WO2002080874A1

WO2002080874A1 - Anhydrous anti-pesrpirant composition based on polymers with sulphonic units

Info

Publication number: WO2002080874A1
Application number: PCT/FR2002/000915
Authority: WO
Inventors: Christophe Courbiere
Original assignee: L'oreal
Priority date: 2001-04-09
Filing date: 2002-03-15
Publication date: 2002-10-17
Also published as: FR2823111A1; FR2823111B1

Abstract

The invention concerns an anhydrous anti-perspirant composition comprising in a cosmetically acceptable lipophilic phase: (a) at least an active anti-perspirant, and (b) at least a crosslinked or non-crosslinked polymer, including at least an ethylenically unsaturated monomer with a sulphonic group, in free form, or partly or completely neutralised, said polymer capable of further including a hydrophobic part.

Description

ANHYDROUS ANT1TRANSPIRANT COMPOSITION BASED ON SULPHONIC POLYMERS

The present application relates to an anhydrous antiperspirant composition comprising, in a cosmetically acceptable lipophilic phase:

(a) at least one antiperspirant active, and,

(b) at least one crosslinked or uncrosslinked polymer comprising at least one ethylenically unsaturated monomer containing a sulfonic group, in free form, or partially or totally neutralized, said polymer possibly also comprising a hydrophobic part.

The anhydrous antiperspirant compositions are generally presented in the form of aerosols, sprays, creams or sticks.

In aerosols and sprays, the antiperspirant active ingredient is most often dispersed in a mixture of volatile silicones and fatty esters, in the presence of suspending agents such as, for example, bentones. These dosage forms have the disadvantage of inducing, during spraying, an undesirable cloudy effect.

In creams and sticks, the antiperspirant active ingredient is generally suspended in a matrix of waxes, silicones and emollients. Obtaining these dosage forms requires heating at high temperatures, above 60 ° C. In addition, the waxes induce a feeling of "greasy" on the skin that some users do not support.

After significant research carried out on the question, the Applicant has now discovered that it is possible to obtain, by simple stirring at room temperature (around 25 ° C.), compositions having the consistency of a cream, in mixing, in a lipophilic phase, an antiperspirant active agent in particular based on salt or aluminum complex with a crosslinked or non-crosslinked polymer, comprising at least one ethylenically unsaturated monomer with sulfonic group, in free form, or partially or totally neutralized, said polymer possibly also comprising at least one monomer comprising a hydrophobic part.

The compositions obtained, when they must be presented in the form of an aerosol or spray, generate a cloudy effect that is much less significant than with the compositions of the prior art, and when they must be presented in the form of creams or sticks, they are advantageously prepared at room temperature. This discovery is the basis of the present invention.

The subject of the present invention is therefore an anhydrous antiperspirant composition comprising, in a cosmetically acceptable lipophilic phase: (a) at least one antiperspirant active, and,

(b) at least one polymer comprising at least one ethylenically unsaturated monomer containing a sulfonic group, in free form, or partially or completely neutralized.

However, other characteristics, aspects, objects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

By "anhydrous" is meant within the meaning of the invention, a composition whose free or added water content is less than 3% and preferably whose added water content is less than 1% by weight relative to the total weight of composition.

Polymers according to the invention

The polymers in accordance with the invention are represented by polymers comprising at least one ethylenically unsaturated monomer containing a sulfonic group, in free or partially or totally neutralized form, which can be modified by a fatty chain, or copolymers of at least one monomer ethylenically unsaturated with sulfonic group in free or partially or totally neutralized form and of at least one monomer comprising a hydrophobic part.

The polymers according to the invention can be crosslinked or non-crosslinked.

According to the invention, the crosslinked polymers are more particularly preferred. Preferably, the polymers in accordance with the invention are partially or totally neutralized with an inorganic base (sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di- or tri-ethanolamine, an aminomethylpropanediol, N-methyl - glucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds.

Ethylene unsaturated monomers with sulfonic group

They are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth) acrylamido (CC ₂₂ ) alkylsulfonic acids, N- (C

C ₂₂ ) alkyl (meth) acrylamido (CC ₂₂ ) alkyl sulfonics such as undecyl-acrylamidomethane sulfonic acid and their partially or totally neutralized forms. ^' Preferably, (meth) acrylamido (CC ₂₂ ) alkylsulfonic acids are used such as for example acrylamido-methane-sulfonic acid, acrylamido-ethane-sulfonic acid, acrylamido-propane-sulfonic acid, acid 2-acrylamido-2- methylpropane-sulfonic (AMPS), methacrylamido-2-methylpropane-sulfonic acid, 2-acrylamido-n-butane-sulfonic acid, 2-acrylamido-2,4,4- trimethylpentane-sulfonic, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid, and their partially or fully neutralized forms.

