WO2022123016A1 - Substrat cosmétique d'origine naturelle - Google Patents

Substrat cosmétique d'origine naturelle Download PDF

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Publication number
WO2022123016A1
WO2022123016A1 PCT/EP2021/085209 EP2021085209W WO2022123016A1 WO 2022123016 A1 WO2022123016 A1 WO 2022123016A1 EP 2021085209 W EP2021085209 W EP 2021085209W WO 2022123016 A1 WO2022123016 A1 WO 2022123016A1
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Prior art keywords
polysaccharides
notably
substrate
water
cosmetic
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PCT/EP2021/085209
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English (en)
Inventor
Hervé Andrean
Eric PHALEMPIN
Francis Pruche
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L'oreal
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208—Tissues; Wipes; Patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/732—Starch; Amylose; Amylopectin; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/14—Preparations for removing make-up
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof

Definitions

  • the present invention relates to the field of cosmetic substrates, in particular those for single use, such as a makeup-removing disc or a wipe, for caring for, making up, cleansing and/or removing makeup from keratin materials, notably the skin, the face and the body, the nails and keratin fibres such as the hair or the beard.
  • cosmetic substrates in particular those for single use, such as a makeup-removing disc or a wipe, for caring for, making up, cleansing and/or removing makeup from keratin materials, notably the skin, the face and the body, the nails and keratin fibres such as the hair or the beard.
  • the invention is more particularly directed towards proposing a cosmetic substrate that is as natural as possible, and environmentally friendly, which is capable of efficiently replacing the existing cosmetic substrates, such as makeup-removing cotton wads.
  • cotton discs are fibrous substrates derived from the physical transformation of cotton requiring more than 5000 litres of water per kg of cotton.
  • the cultivation of cotton uses fertilizers and pesticides, and the cotton obtained is generally subjected to a chemical treatment based on chlorine (emission of dioxins) and heavy metals.
  • Cosmetic wipes for their part, consist of a substrate made of a material of natural or synthetic origin, which is preferably a nonwoven, said substrate being impregnated with a composition suited to the desired purpose, for example cleansing or removing makeup from the skin or the eyes, or alternatively skincare or haircare.
  • a composition suited to the desired purpose for example cleansing or removing makeup from the skin or the eyes, or alternatively skincare or haircare.
  • Such wipes are commonly used since they are appreciated for their practical aspect, they are impregnated with the required and sufficient amount of treating or cleansing product, and are disposable. The use of these wipes avoids the handling and transportation of bottles containing the cosmetic compositions.
  • wipes are criticized for their inappropriate use when they are disposed of in toilets instead of being placed in the dustbin, the problem being that, like all fibrous waste, they do not degrade, and block the evacuation pipes, overrun the wastewater networks and disrupt purification plants. Consumers are moreover in search of more natural products and the composition of conventional wipes may be a curb on their use. Finally, consumers are in search of alternatives having a different sensory feel when applied to the skin.
  • the aim of the present invention is thus to find an alternative to the wipes and cotton wads used in cosmetics.
  • novel cosmetic substrates such as konjac sponges or makeup blenders, at the present time, there is still not a cosmetic substrate or support which, simultaneously:
  • hydro-degradable which means that after several hours of immersion in water, such as 4 hours 30 minutes, it does not remain cohesive but rather disintegrates and disperses in the water as biodegradable compounds.
  • An object of the present invention is thus also to develop a novel cosmetic substrate of natural origin, preferably of plant origin, for single use, which is hydro-degradable and multifunctional, notably capable of fulfilling, within a single material, roles as a cotton wad, a wipe, a konjac sponge or even a makeup blender, while at the same time being more natural, more hygienic and more environmentally friendly both in its manufacture and in its destruction.
  • Natural plant structures have excellent properties such as mechanical strength or rigidity combined with secondary properties which allow adaptation, modularity and multifunctionality.
  • secondary properties such as mechanical strength or rigidity combined with secondary properties which allow adaptation, modularity and multifunctionality.
  • their use directly as substrates in the cosmetic industry would give rise to problems of reproducibility.
  • the present invention successfully meets the challenge of providing a substrate of natural origin, which is a biomimetic of the structuring of plant walls, while at the same time being industrially feasible starting with available and controlled raw materials, the substrate being multifunctional, and having the following features:
  • cosmetic active agents notably cosmetic active agents that are usually unstable in liquid or aqueous formulation
  • One subject of the present invention is thus a dry cosmetic substrate based on polysaccharides, intended for cleansing, removing makeup from, caring for and/or making up keratin materials, characterized in that it has an alveolar microscopic structure formed by non-crosslinked association of at least two polysaccharides with respective weight-average molecular masses of greater than 1000 g/mol:
  • a second polysaccharide P2 being chosen: either from homopolysaccharides, or from heteropolysaccharides different from the first heteropolysaccharide and having a weight-average molecular mass of less than 1 000 000 g/mol.
  • a subject of the present invention is also a process for manufacturing a substrate according to the invention, comprising the following steps:
  • a hydrogel of at least two polysaccharides P1 and P2 for example at least partially dissolving in an aqueous phase, such as water, said at least two polysaccharides P1 and P2, by mixing at room temperature, to form a hydrogel, - freezing the hydrogel at a temperature below 0°C, preferably between -100°C and 0°C, preferably between -80 and 0°C, preferably at a temperature within the range from -80°C to -0.01 °C, preferably from -60°C to -4°C,
  • a subject of the present invention is also a cosmetic process for caring for, cleansing, removing makeup from and/or making up keratin materials, which consists in applying thereto, notably to the skin or the hair, preferably to the skin, a substrate according to the invention.
  • Said process may also comprise at least one step consisting in at least partially impregnating said substrate and/or in taking up with the aid of said substrate: water and/or a cosmetic composition and/or a fragrance.
  • Figure 1 is an SEM photo of the structure of a plant wall of Elodeae (aquatic plants).
  • Figure 2 is an SEM photo of a substrate according to the invention consisting of a combination of glucomannan + starch + glycerol, showing the interconnected porous network or the multicellular or alveolar multilayer structure which characterizes its microscopic structure, mimicking that of plant walls, notably of figure 1.
  • Figure 3 schematically represents the application action protocol for evaluating the substrate.
  • Figure 4 schematically represents the cleansing action protocol taken into consideration for testing the efficacy of the substrate according to the invention.
  • the expression “at least one” is equivalent to “one or more” and, unless otherwise indicated (such as “more than...”, “less than...” or “between X and Y”), the limits of a range of values are included in that range (for example “in the range from X to Y”).
  • the term “keratin materials” means the skin of the body, face and/or area around the eyes, the lips, the nails, mucous membranes, the eyelashes, the eyebrows, bodily hair, the scalp and/or head hair, or any other area of bodily skin. More particularly, the keratin materials according to the invention are the scalp, the hair and/or the skin. Preferably, the keratin material according to the invention is the skin.
  • skin refers to all of the skin of the body, and preferably the skin of the face, neckline, neck, arms and forearms, or even more preferably the skin of the face, notably of the forehead, nose, cheeks, chin and area around the eyes.
  • the substrates according to the present invention are cosmetic substrates, intended for topical use.
  • cosmetic refers to a product that is compatible with the skin, mucous membranes and the integuments.
  • the substrate according to the invention is advantageously non-crosslinked.
  • non-crosslinked association of polysaccharides means an association of polysaccharides solely by weak bonds, such as hydrogen bonds, ionic bonds or van der Waals bonds, and not by a strong bond such as a covalent chemical bond.
  • This structure is advantageously derived from cold (without heating) vacuum dehydration of a non-crosslinked hydrogel formed by simple dispersion in cold water (without heating) of at least two specific polysaccharides P1 , P2 as defined by the present invention.
  • each of said polysaccharides P1 and P2 is at least partially water-soluble, at room temperature, notably within a temperature range included in the range from 20 to 25°C, preferably at 25°C.
  • dry substrate means a solid material, which is preferably cohesive, and of anhydrous composition, having a water content by weight of less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%, preferably less than 1.5% by weight of water relative to the total weight of substrate.
  • the term “anhydrous” or “dry” is intended to qualify a substrate composition containing less than 3% water, preferably less than 2% water, preferably less than 1.5% by weight of water, in particular less than 1 % by weight of water, notably less than 0.7% water relative to its total weight, and, preferably, the substrate is free of water, notably in the case of a substrate that has been freeze-dried and then stored in dry form, for example in a hermetic package.
  • the term “natural compound” means a compound which is obtained directly from the earth or soil, notably from plants via, where appropriate, one or more physical processes, for instance grinding, refining, distillation, purification or filtration.
  • compound of natural origin means a natural compound that has undergone one or more additional chemical or industrial treatments, giving rise to modifications that do not affect the essential qualities of this compound and/or a compound predominantly comprising natural constituents that may or may not have undergone transformations as indicated above.
  • the substrate according to the invention has an alveolar microscopic structure formed by association of at least two polysaccharides with respective weightaverage molecular masses of greater than 1000 g/mol:
  • the first polysaccharide P1 being chosen from heteropolysaccharides
  • the second polysaccharide P2 being chosen: either from homopolysaccharides, or from heteropolysaccharides different from the first heteropolysaccharide and having a weight-average molecular mass of less than 1 000 000 g/mol, each of said polysaccharides P1 and P2 preferably being at least partially water-soluble at room temperature, notably at 25°C.
  • polysaccharide means any polymer consisting of several saccharides (or monosaccharides) having the general formula:
  • At least one of said polysaccharides P1 , P2, preferably each of the two P1 and P2, comprises at least one pentose or one hexose, preferably a hexose, preferably glucose.
  • heteropolysaccharides different from the first heteropolysaccharide means essentially the case in which P1 and P2 are heteropolysaccharides of different chemistry, and thus with a different saccharide composition, which is the preferred embodiment in the case of two heteropolysaccharides P1 , P2.
  • this definition may also include (but this embodiment is not preferred) the case in which the two heteropolysaccharides have the same chemistry but a different weight-average molecular mass, in particular greater than 1000 g/mol and less than 1 000 000 g/mol for P2 and outside of this range for P1 , in other words greater than 1 000 000 g/mol for P1 in this case.
  • At least partially water-soluble polysaccharide means any water-soluble or water-dispersible polysaccharide that is capable of giving a gelled solution after implementation at room temperature, notably at a temperature within the range from 20 to 25°C, preferably at 25°C.
  • polysaccharides may be divided into several categories.
  • Polysaccharides are generally distinguished depending on whether or not they are starchy.
  • starchy polysaccharides examples include starches.
