The present invention relates to new cosmetic compositions, especially hairstyling compositions, comprising the combination of at least one cationic polyurethane comprising non ionic units derived from at least one olefinic homo- or copolymer, and at least one specific silicone.
The use of elastic cationic polyurethanes in cosmetic compositions, especially hairstyling compositions is known.
Thus, the French patent application FR 2 815 350 describes cationic polyurethanes of the elastic type and their use for formulating hair sprays and hair styling compositions to enhance hair suppleness, that is to say enabling to hold hair styles elastically, in a more natural way as compared to that obtained with usual fixing polymers.
The French patent application FR-2 833 960 describes cosmetic styling compositions, and more particularly rinse-off hair styling compositions, especially styling shampoos, comprising a self-adhering cationic or amphoteric polyurethane. Such compositions may further comprise a silicone as an additive.
The applicant discovered that using an elastic cationic polyurethane comprising units derived from an olefinic homo- and/or copolymer in a hair styling composition does provide an excellent hold with the time, but does lead to cosmetically poor properties and is difficult to remove with shampoo.
Surprisingly, the applicant discovered that combining certain silicones with these cationic polyurethanes comprising units derived from an olefinic homo-and/or copolymer makes it possible to formulate cosmetic hairstyling compositions resulting in good cosmetic properties, while being easily removable with shampoo, without affecting the hair fixing and its ability to keep in place with the time.
It is thus an object of the present invention to provide a cosmetic composition, and more particularly a hair styling composition, containing, in a cosmetically acceptable medium, at least one cationic polyurethane comprising at least one unit derived from an olefinic homo- and/or copolymer and at least one specific silicone.
It is also an object of the present invention to provide such a composition further comprising a gas propellant and being conditioned in the form of an aerosol.
It is a further object of the present invention to provide a hairstyling method comprising applying onto the hair such composition, then styling and drying the hair.
According to the invention, the cosmetic composition comprises, in a cosmetically acceptable aqueous medium:

(i) at least one cationic polyurethane comprising at least one non ionic unit derived from an olefmic homo- and/or copolymer, and
(ii) at least one silicone chosen from polydialkyl siloxanes and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene), amino and alkoxy groups.
The elastic cationic polyurethane comprising at least one non ionic unit, derived from an olefinic homo- or copolymer represents the first most essential component of the compositions of the present invention.
Preferred cationic polyurethanes to be suitably used in the present invention comprise:
(a) cationic units derived from at least one compound, preferably a tertiary
or a quaternary amine, comprising at least two labile hydrogen-containing reactive
functions,
(b) non ionic units derived from non ionic polymers labile hydrogen-
containing reactive functions at their ends, at least one of the (b) units, preferably
at least 50% by weight of the (b) units and more preferably all the (b) units being
one or more (b1) unit(s) derived from an olefinic homo- or copolymer carrying
labile hydrogen-containing reactive functions at their ends, and
(c) units derived from at least one diisocyanate.
As used herein, a "cationic unit" is intended to mean any unit that, either due to its own chemical nature, or because of its environment and/or the pH value by which it is surrounded is in a cationic form.
As used herein, "labile hydrogen-containing reactive functions" mean functions that are able, after the departure of a hydrogen atom, to form covalent bonds with the isocyanate functions of the compounds forming the (c) units. Suitable examples of such functions include hydroxyl, primary amine (-NH2) or secondary amine (-NHR), or thiol (-SH) groups.
Polycondensation compounds carrying these labile hydrogen-containing reactive functions with diisocyanates results in polyurethanes, polyureas or polythiourethanes, depending on the nature of the labile hydrogen-carrying reactive functions (-OH, -NH2, -NHR or -SH), respectively. For greater convenience, all these polymers are encompassed in the present application within the polyurethane class. The polymers of the present invention are preferably authentic polyurethanes.
When the tertiary or quaternary amines forming the (a) units do carry more than two labile hydrogen-containing functions, the resulting polyurethanes have a branched structure.

In a preferred embodiment of the polyurethane of the present invention, the tertiary or quaternary amines forming the cationic (a) unit only comprises two labile hydrogen-containing reactive functions and consequently the polyurethanes resulting from the polycondensation have a substantially linear structure.
It is of course also possible to use a mixture composed of difunctional amines comprising a small amount of amines carrying more than two labile hydrogen-containing reactive functions.
The tertiary or quaternary amines forming the cationic (a) units are preferably chosen from compounds corresponding to one of the following formulas:
(Formula Removed)
wherein
each Ra independently represents a linear or branched C1-6 alkylene, C3-6 cycloalkylene or arylene group, where all of them may be substituted with one or more halogen atom(s) and comprise one or more heteroatom(s) chosen from 0, N, P and S,
each Rb independently represents a C1-6 alkyl group, C3-6 cycloalkyl or aryl group, where all of them may be substituted with one or more halogen atom(s) and comprise one or more heteroatom(s) chosen from O, N, P and S,
each X independently represents an oxygen or a sulfur atom or a NH or NRc group, where Rc represents a C1-6alkyl group, and
A* represents a physiologically acceptable counter-ion.
N-methyldiethanol amine and N-tert-butyldiethanol amine are tertiary amines that are particularly preferred for producing said cationic polyurethanes.
Tertiary and quaternary amines forming the cationic (a) units of the polyurethanes of the present invention may also be tertiary and/or quaternary amine function-containing polymers, carrying labile hydrogen-containing reactive functions at their ends. Weight average molecular weight of such tertiary and/or