More particularly still, 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) is used as well as its partially or totally neutralized forms.

Monomers comprising a hydrophobic part

When the polymer according to the invention comprises a monomer comprising a hydrophobic part, the hydrophobic part, which is a fatty chain, preferably contains from 6 to 50 carbon atoms, more preferably from 6 to 22 carbon atoms, even more preferably from 6 to 18 carbon atoms, and more particularly from 12 to 18 carbon atoms.

Among the polymers comprising at least one ethylenically unsaturated monomer containing a sulfonic group, and not comprising a monomer with a hydrophobic part, mention may be made in particular of the following homopolymers:

-polyacrylamido-methane-sulfonic acid,

-polyacrylamido-ethane-sulfonic acid,

-polyacrylamido-propane-sulfonic acid, -poly-2-acrylamido-2-methylpropane-sulfonic acid,

-poly-2-methacrylamido-2-methylpropane-sulfonic acid,

-poly-2-acrylamido-n-butane-sulfonic acid, and their forms partially or totally neutralized.

Polymers of this type, and in particular po! Y-2-acrylamido-2-methylpropanesulfonic acids, can be crosslinked and partially or completely neutralized. They are generally characterized by the fact that they comprise, randomly distributed: a) from 90 to 99.9% by weight of units of formula (I) below (AMPS):

in which, X ⁺ denotes a proton, or an alkali metal cation, or an equivalent alkaline earth metal cation, or the ammonium cation, b) from 0.1 to 10% by weight of at least one crosslinking unit having at least two olefinic double bonds, the proportions by weight being defined relative to the total weight of the polymer;

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

The crosslinking units having at least two olefinic double bonds are chosen, for example, from dipropylene glycol-diallylether, polyglycol-diallylethers, triethyiene glycol-divinylether, hydroquinone-diallyl ether, tetra-allyl-oxyethane or other allyl - or vinyl ethers of polyfunctional alcohols, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane-diallylether, methylene-bis-acrylamide or divinylbenzene.

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

in which R 1 denotes a hydrogen atom or a CC ₄ alkyl and more particularly methyl (trimethylol propane triacrylate: TMPTA).

Crosslinked and partially or fully neutralized poly-2-acrylamido-2-methylpropane-sulfonic acids are generally known under the names "Ammonium Polyacrylamido-2-methylpropanesulfonate" or "Ammonium

Polyacryloyldimethyltaurate "(INCI dictionary ed. 2000). They are for example described and prepared in patent application DE-19625810.

They can be obtained according to the known preparation process comprising the following steps:

(a) dispersing or dissolving the ethylenically unsaturated monomer containing a sulfonic group in free form in a solution of tert-butanol or of water and of tert-butanol;

(b) the solution or dispersion of monomer obtained in (a) is neutralized with one or more mineral or organic bases, preferably ammonia, in an amount making it possible to obtain a rate of neutralization of the sulfonic acid functions of the polymer ranging from 0 to 100%;

(c) adding to the solution or dispersion obtained in (b) the crosslinking monomer (s);

(d) a conventional radical polymerization is carried out in the presence of free radical initiators at a temperature ranging from 10 to 150 ° C; the polymer precipitating in the solution or dispersion based on tert-butanol.

A particularly preferred product according to the invention is that sold by the company CLARIANT under the trade name HOSTACERIN AMPS; it is a crosslinked poly-2-acrylamido-2-methylpropane sulfonic acid and partially neutralized by ammonia.

The polymers in accordance with the invention can also be chosen from random polymers of AMPS modified by a fatty chain, by reaction with an n-monoalkylamine or a di-n-C ₆ -C ₂₂ alkylamine, and such as those described in patent application WOOO / 3 154 (forming an integral part of the content of the description). These polymers may also contain other hydrophilic ethylenically unsaturated monomers chosen, for example, from (meth) acrylic acids, their alkyl derivatives substituted in β or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides , vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

Polymers of at least one ethylenically unsaturated monomer with sulfonic group in free form, or partially or totally neutralized, and of at least one monomer with a hydrophobic part.

