WO2002058642A2 - Compositions containing heteropolymers and oil-soluble esters and methods of using same - Google Patents

Compositions containing heteropolymers and oil-soluble esters and methods of using same Download PDF

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Publication number
WO2002058642A2
WO2002058642A2 PCT/US2001/047497 US0147497W WO02058642A2 WO 2002058642 A2 WO2002058642 A2 WO 2002058642A2 US 0147497 W US0147497 W US 0147497W WO 02058642 A2 WO02058642 A2 WO 02058642A2
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WIPO (PCT)
Prior art keywords
composition according
chosen
composition
polymer
oil
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PCT/US2001/047497
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French (fr)
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WO2002058642A3 (en
Inventor
Carlos O. Pinzon
Paul Thau
Isabelle Bara
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L'oreal Sa
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Application filed by L'oreal Sa filed Critical L'oreal Sa
Priority to EP01994184A priority Critical patent/EP1347735A2/en
Priority to JP2002558976A priority patent/JP4612276B2/en
Priority to CA002397586A priority patent/CA2397586A1/en
Priority to AU2002246608A priority patent/AU2002246608A1/en
Priority to BR0108275-2A priority patent/BR0108275A/en
Publication of WO2002058642A2 publication Critical patent/WO2002058642A2/en
Publication of WO2002058642A3 publication Critical patent/WO2002058642A3/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • C08K5/103Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/04Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06Lipsticks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention relates to compositions and methods for care of, for treating, and for making-up at least one keratinous material, for example, at least one human keratinous material, such as skin, including the scalp, lips, superficial body growths, including the nails, and/or at least one keratinous fiber which includes hair, eyelashes, and eyebrows.
  • the compositions of the invention comprise at least one structuring polymer and at least one oil-soluble ester comprising at least one free-hydroxy group.
  • the compositions of the present invention may also comprise at least one structuring polymer and at least one UV blocker.
  • the invention may be in the form of a stable composition such as, for example, make-up sticks, lipsticks, transparent sticks, and sunscreen sticks.
  • the compositions may also, for example, provide a molded composition.
  • the invention provides a composition comprising at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom.
  • the composition further comprises at least one liquid fatty phase comprising at least one oil-soluble ester comprising at least one free-hydroxy group.
  • the at least one structuring polymer, e.g., a polyamide polymer, and the at least one oil-soluble ester comprising at least one free-hydroxy group are present in a combined amount effective to stabilize the composition. Due to the good stability of the compositions of the invention, it is possible to add at least one UV blocker to the composition.
  • the expression "at least one” means one or more and thus includes individual components as well as mixtures and combinations thereof.
  • the invention also provides a method for providing stability to a composition
  • a composition comprising including in the composition at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom.
  • the compositions of the invention may also comprise at least one UV blocker.
  • the invention also provides for a cosmetic process for caring for, making up, and/or treating at least one keratinous material comprising applying to at least one keratinous material a cosmetic composition comprising at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom.
  • a cosmetic composition comprising at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom.
  • the composition further comprises at least one oil-soluble ester comprising at least one free- hydroxy group.
  • keratinous material is meant to comprise hair, lips, skin, scalp and superficial body growths such as eyelashes, eyebrows and nails.
  • One subject of the invention is cosmetic and/or dermatological compositions which are useful for the care, make-up and/or treatment of at least one keratinous material which may be of suitable hardness to allow preparation of these compositions in the form of a stick or other structured form which may be stable.
  • stability can be tested by placing the composition in a controlled environment chamber for 8 weeks at 25°C.
  • the physical condition of the sample is inspected as it is placed in the chamber.
  • the sample is then inspected again at 24 hours, 3 days, 1 week, 2 weeks, 4 weeks and 8 weeks.
  • the sample is examined for abnormalities in the composition such as bending or leaning if the composition is in stick form, phase separation, melting, or syneresis.
  • syneresis is the appearance of droplets on the surface of a composition that are visible to the naked eye.
  • Syneresis or oil release from a composition, such as a stick, that is only apparent as a thin, attractive, and glossy, surface coating is not considered a composition that has failed the stability test.
  • the stability is further tested by repeating the 8 week test at 4°C, 37°C, 45°C, and 50°C, and under freeze-thaw conditions.
  • a composition is considered to lack stability if an abnormality that impedes functioning of the composition is observed in any of these tests. The skilled artisan will readily recognize an abnormality that impedes functioning of a composition based on the intended application.
  • the invention applies not only to make-up products for at least one keratinous material such as lip compositions, lip pencils, foundations including foundations which may be cast in the form of a stick or a dish, concealer products, temporary tattoo products, eyeliners, and mascara bars, but also to body hygiene products such as deodorant sticks, and to care products and products for treating at least one keratinous material such as sunscreen (anti- sun) and after-sun products which may be in stick form and also nail products.
  • a deodorant product is a body hygiene product and does not relate to care, make-up, or treatment of keratinous materials, including keratinous fibers, skin, or lips.
  • the present invention may be in the form of a mascara product, an eyeliner product, a foundation product, a lipstick product, a lip balm, a blush for cheeks or eyelids, a deodorant product, a fragrance product, a make-up product for the body, a make-up-removing product, an eyeshadow product, a face powder product, a night or day care product for the face, a concealer product, a hair conditioning product, a sunscreen, a colorant for the skin or hair, or a skin care formula such as, for example, anti-pimple or shaving cut formulas.
  • the composition is in the form of a substantially clear or substantially transparent composition such as, for example, a clear lipstick, clear sunscreen composition, or clear foundation, for example, for concealing skin imperfections.
  • the composition of the present invention may be in a form chosen from a paste, a solid, a gel, and a cream. It may be an emulsion, i.e., an oil-in-water or water-in-oil emulsion, a multiple emulsion, e.g., an oil-in- water-in-oil emulsion or water-in-oil-in-water emulsion, or a solid, rigid, or supple gel, including anhydrous gels.
  • the composition of the invention comprises an external or continuous liquid fatty phase.
  • the composition of the invention is transparent or clear.
  • the composition can also be in a form chosen from a translucent anhydrous gel and a transparent anhydrous gel.
  • the composition can also be a molded composition or cast as a stick or a dish.
  • the composition in one embodiment is a solid or rigid product, such as a molded stick or a poured stick. Structuring polymer
  • the at least one structuring polymer in the composition of the invention is a solid that is not deformable at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e., 101 kPa).
  • the at least one structuring polymer is capable of structuring the composition without opacifying it. This may be due to the fact that the polymer does not crystallize.
  • the structuring of the liquid fatty phase comprising the at least one structuring polymer may be due to the hydrogen interactions between two molecules of the polymer and/or between the molecules of the polymer and the liquid fatty phase.
  • the at least one structuring polymer of the present invention comprises a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom.
  • the at least one structuring polymer further comprises at least one terminal fatty chain chosen from alkyl and alkenyl chains, such as of at least 4 carbon atoms, and further such as comprising from 8 to 120 carbon atoms, bonded to the polymer skeleton via at least one linking group.
  • the terminal fatty chain may, for example, be functionalized.
  • the at least one structuring polymer may also further comprise at least one pendant fatty chain chosen from alkyl and alkenyl chains, such as of at least 4 carbon atoms, and further such as comprising from 8 to 120 carbon atoms, bonded to any carbon or hetero atom of the polymer skeleton via at least one linking group.
  • the pendant fatty chain may, for example, be functionalized.
  • the at least one structuring polymer may comprise at least one pendant fatty chain as defined above, at least one terminal fatty chain as defined above, or both, and one or both types of chains can be functionalized.
  • the at least one structuring polymer comprises at least two hydrocarbon-based repeating units.
  • the at least one structuring polymer comprises at least three hydrocarbon-based repeating units and as an even further example, the at least three repeating units are identical.
  • “functionalized” means comprising at least one functional (reactive) group.
  • functional groups include hydroxyl groups, ether groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, amide groups, halogen containing groups, including fluoro and perfluoro groups, halogen atoms, ester groups, siloxane groups and polysiloxane groups.
  • the expression "functionalized chain” means, for example, an alkyl chain comprising at least one functional group chosen, for example, from those recited above.
  • the hydrogen atoms of at least one alkyl chain may be substituted at least partially with fluorine atoms.
  • these chains may be linked directly to the polymer skeleton or via an ester function or a perfluoro group.
  • polymer means a compound containing at least 2 repeating units, such as, for example, a compound containing at least 3 repeating units, which may be identical.
  • hydrocarbon-based repeating unit includes a repeating unit comprising from 2 to 80 carbon atoms, such as, for example, from 2 to 60 carbon atoms.
  • the at least one hydrocarbon-based repeating unit may also comprise oxygen atoms.
  • the hydrocarbon-based repeating unit may be chosen from saturated and unsaturated hydrocarbon-based repeating units which in turn may be chosen from linear hydrocarbon-based repeating units, branched hydrocarbon-based repeating units and cyclic hydrocarbon-based repeating units.
  • the at least one hydrocarbon-based repeating unit may comprise, for example, at least one hetero atom that is part of the polymer skeleton, i.e., not pendant.
  • the at least one hetero atom may be chosen, for example, from nitrogen, sulphur, and phosphorus.
  • the at least one hetero atom may be a nitrogen atom, such as a non-pendant nitrogen atom.
  • the at least one hydrocarbon-based repeating unit may comprise at least one hetero atom, with the proviso that the at least one hetero atom is not nitrogen.
  • the at least one hetero atom is combined with at least one atom chosen from oxygen and carbon to form a hetero atom group.
  • the hetero atom group comprises a carbonyl group.
  • the at least one repeating unit comprising at least one hetero atom may be chosen, for example, from amide groups, carbamate groups, and urea groups.
  • the at least one repeating unit comprises amide groups forming a polyamide skeleton.
  • the at least one repeating unit comprises carbamate groups and/or urea groups forming a polyurethane skeleton, a polyurea skeleton and/or a polyurethane-polyurea skeleton.
  • the pendant chains for example, can be linked directly to at least one of the hetero atoms of the polymer skeleton.
  • the at least one hydrocarbon-based repeating unit may comprise at least one hetero atom group, with the proviso that the at least one hetero atom group is not an amide group.
  • the polymer skeleton comprises at least one repeating unit chosen from silicone units and oxyalkylene units, and wherein the at least one repeating unit may be located between the hydrocarbon-based repeating units.
  • the composition of the invention comprises at least one structuring polymer with nitrogen atoms, such as amide, urea, or carbamate units, such as amide units, and at least one polar oil.
  • the percentage of the total number of fatty chains ranges from 40% to 98% relative to the total number of repeating units and fatty chains, such as, for example, from 50% to 95%.
  • the polymer skeleton is a polyamide skeleton
  • the percentage of the total number of fatty chains ranges from 40% to 98% relative to the total number of all amide units and fatty chains, such as, for example, from 50% to 95%.
  • the nature and proportion of the at least one hydrocarbon-based repeating unit comprising at least one hetero atom depends on the nature of a liquid fatty phase of the composition and is, for example, similar to the nature of the liquid fatty phase.
  • the at least one structuring polymer e.g., a polyamide polymer
  • the invention is drawn to a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, wherein the at least one structuring polymer is a polyamide polymer comprising a polymer skeleton comprising at least one amide repeating unit and optionally at least one pendant fatty chain and/or at least one terminal chain that are optionally functionalized and comprise from 8 to 120 carbon atoms, bonded to at least one of the amide repeating units via at least one linking group.
  • the liquid fatty phase further contains at least one oil-soluble ester comprising at least one free-hydroxy group.
  • the at least one liquid fatty phase, the at least one structuring polymer, and the at least one oil-soluble ester comprising at least one free-hydroxy group together form a physiologically acceptable medium.
  • the pendant fatty chains may be linked to at least one of the nitrogen atoms in the amide repeating units.
  • the at least one structuring polymer e.g., a polyamide polymer
  • the weight-average molecular mass may range from 1000 to 30,000, such as from 2000 to 20,000, further such as from 2000 to 10,000.
  • the at least one structuring polymer for example the polyamide polymer, is not soluble in water or in an aqueous phase.
  • the at least one structuring polymer has no ionic groups or functions, i.e., is non-ionic.
  • the at least one structuring polymer can have one ionizable function.
  • the at least one structuring polymer may, for example, be chosen from polyamide polymers.
  • a polyamide polymer in accordance with the invention may comprise, for example, a polymer skeleton which comprises at least one amide repeating unit, i.e., a polyamide skeleton.
  • the polyamide skeleton may further comprise at least one terminal fatty chain and/or at least one pendant fatty chain, wherein said at least one terminal fatty chain and/or at least one pendant fatty chain are chosen from alkyl chains, for example, alkyl chains comprising at least four carbon atoms, and alkenyl chains, for example, alkenyl chains comprising at least four carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group, and/or at least one pendant fatty chain chosen from alkyl chains, for example, alkyl chains comprising at least four carbon atoms, and alkenyl chains, for example, alkenyl chains comprising at least four carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group.
  • the polyamide skeleton may comprise at least one terminal fatty chain chosen from fatty chains comprising from 8 to 120 carbon atoms, such as, for example, from 12 to 68 carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group and/or at least one pendant fatty chain chosen from fatty chains comprising from 8 to 120 carbon atoms, such as, for example, from 12 to 68 carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group, such as bonded to any carbon or nitrogen of the polyamide skeleton via said at least one linking group.
  • the at least one linking group is chosen from single bonds and urea, urethane, thiourea, thiourethane, thioether, thioester, ester, ether and amine groups.
  • the at least one linking group may be chosen from ureas, esters and amines, and in another example, from esters and amines.
  • the bond is, for example, an ester bond.
  • these polymers comprise a fatty chain at each end of the polymer skeleton, such as the polyamide skeleton.
  • the at least one structuring polymer e.g., a polyamide polymer
  • the at least one structuring polymer may be readily soluble in oils (i.e., water-immiscible liquid compounds) and thus may give a macroscopically homogeneous composition even with a high content (at least 25%) of the polyamide polymers, unlike certain polymers of the prior art that do not contain such alkyl or alkenyl chains at the end of the polyamide skeleton.
  • oils i.e., water-immiscible liquid compounds
  • a composition is soluble if it has a solubility of greater than 0.01 g per 100 ml of solution at 25°C.
  • the polyamide polymers can be chosen from polymers resulting from at least one polycondensation reaction between at least one acid chosen from at least one dicarboxylic acid comprising at least 32 carbon atoms, such as from 32 to 44 carbon atoms, and at least one amine chosen from diamines comprising at least 2 carbon atoms, such as from 2 to 36 carbon atoms, and triamines comprising at least 2 carbon atoms, such as from 2 to 36 carbon atoms.
  • the at least one dicarboxylic acid can, for example, be chosen from dimers of at least one fatty acid comprising at least 16 carbon atoms, such as oleic acid, Iinoleic acid, and linolenic acid.
  • the at least one amine can, for example, be chosen from diamines, such as ethylenediamine, hexylenediamine, hexamethylenediamine, and phenylenediamine, and from triamines.
  • the at least one amine can be ethylenetriamine.
  • the polyamide polymers may also be chosen from polymers comprising at least one terminal carboxylic acid group.
  • the at least one terminal carboxylic acid group can, for example, be esterified with at least one alcohol chosen from monoalcohols comprising at least 4 carbon atoms.
  • the at least one alcohol can be chosen from monoalcohols comprising from 10 to 36 carbon atoms.
  • the monoalcohols can comprise from 12 to 24 carbon atoms, such as from 16 to 24 carbon atoms, and, for example, 18 carbon atoms.
  • the at least one polyamide polymer may be chosen from those described in U.S. Patent No. 5,783,657, which are polyamide polymers of formula (I):
  • - n is an integer which represents the number of amide units such that the number of ester groups present in said at least one polyamide polymer ranges from 10% to 50% of the total number of all said ester groups and all said amide groups comprised in the at least one polyamide polymer;
  • R 1 which are identical or different, are each chosen from alkyl groups comprising at least 4 carbon atoms and alkenyl groups comprising at least 4 carbon atoms.
  • the alkyl group comprises from 4 to 24 carbon atoms and the alkenyl group comprises from 4 to 24 carbon atoms;
  • R 2 which are identical or different, are each chosen from C 4 to C 42 hydrocarbon-based groups, with the proviso that at least 50% of all R 2 are chosen from C 3 o to C 42 hydrocarbon-based groups;
  • R 3 which are identical or different, are each chosen from organic groups comprising atoms chosen from carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, with the proviso that R 3 comprises at least 2 carbon atoms;
  • R 4 which are identical or different, are each chosen from hydrogen atoms, Ci to C-io alkyl groups and a direct bond to at least one group chosen from R 3 and another R 4 such that when said at least one group is chosen from another R 4 , the nitrogen atom to which both R 3 and R 4 are bonded forms part of a heterocyclic structure defined in part by R 4 -N-R 3 , with the proviso that at least 50% of all R 4 are chosen from hydrogen atoms.
  • the terminal fatty chains that are optionally functionalized for the purposes of the invention are terminal chains linked to the last hetero atom, in this case nitrogen, of the polyamide skeleton.
  • ester groups of formula (I), which form part of the terminal and/or pendant fatty chains for the purposes of the invention are present in an amount ranging from 15% to 40% of the total number of ester and amide groups (i.e., heteroatom groups), such as from 20% to 35%.
  • n may be an integer ranging from 1 to 10, for example an integer ranging from 1 to 5, and as a further example, an integer ranging from 3 to 5.
  • R 1 which are identical or different, can, for example, each be chosen from C 12 to C 22 alkyl groups, such as from C 16 to C 22 alkyl groups.
  • R 2 which are identical or different, can, for example, each be chosen from C 10 to C 42 hydrocarbon- based groups, e.g., alkylene groups. At least 50% of all R 2 , for example at least 75% of all R 2 , which are identical or different, can, for example, each be chosen from groups comprising from 30 to 42 carbon atoms. In these embodiments, the remaining R 2 , which are identical or different, can, for example, each be chosen from C to C- ⁇ 8 groups, such as from C 4 to C 12 groups.
  • R 3 which can be identical or different, can, for example, each be chosen from C 2 to C 3 ⁇ hydrocarbon-based groups and polyoxyalkylene groups. In another embodiment, R 3 , which can be identical or different, can each, for example, be chosen from C 2 to C 12 hydrocarbon-based groups.
  • R 4 which can be identical or different, can each be chosen from hydrogen atoms.
  • hydrocarbon- based groups may be chosen from linear, cyclic, and branched, saturated and unsaturated groups.
  • the hydrocarbon-based groups can be chosen from aliphatic and aromatic groups. In one example, the hydrocarbon-based groups are chosen from aliphatic groups.
  • the alkyl and alkylene groups may be chosen from linear, cyclic, and branched, saturated and unsaturated groups.
  • the pendant and terminal fatty chains of the at least one structuring polymer may be chosen from linear, cyclic and branched, saturated and unsaturated groups.
  • the pendant and terminal fatty chains can be chosen from aliphatic and aromatic groups. In one example, the pendant and terminal fatty chains are chosen from aliphatic groups.
  • the structuring of the liquid fatty phase can be obtained with the aid of at least one structuring polymer, such as the at least one polyamide polymer of formula (I).
  • the at least one polyamide polymer of formula (I) may, for example, be in the form of a mixture of polymers, and this mixture may also comprise a compound of formula (I) wherein n is equal to zero, i.e., a diester.
  • Non-limiting examples of an at least one polyamide polymer which may be used in the composition according to the present invention include the commercial products made or sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100.
  • these polymers can contain more than two carbonyl groups and more than two amine groups.
  • Examples of these polyamide polymers are those made or sold under the brand name Versamid by the companies General Mills Inc. and Henkel Corp. (Versamid 930, 744, or 1655) or by the company Olin Mathieson Chemical Corp. under the brand name Onamid, for example, Onamid S or C.
