MXPA97008983A - Solid composition based on starch containing expanded thermoplastic hollow cards and susutilizations in application top - Google Patents

Abstract

The present invention relates to expanded solid compositions whose matrix is constituted by an alveolar network formed from a product rich in starch and contains at least expanded thermoplastic hollow particles of polymer or copolymer of a monomer or of a mixture of monomers of ethylenic unsaturation. These compositions constitute new galenic forms for cosmetic or dermatological use. These compositions are presented in the form of round, granular, expanded or expanded flake or powder elements. Reduced to the powder state, they can also be used as makeup or hygiene composition to rehydrate or to use such a

Description

SOLID COMPOSITION BASED ON STARCH CONTAINING EXPANDED THERMOPLASTIC HOLLOW PARTICLES AND ITS UTILIZATIONS IN TOPICAL APPLICATION DESCRIPTION OF THE INVENTION The present invention relates to expanded solid compositions whose matrix is constituted by a starched alveolar network and contains expanded thermoplastic hollow particles as well as their uses in topical application. Expanded products based on starch and edible ingredients are known in the food industry, obtained by extrusion in one or several mono- or bi-screw extruders, particularly the snack preparations, the potato chips, the pineapples, breakfast products based on cereals, -the gal letas. The applicant has surprisingly discovered new dosage forms for cosmetic or dermatological use in the form of an expanded solid composition whose matrix is constituted by an alveolar network formed from a product rich in starch and containing thermoplastic hollow particles. expanded - of polymer or copolymer of a monomer or of a mixture of monomers of ethylenic unsaturation. The Applicant has discovered on the other hand that the compositions of the invention could be obtained by extrusion / expansion, unexpectedly, at temperatures below I00"x: and thus contain cosmetic or dermatological substances. They are unstable or unstable at temperatures above 100 ° C. The compositions according to the invention can themselves constitute new forms of make-up products such as face powders, make-up for the eyelids or cheeks, new products for hygiene products such as dry shampoos or the treatment such as products -of make-up removal. They present the appearance of redolored shapes, granulates, sheets or expanded flakes, which can contain enough fillers to obtain a good -desleido and satisfactory softness qualities. They can also contain carrying amounts of fatty phase that allow to improve comfort and facilitate its application on the skin, for example, being able to apply them directly without any intermediate makeup tool (brush, sponge, tassel). The applicant has unexpectedly discovered that the introduction of hollow particles - expanded thermoplastics of homopolymer or copolymer of a monomer or of a mixture of monomers of ethylenic unsaturation, in a matrix constituted by a starched alveolar network - it decreased the percentage of expansion and allowed the introduction of strong amounts-of fatty substances such as oils and / or waxes. The compositions according to the invention can, in particular, contain, in important quantities, waxes which confer film stability properties, slip properties and matt tones. The compacted powders customarily used for make-up can not contain significant amounts of fatty substances such as waxes (more than 10% by weight). Its incorporation into powders leads to waxing products that can not be loosened. Hollow expanded particles of homopolymer or copolymer formed from a monomer or ethylene-unsaturation monomer mixture are very low density fillers less than 0.1 g.cm and known for their mildness and of absorption of the fatty substances in the make-up or treatment compositions. But they are equally known by the fact that they are hardly co-palatable. By hard-to-compact load, it is understood a raw material that, based on a certain percentage that depends on the material in question, can not be compared by means of a mechanical press. These types of fillers can not be used in general in make-up products in the form of compacted powder. Products that contain this type of charges in small quantities, they do not present a good integrity to the storage, a good solidity to the blows and / or a convenient flat surface. The compositions according to the invention, by virtue of their novel starched alveolar structure, can therefore contain these hardly compactable fillers by conferring a very soft and non-greasy feel without presenting the drawbacks of the prior art makeup compositions containing this type of charges. The compositions of the invention by their novel starched alveolar structure can constitute new forms of makeup products whose cosmetic qualities are original, particularly due to their softness and lightness due to the incorporation of density-shell loads. The compositions according to the invention can be presented in the form of rounds, granules, sheets or expanded copes applied directly on the skin or face or reduced in powder and used as such, in a conventional manner, as make-up powder. They may be presented in the form of a treatment and / or hygiene powder, applied directly to the skin, scalp or hair, for example dry shampoos or free powders for the treatment of the body. They can also be present in foil rounds, granulates, sheets or expanded flakes, stored in the dry state, and very easily rehydrated after immersion in an aqueous medium pa. to reconstitute formulations for make-up such as foundation or formulations for treatment or hygiene such as creams, milks, baths-foaming agents, gels, shampoos. It is thus possible to incorporate these galenic forms, stable to storage at temperatures lower than 45 ° C, active hydrosensitive cosmetics agents. The compositions according to the invention, stored in the dry state and intended to be rehydrated after use to reconstitute the cosmetical formulations such as those mentioned above, present the advantage in relation to the classical replenishment galenic forms, if very easily rehydratable and within the framework of the cleaning compositions, particularly the shampoos, to be less aggressive due to the fact that the surfactants are integrated in a starched expanded matrix. The compositions according to the invention are expanded solid compositions whose matrix is constituted by an alveolar network formed from a starch-containing product and contains at least thermoplastic hollow particles of homopolymer or of copolymer formed from a monomer or monomer mixture of ethylenic unsaturation. The particles which can be used according to the invention can be made from monomers of ethylenic unsaturation, non-toxic and non-irritating to the skin. The particles of the invention can be obtained, for example, according to the methods of the patents and patent applications EP-56219, EP-348372, EP-486080, EP-320473, EP-112807 and US-3615972.

