WO2016001239A1

WO2016001239A1 - Composition comprising an aqueous phase and a fatty phase that are visually distinct

Info

Publication number: WO2016001239A1
Application number: PCT/EP2015/064872
Authority: WO
Inventors: Anne-Sophie BRAC DE LA PERRIERE; Valérie Vieira; Ségolène DE MENTHIERE; Gérard Gabin
Original assignee: L'oreal
Priority date: 2014-06-30
Filing date: 2015-06-30
Publication date: 2016-01-07
Also published as: FR3022774B1; FR3022774A1

Abstract

The present invention relates to a composition comprising: - a fatty phase comprising at least one oil and at least one fatty-phase thickener; - an aqueous phase comprising at least one thickening polymer comprising one or more acrylic and/or methacrylic units and at least one fixing polymer comprising at least one vinylpyrrolidone unit, the two phases being visually distinct.

Description

COMPOSITION COMPRISING AN AQUEOUS PHASE AND A FATTY PHASE THAT

ARE VISUALLY DISTINCT

The present invention relates to a composition comprising a fatty phase and an aqueous phase that are visually distinct, the aqueous phase comprising at least one specific aqueous-phase thickening polymer and a specific fixing polymer and the fatty phase comprising at least one oil, and to a hair treatment process comprising the application of the composition.

In the field of hairstyling, in particular among hair products intended for shaping and/or form retention of the hairstyle, hair compositions are generally in the form of hair gels, lotions, mousses or sprays.

In particular, hair gels allow good form retention of the head of hair. However, many hair gels do not give the hair sufficient cosmeticity and the final result lacks a natural look.

In addition, the majority of hair gels have a uniform appearance that is not very appealing.

It has already been proposed to make compositions comprising visually distinct phases, as described, for example, in patent applications WO 2006/093 742, WO 2006/042 179, WO 2006/010 090 or WO 2007/004 200. In practice, the weight ratio between the various phases can only generally vary within a limited range of values and the preparation of these compositions is often difficult, for a stability of the compositions obtained that is not entirely satisfactory.

Moreover, haircare products often use conditioning agents, especially oils. Anhydrous compositions containing oils very often lead to hair that feels too greasy. In aqueous compositions, a limitation is very often posed by the very low solubility of oils in water, generally imposing the use of surfactants in aqueous compositions containing these oils, often with, as a corollary, an opaque final appearance of creamy emulsion type.

There is thus a real need to find compositions which care for the hair and which allow easy formulation of oils in aqueous medium.

There is also a need to find hairstyling compositions which allow good hairstyle form retention while at the same time giving the hair cosmeticity.

There is also a need to find compositions, especially for hairstyling, which make it possible to obtain a hairstyle with a natural look.

There is also a need to find cosmetic compositions that have a novel, more attractive aesthetic look.

The Applicant has discovered that the choice of an aqueous phase comprising at least one thickening polymer comprising one or more acrylic or methacrylic units and at least one fixing polymer comprising at least one vinylpyrrolidone unit and of a fatty phase comprising at least one oil, in which the two phases are visually distinct, makes it possible to satisfy at least one of these needs.

Thus, one subject of the present invention is a composition, preferably a cosmetic composition, comprising:

- a fatty phase comprising at least one oil and at least one fatty-phase thickener;

- an aqueous phase comprising at least one thickening polymer comprising one or more acrylic and/or methacrylic units and at least one fixing polymer comprising at least one vinylpyrrolidone unit, the two phases being visually distinct.

The present invention makes it possible to produce aesthetic compositions which give the hair cosmeticity while providing a good level of hold.

It is thus possible to obtain a composition which comprises a relatively large amount of oil.

A subject of the invention is also the use of the said composition for shaping the hair.

In the text hereinbelow, the expression "at least one" is equivalent to "one or more" and, unless otherwise indicated, the limits of a range of values are included in that range.

The composition according to the invention comprises two visually distinct phases. The term "two visually distinct phases" means that the phases may be distinguished from each other by a person's naked eye, unlike phases forming homogeneous emulsions or dispersions of particles. Preferably, at least one of the phases occupies zones forming swirls or marbling, preferably more than 1 cm in length. Preferably, one of the phases is not in the form of globules. More preferably still, none of the phases is in the form of globules.

The two phases are visually distinct in a stable manner, namely the zones occupied by the two phases do not move in response to a simple turning of the container which contains them, when no other stress is applied to the composition. The two phases are not capable of mixing when the container which contains them is shaken. The two phases especially do not constitute two-phase liquids, in which two distinct phases occupy zones one above the other which mix together when the container is turned over.

As mentioned previously, the composition according to the invention comprises a fatty phase. The fatty phase of the composition in accordance with the invention comprises at least one oil.

The term "oil" means any fatty substance that is in liquid form at room temperature (25°C) and at atmospheric pressure.

The oil(s) present in the composition may be volatile or non-volatile.

The volatile or non-volatile oils may be hydrocarbon-based oils, in particular of animal or plant origin, synthetic oils, silicone oils or fluoro oils, or mixtures thereof.

For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-0 group.

The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms, and optionally oxygen, nitrogen, sulfur and/or phosphorus atoms. A hydrocarbon-based oil does not comprise any silicon atoms.

Non-volatile oils

For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapour pressure of less than 0.13 Pa (0.01 mmHg).

The non-volatile oils may be chosen in particular from non-volatile hydrocarbon- based oils, which may be fluorinated, and/or non-volatile silicone oils.

As non-volatile hydrocarbon-based oils that are suitable for use in the invention, mention may be made in particular of:

- hydrocarbon-based oils of animal origin,

- hydrocarbon-based oils of plant origin such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate, for example sold under the name Eldew PS203 by Ajinomoto, triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C₄ to C₂₄, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially heptanoic or octanoic triglycerides, sweet almond oil, argan oil, avocado oil, groundnut oil, camellia oil, safflower oil, beauty-leaf oil, rapeseed oil, copra oil, coriander oil, marrow oil, wheatgerm oil, jojoba oil or liquid jojoba wax, linseed oil, macadamia oil, corn germ oil, hazelnut oil, walnut oil, vernonia oil, apricot kernel oil, olive oil, evening primrose oil, palm oil, passion flower oil, grapeseed oil, rose oil, castor oil, rye oil, sesame oil, rice bran oil, camelina oil, soybean oil, sunflower oil, pracaxi oil, babassu oil, mongongo oil, marula oil, arara oil, shea butter oil, Brazil nut oil; or alternatively caprylic/capric acid triglycerides, for instance those sold by Stearinerie Dubois or those sold under the names Miglyol 810®, 812® and 818® by Dynamit Nobel, and the refined plant perhydrosqualene sold under the name Fitoderm by Cognis;

- hydrocarbon-based oils of mineral or synthetic origin, for instance: • synthetic ethers having from 10 to 40 carbon atoms;

• linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and squalane, and mixtures thereof, and in particular hydrogenated polyisobutene;

· synthetic esters, for instance oils of formula RiCOOR₂ in which R-i represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R₂ represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms provided that R-i + R₂≥ 10.