  • polyamides useful in the compositions according to the invention include those made or sold by the company Arizona Chemical under the references Uni-Rez (2658, 2931 , 2970, 2621 , 2613, 2624, 2665, 1554, 2623 and 2662) and the product made or sold under the reference Macromelt 6212 by the company Henkel.
  • Uni-Rez 2658, 2931 , 2970, 2621 , 2613, 2624, 2665, 1554, 2623 and 2662
  • Macromelt 6212 by the company Henkel.
  • U.S. Patent No. 5,500,209 Such polyamides display high melt viscosity characteristics.
  • MACROMELT 6212 for example, has a high melt viscosity at 190°C of 30-40 poise (as measured by a Brookfield Viscometer, Model RVF #3 spindle, 20 RPM).
  • the at least one structuring polymer in the composition according to the invention corresponds to the polyamide polymers of formula (I). Due to fatty chain(s), these polymers may be readily soluble in oils and thus lead to compositions that are macroscopically homogeneous even with a high content (at least 25%) of at least one structuring polymer, unlike polymers not containing a fatty chain.
  • the at least one polyamide polymer may be chosen from polyamide resins from vegetable sources.
  • Polyamide resins from vegetable sources may be chosen from, for example, the polyamide resins disclosed in U.S. Patent Nos. 5,783,657 and 5,998,570.
  • the structuring polymers of the invention may furthermore be non- waxy polymers.
  • the at least one structuring polymer of the present invention comprises a urea urethane having the following formula (II):
  • R represents C n H 2 n+i, or C m H 2m + ⁇ (OC p H 2 p)r -, wherein n represents an integer having a value greater than 22, for example from 23 to 120, and further, for example from 23 to 68, wherein m represents an integer having a value of greater than 18, for example from 19 to 120, and further, for example, from 23 to 68, p represents an integer having a value of from 2 to 4, and r represents an integer having a value of from 1 to 10, R' represents: or — (CH 2 ) 6 — and R" represents:
  • the at least one structuring polymer, e.g., polyamide polymer, in the compositions of the invention may have a softening point greater than 50°C, such as from 65°C to 190°C, such from 65°C to less than 150°C, and further such as from 70°C to less than 130°C, and even further such as from 80°C to 105°C.
  • This softening point may be lower than that of structuring polymers used in the art which may facilitate the use of the at least one structuring polymer of the present invention and may limit the degradation of the liquid fatty phase.
  • the softening point can be measured by the well-known art- recognized method of Differential Scanning Calorimetry ("DSC"), with a temperature rise ranging from 5°C to 10°C per minute.
  • the at least one structuring polymer e.g., polyamide polymer
  • the at least one structuring polymer may be present in the composition in an amount ranging, for example, from 0.5% to 80% by weight relative to the total weight of the composition, such as, for example, from 2% to 60%, and further, for example, from 5 to 40%.
  • the at least one structuring polymer may be present in the composition in an amount ranging, for example, from 5% to 25% by weight relative to the total weight of the composition.
  • the present invention is drawn to a structured composition
  • a structured composition comprising at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom
  • the at least one structuring polymer further comprises at least one terminal fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains, such as alkyl and alkenyl chains having at least four carbon atoms, and further such as alkyl and alkenyl chains comprising from 8 to 120 carbon atoms, bonded to the polymer skeleton via at least one linking group chosen from amines, ureas, and esters, wherein when the at least one linking group is chosen from esters, the at least one terminal fatty chain is chosen from branched alkyl groups.
  • at least one structuring polymer e.g., a polyamide polymer, comprising a polymer skeleton compris
  • the at least one structuring polymer may also comprise at least one pendant fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains, such as alkyl and alkenyl chains having at least four carbon atoms, and further such as alkyl and alkenyl chains comprising from 8 to 120 carbon atoms, bonded to any carbon or hetero atom of the polymer skeleton via at least one linking group chosen from amines, ureas, and esters, wherein when said at least one linking group is chosen from esters, the at least one pendant fatty chain is chosen from branched alkyl groups.
  • the at least one structuring polymer may comprise both at least one pendant fatty chain and at least one terminal fatty chain as defined above in this paragraph, and both may be optionally functionalized.
  • Another embodiment of the invention is drawn to a composition comprising at least one liquid fatty phase which comprises at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • an embodiment of the invention relates to a keratinous material care, treatment, or make-up composition
  • a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • a structuring polymer e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • an embodiment of the invention relates to a keratinous material care or make-up composition
  • a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom, at least one coloring agent, and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • a structuring polymer e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom, at least one coloring agent, and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • Another embodiment of the invention relates to a mascara, an eyeliner, a foundation, a lipstick, a blusher, a make-up-removing product, a make-up product for the body, an eyeshadow, a face powder, a concealer product, a shampoo, a conditioner, an antisun product or a care product for at least one keratinous material comprising a composition comprising at least one liquid fatty phase in the mascara, eyeliner, foundation, lipstick, blusher, make-up- removing product, make-up product for the body, eyeshadow, face powder, concealer product, shampoo, conditioner, antisun product or care product for the skin, lips, or hair which comprises: (i) at least one structuring polymer, e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
  • At least one structuring polymer e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
  • a lip composition in stick form comprising at least one continuous liquid fatty phase, at least one non-waxy structuring polymer, e.g., a polyamide polymer, having a weight- average molecular mass of less than 100,000, and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • a non-waxy structuring polymer e.g., a polyamide polymer, having a weight- average molecular mass of less than 100,000
  • Another embodiment of the invention relates to a method for care, make-up or treatment of at least one keratinous material comprising applying to the at least one keratinous material an anhydrous composition comprising at least one liquid fatty phase which comprises:
  • At least one structuring polymer e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
  • Another embodiment of the invention relates to a method for care, make-up or treatment of at least one keratinous material comprising applying to the at least one keratinous material a composition comprising at least one liquid fatty phase which comprises:
  • At least one structuring polymer e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
  • Another embodiment of the invention relates to a method for providing an anhydrous composition having at least one property chosen from non- exudation, gloss, and comfortable deposit on at least one keratinous material, comprising including in the composition at least one liquid fatty phase which comprises:
  • At least one structuring polymer e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
  • At least one structuring polymer e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
  • R represents C n H n+i- or C m H2m+ ⁇ (C p H 2p O) r -; n represents an integer having a value of from 4 to 22; m represents an integer having a value of from 1 to 18; p represents an integer having a value of from 2 to 4; and r represents an integer having a value of from 1 to 10; R' represents:
  • Another embodiment of the invention relates to a method of making up or caring for at least one keratinous material comprising applying to the at least one keratinous material a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
  • At least one structuring polymer e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least three hydrocarbon- based repeating units comprising at least one hetero atom;
  • R represents C n H 2n +i- or C m H2 + ⁇ (OC p H 2 p)r -, wherein n represents an integer having a value greater than 22, wherein m represents an integer having a value of greater than 18, p represents an integer having a value of from 2 to 4, and r represents an integer having a value of from 1 to 10, R' represents:
  • At least one structuring polymer comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom, with the proviso that the at least one hetero atom is not nitrogen;
  • At least one structuring polymer comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising a non-pendant nitrogen atom, and at least one terminal fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains having at least four carbon atoms, and
  • At least one structuring polymer comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising a non-pendant nitrogen atom, and at least one terminal fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains having at least four carbon atoms, and
  • the at least one liquid fatty phase may comprise at least one oil.
  • the at least one oil may have an affinity for the at least one structuring polymer.
  • the at least one oil may, for example, be chosen from polar oils and apolar oils including hydrocarbon-based liquid oils and oily liquids at room temperature.
  • the composition of the invention comprises at least one structuring polymer and at least one polar oil.
  • the polar oils of the invention may, for example, be added to the apolar oils, the apolar oils acting, for example, as co-solvent for the polar oils.
  • the structuring of the at least one liquid fatty phase may be obtained with the aid of at least one structuring polymer, such as the polyamide polymer of formula (I).
  • the polymers of formula (I) may be in the form of mixtures of polymers, these mixtures also possibly containing a synthetic product corresponding to a compound of formula (I) in which n is 0, i.e., a diester.
  • the liquid fatty phase of the composition may contain more than 30%, for example, more than 40%, of liquid oil(s) having a chemical nature close to the chemical nature of the skeleton (hydrocarbon or silicone based) of the structuring polymer, and for example from 50% to 99.4%.
  • the liquid fatty phase structured with a polyamide-type, polyurea-type, polyurethane-type, or polyurea-urethane-type skeleton contains a high quantity, i.e., greater than 30%, for example greater than 40%, relative to the total weight of the liquid fatty phase, or from 50% to 99.4%, of at least one apolar, such as hydrocarbon-based, oil.
  • hydrocarbon-based oil means an oil comprising carbon and hydrogen atoms, optionally with at least one group chosen from hydroxyl, ester, carboxyl, and ether groups.
  • this fatty phase may contain more than 30%, for example, more than 40%, relative to the total weight of the liquid fatty phase and, for example, from 50% to 99.4%, of at least one silicone-based liquid oil, relative to the total weight of the liquid fatty phase.
  • this fatty phase may contain more than 30%, for example more than 40% by weight, and, as a further example, from 50% to 99.4% by weight, of at least one liquid apolar, such as hydrocarbon-based, oil, relative to the total weight of the liquid fatty phase.
  • oils with a high content of triglycerides comprising fatty acid esters of glycerol in which the fatty acids may have varied chain lengths from C to C 24 , these chains possibly being chosen from cyclic, linear and branched, saturated and unsaturated chains; these oils can be chosen from, for example, wheat germ oil, corn oil, sunflower oil, karite butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, cotton oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, rapeseed oil, avocado oil, hazelnut oil, grape seed oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passion flower oil and musk rose oil; or alternatively caprylic/capric acid triglycerides such as those made or sold by Stearineries Dubois
  • R 5 COOR6 in which R 5 is chosen from cyclic, linear and branched fatty acid residues containing from 1 to 40 carbon atoms and Re is chosen from, for example, a hydrocarbon-based chain containing from 1 to 40 carbon atoms, such as, for example, from 1 to 4 carbon atoms, on condition that R 5 + R 6 > 10, such as, for example, purcellin oil (cetostearyl octanoate), isononyl isononanoate, C 12 -C 15 alkyl benzoates, isopropyl myristate, 2-ethylhexyl palmitate, isostearyl isostearate and alkyl or polyalkyl octanoates, decanoates or ricinoleates; hydroxylated esters such as isostearyl lactate and diisostearyl malate; and pentaerythritol esters;
  • - Cs to C 26 fatty acids such as oleic acid, linolenic acid or linoleic acid.
  • the at least one apolar oil according to the invention may be chosen from, for example, silicone oils chosen from volatile and non-volatile, branched, linear and cyclic polydimethylsiloxanes (PDMSs) that are liquid at room temperature; polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendant and/or at the end of the silicone chain, the groups each containing from 2 to 24 carbon atoms; phenylsilicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxysilicates; hydrocarbons chosen from cyclic, linear and branched, volatile and non-volatile hydrocarbons of synthetic and mineral origin, such as volatile liquid paraffins (such as isoparaffins and isodode
  • the structured oils for example those structured with polyamides such as those of formula (I), or with polyurethanes, polyureas, or polyurea-urethanes, in accordance with the invention, may be, in one embodiment, apolar oils, such as an oil or a mixture of hydrocarbon oils chosen from those of mineral and synthetic origin, chosen from hydrocarbons such as alkanes such as Parleam ® oil, isoparaffins including isododecane, and squalane, and mixtures thereof. These oils may, in one embodiment, be combined with at least one phenylsilicone oil.
  • apolar oils such as an oil or a mixture of hydrocarbon oils chosen from those of mineral and synthetic origin, chosen from hydrocarbons such as alkanes such as Parleam ® oil, isoparaffins including isododecane, and squalane, and mixtures thereof.
  • the liquid fatty phase in one embodiment, contains at least one nonvolatile oil chosen from, for example, hydrocarbon-based oils of mineral, plant and synthetic origin, synthetic esters or ethers, silicone oils, and mixtures thereof.
  • the total liquid fatty phase can be, for example, present in an amount ranging from 1% to 99.4% by weight, relative to the total weight of the composition, for example from 5% to 99.4%, from 5% to 95.5%, from 10% to 80%, or from 20% to 75%.
  • volatile solvent or oil means any non-aqueous medium capable of evaporating on contact with the skin or the lips in less than one hour at room temperature and atmospheric pressure.
  • the volatile solvent(s) of the invention is(are) organic solvents, such as volatile cosmetic oils that are liquid at room temperature, having a non-zero vapor pressure at room temperature and atmospheric pressure, ranging, for example, from 10 "2 to 300 mmHg (1.33 Pa to 10,000 Pa), for example greater than 0.03 mmHg (4 Pa), and, as a further example, greater than 0.3 mmHg (40 Pa).
  • non-volatile oil means an oil which remains on the skin or the lips at room temperature and atmospheric pressure for at least several hours, such as those having a vapor pressure of less than 10 "2 mmHg (1.33 Pa).
  • these volatile solvents or oils may facilitate the staying power or long wearing properties of the composition on the skin, the lips or superficial body growths, such as nails and keratinous fibers.
  • the solvents can be chosen from hydrocarbon-based solvents, silicone solvents optionally comprising alkyl or alkoxy groups that are pendant or at the end of a silicone chain, and a mixture of these solvents.
  • the volatile oil(s) in one embodiment, may be present in an amount ranging up to 95.5% relative to the total weight of the composition, such as from 2% to 75%, and, as a further example, from 10% to 45%. This amount will be adapted by a person skilled in the art according to the desired staying power or long wearing properties.
  • the at least one liquid fatty phase of the compositions of the invention may further comprise a dispersion of lipid vesicles.
  • the compositions of the invention may also, for example, be in the form of a fluid anhydrous gel, a rigid anhydrous gel, a fluid simple emulsion, a fluid multiple emulsion, a rigid simple emulsion or a rigid multiple emulsion.
  • the simple emulsion or multiple emulsion may comprise a continuous phase chosen from an aqueous phase optionally containing dispersed lipid vesicles, or a fatty phase optionally containing dispersed lipid vesicles.
  • the composition has a continuous oily phase or fatty phase and is more specifically an anhydrous composition, for example, a stick or dish form.
  • An anhydrous composition is one that has less than 10% water by weight, such as, for example, less than 5% by weight.
  • compositions of the invention also comprise at least one oil-soluble ester comprising at least one free hydroxy group.
  • any oil- soluble ester comprising at least one free hydroxy group may be within the practice of the invention, with the proviso that the at least one oil-soluble ester comprising at least one free-hydroxy group is not castor oil.
  • a composition of the invention may, for example, further comprise castor oil, castor oil alone in combination with at least one structuring polymer is not within the practice of the invention.
  • the at least one oil-soluble ester is not sucrose acetate isobutyrate.
  • the at least one oil-soluble ester comprising at least one free hydroxy group may be chosen from, for example, castor oil, propylene glycol ricinoleate, isopropyl hydroxystearate, triisocetyl citrate, diisostearyl malate, octyl hydroxystearate, triisoarachidyl citrate, cetyl lactate, dioctyl malate, octyldodecyl hydroxystearate, di-isostearyl malate, and di-isostearyl lactate.
  • the at least one oil-soluble ester comprising at least one free hydroxy group may add stability.
  • the use of these esters may minimize oil droplet formulation at room temperature and elevated temperature storage.
  • the introduction of at least one hydroxy-bearing oil- soluble ester may dramatically improve the overall softening point of a finished clear anhydrous stick.
  • certain at least one oil-soluble esters comprising at least one free hydroxy group may provide the firmest and clearest composition and stick, and may also improve the gelling efficiency in relation to a composition comprising structuring polymers alone.
  • a composition comprising from 16 to 20% structuring polymer with the at least one oil-soluble ester comprising at least one free hydroxy group chosen from isopropyl hydroxystearate has exhibited excellent clarity and structure.
  • compositions may develop syneresis after aging for one day at 25°C, which may be disadvantageous in certain embodiments.
  • the skilled artisan may be able to cure this defect by varying the at least one structuring polymer and/or the at least one oil-soluble ester comprising at least one free hydroxy group.
  • the skilled artisan may also be able to cure this defect by varying the amount of at least one of these ingredients.
  • the at least one oil-soluble ester comprising at least one free hydroxy group may be present in the composition in an amount ranging from 10% to 84% by weight relative to the total weight of the composition, such as, for example, from 20% to 70%.
  • the amounts of the at least one structuring polymer and of the at least one oil-soluble ester comprising at least one free-hydroxy group may be chosen according to the desired hardness and desired stability of the composition, and according to the specific application envisaged.
  • the respective amounts of the at least one structuring polymer and of the at least one oil-soluble ester comprising at least one free-hydroxy group can be such that a disintegrable solid which does not flow under its own weight is obtained.
  • hardness of the composition may also be considered.
  • the hardness of a composition may, for example, be expressed in gram force (gf).
  • the composition of the present invention may, for example, have a hardness ranging from 20 gf to 2000 gf, such as from 20 gf to 900 gf, and further such as from 20 gf to 600 gf.
  • a first test for hardness is according to a method of penetrating a probe into said composition and in particular using a texture analyzer (for example TA-XT2i from Rheo) equipped with an ebonite cylinder of height 25 mm and diameter 8 mm.
  • the hardness measurement is carried out at 20°C at the center of 5 samples of the composition.
  • the cylinder is introduced into each sample of composition at a pre-speed of 2 mm/s and then at a speed of 0.5 mm/s and finally at a post-speed of 2 mm/s, the total displacement being 1 mm.
  • the recorded hardness value is that of the maximum peak observed.
  • the measurement error is ⁇ 50 gf.
  • a second test for hardness is the "cheese wire” method, which involves cutting an 8.1 mm or 12.7 mm stick of composition and measuring its hardness at 20°C using a DFGHS 2 tensile testing machine from Indelco- Chatillon Co. at a speed of 100 mm/minute.
  • the hardness value from this method is expressed in gram force as the shear force required to cut a stick under the above conditions.
  • the hardness of compositions according to the present invention which may be in stick form may, for example, range from 30 gf to 300 gf, such as from 30 gf to 250 gf, and further such as from 30 gf to 200 gf.
  • the hardness of the compositions of the present invention may be such that the compositions are self-supporting and can easily disintegrate to form a satisfactory deposit on at least one keratinous material.
  • this hardness may impart good impact strength to the inventive compositions which may be molded or cast, for example, in stick or dish form.
  • composition may be evaluated using at least one of the tests for hardness outlined above based on the application envisaged and the hardness desired. If one obtains an acceptable hardness value, in view of the intended application, from at least one of these hardness tests, the composition falls within the scope of the invention.
  • compositions in stick form may also possess the properties of deformable, flexible elastic solids and may also have noteworthy elastic softness upon application to at least one keratinous material.
  • the compositions in stick form of the prior art do not have this elasticity and flexibility.
  • compositions of the invention may further comprise at least one fatty alcohol.
  • the at least one fatty alcohol may be chosen from, for example, C 8 to C26, such as from, C12 to C22 fatty alcohols.
  • the at least one fatty alcohol is chosen from myristyl, cetyl, stearyl, and behenyl alcohol.
  • the fatty alcohols may, for example, be present in the composition in an amount ranging from 0.1 % to 15.0% by weight, relative to the total weight of the composition, such as, for example, from 0.5% to 10%, and as a further example, from 0.5% to 8.0%.
  • the skilled artisan may be able to cure a stability defect by the addition of at least one fatty alcohol to the composition.
  • the addition of at least one fatty alcohol may improve stick structure, minimize syneresis, and generally improve application properties without interfering with stick transparency, as compared to a composition that does not contain the at least one fatty alcohol.
  • compositions of the invention may further comprise at least one oil-soluble polymer chosen from alkylated guar gums and alkyl celluloses.
  • Alkylated guar gums include, for example, ethyl guars and C ⁇ _ 5 alkyl galactomannans, such as N-HANCE AG-50 and N-HANCE AG-200 from Aqualon.