  • non-starchy polysaccharides examples include polysaccharides produced by microorganisms; polysaccharides isolated from algae, and higher plant polysaccharides, such as homogeneous polysaccharides, in particular celluloses and derivatives thereof or fructosans, heterogeneous polysaccharides such as acacia gums, galactomannans, glucomannans and pectins, and derivatives thereof.
  • the polysaccharides that are suitable for use in the invention may be homopolysaccharides such as fructans, glucans, galactans and mannans or heteropolysaccharides such as hemicellulose. Similarly, they may be linear polysaccharides such as pullulan or branched polysaccharides such as acacia gum and amylopectin, or mixed polysaccharides such as starch.
  • polysaccharides of homopolysaccharide or heteropolysaccharide type that are suitable for use in the invention may be chosen from the starchy or non- starchy polysaccharides, listed below, and selected from this list according to their heteropolysaccharide or homopolysaccharide nature, as defined for each type of polysaccharide used according to the invention.
  • Said at least two polysaccharides P1 , P2, which constitute the substrate according to the invention may notably be chosen from polysaccharides derived from microorganisms, polysaccharides isolated from algae and polysaccharides from higher plants.
  • the polysaccharides are advantageously chosen from fructans, gellans, glucans, starches, which are preferably unmodified (such as those derived, for example, from cereals, for instance wheat, corn or rice, from vegetables, for instance yellow pea, and tubers, for instance potato or cassava), amylose, amylopectin, glycogen, dextrans, celluloses, mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, chitosans, glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, arabinogalactans, carrageenans, agars, glycosaminoglucans, acacia gums, gum tragacanths, ghatti gums, karaya gums, locust bean gums, galactomannans such as guar gums and non
  • the derivatives obtained may be anionic, cationic, amphoteric or nonionic.
  • the compounds of this type that may be used in the present invention are chosen from those described notably in Kirk-Othmer’s Encyclopedia of Chemical Technology, Third Edition, 1982, volume 3, pages 896-900, and volume 15, pages 439- 458, in Polymers in Nature by E.A. MacGregor and C.T. Greenwood, published by John Wiley & Sons, Chapter s, pages 240-328, 1980, in the book by Robert L.
  • Xanthan is a heteropolysaccharide produced on an industrial scale by the aerobic fermentation of the bacterium Xanthomonas campestris. Its structure consists of a main chain of ⁇ (1 ,4)-linked 0-D-glucoses, similar to cellulose. One glucose molecule in two bears a trisaccharide side chain composed of an a-D-mannose, a 0-D-glucuronic acid and a terminal 0-D-mannose. The internal mannose residue is generally acetylated on carbon 6. About 30% of the terminal mannose residues bear a pyruvate group linked in chelated form between carbons 4 and 6.
  • the charged pyruvic acids and glucuronic acids are ionizable, and are thus responsible for the anionic nature of xanthan (negative charge down to pH 1).
  • the content of the pyruvate and acetate residues varies according to the bacterial strain, the fermentation process, the conditions after fermentation and the purification steps. These groups may be neutralized in commercial products with Na + , K + or Ca 2+ ions (Satia company, 1986).
  • the neutralized form may be converted into the acid form by ion exchange or by dialysis of an acidic solution.
  • Xanthan gums have a molecular weight of between 1 000 000 and 50 000 000 and a viscosity of between 0.6 and 1.65 Pa.s for an aqueous composition containing 1 % of xanthan gum (measured at 25°C on a Brookfield viscometer of LVT type at 60 rpm).
  • Xanthan gums are represented, for example, by the products sold under the names Rhodicare by the company Rhodia Chimie, under the name SatiaxaneTM by the company Cargill Texturizing Solutions (for the food, cosmetic and pharmaceutical industries), under the name NovaxanTM by the company ADM, and under the names Kelzan® and Keltrol® by the company CP-Kelco.
  • Pullulan is a polysaccharide consisting of maltotriose units, known under the name ⁇ (1 ,4)- ⁇ (1 ,6)-glucan. Three glucose units in maltotriose are connected via an ⁇ (1 ,4) glycoside bond, whereas the consecutive maltotriose units are connected to each other via an ⁇ (1,6) glycoside bond. Pullulan is produced by fermentation from starch, with the fungus Aureobasidium pullulans.
  • Pullulan is produced, for example, under the reference Pullulan PF 20 by the group Hayashibara in Japan.
  • Dextran is a neutral polysaccharide not bearing any charged groups, which is biologically inert, prepared by fermentation of beet sugar containing solely hydroxyl groups. It is synthesized from sucrose by fermentation in the presence of certain lactic acid bacteria, the most common being Leuconostoc mesenteroides and Streptococcus mutans. This branched polysaccharide consists of a sequence of glucose molecules forming a chain of variable lengths. The main chain consists of glucose molecules linked together via ⁇ (1 ,6) glycoside bonds and the branches are linked to the main chain via ⁇ (1,3) glycoside bonds (and in some cases by ⁇ (1 ,2) and ⁇ (1,4) bonds). Chemical structure of dextran: It is possible to obtain dextran fractions of different molecular weights from native dextran by hydrolysis and purification. Dextran may in particular be in the form of dextran sulfate.
  • Dextran is represented, for example, by the products sold under the name Dextran or Dextran T by the company Pharmacosmos, or under the name Dextran 40 Powder or Dextran 70 Powder by the company Meito Sangyo Co.
  • Dextran sulfate is sold by the company PK Chemical A/S under the name Dextran sulfate.
  • Succinoglycan is an extracellular polymer of high molecular weight produced by bacterial fermentation, consisting of octasaccharide repeating units (repetition of 8 sugars). These units are synthesized in the membranes of the microorganism linked to the isoprenoid lipids.
  • the main chain contains 3 glucoses and 1 galactose, and the side chain contains 4 glucoses.
  • the sugars are linked together via [3(1 ,4) and ⁇ (1 ,3) glycoside bonds.
  • the pyruvate substituent is attached to the last glucose of the side chain, whereas succinate may be linked to one of the other two glucoses of the same side chain.
  • the base unit of said succinoglycans may contain residues of other organic acids, such as pyruvyl or acetyl residues, and also of other sugars such as glucuronic acid and/or mannose.
  • the mole ratios between glucose and such organic acid residues are generally between (5 to 8)/(0.01 to 2).
  • the mole ratios between said other sugars and glucose are generally between (0 to 1 )/(5 to 8).
  • Succinoglycans may be obtained by microbial fermentation, for example by fermentation of a medium including at least one carbon source, by means of a microorganism which preferably belongs to the Arthrobacter genus, such as Arthrobacter stabilis, to the Agrobacterium genus, such asAgrobacterium tumefaciens, Agrobacterium radiobacter or Agrobacterium rhizogenes, to the Rhizobium genus or to the Alcaligenes genus, such asAlcaligenes faecalis.
  • Arthrobacter stabilis to the Agrobacterium genus, such asAgrobacterium tumefaciens, Agrobacterium radiobacter or Agrobacterium rhizogenes, to the Rhizobium genus or to the Alcaligenes genus, such asAlcaligenes faecalis.
  • the fermentation media including the carbon source and the fermentation processes are widely described in the literature.
  • Succinoglycan is an anionic polysaccharide which has the particular feature of undergoing a helix-coil transition, induced by a temperature change. This conformational transition is highly cooperative, bringing about a substantial change in the rigidity of the polymer.
  • Succinoglycans are sold, for example, under the name Rheozan by the company Rhodia. Scleroglucan
  • Scleroglucan is a nonionic branched homopolysaccharide consisting of p-D-glucan units.
  • the molecules consist of a linear main chain formed from D-glucose units linked via ⁇ (1 ,3) bonds and of which one in three is linked to a side D-glucose unit via a ⁇ (1 ,6) bond.
  • polysaccharides are obtained by fermentation of a medium based on sugar and mineral salts, under the action of a microorganism of Sclerotium type, such as Sclerotium glucanium and Sclerotium rolfsii.
  • Sclerotium type such as Sclerotium glucanium and Sclerotium rolfsii.
  • Scleroglucan is sold, for example, under the name Amigel by the company Alban Muller, or under the name ActigumTM CS by the company Cargill.
  • the polysaccharide of the composition according to the invention may be a galactan chosen notably from agar and carrageenans.
  • Carrageenans are anionic polysaccharides constituting the cell walls of various red algae (Rhodophyceae) belonging to the Gigartinacae, Hypneaceae, Furcellariaceae and Polyideaceae families. They are generally obtained by hot aqueous extraction from natural strains of said algae. These linear polymers, formed by disaccharide units, are composed of two D-galactopyranose units linked alternately by ⁇ (1 ,3) and ⁇ (1 ,4) bonds. They are highly sulfated polysaccharides (20-50%) and the a-D-galactopyranosyl residues may be in 3,6-anhydro form.
  • carrageenans which bear one sulfateester group
  • iota-carrageenans which bear two sulfate-ester groups
  • lambda- carrageenans which bear three sulfate-ester groups.
  • Carrageenans notably have the following chemical structures:
  • Carrageenans are composed essentially of potassium, sodium, magnesium, triethanolamine and/or calcium salts and of sulfate esters of polysaccharides.
  • the physicochemical properties and the uses of these polysaccharides as gelling agents are based on their capacity to establish coil-helix conformational transitions as a function of the thermal and ionic environment [Kloareg et al. Oceanography and Marine Biology - An annual review 26: 259-315 (1988)].
  • Carrageenans are sold notably by the company SEPPIC under the name Solagum®, by the company Gelymar under the names Carragel®, Carralact® and Carrasol®, by the company Cargill under the names SatiagelTM and SatiagumTM, and by the company CP-Kelco under the names Genulacta®, Genugel® and Genuvisco®.
  • Galactans of agar type are galactose polysaccharides contained in the cell wall of some of these species of red algae (Rhodophyceae).
  • Agar-agar is a mixture of polysaccharides (agarose and agaro ⁇ eZtin) of high molecular mass, between 40 000 and 300 000 g.mol -1 . It is obtained by manufacturing algal extraction liquors, generally by autoclaving, and by treating these liquors which comprise about 2% of agar-agar, so as to extract the latter.
  • Agar is produced, for example, by the group B&V Agar Producers under the names Gold Agar, Agarite and Grand Agar by the company Hispanagar, and under the names Agar-Agar, QSA (Quick Soluble Agar), and Puragar by the company Setexam.
  • Furcellaran is obtained commercially from Furcellaria fasztigiata red algae, which are mainly present in the seas of northern Europe. Its structure is very close to that of carrageenans.
  • Furcellaran is produced, for example, by the company Est-Agar.
  • the polysaccharide P1 , P2 present in the composition according to the invention may be a glucosan, notably chosen from native or modified starches, dextrins and derivatives, celluloses and derivatives or fructosans.
