COMPOSITION COMPRISING A POLYIONIC COMPLEX BASED ON HYALURONIC ACID AND A LIPOPHILIC ANTIOXIDANT

Abstract

COMPOSITION COMPRISING A HYALURONIC ACID POLYIONIC COMPLEX AND A LIPOPHILIC ANTIOXIDANT The present invention relates to a composition comprising: (a) at least one complex comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer, or at least one amphoteric polymer and at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof or at least one non-polymeric base having two or more pKb values ​​or salt(s) thereof; (b) at least one lipophilic antioxidant; and (c) water, wherein the anionic polymer is selected from hyaluronic acid, its salts and derivatives, and the amphoteric polymer is selected from cationic hyaluronic acid and its salts. The composition according to the present invention is less sticky and can offer lasting antioxidant effects.Figure for the abridged version: none.

Description

Title of the invention: Composition comprising a polyionic complex based on hyaluronic acid and a lipophilic antioxidant technical field

[0001] The present invention relates to a composition comprising a polyionic complex and a film of a polyionic complex, as well as a process for preparing a film by using a polyionic complex and a cosmetic process using a polyionic complex. PREVIOUS ART

[0002] Hyaluronic acid is a predominant glucosaminoglycan found in the skin. Fibroblasts primarily synthesize collagen, matrix glycoproteins other than collagen (fibronectin, laminin), proteoglycans, and elastin. Keratinocytes, on the other hand, primarily synthesize sulfated glycosaminoglycans and hyaluronic acid. Hyaluronic acid is also called hyaluronan (HA).

[0003] Hyaluronic acid is present in its free state in the epidermis and dermis and is responsible for skin turgor. This polysaccharide can actually retain a large volume of water, corresponding to 1000 times its weight. In this sense, hyaluronic acid plays an important role in increasing the amount of bound water in tissues, as well as in the mechanical properties of the skin and in the formation of wrinkles.

[0004] Hyaluronic acid is widely used as a cosmetic ingredient because of its high moisturizing effects.

[0005] However, an aqueous solution of hyaluronic acid is sticky, which can lead to an uncomfortable texture. Furthermore, a hyaluronic acid film, which forms when an aqueous solution of hyaluronic acid dries on the skin, is sticky and can also lead to an uncomfortable texture.

[0006] WO 2021 / 125069 discloses the reduction of stickiness due to hyaluronic acid by formation of a polyionic complex particle with a cationic polymer and hyaluronic acid as an anionic polymer. DISCLOSURE OF THE INVENTION

[0007] There is a need for a composition including a polyionic complex based on hyaluronic acid, which is less sticky and can offer lasting antioxidant effects.

[0008] Thus, a first objective of the present invention is to propose a composition that is less sticky and can offer lasting antioxidant effects.

[0009] The above objective of the present invention can be achieved by a composition comprising:

[0010] (a) at least one polyionic complex, comprising

[0011] at least one cationic polymer and at least one anionic polymer,

[0012] at least one cationic polymer and at least one amphoteric polymer,

[0013] at least one anionic polymer and at least one amphoteric polymer, or

[0014] at least one amphoteric polymer,

[0015] and

[0016] at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof, or

[0017] at least one non-polymer base having two or more pKb values ​​or salt(s) thereof;

[0018] (b) at least one lipophilic antioxidant; and

[0019] (c) water,

[0020] in which

[0021] The anionic polymer is chosen from hyaluronic acid, its salts, and its derivatives, And

[0022] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

[0023] The cationized hyaluronic acid may have at least one group containing quaternary ammonium and has a degree of cationization of 0.05 to 0.6, preferably of 0.1 to 0.5, and more preferably of 0.15 to 0.4.

[0024] The cationic polymer may have at least one positively chargeable and / or positively charged fraction selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group.

[0025] The cationic polymer can be chosen from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as diallyldialkyl ammonium (co)polychloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as collagen, cationic cellulose polymers, and their salts.

[0026] The total quantity of the cationic and / or anionic and / or amphoteric polymer(s) in the composition according to the present invention can be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and, more preferably, from 0.05% to 5% by weight, relative to the total weight of the composition.

[0027] The non-polymeric acid having two or more pKa values ​​or one (or more) salt(s) thereof may be an organic acid or salts thereof, preferably a hydrophilic or water-soluble organic acid or one (or more) salt(s) thereof and, more preferably, phytic acid or salts thereof.

[0028] The quantity of non-polymer acid having two or more pKa values ​​or of salt(s) thereof or of non-polymer base having two or more pKb values ​​or of salt(s) thereof in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.

[0029] The (b) lipophilic antioxidant may be selected from the group consisting of pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxyanisole, ascorbyl palmitate, tocopherol and mixtures thereof.

[0030] The quantity of the (b) lipophilic antioxidant(s) in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight and, more preferably, from 0.01% to 5% by weight, relative to the total weight of the composition.

[0031] The quantity of (c) water in the composition according to the present invention can be from 10% to 99% by weight, preferably from 30% to 97% by weight and more preferably from 50% to 95% by weight, relative to the total weight of the composition.

[0032] The composition according to the present invention may further comprise (d) at least one surfactant, preferably chosen from non-ionic surfactants, and more preferably chosen from fatty acid polyglyceryl esters.

[0033] A second objective of the present invention is to propose a method for preparing a film that is less sticky and can produce lasting antioxidant effects.

[0034] The above objective of the present invention can be achieved by a process for preparing a film, preferably a cosmetic film, comprising:

[0035] the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

[0036] the drying of the composition.

[0037] A third objective of the present invention is to provide a film that is less sticky and can produce lasting antioxidant effects.

[0038] The above objective of the present invention can be achieved by:

[0039] (1) A film, preferably a cosmetic film, prepared by a process including:

[0040] the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

[0041] drying of the composition,

[0042] or

[0043] (2) A film, preferably a cosmetic film, comprising:

[0044] (a) at least one polyionic complex, comprising

[0045] at least one cationic polymer and at least one anionic polymer,

[0046] at least one cationic polymer and at least one amphoteric polymer,

[0047] at least one anionic polymer and at least one amphoteric polymer, or

[0048] at least one amphoteric polymer, and

[0049] at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof, or

[0050] at least one non-polymer base having two or more pKb values ​​or salt(s) thereof;

[0051] (b) at least one lipophilic antioxidant;

[0052] and

[0053] optionally (d) at least one surfactant, preferably chosen from non-ionic surfactants, and more preferably chosen from fatty acid polyglyceryl esters,

[0054] in which

[0055] the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives; and

[0056] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

[0057] The present invention also relates to a cosmetic process for a keratinous substance such as skin, comprising

[0058] the application to the keratinous substance of the composition according to the present invention; and

[0059] drying the composition to form a cosmetic film on the keratinous substance. Best embodiment of the invention

[0060] After careful research, the inventors discovered that it is possible to provide a composition that is less sticky and can provide lasting antioxidant effects. Thus, the composition according to the present invention comprises:

[0061] (a) at least one polyionic complex, comprising

[0062] at least one cationic polymer and at least one anionic polymer,

[0063] at least one cationic polymer and at least one amphoteric polymer,

[0064] at least one anionic polymer and at least one amphoteric polymer, or

[0065] at least one amphoteric polymer,

[0066] and

[0067] at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof, or

[0068] at least one non-polymer base having two or more pKb values ​​or salt(s) thereof;

[0069] (b) at least one lipophilic antioxidant; and

[0070] (c) water,

[0071] in which

[0072] the anionic polymer is chosen from hyaluronic acid, its salts, and its derivatives, and

[0073] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

[0074] Furthermore, the inventors have discovered that it is possible to propose a process for preparing a film that is less sticky and can produce lasting antioxidant effects. Thus, the process according to the present invention is a process for preparing a film, preferably a cosmetic film, the process comprising:

[0075] the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

[0076] the drying of the composition.

[0077] Furthermore, the inventors discovered that it is possible to produce a film that is less sticky and that can offer lasting antioxidant effects. Thus, the film according to the present invention is

[0078] (1) A film, preferably a cosmetic film, prepared by a process including:

[0079] the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

[0080] the drying of the composition,

[0081] or

[0082] (2) A film, preferably a cosmetic film, comprising:

[0083] (a) at least one polyionic complex, comprising

[0084] at least one cationic polymer and at least one anionic polymer,

[0085] at least one cationic polymer and at least one amphoteric polymer,

[0086] at least one anionic polymer and at least one amphoteric polymer, or

[0087] at least one amphoteric polymer, and

[0088] at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof, or

[0089] at least one non-polymer base having two or more pKb values ​​or salt(s) thereof;

[0090] (b) at least one lipophilic antioxidant;

[0091] and

[0092] optionally (d) at least one surfactant, preferably chosen from non-ionic surfactants, and more preferably chosen from fatty acid polyglyceryl esters,

[0093] in which

[0094] the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives; and

[0095] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

[0096] The stickiness of the composition according to the present invention can be reduced compared to a composition including hyaluronic acid, which does not form a polyionic complex.

[0097] The composition and film according to the present invention can produce lasting antioxidant effects.

[0098] Thus, the present invention may be useful for protecting the skin against damage caused by peroxidation, for example, of unsaturated lipids such as sebum, where the damage may be altered desquamation, decreased squalene, acne and blackheads, dull skin and aging, such as the formation of wrinkles and / or fine lines.

[0099] In addition, the composition according to the present invention can offer lasting cosmetic effects and / or an improved moisturizing texture based on hyaluronic acid or cationized hyaluronic acid.

[0100] In addition, the composition and the film according to the present invention may be transparent or translucent.

[0101] It is possible to easily prepare a film comprising a polyionic complex, where the film may include at least one surfactant, by applying the composition to a substrate, preferably a keratinous substance such as skin and hair, and more preferably skin, and drying the composition.

[0102] The stickiness of the film according to the present invention can be reduced compared to a hyaluronic acid film which does not form a polyionic complex.

[0103] The film according to the present invention may be porous. The surface of the film according to the present invention may not be flat but may be rough.

[0104] The film according to the present invention can have various cosmetic functions. For example, the film can provide moisturizing effects based on hyaluronic acid or cationized hyaluronic acid in the polyionic complex.

[0105] The film according to the present invention is capable of capturing sebum, mattifying the appearance of a keratinous substance such as skin, absorbing or adsorbing bad odors and / or to protect the keratinous substance from, for example, dirt or pollutants.

[0106] If the film contains at least one cosmetic active ingredient such as one or more oils, the film may also have cosmetic effects provided by the cosmetic active ingredient(s). For example, if the polyionic complex film includes at least one cosmetic active ingredient selected from among UV filters, anti-aging agents other than (b) lipophilic antioxidants, sebum-regulating agents, deodorizing agents, antiperspirants, whitening agents, and a mixture thereof, the film may filter UV rays, treat skin aging, absorb sebum from the skin, control odors on the skin, control perspiration on the skin, and / or whiten the skin.

[0107] The film according to the present invention may be transparent or transparent, and consequently, may not be easy to perceive, even when the film is relatively thick.

[0108] In addition, the film according to the present invention is water resistant and, consequently, it can 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.