The internal cavity of the particles contains in principle a gas that can be air, nitrogen or a hydrocarbon such as isobutane or isopentane. Among the monomers used for the production of expanded thermoplastic hollow particles of. In the invention, mention may be made of esters of methacrylic or acrylic acid, such as acrylate or methyl methacrylate; vinylidene chloride; acrylonitrile; styrene and its derivatives, butadiene and its derivatives; its mixtures It is possible, for example, to use the polymers or copolymers of methyl acrylate or methacrylate, the copolymers formed from styrene and acrylonitrile, the copolymers of vinylidene chloride and de-acrylonitrile or of vinyl chloride. A polymer or copolymer containing from 0% to 60% vinylidene chloride or from one of its derivatives, from 20% to 80% of -acrylonitrile or one of its derivatives and of 0% is preferably used. to 50% -of a (meth) acrylic or styrenic monomer, the sum of the percentages (by weight) being equal to 100. The mere (meth) acrylic is, for example, methyl or ethyl (meth) acrylate. Styrenic monomer is for example styrene or thi-methyl-styrene. More preferably, the particles used in the present invention are hollow particles of an expanded co-polymer of vinylidene chloride and of acrylonitrile or of vinylidene chloride. , acrylonitrile and methyl methacrylate. These particles can be dry or hydrated. Advantageously, the particles of the invention have a granule etria ranging from 1 to -100 ^ and even better ranging from 5 ij to 60 pm, and even better between 10 Jim and 50 Jim. Preferentially, the volume density of the particles is chosen from the range between - 15kg / m and 200 kg / m and better between 40 kg / m3 3 1 and 120 kg / m, and even better between 60 kg / m and 80 kg / m3. The particles which can be used in the invention are, for example, expanded terpolymer microspheres of vinylidene chloride, acrylonitrile and methacrylate, sold under the trademark EXPANCEL by the Society - Nobel Casco under references 551 DE 50 (granulometry of approximately 551 DE 20 (granulometry of approximately 30 Jm and density approximately 65 kg / m), 551 DE 12 (granulometry of approximately 12 μm amenté), 551 DE 80 (granulometry of approximately 80 μm), 461 DE 50 (granulometry of approximately 50 um) It is possible to use microspheres formed from the same expanded terpolymer with a granulemetry of approximately 18 jm and a volatile mass of approximately 70 kg / m3, hereinafter referred to as EL 23.

Expanded thermoplastic hollow particles are present in the compositions of the invention in concentrations ranging, preferably, from 2 to 30% by weight relative to the total weight of the composition. The starch-rich products used in the compositions according to the invention are chosen from - preference among cereal flours such as - wheat, corn, rice, oatmeal, wheat germ or wheat flours. potato flour; the pure starches commonly used in food such as corn starch, potato starch, tapioca starch, starch; Modified starches at the amylase / amylopectin ratio level such as the HYLON VII product - sold by the AMYLUM Company; the starches modified by crosslinking or by a functional group such as the cross-linked corn starch sold under the name of RESISTAMYL E2 by the AMYLUM Company, the poorly quaternized corn starch sold under the name MYPLUS W7 by the AMYLUM Company, the starch of potato sold under the name of SUPRAMYL P 60 by AMYLUM or the hydroxypropyl corn starch sold under the name of MERIGEL EF6 by AMYLUM. The matrix constituted by the starched alveolar network formed from these starch-rich products is present in the compositions according to the invention, preferably in a proportion ranging between 70 and 98% by weight relative to the weight of the composition The compositions according to the invention have a water content of preferably less than or equal to 5% by weight and more particularly between 1 and 2% by weight relative to the weight of the composition.

