WO2010069629A1

WO2010069629A1 - Cosmetic composition comprising, in solution or dispersion, a linear diblock polymer, and cosmetic treatment method

Info

Publication number: WO2010069629A1
Application number: PCT/EP2009/063385
Authority: WO
Inventors: Nathalie Mougin; Gwenaëlle JEGOU
Original assignee: L'oreal
Priority date: 2008-12-19
Filing date: 2009-10-14
Publication date: 2010-06-24
Also published as: FR2940099B1; FR2940099A1

Abstract

The invention relates to a cosmetic composition comprising, in a cosmetically acceptable medium, a linear diblock polymer in solution or in dispersion in said medium, said polymer comprising, in a first block, repeating units of formula (I) and, in a second block, repeating units of formula (II): Formulae (I) and (II) in which: -R, R' and R" represent a hydrogen atom or a methyl group; -X represents O or NH; -R3 is a carbon-based divalent radical comprising 1 to 30 carbon atoms, possibly comprising O, N and S heteroatoms; -R1 and R2 represent H, an alkyl group or form a ring with the nitrogen atom. The invention also relates to a cosmetic treatment method, in particular a hair treatment method, using said cosmetic composition.

Description

Cosmetic composition comprising, in solution or dispersion, a linear diblock polymer, and cosmetic treatment method

The present invention relates to cosmetic compositions, in particular capillary compositions, comprising, transported in aqueous medium, particular diblock copolymers.

In the field of so-called "rinsed" hair compositions, such as shampoos, water-soluble or water-dispersible synthetic cationic polymers known to provide good cosmetic properties to hair are used. These polymers are generally cationic and carry amine, quaternary and / or tertiary functions in the form of hydrochloride, acetate and alkylsulphonate. Among the synthetic polymers, homopolymers of the poly (diallyldimethylammonium chloride) type and in particular the "Merquat 100" product, or copolymers such as, for example, the "Merquat 550" product, poly (vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate) copolymers, may be mentioned. ) as the Gafquat 755 product; poly (vinylpyrrolidone / imidazolinium methochloride) copolymers such as the product "Luviquat FC". Among the natural polymers, mention may be made of guars or cationic modified celluloses, quaternary ammonium type such as polymers of the type (steardimonium hydroxyethyl cellulose chloride) and in particular the product "CRODACEL QS" or "Jaguar". However, these polymers are generally not used in post-color conditioner or hair care formulations, for which disentangling of wet hair must be very easy. Indeed, these polymers do not provide enough cosmetic properties.

In the field of hair care, in particular of sensitized hair, in particular having undergone coloring, it is sought to provide cosmetic properties on wet hair, especially an improved feel, as well as shine, softness and disentangling. in dry environment (on dry hair). Indeed, it is known that hair sensitized, that is to say damaged and / or fragile, to varying degrees by the action of atmospheric agents, including light, and by the repeated action of different mechanical or chemical treatments, such as perms, hair straightening, coloring and discoloration, may exhibit an alteration of the hair fiber, in particular a reduction in their mechanical properties such as tensile strength, tensile strength and elasticity. The hair can be more hydrophilic, losing part of the scales, which results in great difficulty in disentangling and styling the hair, and a loss of softness. To remedy this, it is possible to use cationic surfactants of cetylthmethylammonium type, in oil-in-water emulsion, in the presence of fatty alcohols. However, the cosmetic properties are not optimal and the formulation of these compositions is complicated: compromise between the stability emulsion and non-greasy feel to find, among others.

Grafted cationic copolymers, optionally crosslinked, are also known, such as those described in FR2189434 and in FR2312232, which may be used in capillary, in particular in shampooing, to facilitate disentangling. These polymers include in particular polyethylene glycol units and cationic monomers; they have a grafted structure.

WO03 / 075867 also discloses triblock copolymers that can be used in cosmetics, especially in hair compositions, to provide "styling"; these copolymers comprise a central polyethylene glycol block and side sequences comprising cationic monomers; these polymers are used for their film-forming properties.

However, graft copolymers and triblock copolymers do not have optimal hair conditioning properties, especially for wet hair.

The aim of the present invention is to overcome these drawbacks and to propose polymers which, put into a cosmetic composition, in particular a capillary composition, make it possible to provide improved cosmetic properties, especially disentangling and touching in a wet and dry medium. These polymers make it possible to bring a hairline effect to the hair.

The subject of the present invention is therefore a cosmetic composition comprising a cosmetically acceptable medium which comprises, in solution or dispersion in said medium, a linear diblock polymer, or a salt thereof, comprising a first block A which comprises repeating units of formula (I) as defined below, and a second block B which comprises repeating units of formula (II) as defined below.

The polymers according to the invention provide adequate conditioning effects, in particular softness to the touch and disentangling on wet hair (in a humid environment) and on dry hair (in a dry environment). Because of their cationic character, they also have an excellent affinity for keratinous substrates such as the hair, the nails and the stratum corneum of the epidermis to which the keratin confers a negative charge.

The polymers according to the invention are diblock polymers, that is to say they consist of two sequences (or blocks) only.

They are linear, that is to say that the repeating units of formula (I) and (II) are in the polymer chain, and not in grafts; moreover, the polymers according to the invention are uncrosslinked. One of the blocks, or block, constituting the diblock polymer according to the invention, comprises repeating units of formula (I):

in which :

- R 'and R ", which may be identical or different, represent a hydrogen atom or a methyl group, preferably R' = R" = H; and

p is an integer greater than or equal to 2, in particular between 5 and 1200, or even between 13 and 450.

Said sequence A can be a homopolymer or a copolymer comprising a mixture of different repeating units of formula (I).

Preferably, the molecular weight (Mn) of this A block is between 250 and 50,000 g / mol, preferably between 600 and 20,000 g / mol and even more preferably between 1,000 and 10,000 g / mol.