quaternary amine function-containing polymers is preferably between 400 and 10 000.
As suitable examples of such amine function-containing polymers, polyesters resulting from the polycondensation of N-methyldiethanol amine and adipic add may be mentioned.
When the amines forming the cationic (a) units are tertiary amine function compounds, all or part of these amine functions must be neutralized with a suitable neutralizing agent chosen from physiologically acceptable organic or mineral acids. Hydrochloric acid or acetic acid may be mentioned as preferred acid examples.
The second type of units forming the preferred polyurethanes of the present invention includes macromolecular units, called (b) units, derived from non ionic polymers carrying labile hydrogen-containing reactive functions at their ends and preferably with a glass transition temperature (Tg) lower than 10°C, as measured by differential enthalpy analysis.
According to the invention, at least one of these (b1) units is derived from an olefinic homo- or copolymer.
The polyurethane viscoelastic properties are particularly advantageous when (b) units are derived from polymers having a glass transition temperature lower than 0°C and even more preferably lower than -10°C.
These polymers preferably have a weight average molecular weight of between 400 and 10 000 and more particularly between 1000 and 5000.
Non ionic polymers that can form (b2) non ionic units different from (b1) non ionic units derived from olefinic homo- and copolymers, may be chosen from polyethers, polyesters, polysiloxanes, polycarbonates and fluorinated polymers.
Preferably, polymers that can form said (b) non ionic units are only chosen from olefinic homo- and copolymers.
Olefinic polymers having labile hydrogen-containing reactive groups on their terminal ends, to be suitably used in the present invention, include ethylene, propylene, 1-butylene, 2-butylene, isobutylene, 1,2-butadiene, 1,4-butadiene and isoprene random or block homopolymers and copolymers.
Butadiene and isoprene homo- and copolymers may be partially or fully hydrogenated.
Preferred polymers are copolymers of ethylene and butylene, polybutadienes and hydrogenated polybutadienes carrying on their terminal ends labile hydrogen-containing reactive groups and more particularly hydroxyl groups. Even more preferably, these polymers are 1,2- and/or 1,4- polybutadienes.

Such polymers are commercially available for example under the trade name KRATON® L, more particularly KRATON® L 2203 (hydrogenated polybutadiene diol) from the KRATON polymers company, KRASOL LBH® and LBHP®, especially KRASOL LBHP® 2000 (polybutadiene diol) from the SARTOMER company and Gl® 3000 (copolymer of ethylene and butylene) from the NISSO CHEMICAL company.
The diisocyanates forming the (c) units include aliphatic, alicyclic or aromatic diisocyanates.
Preferred diisocyanates are chosen from methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexyl diisocyanate. These diisocyanates may of course be used alone or as a mixture of two or more diisocyanates. Even more preferably, said diisocyanate is isophorone diisocyanate.
As previously mentioned, cationic polyurethanes of the present invention may contain, in addition to (a), (b1) and (c) units, a certain content of (b2) units derived from compounds, that are generally monomer, non ionic compounds, comprising at least two labile hydrogen functions, different from the compounds leading to the (b1) units.
These (b2) units are generally derived from C1-C12 diols, for example from neopentyl glycol, hexaethylene glycol, 1,2-ethanediol, 1,2-propanediol and 1,3-propanediol or from C1-C6aminoalcohols, for example from aminoethanol.
The cationic polyurethanes of the present invention are preferably elastic.
In a particular embodiment of the invention, said cationic polyurethane does not comprise any further unit in addition to (a), (b) and (c) units. The polyurethane (A) described in the examples is a polyurethane corresponding to such definition.
In an alternative embodiment, the cationic polyurethane comprises further units, in addition to (a), (b) and (c) units. The polyurethane (B) described in the examples is a polyurethane corresponding to such definition.
A physical parameter characterizing the viscoelastic properties of the above cationic polyurethanes is their tensile recovery. Such recovery is determined by a tensile creep test consisting in rapidly stretching a specimen to a predetermined degree of elongation, then in releasing the stress, and lastly in measuring the specimen length.
The creep test used to characterize the cationic polyurethanes with elastic character of the present invention is performed as follows:

The specimen used is a film of polyurethane 500 ± 50 mm-thick, cut into 80 mm x 15 mm strips. This copolymer film is obtained by drying at a temperature of 22 ± 2 °C under a 50 ± 5% relative humidity, a 3% by weight solution or dispersion of said polyurethane in water and/or in ethanol.
Each strip is fixed between two jaws, spaced apart from each other by 50 ± 1 mm, and is stretched at a speed of 20 mm/minute (under the hereabove mentioned temperature and relative humidity conditions) up to a 50% elongation (£max), that is to say until a strip is obtained, which size corresponds to 1.5 times its initial length. The stress is then released by setting a return speed equal to the tensile speed, i.e. 20 mm/minute, and the specimen elongation is then measured (as expressed in % relative to the initial length) immediately once it has returned to a zero load (£,).
The instantaneous recovery (Rj) is calculated using the following equation:
(Equation Removed)
The elastic cationic polyurethanes of the present invention preferably have an instantaneous recovery (Ri), such as measured in the hereabove stated conditions comprised between 5% and 95%, more particularly between 20% and 90% and most preferably between 35 and 85%.
The glass transition temperature (Tg) of the non ionic polymers forming the (b) units and of the cationic polyurethanes of the present invention is measured by means of a differential enthalpy analysis (DSC, differential scanning calorimetry) according to ASTM D3418-97 standard.
Elastic cationic polyurethanes of the present invention preferably presents at least two glass transition temperatures, at least one of which is lower than 10°C, preferably lower than 0°C and even more preferably lower than -10°C, the other one being at least higher than or equal to the room temperature (20°C).
The instantaneous recovery and therefore the viscoelastic properties of the polyurethanes of the present invention depend on the contents of the various (a), (b1), (b2) and (c) monomer units.
The (a) unit content should be preferably sufficient to provide the polymers with their positive charge responsible for their good affinity for keratinic substrates. The (b) units should preferably represent a weight content sufficient for the polyurethanes to have preferably at least one glass transition temperature lower than 10 °C and not to form brittle films.