The compositions according to the invention can also contain a fatty phase. This fat phase can comprise oils and / or waxes of animal, vegetable, mineral or synthetic origin, alone or as a mixture. Among the oils which can be used, mention may be made of mink oil, turtle oil, soybean oil, grape seed oil, sesame oil, corn oil, rapeseed oil, sunflower oil, cotton oil, avocado oil, olive oil, castor oil, jojoba oil, peanut oil; hydrocarbon oils, such as paraffin oils, squalane, petrolatum; fatty esters, such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, -isononyl isononate, 2-ethyl-1-hexylo palmitate, laurate 2-hexy 1-deci lo, 2-octylo palmitate 1-deci lo, 2-octy 1-dodecyl mi- ristat or lactate, 2-ethy 1-hexylo succinate, di- isosteary, glycerin or diglyciferin tri- stearate; silicone oils, such as polyesters, loxanes, polymers, loxanes, polysiloxanes modified by fatty acids, fatty alcohols or polyoxylalkins, - fluorinated silicones, perfluorinated oils; higher fatty acids such as myristic acid, paiitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, l-linolenic acid or isostearic acid; higher fatty alcohols such as cetanol, stearyl alcohol or oleyl alcohol. Among the waxes that can be used are: - beeswaxes, lanolin waxes and waxes - of Chinese insects; the waxes of Carnauba, of Candeli lia, of "ouricurry", the waxes of cork fibers, - the waxes of sugar cane, the waxes of Japan, the hydrogenated jojoba cements and the hydrogenated oils - such as hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin; the paraffins, the micro crystalline waxes, the Montan waxes and the ozokerites; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis, waxy copolymers as well as their esters, and silicone waxes such as polyalkoxy and polyalkyl 1-loxanes. The fatty phase is present in oscillating proportions, preferably from 2 to 30% by weight and more particularly from 5 to 15% by weight with reference to the total weight of the composition. The fatty phase may also comprise additives such as lipophilic cosmetic active agents and / or fat-soluble ingredients generally used in cosmetics such as perfumes. Preferably, these additives can be present in an amount of 0-20% relative to the total weight of the fatty phase. The compositions according to the invention can have, in addition to the pigments, preferably in an amount of 0-50% relative to the total weight of the final composition. These pigments can be chosen from mineral pigments, organic pigments and pearlescent pigments. Among the mineral pigments, mention may be made, for example, of titanium dioxide (rutile or anatase), which is optionally treated on the surface; the oxides of black, yellow, red and brown iron; the violet of a ganeso; the ultramarine blue; the chromium oxide eventually hydrated, the ferric blue. Among the organic pigments, there may be mentioned, for example, pigments D & C red, D & C yellow, carbon black, and lacquers based on carmine cochi_ ni 1 la. The pearlescent pigments may be selected, particularly from white pearlescent pigments such as mica coated with titanium oxide or bismuth xichloride; the colored pearlescent pigments such as the micatitanium with iron oxides, the micatitanium with ferric blue or chromium oxide, the mica-titanium with an organic pigment of the aforementioned type, as well as pigments based on oxychloride of bi-uto. The compositions according to the invention can also have other mineral or organic fillers usually used in makeup products - such as, for example, talc, micas, kaolin, silica, zinc and titanium oxides, carbonate of calcium, carbonate and magnesium hydrocarbonate, powders of undiminished synthetic polymers, metal-derived carboxylic acid -GC-C -carbonates - are present in concentrations - preferably ranging from 0 to 50% by weight. weight with relation to the weight of the composition. The compositions according to the invention can also contain one or more nonionic, anionic, cationic or amphoteric surfactants, commonly used in cosmetics. The amount of agent-active agent used is preferably 2 to 30% based on the total weight of the composition. The compositions according to the invention can also contain also cosmetic-water-soluble active agents. Among the active cosmetic agents, there may be mentioned the anti-free radical or anti-free radical agents; moisturizing or moisturizing agents such as glycerol and collagen; UV filter agents such as benzophenone. These water-soluble active agents can be present in the final composition in an amount of 0 to 20%, preferably 5 to 15% by weight. Among the thermosensitive active agents, there may be mentioned vitamins such as vitamin E. Of course, the person skilled in the art will try to choose the possible complementary compounds and / or their amounts in such a way that the properties see tajosas related intrinsic with the composition according to the invention are not, or substantially, altered by the addition or additions considered. The present invention also relates to a process for preparing a composition as defined above, characterized in that it is obtained from a starch product in hollow, thermoplastic hollow particles and constituents. additional possible such as those indicated above in the presence of water, by mixing, kneading and expansion in a twin screw extruder. The extruder used for the process of the invention is chosen from bi-screw extruders such as that described in the application FR 94-00756. The raw materials are introduced, at the entrance of the bi-screw extruder, into the feed zone at room temperature, preferably at about 20 ° C., then they are brought to the transport zone at a temperature, preferably at about 50 ° C. , then they are kneaded and compressed in various zones of the extruder kept at a temperature below 100 ° C, preferably oscillating between 60 and 80 ° C; the mass obtained is transported to the exit of the extruder and extruded through a row to experience an expansion in it; the extruded products are then, if necessary, dried according to a conventional drying process (oven, ventilated stove). During the mixing phase, the rich product - in starch - gelatinizes and forms, after extrusion, an alveolar network that forms the matrix of the final expanded products. A surprising advantage of the process of the invention is that the use of the thermoplastic particles of polymer or copolymer of monomer or mixture of monomers of ethylenic unsaturation, allows to obtain an expansion of the compositions at temperatures of the order of 60-80 * 0. This procedure. - - to allow to obtain expanded products that can contain thermosensible cosmetic or dermatological substances at temperatures above 100 ° C such as vitamins or certain oils that degrade to more than -100 * 0. Another object of the invention consists of new cosmetic or dermatological compositions, characterized in that they are constituted by an expanded solid composition as defined above. These compositions may be in the form of round granules, expanded sheets or flakes or - if reduced to a powder state. These compositions can be products for makeup. They can be applied on the skin either directly or by means of a make-up tool such as a brush, a tassel or an a-plicator pad. They can be stored in the dry state and, at the time of use, rehydrated after immersion in water to reconstitute an aqueous liquid makeup formulation or be liquid-such as a foundation. The compositions according to the invention can be products for the treatment and / or hygiene of the skin, of the mucous membranes, of the scalp or of the hair.

