WO2014098267A1 - Cosmetic composition - Google Patents

Cosmetic composition Download PDF

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Publication number
WO2014098267A1
WO2014098267A1 PCT/JP2013/085304 JP2013085304W WO2014098267A1 WO 2014098267 A1 WO2014098267 A1 WO 2014098267A1 JP 2013085304 W JP2013085304 W JP 2013085304W WO 2014098267 A1 WO2014098267 A1 WO 2014098267A1
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WIPO (PCT)
Prior art keywords
cosmetic composition
composition according
polyglyceryl
weight
fatty acid
Prior art date
Application number
PCT/JP2013/085304
Other languages
French (fr)
Inventor
Makoto Saito
Yasuko HARADA
David Amar
Original Assignee
L'oreal
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Publication date
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Publication of WO2014098267A1 publication Critical patent/WO2014098267A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/068—Microemulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87—Polyurethanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/21—Emulsions characterized by droplet sizes below 1 micron
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26—Optical properties
    • A61K2800/262—Transparent; Translucent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/548—Associative polymers

Definitions

  • the present invention relates to a cosmetic composition in the form of a nano- or micro-emulsion.
  • Oil-in- water (O W) or Water-in-oil (W/O) emulsions are well known in the field of cosmetics and dermatology, in particular for the preparation of cosmetic products, such as milks, creams, tonics, serums or toilet waters.
  • a fine emulsion such as an O W nano- or micro-emulsion is particularly interesting in cosmetic products due to its transparent or slightly translucent aspect.
  • JP-A-H09-110635 discloses a fine emulsion which is formed by using a
  • JP-A-H11-71256 discloses a fine emulsion which is formed by using a combination of polyglyceryl fatty acid ester and a betain.
  • a nano- or micro-emulsion is difficult to have a high viscosity or consistency. 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 shape recovery properties. Furthermore, stickiness is typically given to a highly viscous emulsion.
  • An 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 and shape recovery properties, preferably quick shape recovery properties, and possibly less stickiness.
  • a certain type of a nonionic surfactant when used for preparing a fine emulsion such as a nano- or micro-emulsion, the transparent or slightly translucent aspect of the emulsion as well as stability of the emulsion, may be impaired.
  • Another objective of the present invention is 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, even when the above nonionic surfactant is used.
  • the above objectives of the present invention can be achieved by a cosmetic composition in the form of a nano- or micro-emulsion, comprising:
  • the amount of the (a) oil ranges from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% 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, silicone 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 (b) polyglyceryl fatty acid ester may have a polyglyceryl moiety derived from 2-10 glycerins, preferably 3-6 glycerins.
  • the (b) polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprate comprising 2 to 6 glycerol units, 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.
  • the polyglyceryl fatty acid ester raw material (b) 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 at least 30% by weight of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins.
  • the (b) polyglyceryl fatty acid ester raw material comprises esters of a fatty acid and polyglycerine containing 70% or more of polyglycerine whose polymerization degree is 4 or more, preferably esters of a fatty acid and polyglycerine containing equal to or more than 60% of polyglycerine whose polymerization degree is between 4 and 11, and more preferably esters of a fatty acid and polyglycerine containing equal to or more than 30% of polyglycerine whose polymerization degree is 5.
  • the amount of the (b) polyglyceryl fatty acid ester 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 weight ratio of the (b) polyglyceryl fatty acid ester to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.5 to 1.5.
  • 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 0.5 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 nonionic surfactant different from the above (b) and/or at least one ionic surfactant.
  • the cosmetic composition according to the present invention may further comprise at least one polyol.
  • the cosmetic composition according to the present invention may further comprise at least one hydrotrope.
  • the (c) hydrotrope may have a log P being from -0.7 to 6, preferably from -0.5 to 0.5 for non ionic hydropes, and preferably from -0.5 to 5.5 for hydrotropes with ionic character (acid type).
  • the cosmetic composition according to the present invention be in the form of an 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.
  • the cosmetic composition according to the present invention have a
  • 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 After diligent research, the inventors have discovered that it is possible to provide a cosmetic composition in the form of a nano- or micro-emulsion with a high viscosity or consistency and shape recovery properties, preferably quick shape recovery properties, and possibly less stickiness. Also, the cosmetic composition can be a stable and have a transparent or slightly translucent, preferably transparent, aspect, even when using a nonionic surfactant which was difficult to form a fine emulsion such as a nano- or micro-emulsion.
  • the present invention is a cosmetic composition in the form of a nano- or micro-emulsion, comprising:
  • the amount of the (a) oil ranges from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% 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 hard 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 shape recovery properties. Therefore, for example, even if a part of the cosmetic composition (e.g., cream or gel) in a container is taken by a user from the horizontal surface thereof, the surface can restore to be horizontal. It is preferable that the shape recovery occur as quickly as possible.
  • a part of the cosmetic composition e.g., cream or gel
  • the shape recovery occur as quickly as possible.
  • the cosmetic composition according to the present invention can have less stickiness even though it can have a high viscosity or consistency. Furthermore, the cosmetic composition according to the present invention has a dispersed phase which has a smaller diameter due to a combination of the polyglyceryl fatty acid ester and a relatively small amount of oil. Therefore, the cosmetic composition can be in the form of a nano- or micro-emulsion with transparent or slightly translucent. Since the cosmetic composition according to the present invention can have transparent or slightly translucent, the composition can be preferably used for lotions and the like. Further, as the dispersed phase is finely dispersed, the cosmetic composition according to the present invention can provide unique texture, moisturizing and wet feeling, as well as increased suppleness.
  • the dispersed phase is an oil phase and includes one or more lipophilic or even amphiphilic active ingredients
  • the dispersed oil phase can function as a carrier of the active ingredient and accelerate the penetration of the active ingredients into the skin, or can distribute the active ingredients on the skin.
  • a UV filer is present in the dispersed oil phase, the UV filter can be well spread on the skin to exert better UV filtering effects.
  • 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.
  • the oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil; or a mixture thereof.
  • the (a) oil be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils and hydrocarbon 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.
  • esters oils examples include ester oils and artificial triglyceride.
  • the ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C 1 -C 26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci-C2 6 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
  • At least one from among the alcohol and the acid from which the esters of the invention are derived is branched.
  • 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 22 dicarboxylic or tricarboxylic acids and of C 1 -C 22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C 4 -C 2 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
  • sugar esters and diesters of C 6 -C 30 and preferably C 12 -C 22 fatty acids.
  • sucrose means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.
  • suitable sugars include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.
  • the sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C 6 -C 30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.
  • esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.
  • These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters.
  • monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates.
  • ester oils mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 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,
  • artificial triglycerides mention may be made of, for example, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).
  • silicone oils mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane,
  • silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
  • PDMS liquid polydimethylsiloxanes
  • silicone oils may also be organomodified.
  • organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
  • Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non- volatile.
  • the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and even more particularly from:
  • cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
  • dimethylsiloxane/methylalkylsiloxane such as Silicone Volatile® FZ 3109 sold by the company Union Carbide of formula:
  • Non- volatile polydialkylsiloxanes may also be used. These non- volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.