More preferably, the (a) units represent from 0.1 to 90%, preferably from 1 to 30%, more preferably from 5 to 25% and most preferably from 5 to 10% by weight, the (b1) units from 10 to 99.9%, preferably from 20 to 99% and more preferably from 30 to 85% by weight and the (b2) units from 0 to 50% by weight, preferably from 0 to 30% by weight relative to the total weight of the polyurethane units. Even more preferably, the polyurethanes of the present invention do not comprise any (b2) unit.
Preferably the (c) units represent from 1 to 60%, more preferably from 5 to 50%, most preferably from 10 to 40% of the polyurethane unit total weight.
The (c) units are preferably present in a substantially stoichiometric amount as compared to the sum of (a) and (b) units. Obtaining polyurethanes with high molecular weights requires a number of isocyanate functions almost identical to the number of labile hydrogen functions. The person skilled in the art will be able to choose an optional molar excess of the one function or the other, to adjust the molecular weight to the expected value.
The amount of polyurethane present in a cosmetic composition of the invention of course depends on the composition type and the required properties, and may vary within a very broad range, generally between 0.01 and 40% by weight, preferably between 0.05 and 20%, most preferably between 0.1 and 10% by weight, relative to the final cosmetic composition.
The second main component of the compositions of the present invention is a silicone chosen from polydialkyl siloxanes, and preferably especially polydimethyl siloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene), amino- and alkoxy groups.
Silicones to be used as additives in the cosmetic compositions of the invention are volatile or non volatiles, cyclic, linear or branched silicones, modified with organic groups, or not, and having a viscosity ranging from 5.10"6 to 2.5 m2/s at 25°C and preferably from 1.10"5 to 1 m2/s.
Silicones to be used according to the present invention may be soluble or insoluble in the composition and more particularly may be polyorganosiloxanes insoluble in the composition of the invention. They may be present in the form of oils, waxes, resins or gums.
Organopolysiloxanes are defined in more detail by Walter NOLL in "Chemistry and Technology of Silicones" (1968) Academie Press. They may be volatile or not.

When they are volatile, silicones are more particularly selected from those having a boiling point ranging from 60° C to 260° C, and even more particularly from the following ones:
(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 or 5 silicon atoms. Suitable examples thereof include octamethyl cyclotetrasiloxane marketed in particular under the trade name "VOLATILE SILICONE® 7207" by UNION CARBIDE or "SILBIONE® 70045 V 2" by RHODIA, decamethyl cyclopentasiloxane marketed under the trade name "VOLATILE SILICONE® 7158" by UNION CARBIDE, "SILBIONE® 70045 V 5" by RHODIA, as well as mixtures thereof.
Cyclocopolymers of the dimethyl siloxane / methylalkyl siloxane type may also be mentioned, such as "SILICONE VOLATILE® FZ 3109" marketed by the UNION CARBIDE company, having following formula:

(Formula Removed)

Mixtures of cyclic polydialkyl siloxanes with organic compounds derived from silicon may also be mentioned, such as the octamethyl cyclotetrasiloxane and tetratrimethylsilyl pentaerythritol mixture (50:50) and the octamethyl cyclotetrasiloxane and oxy-1,1'-(hexa-2,2,2',2',3,3'-trimethylsilyloxy) bis-neopentane mixture;
(ii) linear volatile polydialkyl siloxanes having from 2 to 9 silicon atoms and which viscosity is lower than or equal to 5.10-6m2/s at 25° C, as for example decamethyl tetrasiloxane marketed in particular under the trade name "SH 200" by the TORAY SILICONE company. Silicones belonging to this class are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, P. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics".
Non volatile polydialkyl siloxanes are preferably used, polydiaryl siloxanes and polyalkylaryl siloxanes, gums and polydialkyl siloxane resins, polyorganosiloxanes modified with organofunctional groups as well as mixtures thereof.