The esters may be chosen especially from esters, especially fatty acid esters, for instance:

o cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl benzoates, polyethylene glycol diheptanoate, propylene glycol di(2-ethylhexanoate), and mixtures thereof, Ci₂-Ci₅ alcohol benzoates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters, for instance isostearyl lactate and diisostearyl malate;

o polyol esters and pentaerythritol esters, for instance dipentaerythrityl tetrahydroxystearate/tetraisostearate;

o esters of diol dimers and of diacid dimers, such as Lusplan DD-DA5® and Lusplan DD-DA7® sold by Nippon Fine Chemical and described in patent application FR 03/02809;

• fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2- octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol,

• non-salified higher fatty acids such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof, and

· dialkyl carbonates, the two alkyl chains possibly being identical or different, such as the dicaprylyl carbonate sold under the name Cetiol CC® by Cognis; • and mixtures thereof.

The non-volatile silicone oils are chosen, for example, from non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups that are pendent and/or at the end of a silicone chain, these groups each having from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicat.es, and dimethicones or phenyl trimethicones with a viscosity of less than or equal to 100 cSt, and mixtures thereof.

The non-volatile oils may be chosen from mixtures of hydrocarbon-based and silicone non-volatile oils.

Volatile oils

For the purposes of the present invention, the term "volatile oil" means an oil (or non-aqueous medium) that is capable of evaporating on contact with the skin in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at room temperature, especially having a non-zero vapour pressure, at room temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10^"3 to 300 mmHg), in particular ranging from 1 .3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

The volatile hydrocarbon-based oils may be chosen from hydrocarbon-based oils having from 8 to 16 carbon atoms, and in particular branched C₈-Ci₆ alkanes (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar® or Permethyl®.

Volatile fluoro oils such as nonafluoromethoxybutane or perfluoromethyl- cyclopentane, and mixtures thereof, may also be used.

Volatile oils that may also be used include volatile silicones, for instance volatile linear or cyclic silicone oils, especially those with a viscosity < 8 centistokes (8x10⁶ m²/s), and especially having from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made in particular of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyl- cyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof. It is also possible to use a mixture of hydrocarbon-based and silicone volatile oils.

The oil(s) are preferably chosen from C₆-Ci₆ lower alkanes; linear or branched hydrocarbons of mineral or synthetic origin having more than 16 carbon atoms, non- silicone oils of animal origin; oils of plant origin; fluoro oils; liquid fatty alcohols; liquid fatty esters; non-salified liquid fatty acids; silicone oils; or mixtures thereof, and are preferably chosen from C₆-Ci₆ lower alkanes; linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms; liquid fatty alcohols; oils of plant origin; or mixtures thereof; and even more preferably chosen from oils of plant origin and liquid fatty alcohols.

The oil(s) are preferably present in a content ranging from 0.1 % to 20%, more preferentially in an amount ranging from 1 % to 10%, and better still in an amount ranging from 1 .5% to 5% by weight, relative to the total weight of the composition. The fatty phase of the composition comprises also one or more fatty-phase thickener(s) and especially oils.

According to the present invention, the term "fatty-phase thickener" means compounds which, by their presence, increase the viscosity of the fatty phase into which they are introduced by at least 20 cps and preferably by at least 50 cps, at 25°C and at a shear rate of 1 s^"1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheometer or the like).

The notion of a fatty-phase thickener is analogous to the notion of a lipophilic thickener.

The fatty-phase thickener(s) used in the composition according to the invention may be mineral or organic.

The mineral fatty-phase thickeners that may be used in the composition according to the invention are preferably mineral particles constituted essentially of mineral oxides and/or hydroxides.

These particles are preferably insoluble in water at room temperature (25°C) and atmospheric pressure (1 atm). The term "insoluble" means a solubility of less than 0.5% by weight in water.

Preferably, the number-average primary size of these mineral particles ranges from 0.01 to 500 μηη, it preferably ranges from 0.1 to 200 μηη and even more preferentially it ranges from 1 to 100 μηη.

For the purposes of the present invention, the term "primary particle size" means the maximum dimension that it is possible to measure between two diametrically opposite points of an individual particle. The size of the mineral particles may be determined by transmission electron microscopy or by measuring the specific surface area via the BET method or by laser particle size analysis.

The mineral particles that may be used in accordance with the invention may be in various forms, for example in the form of spheres, needles, flakes or platelets.

In a preferred variant of the invention, the mineral fatty-phase thickener(s) are platelet-shaped particles.

The mineral fatty-phase thickener(s) that may be used in the composition according to the invention may preferably be chosen from silicas and silicates.

The silicates of the invention may be natural or chemically modified (or synthetic).

Silicates correspond to optionally hydrated silica in which some of the silicon atoms are replaced with metal cations such as Al³⁺, B³⁺, Fe³⁺, Ga³⁺, Be²⁺, Zn²⁺, Mg²⁺, Co³⁺, Ni³⁺, Na⁺, Li⁺, Ca²⁺, Cu²⁺.

More particularly, the silicates that may be used in the context of the invention are chosen from clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the vermiculite, stevensite and chlorite families.

These clays can be of natural or synthetic origin. Use is preferably made of clays which are cosmetically compatible with and acceptable to keratin materials.

The silicate may be chosen from montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof.

Mention may thus be made of the compounds sold by Laporte under the name Laponite XLG and Laponite XLS. The silicate(s) are preferably chosen from bentonites and hectorites.

The silicate(s) may be modified with a compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.