The other block or block constituting the diblock polymer according to the invention comprises repeating units of formula (II):

in which :

- R represents a hydrogen atom or a methyl group; n is an integer greater than or equal to 2, in particular between 10 and 400, or even between 20 and 200;

X represents O or NH; preferably O;

R 3 being a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, of 1 to 30 carbon atoms, which may comprise 1 to 6 heteroatoms chosen from O, N and S;

R1 and R2 represent, independently of one another, (i) a hydrogen atom,

(ii) a linear, branched or cyclic, saturated or unsaturated, optionally aromatic, alkyl group comprising from 1 to 18 carbon atoms, especially 1 to 12 carbon atoms, which can comprise 1 to 10 heteroatoms chosen from O, N, S; (iii) R1 and R2 may form with the nitrogen atom a ring of formula:

saturated or unsaturated, optionally aromatic, said ring comprising 5 to 6 atoms (forming the ring), and in particular 3 to 6 carbon atoms, said ring being interrupted by 1 to 3 divalent groups chosen from -O-, -S- and -NH- and / or substituted by a group = O.

Preferably, R 3 is a divalent hydrocarbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, of 1 to 30 carbon atoms. In the radical R3, the heteroatom (s), when they are present, may be inserted in the chain of said radical R3, or said radical R3 may be substituted by one or more groups including them such as OH, NH ₂ , NHR 'or NR ¹ R "with R 'and R" identical or different representing a linear or branched C1-C12 alkyl, especially methyl or ethyl. In particular, R 3 may be an alkylene radical such as methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, n-docosanylene; or a phenylene radical - C ₆ H ₄ - (ortho, meta or para); or a benzylene radical -C ₆ H ₄ -CH ₂ -. Preferentially, R 3 is a C 1 -C 4 alkylene, optionally substituted with an OH.

Preferably, R 1 and R 2 are chosen from hydrogen, a methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, octyl, lauryl and stearyl group; preferably, they are chosen, independently of one another, from H, CH ₃ and C ₂ H ₅ . When they form a ring with the nitrogen atom, said ring may be a morpholine, piperazine or piperidine ring.

Preferably, the molecular weight (Mn) of this block B is between 250 and 50,000 g / mol, preferably between 600 and 20,000 g / mol and even more preferably between 1000 and 10,000 g / mol.

The monomers capable of forming all or part of this B block are cationic monomers, that is to say comprising units capable of having a cationic charge in the pH range between 3 and 12. These units do not necessarily have a permanent charge whatever the pH. The cationic unit does not need to be protonated at each of these pH's.

As monomer capable of forming all or part of this sequence B, mention may be made of:

dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide; dimethylaminopropyl (Meth) acrylannide; diethylaminopropyl (meth) acrylannide; the aminopropyl

(Meth) acrylannide;

the following monomers:

Said sequence B may be a homopolymer, a copolymer comprising a mixture of different repeating units of formula (II), or a copolymer comprising, in addition to the repeating units of formula (II), additional repeating units.

These additional units may come from the following monomers, alone or as a mixture:

(i) esters of (meth) acrylic acid of formula CH ₂ = CHCOOR ¹ I or CH ₂ = C (CH ₃ ) COOR ¹ I with R '1 representing a carbon chain, in particular hydrocarbon (alkyl) chain, having 1 to 30 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally aromatic (aryl, aralkyl or alkylaryl), optionally comprising 1 to 8 functions selected from -OH, -OR 'with R' alkyl in C1- C6 (alkoxy), -CN, -X (halogen, especially Cl, F, Br or I); Mention may thus be made of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl and 2-ethylhexyl cyclohexyl (meth) acrylates. octyl, isooctyl, isodecyl, decyl, dodecyl, lauryl, myristyl, cetyl, palmityl, stearyl, behenyl, oleyl, tridecyl, hexadecyl, isobornyl ; hydroxyethyl, hydroxypropyl; phenyl, benzyl, furfuryl; tetrahydrofurfuryl, ethoxyethyl, methoxyethyl; 2,2,2-trifluoroethyl.

(ii) the amides of the (meth) acrylic acid of formula CH ₂ = CHCONR'2R "2 or CH ₂ = C (CH ₃ ) CONR '2 R "2 with R' 2, R" 2, identical or different, representing hydrogen or a carbon chain, in particular hydrocarbon (alkyl), having 1 to 30 carbon atoms, linear , branched or cyclic, saturated or unsaturated, optionally aromatic, optionally comprising 1 to 8 functions selected from -OH, -OR 'with R' C 1 -C 6 alkyl (alkoxy), -CN, -X (halogen, especially Cl, F , Br or I).

There may be mentioned (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tertbutyl (meth) acrylamide, N-octyl (meth) acrylamide, N-undecyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide;

(iii) vinyl esters of formula CH ₂ = CH-OCO-R '3 or CH ₂ = C (CH ₃ ) -OCO-R' _{3 with} R ' ₃ representing a carbon chain, in particular hydrocarbon chain, having 1 to 30 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally aromatic, optionally comprising 1 to 8 functions selected from -OH, -OR 'with R' C 1 -C 6 alkyl (alkoxy), -CN, - X (halogen, especially Cl, F, Br or I);

These include vinyl acetate, vinyl propionate, vinyl butyrate (or butanoate), vinyl ethylhexanoate, vinyl neononanoate and vinyl neododecanoate, vinyl neodecanoate, vinyl pivalate, vinyl cyclohexanoate, vinyl benzoate, vinyl 4-tert-butylbenzoate, vinyl trifluoroacetate.

(iv) vinyl ethers of formula CH ₂ = CHOR '4 or CH ₂ = C (CH ₃ ) OR' 4 with R '4 representing a carbon chain, in particular a hydrocarbon chain, having 1 to 30 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally aromatic, optionally comprising 1 to 8 functions selected from -OH, -OR 'with R' C 1 -C 6 alkyl (alkoxy), -CN, -X (halogen, in particular Cl, F, Br or

I); Mention may be made of methyl vinyl ether, ethyl vinyl ether, ethyl hexyl vinyl ether and butyl vinyl ether, cyclohexyl vinyl ether and isobutyl vinyl ether.