[0109] Furthermore, the film according to the present invention can be easily removed from a keratinous substance such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, whereas it can be easily removed with a soap that can provide alkaline conditions.

[0110] Thus, if the film according to the present invention includes a hydrophilic or water-soluble UV filter, the film according to the present invention can exhibit UV protection effects that are water-resistant (waterproof) and can be durable, but can be easily removed with a soap that can provide alkaline conditions.

[0111] The composition, process, film and similar according to the present invention will be described in more detail below.

[0112] [Polyionic complex]

[0113] The composition according to the present invention may comprise (a) at least one polyionic complex. Two or more different types of (a) polyionic complexes may be used in combination. Thus, a single type of (a) polyionic complex or a combination of different types of (a) polyionic complexes may be used.

[0114] The (a) polyionic complex can take the form of a particle.

[0115] The size of the polyionic complex particle can be from 5 nm to 100 pm, preferably from 100 nm to 50 pm, more preferably from 200 nm to 40 pm and, even more preferably, from 500 nm to 30 pm. Particle sizes smaller than 1 pm can be measured using a dynamic light scattering method, and particle sizes larger than 1 pm can be measured using an optical microscope. This particle size can be based on a number-average diameter.

[0116] The quantity of the (a) polyionic complex(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.

[0117] Furthermore, the quantity of the (a) polyionic complex(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.

[0118] The quantity of the (a) polyionic complex(s) in the composition according to the present invention can 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.

[0119] The (a) polyionic complex comprises at least one polymer or a combination of polymers. Specifically, the (a) polyionic complex includes:

[0120] (1) at least one cationic polymer and at least one anionic polymer;

[0121] (2) at least one cationic polymer and at least one amphoteric polymer;

[0122] (3) at least one anionic polymer and at least one amphoteric polymer; or

[0123] (4) at least one amphoteric polymer.

[0124] There is no limit on the type of cationic polymers. 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.

[0125] In (1) above, the ratio of the quantity, for example the chemical equivalent, of the cationic polymer(s) / of the anionic polymer(s) may be 0.05-18, preferably 0.1-10 and, more preferably, 0.5-5.0. In particular, it may be preferable that the number of cationic groups of the cationic polymer(s) / the number of anionic groups of the anionic polymer(s) be 0.05-18, more preferably 0.1-10, and even more preferably 0.5-5.0.

[0126] In (2) above, the ratio of the quantity, for example the chemical equivalent, of the cationic polymer(s) / of the anionic polymer(s) may be 0.05-18, preferably 0.1-10 and, more preferably, 0.5-5.0. In particular, it may be preferable that the number of cationic groups of the cationic polymer(s) / the number of cationic and anionic groups of the amphoteric polymer(s) be 0.05-18, more preferably 0.1-10, and even more preferably 0.5-5.0.

[0127] In (3) above, the ratio of the quantity, for example the chemical equivalent, of the cationic polymer(s) / the amphoteric polymer(s) may be 0.05-18, preferably 0.1-10 and, more preferably, 0.5-5.0. In particular, it may be preferable that the number of anionic groups of the anionic polymer(s) / the number of cationic and anionic groups of the amphoteric polymer(s) be 0.05-18, more preferably 0.1-10, and even more preferably 0.5-5.0.

[0128] The total amount of the polymer(s) according to any one of (1) to (4) above in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more and more preferably 0.05% by weight or more, relative to the total weight of the composition.

[0129] The total amount of the polymer(s) according to any one of (1) to (4) above 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.

[0130] The total quantity of the polymer(s) according to any one of (1) to (4) above in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and, more preferably, from 0.05% to 5% by weight, relative to the total weight of the composition.

[0131] (Cationic polymer)

[0132] A cationic polymer has a positive charge density. The charge density of the cationic polymer can 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 meq / g.

[0133] It may be preferable that the molecular weight of the cationic polymer be equal to or greater than 500, preferably equal to or greater than 1,000, more preferably equal to or greater than 2,000, and even more preferably equal to or greater than 3,000.

[0134] Unless otherwise specified in the descriptions, "molecular weight" means number average molecular weight.

[0135] The cationic polymer may have at least one positively chargeable and / or positively charged fraction selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group. The term "amino group" (primary) here refers to an -NH2 group.

[0136] The cationic polymer can be a homopolymer or a copolymer. By "copolymer" is meant 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.

[0137] The cationic polymer can be chosen from natural and synthetic cationic polymers. Non-limiting examples of cationic polymers are as follows.

[0138] (1) Homopolymers and copolymers derived from acrylic esters and amides or methacrylics and comprising at least one motif chosen from the motifs of the following formulas: R» 1¾ R; .........GH;........0.....OHî........C...................OHs........Ç.............. GG HH TO A TO FU——Rs A Rf" | Rf R. R§ Lî —CH?—0-- HH i XA —R* R§

[0139] in which:

[0140] Ri and R2, which may be identical or different, are chosen from hydrogen and alkyl groups comprising 1 to 6 carbon atoms, for example methyl and ethyl groups;

[0141] R3, which may be identical or different, is chosen from hydrogen and CH3;

[0142] the symbols A, which may be identical or different, are chosen from linear or branched alkyl groups comprising from 1 to 6 carbon atoms, for example from 2 to 3 carbon atoms and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;

[0143] R4, R5 and R6, which may be identical or different, are chosen from groups alkyl comprising from 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment, alkyl groups comprising from 1 to 6 carbon atoms and

[0144] X is a union derived from an inorganic or organic acid, such as methosulfate anions and halides, for example chloride and bromide.

[0145] The copolymers of the family (1) above may also include at least one motif derived from comonomers which may be selected from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen atom with lower alkyl groups (Ci-C4), groups derived from acrylic or methacrylic acids and their esters, vinyllactams such as vinylpyrrolidone and vinylcaprolactam and vinyl esters.

[0146] Examples of copolymers of family (1) include, but are not limited to:

[0147] copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide,

[0148] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in European Patent Application No. 0 080 976,

[0149] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate,

[0150] quaternized or non-quaternized methacrylate or vinylpyrrolidone / dialkylaminoalkyl acrylate copolymers, described, for example, in French Patents No. 2,077,143 and 2,393,573,

[0151] dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers,

[0152] vinylpyrrolidone / methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymers and

[0153] crosslinked polymers of methacryloyloxy(Ci-C4)alkyltri(Ci-C4)alkylammonium salts such as polymers obtained by homopolymerization of quaternized dimethylaminoethyl methacrylate with methyl chloride, or by copolymerization of acrylamide with quaternized dimethylaminoethyl methacrylate with methyl chloride, the homo- or copolymerization being followed by crosslinking with a compound containing an olefinic unsaturation, in particular methylenebisacrylamide.

[0154] (2) Cationic cellulose polymers such as cellulose ether derivatives comprising one or more quaternary ammonium groups described, for example, in French patent No. 1,492,597, such as the polymers marketed under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammonium compounds of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.

[0155] It is preferable that the cationic cellulosic polymer has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group and, more preferably, a quaternary trimethylammonium group.

[0156] The quaternary ammonium group may be present in a quaternary ammonium group which can be represented by the following chemical formula (I):

[0157] in which

[0158] each of Ri and R2 designates an alkyl group Ci_3, preferably a methyl or ethyl group and, more preferably, a methyl group,

[0159] R3 designates an alkyl group C, 24- preferably a methyl or ethyl group and, more preferably, a methyl group,

[0160] X- denotes an anion, preferably a halide and, more preferably, a chloride,

[0161] n denotes an integer between 0 and 30, preferably between 0 and 10 and, more preferably, equal to 0, and

[0162] R4 designates an alkylene group at C1.4, preferably an ethylene or propylene group.

[0163] The leftmost ether bond (-O-) in the above chemical formula (I) can attach to the sugar ring of the polysaccharide.

[0164] It is preferable that the group containing the quaternary ammonium be -O-CH2-CH(OH)-CH2-N+(CH3)3.

[0165] (3) Cationic cellulose polymers such as cellulosic copolymers and cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and described, for example, in US Patent No. 4,131,576, such as hydroxyalkylcelluloses, for example, hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted, with, for example, a salt selected from the salts of methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium.

[0166] Commercial products corresponding to these polymers include, for example, products marketed under the names "Celquat® L 200" and "Celquat® H 100" by the company National Starch.

[0167] (4) Non-cellulosic cationic polysaccharides described in US patents Nos. 3,589,578 and 4,031,307, such as guar gums comprising groups Cationic trialkylammonium compounds, cationic hyaluronic acid, and dextran hydroxypropyltrimonium chloride are used. Guar gums modified with a salt, for example, 2,3-epoxypropyltrimethylammonium chloride (hydroxypropyltrimonium guar chloride), can also be used.

[0168] These products are marketed, for example, under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162 by the company MEYHALL.

[0169] (5) Polymers comprising piperazinyl units and alkylene groups or divalent hydroxyalkylene comprising straight or branched chains, optionally interrupted with at least one entity selected from oxygen, sulfur, nitrogen, aromatic and heterocyclic rings, as well as the oxidation and / or quaternization products of these polymers. These polymers are described, for example, in French patents Nos. 2,162,025 and 2,280,361.

[0170] (6) Water-soluble polyaminoamides prepared, for example, by polycondensation of an acidic compound with a polyamine; these polyaminoamides being optionally crosslinked with an entity selected from among the epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; biunsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacyidiamines; bisalkyl halides; oligomers resulting from the reaction of a difunctional compound that is reactive with an entity selected from among the bishalohydrins; bisazetidiniums, bishaloacyidiamines, bisalkyl halides; epihalohydrins; dihydroxides and bisunsaturated derivatives; the crosslinking agent being used in an amount from 0.025 to 0.35 mole per amine group of polyaminoamides; These polyaminoamides are optionally alkylated or, if they include at least one tertiary amine function, they can be quaternized. These polymers are described, for example, in French patents Nos. 2,252,840 and 2,368,508.

[0171] (7) Polyamino-amide derivatives resulting from the condensation of polyamines of polyalkylene with polycarboxylic acids, followed by alkylation with difunctional agents, for example, adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, and the alkylene group comprises 1 to 4 carbon atoms, such as an ethylene group. These polymers are described, for example, in French patent No. 1,583,363. In at least one embodiment, these derivatives may be selected from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.

[0172] (8) Polymers obtained by reaction of a polyamine polyalkylene comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid selected from diglycolic acid and aliphatic acids

[0173] Saturated dicarboxylic acids comprising 3 to 8 carbon atoms. The molar ratio of the polyamine polyalkylene to the dicarboxylic acid can vary from 0.8:1 to 1.4:1; the polyamino amide resulting from this reaction with epichlorohydrin has a molar ratio of epichlorohydrin to the secondary amine group of the polyamino amide ranging from 0.5:1 to 1.8:1. These polymers are described, for example, in US Patent Nos. 3,227,615 and 2,961,347. (9) Alkyldiallylamine cyclopolymers and dialkyldiallyl-ammonium cyclopolymers, such as homopolymers and copolymers comprising, as the principal constituent of the chain, at least one unit selected from the units of formulas (la) and (Ib): — ^0(¾) —CHg— HîC,x ...... CHS y / \ Rw Rh

[0174]

[0175]

[0176]

[0177] (Ib) in which: k and t, which can be identical or different, are equal to 0 or 1, the sum k+t being equal to 1; Rn is chosen from among the hydrogen and methyl groups; Rio and Rn, which may be identical or different, are chosen from alkyl groups comprising 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group comprises, for example, 1 to 5 carbon atoms, and lower amidoalkyl groups (C1-C4), or Rio and Rn can form, with the atom of nitrogen to which they are attached, heterocyclic groups such as piperidinyl and morpholinyl and

[0178] Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, and phosphate. These polymers are described, for example, in French patent No. 2,080,759 and its certificate of addition 2,190,406.