  • the starches that may be used in the present invention are more particularly macromolecules in the form of polymers consisting of elementary moieties which are anhydroglucose units (dextrose), linked via ⁇ (1 ,4) bonds, of chemical formula (C 6 H 10 O 5 )n.
  • the number of these moieties and their assembly make it possible to distinguish amylose, a molecule formed from about 600 to 1000 linearly linked glucose molecules, and amylopectin, a polymer branched approximately every 25 glucose residues ( ⁇ (1,6) bond).
  • the total chain may include between 10 000 and 100 000 glucose residues.
  • Starch is described in particular in Kirk-Othmer’s Encyclopedia of Chemical Technology, 3rd edition, volume 21 , pages 492-507, Wiley Interscience, 1983. Chemical structure of starch:
  • amylose and of amylopectin vary as a function of the botanical origin of the starches. On average, a sample of native starch consists of about 25% amylose and 75% amylopectin.
  • Starch may be in the form of semicrystalline granules: amylopectin is organized in leaflets, amylose forms a less well organized amorphous zone between the various leaflets.
  • Amylose is organized in a straight helix with six glucoses per turn. It dissociates into assimilable glucose under the action of enzymes, amylases, all the more easily when it is in amylopectin form. Specifically, the helical formation does not promote the accessibility of starch to the enzymes.
  • Starches are generally in the form of a white powder, which is insoluble in cold water, of which the elemental particle size ranges from 3 to 100 microns.
  • starch paste By treating it with hot water, starch paste is obtained. It is exploited in industry for its thickening and gelling properties.
  • the botanical origin of the starch molecules used in the present invention may be cereals or tubers.
  • the starches are chosen, for example, from corn starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch.
  • the native starches are represented, for example, by the products sold under the names C*AmilogelTM, Cargill GelTM, C* GelTM, Cargill GumTM, DryGelTM and C*Pharm GelTM by the company Cargill, under the name Amidon de Mais by the company Roquette, and under the name Tapioca Pure by the company National Starch.
  • Cyclodextrins are a family of cyclic oligosaccharides composed of ⁇ (1 ,4)-linked glucopyranose subunits. These natural products resulting from the degradation of starch by the bacterium Bacillus macerans were discovered in 1891 by V Amsterdam. Three families are mainly used or studied: a-, ⁇ -and y-cyclodextrins, depending on whether they are formed from 6, 7 or 8 subunits (-families of several tens of subunits have been synthesized for research purposes).
  • Cyclodextrins are notably oligosaccharides of formula:
  • x may be a number equal to 4 (which corresponds to a-cyclodextrin), to 5 (P-cyclodextrin) or to 6 (y-cyclodextrin).
  • cyclodextrins may be obtained from natural cyclodextrins: the hydroxyl groups of the glucopyranose units may be aminated, esterified or etherified. The synthesis of these derivatives is often for the purpose of improving the solubility.
  • cyclodextrins that have been the most extensively studied are p-cyclodextrin (BCD, natural), hydroxypropyl-p-cyclodextrin (HPCD) and methyl-p-cyclodextrin (MCD).
  • Use may notably be made of a p-cyclodextrin sold by the company Wacker under the name Cavamax W7 and a y-cyclodextrin sold by the company Wacker under the name Cavamax W8.
  • the cyclodextrin derivatives are, for example, methyl cyclodextrins such as the methyl- P-cyclodextrin sold by the company Wacker under the name Cavasol W7.
  • the polysaccharide P1 , P2 according to the invention may also be a cellulose or a derivative thereof, notably cellulose ethers or esters (e.g.: methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cellulose acetate, cellulose nitrate, nitrocellulose).
  • cellulose ethers or esters e.g.: methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cellulose acetate, cellulose nitrate, nitrocellulose.
  • the invention may also contain a cellulose-based associative polymer.
  • cellulose-based compound means any polysaccharide compound bearing in its structure linear sequences of anhydroglucopyranose residues (AGUs) linked together via ⁇ (1 ,4) glycoside bonds.
  • the repeating unit is the cellobiose dimer.
  • the AGUs are in chair conformation and bear 3 hydroxyl functions: 2 secondary alcohols (in position 2 and 3) and a primary alcohol (in position 6).
  • the polymers thus formed combine together via intermolecular bonds of hydrogen bond type, thus giving the cellulose a fibrillar structure (about 1500 molecules per fibre).
  • the degree of polymerization differs enormously depending on the origin of the cellulose; its value may range from a few hundred to several tens of thousands.
  • Cellulose has the following chemical structure:
  • the polysaccharide P1 , P2 present in the composition according to the invention may notably be a fructosan chosen from inulin and derivatives thereof (notably dicarboxy and carboxymethyl inulins).
  • Fructans or fructosans are oligosaccharides or polysaccharides comprising a sequence of anhydrofructose units optionally combined with one or more saccharide residues other than fructose.
  • Fructans may be linear or branched.
  • Fructans may be products obtained directly from a plant or microbial source or alternatively products of which the chain length has been modified (increased or decreased) by fractionation, synthesis or hydrolysis, in particular enzymatic.
  • Fructans generally have a degree of polymerization from 2 to about 1000 and preferably from 2 to about 6O.Thr ee groups of fructans are distinguished. The first group corresponds to products of which the fructose units are for the most part linked via ⁇ (2,1) bonds. These are essentially linear fructans such as inulins. The second group also corresponds to linear fructoses, but the fructose units are essentially linked via ⁇ (2,6) bonds. These products are levans. The third group corresponds to mixed fructans, i.e. containing ⁇ (2,6) and ⁇ (2,1) sequences. These are essentially branched fructans, such as graminans. The preferred fructans in the compositions according to the invention are inulins.
  • Inulin may be obtained, for example, from chicory, dahlia or Jerusalem artichoke.
  • the inulin used in the composition according to the invention is obtained, for example, from chicory.
  • Heterogeneous polysaccharides are:
  • the polysaccharides that may be used according to the invention may be gums, for instance cassia gum, karaya gum, konjac gum, gum tragacanth, acacia gum or gum arabic.
  • Acacia gum of which Senegal gum (Acacia seyal, Leguminosae family) is the main variety, consists of a solidified descending sap exudate, amalgamated naturally or by incision, on the trunk and at the foot of trees of the acacia family.
  • Acacia gum is a highly branched acidic polysaccharide which is in the form of mixtures of potassium, magnesium and calcium salts.
  • the monomer elements of the free acid (arabic acid) are D-galactose, L-arabinose, L-rhamnose and D-glucuronic acid. It is acknowledged that acacia gums are composed of at least two polysaccharide fractions of different structures. The fraction of higher molecular mass contains a modest proportion of amino acids but which is decisive for its properties. The indicated average molecular mass oscillates between 200 and 300 kDa.
  • Acacia gum is found commercially in the form of powder or of non-ground crystals that are more or less round of yellow-white to yellow-brownish colour.
  • the outer surface of the crystals is dull and split and their fractures are vitreous; they are often also traversed by fine fissures.
  • the gum is insipid and odourless. It is soluble in water and insoluble in alcohol.
  • Acacia gum is characterized by three main fractions: an arabinogalactan (AG) fraction with a very small protein fraction, representing 88% of the gum and having a molecular mass of 250 000 Da, an arabinogalactan-protein (AGP) complex having a high molecular mass (1.5*10 6 ) - the protein complex (AGP) representing about 10% by weight of the gum, and a glycoprotein (Gl) with a molecular mass of 200 000 Da, making up 1.2% of the gum.
  • AG arabinogalactan
  • AGP arabinogalactan-protein
  • Gl glycoprotein
  • the carbohydrate blocks are linked together by a main polypeptide chain.
  • the carbohydrate blocks consist of a ⁇ (1,3)-linked galactopyranose backbone, with numerous branches (1 ,6)-linked to the galactopyranose residues and containing the sugars arabinofuranose, arabinopyranose (Ara), rhamnopyranose (Rha), glucuronic acid (GlcA) and 4-O-methylglucuronic acid.
  • Acacia gum may be precipitated in the presence of trivalent cations and with salts such as mercury nitrate, borates and silicates.
  • the acacia gum used for the present invention is represented, for example, by the products sold under the name EficaciaTM by the company ColloTdes Naturels International, by the product sold under the name Gum Arabic Quick Gum Type 8074 by the company Max Haenelt, by the product sold under the name Gomme Arabique Poudre 396D sold by the company Alland & Robert, and by the product sold under the name Ticamulsion B-2001 by the company TIC Gums.
  • Gum tragacanth also known as tragacanth or dragon gum, is an exudate obtained from the dried mucilaginous sap of about 20 species of plants of the genus Astracantha (formerly known as Astragalus) originating from south-eastern Europe and from southwestern Asia.
  • This gum is a complex mixture of several polysaccharides.
  • the two main fractions are tragacanthin (60-70%) and bassorin, also known as tragacanthic acid (30-40%).
  • tragacanthin dissolves to form a colloidal hydrosol, whereas the insoluble bassorin swells to form a gel.
  • an adhesive paste is obtained.
  • the constituent sugar residues of this arabinogalactan are 75% L-arabinose, 12% D-galactose, 3% D-galacturonic acid methyl ester and L-rhamnose.
  • Tragacanthic acid is water-soluble and consists of a (1,4)-linked a-D-galactopyranosyluronic acid backbone, with short branches such as (3(1 ,3)-linked D-xylopyranose residues, (3(1 ,3)- linked D-xylopyropyranosyl-1 ,2- a-L-fucopyranose dimers and (3(1 ,3)-linked D-xylopyranose- 1 ,2-D-galactopyranose dimers.
  • the constituent sugars of gum tragacanth are thus, in relative proportions: 43% D-galacturonic acid, 40% D-xylose, 10% L-fucose and 4% D-galactose.
  • the average molecular mass of tragacanthic acid is about 840 000 Da.
  • Karaya gum is a partially acetylated polysaccharide, of high molecular weight, exuded by trees of the species Sterculia (urens and setigera), and is one of the natural gums that is the least water-soluble. It swells to give a viscous colloidal dispersion.
  • Karaya gum is a highly acetylated acidic polysaccharide, with a backbone consisting of an alternation of (1 ,4)-linked ⁇ -D-galacturonopyranosyluronic acid units and of (1,2)- linked a-L-rhamnopyranosyl residues.
  • ⁇ -D-Galactopyranosyl and D- glucuronopyranosyluronic acid groups are branched on the oxygens (02 and 03) of the galacturonic acid residues, whereas half of the rhamnose residues are (1,4)-linked (at 04) to
  • the molecule also contains 13% by weight of acetyl groups.
  • Karaya gum is sparingly water-soluble, but it readily swells in cold water to occupy several times its original volume, particularly at a low particle size ( ⁇ 200 mesh), giving a dispersion which appears homogeneous.
