COMPOSITION COMPRISING A POLYIONIC COMPLEX WITH LOW MOLECULAR WEIGHT CHITOSANS

Abstract

COMPOSITION COMPRISING A POLYIONIC COMPLEX WITH LOW MOLECULAR WEIGHT CHITOSANS The present invention relates to a composition comprising: (a) at least one cationic polymer; (b) at least one anionic polymer; (c) at least one non-polymeric acid having at least two pKa values ​​or salt(s) thereof; and (d) water, wherein (a) the cationic polymer is selected from chitosans of a molecular weight of 20,000 or less. The composition according to the present invention is stable and capable of forming a polyionic complex and exhibiting good spreadability during application and an improved texture such as reduced adhesion after application. Figure for abstract: none

Description

Description Title of the invention: COMPOSITION COMPRISING A POLYIONIC COMPLEX WITH BASIC CHITOSANS MOLECULAR WEIGHT Technical field

[0001] = The present invention relates to a composition comprising a po- complex lyoonic as well as a cosmetic process using the composition. PRIOR ART

[0002] = A polyionic polymer is already known, which can be in the form of a particle and may be formed with a cationic polymer and an anionic polymer.

[0003] For example, WO 2021 / 125069 discloses a composition that is useful for cosmetic treatments and comprises, in one embodiment, at least a polyionic complex particle comprising at least one cationic polymer, at least one anionic polymer based on hyaluronic acid and at least one non-ionic acid polymer having two or more pKa values. In the prior art disclosed in OT 2021 / 125069, poly-e-lysine is used as a cationic polymer. DISCLOSURE OF THE INVENTION

[0004] There is still a need for a stable composition that can form a complex polyionic and provide good spreadability during application and a improved texture such as reduced stickiness after application.

[0005] — Therefore, an object of the present invention is to provide a composition stable capable of forming a polyionic complex and offering good aptitude for spreading during application and improved texture such as adhesion reduced after application.

[0006] — The above objective of the present invention can be achieved by a composition, including:

[0007] (a) at least one cationic polymer;

[0008] (b) at least one anionic polymer;

[0009] = (c) at least one non-polymeric acid having two or more pKa values or salt(s) thereof;

[0010] (d) water,

[0011] = in which

[0012] the (a) cationic polymer is chosen from chitosans of a molecular weight less than or equal to 20,000.

