WO2014037306A1

WO2014037306A1 - Cosmetic composition comprising a modified or unmodified starch, low-density organic particles, a particular amphoteric polymer, an anionic surfactant and a beneficial agent

Info

Publication number: WO2014037306A1
Application number: PCT/EP2013/068091
Authority: WO
Inventors: Claudine PERONA; Céline Sellier
Original assignee: L'oreal
Priority date: 2012-09-04
Filing date: 2013-09-02
Publication date: 2014-03-13

Abstract

Cosmetic composition comprising a modified or unmodified starch, low-density organic particles, a particular amphoteric polymer, an anionic surfactant and a beneficial agent The invention relates to a cosmetic compositioncomprising: - one or more modified or unmodified starches, - one or more types oflow-densitywater-insoluble organic particles, - one or more amphoteric polymers comprising repetition of: (i) one or more unitsderived froma monomer of (meth)acrylamide type, (ii) one or more units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type, and (iii) one or more units derived from an acidic monomer of (meth)acrylic acid type, - one or more anionic surfactants, and - one or more agents that are beneficialto keratin materials.

Description

Cosmetic composition comprising a modified or unmodified starch, low-density organic particles, a particular amphoteric polymer, an anionic surfactant and a beneficial agent

The present invention relates to a cosmetic composition comprising at least one modified or unmodified starch, at least one type of low-density water-inso luble organic particles, at least one particular amphoteric polymer, at least one anionic surfactant and at least one agent that is beneficial to keratin materials. It also relates to the use thereof for cleansing and/or conditioning keratin materials such as the hair, scalp and skin.

Many cosmetic care products are known in the field o f hair and body hygiene. For example, the purpose of the corresponding compositions is to impart good cosmetic properties to the hair.

Conventional care products for keratin materials and in particular for the hair and scalp, for example conditioners or masks, are usually in the form of more or less viscous creams. Similarly, cleansing products for keratin materials, such as shampoos, are usually in the form of more or less viscous liquids, such as gels and creams.

However, these products are difficult to measure out, in particular because they have a tendency to escape between the fingers or to escape from their packaging, which may be very annoying when they come into contact with clothing, for example when travelling.

To modify the texture, and especially to make it more compact, standard means consist in using thickeners, but this is often done to the detriment of the cosmetic effects of the composition. Moreover, the thickest conditioning compositions often have the drawback of requiring a lot of rinsing water in order to remove the surplus of product on the hair. In many countries in which access to water is restricted, the rinsing time and thus the amount required to thoroughly rinse out the product are key indicators of the working qualities of a composition.

In addition, haircare compositions, whether they are rinse-out or leave-in products, consist for the vast majority of water, surfactants and polymers. These starting materials do not always make it possible to incorporate other desired starting materials, or in the desired proportion. Specifically, such an incorporation may occasionally lead to destabilization such as flo cculation or sedimentation o f particles.

In order to overcome some of these problems, solid cosmetic formulations exist. However, they have the drawback of being fractionable, difficult to disintegrate in water at the time of use and difficult to distribute when applied to keratin materials.

There is thus a need for keratin material care compositions which do not run, which are more compact and modellable, which require little water for rinsing and which make it possible to avoid the flocculation or sedimentation of particles. The compositions sought must be easy to apply to keratin materials, very light and very soft.

The Applicant has discovered, surprisingly, that a cosmetic composition comprising a combination of modified or unmodified starch(es), of low-density water-inso luble organic particles, of particular amphoteric polymer(s), of anionic surfactant(s) and of particular beneficial agent(s) makes it possible to solve the problems mentioned above.

One subject of the invention is thus a cosmetic composition comprising :

one or more modified or unmodified starches,

one or more types of low-density water-inso luble organic particle, one or more particular amphoteric polymers as described below, one or more anionic surfactants and

one or more agents that are beneficial to keratin materials.

The composition according to the invention is stable, i.e. it does not show any flo cculation or sedimentation of particles, and has an entirely uncommon texture . The composition has a low density, i.e . less than 1 , preferably ranging from 0.2 to 0.9, better still from 0.2 to 0.8 , or even from 0.2 to 0.6, and is very soft to the touch. It behaves like a more or less firm, non-tacky, deformable (or modellable) solid.

The composition also has a fresh feel on application.

For the purposes of the present invention, the term " fresh feel" means a sensation of freshness when the formula is taken up in wet hands.

The so lid behaviour of the composition according to invention allows easy handling of the product and ease of transport. In particular, there is no risk of it escaping from its packaging, in particular when it is transported. Since the texture is highly modellable, the composition can be gripped easily and does not flow between the fingers. It can be measured out and applied very easily. The composition may be easily divided by hand in order to take up only the necessary amount of product. In particular, this composition may be packaged in the single- unit form and may for example be in the form o f small cubes or cartons.

The composition according to invention is also very comfortable to apply. In particular, no running of the composition is observed, unlike conventional compositions, which carries with it the risk of irritating particularly the face and the eyes. The absence of running is greatly appreciated in the case of permanent waves and dyeing, and also for shampoos intended for children.

In addition, the composition disintegrates rapidly and easily in contact with a liquid, preferably an aqueous liquid.

The term " disintegration" is understood for the purposes of the present invention to mean disintegration with the aid of a liquid and not disintegration upon touch as is the case for certain makeup compositions of eyeshadow type which can be taken up with a finger or using a brush. This disintegration with the aid o f a liquid in fact corresponds to a destructuring of the solid, with solubilization or dispersion o f the particles in the liquid.

A subject of the invention is also the use of the cosmetic composition according to the invention for cleansing and/or conditioning keratin materials, such as the hair and scalp, and the skin.

Other subjects, characteristics, aspects and advantages of the invention will become even more clearly apparent on reading the description and examples that follow.

In that which follows and unless otherwise indicated, the limits o f a range of values are included within this range, in particular in the expressions "between" and "ranging from ... to

Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more" .

According to the invention, the cosmetic composition comprises: one or more modified or unmodified starches,

one or more types of low-density water-inso luble organic particle, one or more amphoteric polymers comprising repetition o f:

(i) one or more units derived from a monomer of (meth)acrylamide type,

(ii) one or more units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type, and

(iii) one or more units derived from an acidic monomer of (meth)acrylic acid type,

one or more anionic surfactants and

one or more agents that are beneficial to keratin materials.

The starch(es) that can be used in the present invention are more particularly macromolecules in the form o f po lymers formed from elemental units that are anhydroglucose units. The number of these units and their assembly make it possible to distinguish amylo se (linear polymer) and amylopectin (branched polymer). The relative proportions of amylo se and of amylopectin, and their degree of polymerization, vary as a function of the plant origin of the starches .

The starch molecules used in the present invention may originate from a plant source such as cereals, tubers, roots, legumes and fruits. Thus, the starch(es) may originate from a plant source chosen from corn, pea, potato , sweet potato, banana, barley, wheat, rice, oat, sago, tapioca and sorghum. The starch is preferably derived from potato.

It is also possible to use the hydro lysates o f the starches mentioned above.

Starches are generally in the form of a white powder, which is insoluble in cold water, the elemental particle size of which ranges from 3 to 100 microns.

The starches used in the composition of the invention may be chemically modified via one or more of the following reactions : pregelatinization, oxidation, crosslinking, esterification, heat treatments.

More particularly, these reactions may be performed in the fo llowing manner:

- pregelatinization by splitting the starch granules (for example drying and cooking in a drying drum);

- oxidation with strong oxidizing agents, leading to the introduction of carboxyl groups into the starch molecule and to depo lymerization of the starch molecule (for example by treating an aqueous starch solution with sodium hypo chlorite);

- crosslinking with functional agents capable of reacting with the hydroxyl groups of the starch mo lecules, which will thus bond together

(for example with glyceryl and/or phosphate groups);

- esterification in alkaline medium for the grafting of functional groups, especially C 1 - C 6 acyl (acetyl), d - C 6 hydroxyalkyl (hydroxyethyl or hydroxypropyl), carboxymethyl or octenylsuccinic groups.

Monostarch phosphates (of the type St-0-PO-(OX) 2 ) , distarch phosphates (of the type St-O-PO-(OX)-O-St) or even tristarch phosphates (of the type St-0-PO-(0-St)2) or mixtures thereof may especially be obtained by crosslinking with phosphorus compounds .

X especially denotes alkali metals (for example sodium or potassium), alkaline-earth metals (for example calcium or magnesium), ammonium salts, amine salts, for instance those of monoethanolamine, diethanolamine, triethanolamine, 3-amino - 1 ,2-propanedio l, or ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine or citrulline.

The phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.

Distarch phosphates or compounds rich in distarch phosphate will especially be used, for instance the products sold under the references Prej el VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) and Prej el 200 (gelatinized acetyl cassava distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized hydroxypropyl corn distarch phosphate).

According to the invention, it is also possible to use amphoteric starches, these amphoteric starches containing one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be linked to the same reactive site of the starch molecule or to different reactive sites; they are preferably linked to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type, preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type.

The amphoteric starches are especially chosen from the compounds having the following formulae : R' R

CH— CH -COOM

/

^■(CH₂)_n-N

CH— CH-COOM

R' R

(I)

COOM R

CH CH -COOM

/

-(CH₂) -N ^

R"

(Ι')

R' R"

N

I

CH, CH -COOM

(I " )

R' R"

St-O— CH— CH— COOM

(I ")

in which formulae:

St-0 represents a starch molecule,

R, which may be identical or different, represents a hydrogen atom or a methyl group,

R', which may be identical or different, represents a hydrogen atom, a methyl group or a -COOH group,

n is an integer equal to 2 or 3 ,

M, which may be identical or different, denotes a hydrogen atom, an alkali metal or alkaline-earth metal such as Na, K, Li or NH₄, a quaternary ammonium or an organic amine,

R" represents a hydrogen atom or an alkyl group containing from 1 to 18 carbon atoms.