  • the karaya gum used for the present invention is represented, for example, by the products sold under the name Gomme Karaya Poudre by the company Alland & Robert.
  • Galactomannans (guar, locust bean, fenugreek, tara gum) and derivatives (guar phosphate, hydroxypropyl guar, etc.):
  • Galactomannans are nonionic polyosides extracted from the endosperm of leguminous seeds, of which they constitute the storage carbohydrate.
  • Galactomannans are macromolecules consisting of a main chain of ⁇ (1 ,4)-linked D-mannopyranose units, bearing side branches consisting of a single D-galactopyranose unit ⁇ (1 ,6)-linked to the main chain.
  • the various galactomannans differ, firstly, by the proportion of a-D-galactopyranose units present in the polymer, and secondly by significant differences in terms of distribution of galactose units along the mannose chain.
  • the mannose/galactose (M/G) ratio is about 2 for guar gum, 3 for tara gum and 4 for locust bean gum.
  • the guar molecule thus contains on average twice as many branches as locust bean gum. However, within one and the same sample, this ratio can vary according to the fractions.
  • Knowledge of the M/G ratio constitutes one of the means for characterizing the sample, although it does not provide any information regarding the statistical distribution of the galactosyl residues on the main chain.
  • Galactomannans have the following chemical structure: Tara gum is characterized by a side chain distribution that is more statistically random, whereas locust bean gum is characterized by a distribution that is not statistically random and irregular, with an alternation of unsubstituted blocks of intermediate length (smooth regions) and branched blocks (hairy regions). Guar meal has very few smooth regions, with a very regular distribution of the galactose side chains.
  • the products that may be used according to the invention may be partially depolymerized galactomannans, consequently having reduced viscosities. These depolymerizations are obtained by acid hydrolysis, oxidation or enzymatic degradation. Guar
  • Guar gum is characterized by a mannose:galactose ratio of the order of 2:1.
  • the galactose group is regularly distributed along the mannose chain.
  • guar gums that may be used according to the invention may be nonionic, cationic or anionic.
  • the unmodified nonionic guar gums are, for example, the products sold under the names Vidogum GH, Vidogum G and Vidocrem by the company Unipektin and under the name Jaguar by the company Rhodia, under the name Meypro® Guar by the company Danisco, under the name ViscogumTM by the company Cargill, and under the name Supercol® guar gum by the company Aquaion.
  • hydrolysed nonionic guar gums that may be used according to the invention are represented, for example, by the products sold under the name Meyprodor® by the company Danisco.
  • modified nonionic guar gums that may be used according to the invention are preferably modified with C 1 -C 6 hydroxyalkyl groups.
  • compositions in accordance with the invention may also comprise a cationic galactomannan gum.
  • the galactomannan gum is a cationic guar gum.
  • the cationic galactomannan gums preferably have a cationic charge density of less than or equal to 1.5 meq./g, more particularly between 0.1 and 1 meq./g.
  • the charge density may be determined by the Kjeldahl method. It generally corresponds to a pH of the order of 3 to 9.
  • Locust bean gum is extracted from the seeds of the locust bean tree (Ceratonia siliqua), which is an evergreen tree originating from AMD and Asia Minor, but which is grown throughout the Mediterranean coastline.
  • locust bean tree Ceratonia siliqua
  • the galactose sugars are not equally regularly distributed along the chain, but have a tendency to be grouped together in blocks.
  • the chains have an irregular structure with alternating “smooth” zones and substituted zones.
  • the locust bean gum that may be used in the present invention may be chemically modified, via the same chemical modifications as those described previously for guar gum.
  • the unmodified locust bean gum that may be used in the present invention is sold, for example, under the name ViscogumTM by the company Cargill, under the name Vidogum L by the company Unipektin and under the name Grinsted® LBG by the company Danisco.
  • the tara gum that may be used in the present invention may be chemically modified, via the same chemical modifications as those described previously for guar gum.
  • the tara gum that may be used is sold, for example, under the name Vidogum SP by the company Unipektin.
  • Glucomannans (konjac gum):
  • Glucomannan is a polysaccharide of high molecular weight (500 000 ⁇ Mglucomannan ⁇ 2 000 000) composed of D-mannose and D-glucose units with a branch every 50 or 60 units approximately. It is found in wood, but is also the main constituent of konjac gum. Konjac (Amorphophallus konjac) is a plant of the Araceae family.
  • Pectins or more broadly pectic substances, are polysaccharides, linked to carbohydrates. They are substances that are exclusively of plant origin. Pectin is present in large amount in certain algae, and in currant, apple, quince and lemon seeds and zests. Pectins are extracted from the raw material by solubilization in acidic medium under hot conditions, and by precipitation from alcohol. The precipitate is then washed with a sodium hydroxide solution in order to obtain the desired pH.
  • Pectins are polymers of acid polysaccharides. Pectins are linear polymers of a-D- galacturonic acid (at least 65%) linked in positions 1 and 4 with a certain proportion of carboxylic groups esterified with a methanol group. About 20% of the sugars constituting the pectin molecule are neutral sugars (L-rhamnose, D-glucose, D-galactose, L-arabinose, D-xylose). L-Rhamnose residues are found in all pectins, incorporated into the main chain in positions 1 ,2. They are responsible for the nonlinear nature of the main chain (cf. chemical structure). Their molecular weight is about 10 5 g/mol.
  • Uronic acid molecules bear carboxyl functions. This function gives pectins the capacity for exchanging ions, when they are in COO- form. Divalent ions (in particular calcium) have the capacity of forming ionic bridges between two carboxyl groups of two different pectin molecules.
  • a certain proportion of the carboxylic groups are esterified with a methanol group.
  • the natural degree of esterification of a pectin may range between 70% (apple, lemon) and 10% (strawberry) depending on the source used.
  • pectins with a high degree of esterification it is possible to hydrolyse the -COOCH3 groups so as to obtain weakly esterified pectins.
  • the chain is thus more or less acidic.
  • HM (high-methoxy) pectins are thus defined as having a degree of esterification of greater than 50%
  • LM (low-methoxy) pectins are defined as having a degree of esterification of less than 50%.
  • the degree of esterification influences the gelling properties of HM pectins.
  • the ester group is less hydrophilic than the acid group and, consequently, an HM pectin (with a high degree of esterification) gels at a higher temperature than an LM pectin (with a low degree of esterification). The difference is reflected in terms of rapid, medium and slow gelling.
  • Pectins are notably sold by the company Cargill under the name UnipectineTM, by the company CP-Kelco under the name Genu, and by Danisco under the name Grinsted Pectin.
  • polysaccharides that may be used according to the invention, mention may also be made of polysaccharides derived from biotechnology. This is the case, for example, for chitin, chitosan and derivatives (chitosan 0-glycerophosphate, carboxymethylchitin, etc.).
  • Chitin is a polysaccharide amino sugar, formed from acetylglucosamine groups (N- acetyl-D-glucose-2-amine) linked together by a bond of the (1 ,4) type. It is this type of bond which links the glucose groups in the cellulose molecule.
  • the chemical name of the molecule is poly-N-acetyl-D-glucosamine, ⁇ (1 ,4)-2- acetamido-2-deoxy-D-glucose.
  • Chitin is one of the constituents of the cuticle of insects, spiders and crustaceans, and thus has a protective role. When combined with calcium carbonate, it becomes rigid and then forms the exoskeleton of crustaceans and of all shell-bearing animals such as snails.
  • Chitosan is a polysaccharide composed of the random distribution of ⁇ (1 ,4)-linked D-glucosamine (deacetylated unit) and of N-acetyl-D-glucosamine (acetylated unit). It is produced by chemical deacetylation (in an alkaline medium) or enzymatic deacetylation of chitin, the component of the arthropod (crustacean) exoskeleton or of the cephalopod (squid, etc.) endoskeleton or else of the fungal wall. This raw material is demineralized by treatment with hydrochloric acid, then deproteinated in the presence of sodium hydroxide or potassium hydroxide and, finally, decolourized using an oxidizing agent.
  • the degree of acetylation is the percentage of acetylated units relative to the number of total units; it can be determined by Fourier transform infrared (FTIR) spectrometry or by titration with a strong base.
  • FTIR Fourier transform infrared
  • the border between chitosan and chitin corresponds to a DA of 50%: below this the compound is called chitosan, above it, it is called chitin.
  • Chitosan is soluble in an acidic medium, unlike chitin which is insoluble. It is important to distinguish between the degree of acetylation (DA) and the degree of deacetylation (DD).
  • Chitin is a particularly efficient moisturizer. Its advantage is twofold: it provides water and prevents dehydration. Furthermore, the great advantage of chitin and derivatives thereof is the persistence of this moisturizing power over time.
  • chitosan forms a protective and tensioning film at the surface of the skin, which is capable of fixing other active principles for the skin.
  • other moisturizers, sunscreens or organic acids or other active principles may be associated with chitin derivatives. Chitin is considered to promote their effects.
  • the products that may be used according to the invention are, for example, those sold by the company France-Chitine.
  • Glycosaminoglycans GAG
  • Mention may notably be made of hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate or heparin and heparan sulfate.
  • glycosaminoglycans GAG
  • AAG glycosaminoglycans
  • glucosamine GlcN
  • galactosamine GalN
  • glucuronic acid GlcA
  • IdoA iduronic acid
  • galactose Gal
  • the glucosamine is either N-sulfated (GIcNS) or N-acetylated (GIcNac).
  • the galactosamine is always N-acetylated (GalNac).
  • GAG chains may be covalently bonded to a protein to form proteoglycans.
  • GAGs comprise chondroitin sulfate (elastic cartilage, hyalin cartilage, bone, dermis, cornea), dermatan sulfate (dermis, tendon, ligament, fibrous cartilage), keratan sulfate (cartilage, cornea), heparin/heparan sulfate (liver, lung, aorta) and hyaluronic acid.
  • Hyaluronic acid is a polymer of disaccharides which are themselves composed of D-glucuronic acid and D-N-acetylglucosamine linked together via alternating ⁇ (1 ,4) and ⁇ (1,3) glycoside bonds.
  • the polymers of this repeating unit may have a size of between 10 2 and 10 4 kDa in vivo.
  • Hyaluronic acid is stable from an energetic viewpoint, partly on account of the stereochemical aspects of the disaccharides of which it is composed.
  • Hyaluronic acid consists of about 50 000 disaccharide units, it is the size of a bacterium and has the appearance of a gel.
  • Hyaluronic acid is mainly obtained industrially via two different processes: extraction of cockerel crests (after grinding, chemical treatment and purification) or bacterial fermentation (hyaluronic acid filaments are synthesized by genetically modified bacteria).
  • Sodium hyaluronate is the sodium salt of hyaluronic acid.