  • oils of the 200 series from the company Dow Corning such as DC200 with a viscosity of 60 000 mm 2 /s;
  • CTFA dimethiconol
  • silicones containing aryl groups are polydiarylsiloxanes, especially
  • polydiphenylsiloxanes and polyalkylarylsiloxanes examples include the products sold under the following names:
  • silicones of the PK series from Bayer such as the product PK20;
  • oils of the SF series from General Electric such as SF 1023, SF 1154, SF 1250 and SF 1265.
  • the organomodified liquid silicones may especially contain polyethyleneoxy and/or
  • 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
  • hydrocarbon oils 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.
  • 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.
  • 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
  • the amount in the cosmetic composition according to the present invention of the (a) oil ranges from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention comprises at least one polyglyceryl fatty acid ester having an HLB (Hydrophilic Lipophilic Balance) value of 8.0 to 14.0.
  • HLB Hydrophilic Lipophilic Balance
  • 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 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 (b) 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 (b) polyglyceryl fatty acid ester may have an HLB value of from 8.0 to 13.0, preferably from 9.0 to 13.0, and more preferably from 10.0 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 (b) 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 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 (b) 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
  • the (b) polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprate comprising 2 to 6 glycerol units, 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.
  • the polyglyceryl fatty acid ester raw material (b) 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 at least 30% by weight of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins.
  • the (b) polyglyceryl fatty acid ester raw material comprises esters of a fatty acid and polyglycerine containing 70% or more of polyglycerine whose polymerization degree is 4 or more, preferably esters of a fatty acid and polyglycerine containing equal to or more than 60% of polyglycerine whose polymerization degree is between 4 and 11, and more preferably esters of a fatty acid and polyglycerine containing equal to or more than 30% of polyglycerine whose polymerization degree is 5.
  • the amount in the cosmetic composition according to the present invention of the (b) 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 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
  • R-X-CP CL- OnJrL'-CP' 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
  • 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 500000, 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:
  • 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, C1-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.
  • 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;
  • R6, Rs and R 9 have the same meanings as Ri and R 3 defined above;
  • Rio 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, 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-sulfoemyldiemanolarnine.
  • 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 quatemizing 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.
  • 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.
  • solutions or dispersions of these polymers in particular in water or in an aqueous-alcoholic medium.
  • Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company RHEOX. It is also possible to use the product DW 1206F and D W 1206 J provided by the company ROHM & HAAS.
  • polyether-polyurethanes which can be used can also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen-CoUoid 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 from Steareth- 100/PEG- 136/HDI Copolymer sold by the company Rheox under the name of Rheolate FX llOO.
  • 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 0.5 to 3% 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 50 to 90% by weight, preferably from 55 to 95% by weight, and more preferably 60 to 80% by weight, relative to the total weight of the composition.
  • the cosmetic composition according to the present invention may further comprise at least one 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.
  • the additional nonionic surfactant is not limited as long as it is different from the above (b) polyglyceryl fatty acid ester.
  • the additional nonionic surfactant may have an HLB value of from 8.0 to 14.0, preferably from 9.0 to 13.5, and more preferably from 10.0 to 13.0. If two or more additional nonionic surfactants are used, the HLB value is determined by the weight average of the HLB values of all the additional nonionic surfactants.
  • the (b) nonionic surfactant with an HLB value of from 8.0 to 14.0, preferably from 9.0 to 13.5, and more preferably from 10.0 to 13.0 may be chosen from:
  • 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 or branched C -C 22 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, and
  • the (1) 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 Q-C6 alkyl radical or a radical
  • R4 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): -
  • A is an integer ranging from 20 to 105
  • B is an integer ranging from 2 to 10
  • y is an integer ranging from 10 to 20.
  • silicone surfactants of formula (I) mention may also be made of the compounds of formula (III):
  • DC 5329, DC 7439-146, DC 2-5695 and Q4-3667 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.
  • the (2) surfactants that are fluid at a temperature of less than or equal to 45°C may be, in particular:
  • the (3) 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 a-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 CFA name:
  • 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 (CTFAname: Glyceryl stearate lactate) sold by the company Danisco under the name Lactodan B30 or Rylo LA30.
  • the (4) 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 Cg-C 2 2 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 Q-C22 or C 14 -C 2 2 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 (4) 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 Ci 4 -C 22 fatty alcohol and of methylglucose. These are in particular alkylpolyglucosides.
  • the C 8 -C 22 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 (5) 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 16 to 22 carbon atoms and from 1 to 10 glycerol units.
  • esters formed from at least one acid comprising a saturated linear alkyl chain containing from 16 to 22 carbon atoms and from 1 to 10 glycerol units One or more of 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 Polyglyceryl-10 stearate, Polyglyceryl-10 distearate, Polyglyceryl-10 tristearate, Polyglyceryl-10 pentastearate
  • CTFA name Polyglyceryl-2 stearate
  • the (5) 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 (5) ethoxylated fatty ethers that are solid at a temperature of less than or equal to 45°C 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, BB10, 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
  • CTFA name stearyl alcohol ether comprising 2 ethylene oxide units
  • the (5) 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, aracbidate 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 Myrj 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.
  • 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 (IV):
  • 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 (IV) having an HLB value ranging from 8.0 to 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:
  • Ri, 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, Q-C 4 alkyl radicals, and alkenyl and alkyl radicals comprising from
  • R 7 is chosen from Q-C 4 alkyl radicals
  • s is chosen from hydrogen and d-C 4 alkyl radicals
  • X " is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates.
  • R 5 and Re 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
  • R 12 , R 13 , R 14 , R 16a , R 17a , and R 18a which may be identical or different, 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.
  • quaternary ammonium salts comprising at least one ester function, such as those of formula (rV) below:
  • R 22 is chosen from Q-Q alkyl radicals and C C 6 hydroxyalkyl and dihydroxyalkyl radicals;
  • R 23 is chosen from:
  • R 25 is chosen from:
  • R 28 C linear and branched, saturated and unsaturated Ci-C 6 hydrocarbon-based radicals R 29 , and hydrogen,
  • R 24 , R 26 , and R 28 which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C 7 -C 21 , 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 R27, 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 27 , 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 26 , and R 2 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 CrC 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 dacyloxyethyl-dimethylammonium, 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 quatemization 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 chlorohydrin; 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 chlorohydrin; and glycerol chlorohydrin.
  • alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and
  • 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 alkyltrimethylammonium chlorides in which the alkyl radical comprises from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium,
  • palmitylarm ⁇ opropyltrimemylammonium 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 a 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
  • 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
  • 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 230K-40® and Arlatone
  • 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, triethanolamine, N-methylglucamine, lysine and arginine.
  • 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;
  • glutamates such as triethanolamine monococoyl glutamate, sold under the name
  • Acylglutamate CT-12® by Ajinomoto triethanolamine lauroyl glutamate, sold under the name Acylglutamate LT-12® by Ajinomoto;
  • aspartates such as the mixture of triethanolamine 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 triemanolarnine 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 (CTFA name: ammonium laureth sulphate), such as that sold under the name Standapol EA-2 by Cognis.
  • CFA name ammonium laureth sulphate
  • sulphonates for example, of a-olefinsulphonates, such as sodium a-olefinsulphohate (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 olefmsulphonate, 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-olefinsulphohate (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
  • 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; Ri 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.