Such polymers generally have a number average molecular weight ranging from 1000 to 20,000,000 g / mole, preferably ranging from 20,000 to 5,000,000 and more preferably still from 100,000 to 1,500,000 g / mole. When they are crosslinked, the crosslinking agents can be chosen from olefinically polyunsaturated compounds commonly used for the crosslinking of polymers obtained by radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol-diallyl ether, polyglycol-diallyl ethers, triethylene glycol-divinyl ether, hydroquinone diallyl ether, di (meth) acrylate of ethylene glycol or of tetraethylene glycol, trimethylol propane triacrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallylamine, triallylcyanurate, diallylmaleate, tetraallylethylenediamine, tetra-allyloxy-ethane, trimethylolpropane-diallylether) allyl, allyl ethers of alcohols from the sugar series, or of other allyl- or vinyl-ethers of polyfunctional alcohols, as well as allyl esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures of these compounds.

More particularly, methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA) are used. The crosslinking rate generally varies from 0.01 to 10% by mole and more particularly from 0.2 to 2% by mole relative to the polymer.

Among said polymers, the copolymers of AMPS of formula (I) and of at least one hydrophobic monomer having from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms and even more preferably are preferred according to the invention. from 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

These copolymers may also contain one or more non-hydrophobic monomers, such as (meth) acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides , vinyipyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

Such copolymers are described in particular in patent application EP-A-750899, US patent 5089578 and in the following publications by Yotaro Morishima: - “Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. "

- "Miscelle formation of random copolymers of sodium 2- (acrylamido) -2- methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules 2000, Vol. 33, No. 10 - 3694-3704 "; "Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: sait effects on rheological behavior - Langmuir, 2000, Vol.16, N ° 12, 5324-5332";

"Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2- methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem. 1999, 40 (2), 220-221 ”.

In these particular AMPS copolymers, the monomers comprising a hydrophobic part are preferably chosen from the acrylates or acrylamides of formula (III) below:

in which R2 and R4, identical or different, denote a hydrogen atom or a linear or branched CC ₆ alkyl radical (preferably methyl); Y denotes O or NH; R3 denotes a hydrophobic hydrocarbon radical comprising at least 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms and even more preferably from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and varies from 0 to 100.

The radical R3 is preferably chosen from linear C ₆ -Cι ₈ alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane ( C ₁₂ ) or adamantane (C ₁₀ )); C ₆ -C ₁₈ alkylperfluorinated radicals (for example the group of formula - (CH ₂ ) ₂ - (CF ₂ ) ₉ -CF ₃ ); the cholesteryl radical (C ₂₇ ) or a residue of cholesterol ester such as the cholesteryl oxyhexanoate group; aromatic polycyclic groups such as naphthalene or pyrene. Among these radicals, more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical. According to a particularly preferred form of the invention, the monomer of formula (III) comprises at least one alkylene oxide unit (x> 1) and preferably a polyoxyalkylene chain. The polyoxyalkylenated chain, preferably, consists of ethylene oxide units and / or propylene oxide units and even more particularly consists of ethylene oxide units. The number of oxyalkylenated units generally varies from 3 to 100 and more preferably from 3 to 50 and even more preferably from 7 to 25.

Among these polymers, there may be mentioned: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C ₈ -C ₁₆ ) alkyl units ( meth) acryiamide or (C ₈ -Cι ₆ ) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A 750 899;

- Terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to - 80% by mole of n- (C ₆ -Cι ₈ ) alkylacrylamide units, such as than those described in US Pat. No. 5,089,578.

Mention may also be made of non-crosslinked and crosslinked copolymers of partially or fully neutralized AMPS and dodecyl methacrylate as well as non-crosslinked and crosslinked copolymers of partially or fully neutralized AMPS and n-dodecylmethacrylamide, such as those described in Morishima's articles cited above.

Mention is more particularly still made of the copolymers consisting of AMPS units of formula (I) described above and of units of formula (IV) below:

in which x denotes an integer varying from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R has the same meaning as that of R2 indicated above in formula (III) and R5 denotes a linear or branched C ₆ -C ₂₂ and more preferably C ₁₀ -C ₂₂ alkyl. Particularly preferred polymers are those for which x = 25, R5 denotes hydrogen or methyl and R5 represents n-dodecyl, or C-jg-C-ig; they are described in the Morishima articles mentioned above.