  • Chondroitin sulfate is a glycosaminoglycan present in connective tissue.
  • Chondroitin sulfate is a component of cartilage matrix. Its function is to maintain the osmotic pressure by absorbing water and to aid in hydrating cartilage. It also contributes towards the flexibility and elasticity of bone. Even more importantly, it serves as a chondro-protective agent by protecting cartilage against enzymatic reactions and against damage mediated by free radicals (including the nitrogen monoxide released by chondrocytes).
  • the base unit of chondroitin sulfate is glucuronic acid ⁇ (1 ,3) N-acetylgalactosamine 6-sulfate. Each unit is linked to the next one by a ⁇ (1 ,4) bond. Chondroitin sulfate varies in its composition as a function of the animal species even though the base structure is mainly unchanged.
  • Heparin is a molecule which is a member of the glycosaminoglycans (GAG).
  • the polysaccharide P1 , P2 is hyaluronic acid.
  • Flour contains fragments of the primary walls of the starchy endosperm of wheat; they belong essentially to one family of polysaccharides: arabinoxylans. These are polymers of xylose and arabinose, all grouped under the name “pentosans”. The arabinoxylan from wheat seeds is composed of ⁇ -D-xylopyranose residues (Rodionova et al., 1992).
  • Xylans are consisting of a main chain of ⁇ (1,4)-linked D-xylose units on which are found three substituents (Rouau & Thibault, 1987): acid units, a-L-arabinofuranose units, side chains which may contain arabinose, xylose, galactose and glucuronic acid.
  • Arabinoxylan generally consists of 1500-5000 a-L-arabinofuranose and D- xylopyranose residues (Chaplin, 2004).
  • the weight-average molecular mass may also be determined by size exclusion chromatography coupled online with multi-angle light scattering and refractometry: SEC/MALS/RI coupling.
  • SLS size exclusion chromatography
  • MALS multi-angle light scattering
  • Multi-angle light scattering is based on measurement of the scattered intensity of a solute in solution which is proportional to its concentration and to its molar mass.
  • the scattered intensity may also vary according to the angle of observation as a function of the size of the scattering object, in particular its radius of gyration (Rg).
  • the analysis of the samples may be performed at 25°C by coupling size exclusion chromatography (SEC) with a multi-angle static light scattering (MALS) detector (Dawn Heleos, Wyatt Technology, USA) 18 angles (normalized with the detector at 90°), and a differential refractive index (DRI) detector (Optilab, Wyatt Technology, USA), indicating the concentration of polysaccharide (Ci) of each fraction eluted by the SEC.
  • SEC size exclusion chromatography
  • MALS multi-angle static light scattering
  • DRI differential refractive index
  • M w weight-average molecular mass of the polysaccharide
  • NA Avogadro number
  • dn/dc refractive index increment of the solution (ml/g)
  • the use of SEC requires the samples to be fully soluble in the analysis eluent and not to be retained on the columns.
  • the polysaccharides are generally dissolved in the chromatography eluents used for their analysis, namely 0.1 M pH 4.5 sodium nitrate.
  • FFF field flow fractionation
  • the polysaccharides that may be used in the invention must in fact have respective weight-average molecular masses of greater than 1000 g/mol, it being pointed out that:
  • the first polysaccharide P1 is chosen from heteropolysaccharides
  • the second polysaccharide P2 is chosen: either from homopolysaccharides, or from heteropolysaccharides different from the first heteropolysaccharide and having a weight-average molecular mass of less than 1 000 000 g/mol.
  • said second polysaccharide P2 is a homopolysaccharide with a weightaverage molecular mass of greater than 1 000 000 g/mol. Even more pore preferably, the substrate according to the invention comprises:
  • said two polysaccharides P1 , P2 are hydrocolloids, i.e. water-soluble polysaccharides which spontaneously form a hydrogel in aqueous solution, when they represent a total weight content of polysaccharides (P1+P2) within the range from 0.5% to 5%, preferably from 1% to 3%, preferably from 1% to 2% by weight relative to the total weight of the aqueous solution (P1+P2+water).
  • the weight ratio P1 :P2 is between 1 :4 and 4:1 , preferably within the range from 1 :3 to 3:1 , preferably within the range from 1 :2 to 2:1 ; preferably, the weight ratio P1 :P2 is 1 :1.
  • P1 and P2 are chosen from the following list of polysaccharides: glucomannan, galactomannan, gellan gum, xanthan, xilogel, starch, cellulose, amylose, curdlan, pullulan, carrageenan, laminarin, agar, alginate, chitosan, guar gum, konjac gum, locust bean gum, sclerotium gum, maltodextrins, modified polysaccharide which is water-soluble at 25°C, such as carboxymethyl starch, distarch phosphate, hydroxymethylcellulose, and mixtures thereof; preferably, P1 is glucomannan and P2 is starch.
  • the substrate according to the invention uses at least one of the combinations (A1 to A22) of polysaccharides of the type P1 , P2 according to the invention, of Table 1 below, as listed in each of the lines 1 to 22.
  • Table 1 indicates for each polysaccharide of each combination whether it is a homopolysaccharide or a heteropolysaccharide, its weight-average molecular mass and its saccharide composition.
  • Mw The weight-average molecular mass, abbreviated hereinbelow as Mw, is indicated as follows: h/m/l, with h for high Mw: hMw > 1 MDa (in the tables hereinbelow, noted as h) m for medium Mw: 1 kDa ⁇ mMw ⁇ 1 MDa (in the tables hereinbelow, noted as m) I for low Mw: IMw ⁇ 1 kDa (in the tables hereinbelow, noted as I).
  • the structure of the substrate of the invention is preferably obtained by freezing and vacuum dehydration starting with a composition comprising said polysaccharides P1, P2, in which P1 and/or P2 are at least partially, or even totally, introduced in the form of a natural fragment, preferably a plant fragment, said at least one natural fragment being chosen from plants, notably plant byproducts, byproducts derived from the agricultural sector or from the food sector, commonly eliminated ingredients of plant origin, preferably chosen from: peels, pulps, peelings, cores, tops, leaves, fibres, stalks, flowers, petals, fruit, berries, vegetables, fruit slices or skins, vegetable slices or skins, seeds, pips, beans, cereals, brans, starch-rich plants, and mixtures thereof; or alternatively from algae and microalgae, bacteria, yeasts and/or fungi, each fragment being, without preference, either in a raw form or in the form of a processed extract, preferably in raw, sparing
  • composition of the substrate according to the invention thus comprises one or more fragments of one or more plants in dehydrated form, notably a part of a plant, fruit or vegetable.
  • fragment means a piece or a part of a plant, obtained, for example, by tearing or milling the plant, or by cutting up said plant.
  • fragments of one or more plants means that the composition of the substrate comprises either several fragments of one and the same species of plant, or that the composition of the substrate comprises several fragments of several different species of plants.
  • a plant may be contained in its entirety in the composition of a substrate according to the invention.
  • the fragments of one or more plants are chosen from flower petals, whole flowers, flower buds, leaves, algae, plant stems, roots, all or a part of fruit or vegetables such as fruit or vegetable skins, in their entirety or in pieces, and mixtures thereof; more preferentially from flower petals, leaves, fruit, vegetables, algae, in their entirety or in pieces, and mixtures thereof.
  • Plant fragments are chosen, for example, from Aloe vera, fruit such as those of Cucurbitaceae such as marrow, fruit skins such as tomato skin, banana skin, mango skin, peach skin, cucumber, flower petals such as rose petals, envelopes such as coffee grain envelopes and leaves such as lettuce leaves or mint leaves.
  • the fragments of one or more plants are chosen from fragments of calendula such as marigold, Lamiaceae such as lavender, Rosaceae such as rose, in particular damask rose, Asteraceae such as cornflower or jasmine, Mimosaceae such as prosopis, Centaureae, helichrysum, crocuses such as Crocus sativus, amaranth, camomile or peony, and mixtures thereof.
  • the plant fragments according to the invention may be chosen from the leaves, flowers and petals of peony, marigold, lavender, damask rose, cornflower, jasmine, prosopis, and white and/or pink helichrysum.
  • the substrate according to the invention may also directly comprise in its structure at least one cosmetic additive chosen in particular from: active agents, notably anticellulite, antiwrinkle, tanning, self-tanning, lightening, astringent, emollient, exfoliant, moisturizing, revitalizing or skin-protecting agents, fragrances, essential oils, surfactants, biosurfactants; colouring active agents and/or dyestuffs that are “activatable” in liquid medium, notably in solvent medium, such as aqueous medium; ingredients that are sensitive to moisture or sensitive in liquid medium, active agents that are unstable in aqueous medium, such as active agents that are sensitive to hydrolysis; active agents that are sensitive to acidic or basic pH; enzymes such as lipases, proteases, notably papain; phycocyanins such as spirulina, carotenoids, such as a-carotene and -carotene, vitamins such as vitamins A, D, E and K, riboflavin, pantothenic
  • the substrate according to the invention contains less than 0.5% by weight, relative to the total weight of the substrate, preferably less than 0.2%, preferably less than 0.1% and preferably is free of at least one ingredient chosen from, and preferably is free of any ingredient chosen from: physical or chemical crosslinking agent, pH- regulating or pH-adjusting compound, basic compound, in particular with a pH in the range from 8 to 12, such as carbonate or bicarbonate, notably of calcium, sodium or potassium, NaOH, NH4OH, preserving agent, chelating agent, such as EDTA, polymer of synthetic origin, such as acrylic polymer, notably superabsorbent, Carbomer®, silicone, and mixtures thereof.
  • the cosmetic substrate of the invention in solid and dry (anhydrous) form, proves to be particularly suitable for containing and protecting certain compounds that are only able to reveal their effect once the substrate has been placed in contact or impregnated with a suitable solvent medium, notably an aqueous medium.
  • a suitable solvent medium notably an aqueous medium.
  • These compounds, which are said to be “activatable” in or “sensitive” to a specific solvent medium may be, for example, active agents (hydrophilic or lipophilic), in particular hydrophilic active agents (which are sensitive or activatable in the presence of water), or alternatively certain pigments or dyes which only manifest their colouring effect when they are in the presence of a specific solvent medium.
  • the substrate of the invention also makes it possible to exploit certain compounds, which are capable of affording advantageous properties, notably in terms of makeup effect and/or care effect, when they are used in or in contact with a certain solvent medium. They are generally referred to as compounds that are “sensitive” or “activatable” in a given solvent medium.
  • the substrate according to the invention may prove to be advantageous with regard to the use, in its anhydrous structure, of hydrophilic active agents that are unstable in solvent medium.
  • a hydrophilic active agent that may be used according to the invention may more particularly be a water-soluble or water-dispersible molecule, having cosmetic or dermatological activity.