  • An alkyl cellulose may be chosen from, for example, ethylcellulose (such as ETHOCEL, from Dow Chemical).
  • the at least one oil-soluble polymer may be present in the composition in an amount ranging from 0.05% to 10.0% by weight relative to the total weight of the composition, such as, for example, from 0.1% to 5%, and as a further example, from 0.1 % to 3%.
  • these ingredients can further stabilize, for example, a clear sunscreen complex composition, against syneresis.
  • a composition according to the invention may be stabilized by the inclusion of at least one oil-soluble polymer chosen from alkyl celluloses.
  • at least one alkyl galactomannan such as N-HANCE AG-50, may be used to stabilize a stick composition against stick syneresis, particularly at elevated temperatures such as, for example, 45°C.
  • Oil-Soluble Cationic Surfactant such as N-HANCE AG-50, may be used to stabilize a stick composition against stick syneresis, particularly at elevated temperatures such as, for example, 45°C.
  • compositions of the invention may further comprise at least one oil-soluble cationic surfactant.
  • the at least one oil-soluble cationic surfactant may be chosen from lauryl methyl gluceth-10-hydroxypropyl dimmonium chloride, which may impart cosmetic elegance to a composition.
  • the at least one oil-soluble cationic surfactant may also, for example, be chosen from quaternary ammonium compounds including salts of quaternary ammonium compounds and fatty amines including salts of fatty amines.
  • cosmetic elegance refers to substantially low tackiness, ease of application, or elegant feel.
  • the at least one oil-soluble cationic surfactant is chosen from water-insoluble surfactants of the formula wherein Ri, R2, R 3 , and R 4 are independently chosen from aliphatic groups of from 1 to 22 carbon atoms and C 1 -C 3 alkyl, hydroxyalkyl, polyalkoxy, aromatic, aryl, and alkylaryl groups having from 12 to 22 carbon atoms, and X is chosen from halogen, acetate, phosphate, nitrate, and alkylsulfate radicals.
  • the aliphatic groups may, for example, contain in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups.
  • the at least one oil-soluble cationic surfactant may also, for example, be chosen from quaternary ammonium salts of the formula
  • Ri is an aliphatic group having from 16 to 22 carbon atoms
  • R 2 , R 3 , R 4 , R5, and R 6 are independently chosen from hydrogen and alkyl having from 1 to 4 carbon atoms
  • X is chosen from halogen, acetate, phosphate, nitrate, and alkyl sulfate radicals.
  • the at least one oil-soluble cationic surfactant may, for example, be tallow propane diammonium dichloride.
  • Non-limiting examples of the at least one oil-soluble cationic surfactant include the quaternary ammonium salts: dialkyldimethyl-ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids yield quaternary compounds wherein Ri and R 2 have predominately from 16 to 18 carbon atoms); ditallowdimethyl ammonium chloride; ditallowdimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium acetate; dihexadecyl dimethyl ammonium chloride, dihexa
  • Non-limiting examples of the at least one oil-soluble cationic surfactant also include salts of primary, secondary, and tertiary fatty amines.
  • the salts of primary, secondary, and tertiary fatty amines may comprise alkyl groups having from 12 to 22 carbon atoms, and may be substituted and unsubstituted.
  • Amines may be chosen from, for example, stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, tridecyl amine, ethyl stearylamine, ethoxylated (2 moles E.O.) stearylamine, dihydroxyethyl stearylamine, and arachidylbehenylamine.
  • Amine salts may be chosen from, for example, halogens, acetates, phosphates, nitrates, citrates, lactates, and alkyl sulfates.
  • the amine salts are chosen from stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diaminedichloride, and stearamidopropyl dimethylamine citrate.
  • the at least one oil-soluble cationic surfactant may also be chosen from cationic amine surfactants disclosed in U.S. Patent No. 4,275,055.
  • the at least one oil-soluble cationic surfactant may be chosen from quaternary imidazolinium compounds including quaternary imidazolinium salts.
  • Quaternary imidazolinium compounds include, for example, imidazolinium compounds containing C 12 - C 22 alkyl groups such as 1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4,5- dihydroimidazolinium chloride, 1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl- 4,5-dihydroimidazolinium chloride and 1-methyl-1-[(tallowamide)-ethyl]-2- tallow-imidazolinium methyl sulfate.
  • the at least one oil-soluble cationic surfactant may also be chosen from conditioning agents that are disclosed in U.S. Patent No. 4,387,090.
  • the at least one oil-soluble cationic surfactant may be present in the composition, for example, in an amount ranging from 0.1% to 10% by weight relative to the weight of the composition, such as, for example, from 0.1 % to 5.0%, and as a further example from 0.5% to 2.0%.
  • Wax may be present in the composition, for example, in an amount ranging from 0.1% to 10% by weight relative to the weight of the composition, such as, for example, from 0.1 % to 5.0%, and as a further example from 0.5% to 2.0%.
  • compositions of the invention may further comprise at least one wax.
  • At least one wax for example, may be used to form a non-transparent composition.
  • a "wax" may be any lipophilic fatty compound which is soluble in the liquid fatty phase, unlike most fillers or pigments.
  • the at least one wax for example, may have a melting point greater than about 45°C, such as, for example greater than about 55°C.
  • Non-limiting examples of such waxes include waxes of natural origin, such as beeswax, carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fiber wax, sugar cane wax, paraffin waxes, lignite wax, microcrystalline waxes, lanolin wax, montan wax and ozokerites, hydrogenated oils such as hydrogenated jojoba oil, jojoba esters, waxes of synthetic origin, such as polyethylene waxes derived from polymerization of ethylene, waxes obtained by Fischer-Tropsch synthesis, fatty acid esters and glycerides, and silicone waxes such as derivatives of poly(di)methylsiloxane.
  • the at least one wax may be present in the composition in an amount up to 3%, and in another embodiment in an amount of at least 3%, such as up to 30% or up to 50%.
  • compositions of the invention should be cosmetically and/or dermatologically acceptable, i.e., they should contain a non-toxic physiologically acceptable medium and should be able to be applied to human keratinous materials.
  • the composition of the present invention in one embodiment, may comprise a physiologically acceptable medium, e.g., a physiologically acceptable oil or solvent.
  • a physiologically acceptable medium e.g., a physiologically acceptable oil or solvent.
  • cosmetically and/or dermatologically acceptable means that compositions of the invention have a pleasant appearance, odor, and taste.
  • compositions may also further comprise at least one suitable additive commonly used in the field concerned chosen from coloring agents, antioxidants, essential oils, preserving agents, fragrances, neutralizing agents, liposoluble or lipodispersible gelling agents, liposoluble polymers, and cosmetically active agents and dermatological active agents (i.e., an agent having a beneficial effect on the skin, lips, or superficial body growths) such as, for example, emollients, moisturizers, vitamins, essential fatty acids, and sunscreens.
  • the compositions of the invention may further comprise at least one additional fatty material.
  • the at least one additional fatty material may, for example, be chosen from gums, fatty materials that are pasty or viscous at ambient temperature, and resins.
  • the at least one additive may be present in an amount ranging from 0.01% to 20% by weight of the total weight of the composition, such as from 0.01% to 10%.
  • compositions of the invention may also comprise at least one coloring agent chosen from pigments, dyes, nacreous pigments (i.e., nacres), and pearling agents.
  • the at least one coloring agent may be chosen, for example, in order to obtain make-up compositions which give good coverage, that is, which do not leave a significant amount of the at least one keratinous material to which it is applied showing through.
  • the pigments may also reduce the sticky feel of the compositions, unlike soluble dyes.
  • the coloring agents are pigments (nacreous or non-nacreous).
  • liposoluble dyes which may be used according to the present invention include Sudan red, DC Red 17, DC Green 6, ⁇ -carotene, soybean oil, Sudan brown, DC Yellow 11 , DC Violet 2, DC Orange 5, quinoline yellow, and annatto.
  • the liposoluble dyes when present, may have an amount ranging up to 20% by weight of the total weight of the composition, such as from 0.1% to 6%.
  • the pigments which may be used according to the present invention may be chosen from white, colored, mineral, organic, coated and uncoated pigments.
  • mineral pigments include titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue.
  • organic pigments include carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium and aluminum. If present, the pigments may have an amount ranging up to 40% by weight of the total weight of the composition, such as from 1% to 35%, and further such as from 2% to 25%.
  • nacreous pigments which may be used according to the present invention may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment chosen from those mentioned above, and nacreous pigments based on bismuth oxychloride.
  • the nacres if present, may have an amount ranging up to 30% by weight of the total weight of the composition, such as from 0.1 % to 20%.
  • compositions comprising at least one structuring polymer, as described herein, and at least one UV blocker.
  • the composition may further comprise a physiologically acceptable medium.
  • the at least one UV blocker may be chosen from, for example, organic filters including hydrophilic and lipophilic organic filters, inorganic nanoparticles and mixtures thereof.
  • compositions of the invention may be sunscreen or anti-sun compositions, and may comprise an effective amount of at least one UV blocker to impart complete or partial protection from UV-A and/or UV-B rays to the surface to which they are applied, such as, for example, keratinous materials.
  • UV blocker any compound or any combination of compounds which, by mechanisms that are known perse of absorption and/or reflection and/or scattering of UV-A and/or UV-B radiation, prevents, or at least limits, the contact between such radiation and a surface (such as, for example, keratinous materials) on which the composition of the invention has been applied, including, for example, any sunscreen agent, sunblock agent, UV screener, or UV blocker.
  • a surface such as, for example, keratinous materials
  • sunscreen agent sunblock agent
  • UV screener or UV blocker.
  • UV blockers may be UV-absorbing organic screening agents or inorganic nanopigments which scatter and/or reflect UV radiation, as well as mixtures thereof.
  • compositions and sunscreen compositions may comprise one or more hydrophilic organic UV blockers and/or one or more lipophilic organic UV blockers and/or one or more mineral or inorganic nanopigments.
  • An example of a UV blocker useful according to the present invention is the dibenzoylmethane sunscreen avobenzone, or 4- (tert-butyl)-4-methoxydibenzoylmethane, which is well known in the art.
  • This UV blocker is commercially available and is marketed, for example, under the trademark "PARSOL 1789" by Givaudan. It has the structural formula;
  • UV blockers which are physical blockers reflect or scatter ultraviolet radiation.
  • Typical examples of physical blockers include red petrolatum, titanium dioxide, and zinc oxide.
  • Physical blockers generally block broad spectrum radiation, including UV-A and UV-B radiation. These physical blockers have been employed in a variety of suspensions and particle sizes and are frequently included in cosmetic formulations. A review of physical blockers may be found at "Sun Protection Effect of Nonorganic Materials," by S. Nakada & H. Konishi, Fragrance Journal, Volume 15, pages 64-70 (1987).
  • UV blockers which are chemical absorbers, like avobenzone, actually absorb harmful ultraviolet radiation. It is well known that chemical absorbers are classified, depending on the type of radiation they protect against, as either UV-A or UV-B absorbers.
  • UV-A absorbers generally absorb radiation in the 320 to 400 nm region of the ultraviolet spectrum. UV-A absorbers include anthranilates, benzophenones, and dibenzoyl methanes.
  • UV-B absorbers generally absorb radiation in the 280 to 320 nm region of the ultraviolet spectrum. UV-B absorbers include p-aminobenzoic acid derivatives, camphor derivatives, cinnamates, and salicylates.
  • UV-A or UV-B absorbers Classifying the chemical absorbers generally as UV-A or UV-B absorbers is accepted within the industry. However, a more precise classification is one based upon the chemical properties of the UV blockers. There are eight major classifications of the chemical properties of UV blockers which are discussed at length in “Sunscreens-Development, Evaluation and Regulatory Aspects,” by N. Shaath et al., 2nd. Edition, pages 269-273, Marcel Dekker, Inc. (1997).
  • the UV blockers that are useful according to the present invention typically include chemical UV absorbers, but may also include physical UV blockers.
  • Exemplary UV blockers which may be formulated into the compositions of the present invention are chemical absorbers such as p- aminobenzoic acid derivatives, anthranilates, benzophenones, camphor derivatives, cinnamic derivatives, dibenzoyl methanes, diphenylacrylate derivatives, salicylic derivatives, triazine derivatives, benzimidazole compounds, bis-benzoazolyl derivatives, methylene bis- (hydroxyphenylbenzotriazole) compounds, sunscreen polymers, sunscreen silicones, and mixtures thereof. Examples of these UV blockers can be found, for example, in U.S.
  • Patents Nos. 2,463,264, 4,367,390, 5,166,355, and 5,237,071 and in EP-0,863,145, EP-0,517,104, EP-0,570,838, EP-0,796,851 , EP-0,775,698, EP-0,878,469, EP-0,933,376, EP-0,893,119, EP-0,669,323, GB-2,303,549, DE-1 ,972,184, and WO-93/04665.
  • UV blockers which may be formulated into the compositions of this invention are physical UV blockers such as cerium oxides, chromium oxides, cobalt oxides, iron oxides, red petrolatum, silicone- treated titanium dioxide, titanium dioxide, zinc oxide, and zirconium oxide, and mixtures thereof.
  • UV blockers useful according to the present invention can be found, for example, in Chapter VIII of Cosmetics and Science and Technology by Segarin et al., pages 189 et seq. (1957), and U.S. Patent No. 5,087,445 and U.S. Patent No. 5,073,372.
  • UV blockers which may be formulated into the compositions of the present invention also include those chosen from aminobenzoic acid, amyldimethyl PABA, cinoxate, diethanolamine p- methoxycinnamate, digalloyl trioleate, dioxybenzone, 2-ethoxyethyl p- methoxycinnamate, ethyl 4-bis(hydroxypropyl)aminobenzoate, 2-ethylhexyl-2- cyano-3,3-diphenylacrylate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl salicylate, glyceryl aminobenzoate, homomenthyl salicylate, homosalate, 3- imidazol-4-ylac ⁇ lic acid and ethyl ester, methyl anthranilate, octyldimethyl PABA, 2-phenyIbenzimidazole-5-sulfonic acid and salts, red petrolate
  • UV blockers active in the UV-A and/or UV-B range include p- aminobenzoic acid, oxyethylene (25 mol) p-aminobenzoate, 2-ethylhexyl p- dimethylaminobenzoate, ethyl N-oxypropylene p-aminobenzoate, glycerol p- aminobenzoate, 4-isopropylbenzyl salicylate, 2-ethylhexyl 4- methoxycinnamate, methyl diisopropylcinnamate, isoamyl 4- methoxycinnamate, diethanolamine 4-methoxycinnamate, 3-(4'- trimethylammunium)-benzyliden-bornan-2-one methylsulfate, 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2,4- dihydroxybenzophenone, 2,2
  • Patent No. 4,585,597 issued to Lang et al. on April 29, 1986
  • urocanic acid 2,4,6-tris[p-(2'-ethylhexyl-1'-oxycarbonyl)-anilino]-1 ,3,5- triazine
  • TINOSORB S marketed by Ciba
  • UV blockers include octyl salicylate, octocrylene, and oxybenzone.
  • the UV blocker may be NEO HELIOPAN 303. Combinations of one of more of any of the above- mentioned UV blockers are also useful according to the present invention.
  • the dibenzoyl methane derivatives other than avobenzone are also useful UV blockers according to the present invention. These are described, for example, in FR-2,326,405, FR-2,440,933 and EP-0,114,607. These include, for example, 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyIdibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4- dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'- diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 2-methyl-5- isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'- methoxydibenzoylmethane, 2,4-dimethyl-4'
  • the at least one UV blocker may be present in the compositions of the invention in amounts ranging from about 0.01% to about 30%, for example, from about 0.1% to about 15%, such as, for example, from 0.5% to 15%, and further, for example, from about 0.5% to about 6%, by weight thereof. Of course, depending upon the nature of the particular formulation, higher or lower amounts may be suitable. Furthermore, one or more UV blockers may be used in a composition.
  • the packaging and application device for any subject of the invention may be chosen and manufactured by persons skilled in the art on the basis of their general knowledge, and adapted according to the nature of the composition to be packaged. Indeed, the type of device to be used may be, for example, linked to the consistency of the composition, for example, to its viscosity; it may also depend on the nature of the constituents present in the composition, such as the presence of volatile compounds.
  • compositions of table 1 were prepared using the following procedure.
  • the ingredients of phase A were added to a main vessel and heated to 110°C - 115°C while mixing with the aid of an impeller mixer.
  • phase B was added to phase A with continued mixing.
  • the beads of polyamide resin were allowed to dissolve and the mixture was removed from the heat and cooled to 80°C - 82°C.
  • Phases C, D, and E were added to the AB mixture while maintaining the temperature at about 80 °C - 82°C with slow impeller mixing.
  • the compositions were mixed until homogeneous (about 1 minute), then used to fill a suitable container or mold.
  • compositions were firm at room temperature (25°C). A very fine uniform oil coat covered the surface of some of the compositions, however, none of the compositions failed the stability test. At elevated temperatures (45°C), the overall structure and stick characteristics remained unchanged. There was a moderate oil coat on the surface of the stick structure of some of the compositions; however, none of the compositions failed the stability test.
  • compositions of table 2 were prepared using the following procedure.
  • the ingredients of phase A were added to a main vessel and heated to 110°C - 115°C while mixing with the aid of an impeller mixer.
  • phase B was added to phase A with continued mixing.
  • the beads of polyamide resin were allowed to dissolve and the mixture was removed from the heat and cooled to 80°C - 82°C.
  • Phases C and D were added to the AB mixture while maintaining the temperature at about 80°C - 82°C with slow impeller mixing.
  • the compositions were mixed until homogeneous (about 1 minute), then used to fill a suitable container or mold.
  • compositions were firm at room temperature (25°C). A very fine uniform oil coat covered the surface of some of the compositions, however, none of the compositions failed the stability test. At elevated temperatures (45°C), the overall structure and stick characteristics remained unchanged. There was a moderate oil coat on the surface of the stick structure of some of the compositions; however, none of the compositions failed the stability test.
  • compositions of table 3 were prepared using the following procedure.
  • the ingredients of phase A were added to a main vessel and heated to 110°C - 115°C while mixing with the aid of an impeller mixer.
  • phase B was added to phase A with continued mixing.
  • the beads of polyamide resin were allowed to dissolve and the mixture was removed from the heat and cooled to 80°C - 82°C.
  • Phases C, D, and E were added to the AB mixture while maintaining the temperature at about 80°C - 82°C with slow impeller mixing.
  • the compositions were mixed until homogeneous (about 1 minute), then used to fill a suitable container or mold.
  • compositions were mixed until homogeneous, then used to fill a suitable container or mold.
  • the compositions have good stability and 47°C, with no exudation.
  • Example 5 Anhydrous Gel Lip Compositions TABLE 5
  • compositions were mixed until homogeneous, then used to fill a suitable container or mold.
  • the compositions have good stability at room temperature and good sunscreen properties.

Abstract

Structured compositions comprising at least one structuring polymer and at least one oil-soluble ester comprising at least one free hydroxy group. The compositions may also comprise at least one structuring polymer and at least one UV blocker. The at least one structuring polymer may be a polyamide polymer. This invention may be in the form of stable compositions such as, for example, make-up sticks, lipsticks, sunscreen sticks, anhydrous lip compositions, and anhydrous foundations.

Description

COMPOSITIONS CONTAINING HETEROPOLYMERS AND OIL-SOLUBLE ESTERS AND METHODS OF USING SAME
The present invention relates to compositions and methods for care of, for treating, and for making-up at least one keratinous material, for example, at least one human keratinous material, such as skin, including the scalp, lips, superficial body growths, including the nails, and/or at least one keratinous fiber which includes hair, eyelashes, and eyebrows. More particularly, the compositions of the invention comprise at least one structuring polymer and at least one oil-soluble ester comprising at least one free-hydroxy group. The compositions of the present invention may also comprise at least one structuring polymer and at least one UV blocker. The invention may be in the form of a stable composition such as, for example, make-up sticks, lipsticks, transparent sticks, and sunscreen sticks. The compositions may also, for example, provide a molded composition.