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

These preferred polymers can be obtained according to conventional radical polymerization processes in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, ABAH (2,2-azobis- [2-amidinopropane ] hydrochloride), organic peroxides such as dilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, etc. , mineral peroxide compounds such as potassium or ammonium persulfate, or H2O2 optionally in the presence of reducing agents. They are especially obtained by radical polymerization in a tert-butanol medium in which they precipitate.

By using precipitation polymerization in tert-butanol, it is possible to obtain a particle size distribution of the polymer which is particularly favorable for its uses. The particle size distribution of the polymer can be determined for example by laser diffraction or image analysis.

An interesting distribution for type of polymer and determined by image analysis is as follows: 60.2% less than 423 microns, 52.0% less than 212 microns, 26.6% less than 106 microns, 2.6% less than 45 microns and 26.6% greater than 850 microns.

The reaction can be carried out at a temperature between 0 and 150 ° C, preferably between 10 and 100 ° C, either at atmospheric pressure or under reduced pressure. It can also be carried out under an inert atmosphere, and preferably under nitrogen.

According to this process, in particular, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its sodium or ammonium salts was polymerized with an ester of (meth) acrylic acid and, of a C-in-C-js alcohol oxyethylenated with 8 moles of ethylene oxide (GENAPOL® C-080 from the company HOECHST / CLARIANT),

of an oxo alcohol in C- _j •} oxyethylenated with 8 moles of ethylene oxide (GENAPOL® UD- 080 from the company HOECHST / CLARIANT),

of a C-i oxo alcohol - oxyethylenated with 7 moles of ethylene oxide (GENAPOL® UD- 070 from the company HOECHST / CLARIANT),

of a C12-14 alcohol oxyethylenated with 7 moles of ethylene oxide (GENAPOL® LA-070 from the company HOECHST / CLARIANT),

of a C-12-C14 alcohol oxyethylenated with 9 moles of ethylene oxide (GENAPOL® LA-090 from the company HOECHST / CLARIANT),

of a C12-C4 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL® LA-110 from the company HOECHST / CLARIANT),

of a Cis-C ^ alcohol oxyethylenated with 8 moles of ethylene oxide (GENAPOL® T-080 from the company HOECHST / CLARIANT),

of a C-ig-C s alcohol oxyethylenated with 15 moles of ethylene oxide (GENAPOL® T-150 from the company HOECHST / CLARIANT),

of a C-] g-C- | 8 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL® T-110 from the company HOECHST / CLARIANT),

of a C-i -C-js alcohol oxyethylenated with 20 moles of ethylene oxide (GENAPOL® T-200 from the company HOECHST / CLARIANT),

of a C- Q-C- \ Q alcohol oxyethylenated with 25 moles of ethylene oxide (GENAPOL® T-250 from the company HOECHST / CLARIANT),

of a C18-C22 alcohol oxyethylenated with 25 moles of ethylene oxide and / or an iso C-15-C-18 alcohol oxyethylenated with 25 moles of ethylene oxide.

The molar concentration in% of the units of formula (I) and of the units of formula (IV) in the polymers according to the invention can vary between 0.1 and 99.9% by moles. Preferably for the most hydrophobic polymers, the molar proportion of units of formula (III) or (IV) varies from 50.1 to 99.9%, more particularly from 70 to 95% and even more particularly from 80 to 90% .

Preferably for slightly hydrophobic polymers, the molar proportion of units of formula (III) or (IV) varies from 0.1 to 50%, more particularly from 5 to 25% and even more particularly from 10 to 20%.

The distribution of the monomers in the polymers of the invention can be, for example, alternating, block (including multiblock) or any.

According to the invention, it is preferred that the polymers have pendant chains sensitive to heat and whose aqueous solution has a viscosity which, beyond a certain threshold temperature, increases, or remains practically constant when the temperature increases.

More particularly still, polymers are preferred whose aqueous solution has a viscosity which is low below a first threshold temperature and which, above this first threshold temperature increases towards a maximum when the temperature increases, and which, above of a second threshold temperature decreases again when the temperature increases. With this in mind, it is preferred that the viscosity of the polymer solutions below the first threshold temperature is from 5 to 50%, in particular from 10 to 30% of the maximum viscosity at the second threshold temperature. These polymers, preferably, lead in water to a phenomenon of demixing by heating resulting in curves having, as a function of the temperature and the concentration, a minimum called LCST (Lower Critical Solution Temperature).