They can be presented as a powder and applied directly to the skin, scalp or hair, such as a dry shampoo or a free powder for body treatment. These compositions can also be in the form of powder or of round, granulated, expanded or rehydrated flakes, rehydratable after immersion in water in order to constitute a water-soluble formulation for treatment and / or hygiene such as a cream, a milk, a gel, a foaming bath, a shampoo. The following examples serve to illustrate the invention without thereby limiting the scope. EXAMPLES Example 1 Dry shampoo in powder form for rehydration The final product has the following formulation: - Wheat flour 35.0% by weight - Corn starch 35.0% by weight - Copolymer expanded particles 15.0% by weight of vinyl chloride 1 ideno / acrylonitrile / methyl methacrylate sold under the name of EXPANCEL 550 DE by the company CASCO NOBEL - Lauryl ether sodium sulfate 15, 0% by weight OPERATING MODE The raw materials were introduced into the extruder entering at a temperature of 309C. The same were then taken to the transport zone at a temperature, preferably at approximately 50 ° C, then kneaded and compressed in various zones of the extruder maintained at 60-80 ° C. The dough was thus kneaded and compressed, transported to the exit of the extruder and extruded through a row of -5 mm in diameter. The rotation speed of the screws was 500 r / minute. The. Round shapes obtained at the exit of the row were reduced in powder form by means of a classic barbed mill located at the exit of the extruder. Example 2 Mask for the face in the form of "expanded sheets" for rehydration. The final product has the following formulation: - Wheat flour 24.0% by weight - Starch 24.0% by weight - Expanded particles of copolymer 10.0% by weight of vinyl chloride 1 ideno / acri lonitide / methyl methacrylate sold under the name of EXPANCEL 550DE by the company CASCO NOBEL - Silica sold under the name of SB700 40, 0% by weight by the Company MAPREC0S - Vitamin E 2.0% by weight OPERATING MODE: The raw materials were introduced at the entrance of a bi-screw extruder at a temperature of 309C They were then taken to the zo-na of transport at a temperature, preferably, - to about 50 ° C., then they were kneaded and compressed in various areas of the extruder maintained at -60-80 ° C. The dough, thus kneaded and compressed, was transported to the exit of the extruder and extruded through a row of 5 mm in diameter. The expanded bands obtained at the exit of the row are cut into sheets to the desired dimension. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims (24)

- R E I V I N D I C A C I O N S

1. - Expanded solid composition whose matrix is constituted by an alveolar network formed from a product rich in starch and containing at least expanded thermoplastic hollow particles of homopolymer or copolymer formed from a monomer or a mixture of monomers of ethylenic unsaturation.

