WO2005070377A2

WO2005070377A2 - Method for improving the ozone stability of cosmetic compositions and such cosmetic compositions

Info

Publication number: WO2005070377A2
Application number: PCT/EP2005/000112
Authority: WO
Inventors: Olivier Jean Christian Poncelet
Original assignee: Eastman Kodak Company
Priority date: 2004-01-22
Filing date: 2005-01-08
Publication date: 2005-08-04
Also published as: WO2005070377A3; FR2865387A1

Abstract

The present invention relates to a method for improving the ozone stability of cosmetic compositions, and such cosmetic compositions. Said method comprises the use of at least one aluminosilicate polymer obtainable by a preparation method consisting in treating an aluminum halide with an alkyl orthosilicate only having hydrolyzable substituents or with a mixture of at least one silicon alkoxide only having hydrolyzable substituents and at least one silicon alkoxide having a non-hydrolyzable substituent with an aqueous alkali in the presence of silanol groups, the aluminum concentration being maintained less than 0.3 mol/l, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/Al molar ratio being maintained between 2.3 and 3; and then stirring the resulting mixture at ambient temperature in the presence of silanol groups for long enough to form the aluminosilicate polymer. The cosmetic composition comprises such aluminosilicate polymer.

Description

METHOD FOR IMPROVING THE OZONE STABILITY OF COSMETIC COMPOSITIONS AND SUCH COSMETIC COMPOSITIONS FIELD OF THE INVENTION The present invention relates to a method for improving the ozone stability of cosmetic compositions, and such cosmetic composition. Cosmetic compositions are used in personal care applications. BACKGROUND OF THE INVENTION The use of colored cosmetic compositions to change the color of human keratinous fibers, such as hair, nails, eyelashes, eyebrows, lips or skin is well known. In particular the coloring of human hair is well known mainly using two major types of capillary coloration: direct coloration and permanent coloration. Direct coloration uses dyes capable of giving the natural hair coloration a more or less marked change resisting several shampoos. Permanent coloration is carried out with "oxidation" dye precursors that are colorless or weakly colored compounds that once mixed with oxidizing products, at the time of use, produce colored compounds and dyes by an oxidative condensation process. To color nails, nail polish compositions are used comprising as coloring matter hydrosoluble dyes such as beet juice or methylene blue, or powder dyes like pigments, mother-of-pearl and glitter. Once the keratinous fiber is colored, it is desirable that the color does not deteriorate too quickly in time, particularly under the effect of ozone, light, the sun or pollution. The cosmetic compositions comprising active ingredients can also deteriorate because some active ingredient can be sensitive to ozone and are not stable. It is therefore necessary to develop a method for improving the ozone stability in time of cosmetic compositions, and more particularly when said cosmetic composition comprises active ingredients or is colored. SUMMARY OF THE INVENTION The method for improving the ozone stability of cosmetic compositions according to the present invention comprises the use of at least one aluminosilicate polymer obtainable by a preparation method that comprises the following steps: a) treating a compound selected from the group consisting of a mixed aluminum and silicon alkoxide of which the silicon has at least three hydrolyzable substituents, and a mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having at least three hydrolyzable substituents, with an aqueous alkali, in the presence of silanol groups, the aluminum concentration being maintained at less than 0.3 mol/1, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/Al molar ratio being maintained between 2.3 and 3; b) stirring the mixture resulting from step a) at ambient temperature in the presence of silanol groups long enough to form the aluminosilicate polymer; and c) eliminating the byproducts formed during steps a) and b) from the reaction medium. The invention method can be used to improve the ozone stability of cosmetic compositions comprising active ingredients, which are sensitive to ozone. The invention method can also be used to improve the color stability to ozone of colored cosmetic compositions, for example a colored cosmetic composition used to treat human keratinous fibers. Such method comprises: i) one step consisting in coloring the keratinous fibers with the colored cosmetic composition ii) one step consisting in applying to the keratinous fibers a cosmetically acceptable composition comprising at least one aluminosilicate polymer obtainable by a preparation method that comprises the following steps: a) treating a compound selected from the group consisting of a mixed aluminum and silicon alkoxide of which the silicon has at least three hydrolyzable substituents, and a mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having at least three hydrolyzable substituents, with an aqueous alkali, in the presence of silanol groups, the aluminum concentration being maintained at less than 0.3 mol/1, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/Al molar ratio being maintained between 2.3 and 3; b) stirring the mixture resulting from step a) at ambient temperature in the presence of silanol groups long enough to form the aluminosilicate polymer; and c) eliminating the byproducts formed during steps a) and b) from the . reaction medium. The present invention also comprises a cosmetic composition comprising at least one aluminosilicate polymer such as described above. Throughout the present description, the expression "hydrolyzable substituent" means a substituent eliminated by hydrolysis during the method and in particular at the time of the treatment with the aqueous alkali. This means that when the silicon atom only has three hydrolyzable substituents, it also has a non- hydrolyzable substituent that does not separate from the silicon atom during the method and in particular at the time of the treatment with the aqueous alkali. Such substituents are for example hydrogen, fluoride or an organic group. In the following, the expression "unmodified mixed duminum and silicon alkoxide" or "unmodified mixed aluminum and silicon precursor" means respectively a mixed aluminum and silicon alkoxide only having hydrolyzable substituents, or a mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only . having hydrolyzable substituents. The expression "modified mixed dunώium and silicon alkoxide" means a mixed aluminum and silicon alkoxide in which the aluminum atom only has hydrolyzable substituents and the silicon atom has three hydrolyzable substituents and one non-hydrolyzable substituent. Similarly, the expression "modified mixed aluminum and silicon precursor" means a precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having three hydrolyzable substituents and one non-hydrolyzable substituent. This non-hydrolyzable substituent enables a hybrid aluminosilicate polymer material to be obtained. More generally, an "unmodified" compound is a compound that only comprises hydrolyzable substituents and a "modified" compound is a compound that comprises one non-hydrolyzable substituent. The method according to the present invention enables the improvement of ozone stability in time of the cosmetic compositions, and then the increase of the life of such compositions. The method according to the invention in particular enables the improvement of the color stability in time to ozone of colored human keratinous fibers, and thus enables the time between two applications of colored cosmetic compositions to be lengthened. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 represents the density loss percentage of colored supports treated according to the method of the present invention and exposed to ozone. DETAILED DESCRIPTION OF THE INVENTION According to the present invention, the method for improving the ozone stability of cosmetic compositions comprises the use of at least one aluminosilicate polymer obtainable by a preparation method that comprises the following steps: a) treating a compound selected from the group consisting of a mixed aluminum and silicon alkoxide which only has hydrolyzable substituents, an unmodified mixed aluniinum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents, a mixed aluminum and silicon alkoxide whose silicon has both hydrolyzable substituents and one non-hydrolyzable substituent, and a modified mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having three hydrolyzable substituents and one non-hydrolyzable substituent, with an aqueous alkali, in the presence of silanol groups, the aluminum concentration being maintained at less than 0.3 mol/1, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/ Al molar ratio being maintained between 2.3 and 3; b) stirring the mixture resulting from step a) at ambient temperature in the presence of silanol groups long enough to form the aluminosilicate polymer; and c) eliminating the byproducts formed during steps a) and b) from the reaction medium. Such aluminosilicate polymers are described in PCT patent applications WO 2004/039724 and WO 2004/009494, hereby incorporated by reference in its entirety. According to one embodiment, the unmodified mixed aluminum and silicon precursor can be formed in situ by mixing in aqueous medium (i) one compound selected from the group consisting of aluminum salts, aluminum alkoxides and aluminum halogenoalkoxides and (ii) at least one compound selected from the group consisting of silicon alkoxides and chloroalkoxides only having hydrolyzable substituents, the silicon compound having at least three hydrolyzable substituents being selected to only have hydrolyzable substituents. The alkoxide radical of the unmodified aluminum compound or silicon compound preferably contains 1 to 5 carbon atoms, such as methoxide, ethoxide, n- propoxide, or i-propoxide. Preferably, an aluminum salt, such as a halide (e.g. chloride or bromide), a perhalogenate, a sulfate, a nitrate, a phosphate or a carboxylate, and at least one unmodified silicon alkoxide, such as tetramethyl or tetraethyl orthosilicate is used. A single unmodified silicon alkoxide or a mixture of unmodified silicon alkoxides, or a single unmodified silicon chloroalkoxide or a mixture of unmodified silicon chloroalkoxides, or a mixture of unmodified silicon alkoxides and chloroalkoxides can be used. Preferably, an aluminum halide, such as chloride, and an unmodified silicon alkoxide only having hydrolyzable substituents is used. In practice, the mixture is made at ambient temperature between 15°C and 35°C, preferably between 20°C and 25°C, by adding the silicon alkoxide, pure or diluted in a co-solvent such as an alcohol, to the aluminum salt in aqueous solution, with stirring, until a clear homogeneous mixture is obtained. An unmodified mixed aluminum and silicon precursor is thus obtained. The stirring time varies from 10 to 180 minutes, and is preferably 120 minutes. According to another embodiment, a modified mixed aluminum and silicon precursor is used that is formed in situ by mixing in aqueous medium (i) one compound selected from the group consisting of aluminum salts, aluminum alkoxides and aluminum halogenoalkoxides and (ii) at least one compound selected from the group consisting of unmodified silicon alkoxides and chloroalkoxides having only hydrolyzable substituents, and (iii) at least one compound selected from the group consisting of modified silicon alkoxides and chloroalkoxides having three hydrolyzable substituents and one non-hydrolyzable substituent. The modified or unmodified alkoxide radical of the aluminum compound or silicon compound preferably contains 1 to 5 carbon atoms, such as methoxide, ethoxide, n-propoxide, or i-propoxide. Preferably, an aluminum salt is used, such as a halide (e.g. chloride or bromide), a perhalogenate, a sulfate, a nitrate, a phosphate or a carboxylate. An aluminum halide, such as chloride, is particularly preferred. Preferably, silicon compounds are used in the form of alkoxides. A single unmodified silicon alkoxide or a mixture of unmodified silicon alkoxides, or a single unmodified silicon chloroalkoxide or a mixture of unmodified silicon chloroalkoxides, or a mixture of unmodified silicon alkoxides and chloroalkoxides can be used. Similarly, a single modified silicon alkoxide or a mixture of modified silicon alkoxides, or a single modified silicon chloroalkoxide or a mixture of modified silicon chloroalkoxides, or a mixture of modified silicon alkoxides and chloroalkoxides can be used. Preferably, a mixture (i) of an aluminum halide and (ii) a mixture comprising at least one unmodified silicon alkoxide having only hydrolyzable substituents and at least one modified silicon alkoxide having three hydrolyzable substituents and one non-hydrolyzable substituent are produced. An unmodified silicon alkoxide can be represented by the formula Si-(OR)₄, and a modified silicon alkoxide having three hydrolyzable substituents and one non-hydrolyzable substituent can be represented by the formula R'-Si-(OR)₃ where R represents an alkyl group comprising 1 to 5 carbon atoms R' represents H, F, or a substituted or unsubstituted linear or branched alkyl or alkenyl group, comprising 1 to 8 carbon atoms, e.g. a methyl, ethyl, n-propyl, n- butyl, 3-chloropropyl group, or a vinyl group. Preferably, the unmodified silicon alkoxide is tetramethyl or tetraethyl orthosilicate, and the modified silicon alkoxide is methyltriethoxysilane or vinyltriethoxysilane. The ratio of unmodified silicon alkoxide to modified silicon alkoxide is between 0.1 and 10 in moles of silicon, and is preferably about 1. In practice, the unmodified silicon alkoxide and modified silicon alkoxide mixture is first produced pure or diluted in a co-solvent such as an alcohol. Said alcohol is preferably ethanol, used in sufficient amount to obtain a clear homogeneous mixture once the silicon compounds are mixed with the aluminum compound. Then, this mixture is added to the alvumnum salt in aqueous solution, with stirring, at ambient temperature between 15°C and 35°C, preferably between 20°C and 25°C, until a clear homogeneous mixture is obtained. A modified mixed aluminum and silicon precursor is thus obtained. The stirring time varies from 10 to 240 minutes, and is preferably 120 minutes. According to step a) of the method for preparing the aluminosilicate polymer useful in the present invention, the precursor or an unmodified or modified mixed aluminum and silicon alkoxide is then put in contact with an aqueous alkali, the aluminum concentration being maintained at less than 0.3 mol/1, the Al/Si molar ratio being maintained between 1 and 3.6, and the alkali/Al molar ratio being maintained between 2.3 and 3. Advantageously, the aluminum concentration is between 1.5 x 10^"2 and 0.3 mol/1 and even more preferably between 4.4 x 10^"2 and 0.3 mol/1. Preferably, the Al/Si molar ratio is between 1 and 2. Preferably, an aqueous solution of sodium, potassium, or lithium hydroxide, diethylamine or triethylamine, with a concentration between 0.5 M and 3 M, and preferably 3 M is used. The alkali can also be in the form of a hydroalcoholic solution. The alkali is added to the precursor or to the unmodified or modified mixed aluminum and silicon alkoxide at a rate preferably between 50 and 650 mmole/hσur. The alkali in step a) is added in the presence of silanol groups.