  • - free-radical scavengers and/or detoxifying agents such as ascorbic acid and derivatives thereof such as ascorbyl glucoside, also known as vitamin Cg, magnesium ascorbyl phosphate, cysteine derivatives, for instance N-acetylcysteine, proteins and enzymes, for example superoxide dismutase (SOD), peroxidases such as lactoperoxidase and lactoferrin, catalase, proteases such as subtilisin and papain, lipases, uricase, peptides and derivatives thereof, ubiquinone and cytochrome C,
  • SOD superoxide dismutase
  • - keratolytic agents such as a-hydroxy acids and a-keto acids, for instance salicylic acid and derivatives thereof, such as n-octanoyl-5-salicylic acid,
  • - tanning accelerators such as tyrosine derivatives
  • UV-screening agents such as screening agents bearing a sulfonic acid function, in particular 2-phenylbenzimidazole-5-sulfonic acid, sulisobenzone and benzene- 1 ,4-bis(3-methylidene-10-camphorsulfonic acid),
  • moisturizers such as sorbitol, xylitol, urea and plant DNA
  • optical brighteners such as stilbene derivatives and dyes such as the sodium salts of tartrazine,
  • unstable cosmetic or dermatological hydrophilic active principles include ascorbic acid and salts thereof, in particular the sodium, potassium, magnesium or calcium salts.
  • a C-glycoside derivative may make it possible to give a substrate according to the invention anti-ageing care properties, notably by exerting a skin-moisturizing and wrinkle-filling effect for a prolonged period over time.
  • a C-glycoside derivative that is suitable for use in the invention may notably be obtained via the synthetic method described in WO 02/051 828.
  • the salts of the C-glycoside derivatives that are suitable for use in the invention may comprise conventional physiologically acceptable salts of these compounds, such as those formed from organic or mineral acids. They may be linear, branched or cyclic aliphatic acids, or alternatively aromatic acids. These acids may also include one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups. Mention may notably be made of propionic acid, citric acid, tartaric acid, aspartic acid and glutamic acid.
  • a C-glycoside derivative that is suitable for use in the invention may notably be hydroxypropyltetrahydropyrantriol, also known as C-p-D-xylopyranoside-2- hydroxypropane, sold notably as a solution at 30% by weight in a 60/40 (v/v) water/propylene glycol mixture under the trade name Mexoryl SBB®.
  • HEPES or 4-(2-hydroxyethyl)piperazin-1 -ethanesulfonic acid is advantageously used as a desquamating agent. It exerts its effect notably by acting on the enzymes involved in desquamation or the degradation of corneodesmosomes, such as glycosidases or “stratum corneum chymotryptic enzyme” (SCCE). hydroxyalkylurea derivatives and also salts thereof and isomers thereof
  • hydroxyalkylurea derivatives that are suitable for use in the invention, mention may be made of N-(2-hydroxyethyl)urea; N-(2-hydroxypropyl)urea; N-(3-hydroxypropyl)urea; N-(2,3-dihydroxypropyl)urea; N-(2,3,4,5,6-pentahydroxyhexyl)urea;
  • N-methyl-N-(1,3,4,5,6-pentahydroxy-2-hexyl)urea N-methyl-N’-(1-hydroxy-2-methyl-2- propyl)urea; N-(1-hydroxy-2-methyl-2-propyl)urea; N-(1 ,3-dihydroxy-2-propyl)urea;
  • N,N-bis(2-hydroxypropyl)urea N,N’-bis(2-hydroxypropyl)urea
  • N,N-bis(2-hydroxyethyl)-N’-propylurea N,N-bis(2-hydroxypropyl)-N’-(2- hydroxyethyl)urea; N-tert-butyl-N’-(2-(hydroxyethyl)-N’-(2-(hydroxypropyl)urea; N-(1 ,3- dihydroxy-2-propyl)-N’-(2-hydroxyethyl)urea; N,N-bis(2-hydroxyethyl)-N’,N’- dimethylurea; N,N,N’,N’-tetrakis(2-hydroxyethyl)urea; N’,N’-bis(2-hydroxyethyl)-N’,N’- bis(2-hydroxypropyl)urea; and mixtures thereof.
  • the hydroxyalkylurea derivative is N-(2-hydroxyethyl)urea.
  • N-(2-hydroxyethyl)urea is also commercially available, in the form of a mixture at 50% by weight in water, from the company National Starch under the trade name Hydrovance.
  • hydrophilic salicylic acid derivatives notably n-octanoyl-5-salicylic acid.
  • Antiwrinkle active agents are also described in DE-A-2 703 185.
  • N-(2-hydroxyethyl)urea is also commercially available, in the form of a mixture at 50% by weight in water, from the company National Starch under the trade name Hydrovance.
  • hydrophilic salicylic acid derivatives notably n-octanoyl-5-salicylic acid.
  • Antiwrinkle active agents notably n-octanoyl-5-salicylic acid.
  • the substrate according to the invention may prove to be most particularly advantageous for the implementation of anti-wrinkle active agents, notably the C-glycoside derivatives as described previously, or adenosine or non-phosphate derivatives thereof.
  • Adenosine is an active agent that is known for its anti-wrinkle activity, and is more particularly advantageous in the targeting of deep wrinkles. It is available in powder form, and may advantageously be formulated in solid compositions of compact powder type or “two-way cakes”.
  • Adenosine has the particular feature of swelling when it is placed in contact with water.
  • the substrate of the invention advantageously allows, for example if it comprises adenosine or a derivative thereof, on being moistened beforehand, the contact of this anti-wrinkle active agent extemporaneously, with water, thus allowing its activation during the application of the substrate to the skin, and leading to efficient filling of the wrinkles.
  • anti-wrinkle active agents may be used according to the invention.
  • Such an agent may be, for example, retinol, nicotinic acid and/or ubiquinone, or even other salicylic acid derivatives, such as n-octanoyl-5-salicylic acid.
  • the dry substrate of the invention may allow the implementation of dyestuffs that are “sensitive” in or “activatable” with a specific solvent medium.
  • activatable dyestuffs is intended, for example, to denote dyestuffs that can be activated to develop a certain colour, by placing them in contact with a specific solvent medium.
  • the colouring effect of the dyestuffs is not perceptible in the anhydrous dry substrate.
  • the substrate may notably have any shade in its packaging, for example white or grey, or any other colour associated with the colour of the other compounds present in its solid composition.
  • the substrate When these dyestuffs are placed in contact with said solvent medium, dispersed and/or dissolved in this solvent medium, during the implementation of the cosmetic process using the substrate according to the invention, the substrate, once applied to the skin, reveals a colour, different from the colour which it had in its packaging before activation of the dyestuffs. This new colour advantageously matches the natural shade of the skin.
  • This activation of the dyestuffs may also partly be exacerbated, for example by mechanical pressure exerted by the applicator at the time of application of the substrate to the keratin material, or by pH or temperature variations arising during the application of the composition to the skin.
  • These dyestuffs may be chosen from water-soluble or water-insoluble organic or mineral pigments.
  • DPPs diketopyrrolopyrroles
  • mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders, for instance aluminium powder and copper powder.
  • the pigment is chosen from iron oxides, titanium oxide, ultramarine blue, and mixtures thereof.
  • the pigments may have a size ranging from 35 to 200 pm and in particular from 40 to 100 pm. Pigments that are suitable for use in the invention may also have a size ranging from 0.05 to 34 pm, preferably from 0.1 to 25 pm, more particularly from 1 to 25 pm and preferably from 1 to 15 pm in diameter.
  • the dyestuffs that are “activatable” with a specific solvent medium may be treated so as to give them sensitivity to said solvent medium.
  • This treatment is generally a specific coating for making them soluble or dispersible in this solvent medium.
  • the dyestuffs may be totally or partially surface-treated with a hydrophobic agent, to facilitate their dispersion in an oily solvent medium.
  • the sensitive or activatable dyestuffs may represent from 0.1% to 50%, preferably from 1 % to 25% and more preferentially from 5% to 20% by weight relative to the total weight of the dry substrate according to the invention.
  • the dry substrate according to the invention may comprise at least one dye.
  • the dye may be hydrophilic or lipophilic.
  • the hydrophilic or lipophilic dye(s) may represent from 0.001% to 10%, preferably from 0.05% to 5% or even from 0.01% to 1% by weight relative to the total weight of dry substrate according to the invention.
  • the present invention is not at all limited to the embodiment variants described previously, but may implement any other may be termed “sensitive” to a specific solvent medium, in as much as they need to be placed in contact with a specific solvent medium, dispersed and/or dissolved in said solvent in order to be able to exploit them in terms of a colour effect.
  • the nature of the solvent medium will be adapted to the nature of the dyestuff used and in particular to its hydrophilic/hydrophobic coating, and in particular so as to promote the revelation of its colour effect.
  • the structure of the substrate according to the invention is advantageously obtained by cold dehydration (i.e. without heating), notably by freeze-drying, of a hydrogel formed by aqueous dispersion, for example of a powder, of said polysaccharides P1 , P2, each of said polysaccharides respectively representing a weight content within the range from 0.1% to 5%, preferably from 0.25% to 2%, preferably from 0.5% to 1.5%, preferably from 0.75% to 1.25%, relative to the total weight of the aqueous dispersion (P1+P2+water).
  • the aqueous phase used for dispersing the polysaccharides and for forming a polysaccharide gel preferably comprises at least 65% water, preferably from 70% to 100% water, preferably from 80% to 100% water, preferably from 90% to 100%, relative to the total weight of aqueous phase.
  • the water used may be sterile demineralized water and/or a floral water such as rose water, cornflower water, camomile water or lime blossom water, and/or a natural spring water or mineral water, for instance: Vittel water, Vichy basin water, Uriage water, Roche Posay water, Bourboule water, Enghien-les-Bains water, Saint Gervais-les- Bains water, Neris-les-Bains water, Allevar-les-Bains water, Digne water, Maizieres water, Neyrac-les-Bains water, Lons-le-Saunier water, Eaux Bonnes water, Rochefort water, Saint Christau water, Fumades water, Tercis-les-bains water and Avene water.
  • the aqueous phase may also comprise reconstituted spring water, i.e. a water containing trace elements such as zinc, copper, magnesium, etc., reconstituting the characteristics of a spring water.
  • the aqueous phase may also contain hydrophilic adjuvants, among which are polyols, such as glycerol; propanediol; glycols such as pentylene glycol, propylene glycol, butylene glycol, isoprene glycol, and polyethylene glycols such as PEG-8; sorbitol; sugars such as glucose, fructose, maltose, lactose and sucrose; and mixtures thereof.