  • 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.
  • 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)
  • the amidoaminecarboxylated derivatives mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos.
  • 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 Ri'-COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, such as a C 7 , C 9 , Cu 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 24 )alkyl amphodiacetates, (C 8 -C 24 )alkyl amphomonopropionates, and (Cg-C 24 )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
  • 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, dkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and
  • alkylamidoalkylsulfobetaines in particular, (C8-C24)alkylbetaines
  • amphoteric surfactants of betaine type are chosen from (C 8 -C2 4 )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, palrnitamidopropylbetaine,
  • 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 further comprise 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 C 2 -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.
  • the cosmetic composition according to the present invention may further comprise at least one hydrotrope.
  • a single type of hydrotrope may be used, but two or more different types of hydrotrope may be used in combination.
  • Hydrotropes are a diverse class of compounds characterized by an amphiphilic molecular structure and ability to dramatically increase the solubility of poorly soluble organic molecules in water. Many hydrotropes have aromatic structure with an ionic moiety, while some of them are linear alkyl chains, as listed in the table below. Although hydrotropes noticeably resemble surfactants and have the ability to reduce surface tension, their small hydrophobic units and relatively shorter alkyl chain distinguish them as a separate class of amphiphiles. 1
  • Common hydrotropic molecules include: sodium 1,3-benzenedisulfonate, sodium benzoate, sodium 4-pyridinecarboxylate, sodium salicylate, sodium benzene sulfonate, caffeine, sodium p-toluene sulfonate, sodium butyl monoglycolsulfate, 4-aminobenzoic acid HCl, sodium cumene sulfonate, N,N-diethylnicotinamide, N-picolylnicotinamide, N-allylnicotinamide,
  • hydrotropes are preferable hydrotropes that can be used in cosmetic compositions. While hydrotropes represent a broad class of molecules used in various fields, cosmetic applications will be limited due to safety and tolerance restrictions,
  • hydrotropes in cosmetics are listed as below:
  • the suitability of a hydrotrope for use in cosmetic compositions can be determined using tests known in the art for determining effects of compounds on skin, and bioavailability methods.
  • hydrotropes An advantage of using hydrotropes is, once a stable solution is obtained, further dilution doesn't influence the stability of the solution. This is very different from organic solvents that are commonly used to increase the water solubility of actives. Typically, an aqueous dilution of organic solvents with pre-dissolved actives results in crystallization or precipitation.
  • the (c) hydrotrope have a log P being from -0.7 to 6, preferably from -0.5 to 0.5 for non-ionic hydrotope, and preferably from -0.5 to 5.5 for ionic hydrotope such as acid type.
  • a log P value is a value for the base-ten logarithm of the apparent octan- 1 -ol/water partition coefficient.
  • the log P values are known and are determined by a standard test which determines the concentration of a compound in octan- 1 -ol and water.
  • the log P may be calculated according to the method described in the article by Meylan and Howard: Atom/Fragment contribution method for estimating octanol-water partition coefficients, J. Pharm. Sci., 84: 83-92, 1995. This value may also be calculated using numerous commercially available software packages, which determine the log P as a function of the structure of a molecule. By way of example, mention may be made of the Epiwin software from the United States Environmental Agency.
  • the values may especially be calculated using the ACD (Advanced Chemistry Development) Solaris software V4.67; they may also be obtained from Exploring QSAR: hydrophobic, electronic and steric constants (ACS professional reference book, 1995). There is also an Internet site which provides estimated values (address: http://esc.syrres orn/interkow/kowdemo.htrn).
  • the hydrotrope be selected from the group consisting of whitening agents, anti-aging agents, UV filters, keratolytic and anti-bacterial agents.
  • the anti-aging agent mention may be made of moisturizers, free-radical scavengers, keratolytic agents, vitamins, anti-elastase and anti-collagenase agents, protides, fatty acid derivatives, steroids, trace elements, bleaching agents, extracts of algae and of planktons, sunscreens, enzymes and coenzymes, flavonoids and ceramides, and mixtures thereof.
  • hydrotrope be selected from the group consisting of
  • oxothiazolidinecarboxylic acid Vitamin B3 and derivatives thereof, preferably niacinamide, xanthine bases, preferably caffeine, camphor benzalkonium methosulfate, ellagic acid, hydroxyphenoxy propionic acid, diethyllutidinate, terephthalylidene dicamphor sulfonic acid, ferulic acid, salicylic acid, phloretine, acetyl trifluoromethylphenyl valylglycine, resveratrol, 4-butylresorcinol, apigenin, phenylethyl resorcinol, prasterone, benzophenone-3, butyl methoxydibenzoylmethane, capryloyl salicylic acid, ethylhexyl salicylate, and jasmonic acid derivatives, preferably sodium tetrahydrojasmonate.
  • Vitamin B3 and derivatives thereof caffeine
  • Vitamin B3 also called vitarnin PP, is a compound of the following formula:
  • R may be -CONH 2 (niacinamide), -COOH (nicotinic acid or niacin), or CH 2 OH
  • Niacinamide is preferable.
  • Vitamin B3 derivatives that may be mentioned include, for example, nicotinic acid esters such as tocopherol nicotinate, amides derived from niacinamide by substitution of the hydrogen groups of -CONH 2 , products from reaction with carboxylic acids and amino acids, esters of nicotinyl alcohol and of carboxylic acids such as acetic acid, salicyclic acid, glycolid acid or palmitic acid. Mention may also be made of the following derivatives: 2-chloronicotinamide,
  • vitamin B3 derivatives that may also be mentioned include its inorganic salts, such as chlorides, bromides, iodides or carbonates, and its organic salts, such as the salts obtained by reaction with carboxylic acids, such as acetate, salicylate, glycolate, lactate, malate, citrate, mandelate, tartrate, etc.
  • carboxylic acids such as acetate, salicylate, glycolate, lactate, malate, citrate, mandelate, tartrate, etc.
  • xanthine bases which may be used according to the present invention, mention may be made of: caffeine, theophylline, theobromine, acefylline, xanthinol nicotinate, diniprophylline, diprophylline, etamiphylline and its derivatives, etophylline, proxyphylline, pentophylline, propentophylline, pyridophylline, and bamiphylline, without this list being limiting.
  • the xanthine base be selected from the group consisting of caffeine, theophylline, theobromine, acefylline and mixtures thereof. These xanthine bases are known as inhibitors of phosphodiesterase, which is the enzyme responsible for the degradation of cAMP. By increasing the intracellular content of cAMP, these x1 ⁇ 2thine bases promote lipolytic activity and thus constitute first-rate slimming active agents.
  • plant extracts containing xanthine bases mention may be made in particular of extracts of tea, of coffee, of guarana, of Paraguay tea, and of cola, without this list being limiting.
  • the jasmonic acid derivative is a compound chosen from those corresponding to the following formula:
  • 3 ⁇ 4 represents a COOR 3 radical, R 3 denoting a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted by one or more hydroxyl groups
  • R 2 represents a hydrocarbon radical which is saturated or unsaturated, which is linear and which has from 1 to 18 carbon atoms or which is branched or cyclic and which has from 3 to 18 carbon atoms; and their optical isomers, and corresponding salts.