The use of high molecular weight polymers, i.e., polyamides, to produce clear stick compositions dates back to the mid 1960's. These systems contained a combination of polyamide polymer, castor oil, esters, amides, and colorants as described in, for example, U.S. Patent Nos. 3,086,914 and 3,148,125. However, there were significant drawbacks associated with such compositions. For example, the sticks were tacky and difficult to apply to the lips. During storage, particularly at slightly elevated temperatures, the stick surface developed distinct oil droplets (syneresis) which were not reabsorbed after the stick cooled to normal room temperature.
There have been many attempts to resolve the aforementioned technical problems with only partial success. The introduction of new specialty cosmetic esters has made it possible to reduce product tackiness and thereby improve application characteristics. However, these modifications did not diminish the tendency of these formulations to have stability problems such as developing distinct and unattractive oil syneresis. In some instances, these modified formulations also displayed poor temperature stability at 50°C. The inventors have found that the use of combinations of at least one structuring polymer, e.g., a polyamide polymer, and at least one oil-soluble ester comprising at least one free-hydroxy group provide a stable composition. In one embodiment, the composition of the invention also may provide good gelling efficiency and/or maintain desirable cosmetic application properties. The inventors have also found that stable compositions can be obtained from combinations of at least one structuring polymer, e.g., a polyamide polymer, and at least one UV blocker.
In one embodiment, the invention provides a composition comprising at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom. The composition further comprises at least one liquid fatty phase comprising at least one oil-soluble ester comprising at least one free-hydroxy group. In a further embodiment, the at least one structuring polymer, e.g., a polyamide polymer, and the at least one oil-soluble ester comprising at least one free-hydroxy group are present in a combined amount effective to stabilize the composition. Due to the good stability of the compositions of the invention, it is possible to add at least one UV blocker to the composition. As used herein, the expression "at least one" means one or more and thus includes individual components as well as mixtures and combinations thereof.
The invention also provides a method for providing stability to a composition comprising including in the composition at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom. The compositions of the invention may also comprise at least one UV blocker.
The invention also provides for a cosmetic process for caring for, making up, and/or treating at least one keratinous material comprising applying to at least one keratinous material a cosmetic composition comprising at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom. The composition further comprises at least one oil-soluble ester comprising at least one free- hydroxy group. As used herein, "keratinous material" is meant to comprise hair, lips, skin, scalp and superficial body growths such as eyelashes, eyebrows and nails.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.
One subject of the invention is cosmetic and/or dermatological compositions which are useful for the care, make-up and/or treatment of at least one keratinous material which may be of suitable hardness to allow preparation of these compositions in the form of a stick or other structured form which may be stable.
As defined herein, stability can be tested by placing the composition in a controlled environment chamber for 8 weeks at 25°C. In this test, the physical condition of the sample is inspected as it is placed in the chamber. The sample is then inspected again at 24 hours, 3 days, 1 week, 2 weeks, 4 weeks and 8 weeks. At each inspection, the sample is examined for abnormalities in the composition such as bending or leaning if the composition is in stick form, phase separation, melting, or syneresis. As used herein, syneresis is the appearance of droplets on the surface of a composition that are visible to the naked eye. Syneresis or oil release from a composition, such as a stick, that is only apparent as a thin, attractive, and glossy, surface coating is not considered a composition that has failed the stability test. The stability is further tested by repeating the 8 week test at 4°C, 37°C, 45°C, and 50°C, and under freeze-thaw conditions. A composition is considered to lack stability if an abnormality that impedes functioning of the composition is observed in any of these tests. The skilled artisan will readily recognize an abnormality that impedes functioning of a composition based on the intended application. The invention applies not only to make-up products for at least one keratinous material such as lip compositions, lip pencils, foundations including foundations which may be cast in the form of a stick or a dish, concealer products, temporary tattoo products, eyeliners, and mascara bars, but also to body hygiene products such as deodorant sticks, and to care products and products for treating at least one keratinous material such as sunscreen (anti- sun) and after-sun products which may be in stick form and also nail products. It is to be noted that a deodorant product is a body hygiene product and does not relate to care, make-up, or treatment of keratinous materials, including keratinous fibers, skin, or lips.
The present invention may be in the form of a mascara product, an eyeliner product, a foundation product, a lipstick product, a lip balm, a blush for cheeks or eyelids, a deodorant product, a fragrance product, a make-up product for the body, a make-up-removing product, an eyeshadow product, a face powder product, a night or day care product for the face, a concealer product, a hair conditioning product, a sunscreen, a colorant for the skin or hair, or a skin care formula such as, for example, anti-pimple or shaving cut formulas. According to one embodiment of the invention, the composition is in the form of a substantially clear or substantially transparent composition such as, for example, a clear lipstick, clear sunscreen composition, or clear foundation, for example, for concealing skin imperfections.
For example, the composition of the present invention may be in a form chosen from a paste, a solid, a gel, and a cream. It may be an emulsion, i.e., an oil-in-water or water-in-oil emulsion, a multiple emulsion, e.g., an oil-in- water-in-oil emulsion or water-in-oil-in-water emulsion, or a solid, rigid, or supple gel, including anhydrous gels. In one embodiment, the composition of the invention comprises an external or continuous liquid fatty phase. By "external or continuous" phase, it is meant, by way of example, the water phase in a water-in-oil emulsion, wherein the oil droplets are dispersed throughout the external or continuous water phase. In another embodiment, the composition of the invention is transparent or clear. The composition can also be in a form chosen from a translucent anhydrous gel and a transparent anhydrous gel. The composition can also be a molded composition or cast as a stick or a dish. The composition in one embodiment is a solid or rigid product, such as a molded stick or a poured stick. Structuring polymer
In one embodiment, the at least one structuring polymer in the composition of the invention is a solid that is not deformable at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e., 101 kPa). In a further embodiment, the at least one structuring polymer is capable of structuring the composition without opacifying it. This may be due to the fact that the polymer does not crystallize. Moreover, the structuring of the liquid fatty phase comprising the at least one structuring polymer may be due to the hydrogen interactions between two molecules of the polymer and/or between the molecules of the polymer and the liquid fatty phase. As defined above, the at least one structuring polymer of the present invention comprises a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom. In one embodiment, the at least one structuring polymer further comprises at least one terminal fatty chain chosen from alkyl and alkenyl chains, such as of at least 4 carbon atoms, and further such as comprising from 8 to 120 carbon atoms, bonded to the polymer skeleton via at least one linking group. The terminal fatty chain may, for example, be functionalized. The at least one structuring polymer may also further comprise at least one pendant fatty chain chosen from alkyl and alkenyl chains, such as of at least 4 carbon atoms, and further such as comprising from 8 to 120 carbon atoms, bonded to any carbon or hetero atom of the polymer skeleton via at least one linking group. The pendant fatty chain may, for example, be functionalized. The at least one structuring polymer may comprise at least one pendant fatty chain as defined above, at least one terminal fatty chain as defined above, or both, and one or both types of chains can be functionalized.
In one embodiment, the at least one structuring polymer comprises at least two hydrocarbon-based repeating units. As a further example, the at least one structuring polymer comprises at least three hydrocarbon-based repeating units and as an even further example, the at least three repeating units are identical.
As used herein, "functionalized" means comprising at least one functional (reactive) group. Non-limiting examples of functional groups include hydroxyl groups, ether groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, amide groups, halogen containing groups, including fluoro and perfluoro groups, halogen atoms, ester groups, siloxane groups and polysiloxane groups.
For purposes of the invention, the expression "functionalized chain" means, for example, an alkyl chain comprising at least one functional group chosen, for example, from those recited above. For example, in one embodiment, the hydrogen atoms of at least one alkyl chain may be substituted at least partially with fluorine atoms.
According to the invention, these chains may be linked directly to the polymer skeleton or via an ester function or a perfluoro group.
For the purposes of the invention, the term "polymer" means a compound containing at least 2 repeating units, such as, for example, a compound containing at least 3 repeating units, which may be identical.
As used herein to describe the structuring polymers, the expression "hydrocarbon-based repeating unit" includes a repeating unit comprising from 2 to 80 carbon atoms, such as, for example, from 2 to 60 carbon atoms. The at least one hydrocarbon-based repeating unit may also comprise oxygen atoms. The hydrocarbon-based repeating unit may be chosen from saturated and unsaturated hydrocarbon-based repeating units which in turn may be chosen from linear hydrocarbon-based repeating units, branched hydrocarbon-based repeating units and cyclic hydrocarbon-based repeating units. The at least one hydrocarbon-based repeating unit may comprise, for example, at least one hetero atom that is part of the polymer skeleton, i.e., not pendant. The at least one hetero atom may be chosen, for example, from nitrogen, sulphur, and phosphorus. For example, the at least one hetero atom may be a nitrogen atom, such as a non-pendant nitrogen atom. In another embodiment, the at least one hydrocarbon-based repeating unit may comprise at least one hetero atom, with the proviso that the at least one hetero atom is not nitrogen. In another embodiment, the at least one hetero atom is combined with at least one atom chosen from oxygen and carbon to form a hetero atom group. In one embodiment, the hetero atom group comprises a carbonyl group.
The at least one repeating unit comprising at least one hetero atom may be chosen, for example, from amide groups, carbamate groups, and urea groups. In one embodiment, the at least one repeating unit comprises amide groups forming a polyamide skeleton. In another embodiment, the at least one repeating unit comprises carbamate groups and/or urea groups forming a polyurethane skeleton, a polyurea skeleton and/or a polyurethane-polyurea skeleton. The pendant chains, for example, can be linked directly to at least one of the hetero atoms of the polymer skeleton. In another embodiment, the at least one hydrocarbon-based repeating unit may comprise at least one hetero atom group, with the proviso that the at least one hetero atom group is not an amide group. In another embodiment, the polymer skeleton comprises at least one repeating unit chosen from silicone units and oxyalkylene units, and wherein the at least one repeating unit may be located between the hydrocarbon-based repeating units.
In one embodiment, the composition of the invention comprises at least one structuring polymer with nitrogen atoms, such as amide, urea, or carbamate units, such as amide units, and at least one polar oil.
In one embodiment, in the at least one structuring polymer, the percentage of the total number of fatty chains ranges from 40% to 98% relative to the total number of repeating units and fatty chains, such as, for example, from 50% to 95%. In a further embodiment wherein the polymer skeleton is a polyamide skeleton, in the at least one structuring polymer, the percentage of the total number of fatty chains ranges from 40% to 98% relative to the total number of all amide units and fatty chains, such as, for example, from 50% to 95%.
In a further embodiment, the nature and proportion of the at least one hydrocarbon-based repeating unit comprising at least one hetero atom depends on the nature of a liquid fatty phase of the composition and is, for example, similar to the nature of the liquid fatty phase. For example, and not to be limited as to theory, the at least one structuring polymer, e.g., a polyamide polymer, may have an affinity for the liquid fatty phase and, for example, with a chemical portion of one of the oils forming the liquid fatty phase of the composition so that physical links with the oils, such as hydrogen bonds, are formed. The more polar the hydrocarbon-based repeating units containing a hetero atom, and in high proportion, which corresponds to the presence of several hetero atoms, the greater the affinity the at least one structuring polymer may have for polar oils. Conversely, the more non-polar, or even apolar, and lesser in proportion the hydrocarbon-based repeating units containing a hetero atom, the greater the affinity the at least one structuring polymer may have for apolar oils.
In another embodiment, the invention is drawn to a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, wherein the at least one structuring polymer is a polyamide polymer comprising a polymer skeleton comprising at least one amide repeating unit and optionally at least one pendant fatty chain and/or at least one terminal chain that are optionally functionalized and comprise from 8 to 120 carbon atoms, bonded to at least one of the amide repeating units via at least one linking group. The liquid fatty phase further contains at least one oil-soluble ester comprising at least one free-hydroxy group. The at least one liquid fatty phase, the at least one structuring polymer, and the at least one oil-soluble ester comprising at least one free-hydroxy group, together form a physiologically acceptable medium.
When the at least one structuring polymer has amide repeating units, the pendant fatty chains may be linked to at least one of the nitrogen atoms in the amide repeating units.
In one embodiment, the at least one structuring polymer, e.g., a polyamide polymer, may have a weight-average molecular mass up to and including 1 ,000,000, such as, for example, up to and including 500,000, and as a further example, up to and including 100,000, and as a further example, up to and including 50,000. For example, the weight-average molecular mass may range from 1000 to 30,000, such as from 2000 to 20,000, further such as from 2000 to 10,000.
The at least one structuring polymer, for example the polyamide polymer, is not soluble in water or in an aqueous phase. In one embodiment of the invention, the at least one structuring polymer has no ionic groups or functions, i.e., is non-ionic. In another embodiment of the invention, the at least one structuring polymer can have one ionizable function.
As discussed, the at least one structuring polymer may, for example, be chosen from polyamide polymers. A polyamide polymer in accordance with the invention may comprise, for example, a polymer skeleton which comprises at least one amide repeating unit, i.e., a polyamide skeleton. In one embodiment, the polyamide skeleton may further comprise at least one terminal fatty chain and/or at least one pendant fatty chain, wherein said at least one terminal fatty chain and/or at least one pendant fatty chain are chosen from alkyl chains, for example, alkyl chains comprising at least four carbon atoms, and alkenyl chains, for example, alkenyl chains comprising at least four carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group, and/or at least one pendant fatty chain chosen from alkyl chains, for example, alkyl chains comprising at least four carbon atoms, and alkenyl chains, for example, alkenyl chains comprising at least four carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group. In one embodiment, the polyamide skeleton may comprise at least one terminal fatty chain chosen from fatty chains comprising from 8 to 120 carbon atoms, such as, for example, from 12 to 68 carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group and/or at least one pendant fatty chain chosen from fatty chains comprising from 8 to 120 carbon atoms, such as, for example, from 12 to 68 carbon atoms, bonded to the at least one polyamide skeleton via at least one linking group, such as bonded to any carbon or nitrogen of the polyamide skeleton via said at least one linking group. In one embodiment, the at least one linking group is chosen from single bonds and urea, urethane, thiourea, thiourethane, thioether, thioester, ester, ether and amine groups. For example, the at least one linking group may be chosen from ureas, esters and amines, and in another example, from esters and amines. The bond is, for example, an ester bond. In one embodiment, these polymers comprise a fatty chain at each end of the polymer skeleton, such as the polyamide skeleton.
In one embodiment, due to the presence of at least one chain, the at least one structuring polymer, e.g., a polyamide polymer, may be readily soluble in oils (i.e., water-immiscible liquid compounds) and thus may give a macroscopically homogeneous composition even with a high content (at least 25%) of the polyamide polymers, unlike certain polymers of the prior art that do not contain such alkyl or alkenyl chains at the end of the polyamide skeleton. As defined herein, a composition is soluble if it has a solubility of greater than 0.01 g per 100 ml of solution at 25°C.
In a further embodiment, the polyamide polymers can be chosen from polymers resulting from at least one polycondensation reaction between at least one acid chosen from at least one dicarboxylic acid comprising at least 32 carbon atoms, such as from 32 to 44 carbon atoms, and at least one amine chosen from diamines comprising at least 2 carbon atoms, such as from 2 to 36 carbon atoms, and triamines comprising at least 2 carbon atoms, such as from 2 to 36 carbon atoms. The at least one dicarboxylic acid can, for example, be chosen from dimers of at least one fatty acid comprising at least 16 carbon atoms, such as oleic acid, Iinoleic acid, and linolenic acid. The at least one amine can, for example, be chosen from diamines, such as ethylenediamine, hexylenediamine, hexamethylenediamine, and phenylenediamine, and from triamines. In one embodiment, the at least one amine can be ethylenetriamine.
The polyamide polymers may also be chosen from polymers comprising at least one terminal carboxylic acid group. The at least one terminal carboxylic acid group can, for example, be esterified with at least one alcohol chosen from monoalcohols comprising at least 4 carbon atoms. For example, the at least one alcohol can be chosen from monoalcohols comprising from 10 to 36 carbon atoms. In a further embodiment, the monoalcohols can comprise from 12 to 24 carbon atoms, such as from 16 to 24 carbon atoms, and, for example, 18 carbon atoms.
In one embodiment, the at least one polyamide polymer may be chosen from those described in U.S. Patent No. 5,783,657, which are polyamide polymers of formula (I):
- (I)
Figure imgf000012_0001
in which:
- n is an integer which represents the number of amide units such that the number of ester groups present in said at least one polyamide polymer ranges from 10% to 50% of the total number of all said ester groups and all said amide groups comprised in the at least one polyamide polymer;
- R1, which are identical or different, are each chosen from alkyl groups comprising at least 4 carbon atoms and alkenyl groups comprising at least 4 carbon atoms. In one embodiment, the alkyl group comprises from 4 to 24 carbon atoms and the alkenyl group comprises from 4 to 24 carbon atoms;
- R2, which are identical or different, are each chosen from C4 to C42 hydrocarbon-based groups, with the proviso that at least 50% of all R2 are chosen from C3o to C42 hydrocarbon-based groups;
- R3, which are identical or different, are each chosen from organic groups comprising atoms chosen from carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, with the proviso that R3 comprises at least 2 carbon atoms; and
- R4, which are identical or different, are each chosen from hydrogen atoms, Ci to C-io alkyl groups and a direct bond to at least one group chosen from R3 and another R4 such that when said at least one group is chosen from another R4, the nitrogen atom to which both R3 and R4 are bonded forms part of a heterocyclic structure defined in part by R4-N-R3, with the proviso that at least 50% of all R4 are chosen from hydrogen atoms.
In the polymer of formula (I), the terminal fatty chains that are optionally functionalized for the purposes of the invention are terminal chains linked to the last hetero atom, in this case nitrogen, of the polyamide skeleton.
In one embodiment, the ester groups of formula (I), which form part of the terminal and/or pendant fatty chains for the purposes of the invention, are present in an amount ranging from 15% to 40% of the total number of ester and amide groups (i.e., heteroatom groups), such as from 20% to 35%.
In formula (I), in one embodiment, n may be an integer ranging from 1 to 10, for example an integer ranging from 1 to 5, and as a further example, an integer ranging from 3 to 5. In one embodiment of the present invention, R1, which are identical or different, can, for example, each be chosen from C12 to C22 alkyl groups, such as from C16 to C22 alkyl groups.
In one embodiment of the present invention, R2, which are identical or different, can, for example, each be chosen from C10 to C42 hydrocarbon- based groups, e.g., alkylene groups. At least 50% of all R2, for example at least 75% of all R2, which are identical or different, can, for example, each be chosen from groups comprising from 30 to 42 carbon atoms. In these embodiments, the remaining R2, which are identical or different, can, for example, each be chosen from C to C-ι8 groups, such as from C4 to C12 groups.
In one embodiment of the invention, R3, which can be identical or different, can, for example, each be chosen from C2 to C3β hydrocarbon-based groups and polyoxyalkylene groups. In another embodiment, R3, which can be identical or different, can each, for example, be chosen from C2 to C12 hydrocarbon-based groups.
In another embodiment, R4, which can be identical or different, can each be chosen from hydrogen atoms.
As used herein to describe the structuring polymers, hydrocarbon- based groups may be chosen from linear, cyclic, and branched, saturated and unsaturated groups. The hydrocarbon-based groups can be chosen from aliphatic and aromatic groups. In one example, the hydrocarbon-based groups are chosen from aliphatic groups. The alkyl and alkylene groups may be chosen from linear, cyclic, and branched, saturated and unsaturated groups.