2. Composition according to claim 1, characterized in that the expanded hollow plastic particles are homopolymer or expanded copolymer particles formed from a monomer or a mixture of monomers selected from the group formed by the esters of methacrylic or acrylic acid; vinylidene chloride, acrylonitrile, styrene and its derivatives; Butadiene and its derivatives.

3. Composition according to claim 1, characterized in that the thermoplastic hollow particles are particles of homopolymer or acrylate or methyl methacrylate, copolymer of styrene and of acrylonitrile or of copolymer of vinylidene chloride and acrylonitrile or vinyl chloride,

4. Composition according to claim 1 62, characterized in that the expended thermoplastic hollow particles are hollow particles of an expanded-copolymer containing from 0% to 60% of units derived from vinylidene chloride, from 20% to 90% of units derived from acrylonitrile and from 0% to 50% of units derived from an acrylic or styrenic monomer, being the sum of the percentages (by weight) - -

5. Composition according to any one of claim 4, characterized in that the expanded thermoplastic hollow particles are hollow particles of a copolymer and of vinylidene chloride and of acrylonitrile or an expanded terpolymer of vinylidene chloride, of acrylonitrile and of methyl methacrylate.

6. Composition according to any one of claims 1 to 5, characterized in that the particles have a granulometry of 1 to 100 um.

7. Composition according to any one of claims 1 to 6, characterized in that the hollow thermoplastic particles have a vo lume mass of between 15 and 200 kg / cm.

8. Composition according to any one of claims 1 to 7, characterized in that it contains from 2 to 30% by weight of expanded thermoplastic hollow particles with respect to the total weight of the composition.

9. Composition according to any one of claims 1 to 8, characterized in that the product rich in starch is chosen from cereal or potato flours; the pure starches; modified starches at the level of amylose / amylopectin ratio; cross-linked starches and starches modified by a functional group.

10. Composition according to any one of claims 1 to 9, in which the matrix constituted by a starched alveolar network represents from 70 to 98% by weight of the total weight of the composition.

11. Composition according to any one of claims 1 to 10, in which the content in -water is less than 5% by weight with respect to the total weight of the composition.

12. Composition according to claim 11, in which the water content varies from 1 to 2% by weight with respect to the total weight of the composition.

13. Composition according to any one of claims 1 to 12, characterized in that it also contains a fatty phase.

14. Composition according to claim 13, comprising from 2 to 30% by weight of fatty phase.

15. Composition according to one of claims 13 and 14, in which the fatty phase comprises oils and / or waxes of animal, vegetable, mineral or synthetic origin, alone or as a mixture.

16. Composition according to one of claims 1 to 15, characterized in that it contains adjuvants selected from pigments., the mineral or organic charges, the surfactants, -the fat-soluble active agents usually used in cosmetics, the anti-oxidants, the anti-free radicals, the moisturizers, the humectants, the -solar filters.

17. Process for preparing the co-position as defined in any one of claims 1 to 16, characterized in that it is obtained from the product rich in starch, hollow polymer particles or copolymer and other optional components in the presence of water, by mixing, kneading, expanding and extruding in a bi-screw extruder.

18. Process according to claim 17, characterized in that the raw materials are introduced at the entrance of the bi-screw extruder, in the feeding zone at room temperature, then they are kneaded and compressed in different areas of the Extruder maintained at a temperature below 100 the mass obtained is transported to the extruder outlet and extruded through a spinneret to experience an expansion in it.; The extruded products are then optionally dried according to a conventional drying method.

19. Process according to claim 18, characterized in that the kneading and compression areas are heated to a temperature between 609 and 80 C.

20. - Composition of cosmetic or dermatological use. the fact that it is constituted by an expanded solid composition as defined according to any one of claims 1 to 16.

21.- Composition according to the indication 20, - characterized by the fact that it is presented in the form of an expanded round element, granulated - expanded, expanded sheet od = expanded flake or because it is reduced to powder state.

22. Composition according to any one of claims 20 21, characterized in that it is rehydratable after immersion in water and - susceptible to reconstitute an aqueous 11-liquid or semi-1-liquid formulation.

23. - Composition according to any one of - claims 20 to 22, characterized in that it is a product for makeup. 24.- Composition according to any one of the claims - 20 to 23, characterized in that it is a product for the treatment and / or hygiene - of the skin, of the mucous membranes, of the scalp or of - hair