The viscosities (measured at 25 ° C. with a Brookfield viscometer needle 7) of the 1% aqueous solutions preferably range from 20,000 mPa.s to 100,000 mPa.s and more particularly from 60,000 mPa.s to 70,000 mPa.s .

The polymers in accordance with the invention can be present in the anhydrous antiperspirant compositions according to the invention in concentrations ranging from approximately 0.01 to 30% by weight, preferably from 0.1 to 20%, and more particularly from 0 , 5 to 15% relative to the total weight of the composition.

Antiperspirants

They include, according to the invention, any substance suitable for application to human skin having an antiperspirant activity, that is to say reducing the sweat flow. They generally consist of organic or mineral salts, aluminum, zirconium and zinc or their mixtures. More particularly, these are aluminum salts, zirconium complexes or complexes of aluminum and zirconium. Such salts or complexes are for example described in patent application WO-01/13867 A1.

Among the aluminum salts, there may be mentioned in particular aluminum chloride and aluminum hydroxyhalides. This type of salt generally corresponds to the general formula: AI ₂ (OH) _a Cl xH ₂ 0, in which, a denotes a number ranging from approximately 2 to approximately 5, (a + b) is equal to 6, x denotes a number ranging from about 1 to about 6.

The zirconium complexes preferably correspond to the general formula:

ZrO (OH) ₂ - _a Cl _a xH ₂ 0, wherein, a denotes a number ranging from approximately 0 to approximately 2, and x denotes a number ranging from approximately 1 to approximately 7.

Among the aluminum and zirconium complexes, it is possible to cite in particular those associated with amino acids and in particular with glycine. Such complexes are generally known by the name ZAG. Such aluminum, zirconium and glycine complexes have in particular been described and prepared in the American patent.

No.. 3792068. The preferred amino acid for preparing such ZAG complexes is glycine.

The said antiperspirant substances currently used and approved by the F.D.A. (Food & Drug Administration) include aluminum chloride, aluminum hydrochloride, aluminum chlorohydrex, aluminum chlorohydrex PEG, aluminum chlorohydrex PG, aluminum dichlorohydrate, aluminum dichlorohydrex PEG, aluminum dichlorohydrex PG, aluminum sesquichlorohydrate, aluminum sesquichlorohydrex PEG, aluminum sesquichlorohydrex PG, aluminum sulfate, aluminum zirconium octachlorohydrate, aluminum zirconium octachlorohydrex GLY, aluminum zirconium pentachlorohydrate, aluminum zirconium pentachlorohydre , aluminum zirconium tetrachlorohydrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate GLY, and aluminum zirconium trichlorohydrate-GLY.

Among the aluminum salts and complexes, there may be mentioned more particularly the aluminum hydrochloride sold by the company Clariant under the name

LOCRON S, the aluminum hydroxychloride marketed by the company REHEIS under the name REACH 301 or by the company GUILINI CHEMIE under the name ALOXICOLL PF 40, the aluminum pentahydroxychloride / zirconium complex sold in aqueous solution at 40% of active material by the company REHEIS under the name REZAL 67 SOLUTION, the aluminum salt and zirconium marketed by the company REHEIS under the name REACH A2P-908-SUF.

According to the present invention, the aluminum salts sold anhydrous and in particular the anhydrous aluminum hydroxychloride are more particularly preferred.

These antiperspirant agents are used in the compositions according to the invention in concentrations of between approximately 5 and 60%, and preferably between 10 and 50% by weight, relative to the total weight of the composition.

Lipophilic phase

It can consist of an oil or a wax, petroleum jelly, paraffin, lanolin, hydrogenated lanolin, acetylated lanolin; or with fatty acids, fatty alcohols such as lauryl alcohol, cetyl alcohol, myristic, stearic, palmitic, oleic and by 2-octyldodecanol, esters of alcohols, C ₃ -C ₁₈ with C ₃ acids -Cι ₈ , ^" esters of fatty acids such as glycerol monostearate, polyethylene glycol monostearate, isopropyl myristate, isopropyl adipate, isopropyl palmitate, octyl palmitate, benzoates C12-C18 fatty alcohols (Finsolv TN from FINETEX), polyoxypropylene myristic alcohol with 3 moles of propylene oxide (WITCONOL APM from WITCO), triglycerides of C ₆ -C <8 fatty acids such as caprylic / capric acid triglycerides, or mixtures thereof. The oils are chosen from animal, vegetable, mineral or synthetic oils and in particular hydrogenated palm oil, hydrogenated castor oil, vaseline oil , paraffin oil, Purcellin oil (stearyl octanoate), silico oils ne and isoparaffins.