[0013] — The quantity of the (a) cationic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition. The (e) anionic polymer may have at least one negatively chargeable and / or negatively charged moiety selected from the group consisting of a sulfuric group, a sulfate group, a sulfonic group, a sulfonate group, a phosphoric group, a phosphate group, a phosphonic group, a phosphonate group, a carboxylic group and a carboxylate group and preferably selected from a group consisting of a carboxylic group and a carboxylate group The (b) anionic polymer may be selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers, anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl sulfates), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polyfumaric acids, (co)polymers of maleic acids and their salts. The (b) anionic polymer may be chosen from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and a mixture thereof and, even better, hyaluronic acid and its salts, carboxymethylcellulose and its salts, and a mixture thereof. The amount of the (b) anionic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition. The (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof may be an organic acid or salts thereof, preferably a hydrophilic or water-soluble organic acid or salt(s) thereof and, more preferably, phytic acid or salts thereof, terephthalylidene dicamphor sulfonic acid or salts thereof, or a mixture thereof. The amount of (c) the non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight and, more preferably, from 0.01% to 1% by weight, based on the total weight of the composition. The amount (d) of water in the composition according to the present invention may be from 50% to 99% by weight, preferably from 60% to 98% by weight and, more preferably, from 70% to 97% by weight, relative to the total weight of the composition. The pH of the composition according to the present invention may be from 3 to 9, preferably from 3.5 to 8.5 and, more preferably, from 4 to 8. The composition according to the present invention may be a cosmetic composition, preferably, a cosmetic composition for the skin and even better, a cosmetic skin care composition. The present invention also relates to a cosmetic process for a keratinous substance such as skin, comprising: the application to the keratin substance of the composition according to the present invention and drying the composition to form a cosmetic film on the keratin substance. The present invention may also relate to a use of (a) at least one cationic polymer, wherein the (a) cationic polymer is selected from chitosans with a molecular weight of 20,000 or less, in a composition comprising: (b) at least one anionic polymer; (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; (d) water, in order to stabilize the composition and / or improve the spreading of the composition. The present invention may also relate to a film, preferably a cosmetic film, comprising: (a) at least one cationic polymer; (b) at least one anionic polymer and (c) at least one non-polymeric acid having two or more pKka values ​​or salt(s) thereof; in which the (a) cationic polymer is chosen from chitosans with a molecular weight less than or equal to 20,000. The present invention may also relate to a use of (a) at least one cationic polymer, wherein the (a) cationic polymer is selected from chitosans with a molecular weight of 20,000 or less, in a film including: (b) at least one anionic polymer and (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; in order to improve the texture of the film, preferably to improve the feeling of hydration, softness and flexibility provided by the film and / or to reduce the stickiness of the film, and more preferably to reduce the stickiness of the film. Best mode for carrying out the invention After careful research, the inventors discovered that it is possible to provide a stable composition capable of forming a polyionic complex and providing good spreadability during application and improved texture such as reduced adhesion after application. Thus, the composition according to the present invention comprises: (a) at least one cationic polymer; (b) at least one anionic polymer; (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; (d) water, in which the (a) cationic polymer is chosen from chitosans with a molecular weight less than or equal to 20,000. The composition according to the present invention is stable and capable of forming a polyionic complex and providing good spreadability during application and improved texture such as reduced adhesion after application. The composition according to the present invention is stable so that it can be homogeneous after its preparation. The composition according to the present invention can form a polyionic complex with the (a) cationic polymer and the (b) anionic polymer, as well as (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof, which can form a polyionic complex, can integrate to form a continuous film. The polyionic complex can take the form of a particle. The composition according to the present invention can have good spreadability during application. Therefore, the composition according to the present invention can be easily spread during application on, for example, a keratinous substance such as skin. The composition according to the present invention can provide an improved texture such as reduced stickiness, improved moisturizing sensation, increased softness and improved flexibility, after application. Improvements in adhesion, moisturizing feel, softness and flexibility, after application, can be provided by a film formed by the composition according to the present invention. The composition, method and other properties according to the present invention will be described in more detail below. [Composition] (Cationic polymer) The composition according to the present invention may comprise (a) at least one cationic polymer. There is no limit on the type of the (a) cationic polymer. Two or more different types of cationic polymers may be used in combination. Thus, a single type of cationic polymer or a combination of different types of cationic polymers may be used. A cationic polymer has a positive charge density. The charge density of the (a) cationic polymer may be between 0.01 meq / g and 20 meq / g, preferably between 0.05 and 15 meq / g and, more preferably, between 0.1 and 10 meg / g. The (a) cationic polymer is selected from chitosans with a molecular weight of 20,000 or less, preferably 10,000 or less and, more preferably, 7,000 or less. Unless otherwise indicated in the descriptions, "molecular weight" means average molecular weight. It may be preferable that the molecular weight of the (a) cationic polymer is equal to or greater than 1,000, preferably equal to or greater than 1,200, more preferably equal to or greater than 3,000, and even more preferably equal to or greater than 1,500. Chitosans include chitosan, chitosan salts such as chitosan hydrochloride, and chitosan glycosides. It is preferable that the (a) cationic polymer is chitosan with a molecular weight of 20,000 or less. Chitosan is well known. Chitosan can be a linear polysaccharide composed of D-glucosamine randomly linked to B-(1—4) (deacetylated unit) and N-acetyl-D-glucosamine (acetylated unit). The degree of actylation of chitosan may be greater than 3% to less than 10%, preferably 3% to 8% and more preferably 3% to 5%. Chitosan can be prepared, for example, by treating the chitin shells of shrimp and other crustaceans with an alkaline substance, such as sodium hydroxide. However, it is preferable for chitosan to be derived from fungi such as Aspergillus niger, as chitosan derived from fungi may be free of any allergens. Therefore, it may be preferable for chitosan to be derived from the fungus. The amount of the (a) cationic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more and, more preferably, 0.1% by weight or more, relative to the total weight of the composition. The amount of the (a) cationic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and, more preferably, 5% by weight or less, relative to the total weight of the composition. The amount of the (a) cationic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition. (Anionic polymer) The composition according to the present invention may include (b) at least one anionic polymer. The type of (b) anionic polymer is not limited. Two or more different types of anionic polymers can be used in combination. Thus, a single type of anionic polymer or a combination of different types of anionic polymers can be used. The anionic polymer(s) can form a po- 1yionic complex(es) with the cationic polymer(s). An anionic polymer has a positive charge density. The charge density of the (b) anionic polymer may be 0.1 meg / g to 20 meg / g, preferably 1 to 15 meq / g and more preferably 4 to 10 meq / g if the (b) anionic polymer is a synthetic anionic polymer, and the average degree of substitution of the (b) anionic polymer may be 0.1 to 3.0, preferably 0.2 to 2.7 and more preferably 0.3 to 2.5 if the (b) anionic polymer is a natural anionic polymer. It may be preferable that the molecular weight of the anionic polymer is greater than or equal to 300, preferably greater than or equal to 1,000, more preferably equal to or greater than 5,000, even more preferably