In general, the pendant and terminal fatty chains of the at least one structuring polymer, e.g., a polyamide polymer, may be chosen from linear, cyclic and branched, saturated and unsaturated groups. The pendant and terminal fatty chains can be chosen from aliphatic and aromatic groups. In one example, the pendant and terminal fatty chains are chosen from aliphatic groups.
According to the invention, the structuring of the liquid fatty phase can be obtained with the aid of at least one structuring polymer, such as the at least one polyamide polymer of formula (I). The at least one polyamide polymer of formula (I) may, for example, be in the form of a mixture of polymers, and this mixture may also comprise a compound of formula (I) wherein n is equal to zero, i.e., a diester. Non-limiting examples of an at least one polyamide polymer which may be used in the composition according to the present invention include the commercial products made or sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100. These are sold, respectively, in the form of an 80% (in terms of active material) gel in a mineral oil and a 100% (in terms of active material) gel. These polymers have a softening point ranging from 88°C to 94 °C, and may be mixtures of copolymers derived from monomers of (i) C36 diacids and (ii) ethylenediamine, and have a weight-average molecular mass of about 6000. Terminal ester groups result from esterification of the remaining acid end groups with at least one alcohol chosen from cetyl alcohol and stearyl alcohol. A mixture of cetyl and stearyl alcohols is sometimes called cetylstearyl alcohol.
Other non-limiting examples of an at least one polyamide polymer which may be used in the compositions according to the present invention include polyamide polymers or polyamide resins resulting from the condensation of at least one aliphatic dicarboxylic acid and at least one diamine, the carbonyl and amine groups being condensed via an amide bond. In one embodiment, these polymers can contain more than two carbonyl groups and more than two amine groups. Examples of these polyamide polymers are those made or sold under the brand name Versamid by the companies General Mills Inc. and Henkel Corp. (Versamid 930, 744, or 1655) or by the company Olin Mathieson Chemical Corp. under the brand name Onamid, for example, Onamid S or C. These resins have a weight-average molecular mass ranging from 6000 to 9000. For further information regarding these polyamides, reference may be made to U.S. Patent Nos. 3,645,705 and 3,148,125. In one embodiment, Versamid 930 or 744 may be used.
Other examples of polyamides useful in the compositions according to the invention include those made or sold by the company Arizona Chemical under the references Uni-Rez (2658, 2931 , 2970, 2621 , 2613, 2624, 2665, 1554, 2623 and 2662) and the product made or sold under the reference Macromelt 6212 by the company Henkel. For further information regarding these polyamides, reference may be made to U.S. Patent No. 5,500,209. Such polyamides display high melt viscosity characteristics. MACROMELT 6212, for example, has a high melt viscosity at 190°C of 30-40 poise (as measured by a Brookfield Viscometer, Model RVF #3 spindle, 20 RPM).
In one embodiment, the at least one structuring polymer in the composition according to the invention corresponds to the polyamide polymers of formula (I). Due to fatty chain(s), these polymers may be readily soluble in oils and thus lead to compositions that are macroscopically homogeneous even with a high content (at least 25%) of at least one structuring polymer, unlike polymers not containing a fatty chain.
In a further embodiment, the at least one polyamide polymer may be chosen from polyamide resins from vegetable sources. Polyamide resins from vegetable sources may be chosen from, for example, the polyamide resins disclosed in U.S. Patent Nos. 5,783,657 and 5,998,570.
The structuring polymers of the invention may furthermore be non- waxy polymers.
In one embodiment, when the at least one structuring polymer of the present invention comprises a urea urethane having the following formula (II):
R-0-CO-NH-R'-NH-CO-NH-R"-NH-CO-NH-R'-NH-CO-OR (II)
then R represents CnH2n+i, or CmH2m+ι (OCpH2p)r -, wherein n represents an integer having a value greater than 22, for example from 23 to 120, and further, for example from 23 to 68, wherein m represents an integer having a value of greater than 18, for example from 19 to 120, and further, for example, from 23 to 68, p represents an integer having a value of from 2 to 4, and r represents an integer having a value of from 1 to 10, R' represents:
Figure imgf000017_0001
or — (CH2)6— and R" represents:
Figure imgf000017_0002
The at least one structuring polymer, e.g., polyamide polymer, in the compositions of the invention may have a softening point greater than 50°C, such as from 65°C to 190°C, such from 65°C to less than 150°C, and further such as from 70°C to less than 130°C, and even further such as from 80°C to 105°C. This softening point may be lower than that of structuring polymers used in the art which may facilitate the use of the at least one structuring polymer of the present invention and may limit the degradation of the liquid fatty phase. The softening point can be measured by the well-known art- recognized method of Differential Scanning Calorimetry ("DSC"), with a temperature rise ranging from 5°C to 10°C per minute. The at least one structuring polymer, e.g., polyamide polymer, may be present in the composition in an amount ranging, for example, from 0.5% to 80% by weight relative to the total weight of the composition, such as, for example, from 2% to 60%, and further, for example, from 5 to 40%. In a further embodiment, the at least one structuring polymer may be present in the composition in an amount ranging, for example, from 5% to 25% by weight relative to the total weight of the composition.
In one embodiment of the invention, the present invention is drawn to a structured composition comprising at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom, wherein the at least one structuring polymer further comprises at least one terminal fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains, such as alkyl and alkenyl chains having at least four carbon atoms, and further such as alkyl and alkenyl chains comprising from 8 to 120 carbon atoms, bonded to the polymer skeleton via at least one linking group chosen from amines, ureas, and esters, wherein when the at least one linking group is chosen from esters, the at least one terminal fatty chain is chosen from branched alkyl groups. The at least one structuring polymer may also comprise at least one pendant fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains, such as alkyl and alkenyl chains having at least four carbon atoms, and further such as alkyl and alkenyl chains comprising from 8 to 120 carbon atoms, bonded to any carbon or hetero atom of the polymer skeleton via at least one linking group chosen from amines, ureas, and esters, wherein when said at least one linking group is chosen from esters, the at least one pendant fatty chain is chosen from branched alkyl groups. The at least one structuring polymer may comprise both at least one pendant fatty chain and at least one terminal fatty chain as defined above in this paragraph, and both may be optionally functionalized. Another embodiment of the invention is drawn to a composition comprising at least one liquid fatty phase which comprises at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Further, an embodiment of the invention relates to a keratinous material care, treatment, or make-up composition comprising a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Additionally, an embodiment of the invention relates to a keratinous material care or make-up composition comprising a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom, at least one coloring agent, and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to a mascara, an eyeliner, a foundation, a lipstick, a blusher, a make-up-removing product, a make-up product for the body, an eyeshadow, a face powder, a concealer product, a shampoo, a conditioner, an antisun product or a care product for at least one keratinous material comprising a composition comprising at least one liquid fatty phase in the mascara, eyeliner, foundation, lipstick, blusher, make-up- removing product, make-up product for the body, eyeshadow, face powder, concealer product, shampoo, conditioner, antisun product or care product for the skin, lips, or hair which comprises: (i) at least one structuring polymer, e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to a deodorant product or a care product for the skin or body comprising an anhydrous composition comprising at least one liquid fatty phase in the product which comprises:
(i) at least one structuring polymer, e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to a lip composition in stick form comprising at least one continuous liquid fatty phase, at least one non-waxy structuring polymer, e.g., a polyamide polymer, having a weight- average molecular mass of less than 100,000, and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to a method for care, make-up or treatment of at least one keratinous material comprising applying to the at least one keratinous material an anhydrous composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker. Another embodiment of the invention relates to a method for care, make-up or treatment of at least one keratinous material comprising applying to the at least one keratinous material a composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to a method for providing an anhydrous composition having at least one property chosen from non- exudation, gloss, and comfortable deposit on at least one keratinous material, comprising including in the composition at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to an anhydrous composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, e.g., a polyamide polymer, comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker, wherein said at least one structuring polymer is not a polymer of formula (II): R-O-CO-NH-R'-NH-CO-NH-R"-NH-CO-NH-R'-NH-CO-OR (II)
wherein R represents CnH n+i- or CmH2m+ι (CpH2pO)r -; n represents an integer having a value of from 4 to 22; m represents an integer having a value of from 1 to 18; p represents an integer having a value of from 2 to 4; and r represents an integer having a value of from 1 to 10; R' represents:
Figure imgf000022_0001
or -(CH2)6-
and R" represents:
Figure imgf000022_0002
Another embodiment of the invention relates to a method of making up or caring for at least one keratinous material comprising applying to the at least one keratinous material a structured composition containing at least one liquid fatty phase structured with at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to an anhydrous composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, e.g., a polyamide polymer, comprising a polymer skeleton which comprises at least three hydrocarbon- based repeating units comprising at least one hetero atom; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker, and for example, the at least three hydrocarbon-based repeating units can be identical.
Another embodiment of the invention relates to a composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer chosen from urea urethanes having the following formula (II):
R-0-CO-NH-R'-NH-CO-NH-R"-NH-CO-NH-R*-NH-CO-OR (II)
wherein R represents CnH2n+i- or CmH2 +ι (OCpH2p)r -, wherein n represents an integer having a value greater than 22, wherein m represents an integer having a value of greater than 18, p represents an integer having a value of from 2 to 4, and r represents an integer having a value of from 1 to 10, R' represents:
Figure imgf000023_0001
and R" represents:
Figure imgf000024_0001
; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to a composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom, with the proviso that the at least one hetero atom is not nitrogen; and
(ii) at least one of (a) and (b), wherein (a) is chosen from at least one oil-soluble ester and (b) is chosen from at least one UV blocker.
Another embodiment of the invention relates to a composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising a non-pendant nitrogen atom, and at least one terminal fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains having at least four carbon atoms, and
(ii) at least one oil-soluble ester.
Another embodiment of the invention relates to a composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising a non-pendant nitrogen atom, and at least one terminal fatty chain, optionally functionalized, chosen from alkyl and alkenyl chains having at least four carbon atoms, and
(ii) at least one UV blocker. Liquid fatty phase
The at least one liquid fatty phase, in one embodiment, may comprise at least one oil. In one embodiment, the at least one oil may have an affinity for the at least one structuring polymer. The at least one oil may, for example, be chosen from polar oils and apolar oils including hydrocarbon-based liquid oils and oily liquids at room temperature. In one embodiment, the composition of the invention comprises at least one structuring polymer and at least one polar oil. The polar oils of the invention may, for example, be added to the apolar oils, the apolar oils acting, for example, as co-solvent for the polar oils.
According to the invention, the structuring of the at least one liquid fatty phase may be obtained with the aid of at least one structuring polymer, such as the polyamide polymer of formula (I). In general, the polymers of formula (I) may be in the form of mixtures of polymers, these mixtures also possibly containing a synthetic product corresponding to a compound of formula (I) in which n is 0, i.e., a diester.
In one embodiment, the liquid fatty phase of the composition may contain more than 30%, for example, more than 40%, of liquid oil(s) having a chemical nature close to the chemical nature of the skeleton (hydrocarbon or silicone based) of the structuring polymer, and for example from 50% to 99.4%. In one embodiment, the liquid fatty phase structured with a polyamide-type, polyurea-type, polyurethane-type, or polyurea-urethane-type skeleton contains a high quantity, i.e., greater than 30%, for example greater than 40%, relative to the total weight of the liquid fatty phase, or from 50% to 99.4%, of at least one apolar, such as hydrocarbon-based, oil. For the purposes of the invention, the expression "hydrocarbon-based oil" means an oil comprising carbon and hydrogen atoms, optionally with at least one group chosen from hydroxyl, ester, carboxyl, and ether groups.
For a liquid fatty phase structured with a polymer containing a partially silicone-based skeleton, this fatty phase may contain more than 30%, for example, more than 40%, relative to the total weight of the liquid fatty phase and, for example, from 50% to 99.4%, of at least one silicone-based liquid oil, relative to the total weight of the liquid fatty phase.
For a liquid fatty phase structured with at least one structuring polymer of the hydrocarbon-based type, this fatty phase may contain more than 30%, for example more than 40% by weight, and, as a further example, from 50% to 99.4% by weight, of at least one liquid apolar, such as hydrocarbon-based, oil, relative to the total weight of the liquid fatty phase.
For example, the at least one polar oil useful in the invention may be chosen from:
- hydrocarbon-based plant oils with a high content of triglycerides comprising fatty acid esters of glycerol in which the fatty acids may have varied chain lengths from C to C24, these chains possibly being chosen from cyclic, linear and branched, saturated and unsaturated chains; these oils can be chosen from, for example, wheat germ oil, corn oil, sunflower oil, karite butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, cotton oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, rapeseed oil, avocado oil, hazelnut oil, grape seed oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passion flower oil and musk rose oil; or alternatively caprylic/capric acid triglycerides such as those made or sold by Stearineries Dubois or those made or sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel;
- synthetic oils or esters of formula R5COOR6 in which R5 is chosen from cyclic, linear and branched fatty acid residues containing from 1 to 40 carbon atoms and Re is chosen from, for example, a hydrocarbon-based chain containing from 1 to 40 carbon atoms, such as, for example, from 1 to 4 carbon atoms, on condition that R5 + R6 > 10, such as, for example, purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alkyl benzoates, isopropyl myristate, 2-ethylhexyl palmitate, isostearyl isostearate and alkyl or polyalkyl octanoates, decanoates or ricinoleates; hydroxylated esters such as isostearyl lactate and diisostearyl malate; and pentaerythritol esters;
- synthetic ethers containing from 10 to 40 carbon atoms;
- Cs to C26 fatty alcohols such as oleyl alcohol; and
- Cs to C26 fatty acids such as oleic acid, linolenic acid or linoleic acid.
The at least one apolar oil according to the invention may be chosen from, for example, silicone oils chosen from volatile and non-volatile, branched, linear and cyclic polydimethylsiloxanes (PDMSs) that are liquid at room temperature; polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendant and/or at the end of the silicone chain, the groups each containing from 2 to 24 carbon atoms; phenylsilicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxysilicates; hydrocarbons chosen from cyclic, linear and branched, volatile and non-volatile hydrocarbons of synthetic and mineral origin, such as volatile liquid paraffins (such as isoparaffins and isododecane) or non-volatile liquid paraffins and derivatives thereof, liquid petrolatum, liquid lanolin, polydecenes, hydrogenated polyisobutene such as hydrogenated polybutene, for example Parleam® from Nippon Oils and Fats, and squalane; and mixtures thereof. The structured oils, for example those structured with polyamides such as those of formula (I), or with polyurethanes, polyureas, or polyurea-urethanes, in accordance with the invention, may be, in one embodiment, apolar oils, such as an oil or a mixture of hydrocarbon oils chosen from those of mineral and synthetic origin, chosen from hydrocarbons such as alkanes such as Parleam® oil, isoparaffins including isododecane, and squalane, and mixtures thereof. These oils may, in one embodiment, be combined with at least one phenylsilicone oil.
The liquid fatty phase, in one embodiment, contains at least one nonvolatile oil chosen from, for example, hydrocarbon-based oils of mineral, plant and synthetic origin, synthetic esters or ethers, silicone oils, and mixtures thereof.
In another embodiment, the total liquid fatty phase can be, for example, present in an amount ranging from 1% to 99.4% by weight, relative to the total weight of the composition, for example from 5% to 99.4%, from 5% to 95.5%, from 10% to 80%, or from 20% to 75%.
For the purposes of the invention, the expression "volatile solvent or oil" means any non-aqueous medium capable of evaporating on contact with the skin or the lips in less than one hour at room temperature and atmospheric pressure. The volatile solvent(s) of the invention is(are) organic solvents, such as volatile cosmetic oils that are liquid at room temperature, having a non-zero vapor pressure at room temperature and atmospheric pressure, ranging, for example, from 10"2 to 300 mmHg (1.33 Pa to 10,000 Pa), for example greater than 0.03 mmHg (4 Pa), and, as a further example, greater than 0.3 mmHg (40 Pa). The expression "non-volatile oil" means an oil which remains on the skin or the lips at room temperature and atmospheric pressure for at least several hours, such as those having a vapor pressure of less than 10"2 mmHg (1.33 Pa).
According to the invention, these volatile solvents or oils may facilitate the staying power or long wearing properties of the composition on the skin, the lips or superficial body growths, such as nails and keratinous fibers. The solvents can be chosen from hydrocarbon-based solvents, silicone solvents optionally comprising alkyl or alkoxy groups that are pendant or at the end of a silicone chain, and a mixture of these solvents. The volatile oil(s), in one embodiment, may be present in an amount ranging up to 95.5% relative to the total weight of the composition, such as from 2% to 75%, and, as a further example, from 10% to 45%. This amount will be adapted by a person skilled in the art according to the desired staying power or long wearing properties.
The at least one liquid fatty phase of the compositions of the invention may further comprise a dispersion of lipid vesicles. The compositions of the invention may also, for example, be in the form of a fluid anhydrous gel, a rigid anhydrous gel, a fluid simple emulsion, a fluid multiple emulsion, a rigid simple emulsion or a rigid multiple emulsion. The simple emulsion or multiple emulsion may comprise a continuous phase chosen from an aqueous phase optionally containing dispersed lipid vesicles, or a fatty phase optionally containing dispersed lipid vesicles. In one embodiment, the composition has a continuous oily phase or fatty phase and is more specifically an anhydrous composition, for example, a stick or dish form. An anhydrous composition is one that has less than 10% water by weight, such as, for example, less than 5% by weight. Oil-Soluble Ester
The compositions of the invention also comprise at least one oil-soluble ester comprising at least one free hydroxy group. In one embodiment, any oil- soluble ester comprising at least one free hydroxy group may be within the practice of the invention, with the proviso that the at least one oil-soluble ester comprising at least one free-hydroxy group is not castor oil. In this embodiment, while a composition of the invention may, for example, further comprise castor oil, castor oil alone in combination with at least one structuring polymer is not within the practice of the invention. In another embodiment embodiment, the at least one oil-soluble ester is not sucrose acetate isobutyrate.
The at least one oil-soluble ester comprising at least one free hydroxy group may be chosen from, for example, castor oil, propylene glycol ricinoleate, isopropyl hydroxystearate, triisocetyl citrate, diisostearyl malate, octyl hydroxystearate, triisoarachidyl citrate, cetyl lactate, dioctyl malate, octyldodecyl hydroxystearate, di-isostearyl malate, and di-isostearyl lactate.
In one embodiment, the at least one oil-soluble ester comprising at least one free hydroxy group, such as, for example, diisostearyl malate and triisocetyl citrate, may add stability. For example, the use of these esters may minimize oil droplet formulation at room temperature and elevated temperature storage. The introduction of at least one hydroxy-bearing oil- soluble ester, in addition, may dramatically improve the overall softening point of a finished clear anhydrous stick.
In a further embodiment, certain at least one oil-soluble esters comprising at least one free hydroxy group may provide the firmest and clearest composition and stick, and may also improve the gelling efficiency in relation to a composition comprising structuring polymers alone. For example, a composition comprising from 16 to 20% structuring polymer with the at least one oil-soluble ester comprising at least one free hydroxy group chosen from isopropyl hydroxystearate has exhibited excellent clarity and structure.
Depending on the at least one structuring polymer and its amount and the at least one oil-soluble ester comprising at least one free hydroxy group and its amount, some compositions may develop syneresis after aging for one day at 25°C, which may be disadvantageous in certain embodiments. The skilled artisan may be able to cure this defect by varying the at least one structuring polymer and/or the at least one oil-soluble ester comprising at least one free hydroxy group. The skilled artisan may also be able to cure this defect by varying the amount of at least one of these ingredients.
In one embodiment, the at least one oil-soluble ester comprising at least one free hydroxy group may be present in the composition in an amount ranging from 10% to 84% by weight relative to the total weight of the composition, such as, for example, from 20% to 70%.