These groups can be supplied by glass or silica (glass wool) particles or beads, which have superficial hydroxy groups. When the volume of liquid to be treated is large, it maybe desirable to increase the quantity of beads. The diameter of the beads can be between 0.2 and 5 mm and preferably between 1 and 3 mm. To simplify the implementation of the method for preparing the aluminosilicate polymer useful in the present invention, the preparation of the mixed aluminum and silicon precursor can also be performed in the presence of silanol groups, for example by circulating the mixture in a bed of glass beads. After the addition of the alkali, step b) of the method for preparing the aluminosilicate polymer useful in the present invention consists in stirring the mixture resulting from step a) at ambient temperature in the presence of silanol groups long enough to form said aluminosilicate polymer. Then, step c) of the method for preparing the duminosilicate polymer useful in the present invention consists in eliminating from the reaction medium the byproducts formed during steps a) and b), such as the residual ions coming essentially from the alkali used in step a). The residual ions can be eliminated by washing, by successive sedimentation or by diafiltration. The aliiminosilicate polymer resulting from step c) can then be concentrated by centrifugation or nanofiltration. When modified compounds are used comprising a non- hydrolyzable substituent, a hybrid aluminosilicate polymer is obtained. The introduction of non-hydrolyzable substituents, such as organic functions, enables providing for example an organophilic character to the resulting hybrid aluminosilicate polymers. In a first mode of embodiment of the method for preparing the alurriinosilicate polymer useful in the present invention, during step a) a quantity of alkali is added in order to obtain an alkali/Al molar ratio of about 2.3. In this case the pH is maintained between 4 and 5, and preferably between 4.2 and 4.3. Then step b) as described above is applied. The aluminosilicate polymer useful in the present invention is thus obtained as a dispersion. Step c) to eliminate the residual ions can then be performed by diafiltration, followed by nanofiltration concentration. In a second embodiment of the method for preparing the aluminosilicate polymer useful in the present invention, during step a) a quantity of alkali is added in order to obtain an alkali/Al molar ratio of about 3. Then step b) as described above is applied. The aluminosilicate polymer useful in the present invention is thus obtained as a suspension. Step c) to eliminate the residual ions can then be performed by diafiltration, followed by nanofiltration concentration, the aluminosilicate polymer having been previously redispersed by adding acid, such as hydrochloric or acetic acid or a mixture thereof. In a third embodiment, the method for preparing the aluminosilicate polymer useful in the present invention comprises an additional step d), after step b) and before step c). Said step d) consists in adding in a few minutes an additional quantity of aqueous alkali to reach an alkali Al molar ratio of 3 if this ratio had not already been reached during step a). The aluminosilicate polymer useful in the present invention is thus obtained as a suspension. Step c) to eliminate the residual ions can then be performed by diafiltration, followed by nanofiltration concentration, the aluminosilicate polymer having been previously redispersed by adding hydrochloric acid. Step c) can also be performed by washing with osmosed water by successive sedimentations, followed by centrifugation concentration. The aluminosilicate polymer useful in the present invention resulting from step c) followed by a concentration has physical gel form. The Al/Si molar ratio is between 1 and 3.6. Subsequent lyophilization enables the aluminosilicate polymer useful in the present invention to be obtained as a powder. Such an aluminosilicate polymer can be characterized in that its Raman spectrum comprises in spectral region 200-600 cm^"1 a wide band at 250 ± 6 cm^"1, a wide intense band at 359 ± 6 cm^"1, a shoulder at 407 ± 7 cm^-1, and a wide band at 501 ± 6 cm^"1, the Raman spectrum being produced for the aluminosilicate polymer resulting from step b) and before step c) and lyophilized. When modified compounds are used and when a hybrid aluminosilicate polymer is obtained, the Raman spectrum also comprises bands corresponding to the non-hydrolyzable silicon substituent, the bands linked to the non-hydrolyzable silicon substituent being capable of juxtaposing with the other bands. The present invention also relates to a cosmetic composition comprising in an acceptable cosmetic medium at least one aluminosilicate polymer such as described above. Such cosmetic composition are used in personal care applications as skincare (creams, lotions, washes, masks, scrubs, eye creams, oils, astringents, lip balms, soaks, serums), hair care (dyes, washes, conditioners, shampoos, styling products, fragrances), fragrance (perfumes, body sprays, lotion, hp balms), sunscreens and sun blocks (face, body, lip, hair, for adults, kids and babies), color cosmetics (extend color staying power both in container and once applied, foundations, lipsticks, eye shadows, blushes, mascaras, nail polishes, eye pencils, lip pencils, liquid powder, cake makeup), baby care products (diaper creams, lotions, teething pain reducers, washes), suntan in a bottle, bleaching creams. The cosmetic composition according to the invention comprises between 5 and 95 percent by weight of aluminosilicate polymer compared to the total weight of dry matter present in the composition. Such a cosmetically acceptable medium is known to those skilled in the art and does not call for special description. For example, the cosmetic composition can