WO2014098268A1 - Cosmetic composition - Google Patents

Cosmetic composition Download PDF

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Publication number
WO2014098268A1
WO2014098268A1 PCT/JP2013/085312 JP2013085312W WO2014098268A1 WO 2014098268 A1 WO2014098268 A1 WO 2014098268A1 JP 2013085312 W JP2013085312 W JP 2013085312W WO 2014098268 A1 WO2014098268 A1 WO 2014098268A1
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WIPO (PCT)
Prior art keywords
cosmetic composition
weight
composition according
polyglyceryl
oil
Prior art date
Application number
PCT/JP2013/085312
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French (fr)
Inventor
Anne-Laure Bernard
AKKARI Remi EL
Original Assignee
L'oreal
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Publication of WO2014098268A1 publication Critical patent/WO2014098268A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • 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
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • 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
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • 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
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61K8/87Polyurethanes
    • 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
    • A61Q1/14Preparations for removing make-up
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/21Emulsions characterized by droplet sizes below 1 micron
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26Optical properties
    • A61K2800/262Transparent; Translucent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/548Associative polymers

Definitions

  • the present invention relates to a cosmetic composition in the form of a nano- or micro-emulsion.
  • Microemulsions oil in water, water in oil or bicontinuous have been developed these last years as an alternative of cleansing oils very much appreciated for their excellent efficacy on foundation and waterproof mascara.
  • the advantage of nano- or micro- emulsion is to present sometimes better rinsibility for usually same make-up removal efficacy.
  • the cost of the nano- or micro-emulsions can be reduced because of their lower oil content.
  • An objective of the present invention is to provide a stable cosmetic, optionally cleansing, composition in the form of a nano- or micro-emulsion with transparent or slightly translucent, preferably transparent, aspect of the emulsion.
  • a nano- or micro-emulsion is difficult to have a high viscosity or consistency, in particular under wet conditions. Even if a high viscosity or consistency is realized by using, for example, a thickener, this often makes it difficult for the emulsion to have stable transparent or slightly translucent appearance. Furthermore, cosmetic properties such as cleansing ability or rinsability as well as texture such as feeling to touch may be impaired.
  • Another objective of the present invention is to provide a cosmetic composition in the form of a nano- or micro-emulsion with a high viscosity or consistency even under wet conditions, so that it can be easily handled by, for example, wet hand, while maintaining stable transparent or slightly translucent appearance.
  • Another objective of the present invention is to provide a cosmetic composition in the form of a nano- or micro-emulsion with good cosmetic properties such as cleansing ability or rinsability as well as good texture such as good feeling to touch.
  • a rinse-off cosmetic composition in the form of a nano- or micro-emulsion comprising:
  • At least one non ionic surfactant with HLB 7-14 preferably one poly glyceryl fatty acid ester, preferably with a polyglyceryl moiety derived from 2 to 10 glycerins, preferably from 4 to 6 glycerins, more preferably 5 or 6 glycerin
  • the amount of the (a) oil ranges at least 20% by weight relative to the total weight of the composition.
  • the (a) oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, and hydrocarbon oils.
  • the (a) oil may be chosen from hydrocarbon oils which are in the form of a liquid at a room temperature. It may be preferable that the (a) oil be chosen from oils with molecular weight below 600 g/mol.
  • the amount of the (a) oil may range from 20 to 60% by weight, preferably from 22 to 50% by weight, and more preferably from 24 to 40% by weight, relative to the total weight of the composition.
  • the (b) nonionic surfactant with HLB 7-14 may be polyglyceryl fatty acid ester with an HLB value of from 7 to 14.0, preferably from 8 to 13.5, and more preferably from 9 to 13.0.
  • the polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprylate comprising 2 to 6 glycerol units, polyglyceryl monolaurate comprising 3 to 6 glycerol units, polyglyceryl mono(iso)stearate comprising 3 to 10 glycerol units, polyglyceryl monooleate comprising 3 to 10 glycerol units, and polyglyceryl dioleate comprising 3 to 10 glycerol units.
  • the polyglyceryl fatty acid ester may be chosen from PG-2 caprate, PG-4 laurate, PG-5 laurate, PG-5 oleate, PG-5 dioleate, PG-6 tricaprylate, PG-10 oleate, PG-10 Dioleate, PG-10 isostearate, PG-2 laurate, PG- 10 trilaurate, PG- 10 myristate, PG- 10 dimyristate, PG-10 stearate, PG- 10 distearate, PG-5 myristate, Pg-5 trimyristate, PG-5 dioleate, PG-5 stearate, PG-5 trioleate, PG-6 caprylate, and PG-6 tricaprylate.
  • the polyglyceryl fatty acid ester raw material is chosen from a mixture of polyglyceryl fatty acid esters, preferably with a polyglyceryl moiety derived from 3 to 6 glycerins, more preferably 5 or 6 glycerins, wherein the mixture preferably comprises at least 30% by weight of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins.
  • the amount of the (b) nonionic surfactant with HLB 7-14 may range from 0.1 to 30% by weight, preferably from 1 to 25%» by weight, and more preferably from 5 to 20% by weight, relative to the total weight of the composition.
  • the weight ratio of the (b) nonionic surfactant with HLB 7-14 to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.45 to 1.5.
  • the (b) nonionic surfactant with HLB 7-14 may be oxyalkylene-including nonionic surfactant.
  • the amount of the oxyalkylene-including nonionic surfactant may range from 0.1 to 25% by weight, preferably from 0.5 to 20% by weight, and more preferably from 1 to 15% by weight, W relative to the total weight of the composition.
  • the (c) associative polyurethane be a copolymer comprising at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, separated by a hydrophilic block.
  • the amount of the (c) associative polyurethane may range from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, and more preferably from 0.4 to 3% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention may further comprise at least one additional nonionic surfactant different from the above (b) and/or at least one additional ionic surfactant.
  • Polyol is preferably bivalent and trivalent, and more preferably bivalent.
  • Preferred polyols are butylene glycol, glycerin, propanediol, dipropylene glycol, hexylene glycol, and PEG8.
  • the amount of total polyols may be between 4% and 50%, preferably between 6% and 40%, and more preferably between 8% and 30% by weight of the total weight of the composition.
  • the cosmetic composition according to the present invention be in the form of an OAV emulsion
  • the (a) oil be in the form of a droplet with a number average particle size of 300 nm or less, preferably from 10 nm to 150 nm.
  • the cosmetic composition according to the present invention have a
  • nephelometric turbidity below 150 NTU, preferably below 100 NTU, more preferably below 50 NTU.
  • the present invention also relates to a non-therapeutic process for treating the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows and/or the scalp, characterized in that the cosmetic composition according to the present invention is applied to the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows or the scalp.
  • the present invention also relates to a use of the cosmetic composition according to the present invention, as or in care products and/or washing products and/or make-up products and/or make-up-removing products for body and/or facial skin and/or mucous membranes and/or the scalp and/or the hair and/or the nails and/or the eyelashes and/or the eyebrows.
  • the inventors have discovered that it is possible to provide a stable cosmetic composition in the form of a nano- or micro-emulsion with transparent or slightly translucent, preferably transparent, aspect of the emulsion by using a relatively little amount of nonionic surfactants compared to the amount of oil.
  • the cosmetic composition according to the present invention can have a high viscosity or consistency even under wetconditions, so that it can be easily handled by, for example, wet hand, while maintaining stable transparent or slightly translucent appearance.
  • the cosmetic composition according to the present invention can have good cosmetic properties such as cleansing ability or rinsability as well as good texture such as good feeling to touch.
  • the present invention is a cosmetic composition in the form of a nano- or micro-emulsion, comprising:
  • At least one non ionic surfactant with HLB 7-14 preferably one poly glyceryl fatty acid ester, preferably with a polyglyceryl moiety derived from 2 to 10 glycerins, preferably from 4 to 6 glycerins, more preferably 5 or 6 glycerin;
  • amount of the (a) oil ranges at least 20% by weight relative to the total weight of the composition.
  • the cosmetic composition according to the present invention can have a high viscosity or consistency, and therefore, it can be in the form of, for example, a viscous gel.
  • the cosmetic composition according to the present invention can avoid or reduce, for example, dripping down of the composition from the skin or hair when being used by a user.
  • the cosmetic composition according to the present invention can have a high viscosity or consistency under wet conditions typically in, for example, a bathroom.
  • the cosmetic composition according to the present invention can be easily handed by, for example wet hand.
  • the cosmetic composition according to the present invention can have good cosmetic properties such as cleansing ability or rinsability as well as good texture such as good feeling to touch, and therefore, it can be used preferably for cleansing products such as a makeup cleansing agent.
  • the cosmetic composition according to the present invention has a dispersed phase which has a smaller diameter. Therefore, the cosmetic composition can be in the form of a nano- or micro-emulsion with transparent or slightly translucent.
  • the cosmetic composition according to the present invention comprises at least one oil.
  • oil means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg).
  • oils those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non- volatile, preferably non- volatile.
  • W 201 is a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg).
  • the oil may be a non-polar oil such as a hydrocarbon oil; a polar oil such as a plant or animal oil and an ester oil; or a mixture thereof. It is preferable that the (a) oil contains at least one hydrocarbon oil chosen from ester, ether and alkane oils.
  • plant oils examples include, for example, linseed oil, camellia oil, macadamia nut oil, com oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.
  • animal oils mention may be made of, for example, squalene and squalane.
  • synthetic oils mention may be made of ester oils and artificial triglyceride.
  • the ester oils are preferably liquid esters of saturated or unsaturated, linear or branched Ci-C 26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci-C 26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
  • esters of monoalcohols at least one from among the alcohol and the acid from which the esters of the invention are derived is branched.
  • monoesters of monoacids and of monoalcohols mention may be made of ethyl palmitate, ethyl hexyl palmitate, ethyl hexyl myristate, isopropyl palmitate, isonononyl isononanoate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate, isopropyl palmitate, octyl isostearate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.
  • Ether oil might include dicaprylyl ether.
  • ethyl palmitate isopropyl palmitate
  • alkyl myristates such as isopropyl myristate or ethyl myristate
  • isocetyl stearate 2-ethylhexyl isononanoate
  • isodecyl neopentanoate isostearyl neopentanoate.
  • Esters of C 4 -C 2 2 dicarboxylic or tricarboxylic acids and of Ci-C 2 2 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C 4 -C 26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
  • ester oils mention may be made of, for example, diisopropyl adipate, dioctyl adipate, isononyl isononanoate, dicaprylyl carbonate, octyl isostearate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, hexy
  • artificial triglycerides mention may be made of, for example, glyceryl trimyristate, glyceryl tripalrnitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).
  • Hydrocarbon oils may be chosen from:
  • linear or branched, optionally cyclic, C 6 -C 16 lower alkanes examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane; and
  • linear or branched hydrocarbons containing more than 16 carbon atoms such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam®, and squalane.
  • hydrocarbon oils examples include linear or branched hydrocarbons such as mineral oil(e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene
  • the (a) oil be chosen from hydrocarbon oils which are in the form of a liquid at a room temperature.
  • the (a) oil be chosen from oils with molecular weight below 600 g/mol.
  • the (a) oil has a low molecular weight such as below 600 g mol, chosen among ester oils with a short hydrocarbon chain or chains (e.g., isopropyl myristate, isopropyl palmitate, isononyl isononanoate, and ethyl hexyl palmitate), hydrocarbon oils with a short alkyl chain or chains (e.g., isododecane, isohexadecane, and squalane), short alcohol type oils such as
  • the amount in the cosmetic composition according to the present invention of the (a) oil ranges at least 20% by weight, and may range from 20 to 60% by weight, preferably from 22 to 50% by weight, and more preferably from 24 to 40% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention comprises at least one nonionic surfactant with HLB 7-14.
  • a single type of the nonionic surfactant may be used, but two or more different types of the nonionic surfactant may be used in combination.
  • the HLB is the ratio between the hydrophilic part and the lipophilic part in the molecule. This term HLB is well known to those skilled in the art and is described in "The HLB system. A time-saving guide to emulsifier selection" (published by ICI Americas Inc., 1984).
  • HLB hydrophilic-lipophilic balance
  • the calculated HLB is defined as being the following coefficient:
  • HLB 20 * molar mass of the hydrophilic part/total molar mass.
  • the hydrophilic part corresponds to the oxyethylene units fused to the fatty alcohol and the calculated HLB then corresponds to the HLB according to Griffin (Griffin W.C., J. Soc. Cosmet. Chemists, 5, 249, 1954).
  • the above nonionic surfactant has an HLB (Hydrophilic Lipophilic Balance) value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0. If two or more nonionic surfactants are used, the HLB value is determined by the weight average of the HLB values of all the nonionic surfactants.
  • HLB Hydrophilic Lipophilic Balance
  • the amount in the cosmetic composition according to the present invention of the (b) nonionic surfactant with an HLB 7-14 is not limited, and may range from 0.1 to 30% by weight, preferably from 1 to 25% by weight, and more preferably from 3 to 20% by weight, relative to the total weight of the composition.
  • the (b) nonionic surfactant with an HLB value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0 may be chosen from: (1) surfactants that are fluid at a temperature of less than or equal to 45 °C, chosen from the esters of at least one polyol chosen from the group formed by polyethylene glycol comprising from 1 to 60 ethylene oxide units, sorbitan, glycerol comprising from 2 to 30 ethylene oxide units, polyglycerols comprising from 2 to 12 glycerol units, and of at least one fatty acid comprising at least one saturated or unsaturated, linear or branched Q-C22 alkyl chain,
  • surfactants that are solid at a temperature of less than or equal to 45 °C, chosen from fatty esters of glycerol, fatty esters of sorbitan and oxyethylenated fatty esters of sorbitan, ethoxylated fatty ethers and ethoxylated fatty esters,
  • the surfactants (1) that are fluid at a temperature of less than or equal to 45°C may be, in particular:
  • the (2) mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol, which can be used as the above nonionic surfactant, may be chosen in particular from the group comprising mixed esters of fatty acid or of fatty alcohol with an alkyl chain containing from 8 to 22 carbon atoms, and of a-hydroxy acid and/or of succinic acid, with glycerol.
  • the -hydroxy acid may be, for example, citric acid, lactic acid, glycolic acid or malic acid, and mixtures thereof.
  • the alkyl chain of the fatty acids or alcohols from which are derived the mixed esters which can be used in the nanoemulsion of the invention may be linear or branched, and saturated or unsaturated. They may especially be stearate, isostearate, linoleate, oleate, behenate,
  • mixed esters which can be used in the nanoemulsion of the invention
  • the mixed ester of succinic acid and of isostearyl alcohol with glycerol (CTFAname: Isostearyl diglyceryl succinate) sold by the company Hiils under the name Imwitor 780 K
  • the mixed ester of citric acid and of stearic acid with glycerol CFAname:
  • Glyceryl stearate citrate sold by the company Hiils under the name Imwitor 370; the mixed ester of lactic acid and of stearic acid with glycerol (CTFA name: Glyceryl stearate lactate) sold by the company Danisco under the name Lactodan B30 or Rylo LA30.
  • the (3) fatty acid esters of sugars which can be used as the above nonionic surfactant, may preferably be solid at a temperature of less than or equal to 45 °C and may be chosen in particular from the group comprising esters or mixtures of esters of Q-C22 fatty acid and of sucrose, of maltose, of glucose or of fructose, and esters or mixtures of esters of C 14 -C 22 fatty acid and of methylglucose.
  • the C8-C22 or C 14 -C22 fatty acids forming the fatty unit of the esters which can be used in the present invention comprise a saturated or unsaturated linear alkyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms.
  • the fatty unit of the esters may be chosen in particular from stearates, behenates, arachidonates, palmitates, myristates, laurates and caprates, and mixtures thereof. Stearates are preferably used.
  • esters or mixtures of esters of fatty acid and of sucrose, of maltose, of glucose or of fructose mention may be made of sucrose monostearate, sucrose distearate and sucrose tristearate and mixtures thereof, such as the products sold by the company Croda under the name Crodesta F50, F70, F110 and F160; and examples of esters or mixtures of esters of fatty acid and of methylglucose which may be mentioned are methylglucose polyglyceryl-3 distearate, sold by the company Goldschmidt under the name Tego-care 450. Mention may also be made of glucose or maltose monoesters such as methyl o-hexadecanoyl-6-D-glucoside and
  • the (3) fatty alcohol ethers of sugars which can be used as the above nonionic surfactant, may be solid at a temperature of less than or equal to 45 °C and may be chosen in particular from the group comprising ethers or mixtures of ethers of C8-C22 fatty alcohol and of glucose, of maltose, of sucrose or of fructose, and ethers or mixtures of ethers of a C 14 -C2 2 fatty alcohol and of methylglucose. These are in particular alkylpolyglucosides.
  • the C 8 -C 2 2 or C 14 -C22 fatty alcohols forming the fatty unit of the ethers which may be used in the nanoemulsion of the invention comprise a saturated or unsaturated, linear alkyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms.
  • the fatty unit of the ethers may be chosen in particular from decyl, cetyl, behenyl, arachidyl, stearyl, palmityl, myristyl, lauryl, capryl and hexadecanoyl units, and mixtures thereof, such as cetearyl.
  • alkylpolyglucosides such as decylglucoside and laurylglucoside, which is sold, for example, by the company Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearyl glucoside optionally as a mixture with cetostearyl alcohol, sold for example, under the name Montanov 68 by the company SEPPIC, under the name Tego-care CG90 by the company Goldschmidt and under the name Emulgade KE3302 by the company Henkel, as well as arachidyl glucoside, for example in the form of a mixture of arachidyl alcohol and behenyl alcohol and arachidyl glucoside, sold under the name Montanov 202 by the company SEPPIC.
  • the surfactant used more particularly is sucrose monostearate, sucrose distearate or sucrose tristearate and mixtures thereof, methylglucose polyglyceryl-3 distearate and alkylpolyglucosides.
  • the (4) fatty esters of glycerol which may be used as the above nonionic surfactant, which are solid at a temperature of less than or equal to 45°C, may be chosen in particular from the group comprising esters formed from at least one acid comprising a saturated linear alkyl chain containing from 12 to 22 carbon atoms and from 1 to 12 glycerol units.
  • these fatty esters of glycerol may be used in the present invention.
  • esters may be chosen in particular from stearates, behenates, arachidates and palmitates, and mixtures thereof. Stearates and palmitates are preferably used.
  • CTFA names Poly glyceryl- 10 stearate, Polyglyceryl-10 distearate, Polyglyceryl-10 tristearate, Polyglyceryl- 10 pentastearate
  • CTFA name Polyglyceryl-2 stearate
  • the (4) fatty esters of sorbitan which may be used as the above nonionic surfactant, which are solid at a temperature of less than or equal to 45°C, may be chosen from the group comprising C 16 -C 22 fatty acid esters of sorbitan and oxyethylenated C 16 -C 22 fatty acid esters of sorbitan.
  • oxyethylenated esters generally comprise from 1 to 100 ethylene glycol units and preferably from 2 to 40 ethylene oxide (EO) units.
  • esters may be chosen in particular from stearates, behenates, arachidates, palmitates, and mixtures thereof. Stearates and palmitates are preferably used.
  • nonionic surfactant can be used in the present invention
  • sorbitan monopalmitate CFA name: Sorbitan palmitate
  • sorbitan tristearate 20 EO CFA name: Polysorbate 65
  • Tween 65 sorbitan tristearate 20 EO
  • the (4) ethoxylated fatty ethers that are solid at a temperature of less than or equal to 45 °C which may be used as the above nonionic surfactant, are preferably ethers formed from 1 to 100 ethylene oxide units and from at least one fatty alcohol chain containing from 16 to 22 carbon atoms.