(v) vinyl compounds of the formula CHR 5 = CR 5 R '5 wherein R "5 is H or COOH; R5 is H, CN or COOH; and R'5 is selected from: - a hydrogen atom, a -OH group, -CH = O, halogen (Cl, Br, I in particular), -COOH, -CH ₂ COOH, -NHC (O) H, -N (CH ₃ ) -C (O) H, -NHC (O) CH ₃ , -N (CH ₃ ) -C (O) CH ₃ ;

a linear or branched alkyl group comprising 1 to 25 carbon atoms,

a C ₃ -C ₈ cycloalkyl group such as cyclohexane,

a C ₆ to C ₂₀ aryl group such as phenyl, a C ₇ to C ₃₀ aralkyl group (C 1 to C ₄ alkyl group) such as 2-phenylethyl or benzyl,

a 4- to 12-membered heterocyclic group comprising one or more heteroatoms selected from O, N, and S, especially a heterocycloalkyl (alkyl) group; from 1 to 4 carbons), such as furfuryl, furfurylmethyl or tetrahydrofurfurylmethyl.

Mention may in particular be made of vinyl alcohol and vinylcyclohexane; vinylpyrrolidone, vinylcaprolactam, N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide; N-methyl-N-vinylacetamide; styrene; methylstyrene; 4-tert-butylstyrene, 4-acetoxystyrene; acidic sulfonic styrene; 4-methoxystyrene, 3-methylstyrene; 4-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, dimethylstyrene, vinyl butyral; vinyl carbazole; vinyl chloride; the vinyl formai; vinylidene chloride, vinylidene fluoride, 2-vinyl naphthalene; N-methyl maleimide; 1-octene, 1-butene; cis-chlorobutadiene, trans-chlorobutadiene; chlorotrifluoroethylene; cis-isoprene, trans-isoprene; 1-octadecene; butadiene; hexadecene, eicosene; 2,6-dichlorostyrene; 2,4-dimethylstyrene; 2,5-dimethylstyrene; 3,5,2,4-tetraethoxystyrene; 4-fluorostyrene.

(vi) the monomers of formula:

in which R'8 is H or a linear or branched, saturated or unsaturated, optionally aromatic, cyclic or non-cyclic alkyl group comprising 1 to 25 carbon atoms, in which is optionally interposed one or more he teratoms chosen from O, N, S and P; said alkyl group may further be optionally substituted by one or more substituents selected from -OH and halogen atoms (Cl, Br, I and F); Mention may be made in particular of maleic anhydride and N-methyl maleimide.

(vii) (meth) acrylic acid, crotonic acid.

Among the preferred additional monomers, mention may be made of vinyl neodecanoate and vinyl terbutylbenzoate; vinylpyrrolidone; vinylcaprolactam; N-vinyl formamide; triethylammoniumethyl (meth) acrylate chloride (MADQUAT), ethyl (meth) acrylate; methyl (meth) acrylate; isobornyl (meth) acrylate; vinyl acetate, crotonic acid; acrylic acid, methacrylic acid, terbutyl (meth) acrylate; octyl (meth) acrylamide; 1-eicosene, terbutyl (meth) acrylamide, (meth) acrylamide; hexadecene, and mixtures thereof.

The amine units of the polymer may optionally be neutralized. Among the salts, mention may be made of the salts of mineral acids, such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and boric acid. Mention may also be made of organic acid salts, which may comprise one or more carboxylic acid, sulphonic acid or phosphonium groups. than. It may be linear, branched or cyclic aliphatic acids or unsaturated or aromatic acids. These acids may comprise, in addition, one or more heteroatoms chosen from O, N, Si, F and P, for example in the form of hydroxyl groups. There may be mentioned in particular propionic acid, acetic acid, terephthalic acid, citric acid, tartaric acid, lactic acid, CO ₂ H-PEG-CO ₂ H acid, betaine HCl [(CH3) 3N + CH2CO2H.Cl-], gluconic acid, 2-ethylcaproic acid, oleic acid, behenic acid and stearic acid. The neutralization of any anionic groups may be carried out with a mineral base, such as LiOH, NaOH, KOH, Ca (OH) ₂ , NH ₄ OH, Mg (OH) ₂ or Zn (OH) ₂ ; or with an organic base such as a primary, secondary or tertiary alkylamine, especially triethylamine or butylamine. This primary, secondary or tertiary alkylamine may comprise one or more nitrogen and / or oxygen atoms and may therefore comprise, for example, one or more alcohol functions; mention may in particular be made of 2-amino-2-methyl-propanol, triethanolamine and dimethylamino-2-propanol. Mention may also be made of lysine or 3- (dimethylamino) propylamine. It should be noted that the polymer according to the invention is not quaternized.

The additional monomer, alone or in admixture, may not be present in said sequence, (0%), or may be present in an amount of 0.1 to 35% by weight, preferably 1 to 25% by weight, for example from 3 to 15% by weight, or even 5 to 10% by weight, relative to the total weight of the sequence. The monomers forming the repeating units of formula (II) are then present in an amount of 65 to 99.9% by weight, preferably 75 to 99% by weight, for example 85 to 97% by weight, or even 90 to 95% by weight. by weight, relative to the total weight of said sequence.

The molecular weight (Mn) of the diblock polymer is preferably between 500 and 100,000 g / mol, preferably between 1,000 and 50,000 g / mol and more preferably between 2,000 and 15,000 g / mol.

Preferably, the ratio between [Mn molecular weight of block A] / [Mn molecular weight of block B] is between 0.02 and 49, especially between 0.1 and 10, more preferably between 0.7 and 5, or even between 0.8 and 2.

Preferably, the diblock polymers according to the invention have a glass transition temperature (Tg) of between -150 ^° C. and 20 ^° C., especially between -20 ° C. and 10 ^° C., better still between -100 ° C. and 0 ° C. vs. In addition, they may have a melting temperature preferably between -100 ⁰ C and 80 ° C, especially between -80 ° C and 50 ⁰ C, preferably between -70 ° C and 45 ° C, or even between -10 ⁰ C and 25 ° C.