These compounds are especially described in patents US 5 455 340 and US 4 017 460. As amphoteric starches, use is made particularly o f the starches of formula (I) or (Γ ) . Use is made more particularly of starches modified with 2-chloroethylaminodipropionic acid, i. e. starches of formula (I) or (Γ) in which R, R', R" and M represent a hydrogen atom and n is equal to 2. Mention may be made in particular o f the potato starch modified with 2-chloroethylaminodipropionic acid neutralized with sodium hydroxide, so ld under the reference Structure Solanace by the company National Starch.

The expression "O-carboxymethyl starch" denotes a starch which has been modified by substitution, in free hydroxyl groups, of a hydrogen by a -CH₂CO OH carboxymethyl group. It may be present as is, or in the form of a salt, for example an alkali metal salt.

O-carboxylmethyl starches may be prepared, for example, by reacting a starch with monochloroacetic acid, or an alkali metal salt of monochloroacetic acid (for example the sodium salt) .

Preferably, use is made o f an O-carboxylmethyl starch that is in the form of an alkali metal salt, and more preferably in the form o f a sodium salt.

Preferably, the O-carboxylmethyl starch is prepared from starch derived especially from potato .

The O-carboxylmethyl starch may also be completely or partly crosslinked. Preferably, it is partially crosslinked. The crosslinking of the starch may be carried out, for example, by heating the starch, or by reacting it with crosslinking agents such as phosphates or glycerol.

More preferably still, the O-carboxylmethyl starch is a sodium salt o f partially crosslinked O-carboxylmethyl starch, in particular potato starch. Such a product is sold, for example, under the name Primoj el by the company Avebe .

Preferably, starch(es) used in the invention are modified, and better still are chosen from mo dified starches, especially potato starch, for instance O-carboxymethyl starches, especially potato starches. The modified or unmo dified starch(es) are present in an amount preferably ranging from 2% to 20% by weight, more preferentially from 2% to 10% by weight and better still from 2% to 6% by weight, relative to the total weight of the composition.

The modified or unmodified starches that may be used in the invention serve especially as absorbents, i. e. as compounds that are capable of rapidly trapping a large amount of water.

For the purposes of the present invention, the term "absorbent" refers to any compound having a static water absorption capacity, at room temperature (25 °C), greater than or equal to 3 times its weight.

Preferably, the absorbents are chosen from compounds having a static water absorption capacity greater than or equal to 5 times their weight, and preferably greater than or equal to 15 times their weight.

The test for measuring the said static water absorption capacity is the fo llowing : at room temperature, the compound to be tested, in an amount of x grams, is placed in a beaker; water is added in an amount of 3x grams. It is left to rest, without stirring, for 1 minute.

If no free water (supernatant water) remains after said minute, the compound can be considered to be an absorbent within the meaning of the invention.

The absorbent makes it possible to obtain a composition in the form o f a solid, especially a deformable solid, which readily disintegrates with the aid of a diluent, which is generally hot or cold water but which may also be water with the addition of one or more cosmetically acceptable po lar solvents, such as alcoho ls having from 2 to 20 carbon atoms (isopropanol and ethanol in particular), propylene glyco l, or else water with the addition of one or more surfactants. It is also possible to use more complex aqueous media.

The composition according to the invention may also comprise at least one absorbent other than modified or unmodified starches. The absorbent is generally a hydrophilic or amphiphilic organic compound. This other absorbent may be chosen from wood meals, which may especially be spruce meal or beech meal, preferably spruce meal.

Preferably, the mean particle size of the wood meals is less than 250 μιη.

Such products are especially sold by the Societe Parisienne des

Sciures under the name T 140 (spruce meal) or H 160/0 (beech meal) .

The total amount of absorbent(s), including the modified or unmodified starch(es), generally ranges from 2% to 20% by weight, preferably from 2% to 10% and better still from 2% to 6% by weight, relative to the total weight of the composition.

According to the invention, the composition comprises one or more types o f low-density water-inso luble organic particle.

The term " low-density particles" means particles with a density o f less than 1 , preferably less than or equal to 0.4, better still less than 0. 1 and even better still less than 0.06. These low-density particles especially give the composition of the invention a light, airy aspect. They act as structuring agent.

They make it possible especially to obtain a uniform structure (deformable so lid) for constituents normally leading to separate phases (immiscible constituents, for example oil and water).

With a view to obtaining a solid composition having a pleasant and so ft feel, it is preferable to use particles having a mean particle size of from 1 to 250 μηι, preferably from 5 to 200 μηι and preferably from 10 to 150 μηι. This particle size is relative to the largest dimension of the particles.

They may have any shape possible and in particular the shape of beads, fibres, platelets or needles, or even a slightly rounded cellular shape.

The term "water-insoluble" refers to particles that have a so lubility in water at 25 °C o f less than or equal to 0.5 %> and better still of less than or equal to 0. 1 % . These particles may be made from various inert materials that do not react chemically with the medium. In particular, these particles do not react with oils, surfactants, water and the various other constituents of the composition such as the active agents.

The low-density water-inso luble organic particles present in the composition according to the invention are advantageously chosen from particles of thermoplastic materials and organic particles of natural origin.

The particles of thermoplastic materials are especially chosen from po lyamides such as Nylon, polymers or copolymers of acrylonitrile, vinylidene chloride, vinyl chloride and/or acrylic or styrene monomer, which are optionally expanded, and microporous microspheres.

The acrylic monomer is, for example, a methyl or ethyl acrylate or methacrylate. The styrene monomer is, for example, a-methylstyrene or styrene.

Nylon particles that may be used are the Orgasol particles so ld by the company Atochem. These particles are porous, filled spheres with a diameter ranging from 5 μηι to 60 μηι.

Preferably, the particles of thermoplastic materials are deformable hollow particles of an expanded copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and (meth)acrylate or styrene monomer. It is possible, for example, to use a polymer containing 0-60% of units derived from vinylidene chloride, 20- 90% of units derived from acrylonitrile and 0-50% of units derived from an acrylic or styrene monomer, the sum of the percentages (by weight) being equal to 1 00%. The acrylic monomer may be methyl or ethyl (meth)acrylate. The styrene monomer may be styrene or a-methylstyrene.

More preferentially, the particles of thermoplastic materials used in the present invention are ho llow particles of an expanded copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate. These particles may be dry or hydrated. The particles of thermoplastic materials that may be used in the invention are, for example, microspheres of expanded terpolymer o f vinylidene chloride, acrylonitrile and methyl methacrylate, sold under the brand name Expancel by the company Nobel Casco and in particular under the references 55 1 DE 12 (particle size D(0.5) of about 12 μηι and mass per unit vo lume of about 40 kg/m³), 55 1 DE 20 (particle size D(0.5) of about 15 to 25 μιη and mass per unit vo lume of about 60 kg/m³), 5 1 DE 50 (particle size D(0.5) of about 40 μιη), 461 DE 50 and 642 WE 50 of about 50 μπι o f particle size D(0.5 ), 55 1 DE 80 (particle size D(0.5) of about 50 to 80 μιη). It is also possible to use particles of this same expanded terpolymer with a particle size D(0.5) of about 1 8 μηι and a mass per unit volume of about 60 to 80 kg/m³ (Expancel EL23) or with a particle size D(0.5 ) of about 34 μιη and a mass per unit volume of about 20 kg/m³. Mention may also be made o f the Expancel particles 55 1 DE 40 d42 (particle size D(0.5 ) of approximately 30 to 50 μηι and mass per unit volume of approximately 42 kg/m³), 55 1 DE 80 d42 (particle size D(0.5) of approximately 50 to 80 μιη and mass per unit vo lume of approximately 42 kg/m³), 46 1 DE 20 d70 (particle size D(0.5) of approximately 15 to 25 μηι and mass per unit vo lume o f approximately 70 kg/m³), 461 DE 40 d25 (particle size D(0.5) of approximately 35 to 55 μιη and mass per unit volume of approximately 25 kg/m³), 461 DE 40 d60 (particle size D(0.5) of approximately 20 to 40 μιη and mass per unit vo lume of approximately 60 kg/m³), 461 DET 40 d25 (particle size D(0.5) of approximately 35 to 55 μηι and mass per unit volume of approximately 25 kg/m³), 05 1 DE 40 d60 (particle size D(0.5 ) of approximately 20 to 40 μηι and mass per unit volume of approximately 60 kg/m³), 091 DE 40 d30 (particle size D(0.5) of approximately 35 to 55 μιη and mass per unit vo lume of approximately 30 kg/m³) or 091 DE 80 d30 (particle size D(0.5) of approximately 60 to 90 μηι and mass per unit volume of approximately 30 kg/m³). It is also possible to use particles o f a polymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate in unexpanded form, for instance those sold under the brand name Expancel with the reference 55 1 DU 10 (particle size D(0.5) of about 10 μπι) or 461 DU 15 (particle size D(0.5) of about 15 μηι) .

Among the microporous microspheres that may be used in the composition according to the invention, mention may be made o f those so ld by Dow Corning under the name Polytrap, which are formed from lauryl methacrylate/ethylene glycol dimethacrylate copolymers; or those so ld by SEPPIC under the name Micropearl.

As other ho llow polymer particles that may be used in the invention, mention may also be made of polymers and copolymers obtained from itaconic, citraconic, maleic or fumaric acids or esters, or vinyl acetate or lactate . (See to this end document JP-A-2- 1 12304) .

Preferentially, the mass per unit vo lume of the hollow particles is chosen in the range from 15 to 200 kg/m³ , better still from 20 to 120 kg/m³, even better still from 30 to 80 kg/m³ and even more preferentially from 60 to 80 kg/m³.

The hollow particles present in the composition according to the invention generally have a mean particle size D(0.5) ranging from 1 μπι to 300 μηι, for example from 5 μιη to 200 μιη, preferably from 10 μιη to 100 μιη and better still from 15 μπι to 50 μηι.

Preferably, the hollow particles present in the composition according to the invention are filled with a gas. This gas may be air, nitrogen, isobutane or isopentane.

As examples of organic particles of natural origin, mention may be made especially of cork oak bark, and wood originating from the trunk or branches of trees, and more particularly of Quercus suber or of Balsa bombax.

