JP2630428B2 (en) 1988-05-24 1997-07-16 株式会社コーセー Coloring pigments and cosmetics containing the same
US5061481A (en) 1989-03-20 1991-10-29 Kobayashi Kose Co., Ltd. Cosmetic composition having acryl-silicone graft copolymer
US5219560A (en) * 1989-03-20 1993-06-15 Kobayashi Kose Co., Ltd. Cosmetic composition
JPH02111340A (en) 1988-10-21 1990-04-24 Omron Tateisi Electron Co Electronic tonometer
EP0412704B1 (en) 1989-08-07 1999-04-28 THE PROCTER &amp; GAMBLE COMPANY Hair conditioning and styling compositions
US4972037A (en) 1989-08-07 1990-11-20 Minnesota Mining And Manufacturing Company Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith
US4981902A (en) * 1989-08-07 1991-01-01 Minnesota Mining And Manufacturing Company Polysiloxane-grafted copolymer non-pressure sensitive topical binder composition and method of coating therewith
US4981903A (en) * 1989-08-07 1991-01-01 Minnesota Mining And Manufacturing Company Polysiloxane-grafter copolymer topical binder composition with novel hydrophilic monomers and method of coating therewith
US5209924A (en) * 1989-08-07 1993-05-11 Minnesota Mining And Manufacturing Company Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith
DE69006556D1 (en) 1989-08-07 1994-03-24 Procter & Gamble Hair conditioning and hair styling agents.
US4991631A (en) 1989-09-07 1991-02-12 Pease Windamatic Systems, Inc. Lead straightening and trimming apparatus
JP2992591B2 (en) * 1989-12-18 1999-12-20 ジーイー東芝シリコーン株式会社 Silica core - silicone shell body, emulsions and methods of producing the emulsion dispersed containing the same
JP2805373B2 (en) 1990-03-30 1998-09-30 株式会社資生堂 Fluorescent cosmetics
JPH03286463A (en) 1990-03-31 1991-12-17 Toshiba Corp Cassette loading device
US5162410A (en) 1990-04-13 1992-11-10 Dow Corning Corporation Hot-melt silicon pressure sensitive adhesives with phenyl-containing siloxane fluid additive and related methods and articles
JPH04108710A (en) * 1990-08-27 1992-04-09 Yoko Shiga Magnetic cosmetic
JPH04198117A (en) 1990-11-29 1992-07-17 Fuji Kasei Kk Make-up cosmetic
JPH04292664A (en) 1991-03-19 1992-10-16 Kao Corp Complex pigment and cosmetic containing the same
JPH0517710A (en) 1991-07-08 1993-01-26 Kansai Paint Co Ltd Metallic paint and method for coating therewith
ES2089822T3 (en) 1992-05-12 1996-10-01 Minnesota Mining & Mfg Polymers for cosmetics and personal care products.
US5468477A (en) * 1992-05-12 1995-11-21 Minnesota Mining And Manufacturing Company Vinyl-silicone polymers in cosmetics and personal care products
CA2135186A1 (en) 1992-05-15 1993-11-25 Peter M. Torgerson Adhesive agent containing polysiloxane-grafted polymer, and cosmetic compositions thereof
US5520917A (en) 1992-07-27 1996-05-28 Suzuki Yushi Industries Co., Ltd. Materials in the form of colored spherical fine particles
DE69332875T2 (en) 1992-07-28 2003-12-04 Mitsubishi Chem Corp A hair cosmetic composition
US5307847A (en) 1992-09-24 1994-05-03 Stanford Pavenick Applicator for fluid products
JP3393903B2 (en) 1992-11-30 2003-04-07 株式会社資生堂 Makeup cosmetics
US5330747A (en) 1993-02-03 1994-07-19 Dow Corning Corporation Cosmetics with enhanced durability
JP2543825B2 (en) * 1993-04-28 1996-10-16 根本特殊化学株式会社 Phosphorescent phosphor
GB9309992D0 (en) * 1993-05-14 1993-06-30 Heller Harry G Tribochromic compounds and their applications
US5476901A (en) 1993-06-24 1995-12-19 The Procter & Gamble Company Siloxane modified polyolefin copolymers
JPH09502467A (en) * 1993-07-08 1997-03-11 エイベリ デニソン コーポレイション Acrylic - saturated rubber hybrid pressure sensitive adhesive
US5472798A (en) 1993-07-16 1995-12-05 Nissan Motor Co., Ltd. Coloring structure having reflecting and interfering functions
JP3424083B2 (en) 1993-08-05 2003-07-07 株式会社コーセー Oil-based solid cosmetic
EP0715638B1 (en) 1993-08-23 2000-05-24 THE PROCTER &amp; GAMBLE COMPANY Silicone grafted thermoplastic elastomeric copolymers and hair and skin care compositions containing the same
US5882774A (en) 1993-12-21 1999-03-16 Minnesota Mining And Manufacturing Company Optical film
US5393526A (en) * 1994-02-07 1995-02-28 Elizabeth Arden Company, Division Of Conopco, Inc. Cosmetic compositions
WO1995023537A1 (en) 1994-03-05 1995-09-08 Peter Nermerich Fingernail lengthening process and device
JP3573481B2 (en) 1994-03-22 2004-10-06 帝人化成株式会社 Resin composition
JP3241535B2 (en) 1994-05-10 2001-12-25 ポーラ化成工業株式会社 Organic - by blending the inorganic composite pigments cosmetics
JP3286463B2 (en) * 1994-05-10 2002-05-27 ポーラ化成工業株式会社 Organic - inorganic composite pigment and manufacturing method thereof
JPH0838992A (en) 1994-05-25 1996-02-13 Nisshin Steel Co Ltd Production of pattern-coated metal plate
JP3531214B2 (en) 1994-05-31 2004-05-24 Nok株式会社 Makeup cosmetic resin co - coating ferromagnetic preparation of aqueous-suspension liquid of fine particles
DE4419173A1 (en) 1994-06-01 1995-12-07 Basf Ag Magnetizable multi-coated metallic luster pigments
JP3166482B2 (en) 1994-06-07 2001-05-14 日産自動車株式会社 Coloring structure having a reflection interference effects
JPH08127513A (en) 1994-10-28 1996-05-21 Pola Chem Ind Inc Cosmetic
DE69600437T2 (en) * 1995-01-06 1998-12-10 Ciba Geigy Ag Triboluminescent lanthanide complexes iii
FR2735689B1 (en) 1995-06-21 1997-08-01 Oreal Composition comprising a polymer particle dispersion in a nonaqueous medium
US5849275A (en) 1995-06-26 1998-12-15 Revlon Consumer Products Corporation Glossy transfer resistant cosmetic compositions
US5658579A (en) 1995-07-31 1997-08-19 The Procter & Gamble Company Cosmetic powder compositions having improved skin coverage
US5658574A (en) * 1995-10-13 1997-08-19 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Cleansing compositions with dendrimers as mildness agents
US6071503A (en) * 1995-11-07 2000-06-06 The Procter & Gamble Company Transfer resistant cosmetic compositions
KR0171254B1 (en) 1996-01-05 1999-02-18 안영호 A case for keeping make-up
JPH09188830A (en) 1996-01-05 1997-07-22 Nisshin Steel Co Ltd Highly bright metallic pigment
FR2744632B1 (en) 1996-02-13 1998-03-27 Oreal Use of an aqueous suspension of microfibrils of natural origin for the preparation of cosmetic or dermatological compositions, cosmetic or dermatological compositions and applications
FR2746640B1 (en) * 1996-03-27 1998-05-07 Oreal Use in cosmetics of a hydrophilic copolymers and rigid skeleton, grafted with hydrophobic and flexible MACROMONOMERS; compositions used
US5919441A (en) 1996-04-01 1999-07-06 Colgate-Palmolive Company Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups
ES2202511T3 (en) 1996-04-22 2004-04-01 Merck Patent Gmbh Sio2 coated particles.