  • polyols such as glycerol
  • propanediol glycols such as pentylene glycol, propylene glycol, butylene glycol, isoprene glycol, and polyethylene glycols such as PEG-8
  • sorbitol sugars such as glucose, fructose, maltose, lactose and sucrose
  • sugars such as glucose, fructose, maltose, lactose and sucrose
  • Said polyol of the aqueous phase is water-miscible at room temperature (25°C) and may notably be chosen from polyols notably containing from 2 to 20 carbon atoms, preferably containing from 2 to 10 carbon atoms and preferentially containing from 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol.
  • polyols notably containing from 2 to 20 carbon atoms, preferably containing from 2 to 10 carbon atoms and preferentially containing from 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol.
  • the polyol that is water- miscible at room temperature may represent in the aqueous phase a content ranging from 0.1 % to 35% by weight, relative to the total weight of the composition, preferably ranging from 0.3% to 10% by weight, relative to the total weight of the aqueous phase.
  • the aqueous phase may optionally also comprise a monoalcohol containing from 2 to 6 carbon atoms such as ethanol or isopropanol, notably in a content ranging from 0.01% to 10% by weight, relative to the total weight of aqueous phase, and preferably ranging from 1% to 7% by weight, relative to the total weight of the aqueous phase.
  • the aqueous phase used for the manufacture of the non-crosslinked polysaccharide gel does not contain any monoalcohol.
  • the aqueous phase may optionally also contain one (or more) water- soluble or water-insoluble cosmetic additive in suspension, as described above.
  • the aqueous phase is homogenized at room temperature, preferably at a temperature within the range from 20 to 25°C, preferably at 25°C, to form a polysaccharide gel or hydrogel, said gel not being crosslinked, since this process does not use any crosslinking agent or any heating.
  • the hydrogel thus obtained is preferably frozen, preferably at a temperature of between -100°C and 0°C, preferably between -80 and 0°C (limits exclusive), and preferably within the range from -80°C to -0.01 °C (limits inclusive here), preferably from -60°C to -4°C.
  • the non-crosslinked polysaccharide hydrogel thus frozen is then dehydrated, preferably under vacuum, preferably at a pressure within the range from 1 Pa to 615 Pa, preferably by sublimation, notably by freeze-drying or else by zeodration, preferably by freeze-drying.
  • the process for manufacturing the substrate according to the invention may also comprise at least one step of shaping, notably by moulding, preferably using at least one of the following processes: filling a mould, compressing, extruding, injecting, chopping, milling, grinding, rolling, stripping from the mould, and mixtures of these processes; said shaping step preferably taking place before or after a dehydration step, such as freeze-drying.
  • the dry cosmetic substrate of the invention is thus obtained, without heating, without crosslinking, without requiring a strong base or an alkaline medium, and has a multicellular alveolar or multilayer microscopic structure, in which the open or closed cells or alvaeoli have a uniform size, forming a cohesive porous substrate of natural origin based on polysaccharides, which is a biomimetic of the cell wall of plants.
  • This characteristic structure is the consequence of the following steps: a combination of specific polysaccharides, mild conditions of mixing (it is not necessary to heat) of these polysaccharides in an aqueous phase for the formation of a non-crosslinked gel, cooling, notably freezing, at ambient pressure followed by vacuum dehydration of the polysaccharide gel, preferably by sublimation.
  • Said cooling (or freezing) of the non-crosslinked polysaccharide gel, followed by drying (or desiccation) of said frozen polysaccharide gel, by sublimation preferably corresponds to a freeze-drying process.
  • the sublimed solvent is preferably essentially water, to more than 95% by weight relative to the weight of sublimed solvent. This freeze-drying may be performed according to conventional methods that are well known to those skilled in the art.
  • zeodration dehydration using zeolites
  • This technique is based on the use of vacuum, with an input of energy, to extract the water more rapidly from the gel in order to dehydrate it.
  • a refrigeration system is not necessary since the water vapours are captured by the zeolites.
  • a step of cooling, or even of freezing is preferably applied to the hydrogel, preferably before the zeodration.
  • This substrate has the advantage of being both:
  • the process for manufacturing a substrate according to the present invention is characterized in that it comprises the following steps:
  • hydrogel comprising said at least two polysaccharides P1 and P2, and optionally at least one water-soluble or water-insoluble cosmetic additive in suspension
  • - freezing the hydrogel preferably at a temperature in the range from -80°C to -0.01 °C, preferably from -60°C to -4°C,
  • dry substrate means an anhydrous substrate, whose residual humidity, i.e. water content, is less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%, and most particularly preferably is less than 1.5%, preferably less than 1%, preferably less than 0.7% by weight of water relative to the total weight of the substrate.
  • composition of the gel and thus also of the dry substrate, to also contain a freeze-drying additive notably to facilitate the freeze-drying via the texturing of the non-crosslinked polysaccharide gel, but also the rehydration of the freeze-dried form (of the dry substrate), notably when the substrate is impregnated.
  • a freeze-drying additive notably to facilitate the freeze-drying via the texturing of the non-crosslinked polysaccharide gel, but also the rehydration of the freeze-dried form (of the dry substrate), notably when the substrate is impregnated.
  • freeze-drying additives examples include silica and derivatives thereof, clays, and also polymers of natural origin, xanthans, locust bean gum, guar gums, pectins, agar-agar, polymers of bacterial origin such as hyaluronic acid, dextran, gellan, which are particularly preferred as optional polysaccharides additional to the oligosaccharides P1 and P2, notably for this role as freeze-drying additive, if they are not already included in P1 , P2.
  • the substrate according to the invention is advantageously free of physical or chemical crosslinking agent, of pH- regulating or pH-adjusting compound, notably of basic compound with a pH of between 8 and 12, or even between 9 and 12, such as carbonate, notably carbonate or bicarbonate, notably of calcium, sodium or potassium, NaOH, NH4OH, and mixtures thereof.
  • pH- regulating or pH-adjusting compound notably of basic compound with a pH of between 8 and 12, or even between 9 and 12
  • carbonate notably carbonate or bicarbonate, notably of calcium, sodium or potassium, NaOH, NH4OH, and mixtures thereof.
  • this substrate also has the capacity for being multifunctional.
  • cosmetic additives such as cosmetic active agents, notably active agents that are unstable in a conventional cosmetic formulation, for example: p-carotene, vitamin C or spirulina, which are then delivered, for example by moistening the substrate and/or applying the substrate to the skin.
  • Said substrate according to the invention also has the capacity for dyeing hair or making up the skin with active agents, preferably natural active agents, added during the preparation of the substrate directly into the aqueous phase, before, notably during or after the formation of the gel described previously.
  • polysaccharide-based means, for the dry substrate of the invention, a total polysaccharide content of at least 55% by weight, preferably within the range from 55% to 100% by weight, relative to the total weight of dry substrate.
  • said polysaccharides P1 , P2 represent in total, in the composition of the dry substrate according to the invention, a content within the range from 60% to 100% by weight, relative to the total weight of the dry substrate, preferably from 65% to 100% by weight and better still from 70% to 100% by weight, or even 100% by weight, relative to the total weight of dry substrate representing 100%.
  • the final dry substrate composition may have a weight content of from 0 to 45% of additives, relative to the weight of dry substrate.
  • additives as a function of the type of drying used, in particular in the case of freezing, it may also prove advantageous to add a cryoprotective agent directed towards protecting the structure of the gel and then that of the dry substrate obtained.
  • composition of the substrate according to the invention may thus comprise at least one cryoprotective agent that is compatible with cosmetic use, preferably chosen from: inositol, mannitol, glucose, sucrose, trehalose, maltose, xylitol, polyhydric alcohols, notably glycols or glycerol; amino acids, oligopeptides, cysteine, ascorbates, and mixtures thereof.
  • cryoprotective agent that is compatible with cosmetic use, preferably chosen from: inositol, mannitol, glucose, sucrose, trehalose, maltose, xylitol, polyhydric alcohols, notably glycols or glycerol; amino acids, oligopeptides, cysteine, ascorbates, and mixtures thereof.
  • the substrate according to the invention comprises at least one cosmetic additive chosen from active agents, notably anti-cellulite, anti- wrinkle, tanning, self-tanning, astringent, emollient, exfoliant, moisturizing, lightening, revitalizing and skin-protecting agents, fragrances, essential oils, surfactants, biosurfactants, and mixtures thereof.
  • active agents notably anti-cellulite, anti- wrinkle, tanning, self-tanning, astringent, emollient, exfoliant, moisturizing, lightening, revitalizing and skin-protecting agents, fragrances, essential oils, surfactants, biosurfactants, and mixtures thereof.
  • the substrate according to the invention comprises in its structure an active agent and/or a dyestuff that is “activatable” in liquid medium, notably in solvent medium, such as aqueous medium, at least one ingredient that is sensitive in liquid medium, notably chosen from active agents that are unstable in aqueous medium (hydrolysable), lycopenes, ⁇ -carotene, soapworts, notably obtained from plants, from dry nuts or from ivy, and mixtures thereof.
  • solvent medium such as aqueous medium
  • lycopenes e.g., ⁇ -carotene
  • soapworts notably obtained from plants, from dry nuts or from ivy, and mixtures thereof.
  • the dry substrate according to the invention does not require, and is thus advantageously free of, at least one of the following ingredients: preserving agent, chelating agent, such as EDTA, polymer of synthetic origin, such as acrylic polymer, notably superabsorbent, Carbomer®, silicone, and mixtures thereof.
  • preserving agent such as EDTA
  • chelating agent such as EDTA
  • polymer of synthetic origin such as acrylic polymer, notably superabsorbent, Carbomer®, silicone, and mixtures thereof.
  • the substrate of the invention advantageously provides a method for conserving active agents without an added preserving agent.
  • the active agents are, for example, stabilized directly in the structure of the substrate, or alternatively in the cellulose matrix of plant part(s) in the case where P1 , P2 are provided by plant byproducts.
  • the substrate according to the invention is, for example, in the form of a wipe, a sheet, a roll, a membrane, a mask, a disc, a pad, a cushion, a wad, solid or hollow beads, capsules, optionally encapsulating at least one cosmetic compound, pearls, pellets, a tablet, a sphere, a half-sphere, a cone, a pyramid, a core, a sponge or a foam, optionally comprising a textured surface, notably textured with undulations, inscriptions, pins, stepped angles, nesting volumes, and mixtures thereof; optionally comprising one or more parts that are detachable or splittable, respectively, as individual part(s), for example as single-dose squares, notably for single use; or having a form that is readily cuttable as a function of the amount of substrate desired for each respective single use.
  • This type of dry substrate and of dry presentation form, and notably of freeze-dried product has the advantage(s) of being “carry-around”, i.e. readily transportable since it is of very reduced bulk, light, dry, readily available, easy to use and not posing any difficulties and/or constraints as regards storage.