comprise active ingredients, which are sensitive to ozone. Such active ingredients can be hydroquinone; azelaic acid; collagen; grape seed oil; jojoba oil; wheat germ oil; antioxidants as vitamin E, vitamin D, vitamin C, vitamin A, selenium; vitamin K; zinc; aloe; tocopherol; vitamin E acetate; Retin- A; retinoid gels as adapalen, isotretinoin, tretinoin; hormones; estrogen; avobenzone; lactic acid; glycolic acid; benzyl peroxide; hydroxycitric acid; urea; proteins; caffeine; DNA; hemoglobin; antibiotic gels as clindamycin, erythromycin; keratolytic agents as sulphur and salicylic acid; antifungal agents as zinc oxide; alpha-hydroxy acids; beta-hydroxy acids. The cosmetic composition of the present invention can also be colored and can comprise colorants, which are sensitive to ozone. In one embodiment of the invention, the aluminosilicate polymer as described above can be added directly to the cosmetic composition, which is sensitive to ozone. In another embodiment, the aluminosilicate polymer can be used in another cosmetically acceptable composition, which is put in contact with the cosmetic composition, which is sensitive to ozone. When applied to the treatment of human keratinous fibers, the method according to the present invention, comprises i) one step consisting in coloring the human keratinous fibers with a colored cosmetic composition using a known and cosmetically acceptable coloring method, and sensitive to ozone, and ii) one step consisting in applying to the keratinous fibers a cosmetically acceptable composition comprising at least one aluminosilicate polymer as described above. The cosmetically acceptable composition used for step ii) can also comprise a hydrosoluble binder, such as the polyvinyl alcohol. Preferably, the cosmetically acceptable composition used for step ii) comprises between 70 and 90 percent by weight of aluminosilicate polymer compared to the total weight of dry matter present in the composition. When the aluminosilicate polymer as obtained above is used as a powder, this powder must be very fine. The cosmetically acceptable composition used for step ii) can comprise any other appropriate additive to make said composition cosmetically acceptable or to give it other advantages. Such additives are known to those skilled in the art. When the keratinous fibers are hair, the application of the color can be achieved by direct or permanent coloration. Such methods are described in the literature and do not call for special description. According to a first embodiment of the method according to the invention when it is applied to the treatment of human keratinous fibers, the keratinous fibers, according to step ii), are treated by applying the cosmetically acceptable composition containing at least one aluminosilicate polymer such as described above on the keratinous fibers before step i) of coloration. Once step ii) is completed, the coloration of the keratinous fibers thus treated is carried out. According to a second embodiment of the method according to the invention when it is applied to the treatment of human keratinous fibers, firstly step i) of coloration of the keratinous fibers is carried out, and then step ii) is carried out consisting in applying to the keratinous fibers thus colored the cosmetically acceptable composition containing at least one aluminosilicate polymer such as described above. The method according to the present invention enables the ozone stability of cosmetic compositions to be improved. Notably, the color stability to ozone of colored human keratinous fibers is improved, and in particular hair having good color stability to ozone in time is obtained. The following examples illustrate the present invention without however limiting the scope. 1) Preparation of aluminosilicate polymer 4.53 moles A1C1₃, 6H₂O, then 2.52 moles tetraethyl orthosilicate were added to 100 1 osmosed water. This mixture was stirred and circulated simultaneously through a bed formed of 1 kg of glass beads 2-mm diameter using a pump with 8 1/min output. The preparation operation of the unmodified mixed aluminum and silicon precursor lasted 120 minutes. Then, according to step a) of the preparation method, 10.5 moles NaOH 3M were added to the precursor in two hours. The reaction medium clouded. According to step b) of the preparation method, the mixture was stirred for 15 to 20 hours. The medium became clear. The circulation was stopped in the glass bead bed. Then, according to step d) of the method used in the present invention, 3.09 moles NaOH 3M were added in ten minutes. The aluminum concentration was 4.4 x 10^"2 mol/1, Al/Si molar ratio 1.8 and alkali/Al ratio 3. The aluminosilicate polymer used in the present invention was thus obtained as a suspension. Step c) of the preparation method consisted in adding 165 g HC1 37 percent first diluted 10 times and stirring for 150 minutes to obtain a dispersion of the aluminosilicate polymer that is left to stand. The dispersion was then diafiltrated using a Filmtec NF 2540 nanofiltration membrane (surface area 6 m²) to eliminate the sodium salts to achieve an Al/Na ratio greater than 100. The retentate resulting from the diafiltration by nanofiltration was concentrated to obtain a gel with about 2 percent by weight of aluminum. 115 g of HC1 37 percent was added to 2 kg of this gel, and then 317 g of water, i.e. 15 percent of the weight of the gel engaged, was distilled. A gel was obtained that was then lyophilized to obtain a solid of constant mass. The aluminosilicate polymer used in the present invention was then obtained as a powder (230 g). 2) Preparation of the support A neutral support is used as described in Patent Application EP-A-1,112,858. A support comprising three polyester layers (one impermeable base layer, one permeable lower layer and one permeable upper layer) is prepared in the following way:

The materials used are: 1) a polyethylene terephthalate) (PET) resin (Viscosity Index NI = 0.70 dl/g) for the base layer 2) a compounded blend for the lower and upper layers consisting of 29 % by weight of an amorphous polyester resin, PETG 6763® (NI = 0.73 dl/g)

5 (marketed by the Eastman Chemical Company), 29 % by weight of polyethylene terephthalate) (PET) resin (NI = 0.70 dl/g), and 42 % by weight of cross-linked poly(methylmethacrylate) (PMMA) particles having a size of 1.7 μm approximately. The cross-linked PMMA particles were compounded with the o PETG 6763 ® and PET resins through mixing in a counter-rotating twin-screw extruder attached to a pelletizing die. The extrudate was passed through a water bath and is pelletized. The two resins for the three layers were dried at 65°C and fed by two plasticating screw extruders into a coextrusion die manifold to produce a three-layered melt stream that was rapidly quenched on a chill roll after issuing from the die. By regulating the throughputs of the extruders, it was possible to adjust the thickness ratio of the layers in the cast laminate sheet. In this case, the thickness ratio of the three layers was adjusted to 1:6:1, the thickness of the two outside layers being 250 μm approximately. The cast sheet was first oriented in the machine direction by sfretching at a ratio of 3.3 and a temperature of 110°C. The oriented support was then stretched the transverse direction in a tenter frame at a ratio of 3.3 and a temperature of 100°C. In this example, no heat setting treatment was applied. The final total thickness of the film was 200 μm, the permeable lower and upper layers each having a thickness of 50 μm, and the layers within the support were fully integrated and strongly bonded. The sfretching of the heterogeneous lower and upper layers created interconnected microvoids around the hard cross-linked PMMA beads, thus rendering these layers opaque (white), highly porous and permeable. The base PET layer was impermeable and retained its natural clarity. 3) Preparation of the composition comprising the aluminosilicate polymer Polyvinyl alcohol (Gohsenol™ GH23 marketed by Nippon Gohsei) diluted 9 percent in osmosed water was used as hydrosoluble polyvinyl alcohol binder and the aluminosilicate polymer as described in paragraph 1 is used. The composition was obtained by mixing:

Composition Aluminosilicate polymer 2.0 g PVA 9% 2.7 g Water qs 14.8 g

The mixture was homogenized overnight. 4) Preparation of the colored cosmetic composition A permanent coloration, "Open Color" 5R sparkling aurora red coloring gel marketed by L'Oreal, was used as colored cosmetic composition. The colored cosmetic composition was prepared by mixing 5 g of developer and 5 g of coloring gel. Then five 10-mm diameter glass beads were added and the mixture was homogenized on a roller pallet for about two minutes. 5) Implementation of the invention method According to a first embodiment of the method according to the invention, the support such as described in paragraph 2 was treated by coating it with a composition comprising the aluminosilicate polymer such as prepared according to paragraph 3 using a 200-μm thick filmograph, Automatic Film Application marketed by BRAIVE INSTRUMENTS. Then, it was left to dry overnight at ambient air temperature (21°C). Then the support was coated with the colored composition as prepared according to paragraph 4 using a 200-μm thick filmograph. Support A was thus obtained. According to a second embodiment of the method according to the invention, the coloration of the support such as described in paragraph 2 was carried out by coating it with the colored composition such as prepared according to paragraph 4 using a 200-μm thick filmograph. Then, it was left to dry overnight at ambient air temperature (21°C). Then the support thus colored was coated with the composition comprising the aluminosilicate polymer as prepared according to paragraph 3 using a 200-μm thick filmograph. Support B was thus obtained. For comparison, the coloration of the support such as described in paragraph 2 was carried out by coating it with the colored composition such as prepared according to paragraph 4 using a 200-μm thick filmograph. Then, it was left to dry overnight at ambient air temperature (21 °C). Treatment with the composition comprising the aluminosilicate polymer was not carried out. Support C was thus obtained. 6) Evaluation of color stability to ozone To evaluate the color stability in time, a dye fading test by exposure to ozone was performed for each resulting support. For this, the color densities of each support were measured using a Nannier-Photelec densitometer. Then the supports were placed in the dark in a room with controlled ozone atmosphere (60 ppb) for eight weeks. Then any deterioration of color density was measured using the densitometer. Figure 1 represents the density loss percentage observed at the end of eight weeks for supports A, B and C, the color of the colored supports being broken down into the three complementary colors cyan, magenta and yellow represented respectively by the letters C, M, Y. It may be seen that the supports prepared according to the method according to the invention and exposed to ozone have good color stability in time compared with the colored support not treated using a composition comprising the aluminosilicate polymer used in the present invention.