In addition, the polymers according to the invention preferably have a water uptake of between 3 and 150% by weight, preferably between 4 and 100% by weight, especially between 5 and 50% by weight, at 75% relative humidity (75% RH). They may also have a water uptake of between 3 and 200% by weight, preferably between 2.5 and 150% by weight, in particular between 3 and 100% by weight, at 85% relative humidity (85% RH). .

The sequence comprising the repeating units of formula (I), or block A, and the sequence comprising the repeating units of formula (II), or block B, can be directly linked by a single bond when the chemistry of blocks A and B allows. Alternatively, block A may be bound to block B via a divalent linker (linker) L, such that diblock A-B is of formula A-L-B. A-L-B polymers fall under the more general definition of A-B diblock. The linker preferably has an average molecular weight of between 14 and 300 g / mol. The linker may in particular be chosen from -O-; -NOT-; -S-; - R'-; -C (= O) -O-; -O-C (= O) -O-; -C (= O) -NR "-; -O-C (= O) -NR" -; -NR "-C (= O) -NR" -, and mixtures thereof; with R 'representing a C1-C18 linear or branched divalent hydrocarbon chain; and R "represents H or a C1 -C12 linear or branched hydrocarbon chain.

Preferably, blocks A and B are linked directly by a single link. When the divalent L radical exists, it preferably represents -C (= O) -C (CH ₃ ) ₂ -.

In a nonlimiting but illustrative manner, the diblock polymer according to the invention can be represented as follows:

the nature of the ends Z1 and Z2 depending on the synthesis method used; especially Z1 can be OH, OCH ₃ or OC ₂ H ₅

Depending on the synthesis mode envisaged, it is possible that the diblock polymer finally obtained is mixed with one of the homopolymers corresponding to one of the blocks, especially in a mixture with free polyethylene glycol.

The diblock polymer according to the invention can be obtained by condensation between the monofunctional block A and the monofunctional block B both already formed, it being understood that said sequences comprise functions that can interact with each other or via a linker.

The diblock polymer can also be prepared by radical polymerization controlled or anionic.

In particular, it is possible to carry out:

an anionic polymerization via an initiator of polyethylene glycol alkoxide type, or assimilated, capable of forming the sequence A, followed by the polymerization of the ethylenic monomers envisaged to form the sequence B; such a polymerization is especially described in "Vamvaki et al., Macromolecules, 1999, 32, 2088";

an ATRP-type polymerization by functionalization of the polyethylene glycol and / or the monomers envisaged for the A-block, via the production of the α- (2-bromoisobutyrylate) -α-methyl-PEG macro-initiator followed by the polymerization of the ethylenic monomers envisaged to form the B sequence, with PMDETA (pentamethyldiethylene triamine) / CuBr type catalysis; such a polymerization by ATRP is described in particular US Pat. No. 6,624,262 to Matyajaszewski, as well as in "From well-defined diblock copolymers prepared by a versatile atom transfer radical polymerization method to supramolecular assemblies" (Journal of Polymer Science, Part A: Polymer Chemistry, 2001 , Volume 39, Issue 22, pp 3861-3874);

radical polymerization via a cerium IV priming (radical generation from a monomethyoxy PEG-mono OH); such a polymerization is especially described "Polycationic block copolymers of poly (ethylene oxide) and poly (propylene oxide) for CeII Transfection Bioconjugate Chem." 16 (3), 626-633, 2005 ".

the production of initiator macro-azo by polycondensation of monomethoxy polyethylene glycol and azobiscyanopentanoyl chloride (ACPC) followed by the polymerization of the ethylenic monomers envisaged to form the sequence B;

a RAFT type polymerization by carrying out the polymerization of an ethylene polymer macromer blocked at the end of the chain by the dithiobenzoate group followed by coupling with a monomethoxy-terminated PEG acrylate in the presence of AIBN. It is also possible to polymerize the PEG sequence according to a controlled radical polymerization technique, followed by a step that converts the initiator group to polymerize in a second step with another PRC technique. Each polymer block can also be obtained by polymerization via a radical or anionic mechanism or coordination (transition metal catalysis) or cationic, or ring opening. In the case of radical polymerization, the process used may be a conventional process or a so-called living or controlled radical polymerization process.

The polymers according to the invention are preferably transportable in an aqueous medium, that is to say that they are preferably water-soluble or water-dispersible. By water-soluble is meant that the polymer is soluble in water, at least 5% by weight, at 25 ° C, 1 atm., And forms a clear solution. By hydrodispersible is meant that it forms in water, at a concentration of 5% by weight, at 25 ° C, a stable dispersion of fine particles, generally spherical. The average particle size constituting said dispersion is less than 1 μm and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm. These particle sizes can be measured by light scattering.

The polymers are therefore preferably present in the cosmetic composition in the form of a solution or dispersion in an aqueous or aqueous-alcoholic medium. Dissolving or dispersing in water or the aqueous-alcoholic medium may be carried out by direct solubilization of the polymer if it is soluble, or by neutralization of the amino units and / or acidic units so as to render the polymer soluble or dispersible in water. The dissolution or aqueous dispersion can also be carried out via an intermediate step of solubilization in an organic solvent followed by the addition of water before evaporation of the organic solvent.

Furthermore, it has been found that the polymers according to the invention advantageously have an adequate viscosity in water with the cosmetic applications envisaged, which can be between 1 and 1000 mPa.s, preferably between 1.5 and 750 mPa. s, and even better between 2 and 500 mPa.s. The viscosity is measured using a BROOKFIELD viscometer, for a solution containing 15% by weight of polymer in water or methyl ethyl ketone (solvent chosen as a function of the solubility of the polymer and / or of the polymerization method) at 25 ° C., with a spindle-type mobile chosen from Brookfield models No. 00 to 07, preferably No. 1 mobile, for a measurement time of 5 minutes, at a speed of between 0.1 and 6 rpm. The viscosity is measured after complete dissolution of the polymer in water or methyl ethyl ketone.