US5849318A (en) 1996-06-26 1998-12-15 Kao Corporation Oil-based solid cosmetic composition
JPH1087437A (en) * 1996-09-10 1998-04-07 Matsui Shikiso Kagaku Kogyosho:Kk Light-stimulable nail enamel
JPH10158541A (en) 1996-11-27 1998-06-16 Nisshin Steel Co Ltd Dark silver color metallic pigment excellent in weather resistance and brilliance
JPH10158450A (en) 1996-11-28 1998-06-16 Shin Etsu Polymer Co Ltd Polyvinyl chloride resin composition for food packaging
US5874069A (en) 1997-01-24 1999-02-23 Colgate-Palmolive Company Cosmetic composition containing silicon-modified amides as thickening agents and method of forming same
FR2758697B1 (en) 1997-01-28 1999-03-12 Daniel Vadot Processes and prosthetic reconstitution devices for restoration or modification of a natural nail
DE69820206D1 (en) 1997-04-11 2004-01-15 Nissan Motor Optical interference fiber and their use
JPH1112493A (en) 1997-06-24 1999-01-19 Kose Corp Composite powder and composition containing the same
US6186686B1 (en) * 1997-07-02 2001-02-13 Henlopen Manufacturing Co., Inc. Applicator for liquid material
US6051216A (en) * 1997-08-01 2000-04-18 Colgate-Palmolive Company Cosmetic composition containing siloxane based polyamides as thickening agents
JP2987770B2 (en) 1997-10-14 1999-12-06 光彌 坂本 Lipstick container
US6117574A (en) * 1997-10-20 2000-09-12 Agency Of Industrial Science And Technology Triboluminescent inorganic material and a method for preparation thereof
JP3788680B2 (en) 1997-12-22 2006-06-21 花王株式会社 The organic and inorganic composite particles and their preparation
KR20010034065A (en) 1998-01-13 2001-04-25 스프레이그 로버트 월터 Visible Mirror Film Glitter
KR20010034064A (en) 1998-01-13 2001-04-25 스프레이그 로버트 월터 Color Shifting Film Glitter
FR2776509B1 (en) 1998-03-31 2001-08-10 Oreal Topical composition containing a fatty acid ester or alcohol branched C24 to c28
FR2777178B1 (en) * 1998-04-10 2000-06-02 Oreal Makeup kit combining a goniochromatic pigment and a monochromatic pigment having a color of goniochromatic pigment, its uses
FR2778561B1 (en) * 1998-05-14 2001-04-20 Oreal optical brighteners such as whiteners
US5981680A (en) 1998-07-13 1999-11-09 Dow Corning Corporation Method of making siloxane-based polyamides
US6515717B1 (en) 1998-08-28 2003-02-04 Reveo, Inc. Computer-based system for producing multi-color multilayer images on substrates using dry multi-colored cholesteric liquid crystal (CLC) pigment materials applied to binder material patterns
JP2000168667A (en) 1998-10-02 2000-06-20 Honda Motor Co Ltd Motorcycle
JP3049641B2 (en) 1998-11-09 2000-06-05 勢津子 井伊 Health beautiful skin pad using the bath salts
CA2257738A1 (en) * 1999-01-04 2000-07-04 Robyn Barwin Liquid dispenser and applicator
JP4036560B2 (en) * 1999-02-23 2008-01-23 三菱鉛筆株式会社 Liquid cosmetic
FR2791560B1 (en) * 1999-03-31 2003-03-07 Oreal Nail polish has hammered effect
FR2791570B1 (en) 1999-03-31 2003-04-04 Oreal Patch magnetic field effect
US6592882B2 (en) * 1999-05-26 2003-07-15 Color Access, Inc. Cosmetic compositions containing fluorescent minerals
JP3511083B2 (en) 1999-08-06 2004-03-29 独立行政法人産業技術総合研究所 High brightness stress light-emitting material, manufacturing method and light emitting method using the same that
JP3856602B2 (en) 1999-08-25 2006-12-13 株式会社トキワ Articulated cosmetic container
DE10039377A1 (en) 1999-09-03 2001-03-08 Merck Patent Gmbh Thermochromic liquid crystal medium, useful for the production of inks for the security marking of documents, comprises a liquid crystalline mixture and a chiral doping agent.