[0179] In one embodiment, Rio and Ru, which may be identical or different, are chosen from alkyl groups comprising 1 to 4 carbon atoms.

[0180] Among these polymers, we can mention, in particular, diallyldialkyl ammonium (co)chloride such as the dimethylidiethylammonium chloride homopolymer sold under the name "MERQUAT® 100" by the company CALGON (and its low weight average molecular weight homologues) and the copolymers of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550 "

[0181] Quaternary diammonium polymers comprising at least one repeating motif of formula (II): Ru N*.....A, | X Ru (II)

[0182] in which:

[0183] Rn, Ru, Rb and R[6, which may be identical or different, are selected from aliphatic, alicyclic and aliphatic aryl groups comprising from 1 to 20 carbon atoms and lower hydroxyalkyl aliphatic groups, or Rn, Ru, R[5 and Ri6, together or separately, with the nitrogen atoms to which they are attached, heterocycles alternatively comprising a second heteroatom other than nitrogen, or Rn, RM, R[5, and R[6, which may be identical or different, are selected from linear or branched Ci-C6 alkyl groups substituted by at least one group selected from alkyl groups, ester groups, acyl groups, amide groups, -CO-O-Rp-E groups and -CO-NH-Rp-E groups, where Rn is an alkylene group and E is a quaternary ammonium group;

[0184] Ai and Bb, which may be identical or different, are selected from polymethylene groups comprising from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may include, bonded or intercalated in the main chain, at least one entity selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, and other groups. amino, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups, and ester groups, and

[0185] X denotes an anion derived from an inorganic or organic acid;

[0186] it being understood that Ab Rn and Ri5 can form, with the two nitrogen atoms to which they are attached, a piperazine cycle;

[0187] If Ai is chosen from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, Bi can be chosen from:

[0188] -(CH2)n—CO-E'-OC-(CH2)n-

[0189] where E' is chosen from:

[0190] a) glycolic residues of formula -OZO-, where Z is selected from linear or branched hydrocarbon groups and groups of the following formulas:

[0191] -(CH2-CH2-O)X-CH2-CH2-

[0192] -[CH2-CH(CH3)-O]y-CH2-CH(CH3)-

[0193] where x and y, which may be identical or different, are chosen from integers from 1 to 4, which represent a defined and unique degree of polymerization, and numbers from 1 to 4, which represent an average degree of polymerization;

[0194] b) a bis-secondary diamine residue such as piperazine derivatives;

[0195] c) bis-primary diamine residues of formula -NH-Y-NH-, wherein Y is selected from linear or branched hydrocarbon groups and the divalent group -CH2-CH2-SS-CH2-CH2-CH2-; and

[0196] d) ureylene groups of formula -NH-CO-NH-.

[0197] In at least one embodiment, X is an anion such as chloride or bromide.

[0198] Polymers of this type are described, for example, in French patents Nos. 2,320,330; 2,270,846; 2,316,271; 2,336,434; and 2,413,907 and in US patents Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261,002; 2,271,378; 3,874,870; 4,001,432; 3,929,990; 3,966,904; 4,005,193; 4,025,617; 4,025,627; 4,025,653; 4,026,945 and 4,027,020.

[0199] Non-limiting examples of these polymers include those comprising at least one repeating formula unit (III): RO (III) h* (CHg)™'" Ri 4 Rj§

[0200] in which

[0201] Rn, Ru, Rb and Ri6, which may be identical or different, are selected from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbon atoms, n and p, which may be identical or different, are integers from 2 to 20, and X is an anion derived from an inorganic or organic acid.

[0202] (11) polyquaterary ammonium polymers comprising formula motifs (IV): Rts Rb ™ N *—A™ X | | Ri§ X"' (IV)

[0203] in which:

[0204] Ri8, R19, R20 and R2B, which may be identical or different, are chosen from hydrogen, methyl groups, ethyl groups, propyl groups, [3-hydroxyethyl] groups, [3-hydroxypropyl] groups, -CH2CH2(OCH2CH2)pOH, where p is chosen from integers from 0 to 6, provided that R[8, Ri9, R20 and R2i are not simultaneously hydrogen,

[0205] r and s, which may be identical or different, are chosen from integers ranging from 1 to 6,

[0206] q is chosen from integers ranging from 0 to 34,

[0207] - X denotes an anion, such as a halide and

[0208] A is chosen from among the radicals of dihalides and -CH2-CH2-O-CH2-CH2-.

[0209] These compounds are described, for example, in European patent application No. 0 122 324.

[0210] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0211] Other examples of suitable cationic polymers include, in particular, cationic proteins and cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers comprising motifs selected from vinylpyridine and vinylpyridinium, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.

[0212] According to one embodiment of the present invention, at least one cationic polymer is selected from cellulose ether derivatives comprising quaternary ammonium groups, such as the products sold under the name "JR 400" by UNION CARBIDE CORPORATION, cationic cyclopolymers, by For example, dimethyldiallylammonium chloride homopolymers and copolymers sold under the names MERQUAT® 100, MERQUAT® 550, and MERQUAT® S by the company CALGON, guar gums modified with a salt of 2,3-epoxypropyltrimethylammonium, and quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0213] (13) Polyamines

[0214] As a cationic polymer, it is also possible to use (co)polyamines, which can be homopolymers or copolymers, with a plurality of amino groups. The amino group can be a primary, secondary, tertiary, or quaternary amino group. The amino group can be present in the backbone of a polymer or in a pendant group, if present, of the (co)polyamines.

[0215] Examples of (co)polyamines include chitosan, (co)polylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polydimethylaminoethylene methacrylates, (co)polyvinylpyridines such as (co)poly-l-methyl-2-vinylpyridines, (co)polyimines such as (co)polyimines, (co)polypyridines such as (co)poly(quaternary pyridines), (co)polybiguanides such as (co)polyaminopropyl biguanides, (co)polylysines, (co)polyomithines, (co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinylacetals and their salts.

[0216] As for (co)polyamines, it is preferable to use (co)polylysines. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine, which can be produced by bacterial fermentation. Polylysine can be α-polylysine or ε-polylysine. For example, polylysine can be ε-polylysine, such as ε-Poly-L-lysine, which is typically used as a natural preservative in food products. Polylysine is a polyelectrolyte that is soluble in polar solvents such as water, propylene glycol, and glycerol. Polylysine is commercially available in various forms, such as poly D-lysine and poly L-lysine. Polylysine can be in the form of a salt and / or a solution.

[0217] (14) Cationic amino acids

[0218] As a cationic polymer, it may be possible to use cationic polyamino acids, which may be homopolymers or cationic copolymers, with a plurality of amino and carboxyl groups. The amino group may be primary, secondary, tertiary, or quaternary. The amino group may be present in the backbone of a polymer or in a pendant group, if present, of the cationic polyamino acids. The carboxyl group may be present in a pendant group, if present, of the cationic polyamino acids.

[0219] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, and hydroxypropyl hydrolyzed wheat protein. steardimonium, hydrolyzed wheat protein hydroxypropyl cocodimonium, hydrolyzed conchiolin protein hydroxypropyltrimonium, hydrolyzed soy protein hydroxypropyl steardimonium, hydrolyzed soy protein hydroxypropyltrimonium, hydrolyzed soy protein hydroxypropyl cocodimonium, and similar products.

[0220] The following descriptions relate to preferred embodiments of the cationic polymer.

[0221] It may be preferable to choose the cationic polymer from among the cationic starches.

[0222] Examples of cationic starches include starches modified with a salt of 2,3-epoxypropyltrimethylammonium (ex: chloride), such as the product called starch hydroxypropyltrimonium chloride according to the INC1 nomenclature and sold under the name SENSOMER Cl-50 by Ondeo or Pencare™ DP 1015 by Ingredion.

[0223] It may also be preferable to choose the cationic polymer from among the cationic gums.

[0224] Gums may, for example, be chosen from the group consisting of cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum and arabic gum.

[0225] Examples of cationic gums include cationic polygalactomannan derivatives such as guar gum derivatives and cassia gum derivatives, for example CTFA: Guar Hydroxypropyltrimonium Chloride, Hydroxypropyl Guar Hydroxypropyltrimonium Chloride, and Cassia Hydroxypropyltrimonium Chloride. Guar hydroxypropyltrimonium chloride is commercially available under the Jaguar™ brand name of Rhodia Inc. and the N-Hance brand name of Ashland Inc. Cassia hydroxypropyltrimonium chloride is commercially available under the Sensomer™ CT-250 and Sensomer™ CT-400 brands of Lubrizol Advanced Materials, Inc. or ClearHance™ of Ashland Inc.

[0226] It may also be preferable to choose the cationic polymer from among the chitosans.

[0227] It may be preferable that the cationic polymer be chosen from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as cationized collagen, cationic polymers and their salts.

[0228] It may be more preferable for the cationic polymer to be chosen from the group consisting of polylysine, polyquaternium-4, polyquaternium-10, the polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan and a mixture thereof.

[0229] The quantity of the cationic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more and, more preferably, 0.05% by weight or more, relative to the total weight of the composition.

[0230] The quantity of the 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.

[0231] The quantity of the cationic polymer(s) in the composition according to the present invention can be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and, more preferably, from 0.05% to 5% by weight, relative to the total weight of the composition.

[0232] (Anionic polymer)

[0233] An anionic polymer has a positive charge density. The charge density of the anionic polymer can be from 0.1 meq / g to 20 meq / g, preferably from 1 to 15 meq / g and, more preferably, from 4 to 10 meq / g if the anionic polymer is a synthetic anionic polymer, and the average degree of substitution of the anionic polymer can be from 0.1 to 3.0, preferably from 0.2 to 2.7 and, more preferably, from 0.3 to 2.5 if the anionic polymer is a natural anionic polymer.

[0234] It may be preferable that the molecular weight of the anionic polymer be 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 100,000, greater than or equal to 1,000,000 or more.

[0235] Unless otherwise specified in the descriptions, "molecular weight" means number average molecular weight.

[0236] According to the present invention, the anionic polymer is selected from hyaluronic acid, its salts, and its derivatives.

[0237] Hyaluronic acid can be represented by the following chemical formula.