Claims

CLAIMS : 1. A method for improving the ozone stability of cosmetic compositions, comprising the use of at least one aluminosilicate polymer obtainable by a preparation method that comprises the following steps: a) treating a compound selected from the group consisting of a mixed aluminum and silicon alkoxide of which the silicon has at least three hydrolyzable substituents, and a mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having at least three hydrolyzable substituents, with an aqueous alkali, in the presence of silanol groups, the aluminum concentration being maintained at less than 0.3 mol/1, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/Al molar ratio being maintained between 2.3 and 3; b) stirring the mixture resulting from step a) at ambient temperature in the presence of silanol groups long enough to form the aluminosilicate polymer; and c) eliminating the byproducts formed during steps a) and b) from the reaction medium.

2. The method according to claim 1, wherein said cosmetic composition comprises at least one active ingredient selected from the group consisting of hydroquinone; azelaic acid; collagen; grape seed oil; jojoba oil; wheat germ oil; antioxidants as vitamin E, vitamin D, vitamin C, vitamin A, selenium; vitamin K; zinc; aloe; tocopherol; vitamin E acetate; Retin-A; retinoid gels as adapalen, isotretinoin, tretinoin; hormones; estrogen; avobenzone; lactic acid; glycolic acid; benzyl peroxide; hydroxycitric acid; urea; proteins; caffeine; DNA; hemoglobin; antibiotic gels as clindamycin, erythromycin; keratolytic agents as sulphur and salicylic acid; antifungal agents as zinc oxide; alpha-hydroxy acids; beta-hydroxy acids.

3. The method according to claim 1 , wherein said cosmetic composition is colored.

4. The method according to claim 3, wherein said colored cosmetic composition is a colored composition for treating human keratinous fibers, and characterized in that it comprises: i) one step consisting in coloring the keratinous fibers with the colored cosmetic composition ii) one step consisting in applying to the keratinous fibers a cosmetically acceptable composition comprising at least one aluminosilicate polymer obtainable by a preparation method that comprises the following steps: a) treating a compound selected from the group consisting of a mixed aluminum and silicon alkoxide of which the silicon has at least three hydrolyzable substituents, and a mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having at least three hydrolyzable substituents, with an aqueous alkali, in the presence of silanol groups, the aluminum concentration being maintained at less than 0.3 mol/1, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/Al molar ratio being maintained between 2.3 and 3; b) stirring the mixture resulting from step a) at ambient temperature in the presence of silanol groups long enough to form the aluminosilicate polymer; and c) eliminating the byproducts formed during steps a) and b) from the reaction medium.

5. The method according to claim 1, wherein the alkali of step a) to prepare the aluminosilicate polymer is selected from the group consisting of sodium, potassium, or lithium hydroxide, diemylamine and triethylamine.

6. The method according to claim 1, wherein said alkali/Al molar ratio to prepare the aliiminosilicate polymer is about 2.3.

7. The method according to claim 1 , wherein said alkali/Al molar ratio to prepare the aluminosilicate polymer is about 3.

8. The method according to claim 1 , wherein the method for preparing the aluminosilicate polymer comprises, after step b) and before step c), a step d), by which alkali is added in order to reach an alkali/Al molar ratio of 3 if this ratio has not already been reached in step a).

