Composition comprising a fixing polymer, a cationic polymer, an organosilane, a non-ionic polysaccharide and a wax

The present invention relates to a cosmetic hair composition comprising one or more fixing polymers, one or more cationic polymers different from the fixing polymer(s), one or more organosilanes, one or more non-ionic polysaccharides and one or more waxes.

The invention also relates to the use of the cosmetic hair composition according to the invention for shaping and/or conditioning keratin fibres, in particular human keratin fibres such as the hair.

Styling products are normally used to construct and structure the hairstyle and to give it shape retention. They are usually in the form of lotions, gels, mousses, creams, sprays, etc. These compositions generally comprise one or more film- forming polymers or "fixing polymers". These polymers allow the formation of a coating film on the hair, thus providing form retention of the hairstyle.

These compositions may be in the form of hair gels or mousses which are generally applied to wet hair, which is shaped before performing blow drying or drying.

To obtain satisfactory fixing power, it is known practice to incorporate into styling products polymers with very high fixing power, and/or to increase the concentration of fixing polymer. However, the use of such extremely fixing products causes a certain number of drawbacks. In particular, these products can result in the hair having a dry and rough feel.

Furthermore, although these products make it possible to ensure fixing, they nevertheless have a tendency to make the hairstyle rigid, in particular producing a "helmet effect". This effect is often poorly perceived by users.

Moreover, these products are generally not entirely satisfactory in terms of persistence with respect to the various external agents (for example shampoos, light, pollution).

There is thus a real need to develop cosmetic hair compositions that can produce long-lasting form retention of the hairstyle, with styling effects that last throughout the day or even for several days, while at the same time retaining for the hairstyle a natural, non-rigid look, and affording the hair a pleasant, uniform and regular cosmetic feel, in particular a soft, smooth feel and good manageability.

In point of fact, the applicant has now just discovered, surprisingly, that a composition comprising the combination of one or more fixing polymers with one or more cationic polymers different from the fixing polymer(s) i), one or more organosilanes, one or more non-ionic polysaccharides, and one or more waxes makes it possible to solve the abovementioned problems.

A subject of the present invention is thus a cosmetic hair composition comprising:

i) one or more fixing polymers,

ii) one or more cationic polymers different from the fixing polymer(s) i), iii) one or more organosilanes, and

iv) one or more non- ionic polysaccharides, and

v) one or more waxes.

The applicant has in particular noted that the composition according to the invention makes it possible in particular to obtain easy shaping of keratin fibres, that is to say good persistence of the head of hair over time under both humid conditions and dry conditions, while at the same time providing the hair with volume, and without making the hairstyle rigid.

In particular, it gives the hair a particularly soft and pleasant feel.

The applicant has also noted that the use of the composition of according to the invention on keratin fibres such as the hair allows a uniform and regular deposit of said composition.

Most particularly, it has also been noted that the composition according to the invention makes it possible to facilitate disentangling of wet hair, provides body and texture to dried hair, and results, on curly hair, in curls having good definition, with tonicity (bounce).

Moreover, the use of the composition according to the invention makes it possible to improve the persistence of the shaping of keratin fibres (or of the conditioning properties); the shaping, the manageability, and the anti-frizz and conditioning properties can in particular be persistent with respect to at least one shampooing operation, in particular to at least 2 shampooing operations, better still to at least 3 shampooing operations, or even to at least 4 shampooing operations. The particularly persistent conditioning properties are in particular the soft feel on dried hair, and/or the ease of disentangling of keratin fibres.

Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the example that follows.

In the present description, the expression "at least one" is equivalent to the expression "one or more" and can be substituted for said expression; the expression "between" is equivalent to the expression "ranging from" and can be substituted for said expression, and implies that the limits are included. The fixing polymers

The composition according to the present invention comprises one or more fixing polymers.

The term "fixing polymer" is intended to mean any polymer that is capable of giving a shape to hair or of maintaining hair in a given shape.

The fixing polymer(s) used may be chosen from anionic, cationic, amphoteric and non- ionic fixing polymers, and mixtures thereof.

Anionic fixing polymers that may be mentioned include polymers containing groups derived from carboxylic, sulfonic or phosphoric acids, and having a number- average molecular weight of between 500 and 5 000 000.

The carboxylic groups are provided by unsaturated monocarboxylic or dicarboxylic acid monomers, such as those corresponding to formula (I).

(I)

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 adjacent 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,

R ₂ denotes a hydrogen atom, an alkyl group comprising from 1 to 4 carbon atoms or a carboxyl group; R3 denotes a hydrogen atom, an alkyl group comprising from 1 to 4 carbon atoms, a -CH2-COOH group, a phenyl group or a benzyl group.

In formula (I) above, the alkyl group containing from 1 to 4 carbon atoms may in particular denote methyl and ethyl groups.

The anionic fixing polymers bearing carboxylic or sulfonic groups that are preferred are:

A) Copolymers of acrylic or methacrylic acid or salts thereof, including copolymers of acrylic acid and acrylamide, and methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers, in particular Amerhold DR 25 sold by the company Amerchol, and sodium salts of polyhydroxycarboxylic acids. Mention may also be made of methacrylic acid/ethyl acrylate copolymers, in particular in aqueous dispersion, such as Luviflex Soft and Luvimer MAE, which are sold by the company BASF.

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 glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1 222 944 and German application No. 2 330 956, the copolymers of this type comprising an optionally N-alkylated and/or hydroxyalkylated acrylamide unit in their chain as described especially in Luxembourg patent applications 75370 and 75371. Mention may also be made of copolymers of acrylic acid and C1-C4 alkyl methacrylate.

As another anionic fixing polymer from this class, mention may also be made of the butyl aery late/acry lie acid/methacrylic acid branched block anionic polymer sold under the name Fixate G-100 L by the company Lubrizol (INCI name AMP- Acrylates/Allyl Methacrylate Copolymer).

C) Copolymers derived from crotonic acid, such as those of which the 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 optionally grafted and crosslinked, or alternatively a vinyl, allyl or methallyl ester of an a- or β-cyclic carboxylic acid. Such polymers are described, inter alia, in French patents Nos. 1 222 944, 1 580 545, 2 265 782, 2 265 781, 1 564 110 and 2 439 798. Commercial products that fall within this category are the resins 282930, 261314 and 281310 sold by National Starch.

Mention may also be made, as copolymer derived from crotonic acid, of crotonic acid/vinyl acetate/vinyl tert-butylbenzoate terpolymers, and in particular Mexomer PW supplied by the company Chimex.

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 patents US 2 047 398, 2 723 248 and 2 102 1 13 and patent GB 839 805, and especially those sold under the names Gantrez® AN or ES by ISP.

Polymers also falling within this category are the copolymers of maleic, citraconic or itaconic anhydrides and of an allylic or methallylic ester optionally comprising an acrylamide or methacrylamide group, an α-olefm, 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.

F) Polymers containing sulfonic groups. These polymers may be polymers comprising vinylsulfonic, styrenesulfonic, naphthalenesulfonic, acrylamidoalkylsulfonic or sulfoisophthalate units.

These polymers may be chosen especially from:

- polyvinylsulfonic acid salts having a molecular weight of between approximately 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 thereof, vinyl ethers and vinylpyrrolidone;

- polystyrenesulfonic acid salts and sodium salts, having a molecular weight of approximately 500 000 and of about 100 000. These compounds are described in patent FR 2198719;

- polyacrylamidesulfonic acid salts such as those mentioned in patent US 4 128 631;

G) Grafted anionic silicone polymers.

The grafted silicone polymers used are preferably chosen from polymers containing a non-silicone organic backbone grafted with monomers containing a polysiloxane, polymers containing a polysiloxane backbone grafted with non-silicone organic monomers, and mixtures thereof.

H) Anionic polyurethanes, possibly comprising silicone grafts and silicones containing hydrocarbon-based grafts.

Examples of fixing polyurethanes that may especially be mentioned include the dimethylolpropionic acid/isophorone diisocyanate/neopentyl gly col/poly ester diols copolymer (also known under the name polyurethane-1, INCI name) sold under the brand name Luviset® PUR by the company BASF, and the dimethylolpropionic acid/isophorone diisocyanate/neopentyl gly col/polyester diols/silicone diamine copolymer (also known under the name polyurethane-6, INCI name) sold under the brand name Luviset® Si PUR A by the company BASF.

Another anionic polyurethane that may also be used is Avalure UR 450. Polymers containing sulfoisophthalate groups, such as the polymers AQ55 and AQ48 sold by the company Eastman, may also be used.

