AU748685B2 - Aerosol device containing a hair composition comprising at least one silicone/acrylate copolymer - Google Patents

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s):

L'OREAL

Invention Title: AEROSOL DEVICE CONTAINING A HAIR COMPOSITION COMPRISING AT LEAST ONE SILICONE/ACRYLATE COPOLYMER The following statement is a full description of this invention, including the best method of performing it known to me/us: 1A AEROSOL DEVICE CONTAINING A HAIR COMPOSITION COMPRISING AT LEAST ONE SILICONE/ACRYLATE

COPOLYMER

The invention relates to an aerosol device containing a cosmetic hair composition comprising at least one specific silicone/acrylate copolymer. The invention also relates to a cosmetic hair process, in particular a process for fixing and/or holding the hairstyle by using this aerosol device.

Among hair products for shaping and/or holding the hairstyle which are most widely available on the cosmetics market, there may be mentioned the spray compositions essentially consisting of a solution, usually an alcoholic or aqueous solution, and 15 one or more materials, generally polymeric resins, whose function is to form welds between the hairs, and these are also known as fixing materials, mixed with various cosmetic adjuvants. This solution is generally packaged either in a suitable aerosol container placed under pressure with the aid of a propellant, or in a pump-dispenser bottle.

The fixing materials are generally fixing polymers, i.e. film-forming polymers which are soluble in water and in alcohol, such as polyvinylpyrrolidone, the vinylpyrrolidone/vinyl acetate copolymers described in particular in US patents 3 929 735 and 3 770 683, vinyl acetate/crotonic acid copolymers and anionic or amphoteric acrylic resins. Although these materials 2 allow the fixing effect to be obtained easily, after brushing or combing, hair under the usual lacquer conditions has a stiffened appearance and a coarse or even sticky feel, as well as a powdering after drying.

These drawbacks are associated with several parameters, among which may be mentioned the nature of the fixing polymer(s) or the nature of the welds. To overcome these drawbacks, it is thus possible to act on these two parameters without, however, reducing the desired fixing effect. To improve the cosmetic properties of fixing materials, it has especially been proposed to combine different polymers (WO 94/12148, WO 96/06592, US 5158762) The applicant has now found that by suitably **selecting the fixing polymer and the propellent gas, it is 15 possible to overcome the various problems listed above, and in particular to obtain a spray of good quality in terms of droplet size and diffusion, satisfactory cosmetic properties and little powdering.

One subject of the invention is an aerosol device S: 20 comprising a container containing an aerosol composition comprising, on the one hand, a liquid phase (or fluid) containing at least one fixing material in at least one suitable solvent, and, on the other hand, at least one propellant, and a means for distributing the said aerosol 25 composition, characterized in that: the at least one fixing material is a silicone/acrylate copolymer obtained by radical-mediated polymerization of at least one ethylenically unsaturated monomer in the presence of at least one silicone derivative comprising at least one oxyalkylene group, and (ii) the at least one propellant is chosen from dimethyl ether and H:\suzannet\Keep\Speci\56488-00.1 SPECI doc 12/04/02 3 (iii) the aerosol composition contains more than water, when the propellant is dimethyl ether alone.

Another subject of the invention relates to a cosmetic hair process, in particular a process for fixing and/or holding the hairstyle using the aerosol device.

The silicone/acrylate copolymers particularly targeted by the present invention are those described in International Patent Application WO 99/04750. In particular, the copolymer sold by BASF under the name Luviflex Silk is preferred. This polymer is a grafted copolymer of tert-butyl acrylate/methacrylic acid and silicone copolyol.

Preferably, the monomer corresponds to formula (Ia)

X-C-CR

7

=CHR

6 (Ia) *o*oo H:\suzannet\Keep\Speci\56488-00.1 SPECI.doc 12/04/02 in which: X is chosen from the group comprising OH, OM, OR NH 2 NHR and N(R )2; M is a cation chosen from Na', Mg",

NH

4 alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium; the radicals R 8 may be identical or different and-are chosen from the group comprising hydrogen, linear or branched C 1 to C 40 alkyl groups, mono- or polyhydroxylated C 1 to C 40 alkyl groups, optionally substituted with one or more alkoxy, amino or carboxyl groups, hydroxylated polyethers, and N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl and 15 ethoxypropyl groups;

R

7 and R 6 are chosen, independently of each other, from the group comprising hydrogen, linear or branched C 1 to C 8 alkyl groups, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl groups, and CN, COOH and COOM groups.