US6585947B1 (en) * 1999-10-22 2003-07-01 The Board Of Trustess Of The University Of Illinois Method for producing silicon nanoparticles
FR2802416B1 (en) * 1999-12-20 2002-07-19 Oreal Cosmetic composition comprising an aminophenol derivative
US6428773B1 (en) 2000-01-13 2002-08-06 Color Access, Inc. Shadow-effect cosmetic composition
JP2001270805A (en) 2000-01-18 2001-10-02 Sakura Color Prod Corp Brilliant cosmetic
US20030019501A1 (en) 2000-01-18 2003-01-30 Keiko Hirota Brilliant cosmetics
JP2001302432K1 (en) * 2000-04-28 2001-10-31
CA2382142C (en) 2000-07-12 2005-08-23 L'oreal Device for packaging and/or applying a product containing fibres comprising at least a magnetised or magnetizable element
US7022752B2 (en) 2000-09-01 2006-04-04 Toda Kogyo Corporation Composite particles, process for producing the same, and pigment, paint and resin composition using the same
FR2814677B1 (en) 2000-10-03 2003-04-18 Oreal Cosmetic composition has hydrophilic continuous phase comprising a multilayer goniochromatic pigment and its use in makeup
JP2002114641A (en) * 2000-10-10 2002-04-16 Asanuma Corporation Water-based manicure preparation
JP2002138010A (en) * 2000-10-31 2002-05-14 Nippon Sheet Glass Co Ltd Cosmetic
JP2002194349A (en) 2000-12-27 2002-07-10 National Institute Of Advanced Industrial & Technology Stress-induced light-emitting material and method for producing the same
WO2002053114A1 (en) 2001-01-03 2002-07-11 Giovanni Cosmetics, Inc. Magnetic body care compositions
DE10114446A1 (en) * 2001-03-23 2002-09-26 Eckart Standard Bronzepulver Flat iron pigment used paints, plastics, printing, glass, ceramics and cosmetics comprises reduced carbonyl iron powder
FR2823103B1 (en) * 2001-04-10 2003-05-23 Oreal coat makeup product containing a goniochromatic pigment and a monochromatic pigment and makeup kit containing this product
DE10120179A1 (en) * 2001-04-24 2002-10-31 Merck Patent Gmbh Colored pigment, used in paint, lacquer, printing ink, plastics, ceramic material, glaze, cosmetic, laser marking or pigment preparation, comprises multi-coated flaky substrate covered with absorbent pigment particles
US7253249B2 (en) 2003-04-22 2007-08-07 Arizona Chemical Company Ester-terminated poly(ester-amide) in personal care products
FR2825246B1 (en) * 2001-06-05 2004-06-04 Oreal A packaging and / or application comprising fibers comprising particles capable of absorbing a liquid or a compound in solution in the liquid or dissolving in a liquid
DE10128354B4 (en) * 2001-06-13 2004-11-18 Georg Fischer Rohrverbindungstechnik Gmbh Device for preventing unintentional restarting of
JP4790931B2 (en) 2001-06-18 2011-10-12 株式会社コーセー Multicolor based cosmetic obtained by filling method and the method of multicolor system cosmetics
JP3798266B2 (en) * 2001-06-25 2006-07-19 花王株式会社 Colored mica titanium
US20030082121A1 (en) * 2001-07-13 2003-05-01 Benny Borsakian Color changing nail polish
EP1424372A4 (en) 2001-08-10 2007-10-31 Nihonkoken Kougyo Kabushiki Ka Titanium oxide composition having high brilliant color, composition comprising coating and cosmetic composition, and method for their preparation
GB0119726D0 (en) 2001-08-14 2001-10-03 Qinetiq Ltd Triboluminescent materials and devices
DE10142659A1 (en) 2001-08-31 2003-03-20 Aventis Pharma Gmbh Using multi-substituted indan-1-ol. Systems for the production of medicaments for the prophylaxis or treatment of obesity
JP2005516890A (en) 2001-09-03 2005-06-09 ロレアル Foundation compositions containing an interference pigment
FR2829022B1 (en) * 2001-09-03 2004-09-24 Oreal foundation composition comprising interference pigments
JP3737411B2 (en) * 2001-10-24 2006-01-18 パイロットインキ株式会社 Metallic luster Chonetsu discoloration liquid composition
JP3837488B2 (en) * 2001-11-30 2006-10-25 独立行政法人産業技術総合研究所 Mechano-luminescent material
JP2003199620A (en) 2001-12-28 2003-07-15 Masachika Hattori Beautification system
EP1487396A1 (en) 2002-03-28 2004-12-22 THE PROCTER &amp; GAMBLE COMPANY Emulsion compositions
DE10219296B4 (en) * 2002-04-25 2013-08-08 Coty B.V. Temperature-dependent mascara
DE10219196B4 (en) 2002-04-29 2010-03-18 Kermi Gmbh End fittings
US8637055B2 (en) 2002-06-24 2014-01-28 Ahava-Dead Sea Laboratories Ltd. Cosmetic compositions containing small magnetic particles
JP4159025B2 (en) 2002-07-12 2008-10-01 独立行政法人産業技術総合研究所 High brightness mechano-luminescent material and a method of manufacturing the same
JP4456797B2 (en) 2002-07-12 2010-04-28 花王株式会社 Lip cosmetics
FR2842417B1 (en) 2002-07-19 2005-01-21 Oreal cosmetic Composition
DE20211045U1 (en) 2002-07-23 2002-09-19 Nordmann Michael An apparatus for heat treatment of the human vaginal or Kolonbereichs
JP3918051B2 (en) 2002-07-29 2007-05-23 独立行政法人産業技術総合研究所 Mechanochemical luminescent material and a method of manufacturing the same
US7306809B2 (en) 2002-09-13 2007-12-11 Lipo Chemicals, Inc. Optically activated particles for use in cosmetic compositions
EP1411069B1 (en) 2002-09-26 2010-11-03 L'Oréal Block copolymers and cosmetic compositions containing such polymers
FR2845277B1 (en) 2002-10-02 2006-06-16 Oreal destiny composition has to be applied on the skin and appendages
JP2004123681A (en) 2002-10-07 2004-04-22 Kao Corp Makeup cosmetic
ES2298483T3 (en) 2002-10-18 2008-05-16 L'oreal Cosmetic composition associated at least two dyes, of which at least one is a photochromic dyestuff.