The polymers according to the invention find a very particular application in the field of cosmetics. They may be present in the composition in solubilized form, for example in water or an organic solvent, or in the form of an aqueous or organic dispersion. The organic solvent may in particular be chosen from isopropyl myristate, ethyl isononanoate, isopropyl palmitate and D5.

The polymers may be present in the cosmetic compositions according to the invention in a proportion of 0.01 to 50% by weight of dry matter, especially 0.1 to 30% by weight, or even 0.3 to 10% by weight, more preferably from 1 to 3% by weight, relative to the total weight of the composition.

The compositions according to the invention can be in any of the galenical forms conventionally used, and especially in the form of an aqueous, alcoholic or aqueous-alcoholic solution or suspension or oily; a solution or a dispersion of the lotion or serum type; an emulsion, in particular of liquid or semi-liquid consistency, of the O / W, W / O or multiple type; a suspension or emulsion of soft consistency of cream (O / W) or (W / O) type; an aqueous or anhydrous gel, or any other cosmetic form. Preferably, the composition is in the form of a lotion, serum or aqueous suspension.

These compositions may be packaged, especially in pump bottles or in aerosol containers, to ensure application of the composition in vaporized form (lacquer) or in the form of foam. Such forms of packaging are indicated, for example, when it is desired to obtain a spray or a mousse, for the treatment of hair. In these cases, the composition preferably comprises at least one propellant.

The compositions according to the invention comprise a cosmetically acceptable medium, that is to say a medium that is compatible with keratin materials, in particular the skin of the face or of the body, the lips, the hair, the eyelashes, the eyebrows and the nails. .

Said medium preferably comprises at least one usual cosmetic ingredient, especially chosen from propellants; water, carbonaceous oils; silicone oils; C8-C40 alcohols, C8-C40 esters, C8-C40 acids; C 1 -C 7 alcohols, ketones, organic solvents, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, zwitterionic surfactants; solar filters; moisturizing agents; antidandruff agents; antioxidants; reducing agents; oxidation bases, couplers, oxidizing agents, direct dyes; hair straightening agents, pearlescent and opacifying agents; plasticizing or coalescing agents; hydroxy acids; pigments; the charges; silicones; thickeners, emulsifiers; polymers. Said medium can of course include several cosmetic ingredients listed above.

Depending on their nature and the destination of the composition, the usual cosmetic ingredients may be present in customary amounts, easily determinable by those skilled in the art, and which may be understood, for each ingredient, between 0.01 to 80% by weight .

The composition may especially comprise water, one or more C 1 -C 7 alcohols, alone or as a mixture with water, and in particular a water / ethanol, water / isopropanol or water / benzyl alcohol mixture. The carbonaceous oils, in particular hydrocarbon oils, and / or the silicone oils may be present in a proportion of 0.01 to 20% by weight, especially 0.02 to 10% by weight relative to the total weight of the composition. Mention may in particular be made of vegetable, animal or mineral oils, hydrogenated or not, synthetic hydrocarbon oils, cyclic or aliphatic, linear or branched, saturated or unsaturated, such as, for example, polyalpha-olefins, in particular polydecenes and polyisobutenes; volatile or nonvolatile silicone oils, organomodified or otherwise, water-soluble or non-water-soluble; fluorinated or perfluorinated oils; their mixtures. Alcohols, esters and acids, having 8 to 40 carbon atoms, can be present in a proportion of 0.01 to 50% by weight, especially 0.1 to 20% by weight relative to the total weight of the composition.

Mention may especially be made of C12-C32 linear or branched chain fatty alcohols, in particular C12-C26 alcohols, and in particular cetyl alcohol, stearyl alcohol, cetylstearyl alcohol, isostearyl alcohol and the like. octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol.

Mention may also be made of C8-C40 fatty alcohols, in particular C16-C20, alkoxylated, in particular ethoxylated, preferably containing from 10 to 50 moles of ethylene oxide and / or propylene oxide, such as oleth-12, ceteareth-12 and ceteareth-20, oxypropylene stearyl alcohol in particular comprising 15 moles of propylene oxide, oxyethylenated lauryl alcohol, including more than 7 oxyethylene groups, and mixtures thereof. Mention may also be made of C16-C40 linear or branched chain fatty acids, and in particular 18-methyl eicosanoic acid, coconut oil acids or hydrogenated coconut oil acids; stearic acid, lauric acid, palmitic acid and oleic acid, behenic acid, and mixtures thereof; Mention may also be made of linear or branched chain C 16 -C 40 fatty esters, such as esters of polyols derived from fatty acids containing from 8 to 30 carbon atoms, and their oxyalkylenated and especially oxyethylenated derivatives, the polyols being preferentially chosen among the sugars, C2-C6-alkylene glycols, glycerol, polyglycerols, sorbitol, sorbitan, polyethylene glycols, polypropylene glycols and mixtures thereof.

The surfactants, nonionic, cationic, anionic, amphoteric or zwitterionic, as well as their mixtures, can be present in a proportion of 0.01 to 50% by weight, especially 0.05 to 40% by weight, or even 0.1 at 30% by weight, relative to the total weight of the composition. The propellants may be present in a proportion of 5 to 90% by weight relative to the total weight of the composition, and more particularly in a proportion of 10 to 60% by weight.

The sunscreens may be present in a proportion of 0.01 to 20% by weight, especially 0.5 to 10% by weight relative to the total weight of the composition. The moisturizing agents may be present in a proportion of 0.01 to 20% by weight, especially 0.1 to 7% by weight relative to the total weight of the composition.

The anti-dandruff agents may be present in a proportion of 0.001 to 20% by weight, especially 0.01 to 10% by weight relative to the total weight of the composition, preferably 0.1 to 5% by weight. The antioxidants may be present in a proportion of 0.05 to 1.5% by weight, relative to the total weight of the composition.