greater than or equal to 10,000, even more preferably greater than or equal to 50,000, and even more preferably greater than or equal to 1,000,000 or more. Unless otherwise indicated in the descriptions, "molecular weight" means weight average molecular mass. The (e) anionic polymer may have at least one negatively chargeable and / or negatively charged moiety selected from the group consisting of a sulfuric group, a sulfate group, a sulfonic group, a sulfonate group, a phosphoric group, a phosphate group, a phosphonic group, a phosphonate group, a carboxylic group and a carboxylate group and preferably selected from a group consisting of a carboxylic group and a carboxylate group The (b) anionic polymer may be a homopolymer or a copolymer. The term "copolymer" includes both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers. The (b) anionic polymer may be selected from natural and synthetic anionic polymers. The (b) anionic polymer may comprise at least one hydrophobic chain. The anionic polymer, which may comprise at least one hydrophobic chain, may Be obtained by copolymerization of a monomer (a) selected from carboxylic acids comprising β,β-ethylenic unsaturation (monomer a') and a 2-acrylamido-2-methylpropanesulfonic acid (monomer a") with a non-surface-active monomer (b) comprising ethyl unsaturation other than (a) and / or a monomer (c) comprising ethyl unsaturation resulting from the reaction of an acrylic monomer comprising β,β-monoethylenic unsaturation or a monomer comprising monoethylenic unsaturation with a non-ionic amphiphilic monohydric component or with a primary or secondary amine. Thus, the anionic polymer with at least one hydrophobic chain can be obtained by two synthetic routes: - either by copolymerization of the monomers (a) and (c), or (a'), (b) and (c), or (a”) and (c), or (a""), (b) and (c), - either by modification (and in particular by esterification or amidation) of a copolymer formed from the monomers (a') or the monomers (a"") and (b), or (a) and (b), by an amphiphilic non-ionic monohydric compound or a primary or secondary fatty amine. Mention may in particular be made, as copolymers of 2-acrylamido-2-methylpropanesulfonic acid, of those mentioned in the article "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer as studied by fluorescence and dynamic light scattering — Macromolecules, 2000, Vol. 33, No. 10 — 3694-3704" and in applications EP-A-0 750 899 and EP-A-1 069 172. The carboxylic acid comprising an α,3-monoethylenic unsaturation constituting the monomer (a') can be chosen from numerous acids and, in particular, acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. Preferably it is acrylic or methacrylic acid. The copolymer may comprise a (b) monomer comprising monoethylenic unsaturation which has no surfactant property. Preferred monomers are those which give water-insoluble polymers when homopolymerized. They may be chosen, for example, from C,-C, alkyl acrylates and methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. The most preferred monomers are methyl acrylate and ethyl acrylate. Other monomers which may be used are, for example, styrene, vinyltoluene, vinyl acetate, acrylonitrile and vinylidene chloride. Unreactive monomers are preferred, these monomers being those in which the single ethylenic group is the only reactive group under the polymerization conditions.However, monomers that include groups that react under heat, such as hydroxyethyl acrylate, can be used in . option. Monomer (c) is obtained by reacting an acrylic monomer comprising α,β-monoethylenic unsaturation, such as (a), or an isocyanate monomer comprising monoethylenic unsaturation with a non-ionic monohydric amphiphilic compound or a primary or secondary fatty amine. Nonionic monohydric amphiphilic compounds or primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. Nonionic monohydric amphiphilic compounds are generally alkoxylated hydrophobic compounds comprising an alkylene oxide forming the hydrophilic portion of the molecule. Hydrophobic compounds are generally composed of an aliphatic alcohol or an alkylphenol, in which compounds a carbon chain comprising at least six carbon atoms constitutes the hydrophobic portion of the amphiphilic compound. Preferred nonionic monohydric amphiphilic compounds are compounds having the following formula (V): R-(OCH,CHR').-(OCH-CH:»),-OH (V) wherein R is selected from alkyl or alkylene groups comprising from 6 to 30 carbon atoms and alkylaryl groups having alkyl radicals comprising from 8 to 30 carbon atoms, R' is selected from alkyl groups comprising from 1 to 4 carbon atoms, n is an average number ranging from about 1 to 150 and m is an average number ranging from about 0 to 50, provided that n is at least as large as m. Preferably, in the compounds of formula (V), the group R is chosen from alkyl groups comprising from 12 to 26 carbon atoms and alkylphenyl groups in which the alkyl group is C;-C;3; the group R' is the methyl group; m=0 and n=1a25. Preferred primary and secondary fatty amines are composed of one or two alkyl chains comprising from 6 to 30 carbon atoms. The monomer used to form the non-ionic urethane monomer (c) may be chosen from a wide variety of compounds. Any compound comprising a copolymerizable unsaturation, such as an acrylic, methacrylic or allyl unsaturation, may be used. The monomer (c) may be obtained in particular from an isocyanate comprising a monoethylenic unsaturation such as, in particular, α,α-dimethyl-m-isopropenylbenzyl isocyanate. The monomer (c) may be chosen, in particular, from acrylates, methacrylates or itaconates of oxyethylated alcohol (1 to 50 EO) Cg-Cxy, such as steareth-20 methacrylate, oxyethylated behenyl methacrylate (25 EO), oxyethylenic monocetyl itaconate (20 EO), oxyethylethylated monostearyl itaconate (20 EO) or acrylate modified with polyoxyethylenic alcohols (25 EO) C12-C24 and among the dimethyl-m-isopropenylbenzyl isocyanates of ethyl alcohol (1 to 50 EO) C; -C3,, such as, in particular, dimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenyl alcohol. According to a specific embodiment of the present invention, the anionic polymer is selected from acrylic terpolymers obtained from (a) a carboxylic acid comprising œ,B-ethylenic unsaturation, (b) a non-surface-active monomer comprising ethylenic unsaturation other than (a), and (c) a non-ionic urethane monomer which is the reaction product of a non-ionic monohydric amphiphilic compound with an isocyanate comprising monoethylenic unsaturation. Mention may in particular be made, as anionic polymers comprising at least one hydrophobic chain of the following compounds: acrylic acid / ethyl acrylate / alkyl acrylate terpolymer, such as the product in the form of a 30% aqueous dispersion marketed under the name Acusol 823 by Rohm & Haas; acrylate / steareth-20 methacrylate copolymer, such as the product marketed under the name Aculyn 22 by Rohm & Haas; (meth)acrylic acid / ethyl acrylate / oxyethylenated behenyl methacrylate (25 EO) terpopolymer, such as the product in the form of an aqueous emulsion marketed under the name Aculyn-28 by Rohm & Haas; acrylic acid / monocetyl oxyethylenated itaconate (20 EO) copolymer, such as the 30% aqueous dispersion product marketed as Structure 3001 by National Starch;acrylic acid / oxyethylenated monostearyl itaconate (20°EO) copolymer, such as the product in the form of a 30% aqueous dispersion marketed under the name Structure 2001 by National Starch; acrylates / acrylate modified with polyoxyethylated (25 EO) C,>-C,, alcohol copolymer, such as the 30-32% copolymer latex marketed under the name Synthalen W2000 by 3V SA; or methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol dimethyl-isopropenylbenzyl isocyanate terpolymer, such as the product in the form of a 24% aqueous dispersion and comprising 40 ethylene oxide groups disclosed in EP-A-0 173 109.; Anionic (e)polymers may also be Polyester-5, such as the product sold as Eastman AQTM 55S Polymer by EASTMAN CHEMICAL having the chemical formula below. HO-GAGAGAGAGAG-AÀ-GAGA-SC-OH SOsNa* SONa* A: dicarboxylic acid fraction G: glycol fraction SOyNat: sodium sulfo group OH: hydroxyl group It may be preferable that the anionic polymer is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulosic polymers (e.g., carboxymethylcellulose), anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polyfumaric acids, (co)polymers of maleic acids and their salts. The maleic acid copolymer may comprise one or more maleic acid comonomers, and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms and styrene. The term "maleic acid copolymer" means any polymer obtained by copolymerization of one or more maleic acid comonomers and one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic acid comonomers being optionally partially or completely hydrolyzed. Hydrophilic polymers will preferably be used, i.e. polymers having a solubility in water greater than or equal to 2 g / L. In an advantageous aspect of the present invention, the maleic acid copolymer may have a mole fraction of maleic acid units of between 0.1 and 1, more preferably between 0.4 and 0.9. The weight average molar mass of the maleic acid copolymer may be between 1,000 and 500,000 and preferably between 1,000 and 50,000. It is preferable that the maleic acid copolymer is a styrene / maleic