Preferably, the low-density water-insoluble organic particles are chosen from expanded terpolymer microspheres of vinylidene chloride, acrylonitrile and methyl methacrylate, cork oak bark, and wood originating from the trunk or branches of trees, and more particularly from expanded terpolymer microspheres of vinylidene chloride, acrylonitrile and methyl methacrylate, Quercus suber wood and Balsa bombax wood.

The low-density water-inso luble organic particle(s) preferably represent from 1 % to 40% by weight, more preferably from 2% to 20% by weight, better still from 3 % to 15% by weight and even better still from 3 % to 10% by weight, relative to the total weight of the cosmetic composition.

As indicated above, the cosmetic composition according to the invention comprises one or more amphoteric po lymers comprising repetition of:

(i) one or more units derived from a monomer of (meth)acrylamide type,

(iii) one or more units obtained from an acidic monomer o f (meth)acrylic acid type.

Preferably, the units derived from a monomer o f (meth)acrylamide type (i) of the amphoteric po lymer are units o f structure (II) below

in which:

- Ri denotes H or CH₃ ,

- P 2 is chosen from an amino, dimethylamino, tert-butylamino or dodecylamino group, or -NH-CH₂OH.

Preferably, the amphoteric po lymer of the invention comprises repetition of only one unit of formula (II).

The unit derived from a monomer o f (meth)acrylamide type o f formula (II) in which i denotes H and 2 is an amino group is particularly preferred. It corresponds to the acrylamide monomer per se. Preferably also, the units derived from a monomer o f (meth)acrylamidoalkyltrialkylammonium type (ii) of the amphoteric polymer are units of structure (III) below:

in which:

- R3 denotes H or CH₃ ,

- R4 denotes a group (CH₂)_k with k being an integer ranging from 1 to 6 and preferably from 2 to 4;

- P 5 and P ₆ , and R7 , which may be identical or different, each denote an alkyl group containing from 1 to 4 carbon atoms;

- Y^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate .

Among these units derived from a monomer o f (meth)acrylamidoalkyltrialkylammonium type, the ones that are preferred are those derived from the methacrylamidopropyltrimethylammonium chloride monomer, for which R₃ denotes a methyl group, k is equal to 3 , R5 , 6 and R7 denote a methyl group, and Y^" denotes a chloride anion.

Preferably, the amphoteric po lymer of the invention comprises repetition of only one unit of formula (III).

Finally, the units derived from an acidic monomer o f (meth)acrylic acid type (iii) of the amphoteric polymer are preferentially chosen from the units of formula (IV) :

in which:

- Rs denotes H or CH₃ ,

- R9 denotes a hydro xyl group or a group -NH-C(CH3)2 - CH2-SC>3 H .

The preferred units o f formula (IV) correspond to the acrylic acid, methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid monomers.

Preferably, the unit derived from an acidic monomer o f (meth)acrylic acid type is that derived from acrylic acid, for which Rs denotes a hydrogen atom and R9 denotes a hydroxyl group.

The acidic monomer(s) of (meth)acrylic acid type may be non- neutralized or partially or totally neutralized with an organic or mineral base.

Preferably, the amphoteric po lymer of the invention comprises repetition of only a single unit of formula (IV) .

According to a preferred embodiment of the invention, the amphoteric polymer(s) comprise at least 30 mo l% of units derived from a monomer of (meth)acrylamide type . Preferably, they comprise from 30 mo l% to 70 mo l% and more preferably from 40 mo l% to 60 mo l% of units derived from a monomer of (meth)acrylamide type, relative to the total number o f moles of monomers present in the amphoteric polymer.

The content of units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type may advantageously be as fo llows: from 10 mol% to 60 mo l% and preferentially from 20 mol% to 55 mo l% relative to the total number of mo les of monomers present in the amphoteric polymer.

The content of units derived from an acidic monomer o f (meth)acrylic acid type may advantageously be the fo llowing: from 1 mo l% to 20 mol% and preferentially from 5 mo l% to 15 mol% relative to the total number of mo les of monomers present in the amphoteric polymer.

According to one preferred embodiment of the invention, the amphoteric polymer comprises :

- from 30 mo l% to 70 mo l% and more preferably from 40 mo l% to 60 mo l% of units derived from a monomer o f (meth)acrylamide type, - from 10 mo l% to 60 mo l% and preferentially from 20 mo l% to 55 mo l% of units derived from a monomer o f

(meth)acrylamidoalkyltrialkylammonium type, and

- from 1 mol% to 20 mol% and preferentially from 5 mol% to 15 mol% of units derived from an acidic monomer of (meth)acrylic acid type, relative to the total number of mo les of monomers present in the amphoteric polymer.

The amphoteric polymer(s) according to the present invention may also comprise additional units, other than the units derived from a monomer of (meth)acrylamide type, of

(meth)acrylamidoalkyltrialkylammonium type and of (meth)acrylic acid type.

According to one preferred embodiment of the invention, the amphoteric polymer(s) consist solely of units derived from monomers (i) of (meth)acrylamide type, (ii) of

(meth)acrylamidoalkyltrialkylammonium type and (iii) of (meth)acrylic acid type.

More particularly, the amphoteric polymer comprises units derived from the fo llowing monomers : (i) acrylamide, (ii) acrylamidopropyltrimethylammonium chloride, and (iii) acrylic acid.

As examples of amphoteric polymers that are particularly preferred, mention may be made o f acrylamide/ methylacrylamidopropyltrimethylammonium chloride (MAPTAC)/acrylic acid terpolymers. Such polymers are listed in the CTFA dictionary International Cosmetic Ingredient Dictionary, 10th edition 2004, under the name Po lyquaternium 53. Corresponding products are especially sold under the names Merquat 2003 or Merquat 2003PR by the company Nalco.

The amphoteric polymer according to the invention may conventionally be prepared by polymerization starting with its various monomers, according to techniques known to those skilled in the art and especially by radical polymerization.

The amphoteric polymer(s) are generally present in the composition according to the invention in an amount of between 0.01 % and 10% by weight, preferably between 0.01 % and 5% by weight, more particularly between 0.02% and 2% by weight and better still between 0.1 %) and 3% by weight, relative to the total weight of the composition.

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups . These anionic groups are preferably chosen from the following groups : -CO₂H, -C0₂ ^~, - SO₃H, -S O3^", -OS O3H, -O SO3^", -H2PO3 , -HPO3^", -PO3^{2 "}, -H₂P0₂, -HP0₂ ^", -PO2^{2 "}, -POH, -PCT.

As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, -olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkylether sulfo succinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkyl sulfosuccinamates, acyl isethionates and N-acyl taurates, salts of alkyl monoesters of polyglycoside-polycarboxylic acids, acyl lactylates, D-galactoside uronic acid salts, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group denoting a phenyl group .

These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units. The salts of C 6 - C24 alkyl monoesters of polyglycoside- polycarboxylic acids can be chosen from C6 - C24 alkyl polyglycoside- citrates, C 6 - C24 alkyl polyglycoside-tartrates and C 6 - C24 alkyl polyglyco side- sulfo succinates.

When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts, such as sodium or potassium salt and preferably sodium salt, ammonium salts, amine salts and in particular amino alcoho l salts, or alkaline-earth metal salts, such as magnesium salt.

Examples of amino alcohol salts that may especially be mentioned include monoethanolamine, diethanolamine and triethano lamine salts, monoisopropano lamine, diisopropanolamine or triisopropanolamine salts, 2 - amino -2-methyl- 1 -prop ano l salts, 2 -amino -2 -methyl- 1 ,3 -propanedio l salts and tris(hydroxy-methyl)-aminomethane salts.

Use is preferably made o f alkali metal or alkaline-earth metal salts, in particular sodium or magnesium salts.

The anionic surfactants that are optionally present may be mild anionic surfactants, i.e. anionic surfactants without a sulfate function.

As regards the mild anionic surfactants, mention may be made in particular of the following compounds and salts thereof, and also mixtures thereof:

polyoxyalkylenated alkyl ether carboxylic acids,

polyoxyalkylenated alkylaryl ether carboxylic acids,

polyoxyalkylenated alkylamido ether carboxylic acids, in particular those comprising from 2 to 50 ethylene oxide groups,

alkyl-D-galactoside uronic acids,

acyl sarcosinates, acyl glutamates, and

alkyl polyglycoside carboxylic esters .

Use may very particularly be made of polyoxyalkylenated alkyl ether carboxylic acids, such as, for example, lauryl ether carboxylic acid (4.5 EO), for example so ld under the name Akypo RLM 45 CA from Kao . The particularly preferred anionic surfactants are chosen from sulfate and sulfonate anionic surfactants and mixtures thereof, better still from (Ce-24 alkyl) sulfate salts and (Ce-24 alkyl) ether sulfate salts, and mixtures thereof.

The anionic surfactant(s) are present in the composition according to the invention in an amount ranging from 1% to 40% by weight, preferably from 4% to 30% by weight and more preferentially from 8% to 20% by weight relative to the total weight of the composition.

The said agent that is beneficial to keratin materials may be chosen from:

(1) amphoteric surfactants,

(2) antidandruff agents,

(3) hydrolysed or non-hydrolysed, modified or unmodified saccharides, oligosaccharides and polysaccharides other than starches,

(4) hydrolysed or non-hydrolysed, modified or unmodified amino acids, oligopeptides, peptides and proteins,

(5) branched or unbranched fatty acids and fatty alcohols,

(6) animal, plant or mineral waxes,

(7) ceramides and pseudoceramides,

(8) hydroxylated organic acids,

(9) UV-screening agents,

(10) antioxidants and free-radical scavengers,

(11) chelating agents,

(12) seborrhoea regulators,

(13) calmatives,

(14) cationic surfactants,

(15) organomodified or non-organomodified silicones,

(16) mineral, plant or animal oils,

(17) polyisobutenes and poly(a-olefins),

(18) fatty esters other than plant oils, preferably containing from 12 to 50 carbon atoms,

(19) soluble or dispersed anionic polymers, (20) soluble or dispersed nonionic polymers,

(21) cationic polymers,

(22) mineral or organic exfoliants, and

(23) mixtures thereof.