As silicates that may be suitable for use, mention may be made of quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst, Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites such as those sold under the names Bentone 27 by by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone APA by Southern Clay; quaternium-18/benzalkonium bentonites such as those sold under the names Claytone HT and Claytone PS by Southern Clay; quaternium-18 hectorites such as those sold under the names Bentone Gel DOA, Bentone Gel EC05, Bentone Gel EUG, Bentone Gel IPP, Bentone Gel ISD, Bentone Gel SS71 , Bentone Gel VS8 and Bentone Gel VS38 by Rheox, and Simagel M and Simagel SI 345 by Biophil.

The silicates that may be used in the composition according to the invention may be chosen, in particular, from modified hectorites such as hectorite modified with a Cio- Ci2 fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride.

As explained previously, the mineral fatty-phase thickener(s) that may be used in the composition according to the invention may be silicas.

The silicas that may be used in the composition according to the invention are preferably fumed silicas.

Fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas which bear a large number of silanol groups at their surface. Such hydrophilic silicas are sold, for example, under the names Aerosil 130^®, Aerosil 200^®, Aerosil 255^®, Aerosil 300^® and Aerosil 380^® by Degussa, and Cab-O-Sil HS-5^®, Cab-O-Sil EH-5^®, Cab-O-Sil LM-130^®, Cab-O- Sil MS-55^® and Cab-O-Sil M-5^® by Cabot.

It is possible to chemically modify the surface of the said silicas, via a chemical reaction generating a reduction in the number of silanol groups. It is possible in particular to replace silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups may be:

(a) trimethylsiloxy groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "Silica silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R812^® by Degussa and Cab-O-Sil TS-530^® by Cabot;

(b) dimethylsilyloxy or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "Silica dimethyl silylate" according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R972^® and Aerosil R974^® by Degussa and Cab-O-Sil TS-610^® and

Cab-O-Sil TS-720^® by Cabot.

Preferably, the fumed silicas that may be used in the composition according to the invention are hydrophilic, such as the product sold under the name Aerosil 200^®.

Preferably, the mineral fatty-phase thickener(s) are chosen from organophilic clays and hydrophilic fumed silicas, and mixtures thereof. More preferentially, the mineral fatty-phase thickeners are chosen from hectorites modified with a C10-C12 fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride, and hydrophilic fumed silicas such as the hydrophilic silicas sold under the name Aerosil 200^®

Even more preferentially, the mineral fatty-phase thickeners are chosen from hectorites modified with a C10-C12 fatty acid ammonium chloride, especially hectorite modified with distearyldimethylammonium chloride, such as the product sold under the name Bentone 38VCG by Elementis, and the hectorite modified with stearylbenzyldimethylammonium chloride, such as the product sold under the name Bentone 27V by Elementis.

As explained previously, the fatty-phase thickener(s) that may be used in the composition according to the invention may also be chosen from organic fatty-phase thickeners.

The organic fatty-phase thickener(s) may be chosen especially from semicrystalline polymers, non-silicone polyamides, silicone polyamides, monoalkyi or polyalkyl esters of saccharides or of polysaccharides, N-acylamino acid amide derivatives, copolymers comprising an alkylene and/or styrene block, and elastomeric organopolysiloxanes, and mixtures thereof. These copolymers may be diblock, triblock or multi-block polymers, radial-block polymers, also known as star copolymers, or alternatively comb polymers.

Preferably, the fatty-phase thickener(s) are chosen from mineral thickeners.

More preferably still, the fatty-phase thickener(s) are chosen from mineral thickeners of silicate type, more preferably still from hectorites and bentonites.

Preferably, the fatty-phase thickeners are present in a content ranging from

0.05% to 10% by weight and preferably from 0.075% to 5% by weight relative to the total weight of the composition.

According to a preferred embodiment, the fatty phase comprises at least one mineral thickener in a content of greater than 0.05% by weight relative to the total weight of the composition.

The fatty phase of the composition may also comprise any usual liposoluble or lipodispersible additive, for instance other solid or pasty fatty substances such as waxes, fatty alcohols and fatty acids. It may also comprise compounds such as alkylene carbonates, for instance propylene carbonate, which can reinforce the efficacy of some fatty-phase thickeners such as the silicates. The amount of fatty phase may range from 0.5% to 50% by weight, preferably from 0.7% to 30% by weight and better still from 1 % to 20% by weight relative to the total weight of the composition. As mentioned previously, the composition according to the invention comprises an aqueous phase.

The aqueous phase of the composition according to the invention comprises at least water.

The amount of water may represent from 30% to 98% by weight, preferably from 50% to 95% by weight and better still from 60% to 92% by weight relative to the total weight of the composition.

Preferably, the weight ratio of the amount of water to the amount of oil(s) in the compositions of the invention ranges from 1 to 80, better still from 5 to 70 and even better still from 10 to 60.

The aqueous phase of the composition according to the invention also comprises an aqueous-phase thickening polymer comprising one or more acrylic and/or methacrylic units.

The term "polymer comprising acrylic and/or methacrylic units" means, within the meaning of the present invention, a polymer resulting from the polymerization of one or more monomers including one or more monomers of structure (I):

Ri denoting a hydrogen atom or a linear or branched CrC₄ alkyl radical,

R₂ denoting a hydrogen atom, a linear or branched C C₄ alkyl radical, an NR₃R₄ radical or a linear or branched Ci-C₃₀ alkoxy radical, optionally substituted by one or more hydroxyl radicals, one or more amino radicals or by one or more quaternary ammonium radicals,

R₃ and R₄ denote a hydrogen atom, an optionally oxyalkylenated Ci-C₃₀ alkyl radical, it being possible for the alkyl radical to comprise one or more sulfonic groups, one or more amino groups or one or more quanternary ammonium groups.

Preferably, Ri denotes a hydrogen atom or a methyl radical. The term "thickening polymer" is understood to mean, within the meaning of the present invention, a polymer capable, by its presence, of increasing the viscosity of the medium by at least 50 centipoise at 25°C and at a shear rate of 1 s^' Preferably, the solution obtained by dissolving the thickening polymer at 1 % by weight in water or in a 50/50 by weight water/alcohol mixture exhibits a viscosity at 25°C and at a shear rate of 1 s^"1 which is greater than 100 centipoise. These viscosities can be measured using in particular viscometers or rheometers having cone-plate geometry.