acid copolymer and, even more preferably, a styrene / maleic acid copolymer. Preferably, a copolymer of styrene and maleic acid in a 50 / 50 ratio will be used. For example, styrene / maleic acid copolymer (50 / 50) in the form of 30% ammonium salt in water, sold under the reference SMA1000H® by Cray Valley, or styrene / maleic acid copolymer (50 / 50) in the form of 40% sodium salt in water, sold under the reference SMA1000HNa® by Cray Valley, can be used. The use of styrene / maleic acid copolymer such as styrene copolymer of sodium / maleic acid can improve the wettability of a film prepared by the composition according to the present invention. According to one embodiment of the present invention, it is preferable that the anionic polymer (e) is selected from hyaluronic acid and its derivatives. Hyaluronic acid can be represented by the following chemical formula. OH OH if AUS te '; So Lo HO O —- 5th OH NH TO OF V4 In the context of the present invention, the term "hyaluronic acid" covers in particular the basic unit of hyaluronic acid of formula: E Particular 1€ MOLUI dE DASE CE ! ACICE NYaAlUTONIQUE CE CH:2O8 CON , NS 9 2 ; OH \ ; #4 + ; Ha he CHr it ü This is the smallest fraction of hyaluronic acid comprising a dimer disaccharide, namely D-glucuronic acid and N-acetylglucosamine. The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, the linear polymer comprising the polymeric unit described above, linked together in the chain via alternating glycosidic bonds B(1,4) and B(1,3), having a molecular weight (MW) which can vary between 380 and 13,000,000 daltons. This molecular weight depends largely on the source from which the hyaluronic acid is obtained and / or the methods of preparation. The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, the salts of hyaluronic acid.As salts, mention may be made of alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts and their mixtures. In its natural state, hyaluronic acid is present in pericellular gels, in the basic substance of connective tissues of vertebrate organs such as the dermis and epithelial tissues and, in particular, in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord and in the apophysis crista galli. Thus, the term “hyaluronic acid and its derivatives” includes all fractions or subunits of hyaluronic acid having a molecular mass in particular in the molecular mass range recalled above. In the context of the present invention, hyaluronic acid fractions which do not have inflammatory activity are preferably used. As an illustration of the different hyaluronic acid fractions, reference may be made to the paper “Hyaluronan fragments: an information-rich system”, R. Stern et al., European Journal of Cell Biology 58 (2006) 699-715, which reviews the listed biological activities of hyaluronic acid as a function of its molecular weight. According to a preferred embodiment of the present invention, the hyaluronic acid fractions suitable for the use covered by the present invention have a molecular mass of between 50,000 and 5,000,000, in particular between 100,000 and 5,000,000, in particular between 400,000 and 5,000,000 Da. In this case, the term used is high molecular mass hyaluronic acid. Alternatively, hyaluronic acid fractions that may also be suitable for the use covered by the present invention have a molecular mass of between 50,000 and 400,000 Da. In this case, the term used is intermediate molecular mass hyaluronic acid. Alternatively, the hyaluronic acid fractions which may be suitable for the use covered by the present invention have a molecular mass of less than 50,000 Da. In this case, the term used is low molecular mass hyaluronic acid. Finally, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid esters, in particular, those in which all or part of the carboxylic groups of the acid functions are esterified with oxyethylated alkyls or alcohols, containing from 1 to 20 carbon atoms, in particular with a degree of substitution at the level of the D-glucuronic acid of the hyaluronic acid of between 0.5 and 50%. Mention may in particular be made of methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. These esters have been described in particular in D. Campoccia et al. “Semisynthetic resorbable materials from hyaluronan esterification”, Biomaterials 19 (1998) 2101-2127. The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof. The molecular masses indicated above are also valid for hyaluronic acid esters. Hyaluronic acid may in particular be hyaluronic acid supplied by the company Hyactive under the trade name CPN (MW: 10 to 150 kDa), by the company Soliance under the trade name Cristalhyal (MW: 1.1 times 105), by the company Bioland under the name Nutra HA (MW: 820,000 Da), by the company Bioland under the name Nutra AF (MW: 69,000 Da), by the company Bioland under the name Oligo HA (MW: 6100 Da) or by the company Vam Farmacos Metica under the name D Factor (MW: 380 Da). The anionic polymer may be chosen from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and a mixture thereof and, more preferably, hyaluronic acid and its salts (for example sodium hyaluronate), carboxymethylcellulose and its salts, and a mixture thereof. The amount of the (b) anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more and, more preferably, 0.1% by weight or more, relative to the total weight of the composition. Furthermore, the amount of the (b) anionic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and, more preferably, 5% by weight or less, relative to the total weight of the composition. The amount of the (b) anionic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition. (Non-polymeric acid having two or more acid dissociation constants) The composition according to the present invention comprises (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof, i.e. at least one non-polymeric acid having two or more acid dissociation constants or salt(s) thereof. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined at a constant temperature such as 25°C. The non-polymeric acid (b) having two or more pKa values ​​or salts thereof can act as a crosslinker for the cationic polymer (a). The cationic polymer(s) (a) can be ionically crosslinked by the non-polymeric acid(s) (c) having two or more pKa values ​​or salt(s) thereof. The non-polymeric acid (c) having at least two pKa values ​​can be included in a polyionic complex which can be formed by the cationic polymer (a) and the (b) anionic polymer. Non-polymeric acid (c) having two or more pKa values ​​can influence the polyionic complex formed by (a) cationic polymer and (b) anionic polymer. The term "non-polymeric" here means that the acid is not obtained by polymerization of two or more monomers. Therefore, non-polymeric acid does not correspond to an acid obtained by polymerizing two or more monomers such as a polycarboxylic acid. It is preferred that the molecular weight of the (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof is less than or equal to 1,000, preferably less than or equal to 800 and more preferably less than or equal to 700. There is no limit to the type of (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof. Two or more different types of non-polymeric acids having two or more pKa values ​​or their salts may be used in combination. Thus, a single type of non-polymeric acid having two or more pKa values ​​or a salt thereof or a combination of different types of non-polymeric acids having two or more pKa values ​​or salts thereof may be used. Herein, the term "salt" means a salt formed by the addition of suitable base(s) to the non-polymeric acid having two or more pKa values, which can be obtained from a reaction with the non-polymeric acid having two or more pKa values ​​with the base(s) according to methods known to those skilled in the art. As a salt, mention may be made of metal salts, for example alkali metal salts such as Na and K and alkaline earth metal salts such as Mg and Ca and ammonium salts. The (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof may be an organic acid or salt(s) thereof, and preferably a hydrophilic or water-soluble organic acid or salt(s) thereof. The (c) non-polymeric acid having two or more pKa values ​​may have at least two acid groups selected from the group consisting of a carboxylic group, a sulfuric group, a sulfonic group, a phosphoric group, a phosphonic group, a phenolic hydroxyl group and a mixture thereof. Non-polymeric acid (c) having two or more pKa values ​​may be a non-polymeric polyvalent acid. The non-polymeric acid (c) having two or more pKa values ​​may be selected from the group consisting of dicarboxylic acids, disulfonic acids and diphosphoric acids, as well as a mixture thereof. The non-polymeric acid (c) having at least two pKa values ​​or salt(s) thereof may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid and their salts; aspartic acid, glutamic acid and their salts; terephthalylidene dicamphor sulfonic acid or their salts (Mexory! SX), Benzophenone- 9; phytic acid and its salts;Red 2 (Amaranth), Red 102 (New Coccine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brillant blue FCF), Blue 2 (Indigo Carmine), Red 201 (Lithol Rubine B), (Lithol Rubine BCA), Red 204 (Lake Red CBA), Red 206 (Litho! Red CA), Red 207 (Lithol Red BA), Red 208 (Lithol Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 