DE60311622D1 (en) * 2002-10-18 2007-03-22 Oreal A cosmetic composition comprising an oil phase and a dye from the group of naphthopyrans and method
US20050276767A1 (en) 2002-10-18 2005-12-15 L'oreal Composition containing an oily phase and a naphthopyran dye, cosmetic treatment processes
US20040228818A1 (en) * 2002-10-18 2004-11-18 L'oreal Cosmetic composition combining at least two dyes including at least one photochromic dye
FR2845899B1 (en) 2002-10-18 2006-05-19 Oreal Cosmetic composition comprising an oily phase and an naptopyranne dye, and processes for the cosmetic treatment
FR2846277B1 (en) 2002-10-28 2005-01-21 Brieuc Chauris Process for the manufacture of assembled parts cover a surface
JP4040957B2 (en) * 2002-11-18 2008-01-30 Agcエスアイテック株式会社 Silica-containing cosmetics
FR2847812B1 (en) 2002-11-28 2006-04-14 Louis Dubertret Cosmetic composition comprising nanoparticles as fluorescent pigments
US7329287B2 (en) * 2002-12-06 2008-02-12 L'oreal S.A. Oxidation dye composition for keratin fibers, comprising at least one oxidation dye, at least one associative polymer, at least one nonionic cellulose-based compound not comprising a C8-C30 fatty chain, and at least one cationic polymer with a charge density of greater than 1 meq/g and not comprising a C8-C30 fatty chain
FR2848826B1 (en) 2002-12-24 2005-03-18 Oreal cosmetic compositions and contrast maps to characterize the
JP2004224782A (en) * 2003-01-22 2004-08-12 Yukipuramu Company:Kk Cosmetic containing magnetic material powder
US20070231940A1 (en) 2003-01-27 2007-10-04 L'oreal S.A. Composition and method of dyeing keratin fibers comprising luminescent semiconductive nanoparticles
FR2850271B1 (en) 2003-01-27 2006-08-04 Oreal Using luminescent semiconductor nanoparticles in cosmetics
JP2004231610A (en) 2003-01-31 2004-08-19 Kao Corp Water in oil-type emulsion cosmetic
US20040228890A1 (en) 2003-02-25 2004-11-18 Xavier Blin Two-coat cosmetic product, its uses, and makeup kit including the product
FR2851463B1 (en) * 2003-02-25 2006-06-30 Oreal bilayer cosmetic product, its uses and makeup kit containing product
JP2004307424A (en) 2003-04-09 2004-11-04 Kao Corp Makeup cosmetic
JP4186191B2 (en) 2003-06-05 2008-11-26 山栄化学株式会社 Plant sterol ester-containing hair cosmetic feel improvers
JP4277738B2 (en) 2003-06-05 2009-06-10 山栄化学株式会社 Hair dye
JP4634019B2 (en) 2003-08-26 2011-02-23 チタン工業株式会社 Low magnetization of black pigment powder and its preparation and use thereof
US20060280705A1 (en) 2004-03-31 2006-12-14 Werner Bruechert Cosmetic preparation
US20050257715A1 (en) 2004-04-08 2005-11-24 Christophe Dumousseaux Compositions for application to the skin, to the lips, to the nails, and/or to hair
US20050260146A1 (en) 2004-04-08 2005-11-24 Xavier Blin Set of at least two solid compositions for application to the skin, to the lips, to the nails, and/or to hair
US7981404B2 (en) 2004-04-08 2011-07-19 L'oreal S.A. Composition for application to the skin, to the lips, to the nails, and/or to hair
US7648298B2 (en) 2004-04-28 2010-01-19 L'oreal Packaging and applicator device comprising a support and a distribution member, and a method of applying a product with such a device
FR2869510B1 (en) 2004-04-28 2006-07-14 Oreal A packaging and applicator device comprising a magnetic carrier and an application member
US9205918B2 (en) 2013-11-08 2015-12-08 Goodrich Corporation System and method for maximum braking

Patent Citations (101)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030967A (en) * 1959-10-06 1962-04-24 Peyron Antoine Francois Process for applying cosmetic material to the skin
US3461885A (en) * 1967-05-09 1969-08-19 Howard W Coveney Cosmetic fingernail mask assembly
US3516422A (en) * 1967-06-26 1970-06-23 Chemway Corp Magnetic false eyelashes and method of affixing to the eyelids
US3910862A (en) * 1970-01-30 1975-10-07 Gaf Corp Copolymers of vinyl pyrrolidone containing quarternary ammonium groups
US3836537A (en) * 1970-10-07 1974-09-17 Minnesota Mining & Mfg Zwitterionic polymer hairsetting compositions and method of using same
US4055377A (en) * 1976-08-03 1977-10-25 Minnesota Mining And Manufacturing Company Magnetically orientable retroreflectorization particles
US4318844A (en) * 1979-06-20 1982-03-09 Bayer Aktiengesellschaft Inorganic pigments with improved gloss and distribution in lacquer binders
US4470715A (en) * 1979-10-26 1984-09-11 Reuchlin Johan George Dispenser/applicator for nail polish and the like
US5122418A (en) * 1985-12-09 1992-06-16 Shiseido Company Ltd. Composite powder and production process
US5127952A (en) * 1986-10-10 1992-07-07 Rohne-Poulenc Chimie Core/oxide/dye pigmentary colorants
US5133805A (en) * 1987-08-28 1992-07-28 Toda Kogyo Corp. Plate-like hematite particles, a pigment comprising the same and showing a golden color, and a process for producing the same
US5000688A (en) * 1987-12-22 1991-03-19 Clamp Esther L Magnetic stencil letters
US5030669A (en) * 1988-05-27 1991-07-09 Minnesota Mining And Manufacturing Company Pigment dispersions
US5188815A (en) * 1988-08-31 1993-02-23 Merck Patent Gesellschaft Mit Beschrankter Haftung Thermochromic mixtures
US5206011A (en) * 1989-02-16 1993-04-27 Amalia Inc. Quick-drying nail enamel compositions
US5040914A (en) * 1989-02-23 1991-08-20 Georg Karl Geka-Brush Gmbh Device for the application of cosmetic materials
US5199808A (en) * 1989-11-30 1993-04-06 L'oreal Device for application of a liquid or pasty product to a surface
US5356617A (en) * 1990-05-14 1994-10-18 Kobo Products, Inc. Pigment-material-microsphere complexes and their production