  • the fatty chain of the ethers may be chosen in particular from behenyl, arachidyl, stearyl and cetyl units, and mixtures thereof, such as cetearyl.
  • ethoxylated fatty ethers which may be mentioned are behenyl alcohol ethers comprising 5, 10, 20 and 30 ethylene oxide units (CTFA names: Beheneth-5, Beheneth-10, Beheneth-20, Beheneth-30), such as the products sold under the names Nikkol BB5, BB 10, BB20 and BB30 by the company Nikko, and stearyl alcohol ether comprising 2 ethylene oxide units (CTFA name: Steareth-2), such as the product sold under the name Brij 72 by the company ICI.
  • CTFA names: Beheneth-5, Beheneth-10, Beheneth-20, Beheneth-30 such as the products sold under the names Nikkol BB5, BB 10, BB20 and BB30 by the company Nikko
  • CTFA name: Steareth-2 stearyl alcohol ether comprising 2 ethylene oxide units
  • the (4) ethoxylated fatty esters that are solid at a temperature of less than or equal to 45°C, which may be used as the above nonionic surfactant, are esters formed from 1 to 100 ethylene oxide units and from at least one fatty acid chain containing from 16 to 22 carbon atoms.
  • the fatty chain in the esters may be chosen in particular from stearate, behenate, arachidate and palmitate units, and mixtures thereof.
  • ethoxylated fatty esters which may be mentioned are the ester of stearic acid comprising 40 ethylene oxide units, such as the product sold under the name Myri 52 (CTFAname: PEG-40 stearate) by the company ICI, as well as the ester of behenic acid comprising 8 ethylene oxide units (CTFAname: PEG-8 behenate), such as the product sold under the name Compritol HD5 ATO by the company Gattefosse.
  • the (5) block copolymers of ethylene oxide (A) and of propylene oxide (B), which may be used as surfactants in the nanoemulsion according to the invention, may be chosen in particular from block copolymers of formula (TV): HO(C 2 H 4 0) x (C 3 H 6 0) y (C 2 H 4 0) z H (IV) in which x, y and z are integers such that x+z ranges from 2 to 100 and y ranges from 14 to 60, and mixtures thereof, and more particularly from the block copolymers of formula (TV) having an HLB value ranging from 8.0 to 14.
  • block copolymers of formula (TV) having an HLB value ranging from 8.0 to 14.
  • silicone surfactants which can be used according to the present invention, mention may be made of those disclosed in documents US-A-5364633 and US-A-5411744.
  • the (6) silicone surfactant as the above nonionic surfactant may preferably be a compound of formula (I):
  • Ri, R 2 and R 3 independently of each other, represent a C ⁇ -C6 alkyl radical or a radical
  • R R 2 or R 3 not being an alkyl radical
  • 4 being a hydrogen, an alkyl radical or an acyl radical
  • A is an integer ranging from 0 to 200;
  • B is an integer ranging from 0 to 50; with the proviso that A and B are not simultaneously equal to zero;
  • x is an integer ranging from 1 to 6;
  • y is an integer ranging from 1 to 30;
  • z is an integer ranging from 0 to 5.
  • the alkyl radical is a methyl radical
  • x is an integer ranging from 2 to 6
  • y is an integer ranging from 4 to 30.
  • silicone surfactants of formula (I) mention may be made of the compounds of formula (II):
  • silicone surfactants of formula (I) mention may also be made of the compounds of formula (III):
  • the nonionic surfactant with HLB 7-14 may be selected from polyglyceryl fatty acid esters.
  • the cosmetic composition according to the present invention may comprise at least one polyglyceryl fatty acid esterwith an HLB value of 7-14.
  • a single type of polyglyceryl fatty acid ester may be used, but two or more different types of polyglyceryl fatty acid ester may be used in combination.
  • the polyglyceryl fatty acid ester have a polyglycol moiety derived from 2 to 10 glycols, more preferably from 3 to 6 glycols, and further more preferably 5 or 6 glycols.
  • the polyglyceryl fatty acid ester may have an HLB value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0. If two or more polyglyceryl fatty acid esters are used, the HLB value is determined by the weight average of the HLB values of all the
  • the polyglyceryl fatty acid ester may be chosen from the mono, di and tri esters of saturated or unsaturated acid, preferably saturated acid, including 2 to 30 carbon atoms, preferably 6 to 30 carbon atoms, and more preferably 8 to 30 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid, and myristic acid.
  • the polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprylate comprising 2 to 6 glycerol units, polyglyceryl monolaurate comprising 3 to 6 glycerol units, polyglyceryl mono(iso)stearate comprising 3 to 10 glycerol units, polyglyceryl monooleate comprising 3 to 10 glycerol units, and polyglyceryl dioleate comprising 3 to 10 glycerol units.
  • the polyglyceryl fatty acid ester may be selected from the group consisting of PG2 caprate, PG2 dicaprate, PG2 tricaprate, PG2 caprylate, PG2 dicaprylate, PG2 tricaprylate, PG2 laurate, PG2 dilaurate, PG2 trilaurate, PG2 myristate, PG2 dimyristate, PG2 trimyristate, PG2 stearate, PG2 distearate, PG2 tristearate, PG2 isostearate, PG2 diisostearate, PG2 triisostearate, PG2 oleate, PG2 dioleate, PG2 trioleare, PG3 caprate, PG3 dicaprate, PG3 tricaprate, PG3 caprylate, PG3 dicaprylate, PG3 tricaprylate, PG3 laurate, PG3 dilaurate, PG3 trilaurate, PG
  • the polyglyceryl fatty acid ester be chosen from PG-2 caprate, PG-4 laurate, PG-5 laurate, PG-5 oleate, PG-5 dioleate, PG-6 tricaprylate, PG-10 oleate, PG-10 Dioleate, PG-10 isostearate, PG-2 laurate, PG-10 trilaurate, PG-10 myristate, PG-10 dimyristate, PG-10 stearate, PG-10 distearate, PG-5 myristate, Pg-5 trimyristate, PG-5 dioleate, PG-5 stearate, PG-5 trioleate, PG-6 caprylate, and PG-6 tricaprylate.
  • polyglyceryl fatty acid ester be chosen from:
  • polyglyceryl monolaurate comprising 3 to 6 glycerol units
  • polyglyceryl monooleate comprising 3 to 6 glycerol units
  • polyglyceryl dioleate comprising 3 to 6 glycerol units.
  • the polyglyceryl fatty acid ester may be chosen from a mixture of polyglyceryl fatty acid esters, preferably with a polyglyceryl moiety derived from 3 to 6 glycerins, more preferably 5 or 6 glycerins, wherein the mixture preferably comprises 30% by weight or more of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins.
  • the amount in the cosmetic composition according to the present invention of the polyglyceryl fatty acid ester is not limited, and may range from 0.1 to 30% by weight, preferably from 1 to 25% by weight, and more preferably from 3 to 20% by weight, relative to the total weight of the composition.
  • the nonionic surfactant with HLB 7-14 may be selected from oxyalkylene-including nonionic surfactants.
  • a single type of oxyalkylene-including nonionic surfactant may be used, but two or more different types of oxyalkylene-including nonionic surfactant may be used in combination.
  • the oxyalkylene-including nonionic surfactant may have an HLB value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0. If two or more
  • the HLB value is determined by the weight average of the HLB values of all the oxyalkylene-including nonionic surfactant.
  • the oxyalkylene-including nonionic surfactant according to the present invention may be selected from mono- or poly-oxyalkylenated fatty acid esters.
  • the mono- or poly-oxyalkylenated fatty acid ester have a (poly)oxyalkylene moiety derived from 1 to 200 oxyalkylenes, preferably from 3 to 150 oxyalkylenes, and more preferably 4 to 120 oxyalkylenes.
  • the (poly)oxyalkylene moiety may be derived from alkylene glycols such as ethyleneglycol, propylene glycol, butyleneglycol, pentyleneglycol, hexyleneglycol, and the like.
  • (poly)oxyalkylene moiety may contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 200 and preferably between 2 and 150.
  • the number of moles of ethylene oxide and/or of propylene oxide of between 1 and 200 and preferably between 2 and 150.
  • oxyalkylene-including nonionic surfactant does not comprise any oxypropylene units.
  • the mono- or poly-oxyalkylenated fatty acid ester may be chosen from the mono and di esters of saturated or unsaturated acid, preferably saturated acid, including 2 to 30 carbon atoms, preferably 6 to 30 carbon atoms, and more preferably 8 to 30 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid, and myristic acid.
  • Examples of mono- or poly-oxyalkylenated fatty acid esters that may be mentioned include esters of saturated or unsaturated, linear or branched, C 2 -C 3 o, preferably C 6 -C 30 and more preferably C 8 -C 30 acids and of polyethylene glycols.
  • Examples of mono- or poly-oxyalkylenated fatty acid esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid or behenic acid, and mixtures thereof, especially those containing from 8 to 120 oxyethylene groups, such as PEG-8 to PEG-120 laurate (as the CTFA names: PEG-8 laurate to PEG-120 laurate); PEG-8 to PEG-120 myristate (as the CTFA names: PEG-8 mysistate to PEG-120 mysistate); PEG-8 to PEG-120 palmitate (as the CTFA names: PEG-8 palmitate to PEG-120 palmitate); PEG-8 to PEG-120 stearate (as the CTFAnames: PEG-8 stearate to PEG-120 stearate); PEG-8 to PEG-120 isostearate (as the CTFA
  • mono- or poly-oxyalkylenated fatty acid esters that may be mentioned include Steareth-100 available as Brij 700 from Uniqema Inc., Pareth alcohols available as Performathox 450, 480 and 490 available from New Phase Technologies, Inc.
  • Suitable examples of di-alkyl substituted polymers include PEG 120 methyl glucose dioleate available as Glutamate DOE- 120 and Glucamate DOE- 120 both from Chemron Corporation.
  • Suitable examples of tri-alkyl substituted polymers include PEG 120 methyl glucose trioleate available as Glucamate LT from Chemron Corporation.
  • Suitable examples of tetra-alkyl substituted polymers include PEG 150 pentaerythrityl tetrastearate available as Crothix from Croda Corporation.
  • polyglycol fatty acid ester be selected from the group consisting of PEG-120 oleate, PEG-120 methyl glucose dioleate, and a mixture thereof.
  • the amount of the oxyalkylene-including nonionic surfactant is not limited, and may range from 0.1 to 25% by weight, preferably from 0.5 to 20% by weight, and more preferably from 1 to 15% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention comprises at least one associative polyurethane.
  • a single type of associative polyurethane may be used, but two or more different types of associative polyurethane may be used in combination.
  • the associative polyurethane may be cationic or nonionic.
  • the associative polyurethane derivatives such as those obtained by polymerization: about 20% to 70% by weight of a carboxylic acid containing an ⁇ , ⁇ -monoethylenic unsaturation, about 20 to 80% by weight of a nonsurfactant monomer containing an ⁇ , ⁇ -monoethylenic unsaturation, about 0.5 to 60% by weight of a nonionic mono-urethane which is the product of the reaction of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate.
  • a nonionic mono-urethane which is the product of the reaction of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate.
  • this polymer is a methacrylic acid/methyl acrylate/dimethyl metaisopropenyl benzyl isocyanate of ethoxylated behenyl alcohol (40EO) terpolymer as an aqueous dispersion at 25%.
  • This product is provided under the reference VISCOPHOBE DB1000 by the company
  • AMERCHOL also suitable are the cationic associative polyurethanes the family of which has been described by the Applicant in French Patent Application No. 0009609. It can be represented more particularly by the following general formula (A): R-X-(P) n -[L-(Y) m ] r -L'-(P%-X'-R' (A) in which: R and R', which are identical or different, represent a hydrophobic group or a hydrogen atom; X and X', which are identical or different, represent a group containing an amine functional group carrying or otherwise a hydrophobic group, or alternatively the group L"; L, L' and L", which are identical or different, represent a group derived from a diisocyanate; P and P', which are identical or different, represent a group containing an amine functional group carrying or otherwise a hydrophobic group; Y represents a hydrophilic group; r is an integer between 1 and 100, preferably between 1 and 50 and in particular
  • the molecule independently of the others between 0 and 1000; the molecule containing at least one protonated or quaternized amine functional group and at least one hydrophobic group.
  • the only hydrophobic groups of these polyurethanes are the groups R and R' at the chain ends.
  • the associative polyurethane corresponds to the formula (A) in which R and R' both represent independently a hydrophobic group, X, X' each represent a group L", n and p are between 1 and 1000, and L, L', L", P, P', Y and m have the meaning indicated in formula (A).
  • the associative polyurethane corresponds to the formula (A) in which R and R' both represent independently a hydrophobic group, X, X' each represent a group L", n and p are equal to 0, and L, L', L", Y and m have the meaning in formula (A) indicated above.
  • n and p are equal to 0 means that these polymers do not contain units derived from a monomer containing an amine functional group, incorporated into the polymer during
  • the protonated amine functional groups of these polyurethanes result from the hydrolysis of isocyanate functional groups, in excess, at the chain end, followed by alkylation of the primary amine functional groups formed by alkylating agents containing a hydrophobic group, that is to say compounds of the RQ or R'Q type, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate and the like.
  • the associative polyurethane corresponds to formula (A) in which R and R' both represent independently a hydrophobic group, X and X' both represent independently a group containing a quaternary amine, n and p are equal to zero, and L, L', Y and m have the meaning indicated in formula (A).
  • the number-average molecular mass of the cationic associative polyurethanes is usually between 400 and 500 000, in particular between 1000 and 400 000, and ideally between 1000 and 300 000 g/mol.
  • X and/or X' denote a group containing a tertiary or quaternary amine
  • X and/or X' may represent one of the following formulae: or R, for X
  • R 2 represents a linear or branched alkylene radical having from 1 to 20 carbon atoms, containing or otherwise a saturated or unsaturated ring, or an arylene radical, it being possible for one or more of the carbon atoms to be replaced by a heteroatom chosen from N, S, O, P;
  • Ri and R 3 which are identical or different, denote a linear or branched, Ci-C 30 alkyl or alkenyl radical, an aryl radical, it being possible for at least one of the carbon atoms to be replaced by a heteroatom chosen from N, S, O, P;
  • a " is a physiologically acceptable counterion.
  • Z represents -0-, -S- or -NH-
  • R4 represents a linear or branched alkylene radical having from 1 to 20 carbon atoms, containing or otherwise a saturated or unsaturated ring, an arylene radical, it being possible for one or more of the carbon atoms to be replaced by a heteroatom chosen from N, S, O and P.
  • the groups P and P', comprising an amine functional group may represent at least one of the followin formulae:
  • R 5 and R 7 have the same meanings as R 2 defined above; 3 ⁇ 4, Rs and R 9 have the same meanings as Ri and R 3 defined above;
  • R 10 represents a linear or branched alkylene group, which is optionally unsaturated and which may contain one or more heteroatoms chosen from N, O, S and P;
  • hydrophilic group is understood to mean a polymeric or nonpolymeric water-soluble group.
  • a hydrophilic polymer there may be mentioned, by way of example, polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers.
  • the hydrophilic compound is a polyether and in particular a polyethylene oxide or a polypropylene oxide.
  • the cationic associative polyurethanes of formula (A) are formed from diisocyanates and from various compounds possessing functional groups containing a labile hydrogen.
  • the functional groups containing a labile hydrogen may be alcohol functional groups, primary or secondary amine functional groups or thiol functional groups which give, after reaction with the diisocyanate functional groups, polyurethanes, polyureas and polythioureas, respectively.
  • polyurethanes of the present invention covers these three types of polymer, namely
  • polyurethanes proper polyureas and polythioureas and copolymers thereof.
  • a first type of compounds entering into the preparation of the polyurethane of formula (A) is a compound containing at least one unit containing an amine functional group.
  • This compound may be multifunctional, but preferably the compound is difunctional, that is to say that according to a preferred embodiment, this compound contains two labile hydrogen atoms carried for example by a hydroxyl, primary amine, secondary amine or thiol functional group. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low.
  • this compound may contain more than one unit containing an amine functional group. It is then a polymer carrying a repeat of the unit containing an amine functional group.
  • This type of compounds may be represented by one of the following formulae: HZ-(P) n -ZH, or HZ-(P')p-ZH, in which Z, P, ⁇ ', n and p are as defined above.
  • a compound containing an amine functional group there may be mentioned N-memyldiemanolamine, N-tert-butyldiethanolamine, N-sulfoethyldiemanolarnine.
  • a third compound entering into the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A).
  • This compound consists of a hydrophobic group and a functional group containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol functional group.
  • this compound may be a fatty alcohol, such as in particular stearyl alcohol, dodecyl alcohol, decyl alcohol.
  • this compound may be for example a-hydroxyl hydrogenated polybutadiene.
  • hydrophobic group of the polyurethane of formula (A) may also result from the
  • This quaternizing agent is a compound of the RQ or R'Q type, in which R and R are as defined above and Q denotes a leaving group such as a halide, a sulfate, and the like.
  • the cationic associative polyurethane may additionally comprise a hydrophilic sequence.
  • This sequence is provided by a fourth type of compound entering into the preparation of the polymer.
  • This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture where the percentage of multifunctional compound is low.
  • the functional groups containing a labile hydrogen are alcohol, primary or secondary amine, or thiol functional groups. This compound may be a polymer terminated at the chain ends by one of these functional groups containing a labile hydrogen.
  • hydrophilic polymer there may be mentioned, by way of example, polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers.
  • the hydrophilic compound is a polyether and in particular a polyethylene oxide or a polypropylene oxide.
  • hydrophilic group noted Y in formula (A) is optional. Indeed, the units containing a quaternary or protonated amine functional group may suffice to provide the solubility or water-dispersibility necessary for this type of polymer in an aqueous solution. Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes are nevertheless preferred which contain such a group.
  • the associative polyurethane used in the present invention may also be nonionic, in particular nonionic polyurethane-polyethers.
  • said polymers contain in their chain both hydrophilic sequences most often of a polyoxyethylenated nature and hydrophobic sequences which may be aliphatic linkages alone and/or cycloaliphatic and/or aromatic linkages.
  • these polyether-polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, preferably from 6 to 20, separated by a hydrophilic sequence, it being possible for the hydrocarbon chains to be pendent chains or chains at the end of a
  • hydrophilic sequence In particular, it is possible for one or more pendent chains to be envisaged.
  • the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic sequence.
  • the polyether-polyurethanes may be polyblocks, in particular in triblock form.
  • the hydrophobic sequences may be at each end of the chain (for example: triblock copolymer with hydrophilic central sequence) or distributed both at the ends and in the chain (polyblock copolymer for example).
  • These same polymers may also be in the form of graft units or may be star-shaped.
  • the associative polyurethane can form a network in water in which the hydrophobic part connects quasi-micelles as shown above.
  • the associative polyurethanes can increase viscosity or consistency of the composition according to the present invention. Thus after application of the composition according to the present invention, it can recover the original elasticity of the composition quickly.
  • the nonionic polyether-polyurethanes containing a fatty chain may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups.
  • the nonionic polyether-polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name.
  • hydrophilic sequences are linked by other chemical bonds to the hydrophobic sequences are also included among the nonionic polyether-polyurethanes containing a hydrophobic chain.