[0238]

[0239] In the context of the present invention, the term "hyaluronic acid" specifically covers the basic hyaluronic acid motif of formula:

[0240]

[0241]

[0242]

[0243]

[0244] This is the smallest fraction of hyaluronic acid comprising a disaccharide dimer, namely D-glucuronic acid and N-acetylglucosamine. The term "derived" hyaluronic acid also includes, in the context of the present invention, the linear polymer comprising the polymeric motif described above, linked together in the chain via alternating [3(1,4) and [3(1,3)] glycosidic bonds, having a molecular weight (MW) that 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 preparation processes. The term "salts" of hyaluronic acid, in the context of the present invention, includes any salt of hyaluronic acid. Examples of salts include alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof. 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 crista galli apophysis. Thus, the term "hyaluronic acid" includes all fractions or subunits of hyaluronic acid having a particular molecular weight within the molecular weight range recalled above.

[0245] In the context of the present invention, hyaluronic acid fractions that do not have inflammatory activity are preferably used.

[0246] As an illustration of the different fractions of hyaluronic acid, reference may be made to the document "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 according to its molecular weight.

[0247] 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 weight between 50 kDa and 5,000 kDa, in particular between 100 kDa and 5,000 kDa, in particular between 400 kDa and 5,000 kDa. In this case, the term used is high molecular weight hyaluronic acid.

[0248] Alternatively, the hyaluronic acid fractions that may also be suitable for the use covered by the present invention have a molecular weight between 50 kDa and 400 kDa. In this case, the term used is intermediate molecular weight hyaluronic acid.

[0249] Alternatively, the hyaluronic acid fractions suitable for the use covered by the present invention have a molecular weight of less than 50 kDa. In this case, the term used is low molecular weight hyaluronic acid.

[0250] It may be preferable to use a combination of two or more hyaluronic acids or salts thereof, such as a combination of high molecular weight hyaluronic acid or a salt thereof, and intermediate molecular weight hyaluronic acid or a salt thereof; a combination of high molecular weight hyaluronic acid or a salt thereof, and low molecular weight hyaluronic acid or a salt thereof; and a combination of intermediate molecular weight hyaluronic acid or a salt thereof, and low molecular weight hyaluronic acid or a salt thereof.

[0251] Finally, the term "derived" from hyaluronic acid also includes hyaluronic acid esters, in particular those in which all or part of the carboxylic groups of the acid functions are esterified with oxyethylenated alkyls or alcohols, containing from 1 to 20 carbon atoms, in particular with a degree of substitution at the level of D-glucuronic acid of hyaluronic acid of between 0.5 and 50%.

[0252] Reference may be made in particular to methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. These esters were notably described in D. Campoccia et al. “Semisynthetic resorbable materials from hyaluronan esterification”, Biomaterials 19 (1998) 2101-2127.

[0253] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.

[0254] The molecular weights indicated above are also valid for hyaluronic acid esters.

[0255] 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 106), 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).

[0256] The amount of the anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more and, more preferably, 0.05% by weight or more, relative to the total weight of the composition.

[0257] The quantity of the 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.

[0258] The quantity of the anionic polymer(s) in the composition according to the present invention can be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and, more preferably, from 0.05% to 5% by weight, relative to the total weight of the composition.

[0259] (Amphoteric polymer)

[0260] An amphoteric polymer has both a positive charge density and a negative charge density.

[0261] The positive charge density of the amphoteric polymer can 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 meq / g.

[0262] The negative charge density of the amphoteric polymer can 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 meq / g.

[0263] It may be preferable that the molecular weight of the amphoteric polymer be equal to or greater than 500, preferably equal to or greater than 1,000, more preferably equal to or greater than 10,000, and even more preferably equal to or greater than 100,000.

[0264] It may be preferable that the molecular weight of the amphoteric polymer be less than or equal to 1,000,000, preferably less than or equal to 900,000 and, more preferably, less than or equal to 800,000.

[0265] Unless otherwise specified in the descriptions, "molecular weight" means number average molecular weight.

[0266] According to the present invention, the amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0267] Cationized hyaluronic acid comprises at least one cationic group, such as an ammonium group, in its molecule. The cationic group does not indicate a counter-cation of the salt, because the counter-cation is not present in the hyaluronic acid molecule.

[0268] As salts, mention may be made of alkali metal salts such as sodium salt, alkaline earth metal salts such as magnesium salts, ammonium salts and mixtures thereof.

[0269] Cationized hyaluronic acid may have at least one group containing a quaternary ammonium group.

[0270] Cationized hyaluronic acid and / or a salt thereof may have a structure represented by the following general formula (1): (1)

[0271] in which

[0272] R4 to R9 individually represent a hydrogen atom or a group containing a quaternary ammonium group (excluding a case where all R4 to R9 represent hydrogen atoms), and n represents an integer from 2 to 5,000.

[0273] Examples of the group containing a quaternary ammonium group represented by R4 to R9 in the general formula (1) above include groups represented by the following general formula (2):

[0274] in which

[0275] R1 to R3 individually represent hydrocarbon groups, and X represents a monovalent anion.

[0276] Examples of hydrocarbon groups represented by R1 to R3 in the general formula (2) above include a linear or branched alkyl group, an unsaturated hydrocarbon group, and an aromatic hydrocarbon group. Of these, the alkyl group is preferred. Examples of the alkyl group include alkyl groups having 1 to 30 (preferably 1 to 6) carbon atoms. Preferably, the hydrocarbon groups represented by R1 to R3 are alkyl groups having 1 to 3 carbon atoms.

[0277] Examples of monovalent pennant represented by X in the general formula (2) above include a halogen ion such as a fluorine ion, a bromine ion, a chloride ion and an iodine ion.

[0278] The group containing a quaternary ammonium group can be introduced by replacing the hydrogen atom of the carboxyl group included in the hyaluronic acid and / or a salt thereof used as a raw material (hereinafter referred to as "raw material hyaluronic acid and / or a salt thereof") with the group containing a quaternary ammonium group. In this case, the group containing a quaternary ammonium group is bonded to the oxygen atom of the (-C(=O)O—) group included in the cationized hyaluronic acid and / or a salt thereof according to this embodiment.The fact that the group containing a quaternary ammonium group is linked to the oxygen atom of the (-C(=O)O-) group included in the cationized hyaluronic acid and / or a salt thereof according to this embodiment can be confirmed by the presence of a peak attributed to the carbon atom of the -C(=O)O- group to which the group containing a quaternary ammonium group is linked via the oxygen atom, determined by analyzing the chemical shift of the nuclear magnetic resonance (13C NMR).

[0279] Specifically, the group containing a quaternary ammonium group can be obtained by reacting the carboxyl group (and / or the hydroxyl group) of the raw material hyaluronic acid and / or a salt thereof with a cationizing agent containing a quaternary ammonium group. Preferably, the cationizing agent should be at least one of a 2,3-epoxypropyltrialkylammonium halide shown by the following general formula (3) and a 3-halo-2-hydroxypropyltrialkylammonium halide shown by the following general formula (4). The reaction of the raw material hyaluronic acid and / or a salt thereof with the cationizing agent is described in the production method below. T'1 CHr 0 * X k O to 2 (3)

[0280] in which

[0281] R1 to R3 are the same as those defined for the general formula (2), and X represents a halogen atom. R 1 ÇHs—CH—CH?—bC—R'* * .X' ¥ ÔH R 2 (4)

[0282] in which

[0283] R1 to R3 are the same as those defined for the general formula (2), and X and Y individually represent halogen atoms.

[0284] Examples of halogen atoms represented by X and Y in the general formulas (3) and (4) above include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.

[0285] The cationized hyaluronic acid may have at least one group containing a quaternary ammonium group and has a degree of cationization of 0.05 to 0.6, preferably of 0.1 to 0.5, and more preferably of 0.15 to 0.4.

[0286] The degree of cationization (i.e. the degree of substitution by the group containing a quaternary ammonium group) of the cationized hyaluronic acid and / or a salt thereof according to this embodiment can be determined by calculating the nitrogen content of the sodium hyaluronate of raw material and the nitrogen content of the cationized hyaluronic acid by the semi-micro Kjeldahl method, and by calculating the degree of cationization by the following expression on the basis of the increase in nitrogen content.

[0287] When the nitrogen content of the raw material sodium hyaluronate is denoted Nn (%) and the nitrogen content of the cationized hyaluronic acid having a degree of cationization of (x) is denoted Ns (%), the relationship between the increase in nitrogen content (Ns-Nn) and the degree of cationization (x) is shown by the following expression.

[0288] Ns-Nn(%)

[0289] = [14x / (molecular weight of the cationized hyaluronic acid disaccharide motif)]xl00

[0290] = [14x / (molecular weight of the disaccharide motif of sodium hyaluronate of raw material) - 129.5x] x 100

[0291] =[14x / (401.3+129.5x)]xl00

[0292] Therefore, the degree of cationization (i.e., the degree of substitution by the group containing the quaternary ammonium) can be calculated by the following expression.

[0293] Degree of cationization(x)=[(Ns-NN)x401.3] / [1400-129.5*(Ns-NN)]

[0294] The degree of cationization of a cationized hyaluronic acid when a raw material hyaluronic acid is unknown can be calculated by the above expression assuming that the raw material sodium hyaluronate is sodium hyaluronate of 99% purity or more.

[0295] It is possible that 1% or more, preferably 5% or more, and more preferably 10% or more and / or 50% or less, preferably 40% or less and more preferably 30% or less of the anionic groups in the hyaluronic acid may be replaced by a cationic group, preferably a group containing a quaternary ammonium group, and more preferably the group containing a quaternary ammonium group represented by the general formula (2) above.

[0296] As an example of cationized hyaluronic acid, hydroxypropyltrimonium hyaluronate, marketed under the names Hyaloveil and Hyaloveul-MPF by Kewpie in Japan, can be cited.

[0297] The amount of the anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.

[0298] The quantity of the amphoteric 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.

[0299] The quantity of the amphoteric polymer(s) in the composition according to the present invention can be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and, more preferably, from 0.05% to 5% by weight, relative to the total weight of the composition.

[0300] (Non-polymeric acid having two or more acid dissociation constants)

[0301] The composition according to the present invention may comprise at least one non-polymer acid having two or more pKa values ​​or salt(s) thereof, i.e., at least one non-polymer 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.

[0302] The non-polymeric acid having two or more pKa values ​​or salt(s) thereof may be included in the (a) polyionic complex. The non-polymeric acid having Two or more pKa values ​​can function as a crosslinker, especially an anionic crosslinker, for the cationic polymer and / or the amphoteric polymer.

[0303] It is preferable that the non-polymeric acid having two or more pKa values ​​or salt(s) thereof be used with a cationic polymer and an anionic polymer.

[0304] The term "non-polymer" here means that the acid is not obtained by polymerizing two or more monomers. Therefore, a non-polymer acid does not correspond to an acid obtained by polymerizing two or more monomers, such as a polycarboxylic acid.

[0305] Preferably the molecular weight of the non-polymer acid having two or more pKa values ​​or of salt(s) thereof is less than or equal to 1000, preferably less than or equal to 800, and more preferably less than or equal to 700.