US5291345A (en) * 1990-07-20 1994-03-01 Mitsubishi Electric Corp. Apparatus for applying magnetic field and magneto-optical disk storage having such apparatus
US5316026A (en) * 1992-01-31 1994-05-31 Fashion Nails, Inc. Method and apparatus for applying decoration to nails
US5486354A (en) * 1992-01-31 1996-01-23 L'oreal Cosmetic make-up composition containing a transparent titanium oxide and silicon oxide pigment
US5380359A (en) * 1992-03-31 1995-01-10 Kyowa Hakko Kogyo Co., Ltd. Cosmetics based on naturally derived melanin-coated pigments
US5643672A (en) * 1992-09-11 1997-07-01 L'oreal Cosmetic composition containing solid particles coated with an amphoteric polymer
US5705093A (en) * 1993-08-06 1998-01-06 Merck Patent Gesellschaft Mit Beschrankter Haftung Thermochromic media
US20020031870A1 (en) * 1993-11-30 2002-03-14 Bryant Frank Randolph Transistor structure and method for making same
US5725483A (en) * 1994-02-22 1998-03-10 Podolsky; Grigory Massaging device
US5512273A (en) * 1994-10-31 1996-04-30 Almell, Ltd. Top nail coat composition
US5562706A (en) * 1995-01-11 1996-10-08 Electro Anti Age, Inc. Device for cosmetic and relaxation treatment
US20040109837A1 (en) * 1995-01-30 2004-06-10 L'oreal Cosmetic composition comprising a silicone-containing compound and a fatty acid ester
US5856653A (en) * 1996-06-13 1999-01-05 Boudreaux; Nona Mascara extender
US6033655A (en) * 1996-10-01 2000-03-07 E-L Management Corp. Magnetic cosmetic compositions
US5954871A (en) * 1996-12-16 1999-09-21 L'oreal Composite melanin pigment in the form of particles comprising a wax-based spherical core, preparation processes and cosmetic uses
US6203909B1 (en) * 1997-01-09 2001-03-20 Ciba Specialty Chemicals Corporation Composite pigment
US6136907A (en) * 1997-08-29 2000-10-24 Taisei Chemical Industries, Ltd. Process for producing dispersion of functional compound
US6477398B1 (en) * 1997-11-13 2002-11-05 Randell L. Mills Resonant magnetic susceptibility imaging (ReMSI)
US6432423B1 (en) * 1997-12-19 2002-08-13 L'oreal Use of hyperbranched polymers and dendrimers comprising a particular group as film-forming agent, film-forming compositions comprising same and use particularly in cosmetics and pharmaceutics
US6254876B1 (en) * 1997-12-22 2001-07-03 L'oreal Transfer-resistant cosmetic composition comprising a dispersion of polymer particles in a liquid fatty phase
US6517818B1 (en) * 1998-01-04 2003-02-11 Coty B.V. Lip or care stick which contains vitamins
US5913631A (en) * 1998-01-30 1999-06-22 Landry; Tina M. Cosmetic applicator
US5873375A (en) * 1998-02-26 1999-02-23 Johnson; James Fingernail stencil system using precut design masks
US6117435A (en) * 1998-06-24 2000-09-12 Color Access, Inc. Natural look cosmetic compositions
US6033648A (en) * 1998-06-26 2000-03-07 Societe L'oreal S.A. Artificial tanning compositions comprising iron oxide nanopigments
US20020039562A1 (en) * 1998-10-02 2002-04-04 Masaru Kobayashi Pigments and extender pigments with enhanced skin adhesion for cosmetic preparations
US6387498B1 (en) * 1998-12-07 2002-05-14 Flex Products, Inc. Bright metal flake based pigments
US5931166A (en) * 1998-12-22 1999-08-03 Weber; Paul J. Fingernail decorating
US6209548B1 (en) * 1999-03-08 2001-04-03 Beauty Innovations Method and apparatus for nail coloring
US6177093B1 (en) * 1999-03-17 2001-01-23 Color Access, Inc. Method and system for color customizing cosmetic mass products
US6582684B1 (en) * 1999-03-23 2003-06-24 Xsight International Body coating composition
US6358495B1 (en) * 1999-03-26 2002-03-19 Shiseido Co., Ltd. Titanium-silica complex and cosmetic preparation compounding the same
US20050191337A1 (en) * 1999-03-31 2005-09-01 L'oreal S.A. Patch with a magnetic field effect
US6517628B1 (en) * 1999-04-16 2003-02-11 Merck Patent Gmbh Pigment mixture
US20010022025A1 (en) * 1999-09-01 2001-09-20 Skipper Adam M. Magnetic shaving system
US20030007942A1 (en) * 1999-10-19 2003-01-09 Koenig David W. Selective removal of contaminants from a surface using colored particles and articles having magnets
US6503761B1 (en) * 1999-10-19 2003-01-07 Kimberly-Clark Worldwide, Inc. Selective removal of contaminants from a surface using articles having magnets
US6545809B1 (en) * 1999-10-20 2003-04-08 Flex Products, Inc. Color shifting carbon-containing interference pigments
US20020070121A1 (en) * 1999-10-22 2002-06-13 The Board Of Trustees Of The University Of Illinois Family of discretely sized slicon nanoparticles and method for producing the same
US6432386B1 (en) * 1999-11-19 2002-08-13 L'oreal, S.A. Cosmetic compositions comprising at least one polymer with specific characteristics and at least one thickening polymer
US6299979B1 (en) * 1999-12-17 2001-10-09 Ppg Industries Ohio, Inc. Color effect coating compositions having reflective organic pigments
US6213131B1 (en) * 1999-12-23 2001-04-10 Larry Vien Fingernail stenciling system
US20010033766A1 (en) * 2000-03-03 2001-10-25 Jean-Louis Gueret Device having a magnetic applicator and/or wiper member
US20020012683A1 (en) * 2000-03-17 2002-01-31 Jean-Christophe Henrion Cosmetic composition comprising at least one ingredient chosen from compounds of formula (1) and salts thereof, use thereof as colouring agent, and novel compounds of formulae (IIa), (IIIa), (IVa), (Va), and (VIa), and salts thereof
US20020041853A1 (en) * 2000-06-05 2002-04-11 Showa Denko K.K. Cosmetic composition
US20020015965A1 (en) * 2000-07-27 2002-02-07 Sweeting Linda Marie Efficient synthesis of triboluminescent lanthanide complexes