Said polyalkyl siloxanes are preferably (CrC8)polydialkyl siloxanes and more preferably (Ci-C4)polydialkyl siloxanes.
These silicones are more particularly chosen from polydialkyl siloxanes, from which polydimethyl siloxanes with trimethylsilyl end groups may be especially mentioned. Silicone viscosity is measured at 25°C according to ASTM 445 standard, Appendix C.
These polydialkyl siloxanes encompass, as non limitative examples, the following commercial products:
- SILBIONE® oils of 47 and 70 047 series or MIRASIL® oils marketed by
RHODIA, such as for example fluid 70 047 V 500 000;
- oils of MIRASIL® series marketed by the RHODIA company;
- oils of the 200 series from the DOW CORNING company, especially, such
as DC200 (viscosity 60 000 mm2/s);
- VISCASIL® oils from GENERAL ELECTRIC and certain oils of the SF (SF
96, SF 18) series from GENERAL ELECTRIC.
Dimethylsilanol end group-containing polydimethyl siloxanes, known under the name dimethiconol (CTFA) may also be mentioned, such as oils of the 48 series from the RHODIA company.
This polydialkyl siloxane class also includes products marketed under the trade names "ABIL WAX® 9800 and 9801" by the GOLDSCHMIDT company, which are (C1-C20) polydialkyl siloxanes.
Silicone gums to be suitably used according to the present invention are especially polydialkyl siloxanes, preferably polydimethyl siloxanes having high number average molecular weights comprised between 200 000 and 1 000 000 used either alone or in combination in a solvent. This solvent may be chosen from volatile silicones, polydimethyl siloxanes (PDMS) oils, polyphenylmethyl siloxanes (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or mixtures thereof.
Products to be more particularly used according to the present invention are mixtures such as:
- mixtures formed from an end chain-hydroxylated polydimethyl siloxane
also called dimethiconol (CTFA) and a cyclic polydimethyl siloxane, also called
cyclomethicone (CTFA), such as the Q2 1401 product marketed by the DOW
CORNING company;
- mixtures formed from a polydimethyl siloxane gum and a cyclic Silicone,
such as the SF 1214 Silicone Fluid from the GENERAL ELECTRIC company, this
product being a SF 30 gum corresponding to a dimethicone, having a number

average molecular weight of 500 000, solubilized in the SF 1202 Silicone Fluid corresponding to decamethyl cyclopentasiloxane;
- mixtures from two PDMS with different viscosities, and more particularly from a PDMS gum and a PDMS oil, such as the SF 1236 product from GENERAL ELECTRIC. SF 1236 is a mixture from a SE 30 gum as defined hereabove with a viscosity of 20 nrVs and a SF 96 oil with a viscosity of S.IO^nrVs. Such product comprises preferably 15% of SE 30 gum and 85% of SF 96 oli.
Organopolysiloxane resins to be used according to the present invention are crosslinked siloxane systems comprising units:
RaSiO1a, RaSiO1/2, RSi03/2 and SiO4/2, wherein R represents an alkyl group having from 1 to 16 carbon atoms. Amongst these products, those particularly preferred are those wherein R represents a lower C1-C4 alkyl group, more particularly a methyl group.
These resins also include the product marketed under the trade name "DOW CORNING 593" or those marketed under the trade names "SILICONE FLUID SS 4230 and SS 4267" by the GENERAL ELECTRIC company and which are dimethyl/ trimethyl siloxane-structured silicones.
Resins of the trimethyl siloxysilicate type marketed in particular under the trade names X22-4914, X21-5034 and X21-5037 by the SHIN-ETSU company may also be mentioned.
Polydiaryl siloxanes may be polydiphenyl siloxanes. Polyalkylaryl siloxanes are particularly chosen from linear and/or branched polydimethyl /methylphenyl siloxanes, polydimethyl /diphenyl siloxanes having viscosities ranging from 1.10"5 to 5.10-2m2/s at 25°C.
Suitable examples of such polyalkylaryl siloxanes include products marketed under the following trade names:
. SILBIONE® oils of the 70 641 series from RHODIA;
. oils of RHODORSIL® 70 633 and 763 series from RHODIA;
. DOW CORNING 556 COSMETIC GRAD FLUID from DOW CORNING;
. silicones of the PK series from BAYER, such as the PK20 product;
. silicones of the PN, PH series from BAYER, such as PN1000 and PH1000
products;
. certain oils of the SF series from GENERAL ELECTRIC, such as SF 1023,
SF 1154, SF 1250, SF 1265.

Organomodified silicones to be suitably used according to the invention are silicones such as previously defined, and comprising in their structure one or more organofunctional group(s) bound through a hydrocarbon group.
Organomodified silicones to be suitably used according to the invention include polyorganosiloxanes comprising:
- polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C6-
C24 alkyl groups, such as products called dimethicone copolyol marketed by the
DOW CORNING company under the trade name DC 1248 or SILWET® L 722, L
7500, L 77, L 711 oils from the UNION CARBIDE company and (C12)alkyl
methicone copolyol marketed by the DOW CORNING company under the trade
name Q2 5200;
- amine groups, substituted or not, such as the products marketed under the
trade name GP 4 Silicone Fluid and GP 7100 by the GENESEE company, or the
products marketed under the trade names Q2 8220 and DOW CORNING 929 or
939 by the DOW CORNING company. Substituted amine groups are especially
C1-C4 aminoalkyl groups. Such amino silicones may carry alkoxy groups and
especially methoxy groups, such as BELSIL ADM LOG 1 silicone marketed by the
WACKER company;
- alkoxyl groups, such as the product marketed under the trade name
"SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX® 2428,
2434 and 2440 by the GOLDSCHMIDT company.
The silicones such as described hereabove may be used either alone or in combination, in an amount of between 0.01 and 20% by weight, preferably between 0.1 and 5% by weight.
The cosmetically acceptable aqueous medium may comprise various additives and solvents commonly used in the cosmetic field such as surfactants, gelling agents and/or thickeners, organic solvents, fragrances, mineral, vegetable and/or synthetic oils or waxes, fatty acid esters, pigments and dyes, mineral or organic particles, pH stabilizing agents, preserving agents and UV absorbers.
Surfactants to be used in the composition of the present invention may be anionic, non ionic, amphoteric or cationic surfactants, or mixtures thereof.
Suitable anionic surfactants to be used either alone or in combination in the context of the present invention include especially salts, and more particularly alkaline metal salts such as sodium salts, ammonium salts, amine salts, aminoalcohol salts or alkaline-earth metal salts, for example, magnesium salts, of following compounds: alkyl sulfates, alkyl ethersulfates, alkyl amidoethersulfates, alkylaryl polyethersulfates, monoglyceride sulfates; alkyl sulfonates, alkyl