[0306] There is no limit to the type of non-polymer acid having two or more pKa values ​​or salt(s) thereof. Two or more different types of non-polymer acids having two or more pKa values ​​or their salts may be used in combination. Thus, a single type of non-polymer acid having two or more pKa values ​​or a salt thereof, or a combination of different types of non-polymer acids having two or more pKa values ​​or salts thereof, may be used.

[0307] The term "salt" herein means a salt formed by the addition of suitable base(s) to a non-polymer acid having two or more pKa values, which can be obtained from a reaction with the non-polymer acid having two or more pKa values ​​with the base(s) according to processes known to those skilled in the art. Examples of salts include metallic salts, for example, alkali metal salts such as Na and K, alkaline earth metal salts such as Mg and Ca, and ammonium salts.

[0308] The 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 a salt(s) thereof.

[0309] The 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.

[0310] The non-polymeric acid having two or more pKa values ​​can be a non-polymeric polyvalent acid.

[0311] The non-polymer acid having two or more pKa values ​​may be chosen from the group consisting of dicarboxylic acids, disulfonic acids and diphosphoric acids, as well as a mixture of these.

[0312] The non-polymer acid having two or more 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; sulfonic acid terephthalylidene diamphr or their salts (Mexoryl 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 Carminé), Red 201 (Lithol Rubine B), Red 202 (Lithol Rubine B), (Lithol Rubine BCA), Red 204 (Lake Red CBA), Red 206 (Lithol 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 F5R), Red 502 (Ponceau 3R), Red 503 (Ponceau R), Red 504 (Ponceau SX), Green 401 (Naphthol Green B), Green 402 (Guinea Green B), and Black 401 (Naphthol Blue Black); acide folique, acide ascorbique, acide erythorbique et leurs sels ; cystine et ses sels ; EDTA et ses sels ; glycyrrhizine et ses sels ; et un mélange de ceux-ci. ;

[0313] It may be preferable that the non-polymer acid having two or more pKa values ​​or one or more of its salts be chosen from the group consisting of terephthalylidene diamphrulfonic acid and its salts (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salts, and a mixture of these.

[0314] The amount of 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% by weight or more, preferably 0.005% by weight or more and, more preferably, 0.01% by weight or more, relative to the total weight of the composition.

[0315] The amount of the non-polymeric acid having two or more pKa values ​​or salt(s) thereof 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.

[0316] The amount of non-polymeric acid having two or more pKa values ​​or of salt(s) thereof in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight and, more preferably, from 0.01% to 5% by weight, relative to the total weight of the composition.

[0317] (Non-polymer base having two or more base dissociation constants)

[0318] The composition according to the present invention may include at least one non-polymer base having two or more pKb values ​​or salt(s) thereof, i.e., at least one non-polymer base having two or more base dissociation constants or salt(s) thereof. The pKb value (base dissociation constant) is well known to those skilled in the art and should be determined at a constant temperature such as 25 °C.

[0319] The non-polymer base having two or more pKb values ​​or salt(s) thereof may be included in the (a) polyionic complex. The non-polymer base having two or more pKb values ​​may function as a crosslinker, in particular a cationic crosslinker, for the anionic polymer and / or amphoteric polymers.

[0320] It is preferable that the non-polymeric acid having two or more pKb values ​​or salt(s) thereof be used with a cationic polymer and an anionic polymer.

[0321] The term "non-polymer" here means that the base is not obtained by polymerization of two or more monomers. Therefore, a non-polymer base does not correspond to a base obtained by polymerization of two or more monomers such as polyallylamine.

[0322] It is preferable that the molecular weight of the non-polymer base having two or more pKb values ​​or of salt(s) thereof be less than or equal to 1000, preferably less than or equal to 800 and, more preferably, less than or equal to 700.

[0323] There is no limit to the type of non-polymer base having two or more pKb values ​​or salt(s) thereof. Two or more different types of non-polymer bases having two or more pKb values ​​or their salts may be used in combination. Thus, a single type of non-polymer base having two or more pKb values ​​or a salt thereof, or a combination of different types of non-polymer bases having two or more pKb values ​​or salts thereof, may be used.

[0324] The term "salt" herein means a salt formed by the addition of suitable acid(s) to a non-polymer acid having two or more pKb values, which can be obtained from a reaction with a non-polymer base having two or more pKb values ​​with the acid or acids according to processes known to those skilled in the art. Examples of salts include ammonium salts, for example, salts with inorganic acids such as HCl and HNO3, and salts with an organic acid such as carboxylic acids and sulfonic acids.

[0325] The non-polymer base having two or more pKb values ​​or salt(s) thereof may be an organic base or salts thereof, and preferably a hydrophilic or water-soluble organic base or salts thereof.

[0326] The non-polymer base having two or more pKb values ​​may have at least two basic groups selected from the group consisting of an amino group, a guanidine group, a biguanide group, an imidazole group, an imino group, a pyridyl group and a mixture thereof.

[0327] The non-polymer base having two or more pKb values ​​may be chosen from the group consisting of non-polymer diamines such as ethylenediamine, propylenediamine, pentanediamine, hexanediamine, urea and its derivatives and guanidine and its derivatives, non-polymer polyamines such as spermine and spermidine, basic amino acids and a mixture thereof.

[0328] The non-polymer base having two or more pKb values ​​or salt(s) thereof may be chosen from the group consisting of arginine, lysine, histidine, cysteine, cystine, tyrosine, tryptophan, omithine and a mixture thereof.

[0329] It may be preferable that the non-polymer base having two or more pKb values ​​or salt(s) thereof be chosen from the group consisting of arginine, lysine, histidine and a mixture thereof.

[0330] The amount of the non-polymer base having two or more pKb values ​​or salt(s) thereof in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more and, more preferably, 0.01% by weight or more, relative to the total weight of the composition.

[0331] The amount of the non-polymer base having two or more pKb values ​​or salt(s) thereof 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.

[0332] The quantity of the non-polymer base having two or more pKb values ​​or of salt(s) thereof in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight and, more preferably, from 0.01% to 5% by weight, relative to the total weight of the composition.

[0333] [Lipophilic antioxidant]

[0334] The composition according to the present invention may include (b) at least one lipophilic antioxidant. Two or more lipophilic antioxidants may be used in combination. Thus, a single type of lipophilic antioxidant or a combination of different types of lipophilic antioxidants may be used.

[0335] According to the present invention, antioxidant agents are compounds or substances that can trap the different forms of radicals that may be present in the skin; preferably, they simultaneously trap all the different forms of radicals present.

[0336] The (b) lipophilic antioxidant means that the partition coefficient of the antioxidant agent between n-butanol and water is > 1, more preferably > 10 and even more preferably > 100.

[0337] The (b) lipophilic antioxidant is hydrophobic, and is not a hydrophilic antioxidant such as ascorbic acid or glutathione.

[0338] As (b) lipophilic antioxidants, phenolic antioxidants which have a hindered phenol structure or a semi-hindrained phenol structure within the molecule may be cited. Specific examples of such compounds include 3,5-bis(1,l-dimethylethyl)-4-hydroxybenzenepropanoic acid (INCI name pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono-, di-, or tri-(α-methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, and 2,5-di-tert-amylhydroquinone, tris[N-(3,5-di-tert-butyl-4-hydroxybenzyl)]isocyanurate, l,l,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, butylidene-l,lbis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3-(3,octadecyl 5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionato]methane, triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], the N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], l,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-l,3,5-triazine-2,4,6-trione, 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-l,3,5-triazine, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, acrylate 2-[l-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl, the 4,6-bis[(octylthio)methyl]-o-cresol, 2,4-di-tert-butyl-4-hydroxybenzoate, and 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. ,

[0339] Examples of (b) lipophilic antioxidants include BHA (butylated hydroxyanisole) and BHT (butylated hydroxytoluene), vitamin E (or tocopherols and tocotrienol) and their derivatives, such as the phosphate derivative, for example TPNA® sold by Showa Denko, coenzyme Q10 (or ubiquinone), idebenone, certain carotenoids such as lutein, astaxanthin, beta-carotene, polyphenols, phenolic acids and derivatives (e.g., chlorogenic acid) and flavonoids, which represent the main subgroup of polyphenols.

[0340] Among the flavonoids, mention may be made in particular of chalcones, hydroxylated chalcones and their reduced derivatives (as described in particular in patent FR 2 608 150), for example phloretin, neohesperidin, phloridzin, aspalathin, etc., flavanones, for example hesperetin and naringin, flavonols, for example quercetin, rutin, flavanols, for example catechin, EGCG, flavones, for example apigenidin, and finally anthocyanins. Tannins may also be mentioned. Reference may also be made to the compounds described in patent applications FR 2 699 818, FR 2 706 478, FR 2 907 339, FR 2 814 943 and FR 2 873 026.

[0341] Polyphenolic compounds may be derived from plant extracts selected from extracts of green tea, apple, hops, guava, cocoa, or woods such as chestnut, oak, horse chestnut, or hazelnut. It is also possible to use an extract of pine bark, for example, obtained according to the processes described in US Patent No. 4,698,360, US Patent No. 6,372,266, and US Patent No. 5,720,956. Examples of such extracts include the compound referenced by the INCI name pinus pinaster (bark extract) and by the CTFA name pine bark extract (pinus pinaster). This may include, in particular, the pine bark extract marketed under the name PYCNOGENOL® by BIOLANDES AROMES and / or HORPHAG Research. Pine bark extract (maritime) from LAYN Natural Ingredients, pine bark from Blue California and oligopin® from DRT (Les Dérivés Résiniques et Terpéniques) can also be mentioned.

[0342] In the context of the present invention, the term "polyphenolic compound" therefore also covers the plant extract itself, which is rich in these polyphenolic compounds.

[0343] The (b) lipophilic antioxidant which may also be mentioned includes dithiolanes, for example asparagusic acid, or its derivatives, for example siliceous dithiolane derivatives, in particular those described in patent application FR 2 908 769.

[0344] The (b) lipophilic antioxidant that may also be mentioned includes:

[0345] glutathione and its derivatives (GSH and / or GSHOEt), such as glutathione alkyl esters (such as those described in patent applications FR 2 704 754 and FR 2 908 769); and

[0346] cysteine ​​and its derivatives, such as N-acetylcysteine ​​or L-2-oxothiazolidine-4-carboxylic acid. Reference may also be made to the cysteine ​​derivatives described in patent applications FR 2 877 004 and FR 2 854 160; and

[0347] ferulic acid and its derivatives (esters, salts, etc.). In particular, we can mention esters of ferulic acid and C1-C30 alcohols, especially methyl ferulate, ethyl ferulate, isopropyl ferulate and octyl ferulate, and oryzanyl ferulate;

[0348] certain enzymes for defense against oxidative stress, such as catalase, superoxide dismutase (SOD), lactoperoxidase, glutathione peroxidase and quinone reductases;

[0349] benzylcyclanones; substituted naphthalenones; pidolates (as described in particular in patent application EP 0 511 118); caffeic acid and its derivatives, gamma-oryzanol; melatonin, sulforaphane and extracts containing it (excluding cress);

[0350] the diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, as described in particular in patent applications WO 94 / 11338, FR 2 698 095, FR 2 737 205 or EP 0 755 925; and

[0351] deferoxamine (or desferal) as described in patent application FR 2 825 920.