In particular, the monomers of formula (Ia) are acrylic acid and its salts, esters or amides.

The esters may be derivatives of linear C 1 to C 40 alkyls, of branched C 3 to C 40 alkyls or of C 3 to C 40 carboxylic alcohols, of polyfunctional alcohols containing 2 to 8 hydroxyls, such as ethylene glycol, hexylene glycol, glycerol and 1,2,6-hexanetriol, of amino alcohols or of alcohol ethers such as methoxymethanol and ethoxyethanol, or polyalkylene glycols.

The monomers of formula (Ia) may also be chosen from N,N-dialkylaminoalkyl acrylates and methacrylates and N-dialkylaminoalkyl-acrylamides and -methacrylamides, the amide group possibly being unsubstituted, N-alkyl- or N-alkylamino-monosubstituted or N,N-dialkylamino-disubstituted, the alkyl or alkylamino groups being derived from linear C 1 to C 40 or branched C 3 to C 40 carboxylic units.

The monomers of formula (Ia) which can be used may also be substituted compounds derived from acrylic acid or its salts, esters or amides. Mention may be made, for example, of methacrylic acid, 15 ethacrylic acid and 3-cyanoacrylic acid.

Other monomers which are particularly suitable are C 1 to C 40 vinyl and allyl esters, linear C 3 to C 40 carboxylic acids or C 3 to C 40 carboxycyclic acids, vinyl or allyl haldides, vinyllactams, preferably vinylpyrrolidone and vinylcaprolactam, heterocyclic compounds substituted with vinyl or allyl groups, preferably vinylpyridine, vinyloxazoline and allylpyridine, N-vinylimidazoles, diallylamines, vinylidene chloride, carbon-based unsaturated compounds, such as styrene or isoprene, and acrylic or methacrylic acid derivatives quaternized with epichlorohydrin.

Other monomers which may finally be mentioned are N-vinylimidazoles, diallylamines, vinylidene chloride, carbon-based unsaturated compounds such as styrene and isoprene, and acrylic or methacrylic acid derivatives quaternized with epichiorohydrin.

Monomers which are most particularly preferred are acrylic, methacrylic and ethacrylic acid; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-thylhexyl and decyl acrylate; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl and decyl methacrylate; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl and decyl ethacrylate; 2,3-ihydroxypropyl acrylate; 2,3-dihydroxypropyl 0 0% methacrylate; 2-dihydroxyethyl acrylate; hydroxypropyl c 2 h e acrylate; 2-hydroxyethyl methacrylate; 2-hydroxyethyl see. ethacrylate; 2-methoxyethyl acrylate; 2-ethoxyethyl so. 9 methacrylate; 2-ethoxyethyl ethacrylate; hydroxypropyl a methacrylate; glyceryl monoacrylate; glyceryl sees 20 monomethacrylate; polyalkylene glycol (meth)acrylates, unsaturated sulphonic acids, acrylamide, 9999 0 methacrylamide, ethacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, 1-vinylimidazole, N,N-dimethylaminoethyl (meth)acrylate, maleic acid, fumaric acid, maleic anhydride and its monoesters, crotonic acid, itaconic acid, vinyl ethers, vinylformamide, vinylamine, vinylpyridine, vinylimidazole, vinylfuran, styrene, styryl sulphonate and allyl alcohol, and mixtures thereof.

The monomer can also contain silicon or fluorine atoms or alternatively thio groups. The monomers can be neutralized if they contain acid groups, this being carried out before or after the polymerization, and partially or totally, so as to adjust the solubility or the degree of dispersion in water to the desired level. Agents serving for the neutralization which may be used are mineral bases, such as sodium carbonate, and organic bases such as amino alcohols, for instance alkanolamines such as methanolamine, 2 -amino-2-methyl-l-propanol or

V.

ego* triethanolamine, and diamines such as lysine.