The thickening polymers comprising acrylic and/or methacrylic units can be chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (CrC₆)alkyl acrylate;

(d) non-ionic homopolymers and copolymers comprising ethylenically unsaturated monomers of ester and/or amide type;

(e) ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide;

(f) (meth)acrylamido(Ci-C₄)alkylsulfonic acid homopolymers and copolymers;

(g) crosslinked methacryloyl(Ci-C₄)alkyltri(Ci-C₄)alkylammonium homopolymers and copolymers.

The thickening polymers comprising acrylic and/or methacrylic units can be chosen from acrylic associative thickeners.

The term "associative thickener" is understood to mean, according to the invention, an amphiphilic thickener comprising both hydrophilic units and hydrophobic units, in particular comprising at least one C₈-C₃₀ fatty chain and at least one hydrophilic unit.

Mention may be made, as acrylic associative thickeners which can be used in the composition according to the invention, of acrylic associative polymers chosen from:

(i) non-ionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;

(ii) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit having a fatty chain;

(iii) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit having a fatty chain;

(iv) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one unit having a fatty chain;

the fatty chains having from 10 to 30 carbon atoms.

The non-ionic amphiphilic polymers may preferably be chosen from: (1 ) copolymers of Ci-C₆ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain (for example oxyethylenated (C₈- C₂2)alkyl acrylates), such as, for example, the oxyethylenated methyl methacrylate/stearyl acrylate copolymer sold by Goldschmidt under the name Antil 208;

(2) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain (for example (C₈-C₂2)alkyl (meth)acrylates), such as, for example, polyethylene glycol methacrylate/lauryl methacrylate copolymer.

The anionic amphiphilic polymers can be chosen from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of unsaturated carboxylic acid (Ci₀-C₃o)alkyl ester type. They are preferably chosen from those for which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of following formula (II):

in which formula R₃ denotes H or CH₃ or C₂H₅, that is to say acrylic acid, methacrylic acid or ethacrylic acid units, and for which the hydrophobic unit of unsaturated carboxylic acid (Ci₀-C₃o)alkyl ester type corresponds to the monomer of following formula (III):

in which formula R₄ denotes H or CH₃ or C₂H₅ (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate units), R₅ denoting a Ci₀-C₃₀ and preferably Ci₂-C₂₂ alkyl radical.

(Cio-C₃₀)Alkyl esters of unsaturated carboxylic acids in accordance with the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic amphiphilic polymers of this type are, for example, described and prepared according to Patents US-3 915 921 and US-4 509 949. The anionic amphiphilic polymers which can be used in the context of the present invention can more particularly denote polymers formed from a mixture of monomers comprising:

(i) acrylic acid and one or more esters of following formula (IV):

H₂C=C C— OR₇

in which R₆ denotes H or CH₃, R₇ denoting an alkyl radical having from 12 to 22 carbon atoms, and a crosslinking agent, such as, for example, those constituted of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0% to 6% by weight of crosslinking polymerizable monomer, or 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer,

(ii) essentially acrylic acid and lauryl methacrylate, such as the product formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacr late.

The said crosslinking agent is a monomer comprising a

group with at least one other polymerizable group, the unsaturated bonds of which are non- conjugated with respect to one another. Mention may in particular be made of polyallyl ethers, such as, in particular, polyallyl sucrose and polyallyl pentaerythritol.

Among the said polymers above, preference is very particularly given, according to the present invention, to the products sold by Lubrizol under the trade names Pemulen TR1 , Pemulen TR2 and Carbopol 1382, and more preferably still Pemulen TR1 , and to the product sold by S.E.P.C. under the name Coatex SX.

Mention may also be made, as anionic amphiphilic polymers having fatty chains, of the methacrylic acid/methyl acrylate/ethoxylated alcohol dimethyl-meta- isopropenylbenzyl isocyanate copolymer sold under the name Viscophobe DB 1000 by Amerchol.

Mention may be made, as other anionic amphiphilic polymers having fatty chains, of those comprising at least one acrylic monomer having sulfonic group(s), in free or partially or completely neutralized form, and comprising at least one hydrophobic portion. The hydrophobic portion present in the polymers of the invention preferably comprises from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.

Preferably, the sulfonic polymers in accordance with the invention are partially or completely neutralized by an inorganic base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base, such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, such as arginine and lysine, and mixtures of these compounds.

The sulfonic amphiphilic polymers in accordance with the invention generally have a number-average molecular weight ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 g/mol and more preferably still ranging from 100 000 to 1 500 000 g/mol.

The sulfonic amphiphilic polymers according to the invention may or may not be crosslinked. Crosslinked amphiphilic polymers are preferably chosen.

When they are crosslinked, the crosslinking agents can be chosen from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol di(meth)acrylate or tetraethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA) will more particularly be used. The degree of crosslinking will generally vary from 0.01 mol% to 10 mol% and more particularly from 0.2 mol% to 2 mol%, with respect to the polymer.

The acrylic monomers having sulfonic group(s) are chosen in particular from

(meth)acrylamido(Ci-C₂2)alkylsulfonic acids and N-(Ci-C₂2)alkyl(meth)acrylamido(Ci- C₂2)alkylsulfonic acids, such as undecylacrylamidomethanesulfonic acid, and also their partially or completely neutralized forms.

More preferably, use will be made of (meth)acrylamido(Ci-C22)alkylsulfonic acids, such as, for example, acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also their partially or completely neutralized forms.

More particularly, use will be made of 2-acrylamido-2-methylpropanesulfonic acid (AMPS®), and also its partially or completely neutralized forms.

The amphiphilic polymers in accordance with the invention can in particular be chosen from random amphiphilic AMPS® polymers modified by reaction with an n- mono(C₆-C22)alkylamine or a di[n-(C₆-C₂2)alkyl]amine, such as those described in Patent Application WO 00/31 154; the polymers described in this patent application form part of the content of the present description. These polymers can also comprise other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

The polymers of the invention can be chosen from amphiphilic copolymers of AMPS® and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion having from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.

These same copolymers can additionally comprise one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

These copolymers are described in particular in Patent Application EP-A-750 899, in Patent US 5 089 578 and in the following Yotaro Morishima publications:

"Self-assembling amphiphilic polyelectrolytes and their nanostructures", Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336; "

"Micelle formation of random copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering", Macromolecules, 2000, Vol. 33, No. 10, 3694-3704;

"Solution properties of micelle networks formed by non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior", Langmuir, 2000, Vol. 16, No. 12, 5324-5332; - "Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and associative macromonomers", Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221.