The waxes are chosen from animal, fossil, vegetable, mineral or synthetic waxes. Mention may in particular bees beeswaxes, Camauba, Candelila, sugarcane, Japanese waxes, ozokerites, Montan wax, microcrystalline waxes, paraffins, waxes and silicone resins.

The silicones can be volatile or non-volatile.

Volatile silicones are defined in a known manner as volatile compounds at room temperature. Among these compounds, mention may be made of cyclic volatile silicones and linear of the dimethylsiloxane type, the chains of which comprise from 3 to 9 silicone residues. Preferably, cyclomethicones D4 or D5 are chosen. Non-volatile silicones are defined in a known manner as compounds with low vapor pressure at room temperature. Among these compounds are included: polyalkylsiloxanes, in particular linear polyalkylsiloxanes such as, for example, linear polydimethylsiloxanes, or dimethicones, sold by the company Dow Corning under the name of "Dow Corning 200 Fluid"; polyalkylarylsiloxanes such as, for example, polymethylphenylsiloxanes, sold by the company Dow Corning under the name of "Dow Corning 556 Fluid"; polyether and siloxane copolymers, such as, for example, dimethicone copolyols.

According to the invention, the lipophilic phase is preferably chosen from volatile silicones.

In the compositions according to the invention, the lipophilic phase can represent approximately 30 to 90% by weight, and preferably 35 to 65% by weight of the total composition.

additives

The anhydrous antiperspirant composition according to the invention may also contain linear or branched aliphatic alcohols having from 2 to 4 carbon atoms such as ethanol or isopropanol in the proportion of 0 to 20% by weight relative to the total weight of the composition.

The anhydrous antiperspirant composition according to the invention may also contain other adjuvants such as, for example, emollients, humectants, soothing agents such as aloe vera, allantoin, D-panthenol, pigments and dyes and preservatives.

The anhydrous antiperspirant composition according to the invention, which has the texture of a cream, can be in the form of an aerosol, spray, stick, or any other form requiring the use of a cream, and may contain the ingredients used in a known manner for the type of presentation envisaged.

Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the antiperspirant composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged. The invention also ^'relates to a preparation of an anhydrous antiperspirant composition method for application to human skin which comprises mixing with stirring at ambient temperature (20 ° C-25 ° C), an active antiperspirant, a lipophilic phase and a polymer as described above.

It also relates to a method for controlling the bad odors associated with perspiration consisting in applying to human skin an effective amount of an antiperspirant composition as described above.

Concrete examples illustrating the invention are indicated below, without however being limiting in nature.

EXAMPLES OF PREPARATION OF AMPS AND MONOMER POLYMERS COMPRISING A HYDROPHOBIC PART Preparation of ethoxylated (meth) acrylic esters.

They can in particular be obtained by the action of glycidyl (meth) acrylate, or of (meth) acrylic acid, or of an alkyl (meth) acrylate, or of a (meth) acryloyl halide. on an ethoxylated fatty alcohol. There may be mentioned, by way of nonlimiting examples, the following preparations: a) from glycidyl methacrylate and GENAPOL T-250 b) from (meth) acrylic acid. and GENAPOL UD-070 c) from methyl (meth) acrylate and GENAPOL LA-090 d) from (meth) acryloyl chloride and GENAPOL UD-070.

a) 500 g of Genapol T-250 and 75 g of glycidyl methacrylate are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. The reaction mixture is heated to the temperature of 100 ° C for 2 hours, and the excess glycidyl methacrylate is removed by distillation under reduced pressure. The monomer obtained can be used for polymerization without further purification.

b) 500 g of Genapol UD-070, 100 g of (meth) acrylic acid and acid are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. p-toluenesulfonic as a catalyst. The reaction mixture is heated at reflux for 2 hours, and the excess acid and water formed during the reaction are separated by distillation under reduced pressure. The monomer obtained can be used for polymerization without further purification.

c) 500 g of Genapol LA-090, 100 g of methyl (meth) acrylate and 20 g of tetraisopropoxide are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. titanium. The reaction mixture is heated at reflux for 2 hours, and after separation by distillation of the alcohol formed, the ester is distilled which remains under reduced pressure. The monomer obtained can be used for polymerization without further purification.

d) 500 g of Genapol UD-070, 110 g of chloride are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. (meth) acryloyl and 50g of sodium carbonate. The reaction mixture is heated at reflux for 2 hours, and the excess acid chloride is separated by distillation under reduced pressure. The monomer obtained can be used for polymerization without further purification.