0 The monomers can also be quaternized when they contain a basic nitrogen atom. If they contain at least two ethylenic double bonds, the monomers can be partially crosslinked.

The silicone derivatives are in particular the compounds known under the INCI name of dimethicone copolyols or silicone surfactants. Mention may be made of those sold under the brand names Abil® by Goldschmidt, Alkasil® by Rh6ne-Poulenc, silicone Polyol Copolymer® by Genesee, Besil® by Wacker, Silwet by OSI or Dow Corning 190® by Dow Corning.

Among the preferred silicone derivatives(b) are those which have the formula I below: 8 in which formula R 2 is chosen from CH 3 and the group

R

3 is chosen from CH 3 and the group R

R

4 is chosen from hydrogen, CH 3 and the groups

F

LRJ

j X

C

R

6 is an organic C 1 to C 40 group which can contain amino, carboxyl or sulphonate groups, and if c=0, R 6 is the anion of an inorganic acid; the radicals R1 may be identical or different and are chosen from C 1 to C 20 aliphatic hydrocarbons,

C

3 to C 20 aliphatic or cycloaliphatic hydrocarbons, and the groups R 5 corresponding to the formula below: FL -(CH^-Onz-i'O-b n is an integer between 1 and 6, x and y are integers chosen such that the molecular weight of the polysiloxane is between 300 and 30,000, a and b are integers between 0 and 50, and c is 0 or 1.

R

1 is preferably chosen from methyl, ethyl, 10 propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and octadecyl groups, cycloaliphatic radicals, in particular cyclohexyl groups, aromatic groups, in particular phenyl or naphthyl groups, and mixtures of aromatic and aliphatic 15 radicals, such as benzyl and phenylethyl, and also tolyl and xylyl.

The preferred radicals R 4 are those having the formula -(CO)c-R 6

R

6 being an alkyl, cycloalkyl or aryl containing 1 to 4 carbon atoms which can contain additional groups such as NH 2 COOH and/or S0 3

H.

The preferred radicals R 6 are those for which c=0, which are phosphates or sulphates.

The silicone derivatives which are particularly preferred are those having the general formula below: Ha3- -Si- -3 x yCH The relative proportion of derivative in the copolymer is generally from 0.1% to 50% and preferably from 1% to 20% by weight.

The preferred copolymers are the watersoluble silicone/acrylate copolymers or those whose dispersibility in water is such that, in a water/ethanol mixture dosed at 50/50 by volume, they are soluble in a proportion of greater than 0.1 g/l and preferably greater than 0.2 g/l. Advantageously, the composition according to the invention comprises, as a relative percentage by weight, from 0.1% to 20% of silicone/acrylate copolymer and more preferably from to 10% of this copolymer. The aerosol device advantageously comprises from 10% to 90% of propellant and preferably from 20% to According to a first advantageous embodiment of the device in accordance with the invention, the propellant is dimethyl ether, and this propellant is advantageously present in the aerosol device at a concentration ranging from 30% to According to a second advantageous embodiment of the device in accordance with the invention, the propellant is a C3 to C4 hydrocarbon, and this 11 propellant is advantageously present in the aerosol device at a concentration ranging from 10% to 70%. The hydrocarbon is preferably chosen from n-butane, propane, isobutane and halohydrocarbons, and mixtures thereof.

According to a third advantageous embodiment of the device in accordance with the invention, the propellant is a mixture of dimethyl ether and of C3 to hydrocarbon(s), and the dimethyl 10 ether/hydrocarbon(s) ratio is advantageously between 90 and 90 The cosmetically acceptable medium preferably consists of water or one or more cosmetically acceptable solvents or water/solvent mixtures. These solvents are preferably Cl-C4 alcohols, ethanol being particularly preferred.

"•The appropriate solvent advantageously contains at least 50% by volume of alcohol, preferably at least 70% by volume of alcohol.

The composition of the invention can also contain at least one additive chosen from anionic, cationic, nonionic and amphoteric surfactants, fragrances, screening agents, preserving agents, proteins, vitamins, polymers other than those of the invention, and in particular anionic, amphoteric or nonionic fixing polymers, plant, mineral or synthetic oils and any other additive conventionally used in cosmetic compositions.