227 (Fast Acid Magenta), Yellow 203 (Quinoline Yellow WS), Green 201 (Alizanine Cyanine Green F), Green 204 (Pyranine Conc), Green 205 (Light Green SF Yellowish), Blue 203 (Patent Blue CA), Blue 205 (Alfazurine FG), Red 401 (Violamine R), Red 405 (Permanent Re FSR), Red 502 (Ponceau 3R), Red 503 (Ponceau R), Red 504 (Ponceau SX), Green 401 (Naphthol Green B), Green 402 (Guinea Green B) et Black 401 (Naphthol Blue Black) ; l’acide folique, l’acide as- corbique, l’acide érythorbique et sels de ces derniers ; la cystine et sels de cette dernière, l’EDTA et ses sels;glycyrrhizin and its salts and a mixture thereof.; It may be preferred that the (c) non-polymeric acid having two or more pKa values ​​or one or more of its salts is selected from the group consisting of terephthalidene sulfonic acid and its salts (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salts, and a mixture thereof. It may be preferred that the (c) non-polymeric acid having two or more pKa values ​​or one or more of its salts is selected from the group consisting of terephthalylidene dicamphor sulfonic acid and its salts (Mexoryl SX), phytic acid and its salts, and a mixture thereof. The amount of (c) the non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be 0.001 wt% or more, preferably 0.005 wt% or more and more preferably 0.01 wt% or more, based on the total weight of the composition. The amount (c) of non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the composition. The amount of (c) the non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight and, more preferably, from 0.01% to 1% by weight, based on the total weight of the composition. (Water) The composition according to the present invention comprises {d) water: The amount of water (d) in the composition according to the present invention may be 50% by weight or more, preferably 60% by weight or more and, more preferably, 70% by weight or more, relative to the total weight of the composition. Furthermore, the amount (d) of water may be 99% by weight or less, preferably 98% by weight or less and, more preferably, 97% by weight or less, relative to the total weight of the composition. The amount (d) of water may be from 50% to 99% by weight, preferably from 60% to 98% by weight and, more preferably, from 70% to 97% by weight, relative to the total weight of the composition. (pH) The pH of the composition according to the present invention may be from 3 to 9, preferably from 3.3 to 8.5 and, more preferably, from 3.5 to 8. At a pH between 3 and 9, the (a) anionic polymer and the (b) anionic polymer, as well as the (c) non-polymeric acid having at least two pKa values ​​or salt(s) thereof, can form a stable polyionic complex which can be in the form of a particle. Therefore, at a pH between 3 and 9, the composition according to the present invention can be very stable. The pH of the composition according to the present invention may be corrected by adding at least one alkaline agent and / or at least one acid, other than (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof. The pH of the composition according to the present invention may also be corrected by adding at least one buffering agent. (Alkaline agent) The composition according to the present invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used. The alkaline agent may be an inorganic alkaline agent. The inorganic alkaline agent may be selected from the group consisting of the following: ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates, and monohydrogen phosphates such as sodium phosphate or sodium monohydrogen phosphate. Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. As an inorganic alkaline agent, sodium hydroxide is preferable. The alkaline agent may be an organic alkaline agent. It is preferable that the organic alkaline agent is selected from the group consisting of monoamines and their derivatives; diamines and their derivatives; polyamines and their derivatives; basic amino acids and their derivatives; oligomers of basic amino acids and their derivatives; polymers of basic amino acids and their derivatives; urea and its derivatives and guanidine and its derivatives. Examples of organic alkaline agents include alkanolamines such as mono-, di- and triethanolamine, and isopropanolamine; urea, guanidine and their derivatives; basic amino acids such as lysine, ornithine or arginine and diamines such as those described in the structure below: has wherein R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a C1-C4 alkyl radical, and R1, R2, R3 and R4 independently denote a hydrogen atom, an alkyl radical or a C1-C4 hydroxyalkyl radical, as exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferable. The alkaline agent(s) may be used in an amount ranging from 0.01% to 15% by weight, preferably from 0.02% to 10% by weight and, more preferably, from 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility. (Acid) The composition according to the present invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used. Acids include all inorganic or organic acids, preferably inorganic, commonly used in cosmetic products. A monovalent acid and / or a polyvalent acid can be used. Monovalent acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid, and hydrochloric acid (HCl) can be used. HCl is preferred. The acid(s) may be used in an amount ranging from 0.01% to 15% by weight, preferably from 0.02% to 10% by weight and, more preferably, from 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility. (Buffering agent) The composition according to the present invention may comprise at least one buffering agent. Two or more buffering agents may be used in combination. Thus, a single type of buffering agent or a combination of different types of buffering agents may to be used. As a buffering agent, mention may be made of an acetate buffer (e.g., acetic acid + sodium acetate), a phosphate buffer (e.g., sodium dihydrogen phosphate + disodium hydrogen phosphate), a citrate buffer (e.g., citric acid + sodium citrate), a borate buffer (e.g., boric acid + sodium borate), a tartrate buffer (e.g., tartaric acid + sodium tartrate dihydrate), a Tris buffer (e.g., tris(hydroxymethyl)aminomethane) and a Hepes buffer (acid 4-(2-hydroxyethyl)-1-pipeineethanesulfonic acid). (Optional additives) The composition according to the present invention may comprise, in addition to the above-mentioned components, components generally used in cosmetics, in particular, oils, surfactants (in particular, non-ionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, volatile or non-volatile organic solvents, hydrophilic or hydrophobic UV filters, silicones and silicone derivatives, natural extracts derived from animals or plants, waxes, and the like, in a range which does not affect the effects of the present invention. The composition according to the present invention may comprise the above optional additive(s) in an amount of 0.01% to 50% by weight, preferably 0.05% to 30% by weight and more preferably 0.1% to 10% by weight, relative to the total weight of the composition. (Preparation) The composition according to the present invention can be prepared by mixing the essential ingredient(s) as explained above, and the optional ingredient(s), if necessary, as explained above. The method and means for mixing the above essential and optional ingredients are not limited. Any conventional method and means can be used for mixing the above essential and optional ingredients to prepare the composition according to the present invention. [Composition] The composition according to the present invention can be used as a cosmetic composition. Thus, the cosmetic composition according to the present invention can be intended to be applied to a keratin fiber. By keratin substance is meant here a material containing keratin as a main constituent element and, by way of example, the skin, the scalp, the lips, the hair or body hair and the like. Therefore, it is preferable that the cosmetic composition according to the present invention is used for a cosmetic process for the keratin substance, in particular the skin. Thus, the composition according to the present invention may be a cosmetic composition for the skin, preferably a cosmetic skin care composition or a skin makeup composition, and more preferably a cosmetic skin care composition. The composition according to the present invention can be used to easily prepare a film. Thus, the present invention may also relate to a method of preparing a film, preferably a cosmetic film, optionally having a thickness of 0.1 µm or more, more preferably 0.5 µm or more, and even more preferably 1.0 µm or more, comprising: the application to a substrate, preferably a keratinous substance, better still the skin, of the composition according to the present invention and drying of the composition. The upper limit of the above film thickness is not limited. Thus, for example, the film thickness may be 1 mm or less, preferably 500 µm or less, more preferably 300 µm or less, and even more preferably 100 µm or less. Since the method for preparing the film according to the present invention comprises the steps of applying the composition according to the present invention to a substrate, preferably a keratinous substance and, more preferably, the skin, and drying the composition, the