The reducing agents may be present in a proportion of 0.1 to 30% by weight, especially 0.5 to 20% by weight relative to the total weight of the composition. The oxidation bases may be present in an amount of from 0.001 to 10% by weight, preferably from 0.005 to 6% by weight, of the total weight of the composition.

The couplers may be present in an amount of from 0.001 to 10% by weight, preferably from 0.005 to 6% by weight, of the total weight of the composition. The oxidizing agents may be present in an amount of between 1 and 40% by weight, preferably between 1 and 20% by weight, relative to the weight of the composition.

The direct dyes may be present in an amount of from 0.001 to 20% by weight, preferably from 0.01 to 10% by weight, relative to the total weight of the composition.

The relaxing agents may be present in a proportion of 0.01 to 3.5% by weight, especially 0.05 to 1.5% by weight relative to the total weight of the composition. The pearlescent and opacifying agents may be present in a proportion of 0.01 to 3% by weight, especially 0.05 to 2.5% by weight relative to the total weight of the composition.

The plasticizing or coalescing agents may be present in a proportion of 0.1 to 25% by weight, especially 1 to 10% by weight relative to the total weight of the composition. The hydroxy acids may be present in a proportion of 1 to 10% by weight, in particular 2 to 5% by weight relative to the total weight of the composition.

The pigments and fillers may be present in a proportion of 0.01 to 50% by weight, especially 0.02 to 30% by weight relative to the total weight of the composition. Silicones can be volatile or not; polyorganosiloxanes, which may or may not be modified, namely oils, gums and resins of polyorganosiloxanes, may be mentioned in particular, or in the form of solutions in organic solvents, or in the form of emulsions or microemulsions. They may be present in an amount of 0.01 to 40% by weight, especially 0.05 to 20% by weight, relative to the total weight of the composition. The thickeners may be present in a proportion of from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight relative to the total weight of the composition.

The polymers, in particular water-soluble or soluble in carbonaceous and / or silicone oils, can be present in a proportion of 0.01 to 20% by weight, especially 0.1 to 10% by weight relative to the total weight of the composition. Those skilled in the art will take care to choose the ingredients in the composition, as well as their amounts, so that they do not adversely affect the properties of the compositions of the present invention.

The cosmetic composition according to the invention can be in the form of a care product, cleaning and / or makeup of the skin of the body or face, lips, eyebrows, eyelashes, nails and hair, a suntan or self-tanning product, a hygiene product body, a hair product, including care, cleaning, styling, shaping, hair coloring.

It finds particularly a particularly interesting application in the hair field, including the maintenance of the hairstyle or the shaping of the hair, or the care, the cosmetic treatment or the cleaning of the hair. The hair compositions are preferably shampoos, conditioners, styling or care gels, lotions or care creams, conditioners, styling lotions, blow-dry lotions, fixing compositions and the like. styling such as lacquers or spray; restructuring lotion for hair; lotion or anti-hair loss gel, anti-parasitic shampoo, anti-dandruff lotion or shampoo, anti-seborrhoeic shampoo. It may especially be in the form of a hair coloring product, in particular oxidation dye, optionally in the form of a coloring shampoo; in the form of a composition of perm, straightening or discoloration, or in the form of a composition to be rinsed or not, to be applied before or after a coloring, a discoloration, a permanent or a straightening or between the two stages of a permanent or a straightening.

The composition according to the invention may also be in the form of a care composition, in particular a moisturizer, for the skin of the body or of the face, the lips and / or the integuments, in particular of a care product intended to treat cosmetically the skin and in particular to moisturize it, smooth it, depigment it, nourish it, protect it from the sun's rays, or give it a specific cosmetic treatment. So it can be a base of care for the lips, a fixing base for lipstick, a composition of sunscreen or artificial tanning, a composition of care (day, night, anti-aging, moisturizing) for the face; a mattifying composition; a skin cleansing composition, for example a makeup remover or a bath or shower gel, or a cleansing bar or bar; a personal hygiene composition including a deodorant product, antiperspirant, or a depilatory composition, a gel or aftershave lotion. It can still be in the form of a makeup product for the skin of the body or the face, lips, eyelashes, nails or hair; in particular a foundation, a blush, a blush, an eyeliner, an eyeliner, an eyeliner, a mascara, a lipstick, a lip gloss, a lip liner; nail polish, nail care; a temporary tattoo product of the body skin.

Even more particularly, the composition according to the invention finds an interesting application for the care and the cosmetic treatment, especially the protection of the hair, in particular weakened and / or damaged hair, for example by chemical or mechanical treatments; the compounds according to the invention may in particular be used after the treatment, after a step of coloring, bleaching or straightening the hair.

The subject of the invention is therefore a process for the cosmetic treatment, in particular of makeup, care, cleaning, coloring, shaping, keratin materials, in particular of the skin of the body or of the face, lips, nails , hair and / or eyelashes, comprising the application on said materials of a cosmetic composition according to the invention.

Preferably, it is a cosmetic treatment method for conditioning the hair, in particular to provide them with body and / or nervousness, or to improve disentangling, smoothing, combing, repair and / or the maneuverability of the hair. It may be a method of repairing and / or protecting damaged or weakened hair.

The invention is illustrated in more detail in the following exemplary embodiments.

EXAMPLE 1 Synthesis of a PEG-b-polvMADAME Diblock Polymer (5000/5000) This synthesis is carried out by anionic polymerization, according to the procedure described in Macromolecules 1999, 32 (6) 2088-2090.