Needless to say, a person skilled in the art will take care to select the optional compound(s) to be added to the composition according to the invention such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the addition envisaged.

The compositions in accordance with the invention are particularly suitable for dry or wet 10 hair, as styling products.

*"The compositions in accordance with the invention can be applied to the skin, the nails, the lips, the hair, the eyebrows and the eyelashes.

The invention will be illustrated more fully **15 with the aid of the non-limiting examples which follow.

All the percentages are relative percentages "•by weight with respect to the total weight of the composition, and a.m. means active material.

EXAMPLE:

The aerosol device below in accordance with the invention is prepared.

Composition A Fluid: Luviflex Silk* 6%

AMP

Ethanol qs 100% neutralization qs 100 g Pressurization scheme: Fluid

DME

Pentane 37% 43% Composition B Fluid: Luviflex Silk* 15 Amphomer LV 71

AMP

Water Ethanol 4% 2% qs 100% neutralization 16% 78% Pressurization scheme: Fluid

DME

These two compositions are individually sprayed on European chestnut-brown hair. The hair has good cosmetic properties in both cases, after drying.

silicone/acrylate copolymer sold by BASF (t-butyl acrylate/methacrylic acid/PDMS polyether) It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.

For the purposes of this specification it will be clearly understood that the word "comprising" means "including but not limited to", and that the word "comprises" has a corresponding meaning.

Claims (14)

1. Aerosol device comprising a container containing an aerosol composition comprising, on the one hand, a liquid phase (or fluid) containing at least one fixing material in at least one suitable solvent, and, on the other hand, at least one propellant, and a means for distributing the said aerosol composition, characterized in that: the at least one fixing material is a silicone/acrylate copolymer obtained by radical-mediated polymerization of at least one ethylenically unsaturated monomer in the presence of at least one silicone derivative comprising at least one oxyalkylene group, 15 and (ii) the at least one propellant is chosen from dimethyl ether C3-C5 hydrocarbons, and (iii) the aerosol composition contains more than water, when the propellant is dimethyl ether alone. S.

2. Device according to claim 1, characterized in that the monomer corresponds to formula (Ia): X-C-CR 7 =CHR 6 (a) 0 H:\suzannet\Keep\Speci\56488-00.1 SPECIdoc 12/04/02 in which: X is chosen from the group comprising OH, OM, OR 8 NH 2 NHR 8 and N(R 8 2 M is a cation chosen from Na', K, Mg", NH 4 alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium; the radicals R 8 may be identical or different and are chosen from the group comprising hydrogen, linear or branched CI to C 40 alkyl groups, 10 mono- or polyhydroxylated C 1 to C 4 0 alkyl groups, optionally substituted with one or more alkoxy, amino or carboxyl groups, hydroxylated polyethers, and N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl and ethoxypropyl groups; R 7 and R 6 are chosen, independently of each other, from the group comprising hydrogen, linear or branched C 1 to C 8 alkyl groups, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl groups, and CN, COOH and COOM groups.

3. Device according to Claim 1, characterized in that the silicone derivative (b) corresponds to the formula below: O II t ^i R R L. in which formula R 2 is chosen from CH 3 and the group 1J R 3 is chosen from CH 3 and the group R 2 R 4 is chosen from hydrogen, CH 3 and the groups r 1 Rl1 R 0 Si. H 3 (oN a a R6 is the anion of an inorganic acid; the radicals R1 may be identical or a. .::different and are chosen from C to C20 aliphatic a c hydrocarbons, C3is to C20 aliphatic or cycloaliphatich can hydrocarbcontain amino, carboxyl or sund thphonate groups R 5 corresponding to theand if a.* c=0, R 6 is the anion of an inorganic acid; a formula0 the radicals R may be identical orbelow: different and are chosen from C 1 to C 20 aliphatic hydrocarbons, C 3 to C 20 aliphatic or cycloaliphatcic hydrocarbons, and the groups R 5 corresponding to the formula below: (cH.-o L b n. is an integer between 1 and 6, 18 x and y are integers chosen such that the molecular weight of the polysiloxane is between 300 and 30,000, a and b are integers between 0 and 50, and c is 0 or 1.