According to the invention, the anionic fixing 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, methacrylic acid/ethyl acrylate copolymers, in particular in aqueous dispersion, such as Luviflex Soft and Luvimer MAE sold by the company BASF, crotonic acid- derived copolymers, 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, acrylic acid and its esters, such as the monoesterified methyl vinyl ether/maleic anhydride copolymer sold under the name Gantrez® ES 425 by the company ISP, Luviset Si PUR, Mexomer PW, elastomeric or non-elastomeric anionic polyurethanes, polymers comprising sulfoisophthalate groups, and anionic fixing polymers of the B) class; and even more particularly use is preferably made of the butyl acrylate/acrylic acid/methacrylic acid branched block anionic polymer sold under the name Fixate G-100 L by the company Lubrizol (INCI name AMP-Acrylates/Allyl Methacrylate Copolymer).

The cationic fixing polymers that may be used according to the present invention are preferably chosen from polymers comprising primary, secondary, tertiary and/or quaternary amine groups forming part of the polymer chain or directly attached thereto, and having a molecular weight of between 500 and approximately 5 000 000 and preferably between 1000 and 3 000 000.

Among these cationic fixing polymers, mention may be made more particularly of the following cationic polymers:

- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the products known as Copolymer 845, 958 and 937. These polymers are described in detail in French patents 2 077 143 and 2 393 573;

dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP;

quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP;

- quaternary polymers of vinylpyrrolidone and of vinylimidazole, such as, for example, the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the company BASF;

- vinylamine polymers comprising in their structure:

(a) one or more units corresponding to formula (A) below:

— CH— CH—

NH ₂ (A)

(b) optionally one or more units corresponding to formula (B) below:

— CH;— CH—

(B)

NH— C-H

I I

O

In other words, these polymers may be chosen in particular from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.

Preferably, these cationic polymers are chosen from polymers comprising, in their structure, from 5 mol% to 100 mol% of units corresponding to the formula (A) and from 0 to 95 mol% of units corresponding to the formula (B), preferably from 10 mol% to 100 mol% of units corresponding to the formula (A) and from 0 to 90 mol% of units corresponding to the formula (B).

These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium. The weight-average molecular weight of said polymer, measured by light scattering, may range from 1000 to 3 000 000 g/mol, preferably from 10 000 to 1 000 000 and more particularly from 100 000 to 500 000 g/mol.

The polymers comprising units of formula (A) and optionally units of formula (B) are sold in particular under the Lupamin name by the company BASF, for instance, in a non- limiting way, the products provided under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010;

- polymers comprising a fatty chain and comprising a vinylpyrrolidone unit, such as the products sold under the names Styleze W20 and Styleze W10 by the company ISP;

- chitosans or salts thereof; the salts that may be used are in particular the acetate, lactate, glutamate, gluconate or pyrrolidonecarboxylate of chitosan.

Among these compounds, mention may be made of chitosan having a degree of deacetylation of 90.5% by weight, sold under the name Kytan Brut Standard by the company Aber Technologies, and chitosan pyrrolidonecarboxylate sold under the name Kytamer® PC by the company Amerchol.

The amphoteric fixing polymers that can be used in accordance with the invention may be chosen from polymers comprising units B and C distributed randomly in the polymer chain, in which B denotes a unit deriving from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acid monomer comprising one or more carboxylic or sulfonic groups, or alternatively B and C may denote groups deriving from carboxybetaine or sulfobetaine zwitterionic monomers; B and C can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulfonic group connected via a hydrocarbon-based group, or alternatively B and C form part of a chain of a polymer containing an ethylenedicarboxylic unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups. The amphoteric fixing polymers corresponding to the definition given above that are more particularly preferred are chosen from the following polymers:

1) Polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group, such as, more particularly, acrylic acid, methacrylic acid, maleic acid, a-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylamino alkyl methacrylamide and acrylamide. Such compounds are described in United States patent No 3 836 537.

The vinyl compound may also be a dialkyldiallylammonium salt such as diethyldiallylammonium chloride.

2) Polymers containing units deriving:

a) from at least one monomer chosen from acrylamides or methacrylamides which are substituted on the nitrogen by an alkyl group,

b) from at least one acidic comonomer containing one or more reactive carboxylic groups, and

c) from at least one basic comonomer such as acrylic and methacrylic acid esters containing primary, secondary, tertiary and quaternary amine substituents, and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides that are more particularly preferred according to the invention are groups in which the alkyl groups contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert- butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N- dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are more particularly chosen from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, containing 1 to 4 carbon atoms, of maleic or fumaric acids or anhydrides. The preferred basic comonomers are aminoethyl, butylaminoethyl, Ν,Ν'- dimethylaminoethyl and N-tert-butylaminoethyl methacrylates. The copolymers of which the CTFA (4th edition, 1991) name is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the name Amphomer® or Lovocryl® 47 by the company National Starch, are particularly used. 3) Crosslinked and alkylated polyamino amides partially or totally deriving from polyamino amides of general formula (II):

in which R ₄ represents a divalent group derived from a saturated dicarboxylic acid, from a mono- or dicarboxylic aliphatic acid with an ethylenic double bond, from an ester of an alcohol containing 1 to 6 carbon atoms of these acids, or from a group deriving from the addition of any one of said acids with a bis-primary amine or bis- secondary-derived amine, and Z denotes a group of a bis-primary or mono- or bis-secondary polyalkylene-polyamine, and preferably represents:

a) in proportions of from 60 mol% to 100 mol%, the group (III)

NH- (CH ₂ )— NH-

I ^* ' X I n

(in)

where x = 2 and p = 2 or 3, or else x = 3 and p = 2,

this group deriving from diethylenetriamine, from triethylenetetramine or from dipropylenetriamine;

b) in proportions of 0 to 40 mol%, the group (IV) above, in which x = 2 and p = l, which derives from ethylenediamine, or the group deriving from piperazine;

— N N—

(iv)

c) in proportions of from 0 to 20 mol%, the group -NH-(CH ₂ ) ₆ -NH- deriving from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a difunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide, and being alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone or of salts thereof.

The saturated carboxylic acids are preferably chosen from acids containing 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid, 2,4,4- trimethyladipic acid and terephthalic acid, and acids bearing an ethylenic double bond, for instance acrylic, methacrylic and itaconic acids. The alkane sultones used in the alkylation are preferably propane sultone or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

(4) Polymers comprising zwitterionic units of formula (V):

in which

P 5 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group,

y and z each represent an integer from 1 to 3,

P6 and P 7 represent a hydrogen atom or a methyl, ethyl or propyl group,

P 8 and P 9 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in Rio and Rn does not exceed 10.

The polymers comprising such units may also comprise units derived from non-zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.

5) Polymers derived from chitosan comprising monomer units corresponding to the following formulae (VI), (VII) and (VIII) below:

(VI) (VII) (VIII) the unit (VI) being present in proportions of between 0 and 30%, the unit (VII) in proportions of between 5% and 50%> and the unit (VIII) in proportions of between 30%> and 90%>, it being understood that, in this unit (VIII), Rio represents a group of formula (IX):

in which, if q = 0, Rn , R12 and R13, which may be identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue that are optionally interrupted with one or more nitrogen atoms and/or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the alkyl group bears an amino residue, at least one of the groups Rn , R12 and Rn being, in this case, a hydrogen atom;

or, if q = 1, Rn, R12 and R13 each represent a hydrogen atom, and also the salts formed by these compounds with bases or acids.

6) Polymers derived from the N-carboxyalkylation of chitosan.

7) Polymers of units corresponding to the general formula (X) described, for example, in French patent 1 400 366:

in which R14 represents a hydrogen atom or a CH3O, CH3CH2O, or phenyl group, Ri5 denotes hydrogen or a C1-C4 alkyl group such as methyl and ethyl, Ri ₆ denotes hydrogen or a C1-C4 alkyl group such as methyl and ethyl, R17 denotes a C1-C4 alkyl group such as methyl and ethyl or a group corresponding to the formula: -R ₁₈ - N(Ri6>2, with Rig representing a -CH2-CH2-, -CH2-CH2-CH2-, or -CH ₂ -CH(CH ₃ )- group and Ri6 having the meanings given above,

and also the higher homologues of these groups, containing up to 6 carbon atoms.

8) Amphoteric polymers of the type -D-X-D-X-, chosen from:

a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula:

-D-X-D-X-D- (XI)

where D denotes a group

and X denotes the symbol E or E', where E or E', which may be identical or different, denote a divalent group that is an alkylene group with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with hydroxyl groups and which can comprise, in addition to oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups.

b) polymers of formula:

-D-X-D-X- (XII)

where D denotes a group

and X denotes the symbol E or E' and at least once E'; E having the meaning given above and E' is a divalent group that is an alkylene group with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl groups and which contains one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain that is optionally interrupted with an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions, betainized by reaction with chloroacetic acid or sodium chloroacetate.