  • nonionic polyether-polyurethanes containing a hydrophobic chain which can be used in the invention, it is also possible to use Rheolate® 205 containing a urea functional group sold by the company RHEOX or else the Rheolates® 208, 204 or 212, as well as Acrysol RM 184®.
  • the product DW 1206B® from ROHM & HAAS containing a C 20 alkyl chain and with a urethane bond, sold at 20% dry matter content in water, may also be used.
  • polyether-polyurethanes which can be used can also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen-Colloid Polym. Sci 271, 380-389 (1993).
  • a polyether-polyurethane which can be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.
  • ACULYN 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, stearyl alcohol and methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %);
  • ACULYN 440 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, decyl alcohol and methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
  • the associative polyurethane be selected Steareth-100/PEG-136/HDI Copolymer sold by the company Rheox under the name of Rheolate FX 1100.
  • the amount of the (c) associative polyurethane is not limited, and may range from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, and more preferably from 0.4 to 3% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention further comprises at least one polyol.
  • a single type of polyol may be used, but two or more different types of polyol may be used in combination.
  • polyol here means an alcohol having two or more hydroxy groups, and does not encompass a saccharide or a derivative thereof.
  • the derivative of a saccharide includes a sugar alcohol which is obtained by reducing one or more carbonyl groups of a saccharide, as well as a saccharide or a sugar alcohol in which the hydrogen atom or atoms in one or more hydroxy groups thereof has or have been replaced with at least one substituent such as an alkyl group, a
  • the polyol may be a C 2 -C 12 polyol, preferably a C 2-9 polyol, comprising at least 2 hydroxy groups, and preferably 2 to 5 hydroxy groups.
  • the polyol may be a natural or synthetic polyol.
  • the polyol may have a linear, branched or cyclic molecular structure.
  • the polyol may be selected from glycerins and derivatives thereof, and glycols and derivatives thereof.
  • the polyol may be selected from the group consisting of glycerin, diglycerin, polyglycerin, ethyleneglycol, diethyleneglycol, propyleneglycol, dipropyleneglycol,
  • butyleneglycol pentyleneglycol, hexyleneglycol, 1,3 -propanediol, and 1,5-pentanediol.
  • the polyol may be present in an amount ranging from 0.01% to 30% by weight, and preferably from 0.1% to 20% by weight, such as from 1% to 10% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention comprises water.
  • the amount of water is not limited, and may be from 10 to 80% by weight, preferably from 20 to 75% by weight, and more preferably 30 to 60% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention may further comprise at least one additional nonionic surfactant different from the above (b) and/or at least one additional ionic surfactant.
  • additional surfactant may be selected from cationic surfactants, anionic surfactants, and amphoteric surfactants.
  • the additional nonionic surfactant may be selected from the following, as long as it has an HLB value of less than 7.0 or more than 14.0:
  • surfactants that are fluid at a temperature of less than or equal to 45°C, chosen from the esters of at least one polyol chosen from the group formed by polyethylene glycol comprising from 1 to 60 ethylene oxide units, sorbitan, glycerol comprising from 2 to 30 ethylene oxide units, polyglycerols comprising from 2 to 10 glycerol units, and of at least one fatty acid comprising at least one saturated or unsaturated, linear of branched Q-C22 alkyl chain,
  • surfactants that are solid at a temperature of less than or equal to 45 °C, chosen from fatty esters of glycerol, fatty esters of sorbitan and oxyethylenated fatty esters of sorbitan, ethoxylated fatty ethers and ethoxylated fatty esters,
  • the additional nonionic surfactant may be selected from oxyalkylene-including nonionic surfactants as long as they have an HLB value of less than 7.0 or more than 14.0.
  • the cationic surfactant is not limited.
  • the cationic surfactant may be selected from the group consisting of optionally polyoxyalkylenated, primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
  • quaternary ammonium salts examples include, but are not limited to: those of general formula (I) below:
  • Rj, R 2 , R 3 , and R4 which may be identical or different, are chosen from linear and branched aliphatic radicals comprising from 1 to 30 carbon atoms and optionally comprising heteroatoms such as oxygen, nitrogen, sulfur and halogens.
  • the aliphatic radicals may be chosen, for example, from alkyl, alkoxy, C 2 -C 6 polyoxyalkylene, alkylamide,
  • R 5 is chosen from alkenyl and alkyl radicals comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or of coconut;
  • 3 ⁇ 4 is chosen from hydrogen, -C4 alkyl radicals, and alkenyl and alkyl radicals comprising from
  • R 7 is chosen from Q-C 4 alkyl radicals
  • Rs is chosen from hydrogen and C 1 -C 4 alkyl radicals
  • X " is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates.
  • R 5 and R ⁇ are, for example, a mixture of radicals chosen from alkenyl and alkyl radicals comprising from 12 to 21 carbon atoms, such as fatty acid derivatives of tallow, R 7 is methyl and Rs is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W75PG and W75HPG by the company Witco;
  • R 9 is chosen from aliphatic radicals comprising from 16 to 30 carbon atoms
  • R 10 is chosen from hydrogen or alkyl radicals comprising from 1 to 4 carbon atoms or a group
  • Rn, R 12 , R 13 , R 14 , R 16a , R 17a , and Ri 8a are chosen from hydrogen and alkyl radicals comprising from 1 to 4 carbon atoms;
  • X " is chosen from halides, acetates, phosphates, nitrates, ethyl sulfates, and methyl sulfates.
  • R 22 is chosen from Q-Q alkyl radicals and Q-Q hydroxyalkyl and dihydroxyalkyl radicals;
  • R 23 is chosen from:
  • R 25 is chosen from:
  • R » 28 linear and branched, saturated and unsaturated C ⁇ -C hydrocarbon-based radicals R 29 , and hydrogen
  • R-4, R2 6 , and R 28 which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C 7 -C 2 i, hydrocarbon-based radicals;
  • r, s, and t which may be identical or different, are chosen from integers ranging from 2 to 6;
  • y is chosen from integers ranging from 1 to 10;
  • x and z which may be identical or different, are chosen from integers ranging from 0 to 10;
  • X " is chosen from simple and complex, organic and inorganic anions; with the proviso that the sum x+y+z ranges from 1 to 15, that when x is 0, R 23 denotes R 27 , and that when z is 0, R 25 denotes R 29 .
  • R 22 may be chosen from linear and branched alkyl radicals. In one embodiment, R 22 is chosen from linear alkyl radicals. In another embodiment, R 22 is chosen from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example methyl and ethyl radicals. In one embodiment, the sum x+y+z ranges from 1 to 10.
  • R 23 is a hydrocarbon-based radical R 2 7, it may be long and comprise from 12 to 22 carbon atoms, or short and comprise from 1 to 3 carbon atoms.
  • R 25 is a hydrocarbon-based radical R 29 , it may comprise, for example, from 1 to 3 carbon atoms.
  • R 24 , R 2 , and R 28 which may be identical or different, are chosen from linear and branched, saturated and
  • x and z which may be identical or different, are 0 or 1.
  • y is equal to 1.
  • r, s and t which may be identical or different, are equal to 2 or 3, for example equal to 2.
  • the anion X " may be chosen from, for example, halides, such as chloride, bromide, and iodide; and C 1 -C 4 alkyl sulfates, such as methyl sulfate.
  • methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other anion that is compatible with the ammonium comprising an ester function are other non-limiting examples of anions that may be used according to the invention.
  • the anion X " is chosen from chloride and methyl sulfate.
  • ammonium salts of formula (IV) may be used, wherein:
  • R 22 is chosen from methyl and ethyl radicals
  • x and y are equal to 1 ;
  • z is equal to 0 or 1;
  • r, s and t are equal to 2;
  • R 23 is chosen from:
  • R 2 5 is chosen from:
  • R 24 , R 26 , and R 28 which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C 13 -C 17 hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated, C 13 -C 17 alkyl and alkenyl radicals.
  • the hydrocarbon-based radicals are linear.
  • Non-limiting examples of compounds of formula (IV) that may be mentioned include salts, for example chloride and methyl sulfate, of diacyloxyemyl-dimemylammonium, of
  • the acyl radicals may comprise from 14 to 18 carbon atoms, and may be derived, for example, from a plant oil, for instance palm oil and sunflower oil. When the compound comprises several acyl radicals, these radicals may be identical or different.
  • These products may be obtained, for example, by direct esterification of optionally oxyalkylenated triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine onto fatty acids or onto mixtures of fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof.
  • This esterification may be followed by a quaternization using an alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol cMorohydrin; and glycerol chlorohydrin.
  • alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol cMorohydrin; and glycerol chlorohydrin.
  • alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates
  • ammonium salts that may be used in the compositions according to the invention include the ammonium salts comprising at least one ester function described in U.S. Pat. Nos. 4,874,554 and 4,137,180.
  • quaternary ammonium salts mentioned above that may be used in compositions according to the invention include, but are not limited to, those corresponding to formula (I), for example tetraalkylammonium chlorides, for instance dialkyldimethylammonium and
  • alkyltrimemylammonium chlorides in which the alkyl radical comprises from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium,
  • cetyltrimethylammonium and benzyldimemylstearylammonium chloride cetyltrimethylammonium and benzyldimemylstearylammonium chloride
  • palmilylamidopropyllrimethylammonium chloride and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk.
  • the cationic surfactant that may be used in the compositions of the invention is chosen from quaternary ammonium salts, for example from
  • the anionic surfactant is not limited.
  • the anionic surfactants may be chosen in particular from anionic derivatives of proteins of vegetable origin or of silk proteins, phosphates and alkyl phosphates, carboxylates, sulphosuccinates, amino acid derivatives, alkyl sulphates, alkyl ether sulphates, sulphonates, isethionates, taurates, alkyl sulphoacetates, polypeptides, anionic derivatives of alkyl polyglucosides, and their mixtures.
  • Anionic derivatives of proteins of vegetable origin are protein hydrolysates comprising a hydrophobic group, it being possible for the said hydrophobic group to be naturally present in the protein or to be added by reaction of the protein and/or of the protein hydrolysate with a hydrophobic compound.
  • the proteins are of vegetable origin or derived from silk, and the hydrophobic group can in particular be a fatty chain, for example an alkyl chain comprising from 10 to 22 carbon atoms. Mention may more particularly be made, as anionic derivatives of proteins of vegetable origin, of apple, wheat, soybean or oat protein hydrolysates comprising an alkyl chain having from 10 to 22 carbon atoms, and their salts.
  • the alkyl chain can in particular be a lauryl chain and the salt can be a sodium, potassium and/or ammonium salt.
  • protein hydrolysates comprising a hydrophobic group for example, of salts of protein hydrolysates where the protein is a silk protein modified by lauric acid, such as the product sold under the name Kawa Silk by Kawaken; salts of protein hydrolysates where the protein is a wheat protein modified by lauric acid, such as the potassium salt sold under the name Aminofoam W OR by Croda (CTFA name: potassium lauroyl wheat amino acids) and the sodium salt sold under the name Proteol LW 30 by Seppic (CTFA name: sodium lauroyl wheat amino acids); salts of protein hydrolysates where the protein is an oat protein comprising an alkyl chain having from 10 to 22 carbon atoms and more especially salts of protein hydrolysates where the protein is an oat protein modified by lauric acid, such as the sodium salt sold under
  • phosphates and alkyl phosphates for example, of monoalkyl phosphates and dialkyl phosphates, such as lauryl monophosphate, sold under the name MAP 20® by Kao Chemicals, the potassium salt of dodecyl phosphate, the mixture of mono- and diesters (predominantly diester) sold under the name Crafol AP-31® by Cognis, the mixture of octyl phosphate monoester and diester, sold under the name Crafol AP-20® by Cognis, the - mixture of ethoxylated (7 mol of EO) 2-butyloctyl phosphate monoester and diester, sold under the name Isofol 12 7 EO-Phosphate Ester® by Condea, the potassium or triethanolamine salt of mono(C 12 -C 13 )alkyl phosphate, sold under the references Arlatone MAP 230 -40® and Ar
  • amido ether carboxylates such as sodium lauryl amido ether carboxylate (3 EO), sold under the name Akypo Foam 30® by Kao Chemicals;
  • polyoxyethylenated carboxylic acid salts such as oxyethylenated (6 EO) sodium lauryl ether carboxylate (65/25/10 C 12 -C 14 -C 16 ), sold under the name Akypo Soft 45 NV® by Kao
  • organic or inorganic base such as potassium hydroxide, sodium hydroxide, triemanolamine, N-memylglucamine, lysine and arginine.
  • sarcosinates such as sodium lauroyl sarcosinate, sold under the name Sarkosyl NL 97® by Ciba or sold under the name Oramix L 30® by Seppic
  • sodium myristoyl sarcosinate sold under the name Nikkol Sarcosinate MN® by Nikkol
  • sodium palmitoyl sarcosinate sold under the name Nikkol Sarcosinate PN® by Nikkol
  • glutamates such as triethanolamine monococoyl glutamate, sold under the name
  • Acylglutamate CT- 12® by Aj inomoto triethanolamine lauroyl glutamate, sold under the name Acylglutamate LT-12® by Ajinomoto;
  • aspartates such as the mixture of triemanolamine N-lauroyl aspartate and triethanolamine N-myristoyl aspartate, sold under the name Asparack® by Mitsubishi;
  • glycine derivatives such as sodium N-cocoyl glycinate, sold under the names Amilite GCS- 12® and Amilite GCK 12 by Aj inomoto;
  • citrates such as the citric monoester of oxyethylenated (9 mol) coco alcohols, sold under the name Witconol EC 1129 by Goldschmidt; and
  • galacturonates such as sodium dodecyl D-galactoside uronate, sold by Soliance. 5
  • alkyl sulphates for example, of triemanolamine lauryl sulphate (CTFA name: TEA lauryl sulphate), such as the product sold by Huntsman under the name Empicol TL40 FL or the product sold by Cognis under the name Texapon T42, which products are at 40% in aqueous solution.
  • CTFA name ammonium lauryl sulphate
  • Empicol AL 30FL ammonium lauryl sulphate
  • alkyl ether sulphates for example, of sodium lauryl ether sulphate (CTFA name: sodium laureth sulphate), such as that sold under the names Texapon N40 and
  • Texapon AOS 225 UP by Cognis or ammonium lauryl ether sulphate (CTFAname: ammonium laureth sulphate), such as that sold under the name Standapol EA-2 by Cognis.
  • CFAname ammonium laureth sulphate
  • sulphonates for example, of a-olefinsulphonates, such as sodium a-olefmsulphonate (C 14 -C 16 ), sold under the name Bio-Terge AS-40® by Stepan, sold under the names Witconate AOS Protege® and Sulframine AOS PH 12® by Witco or sold under the name Bio-Terge AS-40 CG® by Stepan, secondary sodium olefinsulphonate, sold under the name Hostapur SAS 30® by Clariant; or linear alkylarylsulphonates, such as sodium xylenesulphonate, sold under the names Manrosol SXS30®, Manrosol SXS40® and Manrosol SXS93® by Manro.
  • a-olefinsulphonates such as sodium a-olefmsulphonate (C 14 -C 16 )
  • Bio-Terge AS-40® by Stepan
  • taurates of the sodium salt of palm kernel oil methyltaurate, sold under the name Hostapon CT Pate® by Clariant; N-acyl-N-methyltaurates, such as sodium
  • alkyl polyglucosides can in particular be citrates, tartrates, sulphosuccinates, carbonates and glycerol ethers obtained from alkyl polyglucosides.
  • the amino acid derivatives be acyl glycine derivatives or glycine derivatives, in particular acyl glycine salt.
  • the acyl glycine derivatives or glycine derivatives can be chosen from acyl glycine salts (or acyl glycinates) or glycine salts (or glycinates), and in particular from the following. i) Acyl glycinates of formula (I):
  • - X represents a cation chosen, for example, from the ions of alkali metals, such as Na, Li or K, preferably Na or K, the ions of alkaline earth metals, such as Mg, ammonium groups and their mixtures.
  • the acyl group can in particular be chosen from the lauroyl, myristoyl, behenoyl, palmitoyl, stearoyl, isostearoyl, olivoyl, cocoyl or oleoyl groups and their mixtures.
  • R is a cocoyl group.
  • Ri represents a saturated or unsaturated, linear or branched, hydrocarbon chain comprising from 10 to 30 carbon atoms, preferably from 12 to 22 carbon atoms and better still from 16 to 20 carbon atoms;
  • R is advantageously chosen from the lauryl, myristyl, palmityl, stearyl, cetyl, cetearyl or oleyl groups and their mixtures and preferably from the stearyl and oleyl groups,
  • R.2 groups which are identical or different, represent an R"OH group, R" being an alkyl group comprising from 2 to 10 carbon atoms, preferably from 2 to 5 carbon atoms.
  • compound of formula (I) Mention may be made, as compound of formula (I), for example, of the compounds carrying the INCI name sodium cocoyl glycinate, such as, for example, Amilite GCS-12, sold by Ajinomoto, or potassium cocoyl glycinate, such as, for example, Amilite GCK-12 from Ajinomoto.
  • Use may be made, as compounds of formula (II), of dihydroxyethyl oleyl glycinate or
  • amphoteric surfactant is not limited.
  • the amphoteric or zwitterionic surfactants can be, for example (nonlimiting list), amine derivatives such as aliphatic secondary or tertiary amine, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain comprising 8 to 22 carbon atoms and containing at least one water-solubilizing anionic group (for example, carboxylate, sulphonate, sulphate, phosphate or phosphonate).
  • amidoaminecarboxylated derivatives mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982 (the disclosures of which are incorporated herein by reference), under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures:
  • Ri denotes an alkyl radical of an acid R ⁇ COOH present in hydrolysed coconut oil, a heptyl, nonyl or undecyl radical,
  • R 2 denotes a beta-hydroxyethyl group
  • R 3 denotes a carboxymethyl group
  • X' denotes a -CH 2 CH 2 -COOH group, -CH 2 -COOZ' , -CH 2 CH 2 -COOH, -CH 2 CH 2 -COOZ' or a hydrogen atom
  • Y' denotes -COOH, -COOZ', -CH 2 -CHOH-S0 3 Z' or a -CH 2 -CHOH-S0 3 H radical
  • Z' represents an ion of an alkaline or alkaline earth metal such as sodium, an ammonium ion or an ion issued from an organic amine, and
  • Ri denotes an alkyl radical of an acid Rj'-COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, such as a C 7 , C 9 , Cn or C 13 alkyl radical, a C 17 alkyl radical and its iso form, or an unsaturated C 17 radical.
  • amphoteric surfactant be selected from (C 8 -C 24 )-alkyl amphomonoacetates, (C 8 -C 2 4)alkyl amphodiacetates, (C 8 -C 24 )alkyl amphomonopropionates, and (C 8 -C 24 )alkyl amphodipropionates
  • Caprylamphodiacetate Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium
  • cocoamphodiacetate sold under the trade name Miranol® C2M concentrate by the company Rhodia Chimie.
  • amphoteric surfactant may be a betaine.
  • the betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and
  • alkylamidoalkylsulfobetaines in particular, (C 8 -C2 4 )alkylbetaines
  • amphoteric surfactants of betaine type are chosen from (C 8 -C 24 )alkylbetaines,
  • Non-limiting examples that may be mentioned include the compounds classified in the CTFA dictionary, 9th edition, 2002, under the names cocobetaine, laurylbetaine, cetylbetaine, coco/oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine,
  • oleamidopropylhydroxysultaine cocohydroxysultaine, laurylhydroxysultaine, and cocosultaine, alone or as mixtures.