The ethylenically unsaturated hydrophobic monomers of these specific copolymers are preferably chosen from the acrylates or acrylamides of following formula (V):

in which R₈ and Rio, which are identical or different, denote a hydrogen atom or a linear or branched Ci-C₆ alkyl radical (preferably methyl); Y denotes O or NH; R₉ denotes a hydrophobic hydrocarbon radical comprising at least from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; and x denotes a number of moles of alkylene oxide and varies from 0 to 100.

The R₉ radical is preferably chosen from C₆-Ci₈ alkyl radicals that are linear (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl or n-dodecyl radicals) or branched or cyclic (for example cyclododecane (Ci₂) or adamantane (Cio)) radicals; C₆-Ci₈ perfluoroalkyl radicals (for example the group of formula -(CH₂)2-(CF₂)9-CF₃); the cholesteryl (C27) radical or a cholesterol ester residue, such as the cholesteryl oxyhexanoate group; or polycyclic aromatic groups, such as naphthalene or pyrene. Preference is more particularly given, among these radicals, to linear alkyl radicals and more particularly to the n-dodecyl radical.

According to a particularly preferred form of the invention, the monomer of formula (V) comprises at least one alkylene oxide unit (x≥ 1 ) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain preferably is constituted of ethylene oxide units and/or of propylene oxide units and more particularly still is constituted of ethylene oxide units. The number of oxyalkylene units generally varies from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.

Mention may be made, among these polymers, of: - copolymers which are or are not crosslinked and which are or are not neutralized, comprising from 15% to 60% by weight of AMPS® units and from 40% to 85% by weight of (C₈-Ci6)alkyl(meth)acrylamide units or of (C₈-Ci₆)alkyl (meth)acrylate units, with respect to the polymer, such as those described in Application EP-A-750 899;

- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from

0.1 mol% to 10 mol% of AMPS® units and from 5 mol% to 80 mol% of n-(C₆- Ci₈)alkylacrylamide units, such as those described in Patent US-5 089 578.

Mention may also be made of copolymers of completely neutralized AMPS® and of dodecyl methacrylate, and also non-crosslinked and crosslinked copolymers of AMPS® and of n-dodecylmethacrylamide, such as those described in the abovementioned papers by Morishima.

Mention will more particularly be made of the copolymers constituted of 2- acrylamido-2-methylpropanesulfonic acid (AMPS®) units of following formula (VI):

in which X⁺ is a proton, an alkali metal cation, an alkaline earth metal cation or the ammonium ion,

and of units of following formula (VII):

in which x denotes an integer varying from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25, Rn has the same meaning as that indicated above for R₈ in the formula (V) and Ri₂ denotes a linear or branched C₆-C₂2 and more preferably C10-C22 alkyl. The polymers which are particularly preferred are those for which x = 25, Rn denotes methyl and Ri₂ represents n-dodecyl; they are described in the abovementioned papers by Morishima.

The polymers for which X⁺ denotes sodium or ammonium are more particularly preferred.

As explained above, the acrylic associative thickeners which can be used in the composition according to the invention can be chosen from cationic amphiphilic polymers and amphoteric amphiphilic polymers.

The cationic amphiphilic polymers which can be used in the composition according to the present invention are preferably chosen from polyacrylates having aminated side groups.

The polyacrylates having quaternized or non-quaternized aminated side groups possess, for example, hydrophobic groups of the steareth-20 (polyoxyethylenated (20) stearyl alcohol) or (Ci₀-C₃o)alkyl PEG-20 itaconate type.

Mention may be made, as examples of polyacrylates having aminated side chains, of the polymers 8781 -124B or 9492-103 or Structure Plus from National Starch.

Mention may be made, as amphoteric amphiphilic polymers, of methacrylamidopropyltrimethylammonium chloride/acrylic acid/Cio-C₃₀ alkyl methacrylate copolymers, the alkyl radical preferably being a stearyl radical.

As explained above, the thickening polymers comprising acrylic and/or methacrylic units can also be chosen from:

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (CrC₆)alkyl acrylate;

(f) (meth)acrylamido(Ci-C₄)alkylsulfonic acid homopolymers and copolymers;

Mention may be made, among crosslinked acrylic acid homopolymers, of those crosslinked by an allyl ether of an alcohol of the sugar series, such as, for example, the products sold under the names Carbopol 980, 981 , 954, 2984 and 5984 by Lubrizol or the products sold under the names Synthalen M and Synthalen K by 3VSA, Cosmedia SP® or crosslinked sodium polyacrylate comprising 90% of dry matter and 10% of water, Cosmedia SPL® or sodium polyacrylate as inverse emulsion comprising approximately 60% of dry active matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by Cognis, or partially neutralized crosslinked sodium polyacrylates occurring in the form of an inverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel® EM by BASF.

Mention may be made, among crosslinked copolymers of (meth)acrylic acid and of Ci-C₆ alkyl acrylate, of the product sold under the name Viscoatex 538C by Coatex, which is a crosslinked copolymer of methacrylic acid and of ethyl acrylate as an aqueous dispersion comprising 38% of active material, or the product sold under the name Aculyn 33 by Rohm & Haas, which is a crosslinked copolymer of acrylic acid and of ethyl acrylate as an aqueous dispersion comprising 28% of active material. Mention may more particularly be made of the crosslinked methacrylic acid/ethyl acrylate copolymer in the form of an aqueous 30% dispersion manufactured and sold under the name Carbopol Aqua SF-1 by Noveon.

Mention may be made, among non-ionic homopolymers or copolymers comprising ethylenically unsaturated monomers of ester and/or amide type, of the products sold under the names of: Cyanamer P250 by Cytec (polyacrylamide); PMMA MBX-8C by US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate copolymer); Acryloid B66 by Rohm & Haas (butyl methacrylate/methyl methacrylate copolymer); or BPA 500 by Kobo (polymethyl methacrylate).

Mention may be made, among ammonium acrylate homopolymers, of the product sold under the name Microsap PAS 5193 by Hoechst.

Mention may be made, among copolymers of ammonium acrylate and of acrylamide, of the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by Hoechst (they are described and prepared in the documents FR-2 416 723, US-2 798 053 and US-2 923 692).