  • Ri denotes a radical chosen from -COOH, -COOMe (Me: methyl group),
  • Ri denotes a -COOH radical.
  • R 2 denotes a saturated or unsaturated linear hydrocarbon radical preferably having from 2 to carbon atoms.
  • R 2 can be a pentyl, pentenyl, hexyl or heptyl radical.
  • the compound of formula (I) is chosen from
  • the salts of the compounds which can be used according to the invention are chosen in particular from alkali metal salts, for example sodium or potassium salts; alkaline earth metal salts, for example calcium, magnesium or strontium salts; metal salts, for example zinc, aluminum, manganese or copper salts; salts of ammonium of formula N3 ⁇ 4 + ; quaternary ammonium salts; organic amine salts, such as, for example, memylamine, dimethylamine, trimemylamine, triemylamine, ethylarnine, 2-hydroxyemylamine, bis(2-hydroxyemyl)amine or
  • tris(2-hydroxyethyl)amine salts or lysine or arginine salts.
  • Use is preferably made of salts chosen from sodium, potassium, calcium, magnesium, strontium, copper, manganese or zinc salts.
  • the amount of the hydrotrope is not limited, and may range from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 1 to 10% by weight, further more preferably 2 to 9% by weight, and eve more preferably 3 to 8% by weight, 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, C 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).
  • W 201 a high pressure homogenizer
  • 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) polyglyceryl fatty acid ester to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.5 to 1.5.
  • the weight ratio of the (b) polyglyceryl fatty acid ester/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 0.5 to 1.
  • the cosmetic composition according to the present invention is in the form of a nano- or micro-emulsion.
  • 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 mfinite 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.
  • 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) polyglyceryl fatty acid ester and the like that may optionally form a liquid crystal phase of lamellar type, at the dispersed phase/continuous phase interface.
  • 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.
  • micro-emulsions are thermodynamically stable dispersions formed from, for example, the (b) polyglyceryl fatty acid ester 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.
  • the cosmetic composition according to the present invention be in the form of an 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 transparency may be measured by measuring the transmittance with absorption spectrometer in the visible region (for example, Lambda 14 spectrometer from Perkin Elmer or the UV2101 PC spectrometer from Shimazu). The measurement is taken on the undiluted composition. The blank is determined with distilled water.
  • absorption spectrometer in the visible region (for example, Lambda 14 spectrometer from Perkin Elmer or the UV2101 PC spectrometer from Shimazu). The measurement is taken on the undiluted composition. The blank is determined with distilled water.
  • the cosmetic composition according to the present invention may preferably have a transparency greater than 50%, preferably greater than 60%, and more preferably greater than 70%.
  • 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 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.
  • 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: The phase A and B were separately heated at 70 to 75 °C under agitation. After the components in each phase were fully dissolved, both were mixed and cooled down to room temperature to obtain an emulsion. Then, the phases C and D, E were introduced into the mixture under agitation in order. 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 had a higher viscosity. It was also found that the compositions according to Examples 1 and 2 had sufficient consistency, and showed rheology as hard gel, while the composition according to Comparative Example 1 had insufficient consistency, and showed rheology as liquid.
  • the shape recovery property was measured in accordance with texture meter analysis.
  • 70 g of each of the compositions according to Examples 1-2 and Comparative Example 1 was filled into a container with an open top.
  • An applicator in the form of a cone (40' conical Perspex Part code P/40C) was pushed into the surface of each composition at a speed of 20 mm/sec at a force of 0.01 g.
  • the applicator was allowed to more into the composition for a distance of 15 mm from the surface of the composition.
  • the applicator was pulled up at a speed of 40 mm/sec, and extracted from the composition.
  • compositions according to Examples 1 and 2 had a capability of shape recovery. It was also found that the composition according to Example 1 had a quick shape recovery property. The composition according to Comparative Example 1 could not keep the shape of the corn applicator.
  • Examples 1-2 and Comparative Example 1 was applied onto the forearm of each panelist.
  • the stickiness immediate after the application was evaluated in accordance with 3 levels of score (Level 1 : low, Level 2: medium, Level 3: High). The score was averaged. The results are shown in Table 4.
  • compositions according to Examples 1 and 2 had both high viscosity (or consistency) and shape recovery property.
  • the composition according to Example 1 had a high viscosity, quick shape recovery property and unstickiness, and therefore, it is most preferable.

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 polyglyceryl fatty acid ester having an HLB value from 8.0 to 13.0, preferably from 9.0 to 13.0, and more preferably from 10.0 to 13.0; (c) at least one associative polyurethane; and (d) water, wherein the amount of the (a) oil ranges from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% 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 shape recoverying properties. Further, the cosmetic composition according to the present invention can be less sticky. Furthermore, the cosmetic composition according to the present invention 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 transparent or slightly translucent.

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
Oil-in- water (O W) or Water-in-oil (W/O) emulsions are well known in the field of cosmetics and dermatology, in particular for the preparation of cosmetic products, such as milks, creams, tonics, serums or toilet waters. In particular, a fine emulsion such as an O W nano- or micro-emulsion is particularly interesting in cosmetic products due to its transparent or slightly translucent aspect.
For example, JP-A-H09-110635 discloses a fine emulsion which is formed by using a
combination of polyglyceryl fatty acid ester, as a surfactant, and C10-C 22 2-hydroxy fatty acid. In addition, JP-A-H11-71256 discloses a fine emulsion which is formed by using a combination of polyglyceryl fatty acid ester and a betain.
DISCLOSURE OF INVENTION
However, in some cases, a nano- or micro-emulsion is difficult to have a high viscosity or consistency. 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 shape recovery properties. Furthermore, stickiness is typically given to a highly viscous emulsion.
An 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 and shape recovery properties, preferably quick shape recovery properties, and possibly less stickiness.
In addition, when a certain type of a nonionic surfactant is used for preparing a fine emulsion such as a nano- or micro-emulsion, the transparent or slightly translucent aspect of the emulsion as well as stability of the emulsion, may be impaired.
Another objective of the present invention is 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, even when the above nonionic surfactant is used. The above objectives of the present invention can be achieved by a cosmetic composition in the form of a nano- or micro-emulsion, comprising:
(a) at least one oil;
(b) at least one polyglyceryl fatty acid ester having an HLB value from 8.0 to 14.0, preferably from 9.0 to 13.0, and more preferably from 10.0 to 13.0;
(c) at least one associative polyurethane; and (d) water,
wherein the amount of the (a) oil ranges from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% 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, silicone 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 (b) polyglyceryl fatty acid ester may have a polyglyceryl moiety derived from 2-10 glycerins, preferably 3-6 glycerins.
It is preferable that the (b) polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprate comprising 2 to 6 glycerol units, 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. The polyglyceryl fatty acid ester raw material (b) 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 at least 30% by weight of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins. According to one embodiment, the (b) polyglyceryl fatty acid ester raw material comprises esters of a fatty acid and polyglycerine containing 70% or more of polyglycerine whose polymerization degree is 4 or more, preferably esters of a fatty acid and polyglycerine containing equal to or more than 60% of polyglycerine whose polymerization degree is between 4 and 11, and more preferably esters of a fatty acid and polyglycerine containing equal to or more than 30% of polyglycerine whose polymerization degree is 5.