amidesulfonates, alkyl-aryl sulfonates, α-olefin sulfonates, paraffin sulfonates; alkyl sulfosuccinates, alkyl ethersulfosuccinates, alkylamide sulfosuccinates; alkyl sulfoacetates; acyl sarconisates; and acylglutamates, alkyl and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group preferably corresponding to a phenyl or benzyl group.
Polyglycoside carboxylic acid and C6-C24 alkyl esters may also be used in the context of the present invention, such as alkyl glucoside citrates, alkyl polyglycoside tartrates and alkyl polyglycoside sulfosuccinates; as well as alkyl sulfosuccinamates, acyl isethionates and N-acyl taurates, the alkyl or acyl group of all these compounds comprising from 12 to 20 carbon atoms. As further anionic surfactants to be suitably used, acyl lactylates the acyl group of which comprises from 8 to 20 carbon atoms may also be mentioned.
Moreover, alkyl-D-galactoside uronic acids and salts thereof may also be mentioned, as well as polyoxyalkylene (C6-C24)alkylether carboxylic acids, polyoxyalkylene (C6-C24)alkyl(C6-C24)arylether carboxylic acids, polyoxyalkylene (C6-C24)alkylamidoether carboxylic acids and salts thereof, more particularly those comprising from 2 to 50 ethylene oxide groups, and mixtures thereof.
Amongst the hereabove mentioned anionic surfactants, it is preferred to use according to the present invention (C6-C24)alkyl sulfates, (Ce-C24)alkyl ethersulfates, (C6-C24)alkyl ethercarboxylates and mixtures thereof, for example ammonium lauryl sulfate, sodium lauryl sulfate, magnesium lauryl sulfate, sodium lauryl ethersulfate, ammonium lauryl ethersulfate and magnesium lauryl ethersulfate.
Non ionic surfactants to be used in the context of the present invention are also compounds that are well known per se (for a review thereof, see especially "Handbook of Surfactants" M.R. PORTER, Blackie & Son Editor (Glasgow and London), 1991, pp 116-178). They may be especially chosen from alcohols, alpha-diols, (Ci-C2o)alkyl phenols or polyethoxylated, polypropoxylated or polyglycerolated fatty acids, having a fatty chain comprising for example from 8 to 18 carbon atoms, where the number of ethylene oxide or propylene oxide groups may especially amount up to from 2 to 50 and the number of glycerol groups may especially amount up to from 2 to 30. Also to be mentioned are copolymers of ethylene oxide and propylene oxide, condensation products of ethylene oxide and propylene oxide on fatty alcohols; polyethoxylated fatty amides having preferably from 2 to 30 moles of ethylene oxide; polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and more particularly from 1.5 to 4; polyethoxylated fatty amines having preferably from 2 to 30 moles of ethylene

oxide; sorbitane fatty acid esters ethoxylated with from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, (Ce-C24)alkyl polyglucosides, (C6-C24)N-alkyl glucamine derivatives, amine oxides such as (Cio-Ci4)alkyl amine oxides or (C10-C14)N-acyl aminopropylmorpholine oxides; and mixtures thereof.
Amongst the previously mentioned non ionic surfactants, the (C6-C24)alkyl polyglycosides are preferably used, more particularly decyl polyglucoside.
Amphoteric surfactants to be suitably used in the present invention may be especially secondary or tertiary aliphatic amine derivatives, wherein the aliphatic group is a linear or a branched chain comprising from 8 to 22 carbon atoms and containing, at least one hydrosolubilizing anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group; (C8-C2o)alkyl betaines, sulfobetaines, (C8-C2o)alkyl (C6-C8)amidoalkyl betaines or (C8-C2o)alkyl (C6-C8)amidoalkyl sulfobetaines; as well as mixtures thereof, may also be mentioned.
Amongst the amine derivatives, products marketed under the trade name MIRANOL® may be mentioned, such as those described in patents US 2,528,378 and US 2,781,354 and classified in the CTFA dictionary, third Edition, 1982, under the names amphocarboxyglycinate and amphocarboxypropionate having respectively following structures (1) and (2): R2 -CONHCH2CH2 -N+(R3)(R4)(CH2COO') (1)
wherein:
R2 represents an alkyl group derived from a R2-COOH acid present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl group,
R3 represents a beta-hydroxyethyl group, and
R4 represents a carboxymethyl group; and R2 -CONHCH2CH2 -N(B)(C) (2)
wherein:
B represents -CH2CH2OX',
C represents -(CH2)Z -Y', with z = 1 or 2,
X1 represents a -CH2CH2-COOH group or a hydrogen atom,
Y' represents -COOH or a -CH2 - CHOH - SO3H group,
R2 represents the alkyl group of a R2-COOH acid present in hydrolyzed coconut oil or linseed oil, an alkyl group, especially a C17alkyl group and its iso-form, an unsaturated C17 group.