  • a subject of the present invention is also a cosmetic process for caring for, cleansing, removing makeup from and/or making up keratin materials, comprising at least one step consisting in applying a substrate according to the invention to the keratin materials, notably to the skin.
  • the process also comprises at least one step, prior to the step of application to the keratin materials, consisting in at least partially impregnating said substrate and/or in taking up with the aid of said substrate: water, a cosmetic composition and/or a fragrance.
  • the dry cosmetic substrates according to the invention may be used on all keratin materials such as the skin, the scalp, the hair, the eyelashes, the eyebrows, the nails or mucous membranes, notably in the form of a hygiene product, for example in the form of an article for cleansing the skin, mucous membranes and/or the hair or the beard, in particular in the form of an article for cleansing and/or removing makeup from the skin (of the face and/or the body), in the form of a mask or a patch, in the form of an exfoliant (also known as a desquamating or de-encrusting) wipe or pad or disc both for the face and for the body or for the hands, the exfoliant particles, as additives, preferably being already included within the structure of the dry substrate according to the invention.
  • a hygiene product for example in the form of an article for cleansing the skin, mucous membranes and/or the hair or the beard, in particular in the form of an article for cleansing and/or removing makeup from the skin (of the face
  • Another subject of the invention is a process for cleansing a keratin material, such as the skin, including the scalp, the hair, the eyelashes, the eyebrows, the nails or mucous membranes, comprising at least one step of applying a substrate as defined above to the keratin material and, where appropriate, at least one step of rinsing.
  • a keratin material such as the skin, including the scalp, the hair, the eyelashes, the eyebrows, the nails or mucous membranes
  • the gel composition to be freeze-dried is poured into a stainless-steel crystallizing dish (diameter 6.5 cm, height 2.2 cm) in a proportion of 30 g per crystallizing dish.
  • the whole is placed in a lyophilizer and a person skilled in the art sets the freeze-drying parameters in the tests below:
  • the final composition of the dry substrate is of the order of:
  • Tests Cp2 to Cp6 are comparative tests.
  • a crosslinked polysaccharide gel is manufactured with thermal physical and chemical crosslinking.
  • the medium is very viscous, the calcium carbonate, at room temperature, does not enable crosslinking.
  • Such a basic and/or thermal treatment leads to the formation of a non-cosmetic Pad, on account of insufficient sensory properties: rigid Pad, polystyrene noise, not soft, coarse.
  • Example 1 non-crosslinked Ex. 1 according to the present invention, is the only substrate obtained which, simultaneously:
  • This test is directed towards evaluating the cleansing power of the substrate on soiling formed from a mixture of charcoal particles and avocado oil, described in detail below, which is deposited on a skin model.
  • the cleansing efficacy is assessed by visual observation of the state of the skin and the state of the cotton wad or dry substrate of the invention. This efficacy is characterized on a performance scale ranging from “+++++”, i.e. the state of the skin observed is clean and perfectly decent, to “+”, i.e. the state of the skin is not clean and soiling is still observed.
  • An expert assesses whether the feel is more or less film-forming and if it has a moisturized effect (as opposed to a dehydrated effect) after the cleansing operation.
  • the scoring is performed 3 minutes after applying the product. This perception is noted on a scale from +++++ (moisturized feel) to - (dehydrated feel).
  • the Pad is more pleasant than the cotton wad, since it affords a filmforming effect and no dehydrating effect as obtained with the conventional commercial cotton wad.
  • Each line of the table corresponds to a different substrate evaluation, performed using one or more polysaccharides P1 and P2, for which it is pointed out, respectively, whether it is a homopolysaccharide (“O”) or a heteropolysaccharide (“E”), and whether its weight-average molecular mass is h/m/l, with h for high molecular weight: hMw > 1 MDa (in the table, noted as h) m for medium molecular weight: 1 kDa ⁇ mMw ⁇ 1 MDa (in the table, noted as m)
  • Cohesive substrate 0 (disintegrates totally) - 5 (cohesive substrate)
  • the substrates with a polysaccharide composition in accordance with the invention are, simultaneously, alveolar (3), flexible in dry form (score of at least 3), soft (at least 2), cohesive (at least 2) and film-forming (1) during or
  • Table 5 collates the average of the scores obtained for each substrate or Benchmark (commercial reference, referred to hereinbelow as “Bench”) with respect to each evaluated attribute.
  • the foaming power is less than that with the wipe but greater than that for all the other Benches.
  • the fresh effect is greater than that observed for the Benches, including Cotton wad + Aqua-source Biotherm in the case of Ex. 1 and 7.
  • the “skin-tensioning” effect is greater for the three types of Pads tested according to the invention, whether or not they are pressed.
  • the film-forming effect (protective or moisturizing) of the Pads of the invention comes just after that of the cotton wad + blue-jar Nivea cream in the case of Ex. 1 and 7, and is greater than that of the other cotton wad + water or wipe Benches for all the Pads according to the invention.
  • Examples Ex. 13 to Ex. 26 of Table 6 below contain, in addition to the polysaccharides P1 and P2, at least one additive indicated as P3.
  • the contents of each compound are indicated in dispersed form in water, as is the sum of the contents of P1 , P2, P3 in water, and the content of each compound in the final composition of the dry substrate.
  • the sensory evaluation parameters of the Pads remain very good and compatible with cosmetic use of the Pads: in all cases, the dry substrate is flexible, soft, remains cohesive when it is partially impregnated with water, and deposits a film with a comfortable, fresh and moisturizing effect.
  • the Pad is placed in 50 ml of TSB (stock solution: Trypticase soy broth)
  • the cotton wad is massaging and then left for 5 minutes
  • the stock solution is diluted tenfold in 9 ml of TSB (tenfold dilution) 2 x 0.5 ml of the stock solution and 2 x 0.5 ml of the tenfold dilution are deposited
  • TSA Trypticase soy agar
  • the stock solution is incubated at 32°C ⁇ 2°C for 24 hours (enrichment) and 0.5 ml is then subcultured and placed on TSA.
  • the sample controlled shows low contamination (level ⁇ 50 cfu/g) with an unspecified microorganism.
  • the Aw of the Pad of Ex. 1 is measured, in triplicate, bearing in mind that the Pad of Ex. 1 had been potentially handled several times (but not used) and stored in a hermetic box for six months before this Aw measurement.
  • the results are collated in Table 8 below.
  • a product may be considered as a medium that is not favourable for microbial growth if its Aw is less than or equal to 0.6.
  • condition unfavorable for microbial growth Microbiologically stable Pad
  • Aw > 0.6 condition favourable for microbial growth: antimicrobial protection of the Pad is to be envisaged (e.g. preserving agent).
  • the dry substrate of the invention does not require any preserving agent.
  • the Aloe vera leaves are obtained from the retail sector.
  • the gel is recovered from the leaf and then washed three times with distilled water (removal of sensitizing agents, for example aloin).
  • the mucilage of the gel is then ground coarsely with a hand mixer (Bosch MSM66110 ErgoMixx model, 600 W) until a fluid solution is obtained, and is then centrifuged at room temperature for 10 minutes at 10 000 rpm (Lynx 6000 model).
  • the Aloe vera gel is separated from the insoluble fibres and used as polysaccharide mixing water.
  • a dry extract of the gel obtained shows a concentration of dry compound of 1 % by weight, of which at least 50% of this dry extract is glucomannan with a weightaverage molecular mass of greater than 1000 g/mol (“m” or medium molecular weight).
  • composition to be freeze-dried is poured into a stainless-steel crystallizing dish (diameter 6.5 cm, height 2.2 cm) in a proportion of 30 g per crystallizing dish.
  • the whole is placed in a lyophilizer with the freeze-drying parameters set in the following manner: freezing temperature at -30°C, condenser temperature at -80°C, vacuum of about 0.025 mbar.
  • a pad about 5.8 cm in diameter and 1 cm thick with a weight of about 0.6 g is obtained.
  • the final composition of the substrate is of the order of:
  • the cohesion of the substrate obtained after freeze-drying is compatible with cosmetic use.
  • Comparative 31 shows that Aloe vera gel alone did not make it possible to obtain a cohesive substrate, notably when it is at least partially impregnated with water.
  • the substrates according to the invention made from byproducts and comprising a combination of polysaccharides in accordance with the invention, the flexibility, softness, cohesion and film-forming effect properties obtained make it compatible with the desired cosmetic use.
  • the lettuce leaves are obtained from a factory outlet (confidential contact).
  • the banana skins are obtained from retail bananas.
  • composition of the formulation before freeze-drying is a composition of the formulation before freeze-drying:
  • Food byproduct e.g. lettuce or banana 0.6%
  • the mixture is ground coarsely with a hand mixer (Bosch MSM66110 Ergomixx model, 600>) until a homogeneous dispersion which forms a hydrogel is obtained.
  • the composition to be freeze-dried is poured into a stainless-steel crystallizing dish (diameter 6.5 cm, height 2.2 cm) in a proportion of 30 g per crystallizing dish. The whole is placed in a lyophilizer and the freeze-drying parameters set: freezing temperature -30°C, vacuum of 0.025 mbar.
  • composition 1 A pad about 5.8 cm in diameter and 1 cm thick with a weight of about 0.6 g is obtained. After freeze-drying, the final composition is of the order of: Composition 1 :
  • Composition 2 is a composition of Composition 2:

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Abstract

La présente invention concerne un substrat cosmétique sec à base de polysaccharides, destiné au nettoyage, au démaquillage, au soin et/ou au maquillage de matières kératiniques, caractérisé en ce qu'il présente une structure microscopique alvéolaire formée par l'association non réticulée d'au moins deux polysaccharides spécifiques ; ainsi qu'un procédé cosmétique de soin, de nettoyage, de démaquillage et/ou de maquillage de matières kératiniques mettant en œuvre ce substrat.
PCT/EP2021/085209 2020-12-10 2021-12-10 Substrat cosmétique d'origine naturelle WO2022123016A1 (fr)

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US20200129416A1 (en) * 2018-10-29 2020-04-30 Tenart Biotech Limited Facial cleansing tissue with natural plant origin and preparation method thereof
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WO2002051828A2 (fr) 2000-12-22 2002-07-04 L'oreal Nouveau derives c-glycosides et utilisation
EP1892015A2 (fr) * 2006-08-10 2008-02-27 L'Oréal Film à dissolution améliorée et produit cosmétique le contenant
US20200129416A1 (en) * 2018-10-29 2020-04-30 Tenart Biotech Limited Facial cleansing tissue with natural plant origin and preparation method thereof
CN111514034A (zh) * 2020-05-27 2020-08-11 长沙蓝姿生物科技有限公司 一种具有保湿作用的卸妆干巾及其制备方法

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