9) (C ₁ -C ₅ )alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an Ν,Ν-dialkylaminoalkylamine such as N,N- dimethylaminopropylamine or by semiesterification with an N,N-dialkanolamine. These copolymers may also comprise other vinyl comonomers such as viny lcapro lactam.

According to a preferred embodiment, the amphoteric fixing polymers that may be used in the invention may be chosen from branched block copolymers comprising:

(a) non-ionic units derived from at least one monomer chosen from C1-C20 alkyl (meth)acrylates, N-mono-(C2-Ci2 alkyl)(meth)acrylamides and N,N-di(C ₂ -Ci2 alkyl)(meth)acrylamides,

(b) anionic units derived from at least one monomer chosen from acrylic acid and methacrylic acid, and

(c) polyfunctional units derived from at least one monomer comprising at least two polymerizable unsaturated functional groups,

and preferably having a structure constituted of hydrophobic blocks onto which are fixed, via polyfunctional units (c), several blocks that are more hydrophilic.

Preferably, the amphoteric polymers have at least two glass transition temperatures (Tg), at least one of which is greater than 20 °C and the other is less than 20°C.

The preferred amphoteric polymers are polymers comprising units deriving: a) from at least one monomer chosen from acrylamides or methacrylamides which are substituted on the nitrogen by an alkyl group,

b) from at least one acidic comonomer containing one or more reactive carboxylic groups, and

c) from at least one basic comonomer such as acrylic and methacrylic acid esters containing primary, secondary, tertiary and quaternary amine substituents, and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

Mention may be made in particular of the polymers sold under the name Amphomer by the company National Starch.

The non-ionic fixing polymers that may be used according to the present invention are chosen, for example, from:

- polyalkyloxazolines;

- vinyl acetate homopolymers; - vinyl acetate copolymers, for instance copolymers of vinyl acetate and of acrylic ester, copolymers of vinyl acetate and of ethylene, or copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate,

- acrylic ester homopolymers and copolymers, for instance copolymers of alkyl acrylates and of alkyl methacrylates, such as the products provided by the company Rohm & Haas under the names Primal® AC-261 K and Eudragit® NE 30 D, by the company BASF under the name 8845, or by the company Hoechst under the name Appretan® N9212,

- copolymers of acrylonitrile and of a non-ionic monomer chosen, for example, from butadiene and alkyl (meth)acrylates, such as the products provided under the name CJ 0601 B by the company Rohm & Haas,

- styrene homopolymers,

- styrene copolymers, for instance copolymers of styrene and of alkyl (meth)acrylate, such as the products Mowilith® LDM 6911, Mowilith® DM 611 and Mowilith® LDM 6070 sold by the company Hoechst, and the products Rhodopas® SD 215 and Rhodopas® DS 910 sold by the company Rhone-Poulenc; copolymers of styrene, of alkyl methacrylate and of alkyl acrylate; copolymers of styrene and of butadiene; or copolymers of styrene, of butadiene and of vinylpyridine;

- polyamides,

- vinyllactam homopolymers such as vinylpyrrolidone homopolymers and the polyvinylcapro lactam sold under the name Luviskol® Plus by the company BASF,

- vinyllactam copolymers such as a poly(vinylpyrrolidone/vinyllactam) copolymer sold under the trade name Luvitec® VPC 55K65W by the company BASF, poly(vinylpyrrolidone/vinyl acetate) copolymers, such as those sold under the name PVPVA® S630L by the company ISP, Luviskol® VA 73, VA 64, VA 55, VA 37 and VA 28 by the company BASF; and poly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers, for instance the product sold under the name Luviskol® VAP 343 by the company BASF, and

- poly( vinyl alcohols).

The alkyl groups of the non-ionic polymers mentioned above preferably contain from 1 to 6 carbon atoms.

Preferably, the fixing polymer(s) are chosen from non-ionic fixing polymers and anionic fixing polymers, and mixtures thereof. More preferentially, the fixing polymer(s) are chosen from non- ionic fixing polymers such as those described above, and even more preferentially from vinyllactam homopolymers and/or copolymers, such as vinylpyrrolidone homopolymers, poly(vinylpyrrolidone/vinyllactam) copolymers, poly(vinylpyrrolidone/vinyl acetate) copolymers, poly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers and mixtures thereof.

Preferably, the content of the fixing polymer(s) present in the composition is between 0.01% and 20%> by weight, more preferably between 0.1 % and 15% by weight, and even more preferentially between 0.2% and 10% by weight, relative to the total weight of the composition.

The cationic polymers different from the fixing polymer(s) i)

The composition according to the present invention comprises one or more cationic polymers different from the fixing polymer(s) i), preferably having a cationic charge density greater than or equal to 4 milliequivalents/gram (meq/g), better still greater than or equal to 5 meq/g, or even ranging from 5 to 20 meq/g.

The cationic charge density of a polymer corresponds to the number of moles of cationic charges per unit mass of polymer under conditions in which it is totally ionized. It may be determined by calculation if the structure of the polymer is known, i.e. the structure of the monomers constituting the polymer and their molar proportion or weight proportion. It may also be determined experimentally by the Kjeldahl method.

For the purposes of the present invention, the term "cationic polymer" denotes any non-silicone (not comprising any silicon atoms) polymer containing cationic groups and/or groups that can be ionized into cationic groups and not containing any anionic groups and/or groups that can be ionized into anionic groups.

The cationic polymers different from the fixing polymer(s) i) that may be used preferably have a weight-average molar mass (Mw) of between 500 and 5x 10 ⁶ approximately and preferably between 10 ³ and 3x 10 ⁶ approximately. Among the cationic polymers different from the fixing polymer(s) i), mention may be made more particularly of:

(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formulae (XIII), (XIV), (XV) and (XVI) below: — C

(XIII) (XIV) (XV) (XVI)

in which:

- P 3, which may be identical or different, denote a hydrogen atom or a CH ₃ radical; - A, which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;

- P 4, P 5 and Re, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, and preferably an alkyl group containing from 1 to 6 carbon atoms;

- Ri and R ₂ , which may be identical or different, represent a hydrogen atom 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 family (1) may also contain one or more units deriving from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1-C4) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Among these copolymers of family (1), mention may be made of:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as that sold under the name Hercofloc by the company Hercules,

- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, such as those sold under the name Bina Quat P 100 by the company Ciba

Geigy, the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, such as that sold under the name Reten by the company Hercules,

- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as the copolymers sold under the name Styleze CC 10 by ISP;

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

More preferentially, the cationic polymers of the family (1) are chosen from quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl (meth)acrylate copolymers; 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 olefmically unsaturated compound, in particular methylenebisacrylamide; and mixtures thereof.

(2) Cationic polysaccharides, in particular cationic celluloses and galactomannan gums. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water- soluble quaternary ammonium monomer and cationic galactomannan gums.

The cellulose ether derivatives comprising quaternary ammonium groups are in particular described in FR 1 492 597, and mention may be made of the polymers sold under the name Ucare Polymer JR (JR 400 LT, JR 125 and JR 30M) or LR (LR 400 and LR 30M) by the company Amerchol. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.

Cationic cellulose copolymers or cellulose derivatives grafted with a water- soluble quaternary ammonium monomer are described in particular in patent US 4 131 576, and mention may be made of hydro xyalkyl celluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The products sold which correspond to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.

The cationic galactomannan gums are described more particularly in patents US 3 589 578 and US 4 031 307, and mention may be made of guar gums comprising cationic trialkylammonium groups. Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (for example, a chloride). Such products are in particular sold under the names Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar CI 62 by the company Rhodia.

(3) Polymers constituted of piperazinyl units and divalent alkylene or hydroxyalkylene radicals containing linear or branched chains, optionally interrupted with oxygen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers.

(4) Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides 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- haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer 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 of the polyaminoamide; these polyaminoamides can be alkylated or, if they comprise one or more tertiary amine functions, they can be quaternized.

(5) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylamino hydroxy alky ldialkylenetriamine polymers in which the alkyl radical comprises from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.

(6) Polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms; the mole ratio between the polyalkylene polyamine and the dicarboxylic acid preferably being between 0.8: 1 and 1.4: 1; the resulting polyaminoamide being reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide preferably of between 0.5: 1 and 1.8:1. Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or else under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/ epoxypropyl/ diethylenetriamine copolymer.

(7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formula (XVII) or (XVIII): (R^2)-CH2 ^_

(CH ₂ )t- C

H ₂ C ^H 2

XVII

in which

- k and t are equal to 0 or 1 , the sum k + 1 being equal to 1 ;

- Ri2 denotes a hydrogen atom or a methyl radical;

- Rio and Rn , independently of one another, denote a Ci-C ₆ alkyl group, a C1-C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively Rio and Rn may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidyl or morpholinyl; Rio and Rn , independently of one another, preferably denote a C1-C4 alkyl group;

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

Mention may be made more particularly of the homopolymer of dimethyldiallylammonium salts (for example chloride) for example sold under the name Merquat 100 by the company Nalco and the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide, sold in particular under the name Merquat 550 or Merquat 7SPR.