These compounds are classified in the CTFA dictionary, 5th Edition, 1993,
under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate,
disodium capryl amphodiacetate capryloamphodiacetate, disodium
cocoamphodipropionate, disodium lauroamphodipropionate, disodium
caprylamphodipropionate, disodium capryloamphodipropionate,
lauroamphodipropionic acid, cocoamphodipropionic acid.
The cocoamphodiacetate marketed under the trade name MIRANOL® C2M concentrated by the RHODIA company is a suitable example thereof.
Amongst suitable amphoteric surfactants, (C8-C2o)alkyl betaines are preferably used, such as coco betaine, (C8-C2o)alkyl (C6-C8)amidoalkyl betaines such as cocamido betaine, alkyl amphodiacetates such as disodium cocoamphodiacetate, and mixtures thereof.
Moreover, the composition of the present invention may further comprise one or more cationic surfactant(s) that are well known per se, such as salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated, quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyl trialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides, imidazoline derivatives; or amine oxides of cationic nature.
The previously described non ionic, amphoteric, anionic and cationic surfactants may be used either alone or in combination. The surfactant(s) do(es) represent from 0.01 to 60% by weight, preferably from 0.1 to 30% and most preferably from 1 to 20% by weight relative to the composition total weight.
Gelling agents and/or thickeners that may be suitably used in the compositions of the present invention are well known in the art and may be chosen from carboxyvinyl polymers and copolymers, (alkyl) acrylic polymers and copolymers, (alkyl) acrylamide polymers and copolymers, poly(oxyalkylene) glycols, poly(oxyalkylene) glycol esters, alginates, biosaccharides, polysaccharides such as cellulose and starch derivatives, naturally occurring gums such as xanthan gum, guar gum, locust bean gum, scleroglucans, chitin and chitosan derivatives, carrageenans, clays, and mixtures thereof.
As an example of gelling agents, especially in an aqueous phase, SEPIGEL® 305 marketed by the SEPPIC company, FUCOGEL® 1000 PP marketed by the SOLABIA company, SYNTHALEN® K marketed by the 3VSA company, LUVISKOL® VA 64 P marketed by the BASF company, HOSTACERIN® AMPS marketed by the CLARIANT company, PEMULEN® TR1 marketed by the GOODRICH company, LUBRAGEL® MS marketed by the GUARDIAN company,

SATIAGEL® KSO marketed by DEGUSSA and KELTROL® marketed by the KELCO company may be mentioned.
The gelling agent represents generally from 0.1 to 15%, preferably from 0.5 to 10% by weight of the composition.
The compositions of the present invention may also comprise fatty components such as mineral, vegetable, animal and synthetic oils, waxes, fatty esters, fatty alcohols, and fatty acids.
Suitable examples of oils to be used in the composition of the invention include:
- animal-based hydrocarbon oils, such as perhydrosqualene;
- vegetable-based hydrocarbon oils, such as liquid triglycerides of fatty acids
comprising from 4 to 10 carbon atoms such as triglycerides of the heptanoic or
octanoic acids, or for example sunflower oil, corn oil, soja bean oil, pumpkin oil,
grape seed oil, sesame oil, nut oil, apricot kernel oil, macadamia nut oil, arara oil,
castor oil, avocado oil, triglycerides of caprylic/capric acids such as those
marketed by the Stearineries Dubois company or those sold under the names
Miglyol® 810, 812 and 818 by the Dynamit Nobel company, jojoba oil, shea butter
oil;
- linear or branched, mineral or synthetic hydrocarbons, such as volatile or non
volatile paraffin oils, and their derivatives, petrolatum, polydecenes, hydrogenated
polyisobutene such as Parleam®; isoparaffines such as isohexadecane and
isodecane.
- partly hydrocarbon-based and/or silicone-based fluorinated oils, such as those
described in the patent application JP-A-2-295912; fluorinated oils also
encompass perfluoromethyl cyclopentane and perfluoro-1,3 dimethylcyclohexane,
sold under the names "FLUTEC® PC1" and "FLUTEC® PC3" by the BNFL
Fluorochemicals company; perfluoro-1,2-dimethyl cyclobutane; perfluoroalkanes
such as dodecafluoropentane and tetradecafluorohexane, sold under the names
"PF 5050®" and "PF 5060®" by the 3M company, or bromoperfluorooctyle sold
under the trade name "FORALKYL®" by the Atochem company;
nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine
derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the trade
name "PF 5052®" by the 3M company;
The wax(es) is or are in particular chosen from Carnauba wax, Candellila wax, and Alfa wax, paraffin, ozokerite, vegetable waxes such as olive tree wax, rice wax, hydrogenated jojoba wax or flower absolute waxes such as Ribes nigrum (blackcurrant) flower wax sold by the BERTIN company (France), animal waxes

such as beeswax, or modified beeswaxes (cerabellina); other waxes or wax-based raw materials to be used according to the present invention are also marine waxes such as the one sold by the SOPHIM company under the reference M82, polyethylene waxes or polyolefms in general.
Saturated or unsaturated fatty acids are more particularly chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid.
Fatty esters are especially carboxylic acid esters, more particularly mono, di, tri or tetracarboxylic esters.
Carboxylic acid esters are especially saturated or unsaturated, linear or branched, Ci-C26 aliphatic acid esters and saturated or unsaturated, linear or branched, Ci-C26 aliphatic alcohol esters, where the total number of the ester carbon atoms is higher or equal to 10.
Suitable examples of monoesters to be mentioned include dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate, isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates, such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; di octyl malate, hexyl laurate, 2-hexyldecyl laurate.
C4-C22 di- or tricarboxylic acid and Ci-C22 alcohol esters may also be used, as well as mono-, di- or tricarboxylic acid esters and di-, tri-, tetra- or pentahydroxy C2-C26 alcohol esters.
To be especially mentioned are diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di n-propyl adipate; dioctyl adipate; di isostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetraerygonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl .citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; and polyethylene glycol distearates.