[0352] The (b) lipophilic antioxidants that are preferably used are chalcones, more particularly phloretin or neohesperidin, diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, or a pine bark extract such as PYCNOGENOL®.

[0353] Examples of (b) lipophilic antioxidants include pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxyanisole, ascorbyl palmitate, tocopherol and mixtures thereof.

[0354] The quantity of the (b) lipophilic antioxidant(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.

[0355] The quantity of the (b) lipophilic antioxidant(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.

[0356] The quantity of the (b) lipophilic antioxidant(s) in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight and, more preferably, from 0.01% to 5% by weight, relative to the total weight of the composition.

[0357] [Water]

[0358] The composition according to the present invention comprises (c) water.

[0359] The quantity of (c) water may be 10% by weight or more, preferably 30% by weight or more and, more preferably, 50% by weight or more, relative to the total weight of the composition.

[0360] Furthermore, the quantity of (c) water may be 99% by weight or less, preferably 97% by weight or less and, more preferably, 95% by weight or less, relative to the total weight of the composition.

[0361] The quantity of (c) water may be from 10% to 99% by weight, preferably from 30% to 97% by weight and, more preferably, from 50% to 95% by weight, relative to the total weight of the composition.

[0362] [Surfactant]

[0363] The composition according to the present invention may further include (d) at least one surfactant. Two or more surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used.

[0364] The surfactant used in the present invention can be chosen from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants and non-ionic surfactants.

[0365] (Anionic surfactants)

[0366] The composition according to the present invention may comprise at least one anionic surfactant. Two or more anionic surfactants may be used in combination.

[0367] It is preferable that the anionic surfactant be chosen from the group consisting of (C6-C3o)alkyl sulfates, (C6-C30)alkyl ether sulfates, (C6-C3o)alkylamido ether sulfates, alkylaryl polyether sulfates, and monoglyceride sulfates; (C6-C3o)alkylsulfonates, (C6-C3o)alkylamide sulfonates, (C6-C30)alkylaryl sulfonates, α-olefin sulfonates, and paraffin sulfonates; (C6-C3o)alkyl phosphates; (C6-C30)alkyl sulfosuccinates, (C6-C3o)alkyl ether sulfosuccinates, and (C6-C30)alkylamide sulfosuccinates; (C6-C30)alkyl sulfoacetates; (C6-C24)acyl sarcosinates; (C6-C24)acyl glutamates; (C6-C30)alkylpolyglycoside carboxylic ethers; (C6-C30)alkylpolyglycoside sulfosuccinates; (C6-C30)alkyl sulfosuccinamates; (C6-C24)acyl isethionates; N-(C6-C24)acyl taurates; C6-C30 fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (C8-C20)acyl lactylates; uronic acid (C6-C30)alkyl-D-galactoside salts;salts of (C6-C30)alkyl ether polyoxyalkylenated carboxylic acids; salts of (C6-C30)alkylaryl ether polyoxyalkylenated carboxylic acids; and salts of (C6-C30)alkylamido ether polyoxyalkylenated carboxylic acids; and the corresponding acidic forms.

[0368] In at least one embodiment, the anionic surfactants are in the form of salts such as alkali metal salts, for example sodium; metal salts Alkaline earth metals, for example magnesium; ammonium salts; amine salts; amino alcohol salts. Depending on the conditions, they can also be in acidic form.

[0369] It is preferable that the anionic surfactant be chosen from among the salts of (C6-C30)alkyl sulfate, (C6-C3o)alkyl ether sulfates or of polyoxyalkylened (C6-C30)alkyl carboxylic ether acid, salified or not.

[0370] (Amphoteric surfactants)

[0371] The composition according to the present invention may comprise at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.

[0372] Amphoteric or zwitterionic surfactants may be, for example (non-limiting list), derivatives of amines such as secondary or tertiary aliphatic amines, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain comprising 8 to 22 carbon atoms and containing at least one water-soluble anionic group (e.g., carboxylate, sulfate, phosphate or phosphonate).

[0373] The amphoteric surfactant may preferably be chosen from the group consisting of betaines and amidoaminecarboxylated derivatives.

[0374] It is preferable that the amphoteric surfactant be chosen from among the betaine type surfactants.

[0375] The amphoteric surfactant of the betaine type is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and alkylamidoalkylsulfobetaines, in particular, (C8-C24)alkylbetaines, (C8-C24)alkylamido(Ci-C8)alkylbetaines, sulfobetaines, and (C8-C24)alkylamido(Ci-C8)alkylsulfobetaines. In one embodiment, the amphoteric surfactants of the betaine type are selected from (C8-C24)alkylbetaines, (C8-C24)alkylamido(Ci-C8)alkylsulfobetaines, sulfobetaines, and phosphobetaines.

[0376] Non-limiting examples that may be mentioned include compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th edition, 2014, under the names cocobetaine, laurylbetaine, cetylbetaine, coco / oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine, stearamidopropylbetaine, cocamidoethylbetaine, cocamidohydroxysultaine, oleamidopropylhydroxysultaine, cocohydroxysultaine, laurylhydroxysultaine and cocosultaine, alone or in mixtures.

[0377] The amphoteric surfactant of the betaine type is preferably an alkylbetaine and an alkylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine.

[0378] Among the amidoaminecarboxylated derivatives, one can cite the products sold under the name Miranol, as described in US patents Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures:

[0379] RrCONHCH2CH2-N+(R2)(R3)(CH2COO) M+

[0380] in which:

[0381] Ri designates an alkyl radical of an acid RrCOOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical,

[0382] R2 designates a beta-hydroxyethyl group,

[0383] R3 designates a carboxymethyl group,

[0384] M+ denotes a cationic ion derived from alkali metals such as sodium; an ammonium ion; or an ion derived from an organic amine;

[0385] X designates an organic or inorganic anionic ion such as halides, acetates, phosphates, nitrates, alkyl(Ci-C4)sulfates, alkyl(Ci-C4)- or alkyl(Ci-C4)aryl-sulfonates, in particular methylsulfate and ethylsulfate; or M+ and X are not present;

[0386] Ri'-CONCH2CH2-N(B)(C) (B2)

[0387] in which:

[0388] R / designates an alkyl radical of an acid Ri'-COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, such as an alkyl radical in C7, C9, Cn or Ci3, an alkyl radical in Cp and its isoform, or an unsaturated radical in Cp,

[0389] B represents -CH2CH2OX',

[0390] C represents -(CH2)Z-Y', with z=l or 2,

[0391] X' denotes a group -CH2-COOH, -CH2-COOZ', -CH2CH2-COOH, -CH2CH2-COOZ' or a hydrogen atom, and

[0392] Y' denotes a radical -COOH, -COOZ', -CH2-CHOH-SO3Z', -CH2-CHOH-SO3H or a radical -CH2-CH(OH)-SO3-Z',

[0393] where Z' represents an ion of an alkali or alkaline earth metal such as sodium, an ion derived from an organic amine or an ammonium ion;

[0394] and

[0395] Ra » -NH-CH(Y")-(CH2)nC(O)-NH-(CH2)nN(Rd)(Re) (B'2)

[0396] in which:

[0397] Y" denotes -C(O)OH, -C(O)OZ", -CH2-CH(OH)-SO3H or -CH2-CH(OH)-SO3-Z", where Z" denotes a cationic ion derived from an alkali or alkaline earth metal such as sodium, an ion derived from an organic amine or an ammonium ion;

[0398] Rd and Re denote an alkyl radical in CrC4 or hydroxyalkyl in CrC4;

[0399] Ra denotes an alkyl or alkenyl group Cio-C3O of an acid, and

[0400] n and n' independently denote an integer from 1 to 3.

[0401] It is preferable that the amphoteric surfactant of formula B1 and B2 be chosen from among the (C8-C24)-alkyl amphomonoacetates, (C8-C24)alkyl amphodiacetates, (C8-C24)alkyl amphomonopropionates and (C8-C24)alkyl amphodipropionates.

[0402] These compounds are listed in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium Caprylamphodipropionate, Lauroamphodipropionic acid and Cocoamphodipropionic acid.

[0403] As an example, we can cite cacaomphodiacetate sold by the company Rhodia Chimie under the trade name Miranol® C2M concentrate.

[0404] Among the compounds of formula (B'2) we can mention sodium diethylaminopropyl cacaospartamide (CTFA) marketed by CHIMEX under the name CHIMEXANE HB.

[0405] (Cationic surfactants)

[0406] The composition according to the present invention may comprise at least one cationic surfactant. Two or more cationic surfactants may be used in combination.

[0407] The cationic surfactant may be chosen from the group optionally consisting of primary, secondary or tertiary polyoxyalkylated fatty amine salts, quaternary ammonium salts and mixtures thereof.

[0408] Examples of quaternary ammonium salts that may be mentioned include, but are not limited to:

[0409] those of general formula (B3) below:

[0410] in which

[0411] Ri, R2, R3, and R4, which may be identical or different, are selected from linear and branched aliphatic radicals comprising from 1 to 30 carbon atoms and optionally including heteroatoms such as oxygen, nitrogen, sulfur, and halogens. The aliphatic radicals may be selected, for example, from alkyl, alkoxy, polyoxyalkylene C2-C6 alkylamide, (C2-C22)alkylamido(C2-C6)alkyl, (C2-C22)alkylacetate, and hydroxyalkyl radicals; and aromatic radicals such as aryl and alkylaryl; and X is selected from halides, phosphates, acetates, lactates, (C2-C6) alkyl sulfates, and alkyl- or alkylaryl-sulfonates;

[0412] quaternary ammonium salts of imidazoline, for example those of formula (B4) below: (B4)

[0413] in which:

[0414] R5 is chosen from alkenyl and alkyl radicals, comprising 8 to 30 carbon atoms, for example, derivatives of fatty acids from tallow or coconut;

[0415] R6 is selected from hydrogen, CrC4> alkyl radicals and alkenyl and alkyl radicals including 8 to 30 carbon atoms;

[0416] R7 is chosen from among the Cr C4 alkyl radicals;

[0417] R8 is selected from hydrogen and CrC4 alkyl radicals; and

[0418] X is selected from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates and alkylaryl sulfonates. In one embodiment, R5 and R6 are, for example, a mixture of radicals selected from alkenyl and alkyl radicals including 12 to 21 carbon atoms, such as tallow fatty acid derivatives, R7 is methyl, and R8 is hydrogen. Examples of these products include, but are not limited to, Quatemium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W / 75PG, and W75HPG by the Witco company;

[0419] Quaternary di- or tri-ammonium salts of formula (B5): (B5)

[0420] in which:

[0421] R9 is chosen from aliphatic radicals comprising 16 to 30 carbon atoms;

[0422] Rio is selected from hydrogen or alkyl radicals including 1 to 4 carbon atoms or a -(CH2)3 (Ri6a)(Ri7a)(Ri8a)N+X-_ group;

[0423] Ru, Rn, Rb, Ri4, Riôa, Rna, and R18a, which may be identical or different, are selected from hydrogen and alkyl radicals including 1 to 4 carbon atoms; and

[0424] X is selected from among halides, acetates, phosphates, nitrates, ethyl sulfates and methyl sulfates.