5 g POE monomethoxy POE of 5000 g / mol (1 mmol) in 100 ml of dry THF are dissolved in a flask placed under nitrogen. Potassium naphthalene (mmol, 0.16 g) is added and the reaction is maintained at 30 ^° C. for 2 hours in order to form the corresponding alkoxide. Dimethylaminoethyl methacrylate (MADAME) (5 g, 31.8 mmol), previously distilled, is added and then allowed to polymerize at 50 ^° C. for 4 hours. The polymerization is stopped by adding isopropanol. The solvents are evaporated under vacuum, the polymer is dissolved in a dilute aqueous solution of HCl to remove the water-insoluble naphthalene by filtration. Any remaining traces of naphthalene after precipitation are removed by precipitation in n-hexane. An aqueous soda solution is added to pH = 12, the solution is heated without stirring at 90 ^° C. The polymer precipitates. The supernatant is decanted and the lyophilized polymer. THF is then added to precipitate the residual salts. The THF is then evaporated under vacuum, and the polymer obtained is dried under vacuum. The desired polymer is obtained in the form of a pale yellow powder.

Example 2 Synthesis of a PEG-b-polvMADAME Diblock Polymer (5000/5000)

This synthesis is carried out by radical polymerization controlled by ATRP, according to a procedure adapted from that described in US2003 / 0130160.

a / preparation of the PEG macroinitiator

PO Mw 5000 monomethoxy (500 g, 0.1 mole) is dissolved in 250 ml of anhydrous toluene in a round bottom flask equipped with two inlets, one closed by a septum, the second equipped with a bubbler and a CaCl ₂ trap. Polymer-supported 4-dimethylaminopyhdine (2 g, 1.25 mmol N / g), thymylamine (2.02 g, 0.02 moles) and a magnetized bar were added to the solution and then, dropwise, via a syringe. through the septum, 2-bromoisobutyryl bromide (4.6 g, 0.02 mol). The initially transparent solution turns quickly into a milky solution. After stirring overnight at room temperature, the reaction medium is filtered through a bed of silica beads to remove the insolubles. The recovered filtrate is evaporated to about 1 third of its original volume and added to a large volume of petroleum ether; the precipitate is filtered and recovered.

After drying under vacuum, the product is obtained in the form of a white powder whose characteristics are:

IR: 1734 cm- ¹ (C = O)

NMR (1H, CDCl ₃ ) (ppm): 1.94 (d, CH ₃ ester); 3.38 (s, methoxy, CH ₃ ), 3.64 (s, PEG, CH ₂ ); 4.32 (m, CH ₂ -OCO).

b / preparation of the diblock polymer PEG-b-polvMADAME (5000/5000)

The dimethylaminoethyl methacrylate (MADAME) (7.75 g, 49.38 mmol) and the macro-initiator prepared above (8 g, 1.553 mmol) are dissolved in 35 ml of water. Demineralized, in a three-necked 50 ml equipped with a magnetic bar, a thermometer, a nitrogen inlet and a septum connected to a bubbler. The solution is degassed with nitrogen for 45 minutes. Then, copper bromide (0.22 g, 1.553 mol) and 2,2'-dipyridyl (0.485 g, 3.11 mmol) are added to the solution, removing the thermometer and then putting it back immediately afterwards. addition of solids. The reaction mixture takes on a green color, and an increase in viscosity is noticed. An exotherm of 25 ° C is recorded for 5 minutes. After stirring for 2 hours, the contents of the tricolor are poured on a bed of silica in order to remove the copper residues and the aqueous solution is freeze-dried to obtain the desired polymer, in the form of a white powder whose characteristics are: IR: 1723 cm- ¹ (C = O)

NMR (1H, CDCl ₃ ) (ppm): 0.8-1.4 (CH ₃ backbone, methacrylate); 1.7-2.1 (CH ₂ methacrylate skeleton); 2.4 (m, N-CH ₃ , 6H); 2.7 (s, N-CH ₂ , 2H); 3.38 (s, methoxy 1.94 (d, ester CH ₃ ), 3.38 (s, methoxy, CH ₃ ), 3.64 (s, PEG, CH ₂ ), 4.32 (m, CH ₂ -OCO), 3.38 (s, CH ₃ , 3H), 3.65 (s, 0-CH ₂ -CH ₂ -O, 4H), 4.13 (s, CH ₂ -O, 2H).

Example 3: Dissolving the polymer

To 5 g of the polymer prepared in Example 2, in the form of a white powder, 16 ml of a 1N aqueous HCl solution and 29 ml of HPLC water are added. The mixture is stirred at 50 ^° C. for 1 hour.

A clear polymer solution is obtained which can be used for the cosmetic compositions.

Example 4 Cosmetic Composition

A cosmetic composition is prepared comprising:

- 0.3% (DM) of gelatinized potato diesidon phosphate (DM = dry matter)

- 6.2% (MS) of non-pregelatinized hydroxypropyl potato phosphate phosphate

0.65% (MS) of diblock polymer of Example 2

- q.s. preservative - qs 100% water.

A cosmetic hair care composition is obtained that can be applied to the hair.

Example 5: Conditioner

A conditioner formula according to the invention comprising:

cetearyl alcohol 2.5 g - cetyl esters 0.5 g

lauryl PEG / PPG 18/18 methicone 0.25 g

- PDMS with aminoethyl iminopropyl groups 4.15 g

polymer of example 2 1, 2 g MS Preservative qs - water qs100% A comparative formula is prepared by replacing the polymer of the invention with 1.2% g of dry matter of beetetrimonium chloride.

An evaluation of the formulas is carried out on strands of hair of 2.5 g. A shampoo is first applied to wash the wick. Rinse the shampoo. 1 g of the conditioner formula is applied. Then rinse the wick. The evaluation on wet hair by a panel of testers shows that the lock treated with the conditioner formula of the invention is much smoother than the lock treated with the comparative formula.

Example 6 The wet friction forces were compared for hair treated with the polymer according to the invention or with polymers according to the prior art.

In order to do this, the friction forces acting on a moving wick of hair (specimen) sliding between 2 flexible surfaces have been determined. The treated moving wick is fixed on a mechanical testing machine, and driven in a vertical rectilinear motion between two pads coated with a flexible and compressible material. The force to be exerted to slide the wick between these two surfaces is measured using an electronic gauge connected to the crosshead of the machine. The force is measured at 3 different speeds (10, 50 and 100 mm / min) during the movement. The test pieces are measured before and after treatment.