Amongst the previously mentioned esters, it is preferred to use ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates, such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate.
Suitable fatty alcohols include for example saturated or unsaturated, linear or branched fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol.
Fatty components generally represent from 0.01 to 50%, preferably from 1 to 30%, and even more preferably, from 2 to 20% by weight of the total composition.
The cosmetically acceptable aqueous medium of the composition, in addition to water, may further comprise one or more organic solvent(s).
The organic solvent is typically chosen from Ci-Ce alcohols, preferably alkanols, such as ethanol, propanol and isopropanol, alkanediols such as propylene glycol and pentanediols, benzyl alcohol, Cs-Cio alkanes, acetone, methyl ethylcetone, methyl acetate, butyl acetate, ethyl acetate, dimethoxyethane, diethoxyethane and mixtures thereof.
The organic solvent is generally present in an amount ranging from 0.5 to 80% and preferably from 1 to 50% by weight of the composition total weight.
The person skilled in the art will be able to add some additives without affecting the properties of the compositions of the invention.
The compositions of the present invention are preferably hairstyling compositions which may be rinsed off, such as styling shampoos or not rinsed off, such as styling lotions, foams or gels.
They may be in the form of a styling lotion or a styling gel. They also may be conditioned in the form of an aerosol. In that case, the composition will of course comprise a propellant. As is well known, said propellant may be a gas or a mixture of compressed or liquefied gases, that may optionally be dissolved in the composition. Examples of suitable gas propellants encompass air, carbon dioxide, nitrogen, dimethyl ether, hydrocarbons such as propane, n-butane, isobutane or isopentane and halogenated hydrocarbons, more particularly fluorinated hydrocarbons. Silicones that are present in the compositions of the invention, may be initially introduced into or blend with the composition immediately prior to being applied.

When organomodified silicones by alkoxy groups are used, the silicone will be preferably blend before the application.
Formulation examples
(Table Removed)
Example 2 - Styling gel:
(Table Removed)
1 (A) Polyurethane in an aqueous dispersion formed from 8.7% of N-methyl
diethanol amine, 23.4% of isophorone diisocyanate, 67.9% of KRASOL LBH2000
(polybutadiene with hydroxyl end functions), and neutralized up to 40% using
hydrogen chloride.
2 Amodimethicone
3 Gelling agent (hydroxypropyl guar)
4 Water-dispersible silicone glycol
With the compositions prepared in the examples, good cosmetic properties were obtained without substantially reducing the hair fixation and hold as time goes. "Strand-effect" hair style with short hair and long-lasting hair plastering down with African hair were obtained using these compositions. They were easily removable with shampoo.
A similar result was obtained with a (B) polyurethane in an aqueous dispersion formed from 8.4% of poly(tetramethylene oxide), 8.6% of N-methyl diethanol amine, 21.4% of isophorone diisocyanate, 61,6% of KRATON L2203 (polybutadiene with hydroxyl end functions), and neutralized up to 40% using hydrogen chloride.

CLAIMS
1. A cosmetic composition comprising, in a cosmetically acceptable
aqueous medium:
(i) at least one cationic polyurethane comprising at least one non ionic unit derived from an olefinic homopolymer or copolymer, and
(ii) at least one silicone chosen from polydialkyl siloxanes and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene), amine and alkoxy groups.
2. A cosmetic composition according to claim 1, wherein 50% by weight,
or more, of the polyurethane non ionic units are derived from an olefinic
homopolymer or copolymer.
3. A cosmetic composition according to claim 1, wherein all the
polyurethane non ionic units are derived from an olefinic homopolymer or
copolymer.
4. A cosmetic composition according to any one of claims 1 to 3, wherein
said olefinic homopolymers and copolymers are homopolymers and copolymers
carrying labile hydrogen functions at their ends, and comprising units chosen from
ethylene, propylene, 1-butylene, 2-butylene, isobutylene, 1,2-butadiene, 1,4-
butadiene, isoprene units and mixtures thereof.
5. A cosmetic composition according to claim 4, wherein said olefinic
homopolymers and copolymers are derived from optionally hydrogenated 1,2-
and/or 1,4-butadiene.
6. A cosmetic composition according to any one of the preceding claims,
wherein the cationic polyurethane comprises:

(a) cationic units resulting from the reaction of at least one tertiary or
quaternary amine comprising at least two labile hydrogen-containing reactive
functions,
(b) non ionic units, at least one (b1) unit of which results from the reaction
of at least one polymer chosen from olefinic homopolymers and copolymers
carrying labile hydrogen-containing reactive functions at their ends and having a
glass transition temperature (Tg), such as measured with a differential enthalpy
analysis, lower than 10QC, and
(c) units resulting from the reaction of at least one diisocyanate.
7. A cosmetic composition according to claim 6, wherein the cationic (a)
units result from the reaction of at least one tertiary or quaternary amine
comprising two labile hydrogen-containing reactive functions.