[0425] An example of such a quaternary di-ammonium salt is FINQUAT CT-P from FINETEX (Quatemium-89) or FINQUAT CT (Quatemium-75);

[0426] and

[0427] quaternary ammonium salts including at least one ester function, such as those of formula (B6) below: 0 (CsH2sO)—R25 II R24---C---(OC,H,2(OH)d),---N —(C,Ht2(OH)nO),—R23 x- R22 (B6)

[0428] in which:

[0429] R22 is selected from among the Ci-C6 alkyl radicals and the hydroxyalkyl radicals and dihydroxyalkyl in Ci-C6;

[0430] R23 is chosen from:

[0431] the radical below: ? '

[0432] linear and branched Cr C22 saturated and unsaturated hydrocarbon radicals R27, and hydrogen,

[0433] R25 is chosen from:

[0434] the radical below: O ' R^c—

[0435] R29 hydrocarbon radicals, linear and branched, saturated and unsaturated in Cr C6, and hydrogen,

[0436] -R24, R26 and R28, which may be identical or different, are chosen from the linear or branched hydrocarbon groups, saturated and unsaturated in C7 to C2i;

[0437] -r, s and t, which may be identical or different, are chosen from integers ranging from 2 to 6;

[0438] each of rl and tl, which may be identical or different, is equal to 0 or 1, and r2+rl=2r and tl+2t=2t;

[0439] is chosen from integers ranging from 1 to 10;

[0440] x and z, which can be identical or different, are chosen from integers ranging from 0 to 10;

[0441] X is chosen from simple and complex, organic and inorganic anions, provided that the sum x+y+z ranges from 1 to 15, that when x equals 0, R23 designates R27, and that when z equals 0, R25 designates R29. R22 can be chosen from linear and branched alkyl radicals. In one embodiment, R22 is chosen from linear alkyl radicals. In another embodiment, R22 is chosen from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example, methyl and ethyl radicals. In one embodiment, the sum x+y+z ranges from 1 to 10. When R23 is a hydrocarbon group R27, it can be long and include from 12 to 22 carbon atoms, or short and include from 1 to 3 carbon atoms. When R25 is an R29 hydrocarbon radical, it can include, for example, 1 to 3 carbon atoms.By way of non-limiting example, in one embodiment, R24, R26, and R28, which may be identical or different, are selected from linear and branched, saturated and unsaturated hydrocarbon radicals, Cn-C2i, for example, from linear and branched, saturated and unsaturated alkyl and alkenyl radicals, Cn-C2i. In another embodiment, x and z, which may be identical or different, are equal to 0 or 1. In one embodiment, y is equal to 1. In another embodiment, r, s, and t, which may be identical or different, are equal to 2 or 3, for example, equal to 2. The anion X may be selected, for example, from halides, such as chloride, bromide, and iodide; and CrC4 alkyl sulfates, such as methyl sulfate.However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other ammonium-compatible anion, including an ester functional group, are other non-limiting examples of anions that may be used according to the present invention. In one embodiment, the anion X is selected from chloride and methyl sulfate.

[0442] In another embodiment, ammonium salts of formula (B6) may be used, wherein:

[0443] R22 is chosen from among the methyl and ethyl radicals,

[0444] x and y are equal to 1;

[0445] z is equal to 0 or 1;

[0446] r, s and t are equal to 2;

[0447] R23 is chosen from:

[0448] the radical below: R^—C—

[0449] methyl, ethyl and hydrocarbon radicals in CM-C22, and hydrogen;

[0450] R25 is chosen from:

[0451] the radical below: O, 1 c —

[0452] and hydrogen;

[0453] R24, R26 and R28, which may be identical or different, are chosen from the linear and branched, saturated and unsaturated Cn-Cp hydrocarbon radicals, for example among linear and branched, saturated and unsaturated C13-C17 alkyl and alkenyl radicals.

[0454] In one embodiment, the hydrocarbon radicals are linear.

[0455] Non-limiting examples of compounds of formula (B6) that may be Mentioned include salts, for example chloride and methyl sulfate, of diiacyloxyethyl dimethylammonium, diiacyloxyethyl hydroxyethyl methylammonium, monoacyloxyethyl dihydroxyethyl methylammonium, triacyloxyethyl methylammonium, monoacyloxyethyl hydroxyethyl dimethylammonium, and mixtures thereof. In one embodiment, the acyl radicals may comprise 14 to 18 carbon atoms and may be derived, for example, from a vegetable oil, such as palm oil and sunflower oil. When the compound comprises several acyl radicals, these radicals may be identical or different.

[0456] These products can be obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or optionally oxyalkylated alkyldiisopropanolamine with fatty acids or mixtures of fatty acids of vegetable or animal origin, or by transesterification of their methyl esters. This esterification can be followed by quaternization with an alkylating agent selected from among the alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrin; and glycerol chlorohydrin.

[0457] These compounds are sold, for example, under the names Dehyquart® by the company Cognis, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or "Rewoquat® WE 18" by the company Rewo-Goldschmidt.

[0458] Other non-limiting examples of ammonium salts that can be used in the composition according to the present invention include ammonium salts comprising at least one ester function as described in US patents No. 4,874,554 and 4,137,180.

[0459] The quaternary ammonium salts mentioned above that can be used in the composition according to the present invention include, but are not limited to, those corresponding to formula (I), for example tetraalkylammonium chlorides, for example dialkyldimethylammonium and alkyltrimethylammonium chlorides in which the alkyl radical includes about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium and benzyldimethylstearylammonium chlorides; palmitylamidopropyltrimethylammonium chloride; and stearamidopropyldimethyl(myristyle acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the Van Dyk company.

[0460] According to one embodiment, the cationic surfactant that can be used in the composition according to the present invention is selected from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, quaternium-83, quaternium-87, quaternium-22, behenyllamidopropyl-2,3-dihydroxypropyldimethylammonium chloride, palmitylamidopropyltrimethylammonium chloride and stearamidopropyldimethylamine.

[0461] (Non-ionic surfactants)

[0462] The composition according to the present invention may comprise at least one nonionic surfactant. Two or more nonionic surfactants may be used in combination.

[0463] Nonionic surfactants are well-known compounds in themselves (see, for example, in this regard, "Handbook of Surfactants" by M.R. Porter, Blackie & Son publishers (Glasgow and London), 1991, pages 116-178). Thus, they may, for example, be chosen from alcohols, alpha-diols, alkylphenols and fatty acid esters, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, knowing that the number of ethylene oxide or propylene oxide groups may range from 2 to 50, and the number of glycerol groups may range from 1 to 30. Maltose derivatives may also be mentioned.Other examples include, but are not limited to, copolymers of ethylene oxide and / or propylene oxide; condensates of ethylene oxide and / or propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, 2 to 30 mol of ethylene oxide; polyglycerol fatty amides comprising, for example, 1.5 to 5 glycerol groups, such as 1.5 to 4; ethoxylated fatty acid esters of sorbitan comprising 2 to 30 mol of ethylene oxide; ethoxylated oils of vegetable origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; mono- or diesters of polyethoxylated fatty acids of alkylpolyglycosides (C6-C24) of glycerol; N-alkylglucamine derivatives (in C6-C24), amine oxides such as oxides. alkylamine (C10-C14) or N-acylaminopropylmorpholine oxides (C10-CM); silicone surfactants; and mixtures thereof.

[0464] Nonionic surfactants may preferably be selected from monooxyalkylated, polyoxyalkylated, monoglycerol, or polyglycerol nonionic surfactants. The oxyalkylene motifs are more particularly oxyethylene or oxypropylene motifs, or a combination thereof, and are preferably oxyethylene motifs.

[0465] Examples of monooxyalkylated or polyoxyalkylated nonionic surfactants that may be mentioned include:

[0466] monooxyalkylated or polyoxyalkylated (C8-C24) alkylphenols,

[0467] saturated or unsaturated, linear or branched, monooxyalkylated or polyoxyalkylated alcohols in C8-C30,

[0468] saturated or unsaturated, linear or branched, monooxyalkylated or polyoxyalkylated amides in C8-C30,

[0469] esters of saturated or unsaturated, linear or branched, C8-C30 acids and polyalkylene glycols,

[0470] monooxyalkylated or polyoxyalkylated esters of saturated or unsaturated, linear or branched, C8-C30 acids and sorbitol,

[0471] saturated or unsaturated vegetable oils, monooxyalkylated or polyoxyalkylated,

[0472] ethylene oxide and / or propylene oxide condensates, among others, alone or in mixtures.

[0473] The surfactants preferably contain a number of moles of ethylene oxide and / or propylene oxide between 1 and 100 and most preferably between 2 and 50. According to one of the embodiments of the present invention, the non-ionic polyoxyalkylenated surfactants are selected from a polyoxyethylenated fatty alcohol (fatty alcohol polyethylene glycol ether) and a polyoxyethylenated fatty ester (fatty acid polyethylene glycol ester).

[0474] Examples of polyoxyethylenated fatty alcohols (or C8-C30 alcohols) that may be mentioned include ethylene oxide adducts with lauryl alcohol, in particular those containing 5 to 50 oxyethylene units and more particularly those containing 7 to 12 oxyethylene units (Laureth-7 to Laureth-12, as CTFA names); ethylene oxide adducts with behenyl alcohol, in particular those containing 9 to 50 oxyethylene units (Beheneth-9 to Beheneth-50, as CTFA names); Ethylene oxide adducts with cetearyl alcohol (a mixture of cetyl alcohol and stearyl alcohol), particularly those containing 10 to 50 oxyethylene units (e.g., Ceteareth-10 to Ceteareth-50, Ceteareth-33, as CTFA names); Ethylene oxide adducts with cetyl alcohol, in particular those containing 10 to 50 oxyethylene units (Ceteth-10 to Ceteth-50 as CTFA names); ethylene oxide adducts with stearyl alcohol, in particular those containing 10 to 50 oxyethylene units (Steareth-10 to Steareth-50, for example, Steareth-20, as CTFA names); ethylene oxide adducts with isostearyl alcohol, in particular those containing 10 to 50 oxyethylene units (Isosteareth-10 to Isosteareth-50, as CTFA names); and mixtures thereof.

[0475] Examples of unsaturated polyoxyethylenated fatty alcohols (or C8-C30 alcohols) that may be mentioned include ethylene oxide adducts with oleyl alcohol, in particular those containing 2 to 50 oxyethylene motifs and more particularly those containing 10 to 40 oxyethylene motifs (Oleth-10 to Oleth-40, as CTFA names); and mixtures thereof.

[0476] As examples of non-ionic monoglycerol or polyglycerol surfactants, monoglycerol or polyglycerol alcohols in the C8 to C40 range are preferably used.

[0477] In particular, monoglycerol or polyglycerol alcohols in the C8-C40 range correspond to the following formula:

[0478] RO-[CH2-CH(CH2OH)-O]mH or RO-[CH(CH2OH)-CH2O]mH

[0479] in which R represents an alkyl or alkenyl radical, linear or branched, in C8-C40 and preferably in C8-C30, and m represents a number from 1 to 30 and preferably from 1.5 to 10.