9. The method according to claim 1 , wherein the mixed aluminum and silicon precursor resulting from hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having at least three hydrolyzable substituents is a product resulting from the mixture in an aqueous medium (i) of a compound selected from the group consisting of aluminum salts, aluminum alkoxides and aluminum halogenoalkoxides and (ii) at least one compound selected from the group consisting of silicon alkoxides and chloroalkoxides only having hydrolyzable substituents, the silicon compound having at least three hydrolyzable substituents being selected to only have hydrolyzable substituents.

10. The method according to claim 9, wherein said mixed aluminum and silicon precursor is the product resulting from the mixture (i) of an aluminum halide and (ii) a silicon alkoxide only having hydrolyzable substituents.

11. The method according to claim 1 , wherein said mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having at least three hydrolyzable substituents is a product resulting from the mixture in an aqueous medium (i) of a compound selected from the group consisting of aluminum salts, aluminum alkoxides and aluminum halogenoalkoxides and (ii) at least one compound selected from the group consisting of silicon alkoxides and chloroalkoxides only having hydrolyzable substituents, and (iii) at least one compound selected from the group comprising silicon alkoxides and chloroalkoxides having three hydrolyzable substituents and one non-hydrolyzable substituent.

12. The method according to claim 11 , wherein said mixed aluminum and silicon precursor is the product resulting from the mixture (i) of an aluminum halide and (ii) a mixture having at least one silicon alkoxide only having hydrolyzable substituents and at least one silicon alkoxide having three hydrolyzable substituents and one non-hydrolyzable substituent.

13. The method according to claim 12, wherein the ratio of silicon alkoxide only having hydrolyzable substituents to silicon alkoxide having three hydrolyzable substituents and one non-hydrolyzable substituent is between 0.1 and 10 in moles silicon.

14. The method according to any one of Claims 11 to 13, wherein the silicon alkoxide having three hydrolyzable substituents and one non- hydrolyzable substituent is represented by the formula

R'-Si-(OR)₃ where R represents an alkyl group comprising 1 to 5 carbon atoms R' represents H, F, or a substituted or unsubstituted linear or branched alkyl or alkenyl group comprising 1 to 8 carbon atoms.

15. The method according to claim 14, wherein R' represents a methyl, ethyl, n-propyl, n-butyl, 3-chloropropyl, vinyl group.

16. The method according to claim 15, wherein said silicon alkoxide having three hydrolyzable substituents and one non-hydrolyzable substituent is methyltriethoxysilane or vinyltriethoxysilane.

17. The method according to any one of claims 9 to 13 , wherein said silicon alkoxide only having hydrolyzable substituents is tetramethyl orthosilicate or tetraethyl orthosilicate.

18. The method according to claim 4, wherein step ii) is carried out before step i).

19. The method according to claim 4, wherein step ii) is carried out after step i).

20. The method according to claim 4, wherein the cosmetically acceptable composition applied at step ii) comprises a hydrosoluble binder.

21. A cosmetic composition comprising at least one aluminosilicate polymer obtainable by a preparation method comprising the following steps: a) treating a compound selected from the group consisting of a mixed aluminum and silicon alkoxide of which the silicon has at least three hydrolyzable substituents, and a mixed aluminum and silicon precursor resulting from the hydrolysis of a mixture of aluminum compounds and silicon compounds only having hydrolyzable substituents and silicon compounds having at least three hydrolyzable substituents, with an aqueous alkali, in the presence of silanol groups, the aluminum concentration being maintained at less than 0.3 mol/1, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/Al molar ratio being maintained between 2.3 and 3; b) stirring the mixture resulting from step a) at ambient temperature in the presence of silanol groups long enough to form the aluminosilicate polymer; and c) eliminating the byproducts formed during steps a) and b) from the reaction medium.

22. The cosmetic composition according to claim 21, comprising further at least one active ingredient selected from the group consisting of hydroquinone; azelaic acid; collagen; grape seed oil; jojoba oil; wheat germ oil; antioxidants as vitamin E, vitamin D, vitamin C, vitamin A, selenium; vitamin K; zinc; aloe; tocopherol; vitamin E acetate; Retin-A; retinoid gels as adapalen, isotretinoin, tretinoin; hormones; estrogen; avobenzone; lactic acid; glycolic acid; benzyl peroxide; hydroxycitric acid; urea; proteins; caffeine; DNA; hemoglobin; antibiotic gels as clindamycin, erythromycin; keratolytic agents as sulphur and salicylic acid; antifungal agents as zinc oxide; alpha-hydroxy acids; beta-hydroxy acids.

23. The cosmetic composition according to claim 21, wherein said cosmetic composition is colored.