Preference is preferably given, among (meth)acrylamido(Ci-C₄)alkylsulfonic acid homopolymers and copolymers, to the use of crosslinked polymers.

More particularly still, they are partially or completely neutralized.

These are water-soluble or water-swellable polymers.

Mention may in particular be made, among these polymers, of:

- polyacrylamidomethanesulfonic acid,

- polyacrylamidoethanesulfonic acid,

- polyacrylamidopropanesulfonic acid,

- poly(2-acrylamido-2-methylpropanesulfonic acid),

- poly(2-methacrylamido-2-methylpropanesulfonic acid),

- poly(2-acrylamido-n-butanesulfonic acid). Polymers of this type and in particular crosslinked and partially or completely neutralized poly(2-acrylamido-2-methylpropanesulfonic acids) are known, described and prepared in Patent Application DE-196 25 810.

They are generally characterized in that they comprise, randomly distributed:

i) from 90% to 99.9% by weight of units of following formula (VIII):

CH,

O NH (^— CH₂SO₃

CH₀

(VIII) in which X⁺ denotes a cation or a mixture of cations, including H⁺,

ii) from 0.01 % to 10% by weight of at least one crosslinking unit having at least two olefinic double bonds,

the proportions by weight being defined with respect to the total weight of the polymer;

X⁺ represents a cation or a mixture of cations chosen in particular from a proton, an alkali metal cation, a cation equivalent to that of an alkaline earth metal, or the ammonium ion.

Preferably, the crosslinked and neutralized poly(2-acrylamido-2- methylpropanesulfonic acid) comprises from 98% to 99.5% by weight of units of formula (VIII) and from 0.5% to 2% by weight of crosslinking units.

The crosslinking units having at least two olefinic double bonds are chosen, for example, from dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane or other polyfunctional alcohol allyl or vinyl ethers, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane diallyl ether, methylenebisacrylamide or divinylbenzene.

The crosslinking units having at least two olefinic double bonds are more particularly still chosen from those corresponding to the following general formula (IX):

in which R₁₃ denotes a hydrogen atom or a C1-C4 alkyl and more particularly methyl (trimethylolpropane triacrylate).

The crosslinked and partially or completely neutralized poly(2-acrylamido-2- methylpropanesulfonic acids) are generally known under the names "Ammonium polyacrylamido-2-methylpropanesulfonate" or "Ammonium polyacryldimethyltauramide" (INCI name).

A product which is particularly preferred according to the invention is that sold by Clariant under the trade name Hostacerin AMPS®; this is a crosslinked poly(2- acrylamido-2-methylpropanesulfonic acid) partially neutralized with aqueous ammonia.

Mention may be made, among crosslinked methacryloyl(Ci-C₄)alkyltri(Ci- C₄)alkylammonium homopolymers and copolymers, of crosslinked polymers of methacryloyloxy(Ci-C₄)alkyltri(Ci-C₄)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized by methyl chloride or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by methyl chloride, the homo- or copolymerization being followed by crosslinking by an olefinically unsaturated compound, in particular methylenebisacrylamide.

Use may more particularly be made of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride (20/80 by weight) copolymer in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil. This dispersion is sold under the name of Salcare® SC 92 by Ciba. Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names of Salcare® SC 95 and Salcare® SC 96 by Ciba.

As indicated previously, the thickening polymers having acrylic and/or methacrylic units according to the invention may be non-ionic, anionic, cationic or amphoteric.

Preferably, the thickening polymer or polymers having acrylic and/or methacrylic units according to the invention are anionic. These polymers are more particularly chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (CrC₆)alkyl acrylate.

The thickening polymers comprising acrylic and/or methacrylic units which can be used in the composition according to the invention preferably represent from 0.1 % to 20% by weight, more preferably from 0.2% to 15% by weight and in particular from 0.5% to 10% by weight, with respect to the total weight of the composition.

The aqueous phase also comprises one or more fixing polymers comprising at least one vinylpyrrolidone unit.

For the purposes of the present invention, the term "fixing polymer" means any polymer that is capable, by application to the hair, of giving a shape to the head of hair or of form retention of the hair in an already acquired shape.

The fixing polymer(s) used comprising at least one vinylpyrrolidone unit may be chosen from the cationic and non-ionic fixing polymers comprising at least one vinylpyrrolidone unit, and mixtures thereof.

Among the cationic fixing polymers comprising at least one vinylpyrrolidone unit, mention will be made of the copolymers having one or more vinylpyrrolidone units and also having derivatives of acrylic or methacrylic esters or amides and comprising at least one of the units of following formulae: CH— C , CH— - CH- -C -

R ^R3

— CH₂ - C

O =

NH

I

A N

/ ^\

Ri

² (D)

in which:

R₃ denotes a hydrogen atom or a CH₃ radical;

A is a linear or branched alkyl group comprising from 1 to 6 carbon atoms or a hydroxyalkyl group comprising from 1 to 4 carbon atoms;

R₄, R₅ and R₆, which are identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical;

Ri and R₂, which are identical or different, each represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms;

X denotes a methosulfate anion or a halide, such as chloride or bromide.

Thus, mention may be made of:

- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the Gafquat® name by ISP, such as, for example, Gafquat® 734 or Gafquat® 755 or Gafquat® 755N (INCI name: Polyquaternium-1 1 ), or alternatively the products known as Copolymer® 845, 958 and 937, sold by ISP (INCI name: VP/dimethylaminoethyl methacrylate copolymer). These polymers are described in detail in French patents 2 077 143 and 2 393 573,

- polymers comprising a fatty chain and comprising a vinylpyrrolidone unit, such as the products sold under the names Styleze® W20L and Styleze® W10 by ISP (INCI name: Polyquaternium-55),

- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the products sold under the names Advantage HC 37 or Gaffix® VC 713 by ISP (INCI name Vinyl caprolactam / VP / dimethylaminoethyl methacrylate copolymer), and

- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, such as the products sold under the name Gafquat® HS 100 by ISP (name Polyquaternium-28).

Mention may also be made of quaternary copolymers of vinylpyrrolidone and of vinylimidazole; for example, vinylpyrrolidone/methylvinylimidazolium chloride copolymers, such as the products sold by BASF under the names Luviquat® FC550 or FC370, Luviquat® Excellence or Luviquat® Style (INCI name: Polyquaternium-16), or vinylpyrrolidone/vinylimidazolium methosulfate/vinylcaprolactam terpolymers, such as the product Luviquat® Hold, sold by BASF (INCI name: Polyquaternium-46).