4. Device according to Claim 1, characterized in that the monomer is chosen from Ci to C 40 vinyl and allyl esters, linear C 3 to C 40 carboxylic acids or C 3 to C 40 carboxycyclic acids, vinyl 10 or allyl haldides, vinyllactams, preferably vinylpyrrolidone and vinylcaprolactam, heterocyclic S. compounds substituted with vinyl or allyl groups, preferably vinylpyridine, vinyloxazoline and allylpyridine, N-vinylimidazoles, diallylamines, vinylidene chloride, carbon-based unsaturated compounds, such as styrene or isoprene, and acrylic or o S" methacrylic acid derivatives quaternized with epichlorohydrin.

5. Device according to Claim 1, characterized in that the monomer is chosen from the group comprising acrylic, methacrylic and ethacrylic acid; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl and decyl acrylate; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl and decyl methacrylate; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl and decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-dihydroxyethyl 19 acrylate; hydroxypropyl acrylate; 2-hydroxyethyl methacrylate; 2-hydroxyethyl ethacrylate; 2-methoxyethyl acrylate; 2-ethoxyethyl methacrylate; 2-ethoxyethyl ethacrylate; hydroxypropyl methacrylate; glyceryl monoacrylate; glyceryl monomethacrylate; polyalkylene glycol (meth)acrylates, unsaturated sulphonic acids, acrylamide, methacrylamide, ethacrylamide, N,N- dimethylacrylamide, N-ethylacrylamide, N- ethylmethacrylamide, 1-vinylimidazole, N,N- dimethylaminoethyl (meth)acrylate, maleic acid, fumaric acid, maleic anhydride and its monoesters, crotonic acid, itaconic acid, vinyl ethers, vinylformamide, vinylamine, vinylpyridine, vinylimidazole, vinylfuran, styrene, styryl sulphonate and allyl alcohol, and mixtures thereof.

6. Device according to any one of the preceding claims, characterized in that the silicone derivatives (b) are chosen from dimethicone copolyols and silicone surfactants.

7. Device according to any one of the preceding claims, characterized in that it comprises, as a relative percentage by weight, from 0.1% to 20% of silicone/acrylate copolymer.

8. Device according to claim 7, characterized in that it comprises, as a relative percentage by weight, from 0.5% ,to 10% of silicone/acrylate copolymer.

9. Device according to any one of the preceding claims, characterized in that the propellant is dimethyl ether, and this propellant is advantageously present in H:\suzannet\Keep\Speci\56488-00.1 SPECI.doc 12/04/02 20 the aerosol device at a concentration ranging from 30% to Device according to any one of Claims 1 to 8, characterized in that the propellant is a C3 to C4 hydrocarbon, and this propellant is present in the aerosol device at a concentration ranging from 10% to

11. Device according to any one of Claims 1 to 8, characterized in that the propellant is a mixture of dimethyl ether and of C3 to C5 hydrocarbon(s), and the dimethyl ether/hydrocarbon(s) ratio is between 10 90 and 15 12. Device according to any one of the preceding claims, characterized in that the composition also contains at least one additive chosen from anionic, S: cationic, nonionic and amphoteric surfactants, fragrances, screening agents, preserving agents, proteins, vitamins, 20 polymers other than those of the invention, and in particular anionic, amphoteric or nonionic fixing polymers, and plant, mineral or synthetic oils.

13. Process for holding or shaping a hairstyle, characterized in that it uses a device in accordance with any one of Claims 1 to 12.

14. Use of a device according to any one of Claims 1 to 12, for the manufacture of a cosmetic product, in particular a hair product. Use according to claim 14, characterised in that the cosmetic product is a hair product. H:\suzannet\Keep\Speci\56488-00.1 SPECI.doc 12/04/02 21

16. Use of a composition according to any one of Claims 1 to 12, for the skin, the nails, the lips, the hair, the eyebrows and the eyelashes.

17. Aerosol devices or processes or uses involving them, substantially as hereinbefore described with reference to the example. Dated this 12th day of April 2002 L'OREAL By their Patent Attorneys 15 GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia i. *ooo** H:\suzannet\Keep\Speci\56488-00.1 SPECI.doc 12/04/02