  • the betaine-type amphoteric surfactant is preferably an alkylbetaine and an
  • alkylamidoalkylbetaine in particular cocobetaine and cocamidopropylbetaine.
  • the amount of the additional surfactant(s) may be 0.01 wt% to 20wt%, preferably 0.10 wt% to 10 wt%, and more preferably 1 wt% to 5 wt%, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention may also comprise an effective amount of other ingredients, known previously elsewhere in lightening or coloring compositions, such as various common adjuvants, sequestering agents such as EDTA and etidronic acid, UV screening agents, silicones other than those mentioned before (such as with amine groups), preserving agents, vitamins or provitamins, for instance, panthenol, opacifiers, fragrances, plant extracts, cationic polymers and so on.
  • other ingredients known previously elsewhere in lightening or coloring compositions, such as various common adjuvants, sequestering agents such as EDTA and etidronic acid, UV screening agents, silicones other than those mentioned before (such as with amine groups), preserving agents, vitamins or provitamins, for instance, panthenol, opacifiers, fragrances, plant extracts, cationic polymers and so on.
  • the cosmetic composition according to the present invention may further comprise at least one organic solvent.
  • the organic solvent is preferably water miscible.
  • the organic solvent there may be mentioned, for example, Q-C 4 alkanols, such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol and phenoxyethanol; analogous products; and mixtures thereof.
  • the organic water-soluble solvents may be present in an amount ranging from less than 10% by weight, preferably from 5% by weight or less, and more preferably from 1 % by weight or less, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention can be prepared by mixing the above essential and optional ingredients in accordance with a conventional process.
  • the conventional process includes mixing with a high pressure homogenizer (a high energy process).
  • the cosmetic composition can be prepared by a low energy processes such as phase inversion temperature process (PIT), phase inversion concentration (PIC), autoemulsification, and the like.
  • PIT phase inversion temperature process
  • PIC phase inversion concentration
  • autoemulsification and the like.
  • the weight ratio of the (b) nonionic surfactant with HLB 7-14 to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.45 to 1.5.
  • the weight ratio of the (b) nonionic surfactant with HLB 7-14 /the (a) oil is preferably 1 or less, such as from 0.3 to 1, preferably from 0.4 to 1, and more preferably from 0.45 to 1.
  • the cosmetic composition according to the present invention is in the form of a nano- or micro-emulsion.
  • the "micro-emulsion” may be defined in two ways, namely, in a broader sense and in a narrower sense. That is to say, there are one case (“microemulsion in the narrow sense”) in which the microemulsion refers to a thermodynamically stable isotropic single liquid phase containing a ternary system having three ingredients of an oily component, an aqueous component and a surfactant, and the other case (“micro-emulsion in the broad sense”) in which among
  • microemulsion additionally includes those such emulsions presenting transparent or translucent appearances due to their smaller particle sizes (Satoshi Tomomasa, et al., OilChemistry, Vol. 37, No. 11 (1988), pp. 48-53).
  • the "micro-emulsion” as used herein refers to a "micro-emulsion in the narrow sense," i.e., a thermodynamically stable isotropic single liquid phase.
  • the micro-emulsion refers to either one state of an O/W (oil-in- water) type microemulsion in which oil is solubilized by micelles, a W/O (water-in-oil) type microemulsion in which water is solubilized by reverse micelles, or a bicontinuous microemulsion in which the number of associations of surfactant molecules are rendered infinite so that both the aqueous phase and oil phase have a continuous structure.
  • O/W oil-in- water
  • W/O water-in-oil
  • the micro-emulsion may have a dispersed phase with a number average diameter of 100 nm or less, preferably 50 nm or less, and more preferably 20 nm or less, measured by laser granulometry.
  • the "nano-emulsion” here means an emulsion characterized by a dispersed phase with a size of less than 350 nm, the dispersed phase being stabilized by a crown of the (b) nonionic surfactant with HLB 7-14 and the like that may optionally form a liquid crystal phase of lamellar type, at the dispersed phase/continuous phase interface.
  • the dispersed phase with a number average diameter of 100 nm or less, preferably 50 nm or less, and more preferably 20 nm or less, measured by laser granulometry.
  • the “nano-emulsion” here means an emulsion characterized by a dispersed phase with a size of less than 350 nm, the dispersed phase being stabilize
  • Nanoemulsions can be distinguished from microemulsions by their structure.
  • micro-emulsions are thermodynamically stable dispersions formed from, for example, the (b) nonionic surfactant with HLB 7-14 micells swollen with the (a) oil.
  • microemulsions do not require substantial mechanical energy in order to be prepared.
  • the micro-emulsion may have a dispersed phase with a number average diameter of 300 nm or less, preferably 200 nm or less, and more preferably 100 nm or less, measured by laser
  • the cosmetic composition according to the present invention may be in the form of an O/W nano- or micro-emulsion, a W/O nano- or micro-emulsion or a bicontinuous emulsion. It is preferable that the cosmetic composition according to the present invention be in the form of an O/W nano- or micro-emulsion.
  • the cosmetic composition according to the present invention be in the form of ah O/W emulsion
  • the (a) oil be in the form of a droplet with a number average particle size of 300 nm or less, preferably from 10 nm to 150 nm, and more preferably 20 nm to 140 nm.
  • the cosmetic composition according to the present invention can have a transparent or slightly translucent appearance, preferably a transparent appearacnce.
  • the measurement is taken on the undiluted composition.
  • the blank is determined with distilled water.
  • the transparency may be measured by measuring the nephelometric turbidity (for example, with 2100Q Portable Turbidimeter from HACH).
  • the cosmetic composition according to the present invention may preferably have a
  • nephelometric turbidity lower than 150NTU, preferably lower than 100 NTU, and more preferably lower than 50 NTU.
  • the cosmetic composition according to the present invention can be used for a non-therapeutic process, such as a cosmetic process, for treating the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows and/or the scalp, by being applied to the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows or the scalp.
  • a cosmetic process for treating the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows and/or the scalp, by being applied to the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows or the scalp.
  • the present invention also relates to a use of the cosmetic composition according to the present invention, as it is or in care products and/or washing products and/or make-up products and/or make-up-removing products for body and/or facial skin and/or mucous membranes and/or the scalp and/or the hair and/or the nails and/or the eyelashes and/or the eyebrows.
  • the cosmetic composition according to the present invention can be used, as it is, as the above product.
  • the cosmetic composition according to the present invention may preferably be a rinse-off product such as a make-up removing products for body and/or facial skin.
  • the cosmetic composition according to the present invention can be used as an element of the above product.
  • the cosmetic composition according to the present invention can be added to or combined with any other elements to form the above product.
  • the care product may be a lotion, a cream, a hair tonic, a hair conditioner, a sun screening agent, and the like.
  • the washing product may be a shampoo, a face wash, a hand wash and the like.
  • the make-up product may be a foundation, a mascara, a lipstick, a lip gloss, a blusher, an eye shadow, a nail varnish, and the like.
  • the make-up-removing product may be a make-up cleansing agent and the like.
  • compositions in the form of a transparent O/W emulsion according to Examples 1 -2 and Comparative Example 1 shown in Table 1 were prepared by mixing the components shown in Table 1 as follows: (1) mixing surfactants and oils to form an oil phase; (2) heating the oil phase up to around 70 °C; (3) mixing water and hydrophilic ingredients to form an aqueous phase; and (4) adding the aqueous phase into the oil phase followed by mixing them to obtain an O/W emulsion.
  • the numerical values for the amounts of the components shown in Table 1 are all based on "% by weight" as active raw materials. Table 1
  • the transparency of the composition was measured by measuring the nephelometric turbidity with 2100Q Portable Turbidimeter from HACH. All these 3 compositions showed a nephelometric turbidity below 80 NTU (which means good transparency).
  • the viscosity of each of the compositions according to Examples 1-2 and Comparative Example 1 was measured as follows. The viscosity of the composition itself (bulk) and the viscosity of the composition diluted with 70% by weight of water (diluted) were measured. The diluted composition was prepared by adding 70 g of water to 100 g of the composition.
  • ARES maker: TA Instruments
  • compositions including a variety of a iWckening agent were evaluated.
  • compositions according to Examples 1 and 2 were stored in a transparent container, and maintained at a room temperature (25 °C) for one day. Then, the appearance of the composition was visually observed. The compositions according to Examples 1 and 2 maintained their original transparent aspects, and no phase separation was observed.
  • the numerical values for the amounts of the components shown in Table 1 are all based on "% by weight" as active raw materials.
  • compositions according to Examples 1 and 2 were transparent, stable and could show high viscosity (or consistency) under wet conditions, and therefore, they can be easily handled by, for example, wet hand.
  • compositions according to Comparative Examples 1-10 were either (1) transparent but could not show high viscosity (or consistency) under wet conditions, and therefore, they cannot be easily handled by, for example, wet hand, or (2) translucent or turbid, or unstable such that they cannot have or maintain transparent appearance.

Abstract

The present invention relates to a cosmetic composition in the form of a nano- or micro-emulsion, comprising: (a) at least one oil; (b) at least one nonionic surfactant with HLB 7-14, preferably polyglyceryl fatty acid ester, more preferably with a polyglyceryl moiety derived from 2 to 10 glycerins, more preferably from 3 to 6 glycerins, even more preferably 5 or 6 glycerins; (c) at least one associative polyurethane; (d) at least one polyol; and (e) water, wherein the amount of the (a) oil ranges at least 20% by weight relative to the total weight of the composition. The cosmetic composition according to the present invention, for example, can have a dispersed phase which has a smaller diameter, and therefore, the cosmetic composition can be in the form of a nano- or micro-emulsion with stable transparent or slightly translucent appearance.

Description

DESCRIPTION
COSMETIC COMPOSITION TECHNICAL FIELD
The present invention relates to a cosmetic composition in the form of a nano- or micro-emulsion.
BACKGROUND ART
Microemulsions (oil in water, water in oil or bicontinuous) have been developed these last years as an alternative of cleansing oils very much appreciated for their excellent efficacy on foundation and waterproof mascara. The advantage of nano- or micro- emulsion is to present sometimes better rinsibility for usually same make-up removal efficacy. Besides, the cost of the nano- or micro-emulsions can be reduced because of their lower oil content.
DISCLOSURE OF INVENTION
An objective of the present invention is to provide a stable cosmetic, optionally cleansing, composition in the form of a nano- or micro-emulsion with transparent or slightly translucent, preferably transparent, aspect of the emulsion.
In addition, in some cases, a nano- or micro-emulsion is difficult to have a high viscosity or consistency, in particular under wet conditions. Even if a high viscosity or consistency is realized by using, for example, a thickener, this often makes it difficult for the emulsion to have stable transparent or slightly translucent appearance. Furthermore, cosmetic properties such as cleansing ability or rinsability as well as texture such as feeling to touch may be impaired.
Another objective of the present invention is to provide a cosmetic composition in the form of a nano- or micro-emulsion with a high viscosity or consistency even under wet conditions, so that it can be easily handled by, for example, wet hand, while maintaining stable transparent or slightly translucent appearance.
Another objective of the present invention is to provide a cosmetic composition in the form of a nano- or micro-emulsion with good cosmetic properties such as cleansing ability or rinsability as well as good texture such as good feeling to touch.
The above objectives of the present invention can be achieved by a rinse-off cosmetic composition in the form of a nano- or micro-emulsion, comprising:
(a) at least one oil;
(b) at least one non ionic surfactant with HLB 7-14, preferably one poly glyceryl fatty acid ester, preferably with a polyglyceryl moiety derived from 2 to 10 glycerins, preferably from 4 to 6 glycerins, more preferably 5 or 6 glycerin
(c) at least one associative polyurethane;
(d) at least one polyol; and (e) water,
wherein the amount of the (a) oil ranges at least 20% by weight relative to the total weight of the composition. The (a) oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, and hydrocarbon oils. Preferably, the (a) oil may be chosen from hydrocarbon oils which are in the form of a liquid at a room temperature. It may be preferable that the (a) oil be chosen from oils with molecular weight below 600 g/mol. The amount of the (a) oil may range from 20 to 60% by weight, preferably from 22 to 50% by weight, and more preferably from 24 to 40% by weight, relative to the total weight of the composition.
The (b) nonionic surfactant with HLB 7-14 may be polyglyceryl fatty acid ester with an HLB value of from 7 to 14.0, preferably from 8 to 13.5, and more preferably from 9 to 13.0.
It is preferable that the polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprylate comprising 2 to 6 glycerol units, polyglyceryl monolaurate comprising 3 to 6 glycerol units, polyglyceryl mono(iso)stearate comprising 3 to 10 glycerol units, polyglyceryl monooleate comprising 3 to 10 glycerol units, and polyglyceryl dioleate comprising 3 to 10 glycerol units.
The polyglyceryl fatty acid ester may be chosen from PG-2 caprate, PG-4 laurate, PG-5 laurate, PG-5 oleate, PG-5 dioleate, PG-6 tricaprylate, PG-10 oleate, PG-10 Dioleate, PG-10 isostearate, PG-2 laurate, PG- 10 trilaurate, PG- 10 myristate, PG- 10 dimyristate, PG-10 stearate, PG- 10 distearate, PG-5 myristate, Pg-5 trimyristate, PG-5 dioleate, PG-5 stearate, PG-5 trioleate, PG-6 caprylate, and PG-6 tricaprylate.
According to one embodiment, the polyglyceryl fatty acid ester raw material is chosen from a mixture of polyglyceryl fatty acid esters, preferably with a polyglyceryl moiety derived from 3 to 6 glycerins, more preferably 5 or 6 glycerins, wherein the mixture preferably comprises at least 30% by weight of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins. The amount of the (b) nonionic surfactant with HLB 7-14 may range from 0.1 to 30% by weight, preferably from 1 to 25%» by weight, and more preferably from 5 to 20% by weight, relative to the total weight of the composition.
The weight ratio of the (b) nonionic surfactant with HLB 7-14 to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.45 to 1.5.
The (b) nonionic surfactant with HLB 7-14 may be oxyalkylene-including nonionic surfactant.
The amount of the oxyalkylene-including nonionic surfactant may range from 0.1 to 25% by weight, preferably from 0.5 to 20% by weight, and more preferably from 1 to 15% by weight, W relative to the total weight of the composition.
It is preferable that the (c) associative polyurethane be a copolymer comprising at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, separated by a hydrophilic block.
The amount of the (c) associative polyurethane may range from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, and more preferably from 0.4 to 3% by weight, relative to the total weight of the composition.
The cosmetic composition according to the present invention may further comprise at least one additional nonionic surfactant different from the above (b) and/or at least one additional ionic surfactant. Polyol is preferably bivalent and trivalent, and more preferably bivalent. Preferred polyols are butylene glycol, glycerin, propanediol, dipropylene glycol, hexylene glycol, and PEG8. The amount of total polyols may be between 4% and 50%, preferably between 6% and 40%, and more preferably between 8% and 30% by weight of the total weight of the composition. It is preferable that the cosmetic composition according to the present invention be in the form of an OAV emulsion, and the (a) oil be in the form of a droplet with a number average particle size of 300 nm or less, preferably from 10 nm to 150 nm.
It is preferable that the cosmetic composition according to the present invention have a
nephelometric turbidity below 150 NTU, preferably below 100 NTU, more preferably below 50 NTU.
Further, the present invention also relates to a non-therapeutic process for treating the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows and/or the scalp, characterized in that the cosmetic composition according to the present invention is applied to the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows or the scalp.
Furthermore, the present invention also relates to a use of the cosmetic composition according to the present invention, as or in care products and/or washing products and/or make-up products and/or make-up-removing products for body and/or facial skin and/or mucous membranes and/or the scalp and/or the hair and/or the nails and/or the eyelashes and/or the eyebrows.
BEST MODE FOR CARRYING OUT THE INVENTION After diligent research, the inventors have discovered that it is possible to provide a stable cosmetic composition in the form of a nano- or micro-emulsion with transparent or slightly translucent, preferably transparent, aspect of the emulsion by using a relatively little amount of nonionic surfactants compared to the amount of oil. Further, the cosmetic composition according to the present invention can have a high viscosity or consistency even under wetconditions, so that it can be easily handled by, for example, wet hand, while maintaining stable transparent or slightly translucent appearance. Furthermore, the cosmetic composition according to the present invention can have good cosmetic properties such as cleansing ability or rinsability as well as good texture such as good feeling to touch.
Thus, the present invention is a cosmetic composition in the form of a nano- or micro-emulsion, comprising:
(a) at least one oil;
(b) at least one non ionic surfactant with HLB 7-14, preferably one poly glyceryl fatty acid ester, preferably with a polyglyceryl moiety derived from 2 to 10 glycerins, preferably from 4 to 6 glycerins, more preferably 5 or 6 glycerin;
(c) at least one associative polyurethane;
(d) at least one polyol ; and
(e) water,
wherein the amount of the (a) oil ranges at least 20% by weight relative to the total weight of the composition.
The cosmetic composition according to the present invention can have a high viscosity or consistency, and therefore, it can be in the form of, for example, a viscous gel. Thus, the cosmetic composition according to the present invention can avoid or reduce, for example, dripping down of the composition from the skin or hair when being used by a user.
Further, the cosmetic composition according to the present invention can have a high viscosity or consistency under wet conditions typically in, for example, a bathroom. Thus, the cosmetic composition according to the present invention can be easily handed by, for example wet hand.
Also, the cosmetic composition according to the present invention can have good cosmetic properties such as cleansing ability or rinsability as well as good texture such as good feeling to touch, and therefore, it can be used preferably for cleansing products such as a makeup cleansing agent.
Furthermore, the cosmetic composition according to the present invention has a dispersed phase which has a smaller diameter. Therefore, the cosmetic composition can be in the form of a nano- or micro-emulsion with transparent or slightly translucent.
Hereinafter, the cosmetic composition according to the present invention will be explained in a more detailed manner.
[Oil]
The cosmetic composition according to the present invention comprises at least one oil. Here, "oil" means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non- volatile, preferably non- volatile. W 201
The oil may be a non-polar oil such as a hydrocarbon oil; a polar oil such as a plant or animal oil and an ester oil; or a mixture thereof. It is preferable that the (a) oil contains at least one hydrocarbon oil chosen from ester, ether and alkane oils.
As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, com oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.
As examples of animal oils, mention may be made of, for example, squalene and squalane. As examples of synthetic oils, mention may be made of ester oils and artificial triglyceride.
The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched Ci-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci-C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the invention are derived is branched. Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, ethyl hexyl myristate, isopropyl palmitate, isonononyl isononanoate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate, isopropyl palmitate, octyl isostearate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.
Ether oil might include dicaprylyl ether.
Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, isopropyl palmitate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.
Esters of C4-C22 dicarboxylic or tricarboxylic acids and of Ci-C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C4-C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
Mention may especially be made of: diethyl sebacate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate. As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, isononyl isononanoate, dicaprylyl carbonate, octyl isostearate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.
As examples of artificial triglycerides, mention may be made of, for example, glyceryl trimyristate, glyceryl tripalrnitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).
Hydrocarbon oils may be chosen from:
linear or branched, optionally cyclic, C6-C16 lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane; and
linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam®, and squalane.
As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as mineral oil(e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene
copolymer; and mixtures thereof.
It is preferable that the (a) oil be chosen from hydrocarbon oils which are in the form of a liquid at a room temperature.
It is also preferable that the (a) oil be chosen from oils with molecular weight below 600 g/mol.