Among the non-ionic fixing polymers comprising at least one vinylpyrrolidone unit, mention will be made of vinylpyrrolidone homopolymers, such as the PVP products K30L, K60 solution and K90 sold by ISP, or the product Luviskol K30 sold by BASF, the poly(vinylpyrrolidone/vinyllactam) copolymers sold under the trade name Luvitec® VPC 55K65W by BASF, poly(vinylpyrrolidone/vinyl acetate) copolymers, such as those sold under the names PVPA A® S630L, E735, E635 and W735 by ISP and Luviskol® VA 73, VA 64 and VA 37 by BASF (INCI name: VPA A copolymer), and vinylpyrrolidone/methacrylamide/vinylimidazole terpolymers, such as, for example, that sold under the name Luviset® Clear by BASF (INCI name: VP/methacrylamide/vinyl imidazole copolymer).

The fixing polymers comprising at least one vinylpyrrolidone unit are preferably present in the composition in an amount ranging from 0.1 % to 20%, preferably from 0.5% to 15% and more preferably still from 1 % to 10% by weight, relative to the total weight of the composition. The composition according to the invention may optionally contain one or more fixing polymers other than the fixing polymers having a vinylpyrrolidone unit.

The aqueous phase may comprise at least one organic hydrophilic solvent, for instance substantially linear or branched lower monoalcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol or isobutanol; polyols, such as propylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, polyethylene glycols and derivatives thereof; and mixtures thereof. Preferably, the composition according to the invention does not comprise any surfactant. When it does comprise the same, the composition according to the invention comprises less than 2% of surfactant.

The amount of aqueous phase may range from 50% to 99.5% by weight, preferably from 60% to 99% by weight and better still from 70% to 98.5% by weight, relative to the total weight of the composition. The composition according to the invention may comprise active agents conventionally used in the field of cosmetics, other than those described previously, and chosen from silicones, direct dyes, in particular cationic or natural direct dyes, or oxidation dyes, organic or mineral pigments, UV-screening agents, fragrances, peptizers, vitamins, amino acids, preserving agents, long-lasting hair shaping agents, especially thiolated organic reducing agents, non-thiolated organic reducing agents, alkaline agents, etc.

Needless to say, a person skilled in the art will take care to select the optional additional compounds and/or the amount thereof such that the advantageous properties of the compositions used according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

Preferably, the composition is in the form of a gel, namely a thickened aqueous solution which comprises oily inclusions, such as oily swirls. More preferably still, the composition is in the form of a transparent gel with oily inclusions, such as oily swirls. More preferably still, the composition is entirely in the form of a gel, with the two phases being thickened.

Preferably, the compositions have a viscosity of greater than or equal to 0.1 Pa.s and better still ranging from 0.1 Pa.s to 500 Pa.s and even better still from 0.5 Pa.s to 300 Pa.s, more preferably still from 1 Pa.s to 200 Pa.s, at a temperature of 25°C and atmospheric pressure (1 atm) and at a shear rate of 1 s^"1 (measurable, for example, with a Haake RS600 rheometer).

The composition according to the invention may have a threshold stress at 25°C greater than or equal to 0.1 Pa.

The composition according to the invention may have a threshold stress at 25°C ranging from 0.1 Pa to 300 Pa, preferably from 1 Pa to 250 Pa, and more preferably still from 10 Pa to 200 Pa.

Preferably, each phase has a threshold stress at 25°C ranging from 0.1 Pa to 300 Pa, preferably from 1 Pa to 250 Pa, and more preferably still from 10 Pa to 200 Pa.

The threshold stress is determined by scanning under stress at 25°C and atmospheric pressure (1 atm). An imposed-stress Thermo Haake RS600 rheometer with sandblasted cone-plate geometry is used. The temperature is regulated by a Peltier-effect plate and an anti-evaporation device (solvent trap filled with water for the measurements at 25°C).

A logarithmic stress elevation from 0.5 to 500 Pa is performed over a period of 3 minutes. Two adjustment lines corresponding to the stationary regimes (solid and liquid behaviours) are plotted on the curve representing the strain as a function of the stress (logarithmic coordinates). The intersection of these two lines gives the value of the stress threshold.

In order to measure the stress threshold of each phase, the measurement is carried out before mixing the two phases.

The composition according to the invention may be obtained by mixing the two phases using a static mixer.

In particular, to make the composition according to the invention, the ingredients of the fatty phase are mixed together, on the one hand, and the ingredients of the aqueous phase are mixed together, on the other hand. Each phase is introduced separately into the static mixer, namely a tube inside which is a three-dimensional structure promoting the appearance of turbulence during the passage of a fluid. The phases are mixed by a static device, i.e. a device that is not driven by a rotary system, thus avoiding dispersion of the fatty phase in the aqueous phase, especially in the form of globules. A mixture in which the two phases are visually distinct is obtained.

A subject of the invention is also a composition according to the invention made using a static mixer.

The composition according to the invention may especially be used as a leave-in or rinse-out application for the hair.

A subject of the invention is also a hair treatment process, which consists in applying to the hair an effective amount of a composition as has just been described and then in optionally rinsing after an optional leave-in time, in the presence or absence of heat.

The example that follows is given as an illustration of the present invention. In this example, all the amounts are indicated as weight percentages of active material (AM) relative to the total weight of the composition.

INCI Name A B

1 Persea gratissima (avocado) oil 1 .83 1 .83

2 Stearalkonium hectorite ⁽¹⁾ 0.12 0.12

3 Propylene carbonate 0.04 0.04

4 Tocopherol 0.01 0.01

5 Carbomer ⁽²⁾ 1 .27 - 6 Acrylates / C10-30 alkyl acrylate 1 .37 crosspolymer ⁽³⁾

7 VPA A copolymer ⁽⁴⁾ 2.45 4.90

8 VP/dimethylaminoethyl methacrylate 2.35

copolymer ⁽⁵⁾

9 PEG-40 hydrogenated castor oil 1 .37 1 .66

10 Polysorbate 20 0.09 -

1 1 Triethanolamine 1 .86 -

12 Aminomethylpropanol - 0.78

13 Dyes (Yellow 5 and Red 33) 0.0005 0.001

14 Water qs 100 qs 100 sold under the reference Bentone 27 V CG by Elementis

⁽ ' sold under the reference Synthalen K by 3V

<³⁾ sold under the reference Pemulen TR-1 by Lubrizol

(⁴⁾ sold under the reference Luviskol VA 64 W by BASF

<⁵⁾ sold under the reference Copolymer 845-0 by ISP

Compositions A and B, which are hairstyling gels, are made.