(8) Quaternary diammonium polymers comprising repeating units of formula (XIX) below:

in which:

- Rn, Ri4, Ri5 and Ri6, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals, or else R13, R14, R15 and Ri6, together or separately, form, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second heteroatom different from nitrogen atom;

or else R13, R14, R15 and Ri6 represent a linear or branched Ci-C ₆ alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-R17-D or -CO-NH-Rn-D group, where R17 is an alkylene and D is a quaternary ammonium group;

- Ai and Bi represent divalent polymethylene groups comprising 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;

it being understood that Ai, R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring;

in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi may also denote a group (CH2) _n -CO-D-OC-(CH2) _P - with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting:

a) a glycol residue of formula -O-Z-O-, in which Z denotes a linear or branched hydrocarbon-based radical, or a group corresponding to one of the following formulae: -(CH ₂ CH20) _X -CH ₂ CH2- and -[CH2CH(CH ₃ )0] _y -CH2CH(CH ₃ )-, 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-, in which Y denotes a linear or branched hydrocarbon-based radical, or else the divalent radical -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 have a number-average molar mass (Mn) generally of between 1000 and 100 000.

Mention may be made more particularly of polymers that are constituted of repeating units corresponding to formula (XX): R ₁ R 3

N (CH ₂ ) _n - N- (CH ₂ ) _p

. ' X

Λ X- R,

(XX)

in which Ri, R ₂ , R ₃ and R ₄ , which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X ^" is an anion derived from a mineral or organic acid.

A compound of formula (XX) that is particularly preferred is the one for which Ri, R ₂ , R ₃ and R ₄ represent a methyl radical, n = 3, p = 6 and X = CI, which is known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

(9) Polyquaternary ammonium polymers comprising units of formula (XXI):

^R 18 R ₂₀

— N+ - (CH ₂ ) _r - NH - CO - (CH ₂ ) _q - CO - NH (CH ₂ ) _S - N+ - A—

X- ' I

^R 19 _v ^R 21

X- (XXI) in which:

- Ris, Ri9, R20 and R21, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or -CH ₂ CH2(OCH ₂ CH2)pOH radical, where p is equal to 0 or to an integer of between 1 and 6, with the proviso that Ris, R1 , 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 divalent radical of a dihalide or preferably represents

Examples that may be mentioned include the products Mirapol® A 15, Mirapol® ADl, Mirapol® AZl and Mirapol® 175 sold by the company Miranol. (10) Polyamines such as Polyquart® H sold by Cognis, referred to under the name Polyethylene glycol (15) tallow poly amine in the CTFA dictionary; and (1 1) Mixtures of the above polymers.

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

Preferably, the cationic polymers different from the fixing polymer(s) i) are chosen from those of the families (1), (7) and (8) mentioned above, and mixtures thereof.

Among the cationic polymers mentioned above, use may preferably be made of cationic cyclopolymers, in particular homopolymers or copolymers of dimethyldiallylammonium salts (for example chloride), sold under the names Merquat 100, Merquat 550 and Merquat S by the company Nalco, optionally crosslinked homopolymers or copolymers of methacryloyloxy(Ci-C4)alkyltri(Ci- C4)alkylammonium salts, and mixtures thereof. According to one preferred embodiment of the invention, the cationic polymer(s) different from the fixing polymer(s) i) are chosen from:

- alkyldiallylamine or dialkyldiallylammonium cyclopolymers,

- homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising units as defined in the family (1),

- and mixtures thereof.

More preferentially, according to this embodiment of the invention, the cationic polymer(s) different from the fixing polymer(s) i) are chosen from 2- methacryloyloxyethyltrimethylammonium chloride homopolymers or copolymers, dimethyldiallylammonium chloride homopolymers, and mixtures thereof.

Preferably, the content of the cationic polymer(s) different from the fixing polymer(s) i) present in the composition is between 0.01% and 15% by weight, more preferably between 0.05% and 10% by weight, and even more preferentially between 0.1% and 5% by weight, relative to the total weight of the composition. Organosilanes

The composition according to the present invention comprises one or more organosilanes.

The organosilane(s) that can be used according to the invention are preferably chosen from the compounds of formula (XXII), oligomers thereof, hydrolysis products thereof and/or mixtures thereof:

RiSi(OR ₂ )z(R3)x(OH) _y (XXII)

in which

- Ri is a cyclic or acyclic, linear or branched, saturated or unsaturated Ci to C ₂₂ and especially C ₂ to C20, hydrocarbon-based chain, which may be substituted with one or more groups chosen from amine groups NH ₂ or NHR, R being a linear or branched Ci to C20 and especially Ci to C ₆ alkyl, a C3 to C40 cycloalkyl or a C ₆ to C30 aromatic radical; the hydroxyl (OH) group; a thiol group; an aryl group, more particularly benzyl, optionally substituted with one or more groups NH ₂ or NHR; Ri possibly being interrupted with one or more oxygen, sulfur and/or nitrogen heteroatoms and/or one or more carbonyl (CO) groups;

- R ₂ and R3, which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms,

- y denotes an integer ranging from 0 to 3,

- z denotes an integer ranging from 0 to 3, and

- x denotes an integer ranging from 0 to 2,

- with z + x + y = 3.

For the purposes of the present invention, the term "oligomer" is intended to mean the polymerization products of the compounds of formula (XXII) comprising from 2 to 10 silicon atoms.

Preferably, Ri is a linear or branched, more preferentially linear, saturated Ci to C22 and especially C ₂ to C ₁₂ hydrocarbon-based chain, which may be substituted with an amine group NH ₂ or NHR, R being a Ci to C20 and especially Ci to C ₆ , alkyl.

Preferably, R ₂ represents an alkyl group comprising from 1 to 4 carbon atoms, more preferentially a linear alkyl group comprising from 1 to 4 carbon atoms, and in particular the ethyl group.

Preferably, z ranges from 1 to 3. Preferably, y is equal to 0.

Preferentially, z is equal to 3.

Even more preferentially, x and y are equal to 0 and z is equal to 3.

In one embodiment of the invention, the organosilane(s) are chosen from the compounds of formula (XXII) in which Ri represents a linear alkyl group comprising from 1 to 18 carbon atoms and more particularly from 1 to 12 carbon atoms, or a Ci to C ₆ , preferably C ₂ to C ₄ , aminoalkyl group.

Particularly preferably, in this embodiment, Ri represents a methyl or octyl group.

In another embodiment of the invention, the organosilane(s) are chosen from the compounds of formula (XXII) in which Ri is a linear or branched, saturated or unsaturated Ci to C ₂₂ hydrocarbon-based chain, substituted with one or more amine groups NH ₂ or NHR, R being a linear or branched Ci to C ₂ o, preferably Ci to C ₆ , alkyl, or a C ₃ to C ₄ o cycloalkyl or a C ₆ to C ₃ o aromatic.

Particularly preferably, in this other embodiment, the organosilane(s) are chosen from the compounds of formula (XXIII), oligomers thereof, hydrolysis products thereof and/or mixtures thereof:

OR

/

H ₂ N(CH ₂ )— Si— OR

\

^{0 R} (XXIII)

in which

the radicals R, which may be identical or different, are chosen from linear or branched Ci to C ₆ , more preferentially C ₂ to C ₄ , alkyl radicals; and n is an integer ranging from 1 to 6, more preferentially from 2 to 4.

Preferably, the organosilane(s) that can be used according to the invention are chosen from methyltriethoxysilane, octyltriethoxysilane (OTES), dodecyltriethoxysilane, octadecyltriethoxysilane, hexadecyltriethoxysilane, 3- aminopropyltriethoxysilane (APTES), 2-aminoethyltriethoxysilane (AETES), 3- aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3 -(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-(2- aminoethylaminomethyl)phenethyltrimethoxysilane, oligomers thereof, hydrolysis products thereof, and mixtures thereof; and preferably the organosilane(s) are chosen from methyltriethoxysilane, octyltriethoxysilane (OTES) and 3- aminopropyltriethoxysilane (APTES), oligomers thereof, hydrolysis products thereof, and mixtures thereof; and even more preferentially from 3-aminopropyltriethoxysilane (APTES), oligomers thereof, hydrolysis products thereof, and mixtures thereof

The organosilanes used in the composition of the invention, especially those comprising a basic function, may be partially or totally neutralized in order to improve the water solubility thereof. In particular, the neutralizer may be chosen from organic or mineral acids, such as citric acid, tartaric acid, lactic acid or hydrochloric acid.