US20030180535A1 (en) * 2000-08-31 2003-09-25 Masaakira Horino Novel composite powders and cosmetics containing the same
US20030180232A1 (en) * 2000-09-11 2003-09-25 Nobuaki Ishii Cosmetic composition
US20020064509A1 (en) * 2000-10-03 2002-05-30 Sabine Grimm Method for producing a goniochromatic effect comprising applying to skin a cosmetic composition comprising at least one continuous lipophilic phase and at least one goniochromatic pigment
US20030118531A1 (en) * 2000-10-31 2003-06-26 Richard Kolodziej Cosmetic composition containing a photochromic colouring agent and its use for skin and/or skin appendage make-up and/or care
US20030012752A1 (en) * 2000-12-12 2003-01-16 Isabelle Bara Transparent or translucent cosmetic compositions colored by pigments
US20020117084A1 (en) * 2000-12-19 2002-08-29 Kazuyuki Hayashi Black composite iron oxide pigment, and paint and resin composition using the same
US20040012683A1 (en) * 2001-01-23 2004-01-22 Masafumi Yamasaki Shake compensating device for optical devices
US20020134282A1 (en) * 2001-03-23 2002-09-26 Eckart Gmbh & Co. Kg Soft iron pigments
US20030039621A1 (en) * 2001-04-10 2003-02-27 L'oreal Two-coat make-up product, its use and a kit containing the make-up product
US20030072602A1 (en) * 2001-04-13 2003-04-17 L'oreal Device comprising magnetizable particles
US20020182383A1 (en) * 2001-05-07 2002-12-05 Flex Products, Inc. Methods for producing imaged coated articles by using magnetic pigments
US20030134761A1 (en) * 2001-07-20 2003-07-17 L'oreal Foaming composition based on silica and on cationic polymer
US20030031870A1 (en) * 2001-07-31 2003-02-13 Flex Products, Inc. Diffractive pigment flakes and compositions
US20030064086A1 (en) * 2001-08-31 2003-04-03 Danuvio Carrion Cosmetic compositions comprising nanoparticles and processes for using the same
US6679825B2 (en) * 2002-02-05 2004-01-20 Pedro J. Alicea Pain eliminator
US20040001869A1 (en) * 2002-04-10 2004-01-01 Yuko Yago Cosmetic composition
US20040009309A1 (en) * 2002-07-15 2004-01-15 Flex Products, Inc., A Jds Uniphase Company Magnetic planarization of pigment flakes
US7258900B2 (en) * 2002-07-15 2007-08-21 Jds Uniphase Corporation Magnetic planarization of pigment flakes
US20050118122A1 (en) * 2002-07-19 2005-06-02 Societe L'oreal S.A. Goniochromatic/light reflective cosmetic makeup compositions
US20060118663A1 (en) * 2002-08-20 2006-06-08 Steiner Gmbh & Co. Kg Copper-based metal flakes, in particular comprising aluminum, and method for production thereof
WO2004028490A2 (en) * 2002-09-26 2004-04-08 L'oréal Cosmetic composition comprising a sequenced polymer and a plasticizer
US20060134044A1 (en) * 2002-09-26 2006-06-22 Xavier Blin Cosmetic composition comprising a sequenced polymer and a plasticizer
US20060099160A1 (en) * 2002-10-02 2006-05-11 Christophe Dumousseaux Composition intended to be applied to the skin and the integuments
US20060018854A1 (en) * 2002-10-02 2006-01-26 Christophe Dumousseaux Cosmetic compositions
US20060041054A1 (en) * 2002-10-02 2006-02-23 Christophe Dumousseaux Compositions to be applied to the skin and the integuments
US20060039876A1 (en) * 2002-10-02 2006-02-23 Christophe Dumousseaux Compositions to be applied to the skin and the integuments
US20050025728A1 (en) * 2002-12-24 2005-02-03 L'oreal Cosmetic compositions and contrast cards for characterizing them
US20050036964A1 (en) * 2002-12-24 2005-02-17 L'oreal Makeup compositions for dark skins
US20040175338A1 (en) * 2003-03-06 2004-09-09 L'oreal Cosmetic composition containing an ester and a pasty compound
US20050238979A1 (en) * 2004-04-08 2005-10-27 Christophe Dumousseaux Compositions for application to the skin, to the lips, to the nails, and/or to hair
US20060051382A1 (en) * 2004-09-07 2006-03-09 Richard Vidal Compositions for body hairs and/or head hair
US20060088484A1 (en) * 2004-10-05 2006-04-27 Ludovic Thevenet Method of applying makeup to a surface and a kit for implementing such a method
US20080127990A1 (en) * 2004-10-05 2008-06-05 L'oreal Method of Applying Makeup to a Surface by Means of a Magnetic Composition Including Reflective Particles Having Metallic Luster
US20080044443A1 (en) * 2004-10-05 2008-02-21 L'oreal Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Coloring Agent Producing a Color by Absorbing at Least a Fraction of the Visible Spectrum
US20080050324A1 (en) * 2004-10-05 2008-02-28 L'oreal Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Differactive Pigment
US20080105272A1 (en) * 2004-10-05 2008-05-08 L'oreal Method Of Applying Makeup By Means Of A Magnetic Composition Including At Least One Interferential Pigment
US20080124288A1 (en) * 2004-10-05 2008-05-29 L"Oreal Method of Applying Makeup by Means of a Magnetic Composition Incorporating at Least one Coloring Agent Having Optical Properties that are Sensitive to an External Stimulus
US20070009454A1 (en) * 2005-07-08 2007-01-11 L'oreal Make-up method involving a magnetic interaction

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
21-USC-Chapter-9-subchapter -II, definition of "cosmetic," p. 32. *
Blakely, Richard J.; "Potential Theory in Gravity and Magnetic Applications," 1996, Cambridge University Press; pp. 87-90. *
Kurtus, Ron; "Detection of a Magnetic Field," dated 23-MAY-2004, as captured by internet archive () on 04-JUN-2004 from , pp. 1-5 as provided. *
Merriam-Webster(TM) "Merriam-Webster's Collegiate Dictionary, 1 lth edition," 2003; MERRIAM-WEBSTERS INC; entry for "cosmetic," pp. 1-20. *
Roeben, Scott; "Ferreting Out Funny Money: Fighting Counterfeiting," as captured by interet archive () on 03-FEB-2004 from , pp. 1-7 as provided. *