The amount of the (b) polyglyceryl fatty acid ester 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 weight ratio of the (b) polyglyceryl fatty acid ester to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.5 to 1.5.
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 0.5 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 nonionic surfactant different from the above (b) and/or at least one ionic surfactant. The cosmetic composition according to the present invention may further comprise at least one polyol.
The cosmetic composition according to the present invention may further comprise at least one hydrotrope. the (c) hydrotrope may have a log P being from -0.7 to 6, preferably from -0.5 to 0.5 for non ionic hydropes, and preferably from -0.5 to 5.5 for hydrotropes with ionic character (acid type).
It is preferable that the cosmetic composition according to the present invention be in the form of an 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.
It is preferable that the cosmetic composition according to the present invention have a
transparency greater than 50%, more preferably greater than 60%, and further more preferably greater than 70%.
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 cosmetic composition in the form of a nano- or micro-emulsion with a high viscosity or consistency and shape recovery properties, preferably quick shape recovery properties, and possibly less stickiness. Also, the cosmetic composition can be a stable and have a transparent or slightly translucent, preferably transparent, aspect, even when using a nonionic surfactant which was difficult to form a fine emulsion such as a nano- or micro-emulsion.
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 polyglyceryl fatty acid ester having an HLB value from 8.0 to 14.0,.preferably from 9.0 to 13.0, and more preferably from 10.0 to 13.0; (c) at least one associative polyurethane; and
(d) water,
wherein the amount of the (a) oil ranges from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% 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 hard 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.
On the other hand, the cosmetic composition according to the present invention can have shape recovery properties. Therefore, for example, even if a part of the cosmetic composition (e.g., cream or gel) in a container is taken by a user from the horizontal surface thereof, the surface can restore to be horizontal. It is preferable that the shape recovery occur as quickly as possible.
Further, the cosmetic composition according to the present invention can have less stickiness even though it can have a high viscosity or consistency. Furthermore, the cosmetic composition according to the present invention has a dispersed phase which has a smaller diameter due to a combination of the polyglyceryl fatty acid ester and a relatively small amount of oil. Therefore, the cosmetic composition can be in the form of a nano- or micro-emulsion with transparent or slightly translucent. Since the cosmetic composition according to the present invention can have transparent or slightly translucent, the composition can be preferably used for lotions and the like. Further, as the dispersed phase is finely dispersed, the cosmetic composition according to the present invention can provide unique texture, moisturizing and wet feeling, as well as increased suppleness.
Furthermore, if the dispersed phase is an oil phase and includes one or more lipophilic or even amphiphilic active ingredients, the dispersed oil phase can function as a carrier of the active ingredient and accelerate the penetration of the active ingredients into the skin, or can distribute the active ingredients on the skin. For example, if a UV filer is present in the dispersed oil phase, the UV filter can be well spread on the skin to exert better UV filtering effects. 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. The oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; 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 be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils and hydrocarbon 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 C1-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, 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 C1-C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C4-C2 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 ester oils, one can use sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides. Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.
The esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof. These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters.
More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 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 tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).
As examples of silicone oils, mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof. Preferably, silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
These silicone oils may also be organomodified. The organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group. Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non- volatile.
When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and even more particularly from:
(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia,
decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof.
Mention may also be made of cyclocopolymers of the type such as
dimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 3109 sold by the company Union Carbide of formula:
Figure imgf000008_0001
with D" : - Si - O— wjth D' : - Si - O -
CH3 C8H17
Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and
tetratrimemylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '-bis(2,2,2 2 3,3'-hexa1rimethylsilyloxy)neopentane;
(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5 χ 10" m Is at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM standard 445 Appendix C.
Non- volatile polydialkylsiloxanes may also be used. These non- volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.
Among these polydialkylsiloxanes, mention may be made, in a non-limiting manner, of the following commercial products:
- the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for
instance the oil 70 047 V 500 000;
the oils of the Mirasil® series sold by the company Rhodia;
the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm2/s;
- the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.
Among the silicones containing aryl groups are polydiarylsiloxanes, especially
polydiphenylsiloxanes and polyalkylarylsiloxanes. Examples that may be mentioned include the products sold under the following names:
- the Silbione® oils of the 70 641 series from Rhodia;
the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;
the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;
the silicones of the PK series from Bayer, such as the product PK20;
certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.
The organomodified liquid silicones may especially contain polyethyleneoxy and/or
polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.
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 from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% by weight, relative to the total weight of the composition.
[Polyglyceryl Fatty Acid Ester]
The cosmetic composition according to the present invention comprises at least one polyglyceryl fatty acid ester having an HLB (Hydrophilic Lipophilic Balance) value of 8.0 to 14.0. 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 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 χ 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).
It is preferable that the (b) 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 (b) polyglyceryl fatty acid ester may have an HLB value of from 8.0 to 13.0, preferably from 9.0 to 13.0, and more preferably from 10.0 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 (b) 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 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 (b) 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. It is preferable that the (b) polyglyceryl fatty acid ester be chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprate comprising 2 to 6 glycerol units, 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.
The polyglyceryl fatty acid ester raw material (b) 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 at least 30% by weight of a polyglyceryl fatty acid ester with a polyglyceryl moiety consisting of 5 or 6 glycerins.
In one embodiment, the (b) polyglyceryl fatty acid ester raw material comprises esters of a fatty acid and polyglycerine containing 70% or more of polyglycerine whose polymerization degree is 4 or more, preferably esters of a fatty acid and polyglycerine containing equal to or more than 60% of polyglycerine whose polymerization degree is between 4 and 11, and more preferably esters of a fatty acid and polyglycerine containing equal to or more than 30% of polyglycerine whose polymerization degree is 5. The amount in the cosmetic composition according to the present invention of the (b) 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. [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-CP CL- OnJrL'-CP' 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 500000, 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 imgf000014_0001
or ¾ forX' 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, C1-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 imgf000014_0002
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 imgf000014_0003
Figure imgf000015_0001
in which:
R5 and R7 have the same meanings as R2 defined above; R6, Rs and R9 have the same meanings as Ri and R3 defined above;
Rio 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, P, 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-sulfoemyldiemanolarnine.
The second compound entering into the preparation of the polyurethane of formula (A) is a diisocyanate corresponding to the formula O=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 quatemizing agent. This quatemizing 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 imgf000017_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 D W 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-CoUoid 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 from Steareth- 100/PEG- 136/HDI Copolymer sold by the company Rheox under the name of Rheolate FX llOO.
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 0.5 to 3% 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 50 to 90% by weight, preferably from 55 to 95% by weight, and more preferably 60 to 80% 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 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.
(Nonionic Surfactant)
The additional nonionic surfactant is not limited as long as it is different from the above (b) polyglyceryl fatty acid ester.
The additional nonionic surfactant may have an HLB value of from 8.0 to 14.0, preferably from 9.0 to 13.5, and more preferably from 10.0 to 13.0. If two or more additional nonionic surfactants are used, the HLB value is determined by the weight average of the HLB values of all the additional nonionic surfactants.