Preferably, the optionally neutralized organosilane(s) that can be used according to the invention are water-soluble and especially soluble at a concentration of 2% by weight, better still at a concentration of 5% by weight and even better still at a concentration of 10% by weight in water at a temperature of 25°C and at atmospheric pressure (1 atm). The term "soluble" is intended to mean the formation of a single macroscopic phase.

Preferably, the content of the organosilane(s) present in the composition is between 0.1% and 15% by weight, more preferably between 1% and 10% by weight, and even more preferentially between 2% and 8% by weight, relative to the total weight of the composition. The non-ionic polysaccharides

The composition according to the invention comprises one or more non- ionic polysaccharides.

Mention may in particular be made, as polysaccharides according to the invention, of those chosen from glucans, modified or unmodified starches (such as those resulting, for example, from cereals, such as wheat, maize or rice, from legumes, such as yellow pea, or from tubers, such as potato or cassava), amylose, amylopectin, glycogen, dextrans, celluloses and derivatives thereof (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses), mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, chitosans, glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, arabinogalactans, carrageenans, agars, gums arabic, gums tragacanth, ghatti gums, karaya gums, locust bean gums, galactomannans such as guar gums and non-ionic derivatives thereof (hydroxypropyl guar), and mixtures thereof. Preferably, the non-ionic polysaccharide(s) are chosen from starches, guar gums, celluloses and derivatives thereof, and mixtures thereof.

As indicated above, the polysaccharide(s) according to the invention may be modified or non-modified.

The unmodified guar gums are, for example, the products sold under the name Vidogum GH 175 by the company Unipectine and under the names Meypro-Guar 50 and Jaguar C by the company Rhodia Chimie.

The modified non-ionic guar gums are in particular modified with Ci-C ₆ hydroxyalkyl groups.

Among the hydroxyalkyl groups, mention may be made, by way of example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known from the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance, propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

The degree of hydroxy alky lation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, preferably ranges from 0.4 to 1.2.

Such non-ionic guar gums optionally modified by hydroxyalkyl groups are, for example, sold under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120, Jaguar DC 293 and Jaguar HP 105 by Rhodia Chimie or under the name Galactasol 4H4FD2 by Aqualon.

Use is made in particular, among the celluloses, of hydroxyethylcelluloses and hydroxypropylcelluloses. Mention may be made of the products sold under the names Klucel EF, Klucel H, Klucel LHF, Klucel MF and Klucel G by Aqualon and Cellosize Polymer PCG-10 by Amerchol.

Preferably, the non-ionic polysaccharide(s) according to the invention are chosen from guar gums and/or derivatives thereof which are non- ionic, and/or mixtures thereof; more preferentially from non-ionic guar gums modified with hydroxyalkyl groups.

Preferably, the content of the non- ionic polysaccharide(s) is between 0.01% and 20% by weight, preferentially between 0.1 % and 10%> by weight, even better still between 0.2% and 5% by weight, relative to the total weight of the composition. The waxes

The composition according to the present invention also comprises one or more waxes.

For the purposes of the present invention, a wax is a lipophilic compound, which is solid at ambient temperature (25°C) and atmospheric pressure, 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 an anisotropic crystal organization.

By way of examples, the wax(es) may be chosen from mineral waxes, for instance paraffin, petroleum jelly, lignite wax or ozokerite; plant waxes, for instance cocoa butter, cork fibre or sugar cane waxes, olive tree wax, rice wax, hydrogenated jojoba wax, ouricury wax, carnauba wax, candelilla wax, alfalfa wax, or absolute waxes of flowers, such as essential wax of blackcurrant flower sold by the company Bertin (France); waxes of animal origin, for instance beeswaxes or modified beeswaxes (cerabellina), spermaceti, lanolin wax and lanolin derivatives; microcrystalline waxes; non-silicone synthetic waxes, such as polyethylene waxes, polypropylene waxes and/or polytetrafluoroethylene waxes; and mixtures thereof.

According to one preferred embodiment of the invention, the wax(es) suitable for the invention are chosen from waxes of animal, plant or mineral origin, non-silicone synthetic waxes and mixtures thereof; preferably chosen from waxes of plant origin, non-silicone synthetic waxes, and mixtures thereof; and more preferentially chosen from cocoa butter, cork fibre waxes, sugarcane waxes, olive tree wax, rice wax, hydrogenated jojoba wax, ouricury wax, carnouba wax, candelilla wax, alfalfa wax, absolute waxes of flowers, such as essential wax of blackcurrant flower, polyethylene waxes, propylene microwaxes, polytetrafluoroethylene waxes, and mixtures thereof.

Even more preferentially in this preferred embodiment, the wax(es) are chosen from carnauba wax, candelilla wax, polyethylene waxes, polypropylene waxes, polytetrafluoroethylene waxes, and mixtures thereof; even better still from carnauba wax. Preferably, the composition according to the invention comprises the wax or waxes in a total amount of advantageously between 0.001% and 10%> by weight, preferably between 0.005%> and 5% by weight, and more preferentially between 0.01% and 2% by weight, relative to the total weight of the composition.

Preferably, the wax(es) are in the form of a microdispersion.

For the purposes of the present invention, the expression "wax(es) in the form of a microdispersion" or "microdispersion of wax(es)" is intended to mean one or more waxes dispersed in the form of particles in a continuous phase.

It should be noted that, when several waxes are present in a microdispersion in the composition according to the invention, the particles may be constituted of a mixture of said waxes, or else different particles, formed from waxes of different natures, may coexist in the composition.

Preferably, the particles of wax(es) typically have a volume-average size of less than or equal to 10 μιη, more preferably less than 5 μιη, even more preferentially ranging from 0.01 to 1 μιη, better still ranging from 0.05 to 0.5 μιη, or even ranging from 0.1 to 0.4 μιη.

The size of the particles of wax(es) can be determined by laser diffraction granulometry, in particular using a Coulter N5 or LSI 3320 laser particle sizer.

Microdispersions of wax(es) that can be used according to the present invention are for example described in application EP394078 or EP446094.

The wax(es) may be introduced into the composition according to the invention in the form of preformed microdispersions, which preferably comprise the wax(es) in a total amount ranging from 0.1% to 60% by weight, preferentially from 1% to 50% by weight, even more preferentially from 10% to 40% by weight, better still from 15% to 35% by weight, relative to the total weight of the microdispersion of wax(es).

This (these) microdispersion(s) may comprise one or more surfactants, preferably non- ionic surfactants, as described below, in a total amount preferably ranging from 0.1% to 30% by weight, more preferentially from 0.5% to 20% by weight, better still from 1% to 15% by weight, or even from 3% to 10% by weight, relative to the total weight of the microdispersion of wax(es). Such microdispersions of wax(es) may be present in the composition preferably in an amount ranging from 0.001% to 20% by weight, more preferentially from 0.01 o to 10%> by weight, even more preferentially from 0.05%> to 5% by weight, better still from 0.1% to 4% by weight, relative to the total weight of the composition.

The aqueous phase

Preferably, the composition according to the invention is aqueous, more preferentially it comprises an aqueous continuous phase, in which the particles of wax(es) are dispersed.

In this embodiment, the composition according to the invention comprises water in an amount preferably ranging from 10% to 98% by weight, more preferentially from 20%o to 95% by weight, even more preferentially from 30%> to 90%> by weight, better still from 40%> to 88% by weight, or even from 55% to 88% by weight, relative to the total weight of the composition.

The surfactants

The composition according to the invention may optionally further comprises one or more surfactants chosen from non-ionic surfactants, anionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants, and mixtures thereof. Preferentially, the surfactant(s) are chosen from non-ionic surfactants.

The non-ionic surfactants may be chosen from those described in the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pages 1 16-178.

Examples of non-ionic surfactants that may be mentioned include the following compounds, alone or as a mixture:

- oxyalkylenated (Cs-C24)alkylphenols;

- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated C8 to C ₄ o alcohols, preferably comprising one or two fatty chains;

- saturated or unsaturated, linear or branched, oxyalkylenated Cs to C30 fatty acid amides;

- esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of polyethylene glycols and/or of glycerol, which are preferably (poly)oxyethylenated; such as PEG-30 glyceryl stearate. - preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of sorbitol;

- esters of fatty acids and of sucrose;

- (C8-C3o)alkyl(poly)glucosides, (C8-C3o)alkenyl(poly)glucosides, which are optionally oxyalkylenated (0 to 10 oxyalkylene units) and comprising from 1 to 15 glucose units, (C8-C3o)alkyl(poly)glucoside esters;

- saturated or unsaturated oxyethylenated plant oils;

- condensates of ethylene oxide and/or of propylene oxide;

- N-(C8-C3o)alkylglucamine and N-(C8-C3o)acylmethylglucamine derivatives; - amine oxides.

The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.