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8992903B2 (en) 2002-09-26 2015-03-31 L'oreal Composition comprising at least one block polymer and at least one gelling agent
US9017704B2 (en) 2002-09-26 2015-04-28 L'oreal Composition comprising a block polymer and a film-forming agent
US20060039876A1 (en) * 2002-10-02 2006-02-23 Christophe Dumousseaux Compositions to be applied to the skin and the integuments
US20060041054A1 (en) * 2002-10-02 2006-02-23 Christophe Dumousseaux Compositions to be applied to the skin and the integuments
US8007772B2 (en) 2002-10-02 2011-08-30 L'oreal S.A. Compositions to be applied to the skin and the integuments
US20050257335A1 (en) * 2004-04-08 2005-11-24 Christophe Dumousseaux Composition for application to the skin, to the lips, to the nails, and/or to hair
US20080044366A1 (en) * 2004-04-08 2008-02-21 L'oreal S.A. Compositions for application to the skin, to the lips, to the nails, and/or to hair
US7981404B2 (en) 2004-04-08 2011-07-19 L'oreal S.A. Composition for application to the skin, to the lips, to the nails, and/or to hair
US20050238979A1 (en) * 2004-04-08 2005-10-27 Christophe Dumousseaux Compositions for application to the skin, to the lips, to the nails, and/or to hair
US20080050324A1 (en) * 2004-10-05 2008-02-28 L'oreal Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Differactive Pigment
US20060088483A1 (en) * 2004-10-05 2006-04-27 Ludovic Thevenet Kit and method of applying makeup
US20080105272A1 (en) * 2004-10-05 2008-05-08 L'oreal Method Of Applying Makeup By Means Of A Magnetic Composition Including At Least One Interferential Pigment
US9649261B2 (en) 2004-10-05 2017-05-16 L'oreal Method of applying makeup to a surface and a kit for implementing such a method
US9609934B2 (en) 2004-10-05 2017-04-04 L'oreal Method of applying makeup by means of a magnetic composition including at least one interferential pigment
US20080044443A1 (en) * 2004-10-05 2008-02-21 L'oreal Method of Applying Makeup by Means of a Magnetic Composition Including at Least One Coloring Agent Producing a Color by Absorbing at Least a Fraction of the Visible Spectrum
US20080124288A1 (en) * 2004-10-05 2008-05-29 L"Oreal Method of Applying Makeup by Means of a Magnetic Composition Incorporating at Least one Coloring Agent Having Optical Properties that are Sensitive to an External Stimulus
US20090081261A1 (en) * 2005-07-08 2009-03-26 L'oreal Liquid foundation, a makeup method, and a kit for implementing such a method
US8544475B2 (en) 2005-08-30 2013-10-01 L'oreal Packaging and applicator assembly including a magnetic device, a magnetic device, a method of forming a pattern on a nail using a magnetic device and a method of manufacturing a magnetic device
US20100310489A1 (en) * 2007-12-05 2010-12-09 L'oreal Cosmetic makeup and/or care process using a siloxane resin and a film-forming polymer
US9023387B2 (en) 2008-12-09 2015-05-05 L'oreal Transfer-resistant emulsion containing a surfactant
US9040593B2 (en) 2008-12-16 2015-05-26 L'oreal Water-insoluble reaction product of a polyamine and an oil-soluble high carbon polar modified polymer
US9308396B2 (en) 2008-12-16 2016-04-12 L'oreal Transfer-resistant and long wear foundation in emulsion form containing oil absorbing powders
US20110020263A1 (en) * 2009-06-01 2011-01-27 L'oreal Composition containing a block polymer and a nonvolatile ester oil
US9895561B2 (en) 2009-06-01 2018-02-20 L'oreal Composition containing a block polymer and a nonvolatile ester oil
US8663667B2 (en) 2009-06-29 2014-03-04 L'oreal Refreshing cream foundation in gel form
US20110020261A1 (en) * 2009-06-29 2011-01-27 L'ORéAL S.A. Long wear, waterproof mascara composition with water washability
US8828366B2 (en) 2009-06-29 2014-09-09 L'oreal Hydrating cream foundation in emulsion form
US20110020257A1 (en) * 2009-06-29 2011-01-27 L'oreal S.A. Composition comprising a polyol, a sugar silicone surfactant and a oil-soluble polar modified polymer
US8932566B2 (en) 2009-06-29 2015-01-13 L'oreal Composition comprising a polyol and a oil-soluble polar modified polymer
US8663609B2 (en) 2009-06-29 2014-03-04 L'oreal Composition comprising a polyol, a sugar silicone surfactant and a oil-soluble polar modified polymer
US8647611B2 (en) 2009-06-29 2014-02-11 L'oréal Composition containing a polyol and a reaction product
US8597626B2 (en) 2009-06-29 2013-12-03 L'oreal Long wear, waterproof mascara composition with water washability
US20110038819A1 (en) * 2009-06-29 2011-02-17 L'ORéAL S.A. Composition comprising a sugar silicone surfactant and a oil-soluble polar modified polymer
US8652451B2 (en) 2009-06-29 2014-02-18 L'oreal Composition comprising a sugar silicone surfactant and a oil-soluble polar modified polymer
US20120156270A1 (en) * 2009-07-07 2012-06-21 L'oreal Method for smoothing out the skin by filling in recessed portions
US20160068004A1 (en) * 2010-03-03 2016-03-10 Sicpa Holding Sa Security thread or stripe, magnetic orienting cylinder, and methods of making and using magnetic orienting cylinder
US9192561B2 (en) 2010-05-14 2015-11-24 L'oreal Compositions containing hyperbranched polyol and acrylic film former
US9073804B2 (en) 2010-12-21 2015-07-07 Dow Global Technologies Llc Enhanced conversion of syngas to propylene
US8846062B2 (en) 2010-12-30 2014-09-30 L'oreal Reaction product of a polar modified polymer and an alkoxysilane and a composition containing the reaction product