Using a static mixer, the oil phase comprising ingredients 1 to 4 is mixed with the aqueous phase comprising the other ingredients of the compositions.

The compositions obtained are in the form of a translucent marbled orange gel containing very aesthetic whitish swirls.

The compositions are applied to dry or wet hair. They spread well on the hands and are easily distributed through the hair.

The hair is shaped by hand.

The compositions provide good cosmeticity to the hair, and in particular softness, manageability and flexibility, also with a less tacky sensation and no sensation of dryness.

Moreover, the compositions provide a high level of hold with long-lasting shape retention.

Claims

1 . Composition comprising:

2. Composition according to Claim 1 , characterized in that the oil(s) are chosen from C₆-Ci₆ lower alkanes; linear or branched hydrocarbons of mineral or synthetic origin having more than 16 carbon atoms, non-silicone oils of animal origin; oils of plant origin; fluoro oils; liquid fatty alcohols; liquid fatty esters; non-salified liquid fatty acids; silicone oils; or mixtures thereof, and are preferably chosen from C₆-Ci₆ lower alkanes; linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms; liquid fatty alcohols; oils of plant origin; or mixtures thereof; and even more preferably chosen from oils of plant origin; liquid fatty alcohols; or mixtures thereof.

3. Composition according to either one of the preceding claims, characterized in that the oil(s) are present in an amount ranging from 0.1 % to 20%, more preferentially in an amount ranging from 1 % to 10% and better still in an amount ranging from 1 .5% to 5% by weight, relative to the total weight of the composition.

4. Composition according to any one of the preceding claims, characterized in that the fatty phase comprises at least one fatty-phase thickener chosen from mineral fatty- phase thickener(s) and organic fatty-phase thickener(s).

5. Composition according to the preceding claim, characterized in that the mineral fatty- phase thickener(s) are chosen from silicates and silicas, preferably from silicates.

6. Composition according to Claim 4, characterized in that the organic fatty-phase thickener(s) are chosen from semicrystalline polymers, non-silicone polyamides, silicone polyamides, monoalkyl or polyalkyl esters of saccharides or of polysaccharides, N-acylamino acid amide derivatives, copolymers comprising one or more alkylene and/or styrene blocks, and elastomeric organopolysiloxanes, and mixtures thereof.

7. Composition according to any one of the preceding claims, characterized in that the fatty-phase thickener(s) is/are present in a content ranging from 0.05% to 10% by weight relative to the total weight of the composition, preferably from 0.075% to 5% by weight relative to the total weight of the composition.

8. Composition according to any one of the preceding claims, characterized in that the amount of fatty phase ranges from 0.5% to 50% by weight, preferably from 0.7% to 30% by weight and better still from 1 % to 20% by weight, relative to the total weight of the composition.

9. Composition according to any one of the preceding claims, characterized in that the thickening polymer(s) comprising one or more acrylic and/or methacrylic units are chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (CrC₆)alkyl acrylate;

(f) (meth)acrylamido(Ci-C₄)alkylsulfonic acid homopolymers and copolymers;

10. Composition according to Claim 9, characterized in that the thickener(s) comprising one or more acrylic and/or methacrylic units are chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (CrC₆)alkyl acrylate;

and are preferably chosen from acrylic associative thickeners and crosslinked acrylic acid homopolymers.

1 1. Composition according to any one of the preceding claims, characterized in that the thickening polymer(s) comprising at least one acrylic or methacrylic unit is/are anionic.

12. Composition according to any one of the preceding claims, characterized in that the thickening polymer(s) comprising at least one acrylic or methacrylic unit is/are present in an amount ranging from 0.1 % to 20%, more preferentially in an amount ranging from 0.2% to 15% and better still in an amount ranging from 0.5% to 10% by weight, relative to the total weight of the composition.

13. Composition according to any one of the preceding claims, characterized in that the fixing polymer(s) comprising at least one vinylpyrrolidone unit is/are chosen from vinylpyrrolidone homopolymers, vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers; polymers comprising a fatty chain and comprising a vinypyrrolidone unit, quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers; quaternary copolymers of vinylpyrrolidone and of vinylimidazole; poly(vinylpyrrolidone/vinyllactam) copolymers; and vinylpyrrolidone/vinylimidazolium methosulfate/vinylcaprolactam terpolymers.

14. Composition according to any one of the preceding claims, characterized in that the fixing polymer(s) comprising at least one vinylpyrrolidone unit is/are present in an amount varying from 0.1 % to 20%, preferably from 0.5% to 15% and more preferably still from 1 % to 10% by weight, relative to the total weight of the composition.

15. Composition according to any one of the preceding claims, characterized in that the amount of aqueous phase ranges from 50% to 99.5% by weight, preferably from 60% to 99% by weight and better still from 70% to 98.5% by weight, relative to the total weight of the composition.

16. Composition according to any one of the preceding claims, characterized in that it comprises less than 2% of surfactant and preferably does not comprise any surfactant.

17. Composition according to any one of the preceding claims, characterized in that it has a viscosity of greater than or equal to 0.1 Pa.s, better still ranging from 0.1 Pa.s to 500 Pa.s, even better still from 0.5 Pa.s to 300 Pa.s, more preferably still from 1 Pa.s to 200 Pa.s at a temperature of 25°C and at a shear rate of 1 s^"1.

18. Composition according to any of the preceding claims, characterized in that it is in the form of a gel with oily insertions such as oily swirls.

19. Composition according to any one of the preceding claims, characterized in that it is obtained by mixing the two phases using a static mixer.

20. Hair treatment process, characterized in that it consists in applying to the hair an effective amount of a composition according to any one of Claims 1 to 19 and then in optionally rinsing after an optional leave-in time, in the presence or absence of heat.

21. Use of the composition according to any one of Claims 1 to 19 for shaping the hair.