The number of moles of ethylene oxide and/or of propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol ranges in particular from 1 to 50 and better still from 1 to 10.

Advantageously, the non-ionic surfactants according to the invention do not comprise any oxypropylene units.

Preferably, they comprise a number of moles of ethylene oxide ranging from 1 to 250, in particular from 2 to 100 and better still from 2 to 50.

As examples of glycerolated non-ionic surfactants, use is preferably made of monoglycerolated or polyglycerolated Cs to C40 alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol.

Mention may be made, as examples of compounds of this type, of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol and octadecanol containing 6 mol of glycerol.

Among the glycerolated alcohols, it is more particularly preferred to use the Cs to Cio alcohol containing 1 mol of glycerol, the C10 to C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol. The non-ionic surfactant(s) preferably present in the composition according to the invention are preferentially chosen, alone or as a mixture, from:

- saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and preferably comprising one or two fatty chains;

- saturated or unsaturated oxyethylenated plant oils comprising from 1 to 100 and preferably from 2 to 50 mol of ethylene oxide;

- (C8-C3o)alkyl(poly)glucosides, which are optionally oxyalkylenated, preferably with 0 to 10 mol of ethylene oxide and comprising 1 to 15 glucose units;

- monoglycerolated or polyglycerolated Cs to C40 alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol;

- saturated or unsaturated, linear or branched, oxyalkylenated Cs to C30 fatty acid amides;

- preferably (poly)oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of polyethylene glycols and/or of glycerol;

- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of sorbitol. More preferentially, the non-ionic surfactant(s) present in the composition according to the invention are chosen, alone or as a mixture, from:

- saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and comprising one or two fatty chains, in particular at least one C8-C20, in particular Cio-Cis, alkyl chain;

- preferably (poly)oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of polyethylene glycols and/or of glycerol;

- (C8-C3o)alkyl(poly)glucosides, which are optionally oxyalkylenated, preferably with 0 to 10 mol of ethylene oxide and comprising 1 to 15 glucose units.

Particularly preferably, the non- ionic surfactant(s) present in the composition are chosen from preferably (poly)oxyethylenated, esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of polyethylene glycols and/or of glycerol. According to one preferred embodiment of the invention, the non-ionic surfactant(s) are chosen, alone or as a mixture, from esters of saturated or unsaturated, linear or branched, Cs to C30, in particular C12-C24, acids and of glycerol, which are (poly)oxyethylenated, the number of moles of ethylene oxide possibly ranging from 1 to 100, preferably from 2 to 50, better still from 10 to 40; preferentially from PEG-30 glyceryl stearate.

Preferably, when they are present, the composition according to the invention comprises the non-ionic surfactant(s) in an amount ranging from 0.005% to 20% by weight, in particular from 0.01%> to 15% by weight, better still from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, even better still from 0.5% to 5% 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.

In the present description, a species is termed "anionic" when it bears at least one permanent negative charge or when it can be ionized into a negatively charged species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.

The anionic surfactants may be sulfate, sulfonate, carboxylic (or carboxylate) surfactants, and mixtures thereof.

Preferably, the anionic surfactant(s) are chosen from:

- C6-C24 and especially C12-C20 alkyl sulfates;

- C6-C24 and in particular C12-C20 alkyl ether sulfates; preferably comprising from 2 to 20 ethylene oxide units,

- C6-C24 alkyl sulfo succinates and especially C12 -C20 alkyl sulfo succinates; especially lauryl sulfo succinates;

- C6-C24 and especially C12-C20 alkyl ether sulfo succinates;

- (C6-C24)acylisethionates, preferably (Ci2-Ci8)acylisethio nates;

- C6-C24 and especially C12-C20 acylsarcosinates; especially palmitoylsarcosinates;

- (C ₆ -C24)alkyl ether carboxylates, preferably (Ci2-C2o)alkyl ether carboxylates,

- polyoxyalkylenated (C6-C24)alkyl(amido) ether carboxylic acids and salts thereof, in particular those comprising from 2 to 50 alkylene oxide and in particular ethylene oxide groups; - C6-C24 and especially C12-C20 acylglutamates;

- C6-C24 and especially C12 -C20 acylglycinates;

- and mixtures thereof;

in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.

When the anionic surfactant is in salt form, said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magnesium salt.

Examples of amino alcohol salts that may be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2- methyl-l-propanol salts, 2-amino-2-methyl-l,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.

Preferably, when they are present, the composition according to the invention comprises the anionic surfactant(s) in an amount ranging from 0.1% to 20% by weight, in particular from 0.2%> to 10%> by weight, better still from 0.5%> to 5% by weight, relative to the total weight of the composition.

The cationic surfactant(s) can be chosen from optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

More particularly, the cationic surfactant(s) may be chosen from a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts. Use may also be made of the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180. Use may also be made of behenoylhydroxypropyltrimethylammonium chloride, for example, sold by the company Kao under the name Quartamin BTC 131.

Preferably, the cationic surfactant(s) are chosen from cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts and mixtures thereof; and more particularly from behenyltrimethylammonium chloride or methosulfate, cetyltrimethylammonium chloride or methosulfate, dipalmitoylethylhydroxyethylmethylammonium chloride or methosulfate, and mixtures thereof.

Preferably, when they are present, the composition according to the invention comprises said cationic surfactant(s) in an amount ranging from 0.1% to 10% by weight, preferably ranging from 0.2% to 8% by weight, preferentially from 0.5% to 5% by weight, relative to the total weight of the composition.

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

Mention may in particular be made of (C8-C2o)alkylbetaines, sulfobetaines, (C8-C2o)alkylsulfobetaines, (C8-C2o)alkylamido(Ci-C6)alkylbetaines, such as cocoamidopropylbetaine, (C8-C2o)alkylamido(Ci-C6)alkylsulfobetaines, and also mixtures thereof.

Among the derivatives of optionally quaternized secondary or tertiary aliphatic amines that may be used, mention may also be made of the products having the following respective structures (Al) and (A2):

(Al) R _a -CON(Z)CH2-(CH2) _m -N ⁺ (Rb)(R _c )(CH ₂ COO-)

in which:

Pa represents a C10-C30 alkyl or alkenyl group derived from an acid Ra-COOH preferably present in hydrolyzed coconut oil, or a heptyl, nonyl or undecyl group, Rb represents a β-hydroxyethyl group,

Rc represents a carboxymethyl group,

m is equal to 0, 1 or 2,

Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group,

in which:

B represents -CH ₂ CH ₂ OX ^* , with X' representing -CH ₂ -COOH, CH ₂ -COOZ', - CH ₂ CH ₂ -COOH, -CH ₂ CH ₂ -COOZ', or a hydrogen atom, B ^* represents -(CH ₂ ) _Z -Y', with z = 1 or 2, and Y' representing -COOH, -COOZ', - CH2-CHOH-SO3H or CH2-CHOH-SO3Z',

m' is equal to 0, 1 or 2,

Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group,

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

Ra' represents a C10-C30 alkyl or alkenyl group of an acid Ra'COOH preferably present in hydrolyzed linseed oil or coconut oil, an alkyl group, especially a C ₁₇ alkyl group, and its iso form, or an unsaturated C ₁₇ group.

Use may also be made of the compounds of formula (A3):

(A3) Ra"-NH-CH(Y")-(CH ₂ )„-C(0)-NH-(CH ₂ V-N(Rd)(Re)

in which:

- Ra" represents a C10-C30 alkyl or alkenyl group of an acid

Ra"-C(0)OH, which is preferably present in hydrolyzed linseed oil or coconut oil;

- Y" represents the group -C(0)OH, -C(0)OZ", -CH ₂ -CH(OH)-S0 ₃ H or the group CH ₂ -CH(OH)-S03-Z", with Z" representing a cation resulting from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine;

- Rj and Re, independently of one another, represent a C1-C4 alkyl or hydroxy alkyl radical; and

- n and n', independently of one another, denote an integer ranging from 1 to 3.

Preferably the amphoteric surfactants are chosen from alkyl(C8-C ₂ o)betaines, alkyl(C8-C ₂ o)amidoalkyl(Ci-C6)betaines, alkyl(C8-C ₂ o)amphoacetates and alkyl(C8- C ₂ o)amphodiacetates, and mixtures thereof, and in particular from cocobetaine and cocoamidopropylbetaine.

Preferably, when they are present, the composition according to the invention comprises said amphoteric or zwitterionic surfactant(s) in an amount ranging from 0.1% to 10% by weight, preferably ranging from 0.2%> to 8% by weight, preferentially from 0.5% to 5% by weight, relative to the total weight of the composition. Preferably, when they are present, the composition according to the invention comprises said surfactant(s) in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, and even better still from 0.5% to 5% by weight, relative to the total weight of the composition.

The solid particles

The composition according to the present invention may optionally also comprise one or more solid particles different from the waxes previously described.