The amounts of the at least one structuring polymer and of the at least one oil-soluble ester comprising at least one free-hydroxy group, however, may be chosen according to the desired hardness and desired stability of the composition, and according to the specific application envisaged. The respective amounts of the at least one structuring polymer and of the at least one oil-soluble ester comprising at least one free-hydroxy group can be such that a disintegrable solid which does not flow under its own weight is obtained.
Depending on the intended application, such as a stick, hardness of the composition may also be considered. The hardness of a composition may, for example, be expressed in gram force (gf). The composition of the present invention may, for example, have a hardness ranging from 20 gf to 2000 gf, such as from 20 gf to 900 gf, and further such as from 20 gf to 600 gf.
This hardness can be measured in one of two ways. A first test for hardness is according to a method of penetrating a probe into said composition and in particular using a texture analyzer (for example TA-XT2i from Rheo) equipped with an ebonite cylinder of height 25 mm and diameter 8 mm. The hardness measurement is carried out at 20°C at the center of 5 samples of the composition. The cylinder is introduced into each sample of composition at a pre-speed of 2 mm/s and then at a speed of 0.5 mm/s and finally at a post-speed of 2 mm/s, the total displacement being 1 mm. The recorded hardness value is that of the maximum peak observed. The measurement error is ± 50 gf.
A second test for hardness is the "cheese wire" method, which involves cutting an 8.1 mm or 12.7 mm stick of composition and measuring its hardness at 20°C using a DFGHS 2 tensile testing machine from Indelco- Chatillon Co. at a speed of 100 mm/minute. The hardness value from this method is expressed in gram force as the shear force required to cut a stick under the above conditions. According to this method, the hardness of compositions according to the present invention which may be in stick form may, for example, range from 30 gf to 300 gf, such as from 30 gf to 250 gf, and further such as from 30 gf to 200 gf. The hardness of the compositions of the present invention may be such that the compositions are self-supporting and can easily disintegrate to form a satisfactory deposit on at least one keratinous material. In addition, this hardness may impart good impact strength to the inventive compositions which may be molded or cast, for example, in stick or dish form.
The skilled artisan may choose to evaluate a composition using at least one of the tests for hardness outlined above based on the application envisaged and the hardness desired. If one obtains an acceptable hardness value, in view of the intended application, from at least one of these hardness tests, the composition falls within the scope of the invention.
According to the present invention, the compositions in stick form may also possess the properties of deformable, flexible elastic solids and may also have noteworthy elastic softness upon application to at least one keratinous material. The compositions in stick form of the prior art do not have this elasticity and flexibility. Fatty Alcohol
The compositions of the invention may further comprise at least one fatty alcohol. The at least one fatty alcohol may be chosen from, for example, C8 to C26, such as from, C12 to C22 fatty alcohols. In one embodiment, the at least one fatty alcohol is chosen from myristyl, cetyl, stearyl, and behenyl alcohol. The fatty alcohols may, for example, be present in the composition in an amount ranging from 0.1 % to 15.0% by weight, relative to the total weight of the composition, such as, for example, from 0.5% to 10%, and as a further example, from 0.5% to 8.0%. In a further embodiment, the skilled artisan may be able to cure a stability defect by the addition of at least one fatty alcohol to the composition. For example, the addition of at least one fatty alcohol may improve stick structure, minimize syneresis, and generally improve application properties without interfering with stick transparency, as compared to a composition that does not contain the at least one fatty alcohol. Oil-Soluble Polymer
The compositions of the invention may further comprise at least one oil-soluble polymer chosen from alkylated guar gums and alkyl celluloses. Alkylated guar gums include, for example, ethyl guars and Cι_5 alkyl galactomannans, such as N-HANCE AG-50 and N-HANCE AG-200 from Aqualon. An alkyl cellulose, may be chosen from, for example, ethylcellulose (such as ETHOCEL, from Dow Chemical). In one embodiment, the at least one oil-soluble polymer may be present in the composition in an amount ranging from 0.05% to 10.0% by weight relative to the total weight of the composition, such as, for example, from 0.1% to 5%, and as a further example, from 0.1 % to 3%. These ingredients can further stabilize, for example, a clear sunscreen complex composition, against syneresis.
In one embodiment, a composition according to the invention may be stabilized by the inclusion of at least one oil-soluble polymer chosen from alkyl celluloses. In a further embodiment, at least one alkyl galactomannan, such as N-HANCE AG-50, may be used to stabilize a stick composition against stick syneresis, particularly at elevated temperatures such as, for example, 45°C. Oil-Soluble Cationic Surfactant
As described above, the compositions of the invention may further comprise at least one oil-soluble cationic surfactant. In one embodiment, the at least one oil-soluble cationic surfactant may be chosen from lauryl methyl gluceth-10-hydroxypropyl dimmonium chloride, which may impart cosmetic elegance to a composition. The at least one oil-soluble cationic surfactant may also, for example, be chosen from quaternary ammonium compounds including salts of quaternary ammonium compounds and fatty amines including salts of fatty amines. As used herein cosmetic elegance refers to substantially low tackiness, ease of application, or elegant feel.
In one embodiment, the at least one oil-soluble cationic surfactant is chosen from water-insoluble surfactants of the formula
Figure imgf000034_0001
wherein Ri, R2, R3, and R4 are independently chosen from aliphatic groups of from 1 to 22 carbon atoms and C1-C3 alkyl, hydroxyalkyl, polyalkoxy, aromatic, aryl, and alkylaryl groups having from 12 to 22 carbon atoms, and X is chosen from halogen, acetate, phosphate, nitrate, and alkylsulfate radicals. The aliphatic groups may, for example, contain in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups.
The at least one oil-soluble cationic surfactant may also, for example, be chosen from quaternary ammonium salts of the formula
Figure imgf000034_0002
wherein Ri is an aliphatic group having from 16 to 22 carbon atoms; R2, R3, R4, R5, and R6 are independently chosen from hydrogen and alkyl having from 1 to 4 carbon atoms, and X is chosen from halogen, acetate, phosphate, nitrate, and alkyl sulfate radicals. The at least one oil-soluble cationic surfactant may, for example, be tallow propane diammonium dichloride.
Non-limiting examples of the at least one oil-soluble cationic surfactant include the quaternary ammonium salts: dialkyldimethyl-ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids yield quaternary compounds wherein Ri and R2 have predominately from 16 to 18 carbon atoms); ditallowdimethyl ammonium chloride; ditallowdimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium acetate; dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrate; di(coconutalkyl) dimethyl ammonium chloride; diceltyl dimethyl ammonium chloride; stearyl dimethyl benzyl ammonium chloride; behenyl trimethyl ammonium chloride, and; di- (hydrogenated tallow) dimethyl ammonium chloride.
Non-limiting examples of the at least one oil-soluble cationic surfactant also include salts of primary, secondary, and tertiary fatty amines. In one embodiment, the salts of primary, secondary, and tertiary fatty amines may comprise alkyl groups having from 12 to 22 carbon atoms, and may be substituted and unsubstituted. Amines may be chosen from, for example, stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, tridecyl amine, ethyl stearylamine, ethoxylated (2 moles E.O.) stearylamine, dihydroxyethyl stearylamine, and arachidylbehenylamine. Amine salts may be chosen from, for example, halogens, acetates, phosphates, nitrates, citrates, lactates, and alkyl sulfates. In one embodiment, the amine salts are chosen from stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diaminedichloride, and stearamidopropyl dimethylamine citrate. The at least one oil-soluble cationic surfactant may also be chosen from cationic amine surfactants disclosed in U.S. Patent No. 4,275,055.
In another embodiment, the at least one oil-soluble cationic surfactant may be chosen from quaternary imidazolinium compounds including quaternary imidazolinium salts. Quaternary imidazolinium compounds include, for example, imidazolinium compounds containing C12 - C22 alkyl groups such as 1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4,5- dihydroimidazolinium chloride, 1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl- 4,5-dihydroimidazolinium chloride and 1-methyl-1-[(tallowamide)-ethyl]-2- tallow-imidazolinium methyl sulfate. The at least one oil-soluble cationic surfactant may also be chosen from conditioning agents that are disclosed in U.S. Patent No. 4,387,090.
The at least one oil-soluble cationic surfactant may be present in the composition, for example, in an amount ranging from 0.1% to 10% by weight relative to the weight of the composition, such as, for example, from 0.1 % to 5.0%, and as a further example from 0.5% to 2.0%. Wax
According to another embodiment, the compositions of the invention may further comprise at least one wax. At least one wax, for example, may be used to form a non-transparent composition. As used herein, a "wax" may be any lipophilic fatty compound which is soluble in the liquid fatty phase, unlike most fillers or pigments. The at least one wax, for example, may have a melting point greater than about 45°C, such as, for example greater than about 55°C. Non-limiting examples of such waxes include waxes of natural origin, such as beeswax, carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fiber wax, sugar cane wax, paraffin waxes, lignite wax, microcrystalline waxes, lanolin wax, montan wax and ozokerites, hydrogenated oils such as hydrogenated jojoba oil, jojoba esters, waxes of synthetic origin, such as polyethylene waxes derived from polymerization of ethylene, waxes obtained by Fischer-Tropsch synthesis, fatty acid esters and glycerides, and silicone waxes such as derivatives of poly(di)methylsiloxane. In one embodiment, the at least one wax may be present in the composition in an amount up to 3%, and in another embodiment in an amount of at least 3%, such as up to 30% or up to 50%.
Needless to say, the compositions of the invention should be cosmetically and/or dermatologically acceptable, i.e., they should contain a non-toxic physiologically acceptable medium and should be able to be applied to human keratinous materials. Thus, the composition of the present invention, in one embodiment, may comprise a physiologically acceptable medium, e.g., a physiologically acceptable oil or solvent. For purposes of the invention, "cosmetically and/or dermatologically acceptable" means that compositions of the invention have a pleasant appearance, odor, and taste.
The composition may also further comprise at least one suitable additive commonly used in the field concerned chosen from coloring agents, antioxidants, essential oils, preserving agents, fragrances, neutralizing agents, liposoluble or lipodispersible gelling agents, liposoluble polymers, and cosmetically active agents and dermatological active agents (i.e., an agent having a beneficial effect on the skin, lips, or superficial body growths) such as, for example, emollients, moisturizers, vitamins, essential fatty acids, and sunscreens. The compositions of the invention may further comprise at least one additional fatty material. The at least one additional fatty material may, for example, be chosen from gums, fatty materials that are pasty or viscous at ambient temperature, and resins.
The at least one additive may be present in an amount ranging from 0.01% to 20% by weight of the total weight of the composition, such as from 0.01% to 10%.
Needless to say, the person skilled in the art will take care to select the optional additional additives and the amount thereof such that at least one advantageous property of the composition according to the invention, such as stability, is not, or is not substantially, adversely affected by the addition(s) envisaged.
The compositions of the invention may also comprise at least one coloring agent chosen from pigments, dyes, nacreous pigments (i.e., nacres), and pearling agents. The at least one coloring agent may be chosen, for example, in order to obtain make-up compositions which give good coverage, that is, which do not leave a significant amount of the at least one keratinous material to which it is applied showing through. The pigments may also reduce the sticky feel of the compositions, unlike soluble dyes. In one embodiment, the coloring agents are pigments (nacreous or non-nacreous).
Representative liposoluble dyes which may be used according to the present invention include Sudan red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan brown, DC Yellow 11 , DC Violet 2, DC Orange 5, quinoline yellow, and annatto. The liposoluble dyes, when present, may have an amount ranging up to 20% by weight of the total weight of the composition, such as from 0.1% to 6%.
The pigments which may be used according to the present invention may be chosen from white, colored, mineral, organic, coated and uncoated pigments. Representative examples of mineral pigments include titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Representative examples of organic pigments include carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium and aluminum. If present, the pigments may have an amount ranging up to 40% by weight of the total weight of the composition, such as from 1% to 35%, and further such as from 2% to 25%.
The nacreous pigments (or nacres) which may be used according to the present invention may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment chosen from those mentioned above, and nacreous pigments based on bismuth oxychloride. The nacres, if present, may have an amount ranging up to 30% by weight of the total weight of the composition, such as from 0.1 % to 20%.
Another invention disclosed herein provides a composition comprising at least one structuring polymer, as described herein, and at least one UV blocker. The composition may further comprise a physiologically acceptable medium. The at least one UV blocker, may be chosen from, for example, organic filters including hydrophilic and lipophilic organic filters, inorganic nanoparticles and mixtures thereof.
The compositions of the invention may be sunscreen or anti-sun compositions, and may comprise an effective amount of at least one UV blocker to impart complete or partial protection from UV-A and/or UV-B rays to the surface to which they are applied, such as, for example, keratinous materials.
By "UV blocker" it is meant any compound or any combination of compounds which, by mechanisms that are known perse of absorption and/or reflection and/or scattering of UV-A and/or UV-B radiation, prevents, or at least limits, the contact between such radiation and a surface (such as, for example, keratinous materials) on which the composition of the invention has been applied, including, for example, any sunscreen agent, sunblock agent, UV screener, or UV blocker. It should be noted that these terms are commonly used interchangeably in the art to indicate UV blockers as defined herein. In other words, the UV blockers may be UV-absorbing organic screening agents or inorganic nanopigments which scatter and/or reflect UV radiation, as well as mixtures thereof.
According to the present invention, the compositions and sunscreen compositions may comprise one or more hydrophilic organic UV blockers and/or one or more lipophilic organic UV blockers and/or one or more mineral or inorganic nanopigments. An example of a UV blocker useful according to the present invention is the dibenzoylmethane sunscreen avobenzone, or 4- (tert-butyl)-4-methoxydibenzoylmethane, which is well known in the art. This UV blocker is commercially available and is marketed, for example, under the trademark "PARSOL 1789" by Givaudan. It has the structural formula;
Figure imgf000040_0001
UV blockers according to the present invention which are physical blockers reflect or scatter ultraviolet radiation. Typical examples of physical blockers include red petrolatum, titanium dioxide, and zinc oxide. Physical blockers generally block broad spectrum radiation, including UV-A and UV-B radiation. These physical blockers have been employed in a variety of suspensions and particle sizes and are frequently included in cosmetic formulations. A review of physical blockers may be found at "Sun Protection Effect of Nonorganic Materials," by S. Nakada & H. Konishi, Fragrance Journal, Volume 15, pages 64-70 (1987).
UV blockers according to this invention which are chemical absorbers, like avobenzone, actually absorb harmful ultraviolet radiation. It is well known that chemical absorbers are classified, depending on the type of radiation they protect against, as either UV-A or UV-B absorbers. UV-A absorbers generally absorb radiation in the 320 to 400 nm region of the ultraviolet spectrum. UV-A absorbers include anthranilates, benzophenones, and dibenzoyl methanes. UV-B absorbers generally absorb radiation in the 280 to 320 nm region of the ultraviolet spectrum. UV-B absorbers include p-aminobenzoic acid derivatives, camphor derivatives, cinnamates, and salicylates.
Classifying the chemical absorbers generally as UV-A or UV-B absorbers is accepted within the industry. However, a more precise classification is one based upon the chemical properties of the UV blockers. There are eight major classifications of the chemical properties of UV blockers which are discussed at length in "Sunscreens-Development, Evaluation and Regulatory Aspects," by N. Shaath et al., 2nd. Edition, pages 269-273, Marcel Dekker, Inc. (1997).
The UV blockers that are useful according to the present invention typically include chemical UV absorbers, but may also include physical UV blockers. Exemplary UV blockers which may be formulated into the compositions of the present invention are chemical absorbers such as p- aminobenzoic acid derivatives, anthranilates, benzophenones, camphor derivatives, cinnamic derivatives, dibenzoyl methanes, diphenylacrylate derivatives, salicylic derivatives, triazine derivatives, benzimidazole compounds, bis-benzoazolyl derivatives, methylene bis- (hydroxyphenylbenzotriazole) compounds, sunscreen polymers, sunscreen silicones, and mixtures thereof. Examples of these UV blockers can be found, for example, in U.S. Patents Nos. 2,463,264, 4,367,390, 5,166,355, and 5,237,071 , and in EP-0,863,145, EP-0,517,104, EP-0,570,838, EP-0,796,851 , EP-0,775,698, EP-0,878,469, EP-0,933,376, EP-0,893,119, EP-0,669,323, GB-2,303,549, DE-1 ,972,184, and WO-93/04665.
Also exemplary of the UV blockers which may be formulated into the compositions of this invention are physical UV blockers such as cerium oxides, chromium oxides, cobalt oxides, iron oxides, red petrolatum, silicone- treated titanium dioxide, titanium dioxide, zinc oxide, and zirconium oxide, and mixtures thereof.
Further examples of UV blockers useful according to the present invention can be found, for example, in Chapter VIII of Cosmetics and Science and Technology by Segarin et al., pages 189 et seq. (1957), and U.S. Patent No. 5,087,445 and U.S. Patent No. 5,073,372.
Examples of UV blockers which may be formulated into the compositions of the present invention also include those chosen from aminobenzoic acid, amyldimethyl PABA, cinoxate, diethanolamine p- methoxycinnamate, digalloyl trioleate, dioxybenzone, 2-ethoxyethyl p- methoxycinnamate, ethyl 4-bis(hydroxypropyl)aminobenzoate, 2-ethylhexyl-2- cyano-3,3-diphenylacrylate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl salicylate, glyceryl aminobenzoate, homomenthyl salicylate, homosalate, 3- imidazol-4-ylacιγlic acid and ethyl ester, methyl anthranilate, octyldimethyl PABA, 2-phenyIbenzimidazole-5-sulfonic acid and salts, red petrolatum, sulisobenzone, titanium dioxide, triethanolamine salicylate, N, N, N-trimethyl- 4-(2-oxoborn-3-ylidene methyl)anillinium methyl sulfate, and mixtures thereof. Further examples of UV blockers active in the UV-A and/or UV-B range that can be used in accordance with the present invention include p- aminobenzoic acid, oxyethylene (25 mol) p-aminobenzoate, 2-ethylhexyl p- dimethylaminobenzoate, ethyl N-oxypropylene p-aminobenzoate, glycerol p- aminobenzoate, 4-isopropylbenzyl salicylate, 2-ethylhexyl 4- methoxycinnamate, methyl diisopropylcinnamate, isoamyl 4- methoxycinnamate, diethanolamine 4-methoxycinnamate, 3-(4'- trimethylammunium)-benzyliden-bornan-2-one methylsulfate, 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2,4- dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4'dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- hydroxy-4-methoxy-4'-methoxybenzophenone, -(2-oxobom-3-ylidene)-tolyl-4- sulfonic acid and soluble salts thereof, 3-(4'-suIfo)benzyliden-bornan-2-one and soluble salts thereof, 3-(4'methylbenzylidene)-d,l-camphor, 3- benzylidene-d,l-camphor, benzene 1 ,4-di(3-methylidene-10-camphosulfonic) acid and salts thereof (such as, for example, the product Mexoryl SX described in U.S. Patent No. 4,585,597 issued to Lang et al. on April 29, 1986), urocanic acid, 2,4,6-tris[p-(2'-ethylhexyl-1'-oxycarbonyl)-anilino]-1 ,3,5- triazine, 2-[(p-(tertiobutylamido)anilino]-4,6-bis-[(p-(2'-ethylhexyl-1'- oxycarbonyl)anilino]-1 ,3,5-triazine, 2,4-bis{[4-(2-ethyl-hexyloxy)]-2-hydroxy]- phenyl}-6-(4-methoxy- phenyl)-1 ,3,5-triazine ("TINOSORB S" marketed by Ciba), the polymer of N-(2 et 4)-[(2-oxoborn-3-yliden)methyl]benzyl]- acrylamide, 1 ,4-bisbenzimidazolyl-phenylen-3,3',5,5'-tetrasulfonic acid and salts thereof, the benzalmalonate-substituted polyorganosiloxanes, the benzotriazole-substituted polyorganosiloxanes (Drometrizole Trisiloxane), dispersed 2,2'-methylene-bis-[6-(2H-benzotriazol-2-yI)-4-(1 ,1 ,3,3- tetramethylbutyl)phenol] such as, for example, that marketed under the trademark MIXXIM BB/100 by Fairmount Chemical, or micronized in dispersed form such as, for example, that marketed under the trademark TINOSORB M by Ciba-Geigy, and solubilized 2,2'-methylene-bis-[6-(2H- benzotriazol-2-yI)-4-(methyl)phenol] such as, for example, that marketed under the trademark MIXXIM BB/200 by Fairmount Chemical.