The (b) nonionic surfactant with an HLB value of from 8.0 to 14.0, preferably from 9.0 to 13.5, and more preferably from 10.0 to 13.0 may be chosen from:
(1) silicone surfactants,
(2) 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 or branched C -C22 alkyl chain,
(3) mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol,
(4) fatty acid esters of sugars and fatty alcohol ethers of sugars,
(5) 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, and
(6) block copolymers of ethylene oxide (A) and of propylene oxide (B). As 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 (1) silicone surfactant as the above nonionic surfactant may preferably be a compound of formula (I):
Figure imgf000020_0001
in which:
Ri, R2 and R3, independently of each other, represent a Q-C6 alkyl radical or a radical
-(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4, at least one radical R1? R2 or R3 not being an alkyl radical; R4 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 (ID
(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. The (2) surfactants 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 1 OR by the company Nikko; and oc-butylglucoside cocoate or a-butylglucoside caprate, sold by the company Ulice. The (3) 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 a-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 (CTFA name:
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 (CTFAname: Glyceryl stearate lactate) sold by the company Danisco under the name Lactodan B30 or Rylo LA30.
The (4) 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 Cg-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 Q-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 (4) 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 Ci4-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 (5) 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 16 to 22 carbon atoms and from 1 to 10 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: Polyglyceryl-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 (5) 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 (5) 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, BB10, 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 (5) 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, aracbidate 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 Myrj 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 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 (IV):
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 (IV) having an HLB value ranging from 8.0 to 14.0.
(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
Ri, 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,
(C12-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-C ) alkyl sulfates and alkyl- or alkylaryl-sulfonates;
quaternary ammonium salts of imidazoline, for instance those of formula (II) below:
Figure imgf000024_0002
(Π)
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, Q-C4 alkyl radicals, and alkenyl and alkyl radicals comprising from
8 to 30 carbon atoms;
R7 is chosen from Q-C4 alkyl radicals;
s is chosen from hydrogen and d-C4 alkyl radicals; and
X" is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates. In one embodiment, R5 and Re 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_0001
(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;
R11? R12, R13, R14, R16a, R17a, and R18a, 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 (rV) below:
K24
Figure imgf000025_0002
wherein:
R22 is chosen from Q-Q alkyl radicals and C C6 hydroxyalkyl and dihydroxyalkyl radicals; R23 is chosen from:
the radical blow:
O
R26 C
linear and branched, saturated and unsaturated C1.C22 hydrocarbon-based radicals R27, and hydrogen,
R25 is chosen from:
the radical below:
O
_ l l _
R28 C linear and branched, saturated and unsaturated Ci-C6 hydrocarbon-based radicals R29, and hydrogen,
R24, R26, and R28, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C7-C21, 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, R26, and R2 , 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 CrC4 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
II methyl, ethyl, and Q4-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 dacyloxyethyl-dimethylammonium, of
diacyloxyethyl-hydroxyethyl-methylamm- onium, of
monoacyloxyemyl-dmydroxyemyl-memylammonium, 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 quatemization 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 chlorohydrin; 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 alkyltrimethylammonium chlorides in which the alkyl radical comprises from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium,
celyltrimethylammonium and benzyldimemylstearylammonium chloride;
palmitylarm^opropyltrimemylammonium 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, cetyltrimethylarnmonium chloride, Quaternium-83, Quaternium-87, Quaternium-22, behenylan idopropyl-2,3-dmydroxypropyldimemylammonium chloride, palmitylamidopropyltrimemylammonium chloride, and
stearamidopropyldimemylamine.
(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 a 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 arnino 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 arnino acids (aspartic acid, glutamic acid, glycine, alanine) neutralized with W sodium N-methylglycinate sold under the name Proteol SAV 50 S by Seppic (CTFAname:
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 230K-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, triethanolamine, N-methylglucamine, 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-me1hylalanine, sold under the name Alanone ALTA® by Kawaken;
glutamates, such as triethanolamine monococoyl glutamate, sold under the name
Acylglutamate CT-12® by Ajinomoto, triethanolamine lauroyl glutamate, sold under the name Acylglutamate LT-12® by Ajinomoto;
aspartates, such as the mixture of triethanolamine 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 Cj2/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 triemanolarnine 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 (CTFA name: 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-olefinsulphohate (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 olefmsulphonate, 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 (»)
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; Ri 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 R2 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 dihydroxy ethyl 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:
denotes an alkyl radical of an acid Rt-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
R1 ,-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 Ri'-COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, such as a C7, C9, Cu 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 (Cg-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, dkylamidoalkylbetaines, 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, palrnitamidopropylbetaine,
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.
[Polyol]
The cosmetic composition according to the present invention may further comprise 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.
[Hydrotrope]
The cosmetic composition according to the present invention may further comprise at least one hydrotrope. A single type of hydrotrope may be used, but two or more different types of hydrotrope may be used in combination.
Hydrotropes (or hydrotropic agents) are a diverse class of compounds characterized by an amphiphilic molecular structure and ability to dramatically increase the solubility of poorly soluble organic molecules in water. Many hydrotropes have aromatic structure with an ionic moiety, while some of them are linear alkyl chains, as listed in the table below. Although hydrotropes noticeably resemble surfactants and have the ability to reduce surface tension, their small hydrophobic units and relatively shorter alkyl chain distinguish them as a separate class of amphiphiles. 1
Common hydrotropic molecules include: sodium 1,3-benzenedisulfonate, sodium benzoate, sodium 4-pyridinecarboxylate, sodium salicylate, sodium benzene sulfonate, caffeine, sodium p-toluene sulfonate, sodium butyl monoglycolsulfate, 4-aminobenzoic acid HCl, sodium cumene sulfonate, N,N-diethylnicotinamide, N-picolylnicotinamide, N-allylnicotinamide,
2-methacryloyloxyethyl phosphorylcholine, resorcinol, butylurea, pyrogallol, N-picolylacetamide 3.5, procaine HCl, proline HCl, nicotinamide, pyridine, 3-picolylamine, sodium ibuprofen, sodium xylenesulfonate, ethyl carbamate, pyridoxal hydrochloride, sodium benzoate,
2-pyrrolidone, ethylurea, N,N-dimethylacetamide, N-methylacetamide, and isoniazid.
Hydrotropes can be found in Lee J. et al., "Hydrotropic Solubilization of Paclitaxel: Analysis of Chemical Structures for Hydrotropic Property", Pharmaceutical Research, Vol. 20, No. 7, 2003; and Hodgon T.K., Kaler E.W., "Hydrotropic Solutions", Current Opinion in Colloid and Interface Science, 12, 121-128, 2007.
Cosmetically acceptable hydrotropes are preferable hydrotropes that can be used in cosmetic compositions. While hydrotropes represent a broad class of molecules used in various fields, cosmetic applications will be limited due to safety and tolerance restrictions,
hydrotropes in cosmetics are listed as below:
Figure imgf000035_0001
The suitability of a hydrotrope for use in cosmetic compositions can be determined using tests known in the art for determining effects of compounds on skin, and bioavailability methods.
An advantage of using hydrotropes is, once a stable solution is obtained, further dilution doesn't influence the stability of the solution. This is very different from organic solvents that are commonly used to increase the water solubility of actives. Typically, an aqueous dilution of organic solvents with pre-dissolved actives results in crystallization or precipitation.