Said solid particles are generally water-insoluble. For the purposes of the present invention, the term "water- insoluble" is intended to mean a compound of which the solubility in water at 25°C and at atmospheric pressure is less than 0.1% and better still less than 0.001% by weight.

Preferably, the solid particle(s) of the invention that are different from the waxes previously described are chosen from full solid particles. The term "full particles" is intended to mean non-hollow particles, that is to say particles which are different from particles comprising at least one continuous shell (or one surface layer) and at least one central cavity.

Advantageously, the particles according to the present invention have a number-average primary size ranging from 0.001 to 1000 μιη, preferably from 0.01 to 700 μιη, preferentially from 0.5 to 200 μιη, in particular from 1 to 20 μιη, and even better still from 5 to 10 μιη.

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

The particle(s) optionally used in the composition according to the invention may have different shapes, for example may be sphere-shaped, flake-shaped, needle- shaped or platelet-shaped, and preferably they are substantially spherical.

The composition according to the invention preferably comprises one or more particles of one or more mineral compounds. The particles of one or more mineral compounds (or mineral particles) that may be used in the cosmetic composition according to the invention can be chosen from metal particles, oxides, inorganic salts, carbides, nitrides, borides and hydroxides.

The term "metal particles" is intended to mean particles formed by metals, in particular chosen from alkaline-earth metals, transition metals, rare earth metals, and alloys of these metals.

Preferably, the metals used are boron, aluminium, copper, cadmium, selenium, silver, gold, indium, iron, platinum, nickel, molybdenum, silicon, titanium, tungsten, antimony, palladium, zinc, tin, and alloys of these metals. Among these metals, gold, silver, platinum, cadmium, and alloys of these metals are quite particularly preferred.

The particles of one or more mineral compounds may also be oxides. Mention may be made of the oxides of the elements of columns 1 to 14 of the periodic table of elements. In particular, mention may in particular be made of titanium oxide, zinc oxide, cerium oxide, zirconium oxide, aluminium oxide and bismuth oxychloride. Among these compounds, zinc oxide is quite particularly preferred.

The particles of one or more mineral compounds may be inorganic salts. Mention may in particular be made of barium sulfate, calcium carbonate, calcium sulfate, calcium phosphate and magnesium hydrogen carbonate.

Among these compounds, calcium carbonate is preferred.

Among the particles of one or more mineral compounds belonging to the species described above, mention may also be made of clays, silicates, alumina, silica, kaolin and hydroxyapatite.

In particular, the silicas that can be used may be natural and untreated. Mention may thus be made of the silicas provided under the names Sillitin N85, Sillitin N87, Sillitin N82, Sillitin V85 and Sillitin V88 by the company Hoffman Mineral, or Sunsil 130 by the company Sunjin Chemical, MSS-500-3 H by the company Kobo, Sunsphere H 51 by the company AGC SI-Tech, and the hollow particles of amorphous silica of ellipsoidal shape sold by Kobo under the reference silica shells. They may be fumed silicas. The fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas bearing a large number of silanol groups at their surface.

It is possible to chemically modify the surface of said silica via a chemical reaction which brings about a reduction in the number of silanol groups. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be:

(a) trimethylsiloxy groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as Silica silylate according to the CTFA (6th Edition, 1995).

(b) dimethylsilyloxy or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as silica dimethyl silylate according to the CTFA (6th Edition, 1995).

In particular, among the hydrophobic silicas, mention may be made of silica aerogels. Aerogels are ultralight porous materials which were first produced by Kristler in 1932. They are generally synthesized via a sol-gel process in liquid medium and then dried by extraction of a supercritical fluid. The supercritical fluid most commonly used is supercritical C0 ₂ . This type of drying makes it possible to avoid shrinkage of the pores and of the material. Other types of drying also make it possible to obtain porous materials starting from gel, namely (i) drying by freeze drying, which consists in solidifying the gel at low temperature and in then subliming the solvent, and (ii) drying by evaporation. The materials thus obtained are referred to respectively as cryogels and xerogels. The sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York: Academic Press, 1990.

"Hydrophobic silica" means any silica, the surface of which is treated with silylating agents, for example with halogenated silanes, such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes, such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.

Preferably, the hydrophobic aerogel particles that may be used in the present invention advantageously have a specific surface area per unit mass (SM) ranging from 500 to 1500 m ² /g, preferably from 600 to 1200 m ² /g and better still from 600 to 800 m ² /g and/or have an oil absorption capacity measured at the wet point ranging from 5 to 18 ml/g of particles, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.

The absorption capacity, measured at the wet point and denoted Wp, corresponds to the amount of oil which it is necessary to add to 100 g of particles in order to obtain a homogeneous paste. It is measured according to the "wet point" method or the method for determining the oil uptake of a powder according to the principle described in standard NF T 30-022. It corresponds to the amount of oil adsorbed on the available surface of the powder and/or absorbed by the powder by virtue of the wet point measurement, described below: an amount m = 2 g of powder is placed on a glass plate and then the oil (isononyl isononanoate) is added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is performed using a spatula, and addition of oil is continued until conglomerates of oil and powder have formed. From this point, the oil is added at the rate of one drop at a time and the mixture is subsequently triturated with the spatula. The addition of oil is stopped when a firm and smooth paste is obtained. This paste must be able to be spread over the glass plate without cracks or the formation of lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil uptake corresponds to the ratio Vs/m.

The hydrophobic silica aerogel particles used according to the present invention are preferably silylated silica (INCI name: silica silylate) aerogel particles.

The preparation of hydrophobic silica aerogel particles surface-modified by silylation is described more fully in US 7 470 725. Use will be made in particular of aerogel particles of hydrophobic silica surface-modified with trimethylsilyl groups.

The hydrophobic aerogel particles that may be used in the present invention advantageously have a size, expressed as the mean diameter (D[0.5]), of less than 1500 μιη, and preferably ranging from 1 to 30 μιη, preferably from 5 to 25 μιη, better still from 5 to 20 μιη and even better still from 5 to 15 μιη.

The sizes of the aerogel particles according to the invention may be measured by static light scattering using a commercial particle size analyzer of the MasterSizer 2000 type from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is in particular described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957. According to an advantageous embodiment, the hydrophobic aerogel particles used in the present invention have a specific surface area per unit mass (SM) ranging from 600 to 800 m ² /g and a size expressed as the volume mean diameter (D[0.5]) ranging from 5 to 20 μιη and better still from 5 to 15 μιη.

According to a preferred embodiment, VM-2270 will more particularly be used, the particles of which have a mean size ranging from 5 to 15 microns and a specific surface area per unit mass ranging from 600 to 800 m ² /g.

The hydrophobic aerogel particles used in the present invention may advantageously have a tamped density p ranging from 0.04 g/cm ³ to 0.10 g/cm ³ and preferably from 0.05 g/cm ³ to 0.08 g/cm ³ .

In the context of the present invention, this density may be assessed according to the following protocol, known as the tapped density protocol: 40 g of powder are poured into a measuring cylinder and the cylinder is then placed on a Stav 2003 machine from Stampf Volumeter. The cylinder is then subjected to a series of 2500 tapping actions (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); the final volume Vf of tapped powder is then measured directly on the cylinder. The tapped density is determined by the ratio: mass (m)/V f, in this instance 40/V f (Vf being expressed in cm ³ and m in g).

According to one embodiment, the hydrophobic aerogel particles used in the present invention have a specific surface area per unit of volume SV ranging from 5 to 60 m ² /cm ³ , preferably from 10 to 50 m ² /cm ³ and better still from 15 to 40 m ² /cm ³ .

The specific surface per unit of volume is given by the relationship: SV = SMxp

where p is the tapped density expressed in g/cm ³ and SM is the specific surface area per unit mass expressed in m ² /g, as are defined above.

According to a preferred embodiment, the hydrophobic aerogel particles according to the invention have a specific surface area per unit mass (SM) ranging from 500 to 1500 m ² /g, preferably from 600 to 1200 m ² /g and better still from 600 to 800 m ² /g, and a size expressed as the mean diameter (D[0.5]) ranging from 1 to 30 μιη and/or an oil-absorbing capacity measured at the Wet Point ranging from 5 to 18 ml/g of particles, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.

As hydrophobic silica aerogels of use in the invention, mention may for example be made of the aerogel sold under the name VM-2260 (INCI name: Silica silylate), by Dow Corning, the particles of which have a mean size of about 1000 microns and a specific surface area per unit mass ranging from 600 to 800 m ² /g.

Mention may also be made of the aerogels sold by Cabot under the references Aerogel TLD 201, Aerogel OGD 201 and Aerogel TLD 203, Enova Aerogel MT 1100 and Enova Aerogel MT 1200.