Polymerization according to the precipitation method in tert-butanol

500 ml of tert-butanol and the calculated quantity of AMPS are introduced into a 2-liter reactor fitted with a reflux condenser, a gas outlet, a thermometer and a stirrer. The mixture is neutralized by introducing NH3, and the monomer prepared above is added to the reaction mixture. The reaction mixture is made inert by passing nitrogen or argon and when the internal temperature has reached 60 ° C., the initiator (AIBN) is introduced to initiate the polymerization. After a few minutes, the polymer thus prepared precipitates. The mixture is brought to reflux for 2 hours, and the polymer is separated from the solvent by suction filtration, then it is dried under reduced pressure.

As described above, the following polymers were prepared:

(from the following reactants in quantities expressed in grams)

EXAMPLES OF COMPOSITIONS

The following 6 mixtures A, B, C, D, E and F were made using a mixer

TURRAX and for 1 minute at room temperature (25 ° C).

(quantities expressed in grams):

^* Viscosity measured with the BROOKFIELD viscometer, mobile E, needle 95, 10 rpm,

(1) HOSTACERIN AMPS from CLARIANT,

(2) Copolymer of acrylamido-2-methyl-2-propane-sulfonic / n-dodecylacrylamide [AMPS / formula (III) where x = 0, R ₂ = H, Y = NH, R ₃ = nC ₁₂ ], (3 , 5% / 96.5%) 100% neutralized by soda,

(3) Anhydrous aluminum hydroxychloride (CHLORHYDROL ALUMINUM CHLOROHYDRATE from the company REHEIS).

From the above tests, it is clearly seen that only mixtures C and F, that is to say mixtures with the 3 compounds according to the invention, give thickened and homogeneous formulas, the texture of which is that of a cream. They are also opaque, shiny in appearance and white in color.

Similar results were obtained by replacing the copolymer acrylamido-2-methyl-2-propane-sulfonic / n-dodecylacrylamide neutralized by sodium hydroxide (2) mixtures D, E, F above, by a copolymer crosslinked by methylene-bis-acrylamide consisting of 75% by weight of AMPS ^'units neutralized by NH3 and 25% by weight of units of formula (IV) in which Rg = H, Rδ≈C-ig-C-is and x = 25.

Similar results were obtained by replacing the copolymer acrylamido-2-methyl-2-propane-sulfonic / n-dodecylacrylamide neutralized by soda (2) of the mixtures D, E, F above by a crosslinked copolymer with methacrylate allyl consisting of 90% by weight of AMPS units neutralized by NH3 and 10% by weight of methacrylate units of GENAPOL T-250 [units of formula (IV) in which

R5 = C-iQ-C-i8 ex = 25], or by a copolymer crosslinked with allyl methacrylate consisting of 80% by weight of AMPS units neutralized by NH3 and 20% by weight of methacrylate units of GENAPOL T- 250 [units of formula (IV) in which Rg = CH3, R ₅ = C ₁₆ -C ₈ and x = 25j.

Claims

1. Anhydrous antiperspirant composition comprising, in a cosmetically acceptable lipophilic phase: (a) at least one antiperspirant active, and,

2. Composition according to Claim 1, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen from vinyisulfonic acid, styrene sulfonic acid, (meth) acrylamido (C _r C ₂₂ ) aIkylsulfonic acids, N- (C ₁ -C ₂₂ ) alkyl (meth) acrylamido (C ₁ -C ₂₂ ) alkylsulfonic acids and their partially or fully neutralized forms.

3. Composition according to claim 2, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen from acrylamidomethane-sulfonic acid, acrylamido-ethane-sulfonic acid, acrylamido-propane-sulfonic acid , 2-acrylamido-2-methylpropane-sulfonic acid (AMPS), methacrylamido-2-methylpropane-sulfonic acid, 2-acrylamido-n-butane-sulfonic acid, 2-acrylamido acid 2,4 , 4-trimethylpentane-sulfonic, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid, and their partially or totally neutralized forms.