8. A cosmetic composition according to claim 7, wherein said amine is chosen from amines having following formulas:
(Formula Removed)
wherein
each Ra independently represents a linear or branched C1-C6 alkylene group, a C3-C6 cycloalkylene or an arylene group, or mixtures thereof; where all of them may be substituted with one or more halogen atom(s) and comprise one or more heteroatom(s) chosen from 0, N, P and S,
each Rb independently represents a C1-C6 alkyl group, a C3-C6 cycloalkyl or an aryl group, or mixtures thereof; where all of them may be substituted with one or more halogen atom(s) and comprise one or more halogen atom(s) and comprise one or more heteroatom(s) chosen from 0, N, P and S,
each X independently represents an oxygen or a sulfur atom or a NH or NRc group, where Rc represents a C1-C6 alkyl group, and
A" represents a physiologically acceptable counter-ion.
9. A cosmetic composition according to claim 8, wherein the cationic (a)
units result from the reaction of N-methyldiethanol amine or N-tert-butyldiethanol
amine.
10. A cosmetic composition according to claim 7, wherein the (a) units
result from the reaction of at least one tertiary and/or quaternary amine function-
containing polymer, carrying labile hydrogen-containing reactive functions at their
ends chosen from -OH, -NH2, -NHRC or -SH, and having a weight average molecular weight comprised between 400 and 10 000, where Re represents a C1-C6 alkyl group.
11. A cosmetic composition according to any one of claims 6 to 10,
wherein the cationic polyurethane optionally comprises at least one non ionic (b2)
unit, different from (b1) unit, derived from a non ionic monomer compound
comprising at least two labile hydrogen functions that can react with said (c)
compounds comprising at least one diisocyanate.
12. A cosmetic composition according to claim 11, wherein the cationic (a)
units represent from 0.1 to 90%, preferably from 1 to 30%, more preferably from 1
to 20% by weight, the non ionic units derived from a (b1) olefinic homo- or
copolymer represent from 10 to 99.9%, preferably from 20 to 99% and more
preferably from 30 to 85% by weight, and the (b2) non ionic units represent from 0
to 50%, preferably from 0 to 30% by weight of the cationic polyurethane total units.
13. A cosmetic composition according to any one of claims 6 to 11,
wherein said diisocyanate is chosen from methylenediphenyl diisocyanate,
methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene
diisocyanate, naphthalene diisocyanate, 1,4-butane diisocyanate and 1,6-hexane
diisocyanate.
14. A cosmetic composition according to claim 13, wherein said
diisocyanate is isophorone diisocyanate.
15. A cosmetic composition according to any one of claims 6 to 14,
wherein the (c) units represent from 1 to 60%, preferably from 5 to 50%, and most
preferably from 1 to 40% by weight of the cationic polyurethane total units.
16. A cosmetic composition according to any one of claims 6 to 15,
wherein said non ionic monomer compound(s) forming the (b2) non ionic units are
chosen from C1-C12 diols, preferably neopentyl glycol, hexa(ethylene glycol), 1,2-
ethanediol, 1,2-propanediol and 1,3-propanediol, and C1-C6 aminoalcohols,
preferably aminoethanol.
17. A cosmetic composition according to any one of claims 6 to 16,
wherein the cationic polyurethane does not comprise any further unit in addition to
(a), (b) and (c) units.
18. A cosmetic composition according to any one of claims 6 to 17,
wherein the cationic polyurethane is of the elastic type.
19. A composition according to any one of the preceding claims, wherein
said cationic polyurethane(s) do(es) represent from 0.01% to 40%, preferably from
0.05 to 20% and most preferably from 0.1 to 10% by weight relative to the final cosmetic composition.
20. A composition according to any one of the preceding claims, wherein
said polydialkyl siloxanes are cyclic, linear or branched polydialkyl siloxanes,
preferably polydimethyl siloxanes.
21. A composition according to any one of the preceding claims, wherein
said polydialkyl siloxanes are polydimethyl siloxanes, that have been
organomodified with poly(oxyalkylene) groups, amine groups, substituted or not,
preferably aminoC1-C4 alkyl groups and alkoxy groups, preferably CrC4 alkoxy
groups.
22. A composition according to any one of the preceding claims, wherein
said silicone(s) do(es) represent from 0.01 to 20% by weight, preferably from 0.1
to 5% by weight of the composition.
23. A composition according to any one of the preceding claims, wherein
said polydialkyl siloxanes are polydialkyl(C1-C8)siloxanes and preferably
polydialkyl(C1-C4)siloxanes.
24. A composition according to any one of the preceding claims, which
comprises one or more additives chosen from gelling agents and/or thickeners,
surfactants, organic solvents, fragrances, mineral, vegetable and/or synthetic oils,
fatty add esters, pH stabilizing agents, preserving agents and UV absorbers.
25. A composition according to any one of the preceding claims, which
comprises a gas propellant and is conditioned in the form of an aerosol.
26. A hairstyling method comprising applying onto the hair a composition
according to any one of claims 1 to 25, then optionally rinsing the hair, and styling
and drying the hair.