The tests are carried out under the following conditions:

- Substrate: bleached hair SA16 - prior to treatment, the test pieces are immersed for 6 minutes in water at 30 ⁰ C (to mimic the wet conditions);

the treatment is carried out by dipping flat in 2.85 ml of solution, for 2 test pieces (2 × 30 mg of hair);

the treatment is carried out at 30 ^° C. for 15 minutes; after treatment, the test pieces are rinsed with water.

The tested solutions comprise 1% by weight of dry matter of the following polymers, in water:

The comparative triblock polymers were prepared according to WO03 / 075867.

The following results are obtained:

The lower the force (F in N), the better the friction properties. It is therefore found that the invention makes it possible to obtain a level of friction comparable to, or even better than, the state of the art (cationic surfactant). It is found that the results obtained with the polymer of the invention are better, with equivalent amounts of PEG, than those obtained with a triblock polymer of the prior art; with the triblock polymers, it is necessary to increase the amount of PEG strongly (about 70%) to obtain adequate friction forces, whereas a 50% PEG content gives satisfactory results when a polymer is used. diblock. The use of a diblock polymer thus makes it possible to use a polymer comprising less PEG, and thus to obtain a very satisfactory feel of the strands.

Claims

A cosmetic composition comprising a cosmetically acceptable medium which comprises, in solution or dispersion in said medium, a linear diblock polymer, or a salt thereof, comprising a first block A which comprises repeating units of formula (I), and a second block B which comprises repeating units of formula (II):

in which :

- R 'and R ", identical or different, represent a hydrogen atom or a methyl group;

p is an integer greater than or equal to 2; R represents a hydrogen atom or a methyl group;

n is an integer greater than or equal to 2,

X represents O or NH;

- R3 is a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, from 1 to 30 carbon atoms, which may comprise 1 to 6 heteroatoms selected from O, N and S;

R1 and R2 represent, independently of one another, (i) a hydrogen atom,

(ii) a linear, branched or cyclic, saturated or unsaturated, optionally aromatic, alkyl group comprising from 1 to 18 carbon atoms, which may comprise 1 to 10 heteroatoms selected from O, N, S;

(iii) R1 and R2 may form with the nitrogen atom a ring of formula:

saturated or unsaturated, optionally aromatic, said ring comprising 5 to 6 atoms (forming the ring), and in particular 3 to 6 carbon atoms, said ring being interrupted by 1 to 3 divalent groups chosen from -O-, -S and -NH- and / or substituted with a group = O.

2. Composition according to Claim 1, in which the molecular weight (Mn) of the sequence A is between 250 and 50,000 g / mol, preferably between 600 and 20,000 g / mol and even more preferentially between 1,000 and 10,000 g / mol. .

3. Composition according to one of the preceding claims, wherein the molecular weight (Mn) of the sequence B is between 250 and 50,000 g / mol, preferably between 600 and 20,000 g / mol and even more preferably between 1000 and 10,000. g / mol.

4. Composition according to one of the preceding claims, wherein the sequence B comprises at least one monomer chosen from:

dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide; dimethylaminopropyl (meth) acrylamide; diethylaminopropyl (meth) acrylamide; aminopropyl (meth) acrylamide;

the following monomers:

5. Composition according to one of the preceding claims, wherein the sequence B further comprises at least one additional monomer, selected from vinyl neodecanoate, vinyl terbutylbenzoate; vinylpyrrolidone; vinylca- prolactam; N-vinyl formamide; triethylammoniumethyl (meth) acrylate chloride (MADQUAT), ethyl (meth) acrylate; methyl (meth) acrylate; isobornyl (meth) acrylate; vinyl acetate, crotonic acid; acrylic acid, methacrylic acid, terbutyl (meth) acrylate; octyl (meth) acrylamide; 1-eicosene, terbutyl (meth) acrylamide, (meth) acrylamide; hexadecene, and mixtures thereof.

6. Composition according to one of the preceding claims, wherein the molecular weight (Mn) of the diblock polymer is between 500 and 100000 g / mol, preferably between 1000 and 50,000 g / mol and even better between 2000 and 15,000. g / mol.

7. Composition according to one of the preceding claims, wherein the ratio between [Mn molecular weight of the A block] / [Mn molecular weight of the B block] is between 0.02 and 49, in particular between 0.1 and 10, even better between 0.7 and 5, or even between 0.8 and 2.

8. Composition according to one of the preceding claims, in which the sequence comprising the repeating units of formula (I) and the sequence comprising the repeating units of formula (II) are linked by a single bond or by a linker (agent binding) divalent L selected from -O-; -NOT-; -S-; - R'-; -C (= O) -O-; - O-C (= O) -O-; -C (= O) -NR "-; -O-C (= O) -NR" -; -NR "-C (= O) -NR" -, and mixtures thereof; with R 'representing a C1-C18 linear or branched divalent hydrocarbon chain; and R "represents H or a C1 -C12 linear or branched hydrocarbon chain.

The composition of claim 8 wherein the divalent L-linker is -C (= O) -C (CH ₃ ) ₂ -.

10. Composition according to one of the preceding claims, wherein the polymer is present in a proportion of 0.01 to 50% by weight of dry matter, especially 0.1 to 30% by weight, or even 0.3 to 10% by weight. % by weight, more preferably from 1 to 3% by weight, relative to the total weight of the composition.

11. Composition according to one of the preceding claims, being in the form of a care product, cleaning and / or makeup of the skin of the body or face, lips, eyebrows, eyelashes, nails and hair, a sunscreen or self-tanning product, a personal care product, a hair product, especially care, cleaning, styling, shaping, hair dyeing.

12. Process for the cosmetic treatment of keratin materials, comprising the application to said keratin materials of a cosmetic composition according to one of claims 1 to 11.

13. The method of claim 12, characterized in that it is a cosmetic treatment method for conditioning the hair, in particular to bring them body and / or nervousness, or improve the disentangling, the smoothing, combing, repair and / or maneuverability of the hair.