Preferably, the (a) oil has a low molecular weight such as below 600 g mol, chosen among ester oils with a short hydrocarbon chain or chains (e.g., isopropyl myristate, isopropyl palmitate, isononyl isononanoate, and ethyl hexyl palmitate), hydrocarbon oils with a short alkyl chain or chains (e.g., isododecane, isohexadecane, and squalane), short alcohol type oils such as
octyldodecanol.
The amount in the cosmetic composition according to the present invention of the (a) oil ranges at least 20% by weight, and may range from 20 to 60% by weight, preferably from 22 to 50% by weight, and more preferably from 24 to 40% by weight, relative to the total weight of the composition.
[Nonionic Surfactant with HLB 7-14] The cosmetic composition according to the present invention comprises at least one nonionic surfactant with HLB 7-14. A single type of the nonionic surfactant may be used, but two or more different types of the nonionic surfactant may be used in combination.
The HLB is the ratio between the hydrophilic part and the lipophilic part in the molecule. This term HLB is well known to those skilled in the art and is described in "The HLB system. A time-saving guide to emulsifier selection" (published by ICI Americas Inc., 1984).
The term HLB ("hydrophilic-lipophilic balance") is well known to those skilled in the art, and denotes the hydrophilic-lipophilic balance of a surfactant.
The HLB or hydrophilic-lipophilic balance of the surfactant(s) used according to the invention is the HLB according to Griffin, defined in the publication J Soc. Cosm. Chem., 1954 (Vol 5), pages 249-256 or the HLB determined experimentally and as described in the publication from the authors F. Puisieux and M. Seiller, entitled "Galenica 5: Les systemes disperses [Dispersed systems] - Volume I - Agents de surface et emulsions [Surface agents and emulsions] - Chapter IV - Notions de HLB et de HLB critique [Notions of HLB and of critical HLB], pages 153-194 - paragraph 1.1.2. Determination de HLB par voie experimentale [Experimental determination of HLB], pages 164-180. It is preferably the calculated HLB values that should be taken into account.
The calculated HLB is defined as being the following coefficient:
calculated HLB = 20 * molar mass of the hydrophilic part/total molar mass. For an oxyethylenated fatty alcohol, the hydrophilic part corresponds to the oxyethylene units fused to the fatty alcohol and the calculated HLB then corresponds to the HLB according to Griffin (Griffin W.C., J. Soc. Cosmet. Chemists, 5, 249, 1954).
The above nonionic surfactant has an HLB (Hydrophilic Lipophilic Balance) value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0. If two or more nonionic surfactants are used, the HLB value is determined by the weight average of the HLB values of all the nonionic surfactants.
The amount in the cosmetic composition according to the present invention of the (b) nonionic surfactant with an HLB 7-14 is not limited, and may range from 0.1 to 30% by weight, preferably from 1 to 25% by weight, and more preferably from 3 to 20% by weight, relative to the total weight of the composition.
The (b) nonionic surfactant with an HLB value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0 may be chosen from: (1) surfactants that are fluid at a temperature of less than or equal to 45 °C, chosen from the esters of at least one polyol chosen from the group formed by polyethylene glycol comprising from 1 to 60 ethylene oxide units, sorbitan, glycerol comprising from 2 to 30 ethylene oxide units, polyglycerols comprising from 2 to 12 glycerol units, and of at least one fatty acid comprising at least one saturated or unsaturated, linear or branched Q-C22 alkyl chain,
(2) mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol,
(3) fatty acid esters of sugars and fatty alcohol ethers of sugars,
(4) surfactants that are solid at a temperature of less than or equal to 45 °C, chosen from fatty esters of glycerol, fatty esters of sorbitan and oxyethylenated fatty esters of sorbitan, ethoxylated fatty ethers and ethoxylated fatty esters,
(5) block copolymers of ethylene oxide (A) and of propylene oxide (B), and
(6) silicone surfactants. The surfactants (1) that are fluid at a temperature of less than or equal to 45°C may be, in particular:
the isostearate of polyethylene glycol of molecular weight 400, sold under the name PEG 400 by the company Unichema;
diglyceryl isostearate, sold by the company Solvay;
- glyceryl laurate comprising 2 glycerol units, sold by the company Solvay;
sorbitan oleate, sold under the name Span 80 by the company ICI;
sorbitan isostearate, sold under the name Nikkol SI 10R by the company Nikko; and a-butylglucoside cocoate or a-butylglucoside caprate, sold by the company Ulice. The (2) mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol, which can be used as the above nonionic surfactant, may be chosen in particular from the group comprising mixed esters of fatty acid or of fatty alcohol with an alkyl chain containing from 8 to 22 carbon atoms, and of a-hydroxy acid and/or of succinic acid, with glycerol. The -hydroxy acid may be, for example, citric acid, lactic acid, glycolic acid or malic acid, and mixtures thereof.
The alkyl chain of the fatty acids or alcohols from which are derived the mixed esters which can be used in the nanoemulsion of the invention may be linear or branched, and saturated or unsaturated. They may especially be stearate, isostearate, linoleate, oleate, behenate,
arachidonate, palmitate, myristate, laurate, caprate, isostearyl, stearyl, linoleyl, oleyl, behenyl, myristyl, lauryl or capryl chains, and mixtures thereof.
As examples of mixed esters which can be used in the nanoemulsion of the invention, mention may be made of the mixed ester of glycerol and of the mixture of citric acid, lactic acid, linoleic acid and oleic acid (CTFAname: Glyceryl citrate/lactate/linoleate/oleate) sold by the company Hiils under the name Imwitor 375; the mixed ester of succinic acid and of isostearyl alcohol with glycerol (CTFAname: Isostearyl diglyceryl succinate) sold by the company Hiils under the name Imwitor 780 K; the mixed ester of citric acid and of stearic acid with glycerol (CTFAname:
Glyceryl stearate citrate) sold by the company Hiils under the name Imwitor 370; the mixed ester of lactic acid and of stearic acid with glycerol (CTFA name: Glyceryl stearate lactate) sold by the company Danisco under the name Lactodan B30 or Rylo LA30. The (3) fatty acid esters of sugars, which can be used as the above nonionic surfactant, may preferably be solid at a temperature of less than or equal to 45 °C and may be chosen in particular from the group comprising esters or mixtures of esters of Q-C22 fatty acid and of sucrose, of maltose, of glucose or of fructose, and esters or mixtures of esters of C14-C22 fatty acid and of methylglucose.
The C8-C22 or C14-C22 fatty acids forming the fatty unit of the esters which can be used in the present invention comprise a saturated or unsaturated linear alkyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unit of the esters may be chosen in particular from stearates, behenates, arachidonates, palmitates, myristates, laurates and caprates, and mixtures thereof. Stearates are preferably used.
As examples of esters or mixtures of esters of fatty acid and of sucrose, of maltose, of glucose or of fructose, mention may be made of sucrose monostearate, sucrose distearate and sucrose tristearate and mixtures thereof, such as the products sold by the company Croda under the name Crodesta F50, F70, F110 and F160; and examples of esters or mixtures of esters of fatty acid and of methylglucose which may be mentioned are methylglucose polyglyceryl-3 distearate, sold by the company Goldschmidt under the name Tego-care 450. Mention may also be made of glucose or maltose monoesters such as methyl o-hexadecanoyl-6-D-glucoside and
o-hexadecanoyl-6-D-maltoside.
The (3) fatty alcohol ethers of sugars, which can be used as the above nonionic surfactant, may be solid at a temperature of less than or equal to 45 °C and may be chosen in particular from the group comprising ethers or mixtures of ethers of C8-C22 fatty alcohol and of glucose, of maltose, of sucrose or of fructose, and ethers or mixtures of ethers of a C14-C22 fatty alcohol and of methylglucose. These are in particular alkylpolyglucosides.
The C8-C22 or C14-C22 fatty alcohols forming the fatty unit of the ethers which may be used in the nanoemulsion of the invention comprise a saturated or unsaturated, linear alkyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unit of the ethers may be chosen in particular from decyl, cetyl, behenyl, arachidyl, stearyl, palmityl, myristyl, lauryl, capryl and hexadecanoyl units, and mixtures thereof, such as cetearyl. As examples of fatty alcohol ethers of sugars, mention may be made of alkylpolyglucosides such as decylglucoside and laurylglucoside, which is sold, for example, by the company Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearyl glucoside optionally as a mixture with cetostearyl alcohol, sold for example, under the name Montanov 68 by the company SEPPIC, under the name Tego-care CG90 by the company Goldschmidt and under the name Emulgade KE3302 by the company Henkel, as well as arachidyl glucoside, for example in the form of a mixture of arachidyl alcohol and behenyl alcohol and arachidyl glucoside, sold under the name Montanov 202 by the company SEPPIC.
The surfactant used more particularly is sucrose monostearate, sucrose distearate or sucrose tristearate and mixtures thereof, methylglucose polyglyceryl-3 distearate and alkylpolyglucosides. The (4) fatty esters of glycerol which may be used as the above nonionic surfactant, which are solid at a temperature of less than or equal to 45°C, may be chosen in particular from the group comprising esters formed from at least one acid comprising a saturated linear alkyl chain containing from 12 to 22 carbon atoms and from 1 to 12 glycerol units. One or more of these fatty esters of glycerol may be used in the present invention.
These esters may be chosen in particular from stearates, behenates, arachidates and palmitates, and mixtures thereof. Stearates and palmitates are preferably used.
As examples of surfactants which can be used in the present invention, mention may be made of decaglyceryl monostearate, distearate, tristearate and pentastearate (CTFA names: Poly glyceryl- 10 stearate, Polyglyceryl-10 distearate, Polyglyceryl-10 tristearate, Polyglyceryl- 10 pentastearate), such as the products sold under the respective names Nikkol Decaglyn 1-S, 2-S, 3-S and 5-S by the company Nikko, and diglyceryl monostearate (CTFA name: Polyglyceryl-2 stearate), such as the product sold by the company Nikko under the name Nikkol DGMS.
The (4) fatty esters of sorbitan which may be used as the above nonionic surfactant, which are solid at a temperature of less than or equal to 45°C, may be chosen from the group comprising C16-C22 fatty acid esters of sorbitan and oxyethylenated C16-C22 fatty acid esters of sorbitan.
They are formed from at least one fatty acid comprising at least one saturated linear alkyl chain containing, respectively, from 16 to 22 carbon atoms, and from sorbitol or from ethoxylated sorbitol. The oxyethylenated esters generally comprise from 1 to 100 ethylene glycol units and preferably from 2 to 40 ethylene oxide (EO) units.
These esters may be chosen in particular from stearates, behenates, arachidates, palmitates, and mixtures thereof. Stearates and palmitates are preferably used.
As examples of the above nonionic surfactant can be used in the present invention, mention may be made of sorbitan monostearate (CTFA name: Sorbitan stearate), sold by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA name: Sorbitan palmitate), sold by the company ICI under the name Span 40, and sorbitan tristearate 20 EO (CTFA name: Polysorbate 65), sold by the company ICI under the name Tween 65. The (4) ethoxylated fatty ethers that are solid at a temperature of less than or equal to 45 °C, which may be used as the above nonionic surfactant, are preferably ethers formed from 1 to 100 ethylene oxide units and from at least one fatty alcohol chain containing from 16 to 22 carbon atoms. The fatty chain of the ethers may be chosen in particular from behenyl, arachidyl, stearyl and cetyl units, and mixtures thereof, such as cetearyl. Examples of ethoxylated fatty ethers which may be mentioned are behenyl alcohol ethers comprising 5, 10, 20 and 30 ethylene oxide units (CTFA names: Beheneth-5, Beheneth-10, Beheneth-20, Beheneth-30), such as the products sold under the names Nikkol BB5, BB 10, BB20 and BB30 by the company Nikko, and stearyl alcohol ether comprising 2 ethylene oxide units (CTFA name: Steareth-2), such as the product sold under the name Brij 72 by the company ICI. The (4) ethoxylated fatty esters that are solid at a temperature of less than or equal to 45°C, which may be used as the above nonionic surfactant, are esters formed from 1 to 100 ethylene oxide units and from at least one fatty acid chain containing from 16 to 22 carbon atoms. The fatty chain in the esters may be chosen in particular from stearate, behenate, arachidate and palmitate units, and mixtures thereof. Examples of ethoxylated fatty esters which may be mentioned are the ester of stearic acid comprising 40 ethylene oxide units, such as the product sold under the name Myri 52 (CTFAname: PEG-40 stearate) by the company ICI, as well as the ester of behenic acid comprising 8 ethylene oxide units (CTFAname: PEG-8 behenate), such as the product sold under the name Compritol HD5 ATO by the company Gattefosse.
The (5) block copolymers of ethylene oxide (A) and of propylene oxide (B), which may be used as surfactants in the nanoemulsion according to the invention, may be chosen in particular from block copolymers of formula (TV): HO(C2H40)x(C3H60)y(C2H40)zH (IV) in which x, y and z are integers such that x+z ranges from 2 to 100 and y ranges from 14 to 60, and mixtures thereof, and more particularly from the block copolymers of formula (TV) having an HLB value ranging from 8.0 to 14.
As (6) silicone surfactants which can be used according to the present invention, mention may be made of those disclosed in documents US-A-5364633 and US-A-5411744.
The (6) silicone surfactant as the above nonionic surfactant may preferably be a compound of formula (I):
Figure imgf000012_0001
in which:
Ri, R2 and R3, independently of each other, represent a C\-C6 alkyl radical or a radical
-(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4, at least one radical R R2 or R3 not being an alkyl radical; 4 being a hydrogen, an alkyl radical or an acyl radical;
A is an integer ranging from 0 to 200;
B is an integer ranging from 0 to 50; with the proviso that A and B are not simultaneously equal to zero;
x is an integer ranging from 1 to 6;
y is an integer ranging from 1 to 30;
z is an integer ranging from 0 to 5.
According to one preferred embodiment of the invention, in the compound of formula (I), the alkyl radical is a methyl radical, x is an integer ranging from 2 to 6 and y is an integer ranging from 4 to 30. As examples of silicone surfactants of formula (I), mention may be made of the compounds of formula (II):
(CH3)3SiO - [(CH3)2SiO]A - (CH3SiO)B - Si(CH3)3
I (II)
(CH2)r(OCH2CH2)y-OH in which A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10 and y is an integer ranging from 10 to 20.
As examples of silicone surfactants of formula (I), mention may also be made of the compounds of formula (III):
H-(OCH2CH2)y-(CH2)3-[(CH3)2SiO]A'-(CH2)3-(OCH2CH2)y-OH (III) in which A' and y are integers ranging from 10 to 20. Compounds of the invention which may be used are those sold by the company Dow Corning under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667. The compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II) in which, respectively, A is 22, B is 2 and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12. The compound Q4-3667 is a compound of formula (III) in which A is 15 and y is 13.
(Polyglyceryl Fatty Acid Ester)
The nonionic surfactant with HLB 7-14 may be selected from polyglyceryl fatty acid esters. Thus, the cosmetic composition according to the present invention may comprise at least one polyglyceryl fatty acid esterwith an HLB value of 7-14. A single type of polyglyceryl fatty acid ester may be used, but two or more different types of polyglyceryl fatty acid ester may be used in combination. It is preferable that the polyglyceryl fatty acid ester have a polyglycol moiety derived from 2 to 10 glycols, more preferably from 3 to 6 glycols, and further more preferably 5 or 6 glycols.
The polyglyceryl fatty acid ester may have an HLB value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0. If two or more polyglyceryl fatty acid esters are used, the HLB value is determined by the weight average of the HLB values of all the
polyglyceryl fatty acid esters.
The polyglyceryl fatty acid ester may be chosen from the mono, di and tri esters of saturated or unsaturated acid, preferably saturated acid, including 2 to 30 carbon atoms, preferably 6 to 30 carbon atoms, and more preferably 8 to 30 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid, and myristic acid. It is preferable that the polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprylate comprising 2 to 6 glycerol units, polyglyceryl monolaurate comprising 3 to 6 glycerol units, polyglyceryl mono(iso)stearate comprising 3 to 10 glycerol units, polyglyceryl monooleate comprising 3 to 10 glycerol units, and polyglyceryl dioleate comprising 3 to 10 glycerol units.
The polyglyceryl fatty acid ester may be selected from the group consisting of PG2 caprate, PG2 dicaprate, PG2 tricaprate, PG2 caprylate, PG2 dicaprylate, PG2 tricaprylate, PG2 laurate, PG2 dilaurate, PG2 trilaurate, PG2 myristate, PG2 dimyristate, PG2 trimyristate, PG2 stearate, PG2 distearate, PG2 tristearate, PG2 isostearate, PG2 diisostearate, PG2 triisostearate, PG2 oleate, PG2 dioleate, PG2 trioleare, PG3 caprate, PG3 dicaprate, PG3 tricaprate, PG3 caprylate, PG3 dicaprylate, PG3 tricaprylate, PG3 laurate, PG3 dilaurate, PG3 trilaurate, PG3 myristate, PG3 dimyristate, PG3 trimyristate, PG3 stearate, PG3 distearate, PG3 tristearate, PG3 isostearate, PG3 diisostearate, PG3 triisostearate, PG3 oleate, PG3 dioleate, PG3 trioleare, PG4 caprate, PG4 dicaprate, PG4 tricaprate, PG4 caprylate, PG4 dicaprylate, PG4 tricaprylate, PG4 laurate, PG4 dilaurate, PG4 trilaurate, PG4 myristate, PG4 dimyristate, PG4 trimyristate, PG4 stearate, PG4 distearate, PG4 tristearate, PG4 isostearate, PG4 diisostearate, PG4 triisostearate, PG4 oleate, PG4 dioleate, PG4 trioleare, PG5 caprate, PG5 dicaprate, PG5 tricaprate, PG5 caprylate, PG5 dicaprylate, PG5 tricaprylate, PG5 laurate, PG5 dilaurate, PG5 trilaurate, PG5 myristate, PG5 dimyristate, PG5 trimyristate, PG5 stearate, PG5 distearate, PG5 tristearate, PG5 isostearate, PG5 diisostearate, PG5 triisostearate, PG5 oleate, PG5 dioleate, PG5 trioleare, PG6 caprate, PG6 dicaprate, PG6 tricaprate, PG6 caprylate, PG6 dicaprylate, PG6 tricaprylate, PG6 laurate, PG6 dilaurate, PG6 trilaurate, PG6 myristate, PG6 dimyristate, PG6 trimyristate, PG6 stearate, PG6 distearate, PG6 tristearate, PG6 isostearate, PG6 diisostearate, PG6 triisostearate, PG6 oleate, PG6 dioleate, PG6 trioleare, PG10 caprate, PG10 dicaprate, PG10 tricaprate, PG10 caprylate, PG10 dicaprylate, PG10 tricaprylate, PG10 laurate, PG10 dilaurate, PG10 trilaurate, PG10 myristate, PG10 dimyristate, PG10 trimyristate, PG10 stearate, PG10 distearate, PG10 tristearate, PG10 isostearate, PG10 diisostearate, PG10 triisostearate, PG10 oleate, PG10 dioleate, and PG10 trioleare.
It is preferable that the polyglyceryl fatty acid ester be chosen from PG-2 caprate, PG-4 laurate, PG-5 laurate, PG-5 oleate, PG-5 dioleate, PG-6 tricaprylate, PG-10 oleate, PG-10 Dioleate, PG-10 isostearate, PG-2 laurate, PG-10 trilaurate, PG-10 myristate, PG-10 dimyristate, PG-10 stearate, PG-10 distearate, PG-5 myristate, Pg-5 trimyristate, PG-5 dioleate, PG-5 stearate, PG-5 trioleate, PG-6 caprylate, and PG-6 tricaprylate.