method according to the present invention does not require spin-coating or spray-coating, and therefore it is even possible to easily prepare a relatively thick film. Thus, the method for preparing a film which may relate to the present invention can prepare a film without any special equipment such as spin-coating applicators and spraying machines. Although the film prepared by the above method is relatively thick, it is still thin and may be transparent, and therefore may not be easy to perceive. Thus, the film can be preferably used as a cosmetic film. If the substrate is not a keratinous substance such as skin, the composition according to the present invention can be applied to a substrate made of any material other than keratin. The materials of the non-keratinous substrate are not limited. Two or more materials can be used in combination. Thus, a single type of material or a combination of different types of materials can be used. In any case, it is preferable that the substrate is soft or elastic. If the substrate is not a keratinous substance, it is preferable that the substrate is water-soluble, since it is possible to leave the film by washing the substrate with water. Examples of water-soluble materials include poly(methacrylic) acids, polyethylene glycols, polyacrylamides, polyalcohols vinyl acetate (PVA), starch, cellulose acetates, and the like. PVA is preferred. If the non-keratinous substrate is in the form of a sheet, it may have a thickness greater than that of the film according to the present method, in order to facilitate handling of the film attached to the substrate sheet. The thickness of the non-keratinous substrate sheet is not limited, but may be between 1 µm and 5 mm, preferably from 10 µm to 1 mm and, more preferably, from 50 to 500 µm. It is preferable that the film prepared by the above method is peelable from the non-keratin substrate. The release method is not limited. Therefore, the film prepared by the above method can be peeled from the non-keratin substrate, or released by dissolving the substrate sheet in a solvent such as water. The present invention may also relate to: (1) A film, preferably cosmetic, preferably with a thickness preferably greater than 0.1 um, more preferably greater than 0.5 um, and even more preferably greater than 1.0 um, prepared by a process comprising: the application to a substrate, preferably a keratinous substance and, better still, to the skin, of the composition according to the present invention and drying of the composition, And (2) A film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.1 um, more preferably greater than 0.5 um, even more preferably greater than 1.0 um, comprising: (a) at least one cationic polymer; (b) at least one anionic polymer and (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; in which the (a) cationic polymer is chosen from chitosans with a molecular weight less than or equal to 20,000. The above explanations regarding (a) cationic polymer, (b) anionic polymer and (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof may apply to those of films (1) and (2) above. The resulting film may be self-supporting. The term "self-supporting" here means that the film may be in the form of a sheet and may be handled as an independent sheet without the assistance of a substrate or support. Thus, the term "self-supporting" may have the same meaning as "self-supporting". It is preferable that the above film is hydrophobic. In these specifications, the term "hydrophobic" means that the solubility of the polymer in water (preferably with a volume of 1 liter) at 20-40 °C, preferably 25-40 °C and, more preferably, 30-40 °C is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, relative to the total weight of the polymer. It is most preferable that the polymer is not soluble in water. If the above film is hydrophobic, the film may have water-resistant properties and, therefore, it may remain on a keratinous substance such as skin, even if the surface of the keratinous substance is wet due to, for example, perspiration or rain. Thus, when the film provides a cosmetic effect, the cosmetic effect may last for a long time. On the other hand, the above film can be easily removed from a keratinous substance such as skin under alkaline conditions such as pH 8 to 12, preferably 9 to 11. Therefore, the above film is difficult to remove with water, while it can be easily removed with a soap which can provide such alkaline conditions. The above film may comprise at least one biocompatible and / or biodegradable polymer layer. Two or more biocompatible and / or biodegradable polymers may be used in combination. Thus, a single type of biocompatible and / or biodegradable polymer or a combination of different types of biocompatible and / or biodegradable polymers may be used, The term "biocompatible" polymer in this specification means that the polymer does not have excessive interaction between the polymer and cells of the living body, including the skin, and that the polymer is not recognized by the living body as a foreign material. The term "biodegradable" polymer in this specification means that the polymer can be degraded or broken down in a living body due to, for example, the metabolism of the living body itself or the metabolism of microorganisms that may be present in the living body. In addition, the biodegradable polymer can be degraded by hydrolysis. If the above film includes a biocompatible and / or biodegradable polymer, it is less irritable or non-irritable to the skin, and does not cause any rashes. In addition, due to the use of a biocompatible and / or biodegradable polymer, the above film can adhere well to the skin. The above film can be used for cosmetic treatments of keratin substances, preferably the skin, especially the face. The above film can take any form. For example, it can be used as a full face mask or as a patch for a part of the face such as the cheek, nose and eye area. [Cosmetic process and use] The present invention also relates to: a cosmetic process for a keratinous substance such as skin, comprising applying the composition according to the present invention to the keratin substance and drying the composition to form a cosmetic film on the keratin substance and And a use of the composition according to the present invention for the preparation of a cosmetic film on a keratin substance such as the skin. The cosmetic process here refers to a non-therapeutic cosmetic process for caring for and / or making up the surface of a keratinous substance such as the skin. In both the above method and use, the above cosmetic film is resistant to water of a pH of 7 or less, and can be removed with water of a pH of more than 7, preferably 8 or more, and most preferably 9 or more. In other words, the above film can be water-resistant under neutral or acidic conditions such as a pH of 7 or less, preferably in a range of 6 or more and 7 or less, and more preferably in a range of 5 or more and 7 or less, while the above cosmetic film can be removed under alkaline conditions such as a pH of more than 7, preferably 8 or more, and more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11. Therefore, the above cosmetic film can be water-resistant and thus can remain on a keratin substance such as skin even if the surface of the keratin substance is wet due to, for example, perspiration and rain. On the other hand, the above cosmetic film can be easily removed from a keratin substance such as skin under alkaline conditions. Therefore, the above cosmetic film is difficult to remove with water, while it can be easily removed with a soap that can provide such alkaline conditions. Furthermore, the above cosmetic film may have cosmetic effects such as matting a keratin substance such as skin, absorbing or absorbing sebum or bad odor, and / or protecting the keratin substance from, for example, dirt or pollution, due to the properties of the polyionic complex in the cosmetic film, even if the cosmetic film does not contain any cosmetic active ingredient. In addition, the above cosmetic film can immediately change or modify the appearance of the skin by changing the reflection of light on the skin and the like, even if the cosmetic film does not contain any cosmetic active ingredients. Therefore, it is possible that the above cosmetic film conceals skin defects such as pores or wrinkles. In addition, the above cosmetic film can immediately change or modify the touch feeling of the skin by changing the surface roughness of the skin and the like. In addition, the above cosmetic film can immediately protect the skin by covering the surface of the skin and shielding the skin, as a barrier, against environmental stresses such as pollutants, contaminants and the like. The above cosmetic effects can be adjusted or controlled by changing the chemical composition, thickness and / or surface roughness of the above cosmetic film. If the above cosmetic film contains at least one cosmetic active ingredient, the cosmetic film may have cosmetic effects provided by the cosmetic active ingredient(s). For example, if the cosmetic film contains at least one cosmetic active ingredient selected from anti-aging agents, anti-sebum agents, deodorant agents, antiperspirant agents, whitening agents and a mixture thereof, the cosmetic film may treat skin