It is preferable that the (c) hydrotrope have a log P being from -0.7 to 6, preferably from -0.5 to 0.5 for non-ionic hydrotope, and preferably from -0.5 to 5.5 for ionic hydrotope such as acid type.
It is possible to use a formulator to adjust pH in order to reach the best state of transparency with hydrotropes.
A log P value is a value for the base-ten logarithm of the apparent octan- 1 -ol/water partition coefficient. The log P values are known and are determined by a standard test which determines the concentration of a compound in octan- 1 -ol and water. The log P may be calculated according to the method described in the article by Meylan and Howard: Atom/Fragment contribution method for estimating octanol-water partition coefficients, J. Pharm. Sci., 84: 83-92, 1995. This value may also be calculated using numerous commercially available software packages, which determine the log P as a function of the structure of a molecule. By way of example, mention may be made of the Epiwin software from the United States Environmental Agency.
The values may especially be calculated using the ACD (Advanced Chemistry Development) Solaris software V4.67; they may also be obtained from Exploring QSAR: hydrophobic, electronic and steric constants (ACS professional reference book, 1995). There is also an Internet site which provides estimated values (address: http://esc.syrres orn/interkow/kowdemo.htrn).
It is preferable that the hydrotrope be selected from the group consisting of whitening agents, anti-aging agents, UV filters, keratolytic and anti-bacterial agents.
As examples of the anti-aging agent, mention may be made of moisturizers, free-radical scavengers, keratolytic agents, vitamins, anti-elastase and anti-collagenase agents, protides, fatty acid derivatives, steroids, trace elements, bleaching agents, extracts of algae and of planktons, sunscreens, enzymes and coenzymes, flavonoids and ceramides, and mixtures thereof.
It is preferable that the hydrotrope be selected from the group consisting of
oxothiazolidinecarboxylic acid, Vitamin B3 and derivatives thereof, preferably niacinamide, xanthine bases, preferably caffeine, camphor benzalkonium methosulfate, ellagic acid, hydroxyphenoxy propionic acid, diethyllutidinate, terephthalylidene dicamphor sulfonic acid, ferulic acid, salicylic acid, phloretine, acetyl trifluoromethylphenyl valylglycine, resveratrol, 4-butylresorcinol, apigenin, phenylethyl resorcinol, prasterone, benzophenone-3, butyl methoxydibenzoylmethane, capryloyl salicylic acid, ethylhexyl salicylate, and jasmonic acid derivatives, preferably sodium tetrahydrojasmonate. Vitamin B3 and derivatives thereof, caffeine, and jasmonic acid derivatives, which are described below in more detailed manner, are more preferable.
(Vitamin B3 and Derivatives Thereof)
Vitamin B3, also called vitarnin PP, is a compound of the following formula:
Figure imgf000036_0001
in which R may be -CONH2 (niacinamide), -COOH (nicotinic acid or niacin), or CH2OH
(nicotinyl alcohol), -CO-NH-CH2-COOH (nicotinuric acid) or -CO-NH-OH (niconityl hydroxamic acid). Niacinamide is preferable. Vitamin B3 derivatives that may be mentioned include, for example, nicotinic acid esters such as tocopherol nicotinate, amides derived from niacinamide by substitution of the hydrogen groups of -CONH2, products from reaction with carboxylic acids and amino acids, esters of nicotinyl alcohol and of carboxylic acids such as acetic acid, salicyclic acid, glycolid acid or palmitic acid. Mention may also be made of the following derivatives: 2-chloronicotinamide,
6-methylnicotinamide, 6-aminonicotinamide, N-methylnicotinamide, N,N-dimethylnicotinamide, N-(¾ydroxymemyl)nicotinamide, quinolinic acid imide, nicotinanilide, N-benzylnicotinamide, N-ethylnicotinamide, nifenazone, nicotinaldehyde, isonicotinic acid, methylisonicotinic acid, thionicotinamide, nialamide, 2-mercaptonicotinic acid, nicomol and niaprazine, methyl nicotinate and sodium nicotinate.
Other vitamin B3 derivatives that may also be mentioned include its inorganic salts, such as chlorides, bromides, iodides or carbonates, and its organic salts, such as the salts obtained by reaction with carboxylic acids, such as acetate, salicylate, glycolate, lactate, malate, citrate, mandelate, tartrate, etc. (Xanthine Base)
Among the xanthine bases which may be used according to the present invention, mention may be made of: caffeine, theophylline, theobromine, acefylline, xanthinol nicotinate, diniprophylline, diprophylline, etamiphylline and its derivatives, etophylline, proxyphylline, pentophylline, propentophylline, pyridophylline, and bamiphylline, without this list being limiting.
It is preferable that the xanthine base be selected from the group consisting of caffeine, theophylline, theobromine, acefylline and mixtures thereof. These xanthine bases are known as inhibitors of phosphodiesterase, which is the enzyme responsible for the degradation of cAMP. By increasing the intracellular content of cAMP, these x½thine bases promote lipolytic activity and thus constitute first-rate slimming active agents.
As examples of plant extracts containing xanthine bases, mention may be made in particular of extracts of tea, of coffee, of guarana, of Paraguay tea, and of cola, without this list being limiting.
(Jasmonic Acid Derivative)
The jasmonic acid derivative is a compound chosen from those corresponding to the following formula:
Figure imgf000037_0001
in which: ¾ represents a COOR3 radical, R3 denoting a hydrogen atom or a C1-C4 alkyl radical optionally substituted by one or more hydroxyl groups; R2 represents a hydrocarbon radical which is saturated or unsaturated, which is linear and which has from 1 to 18 carbon atoms or which is branched or cyclic and which has from 3 to 18 carbon atoms; and their optical isomers, and corresponding salts.
Preferably, Ri denotes a radical chosen from -COOH, -COOMe (Me: methyl group),
-COO-CH2-CH3, -COO-CH2--CH(OH)-CH2OH, -COOCH2-CH2-CH20H or
-COOCH2-CH(OH)-CH3. Preferably Ri denotes a -COOH radical.
Preferably, R2 denotes a saturated or unsaturated linear hydrocarbon radical preferably having from 2 to carbon atoms. In particular, R2 can be a pentyl, pentenyl, hexyl or heptyl radical.
According to one embodiment, the compound of formula (I) is chosen from
3-hydroxy-2-[(2Z)-2-pentenyl]cyclopentaneacetic acid or 3-hydroxy-2-pentylcyclopentaneacetic acid and is preferably 3-hydroxy-2-pentylcyclopentaneacetic acid. W
The salts of the compounds which can be used according to the invention are chosen in particular from alkali metal salts, for example sodium or potassium salts; alkaline earth metal salts, for example calcium, magnesium or strontium salts; metal salts, for example zinc, aluminum, manganese or copper salts; salts of ammonium of formula N¾+; quaternary ammonium salts; organic amine salts, such as, for example, memylamine, dimethylamine, trimemylamine, triemylamine, ethylarnine, 2-hydroxyemylamine, bis(2-hydroxyemyl)amine or
tris(2-hydroxyethyl)amine salts; or lysine or arginine salts. Use is preferably made of salts chosen from sodium, potassium, calcium, magnesium, strontium, copper, manganese or zinc salts.