Additional useful UV blockers according to the invention include octyl salicylate, octocrylene, and oxybenzone. For example, the UV blocker may be NEO HELIOPAN 303. Combinations of one of more of any of the above- mentioned UV blockers are also useful according to the present invention.
The dibenzoyl methane derivatives other than avobenzone are also useful UV blockers according to the present invention. These are described, for example, in FR-2,326,405, FR-2,440,933 and EP-0,114,607. These include, for example, 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyIdibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4- dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'- diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 2-methyl-5- isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'- methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6- dimethyl-4-tert.-butyl-4'-methoxydibenzoylmethane, and mixtures thereof.
If present the at least one UV blocker may be present in the compositions of the invention in amounts ranging from about 0.01% to about 30%, for example, from about 0.1% to about 15%, such as, for example, from 0.5% to 15%, and further, for example, from about 0.5% to about 6%, by weight thereof. Of course, depending upon the nature of the particular formulation, higher or lower amounts may be suitable. Furthermore, one or more UV blockers may be used in a composition.
The packaging and application device for any subject of the invention may be chosen and manufactured by persons skilled in the art on the basis of their general knowledge, and adapted according to the nature of the composition to be packaged. Indeed, the type of device to be used may be, for example, linked to the consistency of the composition, for example, to its viscosity; it may also depend on the nature of the constituents present in the composition, such as the presence of volatile compounds.
The invention will be illustrated by, but is not intended to be limited to, the following examples, wherein the amounts are given as percentages by mass.
Example 1: Clear Anhydrous Sunscreen Stick TABLE 1
Figure imgf000045_0001
actives, anti-oxidants, and dermatological actives.
The compositions of table 1 were prepared using the following procedure. The ingredients of phase A were added to a main vessel and heated to 110°C - 115°C while mixing with the aid of an impeller mixer. At 110°C - 115°C, phase B was added to phase A with continued mixing. The beads of polyamide resin were allowed to dissolve and the mixture was removed from the heat and cooled to 80°C - 82°C. Phases C, D, and E were added to the AB mixture while maintaining the temperature at about 80 °C - 82°C with slow impeller mixing. The compositions were mixed until homogeneous (about 1 minute), then used to fill a suitable container or mold.
The resulting compositions were firm at room temperature (25°C). A very fine uniform oil coat covered the surface of some of the compositions, however, none of the compositions failed the stability test. At elevated temperatures (45°C), the overall structure and stick characteristics remained unchanged. There was a moderate oil coat on the surface of the stick structure of some of the compositions; however, none of the compositions failed the stability test.
Example 2: Clear Anhydrous Sunscreen Stick with an Oil-Soluble Cationic Polymer
TABLE 2
Figure imgf000046_0001
The compositions of table 2 were prepared using the following procedure. The ingredients of phase A were added to a main vessel and heated to 110°C - 115°C while mixing with the aid of an impeller mixer. At 110°C - 115°C, phase B was added to phase A with continued mixing. The beads of polyamide resin were allowed to dissolve and the mixture was removed from the heat and cooled to 80°C - 82°C. Phases C and D were added to the AB mixture while maintaining the temperature at about 80°C - 82°C with slow impeller mixing. The compositions were mixed until homogeneous (about 1 minute), then used to fill a suitable container or mold.
The resulting compositions were firm at room temperature (25°C). A very fine uniform oil coat covered the surface of some of the compositions, however, none of the compositions failed the stability test. At elevated temperatures (45°C), the overall structure and stick characteristics remained unchanged. There was a moderate oil coat on the surface of the stick structure of some of the compositions; however, none of the compositions failed the stability test.
Example 3: Clear Anhydrous Sunscreen Sticks with an Oil-Soluble Cationic Polymer
TABLE 3
Figure imgf000047_0001
The compositions of table 3 were prepared using the following procedure. The ingredients of phase A were added to a main vessel and heated to 110°C - 115°C while mixing with the aid of an impeller mixer. At 110°C - 115°C, phase B was added to phase A with continued mixing. The beads of polyamide resin were allowed to dissolve and the mixture was removed from the heat and cooled to 80°C - 82°C. Phases C, D, and E were added to the AB mixture while maintaining the temperature at about 80°C - 82°C with slow impeller mixing. The compositions were mixed until homogeneous (about 1 minute), then used to fill a suitable container or mold.
The resulting compositions were firm at room temperature (25°C). A very fine uniform oil coat covered the surface of some of the compositions; however, none of the compositions failed the stability test. At elevated temperatures (45°C), the overall structure and stick characteristics remained unchanged. There was a moderate oil coat on the surface of the stick structure; however, none of the compositions failed the stability test. Example 4: Lipsticks with an Oil-Soluble Cationic Polymer TABLE 4
Figure imgf000048_0001
The compositions were mixed until homogeneous, then used to fill a suitable container or mold. The compositions have good stability and 47°C, with no exudation. Example 5: Anhydrous Gel Lip Compositions TABLE 5
Figure imgf000049_0001
The compositions were mixed until homogeneous, then used to fill a suitable container or mold. The compositions have good stability at room temperature and good sunscreen properties.

Claims

WE CLAIM:
1. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group, with the proviso that said at least one oil-soluble ester is not castor oil.
2. The composition according to claim 1 , wherein the composition is in a form chosen from a fluid anhydrous gel, rigid anhydrous gel, fluid simple emulsion, rigid simple emulsion, fluid multiple emulsion, and rigid multiple emulsion.
3. A structured anhydrous composition comprising at least one liquid fatty phase structured with at least one structuring polymer comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom and at least one oil-soluble ester comprising at least one free hydroxy group, with the proviso that said at least one oil-soluble ester is not castor oil.
4. An anhydrous composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group, with the proviso that said at least one oil-soluble ester is not castor oil.
5. An anhydrous composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least three hydrocarbon- based repeating units comprising at least one hetero atom; and (ii) at least one oil-soluble ester comprising at least one free hydroxy group, with the proviso that said at least one oil-soluble ester is not castor oil.
6. An anhydrous composition according to claim 5, wherein the at least three hydrocarbon-based repeating units are identical.
7. The composition according to one of claims 1-6, wherein said at least one structuring polymer further comprises at least one of: at least one terminal fatty chain chosen from alkyl chains and alkenyl chains, wherein said at least one terminal fatty chain is bonded to said polymer skeleton via at least one linking group; and at least one pendant fatty chain chosen from alkyl chains and alkenyl chains, wherein said at least one pendant fatty chain is bonded to said polymer skeleton via at least one linking group.
8. The composition according to claim 7, wherein said alkyl chains and said alkenyl chains each comprise at least four carbon atoms.
9. The composition according to one of claims 7 or 8, wherein said alkyl chains and said alkenyl chains each comprise from 8 to 120 carbon atoms.
10. The composition according to one of claims 7-9, wherein said alkyl chains and said alkenyl chains each comprise from 12 to 68 carbon atoms.
11. The composition according to one of claims 7-10, wherein said at least one linking group is chosen from single bonds and urea, urethane, thiourea, thiourethane, thioether, thioester, ester, ether and amine groups.
12. The composition according to one of claims 7-11 , wherein said at least one linking group is chosen from urea, ester, and amine groups.
13. The composition according to one of claims 7-12, wherein said at least one linking group is chosen from ester and amine groups.
14. The composition according to one of claims 7-13, wherein said at least one linking group is an ester group present in a proportion ranging from 15% to 40% of the total number of all ester and hetero atom groups in the at least one structuring polymer.
15. The composition according to one of claims 7-14, wherein said at least one linking group is an ester group present in a proportion ranging from 20%) to 35% of the total number of all ester and hetero atom groups in the at least one structuring polymer.
16. The composition according to one of claims 7-15, wherein said at least one terminal fatty chain is functionalized.
17. The composition according to one of claims 7-16, wherein said at least one pendant fatty chain is functionalized.
18. The composition according to one of claims 7-17, wherein in said at least one structuring polymer, the percentage of the total number of fatty chains ranges from 40% to 98% relative to the total number of all repeating units and fatty chains in the at least one structuring polymer.
19. The composition according to one of claims 7-18, wherein in said at least one structuring polymer, the percentage of the total number of fatty chains ranges from 50% to 95% relative to the total number of all repeating units and fatty chains in the at least one structuring polymer.
20. The composition according to one of claims 1-19, wherein said at least one structuring polymer has a weight-average molecular mass of less than 100,000.
21. The composition according to one of claims 1-20, wherein said at least one structuring polymer has a weight-average molecular mass of less than 50,000.
22. The composition according to one of claims 1-21 , wherein said at least one structuring polymer has a weight-average molecular mass ranging from 1000 to 30,000.
23. The composition according to one of claims 1-22, wherein said at least one hydrocarbon based repeating unit comprises from 2 to 80 carbon atoms.
24. The composition according to one of claims 1-23, wherein said at least one hetero atom of said at least one hydrocarbon-based repeating unit is chosen from nitrogen, sulphur, and phosphorus.
25. The composition according to claim 24, wherein said at least one hetero atom is a nitrogen atom.
26. The composition according to one of claims 1-25, wherein said at least one hetero atom is combined with at least one atom chosen from oxygen and carbon to form a hetero atom group.
27. The composition according to claim 26, wherein said at least one hetero atom group is chosen from amide groups, carbamate groups, and urea groups.
28. The composition according to one of claims 26 or 27, wherein said at least one hetero atom group is an amide group and said polymer skeleton is a polyamide skeleton.
29. The composition according to one of claims 26-28, wherein said at least one hetero atom group is chosen from carbamate groups and urea groups and said polymer skeleton is chosen from a polyurethane skeleton, a polyurea skeleton and a polyurethane-polyurea skeleton.
30. The composition according to one of claims 1-29, wherein said at least one structuring polymer is chosen from polyamide polymers of formula (I):
Figure imgf000053_0001
in which:
- n is an integer which represents the number of amide units such that the number of ester groups present in said at least one polyamide polymer ranges from 10%) to 50% of the total number of all ester groups and all amide groups comprised in said at least one polyamide polymer; - R1, which are identical or different, are each chosen from alkyl groups comprising at least 4 carbon atoms and alkenyl groups comprising at least 4 carbon atoms;
- R2, which are identical or different, are each chosen from C4 to C42 hydrocarbon-based groups, with the proviso that at least 50% of all R2 are chosen from C30 to C42 hydrocarbon-based groups;
- R3, which are identical or different, are each chosen from organic groups comprising atoms chosen from carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, with the proviso that R3 comprises at least 2 carbon atoms; and
- R4, which are identical or different, are each chosen from hydrogen atoms, Cι to C10 alkyl groups and a direct bond to at least one group chosen from R3 and another R4 such that when said at least one group is chosen from another R4, the nitrogen atom to which both R3 and R4 are bonded forms part of a heterocyclic structure defined in part by R -N-R3, with the proviso that at least 50% of all R4 are chosen from hydrogen atoms.
31. The composition according to claim 30, wherein in said formula (I), n is an integer ranging from 1 to 5.
32. The composition according to one of claims 30 or 31 , wherein in said formula (I), said alkyl groups of R1 and said alkenyl groups of R1 each independently comprise from 4 to 24 carbon atoms.
33. The composition according to one of claims 30-32, wherein in said formula (I), R1, which are identical or different, are each chosen from C12 to C22 alkyl groups.
34. The composition according to one of claims 30-33, wherein in said formula (I), R1, which are identical or different, are each chosen from Cι6 to C22 alkyl groups.
35. The composition according to one of claims 30-34, wherein in said formula (I), R2, which are identical or different, are each chosen from C10 to C42 hydrocarbon based groups, with the proviso that at least 50% of all R2 are chosen from C30 to C42 hydrocarbon based groups.
36. The composition according to one of claims 30-35, wherein in said formula (I), R3, which can be identical or different, are each chosen from C2 to C36 hydrocarbon-based groups and polyoxyalkylene groups.
37. The composition according to one of claims 30-36, wherein R3, which can be identical or different, are each chosen from C2 to Cι2 hydrocarbon-based groups.
38. The composition according to one of claims 30-37, wherein in said formula (I), R4, which can be identical or different, are each chosen from hydrogen atoms.
39. The composition according to one of claims 30-38, wherein said at least one polymer of formula (I) is in the form of a mixture of polymers, wherein said mixture optionally also comprises a polymer of formula (I) wherein n is equal to zero.
40. The composition according to one of claims 1-39, wherein said at least one structuring polymer has a softening point greater than 50°C.
41. The composition according to one of claims 1-40, wherein said at least one structuring polymer has a softening point ranging from 65°C to less than 150°C.
42. The composition according to one of claims 1-41 , wherein said at least one structuring polymer has a softening point ranging from 70°C to less than 130°C.
43. The composition according to one of claims 1-42, wherein said at least one structuring polymer is present in the composition in an amount ranging from 0.5% to 80% by weight relative to the total weight of the composition.
44. The composition according to one of claims 1-43, wherein said at least one structuring polymer is present in the composition in an amount ranging from 2% to 60% by weight relative to the total weight of the composition.
45. The composition according to one of claims 1-44, wherein said composition has a hardness ranging from 20 gf to 2000 gf.
46. The composition according to one of claims 1-45, wherein said composition has a hardness ranging from 30 gf to 300 gf.
47. The composition according to one of claims 1-46, wherein said at least one liquid fatty phase of the composition comprises at least one oil, wherein said at least one oil is chosen from at least one polar oil and at least one apolar oil having an affinity with said at least one structuring polymer.
48. The composition according to claim 47, wherein said at least one polar oil is chosen from:
- hydrocarbon-based plant oils with a high content of triglycerides comprising fatty acid esters of glycerol in which the fatty acids comprise chains having from 4 to 24 carbon atoms, said chains optionally being chosen from cyclic, linear and branched, saturated and unsaturated chains;
- synthetic oils or esters of formula R5COOR6 in which R5 is chosen from cyclic, linear and branched fatty acid residues comprising from 1 to 40 carbon atoms and R6 is chosen from hydrocarbon-based chains comprising from 1 to 40 carbon atoms, with the proviso that R5 + R6 > 10;
- synthetic ethers containing from 10 to 40 carbon atoms;
- C8 to C26 fatty alcohols; and
- Cs to C26 fatty acids.
49. The composition according to claim 47, wherein said at least one apolar oil is chosen from:
- silicone oils chosen from volatile and non-volatile, linear and cyclic polydimethylsiloxanes that are liquid at room temperature;
- polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendant and/or at the end of the silicone chain, the groups each containing from 2 to 24 carbon atoms;
- phenylsilicones; and
- hydrocarbons chosen from linear and branched, volatile and non-volatile hydrocarbons of synthetic and mineral origin.
50. The composition according to one of claims 1-49, wherein said at least one liquid fatty phase comprises at least one non-volatile oil.
51. The composition according to claim 50, wherein said at least one non-volatile oil is chosen from hydrocarbon-based oils of mineral, plant and synthetic origin, synthetic esters and ethers, and silicone oils.
52. The composition according to one of claims 1-51 , wherein said at least one liquid fatty phase is present in an amount ranging from 1% to 99.4% by weight relative to the total weight of the composition.
53. The composition according to one of claims 1-52, wherein said at least one liquid fatty phase is present in an amount ranging from 10% to 80% by weight relative to the total weight of the composition.
54. The composition according to one of claims 1-53, wherein said at least one liquid fatty phase comprises at least one volatile solvent chosen from hydrocarbon-based solvents and silicone solvents optionally comprising alkyl or alkoxy groups that are pendant or at the end of a silicone chain.
55. The composition according to claim 54, wherein said at least one volatile solvent is present in an amount up to 95.5% by weight, relative to the total weight of the composition.
56. The composition according to one of claims 54 or 55, wherein said at least one volatile solvent is present in an amount ranging from 10% to 45% by weight, relative to the total weight of the composition.
57. The composition according to one of claims 1-56, wherein said composition further comprises at least one additional fatty material.
58. The composition according to claim 57, wherein said at least one additional fatty material is chosen from gums, fatty materials pasty or viscous at ambient temperature, and resins.
59. The composition according to one of claims 1-58, wherein said composition further comprises castor oil.
60. The composition according to one of claims 1-59, wherein said at least one oil-soluble ester comprising at least one free hydroxy group is chosen from propylene glycol ricinoleate, isopropyl hydroxystearate, triisocetyl citrate, diisostearyl malate, octyl hydroxystearate, triisoarachidyl citrate, cetyl lactate, dioctyl malate, octyldodecyl hydroxystearate, di-isostearyl malate, and di-isostearyl lactate.
61. The composition according to claim 60, wherein said at least one oil-soluble ester is diisostearyl malate.
62. The composition according to claim 60, wherein said at least one oil-soluble ester is triisocetyl citrate.
63. The composition according to one of claims 1-62, wherein said at least one oil-soluble ester comprising at least one free hydroxy group is present in an amount ranging from 10% to 84% by weight relative to the total weight of the composition.
64. The composition according to one of claims 1-63, wherein said at least one oil-soluble ester comprising at least one free hydroxy group is present in an amount ranging from 20% to 70% by weight relative to the total weight of the composition.
65. The composition according to one of claims 1-64, wherein said composition is a solid.
66. The composition according to one of claims 1-65, wherein said composition is a solid chosen from molded and poured sticks.
67. The composition according to one of claims 1-66, further comprising at least one fatty alcohol.
68. The composition according to claim 67, wherein said at least one fatty alcohol is chosen from C8 to C26 fatty alcohols.
69. The composition according to one of claims 67 or 68, wherein said at least one fatty alcohol is chosen from Cι2 to C20 fatty alcohols.
70. The composition according to one of claims 67-69, wherein said Cι2 to C20 fatty alcohols are chosen from myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol.
71. The composition according to one of claims 67-70, wherein said at least one fatty alcohol is present in an amount ranging from 0.1% to 15.0% by weight, relative to the weight of the composition.
72. The composition according to one of claims 67-71 , wherein said at least one fatty alcohol is present in an amount ranging from 0.5% to 8.0% by weight, relative to the weight of the composition.
73. The composition according to one of claims 1-72, further comprising at least one oil-soluble polymer.
74. The composition according to claim 73, wherein said at least oil- soluble polymer is chosen from alkylated guar gums and alkyl celluloses.
75. The composition according to one of claims 73 or 74, wherein said at least one oil-soluble polymer is present in an amount ranging from 0.05% to 10% by weight, relative to the weight of the composition.
76. The composition according to one of claims 73-75, wherein said at least one oil-soluble polymer is present in an amount ranging from 0.1 % to 3% by weight, relative to the weight of the composition.
77. The composition according to one of claims 1-76, further comprising at least one oil-soluble cationic surfactant.
78. The composition according to claim 77, wherein said at least one oil-soluble cationic surfactant is chosen from quaternary ammonium compounds, fatty amines, and salts of fatty amines.
79. The composition according to one of claims 77 or 78, wherein said at least one oil-soluble cationic surfactant is present in an amount ranging from 0.1% to 10% by weight, relative to the weight of the composition.
80. The composition according to one of claims 77-79, wherein said at least one oil-soluble cationic surfactant is present in an amount ranging from 0.5%) to 2% by weight, relative to the weight of the composition.