The composition according to the invention may comprise one or more amphoteric surfactants.

The amphoteric or zwitterionic surfactants that may be used in the present invention may especially be derivatives of optionally quaternized secondary or tertiary aliphatic amines comprising at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group, and in which the aliphatic group or at least one of the aliphatic groups is a linear or branched chain comprising from 8 to 22 carbon atoms.

Mention may be made in particular of (Cs-C2o)alkylbetaines, sulfobetaines, (Cs-C2o)alkylamido(Ci-C6)alkylbetaines such as cocamido- propylbetaine, and (Cs-C2o)alkylamido(Ci-C6)alkylsulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, mention may also be made of the products of respective structures (V) and (VI) below:

R_a-CONHCH₂CH₂- N⁺(R_b)(R_c)(CH₂COO^") (V) in which:

R_a represents a C10-C30 alkyl or alkenyl group derived from an acid Ra-COOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;

Rb represents a β-hydroxyethyl group; and

R_c represents a carboxymethyl group;

Ra'-CONHCHjCHs-N BXB') (VI)

in which:

B represents -CH₂CH₂OX',

X' represents the -CH2-COOH, -CH2-COOZ', -CH₂CH₂-COOH CH₂CH₂-COOZ' group or a hydrogen atom, B' represents -(CH2)_Z-Y', with z = 1 or 2,

Y' represents -COOH, -COOZ ' , the group -CH₂-CHOH-S 0₃H or -CH₂-CH0H-S0₃Z' ,

Z ' represents an ion derived from an alkali or alkaline-earth metal, such as sodium, potassium or magnesium; an ammonium ion; or an ion derived from an organic amine and in particular from an amino alcohol, such as monoethanolamine, diethanolamine and triethanolamine, monoisopropano lamine, diisopropanolamine or triisopropanolamine, 2- amino-2-methyl- l -propanol, 2-amino-2-methyl- 1 ,3 -propanediol and tris(hydroxymethyl)aminomethane.

R_a' represents a C 1₀ - C 30 alkyl or alkenyl group of an acid R_a - COOH preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially of C 1 7 and its iso form, or an unsaturated C 1 7 group.

These compounds are also classified in the CTFA dictionary, 5th edition, 1993 , under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made o f the cocoamphodiacetate sold by the company Rhodia under the trade name Mirano l^® C2M Concentrate.

Use may also be made of the compounds of formula (Via) :

R_a ^> -NH-CH(Y' (CH₂)_n-C(0)-NH-(CH₂)_n -N(R_d)(Re) (Via) in which formula:

Y" represents the group -C(0)OH, -C(0)OZ " , -CH₂-CH(OH)- S O₃H or the group -CH₂-CH(OH)-S0₃-Z " ;

Rd and R_e represent, independently o f each other, a C 1 - C 4 alkyl or hydroxyalkyl group; Z" represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;

R_a" represents a C 10- C30 alkyl or alkenyl group of an acid R_a< - C(0)OH preferably present in coconut oil or in hydrolysed linseed oil; n and n' denote, independently o f each other, an integer ranging from 1 to 3.

Among the compounds o f formula (Via), mention may be made o f the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB.

Preferably, the amphoteric or zwitterionic surfactants are chosen from (C8-C2o)alkylbetaines, (Cs -C2o)alkylamido(C i - C6)alkylbetaines and (C₈ -C2o)alkyl amphodiacetates, the sodium salt of diethylaminopropyl laurylaminosuccinamate, and mixtures thereof.

Preferentially, the amphoteric or zwitterionic surfactants are chosen, alone or as a mixture, from cocoylamidopropylbetaine, cocoylbetaine and cocoamphodiacetate.

When the amphoteric or zwitterionic surfactant(s) are present, the composition according to the invention comprises them in an amount preferably ranging from 0. 1 % to 20%> by weight and especially from 0. 1 % to 10% by weight relative to the total weight of the composition.

The composition according to the invention may comprise one or more antidandruff agents.

The antidandruff agents that may be used according to the invention are especially chosen from the families 1 ) to 10) below:

1 ) pyridinethione salts, especially the calcium, magnesium, barium, strontium, zinc, cadmium, tin and zirconium salts. The zinc salt of pyridinethione is particularly preferred.

The zinc salt of pyridinethione is so ld especially under the name

Omadine zinc by the company Arch Personal Care. 2) l-hydroxy-2-pyrrolidone derivatives represented especially by formula (VII);

in which Kg represents an alkyl group containing from 1 to 17 carbon atoms, an alkenyl group containing from 2 to 17 carbon atoms, a cycloalkyl group containing from 5 to 8 carbon atoms, a bicycloalkyl group containing from 7 to 9 carbon atoms; a cycloalkylalkyl group, an aryl group, an aralkyl group with an alkyl containing from 1 to 4 carbon atoms, an arylalkenyl group with an alkenyl containing from 2 to 4 carbon atoms, aryloxyalkyl or arylmercaptoalkyl with an alkyl containing from 1 to 4 carbon atoms, a furylalkenyl group with an alkenyl or a furyl containing from 2 to 4 carbon atoms, an alkoxy group containing from 1 to 4 carbon atoms, a nitro group, a cyano group or a halogen atom.

Rio represents a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkenyl group, a halogen atom, a phenyl group or a benzyl group;

Y represents an organic base, an alkali metal or alkaline-earth metal ion or an ammonium ion.

Examples of compounds of formula (VII) include 1 -hydro xy-4- methyl-2-pyridone, l-hydroxy-6-methyl-2-pyridone, l-hydroxy-4,6- dimethyl-2-pyridone, 1 - hydroxy- 4-methy 1-6 -(2,4,4 -trimethylpentyl) -2- pyridone, 1 -hydroxy-4-methyl-6-cyclohexyl-2-pyridone, 1 -hydroxy-4- methyl-6-(methylcyclohexyl)-2-pyridone, 1 -hydro xy-4 -methyl- 6- (2- bicyclo[2,2, 1 ]heptyl)-2-pyridone, l-hydroxy-4-methyl-6-(4- methylphenyl)-2-pyridone, l-hydroxy-4-methyl-6-[l-(4- nitrophenoxy)butyl]-2-pyridone, l -hydroxy-4-methyl-6-(4- cyanophenoxymethyl)-2-pyridone, 1 -hydroxy- 4-methy 1-6-

(phenylsulfonylmethyl)-2-pyridone and l -hydroxy-4-methyl-6-(4- bro mo benzyl) -2-pyridone.

The compounds of formula (VII) may be used in the form o f salts with organic or mineral bases.

Examples of organic bases are especially alkanolamines of low mo lecular weight such as ethanolamine, diethanolamine, N- ethylethanolamine, triethanolamine, diethylaminoethanol and 2-amino-2- methylpropanedio l; non-volatile bases such as ethylenediamine, hexamethylenediamine, cyclohexylamine, benzylamine and N- methylpiperazine; quaternary ammonium hydroxides, such as trimethylbenzylammonium hydroxide; guanidine and derivatives thereof, and particularly alkyl derivatives thereof. Examples o f mineral bases are especially salts o f alkali metals, e .g. sodium or potassium; ammonium salts, salts of alkaline-earth metals, such as magnesium and calcium; salts of di-, tri- or tetravalent cationic metals, e. g. zinc, aluminium or zirconium.

Alkano lamines, ethylenediamine and mineral bases such as alkali metal salts are preferred.

A compound o f formula (VII) that is particularly preferred is the one for which:

R9 denotes the group

Ri o denotes a methyl group, and

X⁺ denotes N⁺H₃CH₂CH₂OH.

This compound is sold, for example, under the name Octopirox ( l -hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridone,

monoethano lamine salt) by the company Hoechst. 3) 2,2'-dithiobis(pyridine N-oxide) of formula (VIII) :

The compounds o f formula (VIII) may be introduced into the compositions in the form of mineral salts. An example of a mineral salt is magnesium sulfate.

4) the trihalocarbamides especially of formula (IX) below:

in which Z represents a halogen atom such as chlorine or a C 1 - C 4 trihaloalkyl group such as CF₃ ;

5) triclo san, represented by formula (X) :

6) azo le compounds such as climbazole, ketoconazole, clotrimazole, econazole, isoconazole and miconazole.

7) antifungal polymers such as amphotericin B or nystatin.

8) selenium sulfides, in particular those of formula S_xSes-_x, x ranging from 1 to 7.

9) extracts of one or more non-photosynthetic, non-fruiting filamentous bacteria. The bacterial extracts that may be used according to the invention will be chosen from non-photosynthetic, non-fruiting filamentous bacteria as defined according to the classification in Bergey ' s Manual of Systemic Bacteriology, volume 3 , section 23 , 9th edition 1989.

Among the bacteria that may be used, mention will be made more particularly of bacteria belonging to the order Beggiatoales, and especially bacteria belonging to the genus Beggiotoa, for instance various strains of Beggiotoa alba . According to the definition, B. alba corresponds to the former names Beggiotoa arachnoidea, B. gigantea, B. leptomiformis, B. minima and B. mirabilis o f Bergey' s manual, 8th edition. Mention may moreover be made o f bacteria belonging to the genus Vitreoscilla, which is known to be close to and often difficult to distinguish from the genus Beggiatoa. The bacteria that have just been defined, and several of which have been described, generally have an aquatic habitat, and may be found especially in spring water sources .

Among the bacteria that may be used, mention may be made, for example, of Vitreoscilla beggiatoides (ATCC 43 18 1 ) and Beggiatoa alba (ATCC33555).

Preferentially, according to the invention, the use o f the extract of Vitreoscilla filiformis, in particular the strain ATCC 1555 1 , metabo lites thereof and fractions thereof, are claimed.

Moreover, it is known that culturing non-photosynthetic, non- fruiting filamentous bacteria is relatively difficult, as is the production of pure cultures. Use will preferentially be made of the culture described in patent application WO 94/02158.