It is preferable that the polyglyceryl fatty acid ester be chosen from:
polyglyceryl monolaurate comprising 3 to 6 glycerol units,
- polyglyceryl mono(iso)stearate comprising 3 to 6 glycerol units,
polyglyceryl monooleate comprising 3 to 6 glycerol units, and
polyglyceryl dioleate comprising 3 to 6 glycerol units.
In one embodiment, the polyglyceryl fatty acid ester may be chosen from a mixture of polyglyceryl fatty acid esters, preferably with a polyglyceryl moiety derived from 3 to 6 glycerins, more preferably 5 or 6 glycerins, wherein the mixture preferably comprises 30% by weight or more of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins.
The amount in the cosmetic composition according to the present invention of the polyglyceryl fatty acid ester is not limited, and may range from 0.1 to 30% by weight, preferably from 1 to 25% by weight, and more preferably from 3 to 20% by weight, relative to the total weight of the composition.
(Oxyalkylene-including Nonionic Surfactant)
The nonionic surfactant with HLB 7-14 may be selected from oxyalkylene-including nonionic surfactants. A single type of oxyalkylene-including nonionic surfactant may be used, but two or more different types of oxyalkylene-including nonionic surfactant may be used in combination. The oxyalkylene-including nonionic surfactant may have an HLB value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0. If two or more
oxyalkylene-including nonionic surfactants are used, the HLB value is determined by the weight average of the HLB values of all the oxyalkylene-including nonionic surfactant. The oxyalkylene-including nonionic surfactant according to the present invention may be selected from mono- or poly-oxyalkylenated fatty acid esters.
It is preferable that the mono- or poly-oxyalkylenated fatty acid ester have a (poly)oxyalkylene moiety derived from 1 to 200 oxyalkylenes, preferably from 3 to 150 oxyalkylenes, and more preferably 4 to 120 oxyalkylenes.
The (poly)oxyalkylene moiety may be derived from alkylene glycols such as ethyleneglycol, propylene glycol, butyleneglycol, pentyleneglycol, hexyleneglycol, and the like. The
(poly)oxyalkylene moiety may contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 200 and preferably between 2 and 150. Advantageously, the
oxyalkylene-including nonionic surfactant does not comprise any oxypropylene units.
The mono- or poly-oxyalkylenated fatty acid ester may be chosen from the mono and di esters of saturated or unsaturated acid, preferably saturated acid, including 2 to 30 carbon atoms, preferably 6 to 30 carbon atoms, and more preferably 8 to 30 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid, and myristic acid.
Examples of mono- or poly-oxyalkylenated fatty acid esters that may be mentioned include esters of saturated or unsaturated, linear or branched, C2-C3o, preferably C6-C30 and more preferably C8-C30 acids and of polyethylene glycols.
Examples of mono- or poly-oxyalkylenated fatty acid esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid or behenic acid, and mixtures thereof, especially those containing from 8 to 120 oxyethylene groups, such as PEG-8 to PEG-120 laurate (as the CTFA names: PEG-8 laurate to PEG-120 laurate); PEG-8 to PEG-120 myristate (as the CTFA names: PEG-8 mysistate to PEG-120 mysistate); PEG-8 to PEG-120 palmitate (as the CTFA names: PEG-8 palmitate to PEG-120 palmitate); PEG-8 to PEG-120 stearate (as the CTFAnames: PEG-8 stearate to PEG-120 stearate); PEG-8 to PEG-120 isostearate (as the CTFAnames: PEG-8 isostearate to PEG-120 isostearate); PEG-8 to PEG-120 oleate (as the CTFA names: PEG-8 oleate to PEG-120 oleate); PEG-8 to PEG-120 behenate (as the CTFAnames: PEG-8 behenate to PEG-120 behenate); and mixtures thereof.
Other examples of mono- or poly-oxyalkylenated fatty acid esters that may be mentioned include Steareth-100 available as Brij 700 from Uniqema Inc., Pareth alcohols available as Performathox 450, 480 and 490 available from New Phase Technologies, Inc. Suitable examples of di-alkyl substituted polymers include PEG 120 methyl glucose dioleate available as Glutamate DOE- 120 and Glucamate DOE- 120 both from Chemron Corporation. Suitable examples of tri-alkyl substituted polymers include PEG 120 methyl glucose trioleate available as Glucamate LT from Chemron Corporation. Suitable examples of tetra-alkyl substituted polymers include PEG 150 pentaerythrityl tetrastearate available as Crothix from Croda Corporation.
It is preferable that polyglycol fatty acid ester be selected from the group consisting of PEG-120 oleate, PEG-120 methyl glucose dioleate, and a mixture thereof.
The amount of the oxyalkylene-including nonionic surfactant is not limited, and may range from 0.1 to 25% by weight, preferably from 0.5 to 20% by weight, and more preferably from 1 to 15% by weight, relative to the total weight of the composition. [Associative Polyurethane]
The cosmetic composition according to the present invention comprises at least one associative polyurethane. A single type of associative polyurethane may be used, but two or more different types of associative polyurethane may be used in combination.
The associative polyurethane may be cationic or nonionic.
Among the associative polyurethanes, there may be mentioned the associative polyurethane derivatives such as those obtained by polymerization: about 20% to 70% by weight of a carboxylic acid containing an α,β-monoethylenic unsaturation, about 20 to 80% by weight of a nonsurfactant monomer containing an α,β-monoethylenic unsaturation, about 0.5 to 60% by weight of a nonionic mono-urethane which is the product of the reaction of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate. The like are described in particular in EP 173109 and more particularly in example 3. More precisely, this polymer is a methacrylic acid/methyl acrylate/dimethyl metaisopropenyl benzyl isocyanate of ethoxylated behenyl alcohol (40EO) terpolymer as an aqueous dispersion at 25%. This product is provided under the reference VISCOPHOBE DB1000 by the company
AMERCHOL. Also suitable are the cationic associative polyurethanes the family of which has been described by the Applicant in French Patent Application No. 0009609. It can be represented more particularly by the following general formula (A): R-X-(P)n-[L-(Y)m]r-L'-(P%-X'-R' (A) in which: R and R', which are identical or different, represent a hydrophobic group or a hydrogen atom; X and X', which are identical or different, represent a group containing an amine functional group carrying or otherwise a hydrophobic group, or alternatively the group L"; L, L' and L", which are identical or different, represent a group derived from a diisocyanate; P and P', which are identical or different, represent a group containing an amine functional group carrying or otherwise a hydrophobic group; Y represents a hydrophilic group; r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25; n, m and p are each
independently of the others between 0 and 1000; the molecule containing at least one protonated or quaternized amine functional group and at least one hydrophobic group.
In a very advantageous embodiment, the only hydrophobic groups of these polyurethanes are the groups R and R' at the chain ends.
According to a first preferred embodiment, the associative polyurethane corresponds to the formula (A) in which R and R' both represent independently a hydrophobic group, X, X' each represent a group L", n and p are between 1 and 1000, and L, L', L", P, P', Y and m have the meaning indicated in formula (A).
According to another preferred embodiment of the present invention, the associative polyurethane corresponds to the formula (A) in which R and R' both represent independently a hydrophobic group, X, X' each represent a group L", n and p are equal to 0, and L, L', L", Y and m have the meaning in formula (A) indicated above.
The fact that n and p are equal to 0 means that these polymers do not contain units derived from a monomer containing an amine functional group, incorporated into the polymer during
polycondensation. The protonated amine functional groups of these polyurethanes result from the hydrolysis of isocyanate functional groups, in excess, at the chain end, followed by alkylation of the primary amine functional groups formed by alkylating agents containing a hydrophobic group, that is to say compounds of the RQ or R'Q type, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate and the like. In accordance with another preferred embodiment of the present invention, the associative polyurethane corresponds to formula (A) in which R and R' both represent independently a hydrophobic group, X and X' both represent independently a group containing a quaternary amine, n and p are equal to zero, and L, L', Y and m have the meaning indicated in formula (A). The number-average molecular mass of the cationic associative polyurethanes is usually between 400 and 500 000, in particular between 1000 and 400 000, and ideally between 1000 and 300 000 g/mol.
When X and/or X' denote a group containing a tertiary or quaternary amine, X and/or X' may represent one of the following formulae:
Figure imgf000018_0001
or R, for X
Figure imgf000018_0002
or l for X' in which:
R2 represents a linear or branched alkylene radical having from 1 to 20 carbon atoms, containing or otherwise a saturated or unsaturated ring, or an arylene radical, it being possible for one or more of the carbon atoms to be replaced by a heteroatom chosen from N, S, O, P;
Ri and R3, which are identical or different, denote a linear or branched, Ci-C30 alkyl or alkenyl radical, an aryl radical, it being possible for at least one of the carbon atoms to be replaced by a heteroatom chosen from N, S, O, P;
A" is a physiologically acceptable counterion.
The groups L, L' and L" represent a group of formula:
Figure imgf000018_0003
in which: '
Z represents -0-, -S- or -NH-; and
R4 represents a linear or branched alkylene radical having from 1 to 20 carbon atoms, containing or otherwise a saturated or unsaturated ring, an arylene radical, it being possible for one or more of the carbon atoms to be replaced by a heteroatom chosen from N, S, O and P.
The groups P and P', comprising an amine functional group, may represent at least one of the followin formulae:
Figure imgf000018_0004
Figure imgf000019_0001
in which:
R5 and R7 have the same meanings as R2 defined above; ¾, Rs and R9 have the same meanings as Ri and R3 defined above;
R10 represents a linear or branched alkylene group, which is optionally unsaturated and which may contain one or more heteroatoms chosen from N, O, S and P;
A" is a physiologically acceptable counterion. As regards the meaning of Y, the expression hydrophilic group is understood to mean a polymeric or nonpolymeric water-soluble group. By way of example, there may be mentioned, when polymers are not involved, ethylene glycol, diethylene glycol and propylene glycol. In the case, in accordance with a preferred embodiment, of a hydrophilic polymer, there may be mentioned, by way of example, polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and in particular a polyethylene oxide or a polypropylene oxide.
The cationic associative polyurethanes of formula (A) are formed from diisocyanates and from various compounds possessing functional groups containing a labile hydrogen. The functional groups containing a labile hydrogen may be alcohol functional groups, primary or secondary amine functional groups or thiol functional groups which give, after reaction with the diisocyanate functional groups, polyurethanes, polyureas and polythioureas, respectively. The term
"polyurethanes" of the present invention covers these three types of polymer, namely
polyurethanes proper, polyureas and polythioureas and copolymers thereof.
A first type of compounds entering into the preparation of the polyurethane of formula (A) is a compound containing at least one unit containing an amine functional group. This compound may be multifunctional, but preferably the compound is difunctional, that is to say that according to a preferred embodiment, this compound contains two labile hydrogen atoms carried for example by a hydroxyl, primary amine, secondary amine or thiol functional group. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low.
As indicated above, this compound may contain more than one unit containing an amine functional group. It is then a polymer carrying a repeat of the unit containing an amine functional group. This type of compounds may be represented by one of the following formulae: HZ-(P)n-ZH, or HZ-(P')p-ZH, in which Z, P, Ρ', n and p are as defined above. By way of examples of a compound containing an amine functional group, there may be mentioned N-memyldiemanolamine, N-tert-butyldiethanolamine, N-sulfoethyldiemanolarnine.
The second compound entering into the preparation of the polyurethane of formula (A) is a diisocyanate corresponding to the formula 0=C=N-R4-N=C=0 in which R4 is defined above.
By way of example, there may be mentioned methylenediphenyl diisocyanate,
methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate, hexane diisocyanate. A third compound entering into the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A).
This compound consists of a hydrophobic group and a functional group containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol functional group.
By way of example, this compound may be a fatty alcohol, such as in particular stearyl alcohol, dodecyl alcohol, decyl alcohol. When this compound contains a polymeric chain, it may be for example a-hydroxyl hydrogenated polybutadiene.
The hydrophobic group of the polyurethane of formula (A) may also result from the
quaternization reaction of the tertiary amine of the compound containing at least one tertiary amine unit. Thus, the hydrophobic group is introduced by the quaternizing agent. This quaternizing agent is a compound of the RQ or R'Q type, in which R and R are as defined above and Q denotes a leaving group such as a halide, a sulfate, and the like.
The cationic associative polyurethane may additionally comprise a hydrophilic sequence. This sequence is provided by a fourth type of compound entering into the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture where the percentage of multifunctional compound is low.
The functional groups containing a labile hydrogen are alcohol, primary or secondary amine, or thiol functional groups. This compound may be a polymer terminated at the chain ends by one of these functional groups containing a labile hydrogen.
By way of example, there may be mentioned, when polymers are not involved, ethylene glycol, diethylene glycol and propylene glycol.
In the case of a hydrophilic polymer, there may be mentioned, by way of example, polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and in particular a polyethylene oxide or a polypropylene oxide.
The hydrophilic group noted Y in formula (A) is optional. Indeed, the units containing a quaternary or protonated amine functional group may suffice to provide the solubility or water-dispersibility necessary for this type of polymer in an aqueous solution. Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes are nevertheless preferred which contain such a group. The associative polyurethane used in the present invention may also be nonionic, in particular nonionic polyurethane-polyethers. More particularly, said polymers contain in their chain both hydrophilic sequences most often of a polyoxyethylenated nature and hydrophobic sequences which may be aliphatic linkages alone and/or cycloaliphatic and/or aromatic linkages. Preferably, these polyether-polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, preferably from 6 to 20, separated by a hydrophilic sequence, it being possible for the hydrocarbon chains to be pendent chains or chains at the end of a
hydrophilic sequence. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic sequence.
The polyether-polyurethanes may be polyblocks, in particular in triblock form. The hydrophobic sequences may be at each end of the chain (for example: triblock copolymer with hydrophilic central sequence) or distributed both at the ends and in the chain (polyblock copolymer for example). These same polymers may also be in the form of graft units or may be star-shaped.
Figure imgf000021_0001
The associative polyurethane can form a network in water in which the hydrophobic part connects quasi-micelles as shown above.
Therefore, the associative polyurethanes can increase viscosity or consistency of the composition according to the present invention. Thus after application of the composition according to the present invention, it can recover the original elasticity of the composition quickly.
The nonionic polyether-polyurethanes containing a fatty chain may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups.
The nonionic polyether-polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name.
By extension, those whose hydrophilic sequences are linked by other chemical bonds to the hydrophobic sequences are also included among the nonionic polyether-polyurethanes containing a hydrophobic chain.
By way of examples of nonionic polyether-polyurethanes containing a hydrophobic chain which can be used in the invention, it is also possible to use Rheolate® 205 containing a urea functional group sold by the company RHEOX or else the Rheolates® 208, 204 or 212, as well as Acrysol RM 184®.
There may also be mentioned the product ELFACOS T210® containing a C12-ci4 alkyl chain and the product ELFACOS T212® containing a C18 alkyl chain from AKZO.
The product DW 1206B® from ROHM & HAAS containing a C20 alkyl chain and with a urethane bond, sold at 20% dry matter content in water, may also be used.
It is also possible to use solutions or dispersions of these polymers in particular in water or in an aqueous-alcoholic medium. By way of examples of such polymers, there may be mentioned Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company RHEOX. It is also possible to use the product DW 1206F and DW 1206 J provided by the company ROHM & HAAS.
The above-described polyether-polyurethanes which can be used can also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen-Colloid Polym. Sci 271, 380-389 (1993).
Still more particularly, according to the invention, it is preferable to use a polyether-polyurethane which can be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.
Such polyether-polyurethanes are sold in particular by the company ROHM & HAAS under the names Aculyn 46® and Aculyn 44® [ACULYN 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, stearyl alcohol and methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %);
ACULYN 440 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, decyl alcohol and methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)]. According to the present invention, it is preferable that the associative polyurethane be selected Steareth-100/PEG-136/HDI Copolymer sold by the company Rheox under the name of Rheolate FX 1100.
The amount of the (c) associative polyurethane is not limited, and may range from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, and more preferably from 0.4 to 3% by weight, relative to the total weight of the composition.
[Polyol] The cosmetic composition according to the present invention further comprises at least one polyol. A single type of polyol may be used, but two or more different types of polyol may be used in combination.
The term "polyol" here means an alcohol having two or more hydroxy groups, and does not encompass a saccharide or a derivative thereof. The derivative of a saccharide includes a sugar alcohol which is obtained by reducing one or more carbonyl groups of a saccharide, as well as a saccharide or a sugar alcohol in which the hydrogen atom or atoms in one or more hydroxy groups thereof has or have been replaced with at least one substituent such as an alkyl group, a
hydroxyalkyl group, an alkoxy group, an acylgroup or a carbonyl group.
The polyol may be a C2-C 12 polyol, preferably a C2-9 polyol, comprising at least 2 hydroxy groups, and preferably 2 to 5 hydroxy groups.
The polyol may be a natural or synthetic polyol. The polyol may have a linear, branched or cyclic molecular structure.
The polyol may be selected from glycerins and derivatives thereof, and glycols and derivatives thereof. The polyol may be selected from the group consisting of glycerin, diglycerin, polyglycerin, ethyleneglycol, diethyleneglycol, propyleneglycol, dipropyleneglycol,
butyleneglycol, pentyleneglycol, hexyleneglycol, 1,3 -propanediol, and 1,5-pentanediol.
The polyol may be present in an amount ranging from 0.01% to 30% by weight, and preferably from 0.1% to 20% by weight, such as from 1% to 10% by weight, relative to the total weight of the composition.
[Water]
The cosmetic composition according to the present invention comprises water. The amount of water is not limited, and may be from 10 to 80% by weight, preferably from 20 to 75% by weight, and more preferably 30 to 60% by weight, relative to the total weight of the composition.
[Additional Surfactant] The cosmetic composition according to the present invention may further comprise at least one additional nonionic surfactant different from the above (b) and/or at least one additional ionic surfactant. A single type of additional surfactant may be used, but two or more different types of additional surfactant may be used in combination. The ionic surfactant can be selected from cationic surfactants, anionic surfactants, and amphoteric surfactants.
(Additional Nonionic Surfactant)
The additional nonionic surfactant may be selected from the following, as long as it has an HLB value of less than 7.0 or more than 14.0:
(1) surfactants that are fluid at a temperature of less than or equal to 45°C, chosen from the esters of at least one polyol chosen from the group formed by polyethylene glycol comprising from 1 to 60 ethylene oxide units, sorbitan, glycerol comprising from 2 to 30 ethylene oxide units, polyglycerols comprising from 2 to 10 glycerol units, and of at least one fatty acid comprising at least one saturated or unsaturated, linear of branched Q-C22 alkyl chain,
(2) mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol,
(3) fatty acid esters of sugars and fatty alcohol ethers of sugars,
(4) surfactants that are solid at a temperature of less than or equal to 45 °C, chosen from fatty esters of glycerol, fatty esters of sorbitan and oxyethylenated fatty esters of sorbitan, ethoxylated fatty ethers and ethoxylated fatty esters,
(5) block copolymers of ethylene oxide (A) and of propylene oxide (B), and
(6) silicone surfactants.
The details of the above (1) to (6) are the same as those described above.
The additional nonionic surfactant may be selected from oxyalkylene-including nonionic surfactants as long as they have an HLB value of less than 7.0 or more than 14.0.