aging, absorb sebum on the skin, control perspiration on the skin and / or whiten the skin. It is also possible to apply a cosmetic makeup composition to the above cosmetic film or sheet after applying it to the skin. The present invention may also relate to a use of (a) at least one cationic polymer, wherein the (a) cationic polymer is selected from chitosans with a molecular weight of 20,000 or less, in a composition comprising: (b) at least one anionic polymer; (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; (d) water, in order to stabilize the composition and / or improve the spreadability of the composition. The composition is stable so that it can be homogeneous after its preparation. The composition can be easily spread during application to, for example, a keratinous substance such as skin. The present invention may also relate to a use of (a) at least one cationic polymer, wherein the (a) cationic polymer is selected from chitosans with a molecular weight of 20,000 or less, in a film including: (b) at least one anionic polymer and (c) at least one non-polymeric acid having two or more pKa values or salt(s) thereof; in order to improve the texture of the film, preferably to improve the feeling of hydration, softness and flexibility provided by the film and / or to reduce film stickiness and, more preferably, to reduce film stickiness. The above explanations regarding (a) cationic polymer and (b) anionic polymer as well as (c) non-polymeric acid having two or more pKa values ​​or salt(s) thereof and (d) water may apply to those of the above uses. EXAMPLES The present invention will be described in more detail with the aid of examples. However, these examples should not be construed as limiting the scope of the present invention. [Examples 1 to 9 and comparative examples 1 to 5] [Preparations] Each of the compositions according to Examples 1 to 9 and Comparative Examples 1 and 5 was prepared by mixing the ingredients listed in Tables 1 and 2. The numerical values ​​of the ingredient quantities shown in Tables 1 and 2 are all based on “% by weight” of raw materials. The details of the preparations are as follows. (Example 1) First, sodium hyaluronate was added to water and solubilized to prepare an aqueous solution of a polyanion. After solubilization, an appropriate amount of sodium hydroxide was added to the polyanion aqueous solution to make the aqueous solution alkaline. Then, as a polycation, chitosan with a molecular weight of 3000 was added to the alkaline aqueous solution. The formation of polyionic complex in the aqueous solution was avoided due to the alkaline state of the aqueous solution. Then, an appropriate amount of phytic acid was added to the aqueous solution. A polyionic complex in the form of particles was formed. (Examples 2 and 3) The preparation steps of Example 1 were repeated, except that the amounts of polyanion (sodium hyaluronate) and polycation (chitosan) were modified. (Example 4) The preparation steps of Example 1 were repeated except that the amounts of polyanion and polycation were changed and chitosan with a molecular weight between 10,000 and 20,000 was used instead of chitosan with a molecular weight of 3,000. (Example 5) The preparation steps of Example 1 were repeated, except that carboxymethylcellulose was used instead of sodium hyaluronate. (Example 6) The preparation steps of Example 1 were repeated, except that the molecular weight of chitosan was increased from 3,000 to 5,000. (Example 7) The preparation steps of Example 1 were repeated, except that the molecular weight of chitosan was increased from 3,000 to 7,000. (Example 8) The preparation steps of Example 5 were repeated, except that the molecular weight of chitosan was increased from 3,000 to 5,000. (Example 9) The preparation steps of Example 5 were repeated, except that the molecular weight of chitosan was increased from 3,000 to 7,000. (Comparative example 1) The preparation steps of Example 2 were repeated, except that chitosan with a molecular weight of 100,000 or greater was used instead of chitosan with a molecular weight of 3,000. (Comparative example 2) The preparation steps of Example 2 were repeated, except that phytic acid and sodium hydroxide were not used. (Comparative example 3) The preparation steps of Example 2 were repeated, except that the molecular weight of chitosan was increased from 3,000 to 5,000 and phytic acid and sodium hydroxide were not used. (Comparative example 4) The preparation steps of Example 2 were repeated, except that the molecular weight of chitosan was increased from 3,000 to 7,000 and phytic acid and sodium hydroxide were not used. (Comparative example 5) The preparation steps of Example 1 were repeated except that the amount of polycation was changed and poly-K-lysine was used instead of chitosan with a molecular weight of 3,000. [Tables 1] 7 |Ex. |Ex.9 8 |Ex.1 |Ex.2 |Ex.3 |Ex.4 |Ex. 5 |Ex. 6 |Ex.7 [Water lasp |asp asp asp |asp [asp |asp ° qsp ASP jasP ASP ASP jaSP jasP — jaSP |asp 100 |100 [100 |100 |100 |100 |100 |100j100 [Lo [02 |2o jo1 | [Lo Jo | + F HF HO pH + |L0JLO [Lo + 5 + HE FH HO HO Jos + jos|- FH HO HO FH Jos | Jos F-10656 | FH HE H 0.55 [0.11 |1.1 [0.05 [0.55 |0.55 [0.55 |0.5 10.55 5 Sodium hydroxide 0.29 [0.06 0.58 0.14 0.29 [0.29 |0.29 |0.2 |0.29 9 2 qe je ie je 6 is Stability | Good|Good|Good |GoodGood|Good Correct |Good Correct | tt MW: Molecular weight 1 [Tables 2] Ex. Ex. Ex. Ex. Ex. comp. 1 Jcomp. 2 |comp. 3 |comp. 4 |comp. 5 0.2 0.2 0.2 0.2 1.0 Fe EE FFE 91 HE FF + Jos 1 Jet + FE FE FH HE 0 = pH + + |oss 0.06 | | | | 60 6.0 6.0 6.0 6.0 Bad |Bad |Bad [Bad |Good MW: Molecular weight [Evaluations] (Stability) The compositions according to Example | and Comparative Examples 1-5 immediately after preparation were visually observed using a polarized optical microscope and evaluated according to the following criteria. Good: homogeneous without precipitation Correct: homogeneous without precipitation, but precipitates slowly after a few days Low: heterogeneous with precipitation The results are shown in Tables 1 and 2 below: (Sensory evaluations) Three panelists evaluated each of the compositions according to Examples 1 and 5-9 as well as Comparative Example 5 at the time of application of the composition and after it. Specifically, each panelist applied each composition to their hand and spread it, followed by drying, in order to evaluate the spreadability, the adhesiveness upon drying, the feeling of hydration after drying, the softness after drying and the flexibility after drying and ranked from 1 (low) to 5 (high) taking into account a control which is an aqueous solution of sodium hyaluronate (HA) or carboxymethylcellulose (CMC) at 1% by weight. It was then classified into the following three categories based on the average of the evaluation: Significantly better: significantly better than the control Better: better than the witness Identical: identical to the witness The results are shown in Tables 3 and 4 below: [Tables 3] |Ex. 1 |Ex. 6 |Ex. 7 Best [Best [Best Ex. Comp. Solution 5 JHA 1% Identical [Witness | e [Best [Witness | Spreadability Stickiness Stickiness Good fa Good - [Best [Witness | best best best Feeling Best Best Best Best [Witness | hydration [Softness Best Best Best Best |Witness | |Sweetness Best Best Best Best [Witness | [Sweetness [Best [Best [Best [Best [Witness | [Tables 4] |Ex. 5 |Ex. 8 |Ex. 9 CMC 1% Solution | Spreadability Best [Best | Best [Witness Stickiness Best Best Best Witness Feel Best | Best | Best |Witness Moisture Softness Best Best Best Witness Softness Best | Best | Best |Witness (Summary) The compositions according to Examples 1 to 3 were stable (see Table 1). The spreadability of the compositions according to Examples 1 and 5-9 and the texture provided by the compositions according to Examples 1 and 5-9 were improved due to the formation of a polyionic complex by a combination of a cationic polymer (chitosan with a molecular weight of 20,000 or less) and an anionic polymer (sodium hyaluronate or carboxymethylcellulose), compared to a composition (control) comprising only the anionic polymer (see Tables 3 and 4). The results of the sensory evaluations for Example 1 could also be applied to Examples 2 to 4, since the composition according to Example 1 and the compositions according to Examples 2 to 4 are similar. The composition according to Comparative Example 1 which included higher molecular weight chitosan was not stable (see Table 2). The composition according to Comparative Example 2 which did not include phytic acid was not stable (see Table 2). The composition according to Comparative Example 3 which did not include phytic acid was not stable (see Table 2). The composition according to Comparative Example 4 which did not include phytic acid was not stable (see Table 2). The composition according to Comparative Example 5 which included poly-e-lysine instead of chitosan was stable but less spreadable during application and more sticky after application than the composition according to the present invention (see Tables 2 and 3). Thus, the composition according to the present invention was more spreadable during application and less sticky after application than the composition according to Comparative Example 5 due to the use of chitosan with a molecular weight of 20,000 or less at -e-lysine (see Table 3).