The term "non-photosynthetic, non-fruiting filamentous bacteria" means not only the culture supernatant but also the biomass obtained after culturing the said bacteria, the envelopes or envelope fractions, or the extracts of the biomass obtained by treating this biomass.

To prepare the extract according to the invention, the said bacteria can be cultured and then separated from the biomass obtained, for example by filtration, centrifugation, coagulation and/or lyophilization.

The extracts that may be used may especially be prepared according to the process described in patent application WO-A-93/00741 . Thus, after culturing, the bacteria are concentrated by centrifugation. The biomass obtained is autoclaved. This biomass may be lyophilized to constitute what is known as the lyophilized extract. Any lyophilization method known to those skilled in the art may be used to prepare this extract.

The supernatant fraction of this biomass may also be filtered in a sterile container to remove the particles in suspension.

The terms "envelopes" and "envelope fractions" refer herein to the bacterial wall and possibly the subjacent membranes .

10) other antidandruff agents are sulfur in its various forms, cadmium sulfide, allantoin, coal or wood tars and derivatives thereof, in particular cade oil, salicylic acid, undecylenic acid, fumaric acid, ellagic acid, ellagic acid tannins, and allylamines such as terbinafine.

Even more preferentially, the antidandruff agents that may be used in the invention are chosen from pyridinethione salts, 1 -hydro xy-2- pyrrolidone derivatives, 2 ,2'-dithiobis(pyridine N-oxide) and selenium sulfides, and mixtures thereof.

Zinc pyridinethione, ( 1 -hydroxy-4-methyl-6-(2,4,4- trimethylpentyl)-2-pyridone and salts thereof and selenium sulfides are particularly preferred.

When the antidandruff agent(s) are present in the composition according to the invention, the amount thereof preferentially ranges from 0.001 % to 10% by weight, and more preferentially from 0.05 % to 8% by weight, relative to the total weight of the composition.

The composition according to the invention may comprise one or more identical or different, hydrolysed or non-hydrolysed, modified or unmodified saccharides, oligosaccharides or polysaccharides other than starches . In general, the compounds of this type that may be used in the present invention are chosen from those described especially in Kirk- Othmer' s Encyclopedia of Chemical Technology, Third Edition, 1982, volume 3 , pp . 896-900, and volume 15 , pp. 439-458, in Polymers in Nature by E.A. MacGregor and C .T. Greenwood, published by John Wiley & Sons, Chapter 6, pp. 240-328 , 1980, and in Industrial Gums - Polysaccharides and their Derivatives , edited by Roy L. Whistler, Second Edition, published by Academic Press Inc.

As examples of hydrolysed or non-hydrolysed, modified or unmodified saccharides, oligosaccharides and polysaccharides that may be used in the invention, mention may be made especially o f glucans, amylose, amylopectin, glycogen, dextrans, β-glucans, celluloses and derivatives thereof (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, carboxymethylcelluloses), fructosans, inulin, levan, mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, glucoronoxylans, arabinoxylans, xyloglucans, galactomannans, glucomannans, pectic acids and pectins, alginic acid and alginates, arabinogalactans, carrageenans, agars, glyco saminoglucans, gum arables, gum tragacanths, ghatti gums, karaya gums, locust bean gums, guar gums and xanthan gums, and mixtures thereo f.

The composition according to the invention may comprise one or more hydro lysed or non-hydro lysed, modified or unmodified amino acids, oligopeptides, peptides or proteins . Examples of amino acids that may be mentioned include cysteine, lysine, alanine, N-phenylalanine, arginine, glycine and leucine, and mixtures thereof. As hydrolysed or non-hydrolysed, mo dified or unmo dified oligopeptides, peptides and proteins that may be used in the composition according to the invention, mention may be made especially of modified or unmodified wool or silk protein hydrolysates, and plant proteins such as wheat proteins .

The composition according to the invention may comprise one or more branched or unbranched fatty acids and alcohols. Among the fatty acids that are suitable for use in the present invention, mention may be made especially of C₈ - C30 carboxylic acids such as palmitic acid, oleic acid, linoleic acid, myristic acid, stearic acid and lauric acid, and mixtures thereof. The fatty alcoho ls that may be used in the present invention especially include C ₈ - C 30 alcohols such as, for example, palmityl alcohol, oleyl alcohol, lino leyl alcohol, myristyl alcohol, stearyl alcoho l and lauryl alcoho l, and mixtures thereof.

The composition according to the invention may comprise one or more animal, plant or mineral waxes.

For the purposes of the present invention, a wax is a lipophilic compound, which is so lid at room temperature (about 25°C), with a reversible solid/liquid change of state, having a melting point greater than about 40°C, which may be up to 200°C, and having in the solid state anisotropic crystal organization. In general, the size of the wax crystals is such that the crystals diffract and/or scatter light, giving the composition that comprises them a more or less opaque cloudy appearance. By raising the wax to its melting point, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but on returning the temperature of the mixture to room temperature, a microscopically and macroscopically detectable recrystallization of the wax in the oils of the mixture is obtained (opalescence) .

As waxes that may be used in the present invention, mention may be made o f waxes of animal origin such as beeswax, spermaceti, lano lin wax and lano lin derivatives; plant waxes such as carnauba wax, candelilla wax, ouricury wax, Japan wax, cocoa butter, cork fibre wax or sugar cane wax; mineral waxes, for example paraffin wax, petroleum j elly wax, lignite wax, microcrystalline waxes or ozokerites, and mixtures thereof.

The composition according to the invention may comprise one or more ceramides and/or pseudoceramides. Mention may be made in particular of the ceramides of categories I, II, III and V according to the Dawning classification, and mixtures thereof, and more particularly N- oleyldehydrosphingosine.

The composition according to the invention may comprise one or more hydroxylated organic acids chosen from those that and well known are used in the art. Mention may be made especially of citric acid, lactic acid, tartaric acid and malic acid, and mixtures thereof.

The composition according to the invention may comprise one or more UV-A-active and/or UV-B-active sunscreens that are well known to those skilled in the art. Mention may be made especially o f dibenzoylmethane derivatives such as 4-methyldibenzoylmethane, 4- isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4- dimethyldibenzoylmethane, 4-tert-butyl-4 ' -diisopropyldibenzoylmethane, p-aminobenzoic acid and its esters such as 2-ethylhexyl p- dimethylaminobenzoate and N-propoxylated ethyl p-aminobenzoate, salicylates such as triethanolamine salicylate, cinnamic acid esters such as 2-ethylhexyl 4-methoxycinnamate, methyl diisopropylcinnamate, menthyl anthranilate, benzotriazole derivatives, triazine derivatives, β,β'-diphenylacrylate derivatives such as 2-ethylhexyl 2-cyano-3 ,3 - diphenylacrylate and ethyl 2-cyano-3 ,3 -diphenylacrylate, 2- phenylbenzimidazole-5 -sulfonic acid and its salts, benzophenone derivatives, benzylidenecamphor derivatives, silicone screening agents, etc, and mixtures thereof.

As examples of antioxidants and free-radical scavengers that may be used in the present invention, mention may be made of ascorbic acid, ascorbyl compounds such as ascorbyl dipalmitate, t-butylhydroquinone, polypheno ls such as phloroglucino l, sodium sulfite, erythorbic acid and flavonoids, and mixtures thereof.

The composition according to the invention may comprise one or more chelating agents chosen especially from EDTA (ethylenediaminetetraacetic acid) and salts thereof such as disodium EDTA and dipotassium EDTA, phosphate compounds such as sodium metaphosphate, sodium hexametaphosphate and tetrapotassium pyrophosphate, and phosphonic acids and salts thereof, such as ethylenediaminetetramethylenephosphonic acid salts, and mixtures thereo f.

The composition according to the invention may comprise one or more seborrhoea regulators such as succinylchitosan and poly-P-alanine, and mixtures thereo f.

The composition according to the invention may comprise one or more calmatives such as azulene and glycyrrhetinic acid, and mixtures thereo f.

The composition according to the invention may comprise one or more cationic surfactants that are well known per se, such as optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzyl ammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazoline derivatives; or amine oxides of cationic nature.

The silicones that may be used in accordance with the invention may be soluble or inso luble in the composition, and they may be in particular po lyorganosiloxanes that are insoluble in the composition o f the invention. They may be in the form of oils, waxes, resins or gums .

Organopolysiloxanes are defined in greater detail in Walter Noll' s "Chemistry and Technology of Silicones" ( 1968) Academic Press. They may be volatile or non-vo latile.

When they are volatile, the silicones are more particularly chosen from those with a boiling point of between 60°C and 260°C , and even more particularly from:

(i) cyclic silicones comprising from 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold especially under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, decamethylcyclopentasiloxane sold under the name Vo latile S ilicone 7158 by Union Carbide, and Silbione 70045 V 5 by Rhodia, and mixtures thereof. Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Vo latile Silicone FZ 3 109 so ld by the company Union Carbide, having the chemical structure :

D - D' - D - D'^■

CH, CH,

I I

with D : — Si - O— with D' : - Si - O—

CH₃ C₈H₁₇

Mention may also be made of mixtures of cyclic silicones with organosilicon compounds, such as the mixture o f octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy- 1 , 1 ' - bis (2, 2, 2 ' ,2 ' ,3 ,3 ' -hexatrimethylsilyloxy)neopentane;

(ii) linear volatile silicones containing 2 to 9 silicon atoms and having a viscosity o f less than or equal to 5. 10^"6 m²/s at 25C . An example is decamethyltetrasiloxane so ld in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp . 27-32 , Todd & Byers, Volatile Silicone Fluids for Cosmetics.

Among the non-vo latile silicones, mention may be made especially of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanes modified with organofunctional groups, and also mixtures thereof.

The organomodified silicones which can be used in accordance with the invention are silicones as defined above and comprising, in their structure, one or more organofunctional groups attached via a hydrocarbon group .