The details of the oxyalkylene-including nonionic surfactants are the same as those described above.
(Cationic Surfactant) The cationic surfactant is not limited. The cationic surfactant may be selected from the group consisting of optionally polyoxyalkylenated, primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
Examples of quaternary ammonium salts that may be mentioned include, but are not limited to: those of general formula (I) below:
Figure imgf000024_0001
(I) wherein
Rj, R2, R3, and R4, which may be identical or different, are chosen from linear and branched aliphatic radicals comprising from 1 to 30 carbon atoms and optionally comprising heteroatoms such as oxygen, nitrogen, sulfur and halogens. The aliphatic radicals may be chosen, for example, from alkyl, alkoxy, C2-C6 polyoxyalkylene, alkylamide,
(Ci2-C22)alkylamido(C2-C6)alkyl, (C12-C22)alkylacetate and hydroxyalkyl radicals; and aromatic radicals such as aryl and alkylaryl; and X" is chosen from halides, phosphates, acetates, lactates, (C2-C6) alkyl sulfates and alkyl- or alkylaryl-sulfonates;
quaternary ammonium salts of imidazoline, for instance those of formula (II) below:
Figure imgf000025_0001
(II)
wherein:
R5 is chosen from alkenyl and alkyl radicals comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or of coconut;
¾ is chosen from hydrogen, -C4 alkyl radicals, and alkenyl and alkyl radicals comprising from
8 to 30 carbon atoms;
R7 is chosen from Q-C4 alkyl radicals;
Rs is chosen from hydrogen and C1-C4 alkyl radicals; and
X" is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates. In one embodiment, R5 and R^ are, for example, a mixture of radicals chosen from alkenyl and alkyl radicals comprising from 12 to 21 carbon atoms, such as fatty acid derivatives of tallow, R7 is methyl and Rs is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W75PG and W75HPG by the company Witco;
diquaternary ammonium salts of formula (III):
Figure imgf000025_0002
(III)
wherein:
R9 is chosen from aliphatic radicals comprising from 16 to 30 carbon atoms;
R10 is chosen from hydrogen or alkyl radicals comprising from 1 to 4 carbon atoms or a group
(Rl6a)(Rl7a)(Rl8a)N+(CH2)3;
Rn, R12, R13, R14, R16a, R17a, and Ri8a,, which may be identical or different, are chosen from hydrogen and alkyl radicals comprising from 1 to 4 carbon atoms; and
X" is chosen from halides, acetates, phosphates, nitrates, ethyl sulfates, and methyl sulfates.
An example of one such diquaternary ammonium salt is FINQUAT CT-P of
FINETEX(Quaternium-89) or FINQUAT CT of FINETEX (Quaternium-75); and quaternary ammonium salts comprising at least one ester function, such as those of formula (IV) below:
Figure imgf000026_0001
wherein:
R22 is chosen from Q-Q alkyl radicals and Q-Q hydroxyalkyl and dihydroxyalkyl radicals; R23 is chosen from:
the radical blow:
Figure imgf000026_0002
linear and branched, saturated and unsaturated Q.Czz hydrocarbon-based radicals R27, and hydrogen,
R25 is chosen from:
the radical below:
O
II
R »,28 linear and branched, saturated and unsaturated C\-C hydrocarbon-based radicals R29, and hydrogen,
R-4, R26, and R28, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C7-C2i, hydrocarbon-based radicals;
r, s, and t, which may be identical or different, are chosen from integers ranging from 2 to 6;
each of rl and tl, which may be identical or different, is 0 or 1, and r2+rl=2r and tl+2t=2t;
y is chosen from integers ranging from 1 to 10;
x and z, which may be identical or different, are chosen from integers ranging from 0 to 10;
X" is chosen from simple and complex, organic and inorganic anions; with the proviso that the sum x+y+z ranges from 1 to 15, that when x is 0, R23 denotes R27, and that when z is 0, R25 denotes R29. R22 may be chosen from linear and branched alkyl radicals. In one embodiment, R22 is chosen from linear alkyl radicals. In another embodiment, R22 is chosen from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example methyl and ethyl radicals. In one embodiment, the sum x+y+z ranges from 1 to 10. When R23 is a hydrocarbon-based radical R27, it may be long and comprise from 12 to 22 carbon atoms, or short and comprise from 1 to 3 carbon atoms. When R25 is a hydrocarbon-based radical R29, it may comprise, for example, from 1 to 3 carbon atoms. By way of a non-limiting example, in one embodiment, R24, R2 , and R28, which may be identical or different, are chosen from linear and branched, saturated and
unsaturated, Cn-C21 hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated Cn-C21 alkyl and alkenyl radicals. In another embodiment, x and z, which may be identical or different, are 0 or 1. In one embodiment, y is equal to 1. In another embodiment, r, s and t, which may be identical or different, are equal to 2 or 3, for example equal to 2. The anion X" may be chosen from, for example, halides, such as chloride, bromide, and iodide; and C1-C4 alkyl sulfates, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other anion that is compatible with the ammonium comprising an ester function, are other non-limiting examples of anions that may be used according to the invention. In one embodiment, the anion X" is chosen from chloride and methyl sulfate.
In another embodiment, the ammonium salts of formula (IV) may be used, wherein:
R22 is chosen from methyl and ethyl radicals,
x and y are equal to 1 ;
z is equal to 0 or 1;
r, s and t are equal to 2;
R23 is chosen from:
the radical below:
O
R26 C
methyl, ethyl, and C14^C22 hydrocarbon-based radicals, hydrogen;
R25 is chosen from:
the radical below:
O
and hydrogen;
R24, R26, and R28, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C13-C17 hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated, C13-C17 alkyl and alkenyl radicals.
In one embodiment, the hydrocarbon-based radicals are linear.
Non-limiting examples of compounds of formula (IV) that may be mentioned include salts, for example chloride and methyl sulfate, of diacyloxyemyl-dimemylammonium, of
d^acyloxyethyl-hydroxyethyl-methylamm- onium, of
monoacyloxyemyl-dmydroxyemyl-methylammonium, of triacyloxyethyl-methylammonium, of monoacyloxyethyl-hydroxyethyl-dimethyl- ammonium, and mixtures thereof. In one embodiment, the acyl radicals may comprise from 14 to 18 carbon atoms, and may be derived, for example, from a plant oil, for instance palm oil and sunflower oil. When the compound comprises several acyl radicals, these radicals may be identical or different.
These products may be obtained, for example, by direct esterification of optionally oxyalkylenated triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine onto fatty acids or onto mixtures of fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification may be followed by a quaternization using an alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol cMorohydrin; and glycerol chlorohydrin. Such compounds are sold, for example, under the names Dehyquart® by the company Cognis, Stepanquat® by the company Stepan, Noxamium® by the company Ceca, and "Rewoquat® WE 18" by the company Rewo-Goldschmidt.
Other non-limiting examples of ammonium salts that may be used in the compositions according to the invention include the ammonium salts comprising at least one ester function described in U.S. Pat. Nos. 4,874,554 and 4,137,180.
Among the quaternary ammonium salts mentioned above that may be used in compositions according to the invention include, but are not limited to, those corresponding to formula (I), for example tetraalkylammonium chlorides, for instance dialkyldimethylammonium and
alkyltrimemylammonium chlorides in which the alkyl radical comprises from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium,
cetyltrimethylammonium and benzyldimemylstearylammonium chloride;
palmilylamidopropyllrimethylammonium chloride; and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk.
According to one embodiment, the cationic surfactant that may be used in the compositions of the invention is chosen from quaternary ammonium salts, for example from
behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, Quaternium-83, Quaternium-87, Quaternium-22, behenylamidopropyl-2,3-dmyckoxypropyldimemylammonium chloride, palmitylaniidopropyltrimethylammonium chloride, and
stearamidopropyldimemylaniine.
(Anionic Surfactant)
The anionic surfactant is not limited. The anionic surfactants may be chosen in particular from anionic derivatives of proteins of vegetable origin or of silk proteins, phosphates and alkyl phosphates, carboxylates, sulphosuccinates, amino acid derivatives, alkyl sulphates, alkyl ether sulphates, sulphonates, isethionates, taurates, alkyl sulphoacetates, polypeptides, anionic derivatives of alkyl polyglucosides, and their mixtures.
1) Anionic derivatives of proteins of vegetable origin are protein hydrolysates comprising a hydrophobic group, it being possible for the said hydrophobic group to be naturally present in the protein or to be added by reaction of the protein and/or of the protein hydrolysate with a hydrophobic compound. The proteins are of vegetable origin or derived from silk, and the hydrophobic group can in particular be a fatty chain, for example an alkyl chain comprising from 10 to 22 carbon atoms. Mention may more particularly be made, as anionic derivatives of proteins of vegetable origin, of apple, wheat, soybean or oat protein hydrolysates comprising an alkyl chain having from 10 to 22 carbon atoms, and their salts. The alkyl chain can in particular be a lauryl chain and the salt can be a sodium, potassium and/or ammonium salt. Thus, mention may be made, as protein hydrolysates comprising a hydrophobic group, for example, of salts of protein hydrolysates where the protein is a silk protein modified by lauric acid, such as the product sold under the name Kawa Silk by Kawaken; salts of protein hydrolysates where the protein is a wheat protein modified by lauric acid, such as the potassium salt sold under the name Aminofoam W OR by Croda (CTFA name: potassium lauroyl wheat amino acids) and the sodium salt sold under the name Proteol LW 30 by Seppic (CTFA name: sodium lauroyl wheat amino acids); salts of protein hydrolysates where the protein is an oat protein comprising an alkyl chain having from 10 to 22 carbon atoms and more especially salts of protein hydrolysates where the protein is an oat protein modified by lauric acid, such as the sodium salt sold under the name Proteol OAT (30% aqueous solution) by Seppic (CTFA name: sodium lauroyl oat amino acids); or salts of apple protein hydrolysates comprising an alkyl chain having from 10 to 22 carbon atoms, such as the sodium salt sold under the name Proteol APL (30% aqueous/glycol solution) by Seppic (CTFA name: sodium cocoyl apple amino acids). Mention may also be made of the mixture of lauroyl amino acids (aspartic acid, glutamic acid, glycine, alanine) neutralized with sodium N-methylglycinate sold under the name Proteol SAV 50 S by Seppic (CTFA name:
sodium cocoyl amino acids).
2) Mention may be made, as phosphates and alkyl phosphates, for example, of monoalkyl phosphates and dialkyl phosphates, such as lauryl monophosphate, sold under the name MAP 20® by Kao Chemicals, the potassium salt of dodecyl phosphate, the mixture of mono- and diesters (predominantly diester) sold under the name Crafol AP-31® by Cognis, the mixture of octyl phosphate monoester and diester, sold under the name Crafol AP-20® by Cognis, the - mixture of ethoxylated (7 mol of EO) 2-butyloctyl phosphate monoester and diester, sold under the name Isofol 12 7 EO-Phosphate Ester® by Condea, the potassium or triethanolamine salt of mono(C12-C13)alkyl phosphate, sold under the references Arlatone MAP 230 -40® and Arlatone MAP 230T-60® by Uniqema, potassium lauryl phosphate, sold under the name Dermalcare MAP XC-99/09® by Rhodia Chimie, and potassium cetyl phosphate, sold under the name Arlatone MAP 160K by Uniqema.
3) Mention may be made, as carboxylates, of:
amido ether carboxylates (AEC), such as sodium lauryl amido ether carboxylate (3 EO), sold under the name Akypo Foam 30® by Kao Chemicals;
polyoxyethylenated carboxylic acid salts, such as oxyethylenated (6 EO) sodium lauryl ether carboxylate (65/25/10 C12-C14-C16), sold under the name Akypo Soft 45 NV® by Kao
Chemicals, polyoxyethylenated and carboxymethylated fatty acids originating from olive oil, sold under the name Olivem 400® by Biologia E Tecnologia, or oxyethylenated (6 EO) sodium tridecyl ether carboxylate, sold under the name Nikkol ECTD-6NEX® by Nikkol; and
- salts of fatty acids (soaps) having a C6 to C22 alkyl chain which are neutralized with an
organic or inorganic base, such as potassium hydroxide, sodium hydroxide, triemanolamine, N-memylglucamine, lysine and arginine.
4) Mention may in particular be made, as amino acid derivatives, of alkali salts of amino acids, such as: sarcosinates, such as sodium lauroyl sarcosinate, sold under the name Sarkosyl NL 97® by Ciba or sold under the name Oramix L 30® by Seppic, sodium myristoyl sarcosinate, sold under the name Nikkol Sarcosinate MN® by Nikkol, or sodium palmitoyl sarcosinate, sold under the name Nikkol Sarcosinate PN® by Nikkol;
- alaninates, such as sodium N-lauroyl-N-methylamidopropionate, sold under the name
Sodium Nikkol Alaninate LN 30® by Nikkol or sold under the name Alanone ALE® by Kawaken, or triethanolamine N-lauroyl-N-methylalanine, sold under the name Alanone ALTA® by Kawaken;
glutamates, such as triethanolamine monococoyl glutamate, sold under the name
Acylglutamate CT- 12® by Aj inomoto, triethanolamine lauroyl glutamate, sold under the name Acylglutamate LT-12® by Ajinomoto;
aspartates, such as the mixture of triemanolamine N-lauroyl aspartate and triethanolamine N-myristoyl aspartate, sold under the name Asparack® by Mitsubishi;
glycine derivatives (glycinates), such as sodium N-cocoyl glycinate, sold under the names Amilite GCS- 12® and Amilite GCK 12 by Aj inomoto;
citrates, such as the citric monoester of oxyethylenated (9 mol) coco alcohols, sold under the name Witconol EC 1129 by Goldschmidt; and
galacturonates, such as sodium dodecyl D-galactoside uronate, sold by Soliance. 5) Mention may be made, as sulphosuccinates, for example, of oxyethylenated (3 EO) lauryl (70/30 C12/C14) alcohol monosulphosuccinate, sold under the names Setacin 103 Special® and Rewopol SB-FA 30 K 4® by Witco, the disodium salt of a hemisulphosuccinate of C12-C14 alcohols, sold under the name Setacin F Special Paste® by Zschimmer Schwarz, oxyethylenated (2 EO) disodium oleamidosulphosuccinate, sold under the name Standapol SH 135® by Cognis, oxyethylenated (5 EO) lauramide monosulphosuccinate, sold under the name Lebon A-5000® by Sanyo, the disodium salt of oxyethylenated (10 EO) lauryl citrate monosulphosuccinate, sold under the name Rewopol SB CS 50® by Witco, or ricinoleic monoethanolamide
monosulphosuccinate, sold under the name Rewoderm S 1333® by Witco. Use may also be made of polydimethylsiloxane sulphosuccinates, such as disodium PEG- 12 dimethicone sulphosuccinate, sold under the name Mackanate-DC 30 by Maclntyre.
6) Mention may be made, as alkyl sulphates, for example, of triemanolamine lauryl sulphate (CTFA name: TEA lauryl sulphate), such as the product sold by Huntsman under the name Empicol TL40 FL or the product sold by Cognis under the name Texapon T42, which products are at 40% in aqueous solution. Mention may also be made of ammonium lauryl sulphate (CTFA name: ammonium lauryl sulphate), such as the product sold by Huntsman under the name Empicol AL 30FL, which is at 30% in aqueous solution.
7) Mention may be made, as alkyl ether sulphates, for example, of sodium lauryl ether sulphate (CTFA name: sodium laureth sulphate), such as that sold under the names Texapon N40 and
Texapon AOS 225 UP by Cognis, or ammonium lauryl ether sulphate (CTFAname: ammonium laureth sulphate), such as that sold under the name Standapol EA-2 by Cognis.
8) Mention may be made, as sulphonates, for example, of a-olefinsulphonates, such as sodium a-olefmsulphonate (C14-C16), sold under the name Bio-Terge AS-40® by Stepan, sold under the names Witconate AOS Protege® and Sulframine AOS PH 12® by Witco or sold under the name Bio-Terge AS-40 CG® by Stepan, secondary sodium olefinsulphonate, sold under the name Hostapur SAS 30® by Clariant; or linear alkylarylsulphonates, such as sodium xylenesulphonate, sold under the names Manrosol SXS30®, Manrosol SXS40® and Manrosol SXS93® by Manro.
9) Mention may be made, as isethionates, of acylisethionates, such as sodium cocoylisethionate, such as the product sold under the name Jordapon CI P® by Jordan.
10) Mention may be made, as taurates, of the sodium salt of palm kernel oil methyltaurate, sold under the name Hostapon CT Pate® by Clariant; N-acyl-N-methyltaurates, such as sodium
N-cocoyl-N-methyltaurate, sold under the name Hostapon LT-SF® by Clariant or sold under the name Nikkol CMT-30-T® by Nikkol, or sodium palmitoyl methyltaurate, sold under the name Nikkol PMT® by Nikkol. 11) The anionic derivatives of alkyl polyglucosides can in particular be citrates, tartrates, sulphosuccinates, carbonates and glycerol ethers obtained from alkyl polyglucosides. Mention may be made, for example, of the sodium salt of cocoylpolyglucoside (1,4) tartaric ester, sold under the name Eucarol AGE-ET® by Cesalpinia, the disodium salt of cocoylpolyglucoside (1,4) sulphosuccinic ester, sold under the name Essai 512 MP® by Seppic, or the sodium salt of cocoylpolyglucoside (1 ,4) citric ester, sold under the name Eucarol AGE-EC® by Cesalpinia.
It is preferable that the amino acid derivatives be acyl glycine derivatives or glycine derivatives, in particular acyl glycine salt. The acyl glycine derivatives or glycine derivatives can be chosen from acyl glycine salts (or acyl glycinates) or glycine salts (or glycinates), and in particular from the following. i) Acyl glycinates of formula (I):
R-HNCH2COOX (I)
in which
R represents an acyl group R'C=0, with R', which represents a saturated or unsaturated, linear or branched, hydrocarbon chain, preferably comprising from 10 to 30 carbon atoms, preferably from 12 to 22 carbon atoms, preferably from 14 to 22 carbon atoms and better still from 16 to 20 carbon atoms, and
- X represents a cation chosen, for example, from the ions of alkali metals, such as Na, Li or K, preferably Na or K, the ions of alkaline earth metals, such as Mg, ammonium groups and their mixtures.
The acyl group can in particular be chosen from the lauroyl, myristoyl, behenoyl, palmitoyl, stearoyl, isostearoyl, olivoyl, cocoyl or oleoyl groups and their mixtures.
Preferably, R is a cocoyl group. ii) Glycinates of following formula (II): R2
I
R,— N+ CH2COO - I
Rz (H)
in which:
Ri represents a saturated or unsaturated, linear or branched, hydrocarbon chain comprising from 10 to 30 carbon atoms, preferably from 12 to 22 carbon atoms and better still from 16 to 20 carbon atoms; R is advantageously chosen from the lauryl, myristyl, palmityl, stearyl, cetyl, cetearyl or oleyl groups and their mixtures and preferably from the stearyl and oleyl groups,
the R.2 groups, which are identical or different, represent an R"OH group, R" being an alkyl group comprising from 2 to 10 carbon atoms, preferably from 2 to 5 carbon atoms.
Mention may be made, as compound of formula (I), for example, of the compounds carrying the INCI name sodium cocoyl glycinate, such as, for example, Amilite GCS-12, sold by Ajinomoto, or potassium cocoyl glycinate, such as, for example, Amilite GCK-12 from Ajinomoto. Use may be made, as compounds of formula (II), of dihydroxyethyl oleyl glycinate or
dihydroxyethyl stearyl glycinate.