81. The composition according to one of claims 1-80, further comprising at least one wax.
82. The composition according to claim 81 , wherein said at least one wax is chosen from carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fiber wax, sugar cane wax, paraffin waxes, lignite wax, microcrystalline waxes, lanolin wax, montan wax, polyethylene waxes, waxes obtained by Fischer-Tropsch synthesis, silicone waxes, ozokerites, hydrogenated jojoba oil, fatty acid esters, and fatty acid ester glycerides
83. The composition according to one of claims 81 or 82, wherein said at least one wax is present at an amount of up to 3% relative to the total weight of said composition.
84. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, wherein said at least one structuring polymer is at least one polyamide polymer comprising: a polymer skeleton which comprises at least one amide repeating unit; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group, with the proviso that said at least one oil-soluble ester is not castor oil.
85. The composition according to claim 84, wherein said at least one polyamide polymer is chosen from polymers resulting from at least one polycondensation reaction between at least one dicarboxylic acid comprising at least 32 carbon atoms and at least one amine chosen from diamines comprising at least 2 carbon atoms and triamines comprising at least 2 carbon atoms.
86. The composition according to claim 85, wherein said at least one dicarboxylic acid comprises from 32 to 44 carbon atoms and said at least one amine comprises from 2 to 36 carbon atoms.
87. The composition according to one of claims 85 or 86, wherein said at least one dicarboxylic acid is chosen from dimers of at least one fatty acid comprising at least 16 carbon atoms.
88. The composition according to one of claims 85-87, wherein said at least one fatty acid is chosen from oleic acid, linoleic acid and linolenic acid.
89. The composition according to one of claims 85-88, wherein said at least one amine is chosen from ethylenediamine, hexylenediamine, hexamethylenediamine, phenylenediamine and ethylenetriamine.
90. The composition according to one of claims 85-89, wherein said at least one polyamide polymer is chosen from polymers comprising at least one terminal carboxylic acid group.
91. The composition according to claim 90, wherein said at least one terminal carboxylic acid group is esterified with at least one alcohol chosen from monoalcohols comprising at least 4 carbon atoms.
92. The composition according to claim 84, wherein said at least one oil-soluble ester comprising at least one free hydroxy group is chosen from propylene glycol ricinoleate, isopropyl hydroxystearate, triisocetyl citrate, diisostearyl malate, octyl hydroxystearate, triisoarachidyl citrate, cetyl lactate, dioctyl malate, octyldodecyl hydroxystearate, di-isostearyl malate, and diisostearyl lactate.
93. The composition according to claim 92, wherein said at least one oil-soluble ester is diisostearyl malate.
94. The composition according to claim 93, wherein said at least one oil-soluble ester is triisocetyl citrate.
95. The composition according to one of claims 84-94, wherein the composition is in a form chosen from a fluid anhydrous gel, rigid anhydrous gel, fluid simple emulsion, rigid simple emulsion, fluid multiple emulsion, and rigid multiple emulsion.
96. The composition according to one of claims 84-95, wherein said composition is a solid.
97. The composition according to one of claims 84-96, further comprising at least one wax.
98. A foundation, mascara, eye liner, concealer, lipstick, blush for cheeks or eyelids, body makeup, sun screen, colorant for skin or hair, skin care formula, shampoo, after shampoo treatment, or makeup removing product comprising: at least one liquid fatty phase in said foundation, mascara, eye liner, concealer, lipstick, blush for cheeks or eyelids, body makeup, sun screen, colorant for skin or hair, skin care formula, shampoo, after shampoo treatment, or makeup removing product which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
99. An anhydrous deodorant comprising: at least one liquid fatty phase in said deodorant which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
100. A make-up and/or care and/or treatment composition for at least one keratinous material comprising: at least one liquid fatty phase in said composition which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
101. A lip composition in stick form comprising at least one continuous liquid fatty phase, at least one oil-soluble ester comprising at least one free hydroxy group, and at least one non-waxy structuring polymer having a weight-average molecular mass of less than 100,000 in said lip composition.
102. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer chosen from urea urethanes having the following formula (II): R-0-CO-NH-R'-NH-CO-NH-R"-NH-CO-NH-R'-NH-CO-OR (II)
wherein R represents CnH2n+ι- or CmH2m+ι (OCpH2p)r -, wherein n represents an integer having a value greater than 22, wherein m represents an integer having a value of greater than 18, p represents an integer having a value of from 2 to 4, and r represents an integer having a value of from 1 to 10; R' represents:
Figure imgf000063_0001
or -(CH2)6- and R" represents:
Figure imgf000063_0002
; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
103. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group, wherein said at least one structuring polymer does not include a polymer of formula (II):
R-0-CO-NH-R'-NH-CO-NH-R"-NH-CO-NH-R'-NH-CO-OR (II)
wherein R represents CnH2n+ or CmH2m+ι (CpH2pO)r -; n represents an integer having a value of from 4 to 22; m represents an integer having a value of from 1 to 18; p represents an integer having a value of from 2 to 4; and r represents an integer having a value of from 1 to 10; R' represents:
Figure imgf000064_0001
or -(CH2)6 and R" represents:
Figure imgf000065_0001
104. A make up, care, or treatment composition for the skin or lips comprising a structured composition comprising at least one liquid fatty phase structured with at least one structuring polymer comprising a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom, at least one oil-soluble ester comprising at least one free hydroxy group, and at least one coloring agent.
105. A treatment, care or make-up composition for at least one keratinous material comprising a structured composition comprising at least one liquid fatty phase structured with at least one structuring polymer comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom, at least one oil-soluble ester comprising at least one free hydroxy group, and at least one coloring agent. 06. A structured composition comprising at least one liquid fatty phase structured with at least one structuring polymer comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom, wherein the at least one structuring polymer further comprises at least one terminal fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one terminal fatty chain is bonded to said polymer skeleton via at least one linking group chosen from amides, ureas, and esters, wherein when said at least one linking group is chosen from esters, said at least one terminal fatty chain is chosen from branched alkyl groups and at least one oil-soluble ester comprising at least one free hydroxy group.
107. A structured composition comprising at least one liquid fatty phase structured with at least one structuring polymer comprising a polymer skeleton comprising at least one hydrocarbon-based repeating unit comprising at least one hetero atom, wherein the at least one structuring polymer further comprises at least one pendant fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one pendant fatty chain is bonded to said polymer skeleton via at least one linking group chosen from amides, ureas, and esters, wherein when said at least one linking group is chosen from esters, said at least one pendant fatty chain is chosen from branched alkyl groups and at least one oil-soluble ester comprising at least one free hydroxy group.
108. A method for care, make up, or treatment of at least one keratinous material, comprising applying to said at least one keratinous material a cosmetic composition comprising: at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
109. A method for making a cosmetic composition in the form of a physiologically acceptable composition comprising including in said composition at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon-based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
110. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and at least one terminal fatty chain chosen from alkyl chains and alkenyl chains, wherein said at least one terminal fatty chain is bonded to said polymer skeleton via at least one linking group; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
111. A method for providing at least one property of resistance to shear and stability to a cosmetic composition, comprising including in said cosmetic composition a cosmetic composition at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group, and further wherein said at least one structuring polymer and said at least one oil-soluble ester are present in a combined amount effective to provide at least one property chosen from resistance to shear and stability to said composition.
112. A composition comprising at least one liquid fatty phase which comprises: (i) at least one structuring polymer comprising: a polymer skeleton which comprises a) at least one hydrocarbon-based repeating unit comprising at least one hetero atom and b) at least one of:
- at least one terminal fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one terminal fatty chain is bonded to said polymer skeleton via at least one linking group; and
- at least one pendant fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one pendant fatty chain is bonded to said polymer skeleton via at least one linking group; and
(ii) at least one oil-soluble ester comprising at least one free hydroxy group.
113. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising: a polymer skeleton which comprises at least one amide repeating unit; and
(ii) at least one UV blocker.
114. The composition according to claim 113, wherein said at least one structuring polymer further comprises at least one of: at least one terminal fatty chain chosen from alkyl chains and alkenyl chains, wherein said at least one terminal fatty chain is bonded to said polymer skeleton via at least one linking group; and at least one pendant fatty chain chosen from alkyl chains and alkenyl chains, wherein said at least one pendant fatty chain is bonded to said polymer skeleton via at least one linking group.
115. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer comprising: a polymer skeleton which comprises at least one hydrocarbon- based repeating unit comprising at least one hetero atom; and at least one terminal fatty chain bonded to said polymer skeleton via at least one linking group, wherein said chain has at least four carbon atoms, and (ii) at least one UV blocker.
116. The composition according to one of claims 114 or 115, wherein at least one of said alkyl chains and said alkenyl chains comprise at least four carbon atoms.
117. The composition according to claim 116, wherein at least one of said alkyl chains and said alkenyl chains comprise from 8 to 120 carbon atoms.
118. The composition according to claim 117, wherein at least one of said alkyl chains and said alkenyl chains comprise from 12 to 68 carbon atoms.
119. The composition according to one of claims 114 or 115, wherein said at least one linking group is chosen from single bonds and urea, urethane, thiourea, thiourethane, thioether, thioester, ester, ether and amine groups.
120. The composition according to one of claims 114 or 115, wherein said at least one linking group is an ester group.
121. The composition according to claim 120, wherein said at least one linking group is an ester group present in a proportion ranging from 15% to 40% of the total number of all ester and amide groups in the at least one structuring polymer.
122. The composition according to claim 120, wherein said at least one linking group is an ester group present in a proportion ranging from 20% to 35% of the total number of all ester and amide groups in the at least one structuring polymer.
123. The composition according to one of claims 114 or 115, wherein said at least one terminal fatty chain is functionalized.
124. The composition according to claim 114, wherein said at least one pendant fatty chain is functionalized.
125. The composition according to one of claims 114-124, wherein in said at least one structuring polymer, the percentage of the total number of fatty chains ranges from 40% to 98% relative to the total number of all amide units and fatty chains in the at least one structuring polymer.
126. The composition according to one of claims 114-125, wherein in said at least one structuring polymer, the percentage of the total number of fatty chains ranges from 50% to 95% relative to the total number of all amide units and fatty chains in the at least one structuring polymer.
127. The composition according to one of claims 113-126, wherein said at least one structuring polymer has a weight-average molecular mass of less than 100,000.
128. The composition according to claim 127, wherein said at least one structuring polymer has a weight-average molecular mass of less than 50,000.
129. The composition according to claim 128, wherein said at least one structuring polymer has a weight-average molecular mass ranging from 1000 to 30,000.
130. The composition according to one of claims 114 or 115, wherein said at least one structuring polymer is chosen from polyamide polymers of formula (I):
Figure imgf000070_0001
in which:
- n is an integer which represents the number of amide units such that the number of ester groups present in said at least one polyamide polymer ranges from 10% to 50% of the total number of all ester groups and all amide groups comprised in said at least one polyamide polymer;
- R1, which are identical or different, are each chosen from alkyl groups comprising at least 4 carbon atoms and alkenyl groups comprising at least 4 carbon atoms;
- R2, which are identical or different, are each chosen from C4 to C42 hydrocarbon-based groups, with the proviso that at least 50%> of all R2 are chosen from C30 to C42 hydrocarbon-based groups;
- R3, which are identical or different, are each chosen from organic groups comprising atoms chosen from carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, with the proviso that R3 comprises at least 2 carbon atoms; and
- R4, which are identical or different, are each chosen from hydrogen atoms, Cι to C10 alkyl groups and a direct bond to at least one group chosen from R3 and another R4 such that when said at least one group is chosen from another R4, the nitrogen atom to which both R3 and R4 are bonded forms part of a heterocyclic structure defined in part by R4-N-R3, with the proviso that at least 50% of all R4 are chosen from hydrogen atoms.
131. The composition according to claim 130, wherein in said formula (I), n is an integer ranging from 1 to 5.
132. The composition according to one of claims 130 or 131 , wherein in said formula (I), said alkyl groups of R1 and said alkenyl groups of R1 each independently comprise from 4 to 24 carbon atoms.
133. The composition according to one of claims 130-132, wherein in said formula (I), R1, which are identical or different, are each chosen from Cι2 to C22 alkyl groups.
134. The composition according to one of claims 130-133, wherein in said formula (I), R1, which are identical or different, are each chosen from C-i6 to C22 alkyl groups.
135. The composition according to one of claims 130-134, wherein in said formula (I), R2, which are identical or different, are each chosen from C-io to C42 hydrocarbon based groups, with the proviso that at least 50% of all R2 are chosen from C3o to C42 hydrocarbon based groups.
136. The composition according to one of claims 130-135, wherein in said formula (I), R3, which can be identical or different, are each chosen from C2 to C36 hydrocarbon-based groups and polyoxyalkylene groups.
137. The composition according to one of claims 130-136, wherein R3, which can be identical or different, are each chosen from C2 to Cι2 hydrocarbon-based groups.
138. The composition according to one of claims 130-137, wherein in said formula (I), R4, which can be identical or different, are each chosen from hydrogen atoms.
139. The composition according to one of claims 130-138, wherein said at least one polymer of formula (I) is in the form of a mixture of polymers, wherein said mixture optionally also comprises a compound of formula (I) wherein n is equal to zero.
140. The composition according to one of claims 114 or 115, wherein said at least one polyamide polymer is chosen from polymers resulting from at least one polycondensation reaction between at least one dicarboxylic acid comprising at least 32 carbon atoms and at least one amine chosen from diamines comprising at least 2 carbon atoms and triamines comprising at least 2 carbon atoms.
141. The composition according to claim 140, wherein said at least one dicarboxylic acid comprises from 32 to 44 carbon atoms and said at least one amine comprises from 2 to 36 carbon atoms.
142. The composition according to claim 141 , wherein said at least one dicarboxylic acid is chosen from oleic acid, linoleic acid, and linolenic acid.
143. The composition according to claim 140, wherein said at least one amine is chosen from ethylenediamine, hexylenediamine, hexamethylenediamine, phenylenediamine and ethylenetriamine.
144. The composition according to one of claims 113-143, wherein said at least one structuring polymer has a softening point greater than 50°C.
145. The composition according to one of claims 113-144, wherein said at least one structuring polymer has a softening point ranging from 65°C to less than 150°C.
146. The composition according to one of claims 113-145, wherein said at least one structuring polymer has a softening point ranging from 70°C to less than 130°C.
147. The composition according to one of claims 113-146, wherein said at least one structuring polymer is present in the composition in an amount ranging from 0.5% to 80% by weight relative to the total weight of the composition.
148. The composition according to one of claims 113-147, wherein said at least one structuring polymer is present in the composition in an amount ranging from 2% to 60% by weight relative to the total weight of the composition.
149. The composition according to one of claims 113-148, wherein said at least one UV blocker is chosen from organic screening agents and inorganic nanoparticles.
150. The composition according to one of claims 113-149, wherein said at least one UV blocker is chosen from lipophilic organic filters.
151. The composition according to one of claims 113-150, wherein said at least one UV blocker is present in an amount ranging from 0.1 % to 30% by weight, relative to the total weight of the composition.
152. The composition according to claim 151 , wherein said at least one UV blocker is present in an amount ranging from 0.5% to 15% by weight, relative to the total weight of the composition.
153. The composition according to one of claims 113-152, wherein said at least one liquid fatty phase of the composition comprises at least one oil chosen from at least one polar oil and at least one apolar oil having an affinity with said at least one structuring polymer.
154. The composition according to one of claims 113-153, wherein said at least one liquid fatty phase comprises at least one non-volatile oil.
155. The composition according to one of claims 113-154, wherein said at least one liquid fatty phase is present in an amount ranging from 1 % to 99.4% by weight relative to the total weight of the composition.
156. The composition according to one of claims 113-155, wherein said at least one liquid fatty phase comprises at least one volatile solvent chosen from hydrocarbon-based solvents and silicone solvents optionally comprising alkyl or alkoxy groups that are pendant or at the end of a silicone chain.
157. The composition according to claim 156, wherein said at least one volatile solvent is present in an amount up to 95.5% by weight, relative to the total weight of the composition.
158. The composition according to one of claims 113-157, wherein said composition further comprises at least one oil-soluble ester comprising at least one free-hydroxy group.
159. The composition according to one of claims 113-158, wherein said composition further comprises at least one fatty alcohol.
160. The composition according to one of claims 113-159, wherein said composition further comprises at least one oil-soluble polymer.
161. The composition according to one of claims 113-160, wherein said composition further comprises at least one wax.
162. The composition according to one of claims 113-161 , wherein said composition has a hardness ranging from 20 gf to 2000 gf.
163. The composition according to claim 162, wherein said composition has a hardness ranging from 30 gf to 300 gf.
164. The composition according to one of claims 113-163, wherein the composition is in a form chosen from a fluid anhydrous gel, a rigid anhydrous gel, a fluid simple emulsion, a rigid simple emulsion, a fluid multiple emulsion, and a rigid multiple emulsion.
165. The composition according to one of claims 113-164, wherein said composition is a solid.
166. The composition according to claim 165, wherein said composition is a solid chosen from molded and poured sticks.
167. The composition according to one of claims 113-166, wherein said composition comprises a continuous liquid fatty phase.
168. An anhydrous composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit; and
(ii) at least one UV blocker.
169. A foundation, mascara, eye liner, concealer, lipstick, blush for cheeks or eyelids, body makeup, sunscreen or antisun product, colorant for skin or hair, skin care formula, shampoo, after shampoo treatment, or makeup removing product comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit; and
(ii) at least one UV blocker.
170. A make-up, care, or treatment composition for skin or lips, comprising at least one liquid fatty phase in said composition which comprises:
(i) at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit; and
(ii) at least one UV blocker.
171. A lipstick composition in stick form comprising at least one continuous liquid fatty phase and at least one non-waxy structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer having a weight-average molecular mass of less than 100,000, wherein said lipstick composition further comprises at least one UV blocker.
172. A make-up, care, or treatment composition for at least one keratinous material comprising a structured composition comprising at least one liquid fatty phase in said composition structured with at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit and at least one coloring agent, wherein said make-up, care, or treatment composition further comprises at least one UV blocker.
173. A structured composition comprising at least one liquid fatty phase structured with at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit and wherein the at least one structuring polymer further comprises at least one terminal fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one terminal fatty chain is bonded to said polymer skeleton via at least one linking group chosen from amides, ureas, and esters, wherein when said at least one linking group is chosen from esters, said at least one terminal fatty chain is chosen from branched alkyl groups, and wherein said structured composition further comprises at least one UV blocker.
174. A composition according to claim 173, wherein said at least one structuring polymer further comprises at least one pendant fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one pendant fatty chain is bonded to said polymer skeleton at least one linking group chosen from amides, ureas, and esters, wherein when said at least one linking group is chosen from esters, said at least one pendant fatty chain is chosen from branched alkyl groups.
175. A structured composition comprising at least one liquid fatty phase in said composition structured with at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit, and wherein the at least one structuring polymer further comprises at least one pendant fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one pendant fatty chain is bonded to said polymer skeleton via at least one linking group chosen from amides, ureas, and esters, wherein when said at least one linking group is chosen from esters, said at least one pendant fatty chain is chosen from branched alkyl groups and wherein said structured composition further comprises at least one UV blocker.
176. A method for providing at least one of (a) resistance to shear and (b) stability to a cosmetic composition, comprising including in said cosmetic composition at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit; and
(ii) at least one UV blocker, wherein said at least one structuring polymer and said at least one UV blocker are present in amounts effective to provide at least one property chosen from resistance to shear and stability.
177. A composition comprising at least one liquid fatty phase which comprises:
(i) at least one structuring polymer, wherein said at least one structuring polymer comprises at least one polyamide polymer comprising a polymer skeleton which comprises at least one amide repeating unit, and at least one of:
(a) at least one terminal fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one terminal fatty chain is bonded to said polymer skeleton via at least one linking group; and (b) at least one pendant fatty chain, optionally functionalized, chosen from alkyl chains and alkenyl chains, wherein said at least one pendant fatty chain is bonded to said polymer skeleton via at least one linking group; and (ii) at least one UV blocker.
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CA2397586A1 (en) 2002-08-01
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