Use will be made more particularly of the aerogel sold under the name VM- 2270 (INCI name: Silica silylate), by the company Dow Corning, the particles of which have an average size ranging from 5 to 15 microns and a specific surface area per unit mass ranging from 600 to 800 m ² /g.

The mineral particles according to the invention may also be clay particles.

Clays are products that are already well known per se, which are described, for example, in the publication Mineralogie des argiles [Mineralogy of Clays], S. Caillere, S. Henin, M. Rautureau, 2 ^nd Edition 1982, Masson.

Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof.

Mention may in particular be made of clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the vermiculite, stevensite or chlorite family.

The clays may be of natural or synthetic origin. Preferably, clays that are cosmetically compatible and acceptable with keratin fibres such as the hair are used.

The clay may be chosen from montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof. Preferably, the clay is a bentonite or a hectorite.

The clays may be chosen from organophilic clays. Organophilic clays are clays modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkyl aryl sulfonates and amine oxides, and mixtures thereof. Preferably, the organophilic clays according to the invention are clays modified with a chemical compound chosen from quaternary amines. Organophilic clays that may be mentioned include quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by the company Elementis, Tixogel VP by the company United Catalyst, and Claytone 34, Claytone 40 and Claytone XL by the company Southern Clay; stearalkonium bentonites such as those sold under the names Bentone 27V by the company Elementis, Tixogel LG by the company United Catalyst, and Claytone AF and Claytone APA by the company Southern Clay; quaternium-18/benzalkonium bentonites such as those sold under the names Claytone HT and Claytone PS by the company Southern Clay. The organophilic clay is in particular chosen from modified hectorites such as hectorite modified with C ₁₀ -C ₁₂ fatty acid ammonium chloride, in particular distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride.

Preferably, the particles of one or more mineral compounds are chosen from calcium carbonate, silica and, in particular, silica aerogels. The solid particles, which are in particular water-insoluble, may also be chosen from pigments, in particular pearlescent pigments, such as coloured pearlescent pigments, such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and in particular with ferric blue or chromium oxide or mica covered with titanium and also pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, mention may be made of the nacres Cellini sold by Engelhard (Mica-TiC -lake), Prestige sold by Eckart (Mica-TiC ), Prestige Bronze sold by Eckart (Mica-Fe203), Colorona sold by Merck (Mica-Ti02-Fe203); gold- coloured nacres sold especially by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold especially by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold especially by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold especially by the company Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper glint sold especially by the company Engelhard under the name Copper 340A (Timica); the nacres with a red glint sold especially by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow glint sold especially by the company Engelhard under the name Yellow (4502) (Chromalite); the red nacres with a gold glint sold especially by the company Engelhard under the name Sunstone GO 12 (Gemtone); the pink nacres sold especially by the company Engelhard under the name Tan opale G005 (Gemtone); the black nacres with a gold glint sold especially by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold especially by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery glint sold especially by the company Merck under the name Xirona Silver, and the golden-green pinky-orangey nacres sold especially by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

Among the pearlescent agents, mention may be made more particularly of:

- esters of polyols having at least two carbon atoms and of long-chain fatty acids, which are preferentially C10-C30 and even more preferentially C16-C22; such as monoesters or diesters of polyols and of fatty acids; preferably, the polyols are ethylene glycol and polyalkylene glycols having from 2 to 10 ethylene oxide units;

- ethers of long-chain fatty alcohols which are solid at a temperature less than or equal to approximately 30°C, such as, for example, the dialkyl ethers of formula: R-O-R', in which R and R', which may be identical or different, denote a linear or branched, saturated or unsaturated alkyl radical comprising from 10 to 30 carbon atoms and preferably from 14 to 24 carbon atoms, R and R' being chosen such that the compound is solid at a temperature less than or equal to approximately 30°C.

More particularly, R and R denote a stearyl radical. A distearyl ether that can be used in the context of the present invention is sold under the name Cutina STE by the company HENKEL;

- cyclodextrins and in particular β-cyclodextrin.

The pearlescent agents are preferentially chosen from ethylene glycol mono- or distearates (or glycol distearate), distearyl ether, l-(hexadecyloxy)-2-octadecanol, β-cyclodextrin, and mixtures thereof.

According to one preferred embodiment of the invention, the cosmetic hair composition comprises one or more solid particles different from the waxes previously described, chosen from silicas, clays, pigments, pearlescent agents, and mixtures thereof; more preferentially from silicas, clays, pigments, and mixtures thereof.

Preferably, the solid particle(s) different from the waxes previously described are present in the composition according to the invention in an amount ranging from 0.001% to 15% by weight, preferentially from 0.01% to 10% by weight and better still from 0.1% to 5% by weight, relative to the total weight of the composition.

The additives

The composition according to the invention may also comprise one or more additives, such as for example natural or synthetic thickeners or viscosity regulators different from the compounds described above; vitamins or provitamins; amphoteric or anionic polymers different from the fixing polymers i); preservatives; dyes; fragrances.

Those skilled in the art will take care to select the optional additives and the amount thereof such that they do not harm the properties of the composition of the present invention.

These additives may be present in the composition according to the invention in an amount ranging from 0 to 20% by weight, relative to the total weight of the composition.

Preferably, the pH of the composition according to the invention generally ranges from 3 to 12, more preferably from 5 to 11, even more preferably from 7 to 10.5 and better still from 8 to 10.

The pH of these composition may be adjusted to the desired value by means of basifying agents or acidifying agents that are customarily used. Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkanolamines, and mineral or organic hydroxides. Among the acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

Another subject of the present invention is a process for shaping and/or conditioning keratin fibres, in particular human keratin fibres such as the hair, comprising at least one step of applying to said fibres a composition as described previously.

This or these steps of applying the composition according to the invention may optionally be preceded by at least one step of washing said fibres using a shampoo, and optionally followed by at least one step of rinsing said fibres with water. Moreover, this or these steps of applying the composition according to the invention may optionally be followed by a step of leaving the composition on, for example a leave-on time of 1 to 15 minutes, in particular 2 to 5 minutes; then followed by an optional rinsing step, for example with water; and/or a drying step.

Preferably, the keratin fibres are not rinsed after the step(s) of applying the composition according to the invention. The expression "are not rinsed" is intended to mean that no step of rinsing the keratin fibres is carried out for at least 30 minutes, preferentially 1 hour, after the step of applying the composition according to the invention.

A subject of the present invention is also a use of the composition as described previously, for shaping and/or conditioning keratin fibres, in particular human keratin fibres such as the hair.

Preferably, the composition as described previously is used for hairstyling.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

Example

An example of a composition according to the invention was prepared from the following ingredients of which the contents are indicated in the tables below (in g of starting materials as they are).

Comparative tests

- Control of volume/anti-frizz

Two locks A and B of natural frizzy hair, weighing 2.7 g were washed beforehand with a standard shampoo in a proportion of 0.4 g of shampoo per g of hair.

After rinsing, the lock A is treated with the composition described above in a proportion of 0.15 g of composition per g of hair, then blow drying is carried out with a brush until complete drying.

After rinsing, the lock B is directly subjected to blow drying with a brush until complete drying. Better control of volume of the hair, in particular no frizziness, is noted for the lock A compared with the lock B.

Each of the locks is then subjected to a challenge of 1 to 3 repeated shampooing operations, each shampooing step being followed by drying in the open air.

It is noted that the superiority of performance level in terms of manageability of the lock A endures after 1 to 3 shampooing operations.

- Manageability

The locks A and B treated as described previously are photographed at each step of the protocols described above. The orientation of the fibres relative to the vertical axis is determined by image analysis, thus making it possible to quantify their average degree of alignment Θ (expressed in degrees): the lower the value of Θ, the better the alignment, and therefore the better the performance level in terms of manageability.

The lock A treated with the composition according to the invention exhibits better alignment of the fibres, both before the shampooing challenge and after 1 to 3 repeated shampooing operations, compared with the lock B: the manageability performance level is better and persistent for the lock A.

Conditioning

Two locks A' and B' of natural hair, weighing 1 g were washed beforehand with a standard shampoo in a proportion of 0.4 g of shampoo per g of hair.

After rinsing, the lock A' is treated with the composition described above in a proportion of 0.15 g of composition per g of hair. After rinsing, the lock B' is, for its part, not treated. The surface condition of the locks was evaluated using the method described above on, on the one hand, wet hair and then on, on the other hand, dry hair (after complete drying in an incubator).

The lock A' or B' is attached to a force sensor, then moved vertically between 2 cylindrical rubbing devices. The force required to move the lock is then recorded: the lower the force, the easier the movement, which is representative of a smooth and uniform surface condition.

The average force obtained with the lock A' is much lower than that obtained with the lock B': the surface condition of the lock A' treated with the composition according to the invention has a smoother and more uniform surface condition than the lock B'.