It is preferable to use the following compound as the jasmonic acid derivative.
Figure imgf000038_0001
The amount of the hydrotrope is not limited, and may range from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 1 to 10% by weight, further more preferably 2 to 9% by weight, and eve more preferably 3 to 8% by weight, 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, C 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). W 201
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) polyglyceryl fatty acid ester to the (a) oil may be from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.5 to 1.5. In particular, the weight ratio of the (b) polyglyceryl fatty acid ester/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 0.5 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 mfinite 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) polyglyceryl fatty acid ester 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) polyglyceryl fatty acid ester 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 an 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 transparency may be measured by measuring the transmittance with absorption spectrometer in the visible region (for example, Lambda 14 spectrometer from Perkin Elmer or the UV2101 PC spectrometer from Shimazu). The measurement is taken on the undiluted composition. The blank is determined with distilled water.
The cosmetic composition according to the present invention may preferably have a transparency greater than 50%, preferably greater than 60%, and more preferably greater than 70%.
[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. 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: The phase A and B were separately heated at 70 to 75 °C under agitation. After the components in each phase were fully dissolved, both were mixed and cooled down to room temperature to obtain an emulsion. Then, the phases C and D, E were introduced into the mixture under agitation in order. 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 imgf000041_0001
(Viscosity Measurements)
The viscosity of each of the compositions according to Examples 1-2 and Comparative Example 1 was measured by using a B-type viscometer at a temperature of 25°C, and at 12 rpm with a module No.3. The viscosity data of the compositions according to Examples 1 -2 and
Comparative Example 1 are shown in Table 2.
Table 2
Figure imgf000042_0001
As is clear from the above results, it was found that the compositions according to Examples 1 and 2 had a higher viscosity. It was also found that the compositions according to Examples 1 and 2 had sufficient consistency, and showed rheology as hard gel, while the composition according to Comparative Example 1 had insufficient consistency, and showed rheology as liquid.
(Shape Recovery Test)
The shape recovery property was measured in accordance with texture meter analysis. 70 g of each of the compositions according to Examples 1-2 and Comparative Example 1 was filled into a container with an open top. An applicator in the form of a cone (40' conical Perspex Part code P/40C) was pushed into the surface of each composition at a speed of 20 mm/sec at a force of 0.01 g. The applicator was allowed to more into the composition for a distance of 15 mm from the surface of the composition. Next, the applicator was pulled up at a speed of 40 mm/sec, and extracted from the composition.
First, it was observed as "First Check" whether the corn shape of applicator was kept in the composition after the removal of the applicator. Second, if the corn shape of applicator was kept in the composition after the removal of the applicator, the time required for the corn shape to disappear was recorded as "Shape Recovery Time".
The results are shown in Table 3.
Table 3
Figure imgf000042_0002
As is clear from the above results, it was found that the compositions according to Examples 1 and 2 had a capability of shape recovery. It was also found that the composition according to Example 1 had a quick shape recovery property. The composition according to Comparative Example 1 could not keep the shape of the corn applicator.
(Sensory Test)
The stickiness of the compositions according to Examples 1-2 and Comparative Example 1 was evaluated by sensory test with 3 panelists. 0.15 g of each of the compositions according to
Examples 1-2 and Comparative Example 1 was applied onto the forearm of each panelist. The stickiness immediate after the application was evaluated in accordance with 3 levels of score (Level 1 : low, Level 2: medium, Level 3: High). The score was averaged. The results are shown in Table 4.
Table 4
Figure imgf000043_0001
As is clear from the above results, it was found that the composition according to Example 1 was less sticky than those according to Example 2 and Comparative Example 1.
Accordingly, based on the above all measurement and test results, it was found that the compositions according to Examples 1 and 2 had both high viscosity (or consistency) and shape recovery property. In particular, the composition according to Example 1 had a high viscosity, quick shape recovery property and unstickiness, and therefore, it is most preferable.

Claims

A cosmetic composition in the form of a nano- or micro-emulsion, comprising:
(a) at least one oil;
(b) at least one polyglyceryl fatty acid ester having an HLB value from 8.0 to 14.0, preferably from 9.0 to 13.0, and more preferably from 10.0 to 13.0;
(c) at least one associative polyurethane; and
(d) water,
wherein the amount of the (a) oil ranges from 0.1 to 15% by weight, preferably from 1 to 12% by weight, and more preferably from 2 to 10% 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, silicone 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 (b) polyglyceryl fatty acid ester has a polyglyceryl moiety derived from 2-10 glycerins, preferably 3-6 glycerins.
The cosmetic composition according to any one of Claims 1 to 5, wherein the (b) polyglyceryl fatty acid ester is chosen from polyglyceryl caprate comprising 2 to 6 glycerol units, polyglyceryl tricaprate comprising 2 to 6 glycerol units, polyglyceryl monolaurate comprising 3 to 6 glycerol units, polyglyceryl m no(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.
The cosmetic composition according to any one of Claims 1 to 6, wherein the polyglyceryl fatty acid ester raw material (b) 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 cosmetic composition according to any one of Claims 1 to 7, wherein the (b) polyglyceryl fatty acid ester raw material comprises esters of a fatty acid and polyglycerine containing 70% or more of polyglycerine whose polymerization degree is 4 or more, preferably esters of a fatty acid and polyglycerine containing equal to or more than 60% of polyglycerine whose polymerization degree is between 4 and 11, and more preferably esters of a fatty acid and polyglycerine containing equal to or more than 30% of polyglycerine whose polymerization degree is 5.
9. The cosmetic composition according to any one of Claims 1 to 8, wherein the amount of the (b) polyglyceryl fatty acid ester ranges 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.
10. The cosmetic composition according to any one of Claims 1 to 9, wherein the weight ratio of the (b) polyglyceryl fatty acid ester to the (a) oil is from 0.3 to 6, preferably from 0.4 to 3, and more preferably from 0.5 to 1.5.
11. The cosmetic composition according to any one of Claims 1 to 10, 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.
12. The cosmetic composition according to any one of Claims 1 to 11 , 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 0.5 to 3% by weight, relative to the total weight of the composition.
13. The cosmetic composition according to any one of Claims 1 to 12, further comprising at least one nonionic surfactant different from the above (b) and/or at least one ionic surfactant.
14. The cosmetic composition according to any one of Claims 1 to 13, further comprising at least one polyol.
15. The cosmetic composition according to any one of Claims 1 to 14, further comprising at least one hydrotrope.
16. The cosmetic composition according to Claim 15, wherein the (c) hydrotrope has a log P being from -0.7 to 6, preferably from -0.5 to 0.5 for non ionic hydropes and preferably from -0.5 to 5.5 for hydrotropes with ionic character (acid type).
17. The cosmetic composition according to any one of Claims 1 to 16, 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.
18. The cosmetic composition according to any one of Claims 1 to 17, wherein it has a
transparency greater than 50%, preferably greater than 60%, and more preferably greater than 70%.
19. 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 18 is applied to the skin, the hair, mucous membranes, the nails, the eyelashes, the eyebrows or the scalp.
Use of the cosmetic composition according to any one of Claims 1 to 18, 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.
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