4. Composition according to claim 3, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is 2-acrylamido-2-methylpropane-sulfonic acid (AMPS), as well as its partially or totally neutralized forms, of formula ( I) following:

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

5. Composition according to any one of the preceding claims, characterized in that the polymer also comprises at least one hydrophobic part.

6. Composition according to claim 5, characterized in that the hydrophobic part of the polymer contains from 6 to 50 carbon atoms.

7. Composition according to claim 6, characterized in that the hydrophobic part of the polymer contains from 6 to 22 carbon atoms.

8. Composition according to any one of the preceding claims, characterized in that the polymers are partially or totally neutralized with an inorganic or organic base.

9. Composition according to any one of the preceding claims, characterized in that the polymers are crosslinked or non-crosslinked.

10. Composition according to claim 9, characterized in that the polymers are crosslinked.

11. Composition according to any one of claims 1 to 4 and 10, characterized in that the polymer is poly-2-acrylamido-2-methylpropane-sulfonic acid crosslinked and partially or completely neutralized.

12. Composition according to any one of claims 11, characterized in that the polymer is chosen from copolymers of 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) of formula (I), and at least minus one hydrophobic monomer.

13. Composition according to Claim 12, characterized in that the hydrophobic monomer is chosen from acrylates or acrylamides of formula (III) below:

in which R2 and R4, identical or different, denote a hydrogen atom or a linear or branched CC ₆ alkyl radical (preferably methyl); Y denotes O or NH; R3 denotes a hydrophobic hydrocarbon radical comprising at least 6 to 50 carbon atoms, preferably from 6 to 22 carbon atoms, even more preferably from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and varies from 0 to 100.

14. Composition according to Claim 13, characterized in that the hydrophobic radical R ₃ is chosen from C ₆ -C ₁₈ alkyl radicals, linear, branched or cyclic; C ₆ -C ₁₈ alkylperfluorinated radicals; the cholesteryl radical or a cholesterol ester; aromatic polycyclic groups.

15. Composition according to any one of claims 12 to 14, characterized in that the polymer is chosen from copolymers of 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) of formula (I), and d '' at least one hydrophobic monomer of formula (IV) below:

in which, x denotes an integer varying from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R ₆ has the same meaning as that of R ₂ indicated above in formula (III) and R ₅ denotes a linear or branched C ₆ -C ₂₂ and more preferably C ₁₀ -C ₂₂ alkyl.

16. Composition according to any one of claims 12 to 15 characterized in that the polymer is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) of formula (I), and of n.dodecylacrylamide [formula (III), where x = 0, R ₂ = H, Y = NH, R ₃ = nC ₁₂ ], neutralized.

17. Composition according to any one of claims 12 to 15 characterized in that the polymer is a crosslinked copolymer of 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) of formula (I) neutralized by NH3 and of units of formula (IV) in which Rg denotes hydrogen or a methyl radical,

and x = 25.

18. Composition according to any one of the preceding claims, characterized in that the polymer represents from 0.01 to 30%, preferably from 0.1 to 20% and more particularly from 0.5 to 15% by weight of the total weight of the composition.

19. Composition according to any one of the preceding claims, characterized in that the lipophilic phase is chosen from volatile silicones.

20. Composition according to any one of the preceding claims, characterized in that the lipophilic phase represents from 30 to 90% and preferably from 35 to 65% by weight of the total weight of the composition.

21. Composition according to any one of the preceding claims, characterized in that the antiperspirant active agent is chosen from aluminum salts and complexes.

22. Composition according to Claim 21, characterized in that the aluminum salt is anhydrous aluminum hydroxychloride.

23. Composition according to any one of the preceding claims, characterized in that the antiperspirant active agent represents from 5 to 60% and preferably from 10 to 50% by weight of the total weight of the composition.

24. A method of preparing a composition according to any one of the preceding claims, characterized in that, with stirring at room temperature (20 ° C-25 ° C), an antiperspirant active agent, a lipophilic phase and a polymer as described in any one of claims 1-18.

25. A method for controlling the bad odors associated with perspiration, consisting in applying to the human skin an effective amount of an antiperspirant composition as described in any one of claims 1-23.