(Amphoteric Surfactant) The amphoteric surfactant is not limited. The amphoteric or zwitterionic surfactants can be, for example (nonlimiting list), amine derivatives such as aliphatic secondary or tertiary amine, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain comprising 8 to 22 carbon atoms and containing at least one water-solubilizing anionic group (for example, carboxylate, sulphonate, sulphate, phosphate or phosphonate).
Among the amidoaminecarboxylated derivatives, mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982 (the disclosures of which are incorporated herein by reference), under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures:
R1-CONHCH2CH2-N+(R2)(R3)(CH2COO") in which:
Ri denotes an alkyl radical of an acid R^COOH present in hydrolysed coconut oil, a heptyl, nonyl or undecyl radical,
R2 denotes a beta-hydroxyethyl group, and
R3 denotes a carboxymethyl group; and
Ri,-CONHCH2CH2-N(B)(C) in which:
B represents -CH2CH2OX',
C represents -(CH2)Z-Y', with z=l or 2,
X' denotes a -CH2CH2-COOH group, -CH2-COOZ' , -CH2CH2-COOH, -CH2CH2-COOZ' or a hydrogen atom,
Y' denotes -COOH, -COOZ', -CH2-CHOH-S03Z' or a -CH2-CHOH-S03H radical,
Z' represents an ion of an alkaline or alkaline earth metal such as sodium, an ammonium ion or an ion issued from an organic amine, and
Ri denotes an alkyl radical of an acid Rj'-COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, such as a C7, C9, Cn or C13 alkyl radical, a C17 alkyl radical and its iso form, or an unsaturated C17 radical.
It is preferable that the amphoteric surfactant be selected from (C8-C24)-alkyl amphomonoacetates, (C8-C24)alkyl amphodiacetates, (C8-C24)alkyl amphomonopropionates, and (C8-C24)alkyl amphodipropionates
These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium
Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium
Caprylamphodipropionate, Lauroamphodipropionic acid and Cocoamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol® C2M concentrate by the company Rhodia Chimie.
Preferably, the amphoteric surfactant may be a betaine.
The betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and
alkylamidoalkylsulfobetaines, in particular, (C8-C24)alkylbetaines,
(C8-C24)alkylamido(C1-C8)alkylbetaines, sulphobetaines, and
(C8-C24)alkylamido(C1-C8)alkylsulphobetaines. In one embodiment, the amphoteric surfactants of betaine type are chosen from (C8-C24)alkylbetaines,
(C8-C24)alkylamido(C1-C8)alkylsulphobetaines, sulphobetaines, and phosphobetaines.
Non-limiting examples that may be mentioned include the compounds classified in the CTFA dictionary, 9th edition, 2002, under the names cocobetaine, laurylbetaine, cetylbetaine, coco/oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine,
stearamidopropylbetaine, cocamidoethylbetaine, cocamidopropylhydroxysultaine,
oleamidopropylhydroxysultaine, cocohydroxysultaine, laurylhydroxysultaine, and cocosultaine, alone or as mixtures.
The betaine-type amphoteric surfactant is preferably an alkylbetaine and an
alkylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine. The amount of the additional surfactant(s) may be 0.01 wt% to 20wt%, preferably 0.10 wt% to 10 wt%, and more preferably 1 wt% to 5 wt%, relative to the total weight of the composition. [Other Ingredients]
The cosmetic composition according to the present invention may also comprise an effective amount of other ingredients, known previously elsewhere in lightening or coloring compositions, such as various common adjuvants, sequestering agents such as EDTA and etidronic acid, UV screening agents, silicones other than those mentioned before (such as with amine groups), preserving agents, vitamins or provitamins, for instance, panthenol, opacifiers, fragrances, plant extracts, cationic polymers and so on.
The cosmetic composition according to the present invention may further comprise at least one organic solvent. So the organic solvent is preferably water miscible. As the organic solvent, there may be mentioned, for example, Q-C4 alkanols, such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol and phenoxyethanol; analogous products; and mixtures thereof.
The organic water-soluble solvents may be present in an amount ranging from less than 10% by weight, preferably from 5% by weight or less, and more preferably from 1 % by weight or less, relative to the total weight of the composition. "
[Preparation and Properties] The cosmetic composition according to the present invention can be prepared by mixing the above essential and optional ingredients in accordance with a conventional process. The conventional process includes mixing with a high pressure homogenizer (a high energy process).
Alternatively, the cosmetic composition can be prepared by a low energy processes such as phase inversion temperature process (PIT), phase inversion concentration (PIC), autoemulsification, and the like.
The weight ratio of the (b) nonionic surfactant with HLB 7-14 to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.45 to 1.5. In particular, the weight ratio of the (b) nonionic surfactant with HLB 7-14 /the (a) oil is preferably 1 or less, such as from 0.3 to 1, preferably from 0.4 to 1, and more preferably from 0.45 to 1.
The cosmetic composition according to the present invention is in the form of a nano- or micro-emulsion. The "micro-emulsion" may be defined in two ways, namely, in a broader sense and in a narrower sense. That is to say, there are one case ("microemulsion in the narrow sense") in which the microemulsion refers to a thermodynamically stable isotropic single liquid phase containing a ternary system having three ingredients of an oily component, an aqueous component and a surfactant, and the other case ("micro-emulsion in the broad sense") in which among
thermodynamically unstable typical emulsion systems the microemulsion additionally includes those such emulsions presenting transparent or translucent appearances due to their smaller particle sizes (Satoshi Tomomasa, et al., OilChemistry, Vol. 37, No. 11 (1988), pp. 48-53). The "micro-emulsion" as used herein refers to a "micro-emulsion in the narrow sense," i.e., a thermodynamically stable isotropic single liquid phase.
The micro-emulsion refers to either one state of an O/W (oil-in- water) type microemulsion in which oil is solubilized by micelles, a W/O (water-in-oil) type microemulsion in which water is solubilized by reverse micelles, or a bicontinuous microemulsion in which the number of associations of surfactant molecules are rendered infinite so that both the aqueous phase and oil phase have a continuous structure.
The micro-emulsion may have a dispersed phase with a number average diameter of 100 nm or less, preferably 50 nm or less, and more preferably 20 nm or less, measured by laser granulometry. The "nano-emulsion" here means an emulsion characterized by a dispersed phase with a size of less than 350 nm, the dispersed phase being stabilized by a crown of the (b) nonionic surfactant with HLB 7-14 and the like that may optionally form a liquid crystal phase of lamellar type, at the dispersed phase/continuous phase interface. In the absence of specific opacifiers, the
transparency of the nano-emulsions arises from the small size of the dispersed phase, this small size being obtained by virtue of the use of mechanical energy and especially a high-pressure homogenizer.
Nanoemulsions can be distinguished from microemulsions by their structure. Specifically, micro-emulsions are thermodynamically stable dispersions formed from, for example, the (b) nonionic surfactant with HLB 7-14 micells swollen with the (a) oil. Furthermore,
microemulsions do not require substantial mechanical energy in order to be prepared.
The micro-emulsion may have a dispersed phase with a number average diameter of 300 nm or less, preferably 200 nm or less, and more preferably 100 nm or less, measured by laser
granulometry.
The cosmetic composition according to the present invention may be in the form of an O/W nano- or micro-emulsion, a W/O nano- or micro-emulsion or a bicontinuous emulsion. It is preferable that the cosmetic composition according to the present invention be in the form of an O/W nano- or micro-emulsion.
It is preferable that the cosmetic composition according to the present invention be in the form of ah O/W emulsion, and the (a) oil be in the form of a droplet with a number average particle size of 300 nm or less, preferably from 10 nm to 150 nm, and more preferably 20 nm to 140 nm.
The cosmetic composition according to the present invention can have a transparent or slightly translucent appearance, preferably a transparent appearacnce.
The measurement is taken on the undiluted composition. The blank is determined with distilled water. The transparency may be measured by measuring the nephelometric turbidity (for example, with 2100Q Portable Turbidimeter from HACH).
The cosmetic composition according to the present invention may preferably have a
nephelometric turbidity lower than 150NTU, preferably lower than 100 NTU, and more preferably lower than 50 NTU.
[Process and Use]
The cosmetic composition according to the present invention can be used for a non-therapeutic process, such as a cosmetic process, for treating the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows and/or the scalp, by being applied to the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows or the scalp.
The present invention also relates to a use of the cosmetic composition according to the present invention, as it is or in care products and/or washing products and/or make-up products and/or make-up-removing products for body and/or facial skin and/or mucous membranes and/or the scalp and/or the hair and/or the nails and/or the eyelashes and/or the eyebrows.
In other words, the cosmetic composition according to the present invention can be used, as it is, as the above product. In particular, the cosmetic composition according to the present invention may preferably be a rinse-off product such as a make-up removing products for body and/or facial skin. Alternatively, the cosmetic composition according to the present invention can be used as an element of the above product. For example the cosmetic composition according to the present invention can be added to or combined with any other elements to form the above product.
The care product may be a lotion, a cream, a hair tonic, a hair conditioner, a sun screening agent, and the like. The washing product may be a shampoo, a face wash, a hand wash and the like. The make-up product may be a foundation, a mascara, a lipstick, a lip gloss, a blusher, an eye shadow, a nail varnish, and the like. The make-up-removing product may be a make-up cleansing agent and the like.
EXAMPLES
The present invention will be described in more detail by way of examples, which however should not be construed as limiting the scope of the present invention.
[Examples 1-2 and Comparative Example 1]
The following cosmetic compositions in the form of a transparent O/W emulsion according to Examples 1 -2 and Comparative Example 1 shown in Table 1 , were prepared by mixing the components shown in Table 1 as follows: (1) mixing surfactants and oils to form an oil phase; (2) heating the oil phase up to around 70 °C; (3) mixing water and hydrophilic ingredients to form an aqueous phase; and (4) adding the aqueous phase into the oil phase followed by mixing them to obtain an O/W emulsion. The numerical values for the amounts of the components shown in Table 1 are all based on "% by weight" as active raw materials. Table 1
Figure imgf000037_0001
(1) SUNSOFT A-121E (Taiyo Kagaku)
(2) SUNSOFT Q-83H-C (Taiyo Kagaku)
(3) SUNSOFT Q- 10D-C (Taiyo Kagaku)
(4) RHEOLATE FX 1100 (ELEMENTIS)
(5) GLUCAMATE DOE120 (Lubrizol) (Transparency)
The transparency of the composition was measured by measuring the nephelometric turbidity with 2100Q Portable Turbidimeter from HACH. All these 3 compositions showed a nephelometric turbidity below 80 NTU (which means good transparency).
(Viscosity Measurements)
The viscosity of each of the compositions according to Examples 1-2 and Comparative Example 1 was measured as follows. The viscosity of the composition itself (bulk) and the viscosity of the composition diluted with 70% by weight of water (diluted) were measured. The diluted composition was prepared by adding 70 g of water to 100 g of the composition.
Viscosity measurement:
Apparatus: ARES (maker: TA Instruments)
Geometry: cone-plate (diameter: 5 cm), angle = 0.0404 rad, gap = 0.0532 mm
Temperature: 25°C
Shear rate: 1 s-1 The viscosity data of the compositions according to Examples 1-2 and Comparative Example 1 are shown in Table 2.
Table 2
Figure imgf000038_0001
As is clear from the above results, it was found that the viscosity of the compositions according to Examples 1 and 2 significantly increased in the presence of water, while the composition according to Comparative Example 1 did not show any significant increase in viscosity.
(Stability Test)
The stability of each of compositions including a variety of a iWckening agent was evaluated.
Each of the compositions according to Examples 1 and 2 were stored in a transparent container, and maintained at a room temperature (25 °C) for one day. Then, the appearance of the composition was visually observed. The compositions according to Examples 1 and 2 maintained their original transparent aspects, and no phase separation was observed.
Next, the following cosmetic compositions in the form of a transparent O/W emulsion according to Comparative Examples 2-10 shown in Table 3, were prepared by mixing the components shown in Table 1 as follows: (1) mixing surfactants and oils to form an oil phase; (2) heating the oil phase up to around 70 °C; (3) mixing water and hydrophilic ingredients to form an aqueous phase; and (4) adding the aqueous phase into the oil phase followed by mixing them to obtain an O/W emulsion. The numerical values for the amounts of the components shown in Table 1 are all based on "% by weight" as active raw materials.
Each of the compositions according to Comparative Examples 2-10 were also stored in a transparent container, and maintained at a room temperature (25 °C) for one day. Then, the appearance of the composition was visually observed. The results of the observation are shown in Table 3. Table 3
Figure imgf000039_0001
PS: Phase Separation
(1) SUNSOFT A-121E (Taiyo Kagaku)
(2) SUNSOFT Q-83H-C (Taiyo Kagaku)
(6) ANTIL SOFT SC (Evonik)
(7) Jaguar HP105 (Rhodia)
(8) Aculyn 44 polymer (Rohm And Haas)
(9) Natrosol Plus 330CS (Ashland)
(10) Aculyn 22 Polymer (Rohm And Haas)
(11) Carbopol SF-1 polymer (LUBRIZOL)
(12) Aculyn 38 Polymer (Rohm And Haas)
(13) Satiagum UTC 30 (CARGILL)
(14) Rhodicare CFT
Figure imgf000040_0001
(15) Awaze XT (AKZO Nobel)
As is clear from the above results, it was found that the compositions according to Examples 1 and 2 were stable, while the compositions according to Comparative Examples 2-10 were unstable.
Accordingly, based on the above all measurement and test results, it was found that the compositions according to Examples 1 and 2 were transparent, stable and could show high viscosity (or consistency) under wet conditions, and therefore, they can be easily handled by, for example, wet hand. On the other hand, the compositions according to Comparative Examples 1-10 were either (1) transparent but could not show high viscosity (or consistency) under wet conditions, and therefore, they cannot be easily handled by, for example, wet hand, or (2) translucent or turbid, or unstable such that they cannot have or maintain transparent appearance.

Claims

A rinse-off cosmetic composition in the form of a nano- or micro-emulsion, comprising:
(a) at least one oil;
(b) at least one non ionic surfactant with HLB 7-14, preferably polyglyceryl fatty acid ester preferably with a polyglyceryl moiety derived from 2 to 10 glycerins, preferably from 4 to 6 glycerins, more preferably 5 or 6 glycerins;
(c) at least one associative polyurethane;
(d) at least one polyol; and
(e) water,
wherein the amount of the (a) oil ranges at least 20% by weight relative to the total weight of the composition.
The cosmetic composition according to Claim 1, wherein the (a) oil is selected from the group consisting of oils of plant or animal origin, synthetic oils, and hydrocarbon oils.
The cosmetic composition according to Claim 1 or 2, wherein the (a) oil is chosen from hydrocarbon oils which are in the form of a liquid at a room temperature.
The cosmetic composition according to any one of Claims 1 to 3, where the (a) oil is chosen from oils with molecular weight below 600 g/mol.
The cosmetic composition according to any one of Claims 1 to 4, wherein the amount of the (a) oil ranges from 20 to 60% by weight, preferably from 22 to 50% by weight, and more preferably from 24 to 40% by weight, relative to the total weight of the composition.
The cosmetic composition according to any one of Claims 1 to 5, wherein the (b) nonionic surfactant is a polyglyceryl fatty acid ester with an HLB value of from 7.0 to 14.0, preferably from 8.0 to 13.5, and more preferably from 9.0 to 13.0.
The cosmetic composition according to any one of Claims 1 to 6, wherein the polyglyceryl fatty acid ester is chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprylate comprising 2 to 6 glycerol units, polyglyceryl monolaurate comprising 3 to 6 glycerol units, polyglyceryl mono(iso)stearate comprising 3 to 10 glycerol units, polyglyceryl monooleate comprising 3 to 10 glycerol units, and polyglyceryl dioleate comprising 3 to 10 glycerol units.
The cosmetic composition according to any one of Claims 1 to 7, wherein the polyglyceryl fatty acid ester is chosen from PG-2 caprate, PG-4 laurate, PG-5 laurate, PG-5 oleate, PG-5 dioleate, PG-6 tricaprylate, PG-10 oleate, PG-10 Dioleate, PG-10 isostearate, PG-2 laurate, PG-10 trilaurate, PG-10 myristate, PG-10 dimyristate, PG-10 stearate, PG-10 distearate, PG-5 myristate, Pg-5 trimyristate, PG-5 dioleate, PG-5 stearate, PG-5 trioleate, PG-6 caprylate, and PG-6 tricaprylate.
The cosmetic composition according to any one of Claims 1 to 8, wherein the polyglyceryl fatty acid ester raw material is chosen from a mixture of polyglyceryl fatty acid esters, preferably with a polyglyceryl moiety derived from 3 to 6 glycerins, more preferably 5 or 6 glycerins, wherein the mixture preferably comprises at least 30% by weight of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins.
10. The cosmetic composition according to any one of Claims 1 to 9, wherein the amount of the (b) nonionic surfactant with HLB 7-14 ranges from 0.1 to 30% by weight, preferably from 1 to 25% by weight, and more preferably from 5 to 20% by weight, relative to the total weight of the composition.
11. The cosmetic composition according to any one of Claims 1 to 10, wherein the weight ratio of the (b) non ionic surfactant with HLB 7-14 to the (a) oil is from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.45 to 1.5.
12. The cosmetic composition according to any one of Claims 1 to 11, wherein the (b) nonionic surfactant with HLB 7-14 is oxyalkylene-including nonionic surfactant.
13. The cosmetic composition according to Claim 12, wherein the amount of the
oxyalkylene-including nonionic surfactant ranges from 0.1 to 25% by weight, preferably from 0.5 to 20% by weight, and more preferably from 1 to 15% by weight, relative to the total weight of the composition.
14. The cosmetic composition according to any one of Claims 1 to 13, wherein the (c)
associative polyurethane is a copolymer comprising at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, separated by a hydrophilic block.
15. The cosmetic composition according to any one of Claims 1 to 14, wherein the amount of the (c) associative polyurethane ranges from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, and more preferably from 0.4 to 3% by weight, relative to the total weight of the composition.
16. The cosmetic composition according to any one of Claims 1 to 15, further comprising at least one additional nonionic surfactant different from the above (b) and/or at least one additional ionic surfactant.
17. The cosmetic composition according to any one of Claims 1 to 16, wherin the amount of total polyol is between 4% and 50%, preferably between 6% and 40%, more preferably between 8% and 30% by weight of the total weight of the composition.
18. The cosmetic composition according to any one of Claims 1 to 17, wherein the cosmetic composition is in the form of an O/W emulsion, and the (a) oil is in the form of a droplet with a number average particle size of 300 nm or less, preferably from 10 nm to 150 nm.
19. The cosmetic composition according to any one of Claims 1 to 18, wherein it has a transparency greater than 50%, preferably greater than 60%, and more preferably greater than 70%.
20. A non-therapeutic process for treating the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows and/or the scalp, characterized in that the cosmetic composition according to any one of Claims 1 to 19 is applied to the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows or the scalp.
21. Use of the cosmetic composition according to any one of Claims 1 to 19, as or in care products and/or washing products and/or make-up products and/or make-up-removing products for body and/or facial skin and/or mucous membranes and/or the scalp and/or the hair and/or the nails and/or the eyelashes and/or the eyebrows.
PCT/JP2013/085312 2012-12-21 2013-12-20 Cosmetic composition WO2014098268A1 (en)

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