Mention may be made, among the organomodified silicones, o f polyorganosiloxanes comprising :

- polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C 6 - C24 alkyl groups, such as the products known as dimethicone copolyol so ld by the company Dow Corning under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 71 1 by the company Union Carbide, and the (C 12)alkylmethicone copo lyo l sold by the company Dow Corning under the name Q2 5200;

- substituted or unsubstituted amine groups, such as the products so ld under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee, or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amine groups are, in particular, C 1 - C 4 aminoalkyl groups;

- thio l groups, such as the products sold under the names GP 72 A and GP 71 from Genesee;

- alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt;

- hydroxylated groups, such as the polyorganosiloxanes containing a hydroxyalkyl function, described in French patent application FR-A-85/ 16334;

- acyloxyalkyl groups, for instance the polyorganosiloxanes described in patent US-A-4 957 732;

- anionic groups of the carboxylic acid type, for instance in the products described in patent EP 1 86 507 from the company Chisso Corporation, or of the alkylcarboxylic type, such as those present in the product X-22-3701E from the company Shin-Etsu; 2-hydroxyalkyl sulfonate; 2-hydroxyalkyl thiosulfate such as the products sold by the company Goldschmidt under the names Abil® S201 and Abil® S255 ;

- hydroxyacylamino groups, for instance the polyorganosiloxanes described in patent application EP 342 834. Mention may be made, for example, of the product Q2-8413 from the company Dow Corning.

The composition according to the invention may comprise one or more mineral, plant or animal oils. Mention may be made especially, as oils of plant origin, of sweet almond oil, avocado oil, castor oil, olive oil, jojoba oil, sunflower oil, wheatgerm oil, sesame oil, groundnut oil, grapeseed oil, soybean oil, rapeseed oil, safflower oil, coconut oil, corn oil, hazelnut oil, shea butter oil, palm oil, apricot kernel oil or beauty- leaf oil; as oil of animal origin, perhydrosqualene; as oils of mineral origin, liquid paraffin and liquid petroleum j elly; and mixtures thereof.

The composition according to the invention may comprise one or more polyisobutenes and poly(a-olefins), chosen from those that are well known in the art.

The composition according to the invention may comprise one or more fatty esters other than plant oils. Examples that may be mentioned especially include acid esters preferably containing from 8 to 22 carbon atoms, for instance isopropyl myristate, isopropyl palmitate, 2- ethylhexyl palmitate, purcellin oil (stearyl octanoate), isononyl or isostearyl isononanoate, isopropyl lanolate and menthyl lactate, and mixtures thereo f. Mention may also especially be made of esters of fatty alcohols preferably containing from 8 to 22 carbon atoms.

The composition according to the invention may comprise one or more so luble or dispersed anionic polymers that are well known per se. The anionic polymers generally used in the present invention are polymers comprising groups derived from carboxylic acids, sulfonic acids or phosphoric acids, and having a weight-average mo lecular mass of between 500 and 5 000 000.

The carboxylic groups are provided by unsaturated monocarboxylic or dicarboxylic acid monomers such as those corresponding to the formula:

R (A^- COOH

C = C (XI)

3

in which n is an integer from 0 to 10, A denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1 via a heteroatom such as oxygen or sulfur, Ri denotes a hydrogen atom or a phenyl or benzyl group, R₂ denotes a hydrogen atom or a lower alkyl or carboxyl group, and R3 denotes a hydrogen atom, a lower alkyl group or a -CH2-COOH, phenyl or benzyl group .

In formula (XI) above, a lower alkyl group preferably comprises from 1 to 4 carbon atoms and in particular denotes methyl and ethyl groups.

The anionic polymers containing carboxylic groups that are preferred according to the invention are:

A) acrylic or methacrylic acid homo- or copolymers, or salts thereo f and in particular the products sold under the names Versicol® E or by the company Allied Colloid and Ultrahold® by the company BASF, the copolymers of acrylic acid and of acrylamide sold in the form of their sodium salts under the names Reten® 421 , 423 or 425 by the company Hercules, the sodium salts of polyhydroxycarboxylic acids.

B) copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters and acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glyco l such as po lyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1 222 944 and German patent application 2 330 956, the copolymers of this type comprising an optionally N-alkylated and/or hydroxyalkylated acrylamide unit in their chain as described in particular in Luxembourg patent applications 75370 and 75371 or sold under the name Quadramer® by the company American Cyanamid. Mention may also be made o f copolymers o f acrylic acid and of C 1 - C 4 alkyl methacrylate and the copolymer of methacrylic acid and of ethyl acrylate sold under the name Luvimer® MAEX by the company BASF .

C) copolymers derived from crotonic acid, such as those whose chain comprises vinyl acetate or propionate units and optionally other monomers such as allylic or methallylic esters, vinyl ether or vinyl ester of a saturated, linear or branched carboxylic acid containing a long hydrocarbon-based chain such as those comprising at least 5 carbon atoms, it being possible for these polymers to be grafted and crosslinked, or alternatively a vinyl, allylic or methallylic ester of an a- or β-cyclic carboxylic acid. Such polymers are described, inter alia, in French patents 1 222 944, 1 580 545 , 2 265 782, 2 265 781 , 1 564 1 10 and 2 439 798. Commercial products that fall within this category are the resins 28- 29-30, 26- 13- 14 and 28- 13- 10 so ld by the company National Starch.

D) polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives or acrylic acid and esters thereof; these polymers may be esterified. Such polymers are described in particular in US patents 2 047 398, 2 723 248 and 2 102 1 13 and GB patent 839 805 , and especially those so ld under the names Gantrez® AN or ES by the company ISP.

Polymers also falling within this category are the copolymers o f maleic, citraconic or itaconic anhydrides and of an allylic or methallylic ester optionally comprising an acrylamide or methacrylamide group, an a-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions being monoesterified or monoamidated. These polymers are described, for example, in French patents 2 350 384 and 2 357 241 by the Applicant.

E) polyacrylamides comprising carboxylate groups.

The polymers comprising sulfonic groups are polymers comprising vinylsulfonic, styrenesulfonic, naphthalenesulfonic or acrylamidoalkylsulfonic units .

These po lymers can be chosen in particular from:

- polyvinylsulfonic acid salts with a molecular mass of between about 1000 and 100 000, and also copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and esters thereof, and also acrylamide or derivatives thereo f, vinyl ethers and vinylpyrrolidone;

- polystyrenesulfonic acid salts, the sodium salts having a mo lecular mass of about 500 000 and of about 100 000, sold, respectively, under the names Flexan® 500 and Flexan® 130 by National Starch. These compounds are described in patent FR 2 198 719; - polyacrylamidesulfonic acid salts, such as those mentioned in patent US 4 128 63 1 and more particularly the polyacrylamidoethylpropanesulfonic acid sold under the name Cosmedia Polymer® HSP 1 1 80 by Henkel.

According to the invention, the anionic polymers are preferably chosen from acrylic acid copolymers such as the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymer sold under the name Ultrahold Strong® by the company BASF, copolymers derived from crotonic acid, such as the vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives or acrylic acid and esters thereof, such as the methyl vinyl ether/monoesterified maleic anhydride copolymer sold under the name Gantrez® ES 425 by the company ISP, the copolymers o f methacrylic acid and of methyl methacrylate so ld under the name Eudragit® L by the company Rohm Pharma, the copolymer of methacrylic acid and o f ethyl acrylate sold under the name Luvimer® MAEX by the company BASF, the vinyl acetate/crotonic acid copolymer so ld under the name Luviset® CA 66 by the company BASF and the vinyl acetate/crotonic acid/polyethylene glycol terpolymer sold under the name Aristoflex® A by the company BASF.

The anionic polymers that are most particularly preferred are chosen from the methyl vinyl ether/monoesterified maleic anhydride copolymer so ld under the name Gantrez® ES 425 by the company ISP, the copolymers of methacrylic acid and of methyl methacrylate sold under the name Eudragit® L by the company Rohm Pharma, the copolymer of methacrylic acid and of ethyl acrylate sold under the name Luvimer® MAEX by the company BASF, and the vinylpyrro lidone/acrylic acid/lauryl methacrylate terpolymer sold under the name Acrylidone® LM by the company ISP. According to the invention, the anionic polymers may also be used in the form of a latex or pseudolatex, i.e . in the form o f an aqueous dispersion o f inso luble polymer particles.

The composition according to the invention may comprise one or more so luble or dispersed nonionic po lymers . As nonionic polymers that may be used according to the present invention, mention may be made especially of:

- vinylpyrrolidone homopolymers;

- copolymers o f vinylpyrrolidone and vinyl acetate;

- polyalkyloxazolines such as the polyethyloxazo lines sold by the company Dow Chemical under the names Peox® 50 000, Peox® 200 000 and Peox® 500 000;

- vinyl acetate homopolymers, such as the product sold under the name Appretan® EM by the company Hoechst, or the product sold under the name hodopas® A 012 by the company Rhone-Poulenc;

- copolymers o f vinyl acetate and acrylic ester, such as the product sold under the name Rhodopas® AD 3 10 by Rhone-Poulenc;

- copolymers of vinyl acetate and ethylene, such as the product so ld under the name Appretan® TV by the company Hoechst;

- copolymers o f vinyl acetate and maleic ester, for example o f dibutyl maleate, such as the product sold under the name Appretan® MB Extra by the company Hoechst;

-copolymers of polyethylene and maleic anhydride;

alkyl acrylate homopolymers and alkyl methacrylate homopolymers, such as the product sold under the name Micropearl® RQ 750 by the company Matsumoto or the product sold under the name Luhydran® A 848 S by the company BASF;

- acrylic ester copolymers such as, for example, copolymers o f alkyl acrylates and alkyl methacrylates, such as the products sold by the company Rohm & Haas under the names Primal® AC-261 K and Eudragit® NE 30 D, by the company BASF under the names Acronal® 601 , Luhydran® LR 8833 or 8845 , and by the company Hoechst under the names Appretan® N 9213 or N 9212;

- copolymers of acrylonitrile and a nonionic monomer chosen, for example, from butadiene and alkyl (meth)acrylates; mention may be made of the products sold under the names Nipol® LX 53 1 8 by the company Nippon Zeon or those sold under the name CJ 060 1 8 by the company Rohm & Haas;

- polyurethanes, such as the products sold under the names Acryso l® RM 1020 or Acrysol® RM 2020 by the company Rohm & Haas, and the products Uraflex® XP 401 UZ and Uraflex® XP 402 UZ by the company DSM Resins;

- copolymers of alkyl acetate and urethane, such as the product 8538-33 by the company National Starch;

- polyamides, such as the product Estapor® LO 1 1 sold by the company Rhone-Poulenc;

- unmodified or chemically modified nonionic guar gums.