Claims

Claims

1. Composition, comprising: (a) at least one cationic polymer; (b) at least one anionic polymer; (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; {d) water. in which the (a) cationic polymer is chosen from chitosans of a mo- lecular less than or equal to 20,000.

2. The composition of Claim 1 wherein the (b) anionic polymer has at least one negatively chargeable and / or negatively charged fraction tively selected from the group consisting of a sulfuric group, a sulfate group, a sulfonic group, a sulfonate group, a group phosphoric, a phosphate group, a phosphonic group, a phosphonate group, a carboxylic group and, preferably, se- selected from the group consisting of a carboxylic group and a carboxylate group.

3. The composition according to Claims 1 to 2 wherein (b) the polymer anionic is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellular polymers losic acids, anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamics, (co)polystyrene sulfonate, (co)poly(vinyl sulfates), dextran sulfate, chondroitin sulfate, acids (co)polymaleic, polyfumaric acids, (co)polymers of maleic acids and their salts.

4. Composition according to one of Claims 1 to 3, in which (b) anionic polymer is selected from polysaccharides, preferably hyaluronic acid and its derivatives, polymers of cellulose and their salts, and a mixture of these and, better still, the acid hyaluronic acid and its salts, carboxymethylcellulose and its salts, and a mixture of these.

5. A composition according to any one of Claims 1 to 4, in which (c) non-polymeric acid having two or more pKa values ​​or the salt(s) thereof is an organic acid or a salt(s) thereof, preferably a hydrophilic organic acid or soluble in water or a salt(s) thereof and, better still, acid phytic acid or salts thereof, terephthalylidene dicamphor acid sulfonic acid or its salts, or a mixture thereof.

6. A composition according to any one of Claims | to 5, in in which the pH of the composition is between 3 and 9, preferably between 3.5 and 8.5 and, better still, between 3.5 and 8.

7. Cosmetic process for a keratinous substance such as skin, including the application to the keratin substance of the composition according to one any of claims | to 6 and drying the composition to form a cosmetic film on the keratinous substance.

8. A use of (a) at least one cationic polymer, wherein (a) the cationic polymer is chosen from chitosans of a mo- lecular of 20,000 or less, in a composition comprising: {b) at least one anionic polymer; {c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; {d) water. in order to stabilize the composition and / or improve the spreading of the composition.

9. A film, preferably a cosmetic film, comprising: (a) at least one cationic polymer; (b) at least one anionic polymer and (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; in which the (a) cationic polymer is chosen from chitosans of a mo- lecular less than or equal to 20,000.

10. A use of (a) at least one cationic polymer, wherein (a) the cationic polymer is chosen from chitosans of a mo- lecular of 20,000 or less, in a film including: (b) at least one anionic polymer and (c) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; in order to improve the texture of the film, preferably to improve the feeling of hydration, softness and flexibility provided by the film and / or to reduce film stickiness and, even better, to reduce film stickiness.