US8747868B2 (en) 2010-12-30 2014-06-10 L'oreal Reaction product of a polar modified polymer and an alkoxysilane and a composition containing the reaction product
US9345657B2 (en) 2011-12-30 2016-05-24 L'oreal Compositions containing a silicon resin and a tackifying agent
US9351919B2 (en) 2011-12-30 2016-05-31 L'oreal Compositions containing silicon resin, oil and gelling agent
US9226888B2 (en) 2011-12-30 2016-01-05 L'oreal Compositions containing an acrylic film former, a tackifier and an ester
US20160074303A1 (en) * 2014-09-17 2016-03-17 The Procter & Gamble Company Method of making a skin care product

Also Published As

Publication number Publication date Type
JP4866360B2 (en) 2012-02-01 grant
EP1799067B1 (en) 2016-08-17 grant
US20080050324A1 (en) 2008-02-28 application
US20060088484A1 (en) 2006-04-27 application
JP2008515864A (en) 2008-05-15 application
JP2008515474A (en) 2008-05-15 application
ES2393790T3 (en) 2012-12-28 grant
FR2876011B1 (en) 2006-12-29 grant
EP1799064B1 (en) 2016-08-17 grant
WO2006037902A1 (en) 2006-04-13 application
EP1799066A1 (en) 2007-06-27 application
JP2008515865A (en) 2008-05-15 application
JP4828540B2 (en) 2011-11-30 grant
ES2602735T3 (en) 2017-02-22 grant
ES2602182T3 (en) 2017-02-20 grant
WO2006037903A1 (en) 2006-04-13 application
JP2008515791A (en) 2008-05-15 application
JP4841556B2 (en) 2011-12-21 grant
US20080105272A1 (en) 2008-05-08 application
WO2006037904A1 (en) 2006-04-13 application
WO2006037907A1 (en) 2006-04-13 application
US20080124288A1 (en) 2008-05-29 application
US20080127990A1 (en) 2008-06-05 application
US9609934B2 (en) 2017-04-04 grant
EP1799065B1 (en) 2016-08-17 grant
EP1799069A1 (en) 2007-06-27 application
WO2006037905A1 (en) 2006-04-13 application
JP2008515863A (en) 2008-05-15 application
EP1799068B1 (en) 2016-08-17 grant
JP2008515790A (en) 2008-05-15 application
EP1799068A1 (en) 2007-06-27 application
JP2008515862A (en) 2008-05-15 application
ES2602181T3 (en) 2017-02-20 grant
FR2876011A1 (en) 2006-04-07 application
ES2601704T3 (en) 2017-02-16 grant
JP4841555B2 (en) 2011-12-21 grant
WO2006054002A1 (en) 2006-05-26 application
EP1796503B1 (en) 2012-08-22 grant
JP4879182B2 (en) 2012-02-22 grant
EP1799066B1 (en) 2016-08-17 grant
EP1799065A1 (en) 2007-06-27 application
JP4800315B2 (en) 2011-10-26 grant
EP1796503A1 (en) 2007-06-20 application
JP4834669B2 (en) 2011-12-14 grant
ES2602734T3 (en) 2017-02-22 grant
WO2006037900A1 (en) 2006-04-13 application
WO2006037906A1 (en) 2006-04-13 application
EP1799067A1 (en) 2007-06-27 application
EP1799064A1 (en) 2007-06-27 application
US20080044443A1 (en) 2008-02-21 application

Similar Documents

Publication Publication Date Title
US20040170586A1 (en) Cosmetic composition containing a polyorganosiloxane polymer
US20090151086A1 (en) Process for dyeing the hair using a composition comprising at least one hydrophobic film-forming polymer, at least one pigment, and at least one volatile solvent
US20030017124A1 (en) Two-coat make-up product containing a goniochromatic pigment and monochrome pigment, and make-up kit containing this product
US20050158260A1 (en) Cosmetic composition containing a polyorganosiloxane polymer
US20050106197A1 (en) Cosmetic composition comprising a block polymer and a non-volatile silicone oil
US20070093619A1 (en) Compositions having enhanced cosmetic properties
US20060110345A1 (en) Cosmetic composition containing a polyorganosiloxane polymer
US20040234612A1 (en) Cosmetic composition comprising at least one polymer particle dispersed in at least one liquid fatty phase and at least one compound plasticizing the polymer
US20030235553A1 (en) Cosmetic compositions containing at least one silicone-polyamide polymer, at least one oil and at least one film-forming agent and methods of using the same
US6726900B2 (en) Long wearing composition for making up eyes, skin, and lips
US20040137028A1 (en) Transfer-free cosmetic composition comprising a dispersion of polymer particles and a specific rheological agent
US20050201961A1 (en) Compositions containing a silicone resin film former and a silicone-containing copolymer
US20050019285A1 (en) Cosmetic composition of foundation type for making up dark skins
WO2004028488A2 (en) Glossy liquid composition comprising a sequenced polymer
US20060099160A1 (en) Composition intended to be applied to the skin and the integuments
US20090317432A1 (en) Felt-tip pen for making up or caring for nails, skin, lips eyelashes or teeth
US20060088484A1 (en) Method of applying makeup to a surface and a kit for implementing such a method
WO2007071706A2 (en) Process for making up comprising the application of compounds a and b, at least one of which is silicone based
WO2004055081A2 (en) Composition for coating keratin fibres, comprising a dispersion of polymer particles
US20060165626A1 (en) Cosmetic composition comprising at least one ester of alkoxylated alcohol and at least one film-forming polymer
US20060039876A1 (en) Compositions to be applied to the skin and the integuments
US20050220728A1 (en) Cosmetic composition comprising a polyglycerolated silicone elastomer
US20100310489A1 (en) Cosmetic makeup and/or care process using a siloxane resin and a film-forming polymer
US20060013791A1 (en) Cosmetic composition comprising a defined silicone polymer and a film former
WO2011056332A1 (en) A low flashpoint cosmetic composition comprising solvents of varying evaporation rates

Legal Events

Date Code Title Description
AS Assignment

Owner name: L OREAL, FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:THEVENET, LUDOVIC;BLIN, XAVIER;REEL/FRAME:019715/0809;SIGNING DATES FROM 20070705 TO 20070706