The unmodified nonionic guar gums are, for examp le, the products sold under the name Vidogum® GH 175 by the company

Unipectine and under the name Jaguar® C by the company Meyhall.

The modified nonionic guar gums that can be used according to the invention are preferably modified with C 1 - C 6 hydroxyalkyl groups.

Mention may be made, for example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the state of the art and can be prepared, for example, by reacting corresponding alkene oxides, such as, for example, propylene oxides, with guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar® HP8 , Jaguar® HP60 and Jaguar® HP 120, Jaguar® DC 293 and

Jaguar® HP 105 by the company Meyhall or under the name Galactasol®

4H4FD2 by the company Aqualon. The alkyl groups of the nonionic polymers preferably contain from 1 to 6 carbon atoms.

The cationic polymers are chosen from those which comprise units comprising primary, secondary, tertiary and/or quaternary amine groups that either may form part of the main po lymer chain or may be borne by a side substituent directly attached thereto .

The cationic polymers used generally have a number-average mo lar mass of between 500 and 5 >< 10⁶ approximately and preferably between 10³ and 3 x 10⁶ approximately.

Among the cationic polymers that may more particularly be mentioned are polymers of the polyamine, polyamino amide and polyquaternary ammonium type. These are known products.

Among these polymers, mention may be made of:

(PC I ) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units o f the following formulae :

in which:

R3 , which may be identical or different, denotes a hydrogen atom or a CH₃ group;

A, which may be identical or different, represents a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;

R4 , R5 and Re, which may be identical or different, represent an alkyl group containing from 1 to 1 8 carbon atoms or a benzyl group, and preferably an alkyl group containing from 1 to 6 carbon atoms;

Ri and R₂, which may be identical or different, represent hydrogen or an alkyl group containing from 1 to 6 carbon atoms, and preferably methyl or ethyl;

X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.

The copolymers of the family (PC I ) may also contain one or more units deriving from comonomers which may be chosen from the family o f acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls (C 1 - C 4 ) , acrylic acids or methacrylic acids or esters thereof, vinyllactams such as vinylpyrro lidone or vinylcaprolactam, and vinyl esters .

Thus, among these copo lymers of family (PC I ), mention may be made o f: - copolymers o f acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide,

- copolymers o f acrylamide and of methacryloyloxyethyl- trimethylammonium chloride described, for example, in patent application EP-A-080 976,

- copolymers of acrylamide and methacryloyloxyethyl- trimethylammonium methosulfate,

quaternized or non-quaternized vinylpyrrolidone/ dialkylaminoalkyl acrylate or methacrylate copolymers. These polymers are described in detail in French patents 2 077 143 and 2 393 573 ,

- dimethylamino ethyl methacrylate/vinylcaprolactam/

vinylpyrro lidone terpolymers,

- vinylpyrrolidone/methacrylamidopropyldimethylamine

copolymers,

- and quaternized vinylpyrrolidone/ dimethylaminopropyl- methacrylamide copolymers .

(PC2) Cationic po lysaccharides, especially cationic celluloses and galactomannan gums . Among the cationic polysaccharides, mention may be made more particularly of cellulo se ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-so luble quaternary ammonium monomer and cationic galactomannan gums.

(PC3) Polymers composed of piperazinyl units and of divalent alkylene or hydroxyalkylene groups containing straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers .

(PC4) Water-so luble po lyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-halo acyldiamine, a bis-alkyl halide or alternatively with an o ligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis- azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group o f the polyamino amide; these polyamino amides can be alkylated or, if they contain one or more tertiary amine functions, they can be quaternized.

(PC5) Polyamino amide derivatives resulting from the condensation of polyalkylene po lyamines with po lycarboxylic acids fo llowed by alkylation with difunctional agents . Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl.

Among these derivatives, mention may be made more particularly of adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers.

(PC6) The polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglyco lic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms.

(PC7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (XII) or (ΧΙΓ) :

in which formulae k and t are 0 or 1 , the sum k + t being 1 ; 12 denotes a hydrogen atom or a methyl group ; Ri o and Rn independently of each other denote an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group has preferably 1 to 5 carbon atoms, a lower (C 1 - C 4 ) amidoalkyl group, or else Ri o and Rn may, together with the nitrogen atom to which they are attached, denote heterocyclic groups, such as piperidyl or morpholinyl; Y^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are in particular described in French patent 2 080 759 and in its Certificate of Addition 2 190 406.

Ri o and Rn , independently o f each other, preferably denote an alkyl group having from 1 to 4 carbon atoms.

Among the polymers defined above, mention may be made more particularly of the dimethyldiallylammonium chloride homopolymers so ld in particular under the name Merquat 100 by the company Nalco (and its homologues of low weight-average mo lar masses) and copolymers of diallyldimethylammonium chloride and o f acrylamide;

(P C 8 ) quaternary diammonium polymers, especially those containing repeating units corresponding to the formula:

in which formula (XIII):

Ri3, Ri4, Ri5 and Ri6, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic groups containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic groups, or alternatively Ri3, Ri4, Ri5 and Ri6, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively Rn, Ri4, Ri5 and Ri6 represent a linear or branched C1-C6 alkyl group substituted with a nitrile, ester, acyl or amide group or a group -CO-O- Ri7-D or -CO-NH-R17-D where R17 is an alkylene and D is a quaternary ammonium group;

Ai and Bi represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, and saturated or unsaturated, and which may contain, linked to or inserted in the main chain, one or more aromatic rings, or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X^" denotes an anion derived from a mineral or organic acid;

Ai, Ri3 and R15 may, with the two nitrogen atoms to which they are attached, form a piperazine ring; moreover, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene group, Bi may also denote a group

(CH₂)_n-CO-D-OC-(CH₂)_n- in which D denotes:

a) a glycol residue of formula: -O-Z-O-, where Z denotes a linear or branched hydrocarbon-based group or a group corresponding to one of the following formulae:

-(CH₂-CH₂-0)_x-CH₂-CH₂- -[CH₂-CH(CH₃)-0]_y-CH₂-CH(CH₃)- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization, or any number from 1 to 4, representing an average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon-based group, or else the divalent group

-CH₂-CH₂-S-S-CH₂-CH₂-;

d) a ureylene group of formula: -NH-CO-NH- .

Preferably, X^" is an anion such as chloride or bromide.

These polymers generally have a number-average mo lar mass o f between 1000 and 100 000.

Use may be made more particularly of polymers that are composed of repeating units corresponding to the formula:

- ^"(CH₂)_n-N½CH₂)_p — (a)

R₂ X^" R₄ ^

in which R_{l s} R₂, R3 and R4 , which may be identical or different, each denote an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X^" is an anion derived from a mineral or organic acid.

One compound o f formula (a) which is particularly preferred is the one for which R_{l s} R₂, R₃ and R4 represent a methyl group and n = 3 , p = 6 and X = CI, which is known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

(PC9) Polyquaternary ammonium polymers comprising units o f formula (XIV) :

in which formula:

Ri8, Ri9, R-20 and R₂₁, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β- hydroxypropyl or -CH₂CH₂(OCH₂CH₂)_pOH group,

where p is equal to 0 or to an integer between 1 and 6, with the proviso that Ri₈, R19, R2₀ and R21 do not simultaneously represent a hydrogen atom,

r and s, which may be identical or different, are integers between 1 and 6,

q is equal to 0 or to an integer between 1 and 34,

X^" denotes an anion such as a halide,

A denotes a dihalide group or preferably represents -CH₂-CH₂-0- CH₂-CH₂-.

Such compounds are described especially in patent application EP-A-122324.

Among these, mention may be made, for example, of the products Mirapol® A 15, Mirapol® ADl, Mirapol® AZl and Mirapol® 175, sold by the company Miranol.

(PC 10) Quaternary copolymers of vinyllactam (vinylpyrrolidone and/or vinylcaprolactam) and of vinylimidazole.

(PC11) The crosslinked polymers of methacryloyloxy(Ci-C4)alkyl tri(Ci-C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide.

Other cationic po lymers that can be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates o f polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

Among these cationic po lymers, those of families (PC I ), (PC2), (PC7), (PC8), (PC9) and (PC 10) are preferably used.

The mineral or organic exfoliants are especially chosen from insoluble silicates such as perlite, polyethylene spheres and micronized fruit kernels .

Preferably, the beneficial agents are chosen from classes ( 1 ), (2), (7), (8), (9), (14), ( 15), (21 ) and (22) and even more preferentially from classes ( 1 ), (2), (7), (8), (9), ( 15) and (22).

In one particular embodiment of the invention, the composition comprises one or more beneficial agents from class ( 1 ) optionally mixed with one or more beneficial agents from any one of classes (2) to (22), preferably chosen from those of the classes of beneficial agents (2), (7), (8), (9), ( 14), ( 15), (21 ) and (22) and even more preferentially from those of classes (2), (7), (8), (9), ( 15) and (22) .

When the amphoteric surfactant(s) are present, the weight ratio of the total amount of anionic and amphoteric surfactants to the amount of modified or unmodified starch(es) is preferably greater than or equal to 3 , better still ranging from 3 to 20 and even better still from 3 to 10.

The beneficial agent(s) as described above are present in the composition according to the invention in total preferential proportions ranging from 0.001 % to 20% by weight, more preferentially from 0.01 % to 15% by weight, better from 0.05% to 10% by weight and better still from 0. 1 % to 8% by weight, relative to the total weight of the composition. The composition according to the invention preferably comprises water or a mixture of water and of one or more organic solvents, for instance ethanol, propylene glycol, butylene glyco l, isopropano l, glyco l ethers such as mono-, di- or tripropylene glycol (Ci - C4)alkyl ethers, butylene glycol, isopropanol, glycol ethers such as mono-, di- or tripropylene glycol (Ci -C4)alkyl ethers, mono-, di- or triethylene glycol, dipropylene glycol and diethylene glycol, and mixtures thereof.

In one preferred embodiment, the composition comprises water and does not contain organic solvents.

The composition according to the invention may also comprise any additive that may be used in the field o f application under consideration, for instance fragrances, preserving agents, free-radical scavengers, moisturizers, reducing agents, vitamins, pH regulators and sequestrants .

The composition according to invention may be a shampoo, pre- shampoo, cream rinse, hair shaping, permanent waving or hair straightening composition, a dyeing or bleaching composition, a hair conditioning composition or a foaming composition for the skin (body and/or face).

The composition according to the invention is preferably a rinse- out composition.

The composition according to the invention may be in the form o f a wand, a pencil, a stick, a cake, a paste or a cream.

Preferably, the compositions o f the invention are deformable so lids.

The compositions of the invention may be prepared via standard vat processes or by extrusion.

Another subj ect of the invention is the use of the composition as defined previously for cleansing and/or conditioning keratin materials, such as the hair, the scalp and the skin.

When the composition comprises one or more antidandruff agents as agent that is beneficial to keratin materials, a subject of the invention is also the use of the composition as defined previously for the cosmetic prevention and treatment of dandruff.

In this case, such a composition makes it possible, firstly, to greatly limit, or even to prevent, the appearance of dandruff, and, secondly, to give the head o f hair good cosmetic properties.

In particular, it makes it possible to appreciably reduce the production of dandruff with good efficacy, and to do so in a long-lasting manner, while at the same time having good in-use conditions as described above.

The invention is illustrated by the following examples.

EXAMPLES Examples 1 - 3

Compositions 1 to 3 according to the invention are prepared from the ingredients indicated in the table below. The amounts indicated are expressed as weight percentages of product relative to the total weight of the composition.

Composition 1 2 3

Microspheres (vinylidene

chloride/acrylonitrile/methyl methacrylate

4.9 4.9 4.9 terpolymer) expanded with isobutane

(Expancel 55 1 from Akzo Nobel)

Crosslinked sodium carboxymethyl

4.05 4.05 4.05 (potato) starch

Acrylic acid/MAPTAC/acrylamide

terpolymer ( 10/40/50 mo l%) as an aqueous 2.4 2.4 2.4 20% so lution (Po lyquaternium 53)

Sodium lauryl ether sulfate (2.2 mo l o f 14.3 14.3 14.3 ethylene oxide) as an aqueous solution ( 10 AM) ( 10 AM) ( 10 AM)

Sodium lauryl sulfate powder 4.05 4.05 4.05

Cocoylbetaine in aqueous solution 5.9 5.9 5.9

( 1 .77 ( 1 .77 ( 1 .77 AM) AM) AM)

Apricot kernel powder {Prunus armeniaca

4.05 - - (apricot) seed powder)

Menthyl lactate - 1 -

Perlite - - 1

Citric acid- 1 H₂0 0.2 0.2 0.2

Preserving agents qs qs qs

Fragrance qs qs qs

Deionized water qs 100 100 100

Example 4

Another composition according to the invention is prepared from the ingredients indicated in the table below. The amounts indicated are expressed as weight percentages of product relative to the total weight of the composition.

AM : Active material

The ingredients are mixed together and a composition in the form of a modellable paste is obtained.

It shows very good disintegration in water on application, and very good rinseability.

When applied to the hair, this composition has good cosmetic properties such as a so ft feel, a styling effect and a fresh sensation on application. It shows good efficacy in combating dandruff. Examples 5 -7

Compositions 5 to 7 according to the invention are prepared from the ingredients indicated in the table below. The amounts indicated are expressed as weight percentages of commercial product relative to the total weight of the composition.

AM: Active material The ingredients are mixed together and compositions in the form of a modellable paste are obtained.

They show very good disintegration in water on application, and very good rinseability.

When applied to the hair, these compositions have good cosmetic properties such as a so ft feel, a styling effect and a fresh sensation on application.

Claims

1 . Cosmetic composition comprising:

one or more modified or unmodified starches,

one or more types of low-density water-inso luble organic particles, one or more amphoteric polymers comprising repetition o f:

(i) one or more units derived from a monomer of (meth)acrylamide type,

one or more anionic surfactants, and

one or more agents that are beneficial to keratin materials.

2. Composition according to Claim 1 , characterized in that the starch(es) are modified, and preferably chosen from O-carboxymethyl starches.

3. Composition according to Claim 1 or 2, characterized in that the starch(es) are present in an amount ranging from 2% to 20% by weight, more preferentially from 2% to 10% by weight and better still from 2% to 6% by weight, relative to the total weight of the composition.

4. Composition according to any one o f the preceding claims, characterized in that the water-insoluble organic particles have a density of less than 1 and preferably less than or equal to 0.4.

5. Composition according to any one o f the preceding claims, characterized in that the low-density water-inso luble organic particles are chosen from particles of thermoplastic materials and organic particles of natural origin, preferably from expanded terpolymer microspheres o f vinylidene chloride, acrylonitrile and methyl methacrylate, cork oak bark, and wood originating from the trunk or branches of trees, and more particularly from expanded terpolymer microspheres of vinylidene chloride, acrylonitrile and methyl methacrylate, Quercus suber wood and Balsa bombax wood.

6. Composition according to any one o f the preceding claims, characterized in that the particle(s) are present in an amount ranging from 1 % to 40% by weight, better still from 2% to 20% by weight and even better still from 3 % to 15 % by weight, relative to the total weight of the cosmetic composition.

7. Composition according to any one o f the preceding claims, characterized in that the amphoteric po lymer comprises from 30 mo l%> to 70 mol% of units derived from a monomer of (meth)acrylamide type, from 10 mol% to 60 mol% o f units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type and from 1 mol% to 20 mol% of units derived from an acidic monomer of (meth)acrylic acid type, relative to the total number of moles of monomers present in the amphoteric polymer.

8. Composition according to any one o f the preceding claims, characterized in that the units derived from a monomer of (meth)acrylamide type (i) of the amphoteric polymer are units of structure (II) below :

in which:

- Ri denotes H or C H₃ ,

- R2 is chosen from an amino, dimethylamino, tert-butylamino or dodecylamino group, or -NH-CH₂OH,

and are preferably derived from acrylamide.

9. Composition according to any one o f the preceding claims, characterized in that the units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) of the amphoteric polymer are units of structure (III) below:

in which:

- R3 denotes H or C H₃ ,

- R5 and R6 , and R7 , which may be identical or different, each denote an alkyl group containing from 1 to 4 carbon atoms;

- Y^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate,

and are preferably derived from methacrylamidopropyl- trimethylammonium chloride .

10. Composition according to any one o f the preceding claims, characterized in that the units derived from an acidic monomer of (meth)acrylic acid type (iii) of the amphoteric polymer are chosen from the units of formula (IV) :

in which:

Rs denotes H or CH₃ , - R.9 denotes a hydroxyl group or a group -NH-C(CH3 )2-CH2 -

S0₃H,

and are preferably derived from acrylic acid.

1 1 . Composition according to any one o f the preceding claims, characterized in that the amphoteric polymer is present in the composition in an amount of between 0.01 % and 10% by weight, preferably between 0.01 % and 5 % by weight and more particularly between 0.02% and 2% by weight relative to the total weight of the composition.

12. Composition according to any one of the preceding claims, characterized in that the anionic surfactant(s) are chosen from (C 6 -24 alkyl) sulfate and (Ce-24 alkyl) ether sulfate salts, and mixtures thereof.

13. Composition according to any one o f the preceding claims, characterized in that the beneficial agent(s) are chosen from:

( 1 ) amphoteric surfactants,

(2) antidandruff agents,

(5) branched or unbranched fatty acids and fatty alcoho ls,

(6) animal, plant or mineral waxes,

(?) ceramides and pseudoceramides,

(8) hydroxylated organic acids,

(9) UV-screening agents,

( 10) antioxidants and free-radical scavengers,

( 1 1 ) chelating agents,

( 12) seborrhoea regulators,

( 13) calmatives,

( 14) cationic surfactants,

( 15) organomodified or non-organomodified silicones,

( 16) mineral, plant or animal oils, ( 17) polyisobutenes and poly(a-olefins),

( 18) fatty esters other than plant oils, preferably containing from 12 to 50 carbon atoms,

( 19) so luble or dispersed anionic polymers,

(20) so luble or dispersed nonionic polymers,

(21 ) cationic po lymers,

(22) mineral or organic exfoliants,

(23) and mixtures thereof.

14. Composition according to Claim 13 , characterized in that the beneficial agent(s) are chosen from classes ( 1 ), (2), (7), (8), (9), ( 14),

( 15), (21 ) and (22) and even more preferentially from classes ( 1 ), (2), (7), (8), (9), ( 15) and (22) .

15. Composition according to Claim 13 or 14, characterized in that it comprises one or more beneficial agents from class (1 ) optionally mixed with one or more beneficial agents from any one o f classes (2) to (22), preferably chosen from those of the classes of beneficial agents (2), (7), (8), (9), ( 14), ( 15), (21 ) and (22) and even more preferentially from those of classes (2), (7), (8), (9), ( 15) and (22) .

16. Composition according to Claim 15 , characterized in that the weight ratio of the total amount of anionic and amphoteric surfactants to the amount of modified or unmodified starch(es) is greater than or equal to 3 , preferably ranging from 3 to 20 and better still from 3 to 10.

17. Composition according to any one o f the preceding claims, characterized in that the beneficial agent(s) are present in a total amount ranging from 0.001 % to 20% by weight, more preferentially from 0.01 % to 1 5% by weight and better still from 0.05% to 10% by weight, relative to the total weight of the composition.

18. Use of the cosmetic composition according to any one of the preceding claims, for treating keratin materials.