[0480] By way of examples of suitable compounds in the context of the invention, we may mention lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

[0481] Alcohol can represent a mixture of alcohols in the same way that the value of m represents a statistical value, meaning that, in a commercial product, several species of polyglycerol fatty alcohol can coexist as a mixture.

[0482] Among monoglycerol or polyglycerol alcohols, it is preferable to use a C8 / Ci0 alcohol containing 1 mol of glycerol, a C10 / Ci2 alcohol containing 1 mol of glycerol and a C[2] alcohol containing 1.5 mol of glycerol.

[0483] Monoglycerolated or polyglycerolated C8-C40 fatty esters may correspond to the following formula:

[0484] R'O-[CH2-CH(CH2OR")-O]mR" or R'O-[CH(CH2OR")-CH2O]mR"

[0485] wherein each of the R', R" and R" independently represents a hydrogen atom, or an alkyl-CO- or alkenyl-CO radical in C8-C40 and preferably in linear or branched C8-C3o, provided that at least one of the R', R" and R'" is not a hydrogen atom, and m represents a number from 1 to 30 and preferably from 1.5 to 10.

[0486] Examples of polyoxyethylenated fatty esters that may be mentioned include ethylene oxide adducts with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, in particular those containing 9 to 100 oxyethylene motifs, such as PEG-9 to PEG-50 laurate (CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (INCI names: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (INCI name: PEG-100 stearate) and their mixtures.

[0487] According to one embodiment of the present invention, the surfactant can be selected from polyol esters with fatty acids having a saturated or unsaturated chain containing, for example, 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, or their polyoxyalkylated derivatives, preferably containing 10 to 200, or more preferably 10 to 100 oxyalkylene motifs, such as glyceryl esters of a C8-C24 fatty acid, preferably Ci2-C22, and their polyoxyalkylated derivatives, preferably 10 to 200, or more preferably 10 to 100 oxyalkylene motifs; sorbitol esters of a C8-C24 fatty acid, preferably C2-C22, and their polyoxyalkylated derivatives, preferably with 10 to 200, or more preferably with 10 to 100 oxyalkylene motifs;sugar esters (sucrose, maltose, glucose, fructose and / or alkylglycose) of a C8-C24 fatty acid, preferably C12-C22, and their polyoxyalkylated derivatives, preferably containing 10 to 200, or more preferably 10 to 100 oxyalkylene units; fatty alcohol ethers; sugar ethers and one or more C8-C24 fatty alcohol(s), preferably C12-C22; or mixtures thereof.

[0488] Examples of glyceryl esters of fatty acids include glyceryl stearate (glyceryl mono-, di- and / or tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate and mixtures thereof, or, as their polyoxyalkylated derivatives, mono-, di- or triester of fatty acids with a polyoxyalkylated glycerol (mono-, di- or triester of fatty acids with a polyalkylene glycol ether of glycerol), preferably glyceryl stearate (mono-, di- and / or tristearate). polyoxyethylenated, such as PEG-20 glyceryl stearate (mono-, di-, tristearate and / or triisostearate).

[0489] Mixtures of these surfactants can also be used, such as, for example, the product containing glyceryl stearate and PEG-100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEGIN by Goldschmidt (CTFA name: glyceryl stearate SE).

[0490] Sorbitol esters of C8-C24 fatty acids and their polyoxyalkylated derivatives may be selected from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate, and alkoxylated fatty acid and sorbitan esters containing, for example, 20 to 100 EO, such as sorbitan monostearate (CTFA name: sorbitan stearate), marketed by ICI as Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate), marketed by ICI as Span 40, or sorbitan tristearate 20 EO (CTFA name: polysorbate 65), marketed by ICI as Tween 65, sorbitan polyoxyethylenated trioleate (polysorbate 85), or commercially available compounds under the trade names Tween 20 or Tween 60 by Uniqema.

[0491] Examples of fatty acid and glucose or alkylglucose esters include glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, fatty esters of methylglucoside, methylglucoside and oleic acid diester (CTFA name: methylglucose dioleate), mixed methylglucoside and oleic acid / hydroxystearic acid mixture (CTFA name: methylglucoside dioleate / hydroxystearate), methylglucoside and isostearic acid ester (CTFA name: methylglucose isostearate), methylglucoside and lauric acid ester (CTFA name: methylglucosate laurate), mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesqui-isostearate), the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate),and in particular the product marketed under the name Glucate SS by AMERCHOL and their mixtures.

[0492] Examples of fatty acid and glucose or alkylglucose ethoxylated ethers include fatty acid and methylglucose ethers, and in particular, polyethylene glycol ether of methylglucose and stearic acid diester with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed by AMERCHOL as Glucam E-20 distearate, polyethylene glycol ether of a mixture of methylglucose and stearic acid monoester and diester with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate), and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and their mixtures.

[0493] Examples of sucrose esters include sucrose palmitostearate, sucrose stearate and sucrose monolaurate.

[0494] Alkyl polyglucosides may be used as sugar ethers, and for example, decyl glucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl / capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, lauryl glucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818 / UP by Henkel, cetostearyl glucoside possibly mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, marketed under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, contains arachidyl glucoside,for example, in the form of a mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethyl glucoside, for example in the form of a mixture (35 / 65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof may be cited in particular.

[0495] Mixtures of alkoxylated vegetable oil glycerides such as ethoxylated mixtures of palm (200 EO) and coconut (7 EO) glycerides may also be cited.

[0496] The nonionic surfactant according to the present invention preferably contains a branched C12-C22 alkenyl or acyl chain such as an oleyl or isostearyl group. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

[0497] According to one embodiment of the present invention, the nonionic surfactant can be selected from ethylene oxide and propylene oxide copolymers, in particular copolymers of the following formula:

[0498] HO(C2H4O)a(C3H6O)b(C2H4O)cH

[0499] in which a, b and c are integers such that a+c goes from 2 to 100, and b goes from 14 to 60, and mixtures thereof.

[0500] According to one embodiment of the present invention, the nonionic surfactant can be selected from silicone surfactants. Reference may be made to including but not limited to those disclosed in documents US-A-5364633 and US-A-5411744.

[0501] The silicone surfactant may preferably be a compound of formula (I):

[0502] in which:

[0503] Rb R2 and R3, independently of each other, represent an alkyl radical enCr C6 or a radical -(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4, at least one radical RB R2 or R3 not being an alkyl radical; R4 being a hydrogen, an alkyl radical or an acyl radical;

[0504] A is an integer ranging from 0 to 200;

[0505] B is an integer from 0 to 50; provided that A and B are not simultaneously equal to zero;

[0506] x is an integer from 1 to 6;

[0507] y is an integer between 1 and 30; and

[0508] z is an integer ranging from 0 to 5.

[0509] According to a preferred embodiment of the present invention, in the compound of formula (I), the alkyl radical is a methyl radical, x is an integer from 2 to 6 and y is an integer from 4 to 30.

[0510] Examples of silicone surfactants of formula (I) include compounds of formula (II): (CH3)3SiO - [(CH3)2SiO]A - (CH3SiO)B - Si(CH3)3 i (H) (CH2)2-(OCH2CH2)y-OH

[0511] in which A is an integer from 20 to 105, B is an integer from 2 to 10 and y is an integer from 10 to 20.

[0512] By way of examples of silicone surfactants of formula (I), we may also mention the compounds of formula (III):

[0513] H-(OCH2CH2)y-(CH2)3-[(CH3)2SiO]A -(CH2)3-(OCH2CH2)y-OH (III)

[0514] in which A' and y are integers from 10 to 20.

[0515] The compounds of the present invention that may be used are those sold by Dow Corning under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667. The compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II) in which, respectively, A is 22, B is 2 and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12.

[0516] Compound Q4-3667 is a compound of formula (III) in which A is equal to 15 and y to 13.

[0517] It is preferable that the (b) surfactant be chosen from among non-ionic surfactants.

[0518] It is more preferable that the (b) surfactant be chosen from among the polyglyceryl esters of fatty acids.

[0519] It is preferable that the fatty acid polyglyceryl ester have a fraction of Polyglycerol derived from 2 to 10 glycerols, preferably from 2 to 8 glycerols, and more preferably from 2 to 6 glycerols. In other words, the fatty acid polyglyceryl ester can comprise from 2 to 10 polyglyceryl units, preferably from 2 to 8 polyglyceryl units, and more preferably from 2 to 6 polyglyceryl units. If the entire fatty acid polyglyceryl ester has a shorter polyglyceryl chain (for example, fewer than 10 polyglyceryl units, preferably fewer than 8 polyglyceryl units, and more preferably fewer than 6 polyglyceryl units), the stability of the composition according to the present invention can be enhanced.

[0520] The fatty acid polyglyceryl ester may be selected from mono, di and tri esters of linear or branched fatty acids, saturated or unsaturated, preferably of saturated fatty acids, including from 4 to 32 carbon atoms, preferably from 8 to 26 carbon atoms, and more preferably from 10 to 20 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid and myristic acid.

[0521] It is preferable that the surfactant (b) be chosen in the form of polyglyceryl monoesters of saturated or unsaturated fatty acids.

[0522] The fatty acid polyglyceryl ester may have a hydrophilic-lipophilic balance (HLB) value of 4.0 to 16.0, preferably from 4.5 to 15.5, and more preferably from 5.0 to 15.0. The term HLB (hydrophilic-lipophilic balance) is well known to those skilled in the art and reflects the ratio between the hydrophilic and lipophilic parts in the molecule. If two or more fatty acid polyglyceryl esters are used, the HLB value is determined by the weighted average of the HLB values ​​of all the fatty acid polyglyceryl esters.

[0523] The fatty acid polyglyceryl ester may be selected from the group consisting of PG-2 stearate (HLB: 5.0), PG-2 isostearate (HLB: 5.5), PG-2 oleate (HLB: 6.5), PG-2 caprate (HLB: 9.5), PG-2 laurate (HLB: 8.5), PG-4 oleate (HLB: 8.8), PG-4 laurate (HLB: 10.4), PG-4 isostearate (HLB: 8.2), PG-5 laurate (HLB: 15.8), PG-6 isostearate (HLB: 10.8), PG-3 cocoate (HLB: 12.0), PG-3 caprate (HLB: 10.0), caprylate of PG-4 (HLB: 14), PG-4 caprate (HLB: 14.0), PG-5 myristate (HLB: 15.4), PG-5 stearate (HLB: 15.0), PG-5 oleate (HLB: 14.9), PG-6 caprylate (HLB: 14.6), PG-6 caprate (HLB: 13.1), PG-6 laurate (HLB: 14.5), and mixtures thereof.

[0524] It may be preferable that the (d) surfactant be chosen from the group consisting of PG-4 caprate (HLB: 14.0), PG-2 isostearate (HLB: 5.5) and a mixture of these.

[0525] It is preferable that the composition according to the present invention comprise at least two fatty acid polyglyceryl esters.

[0526] It is preferable to choose the (d) surfactant from

[0527] at least a first fatty acid polyglyceryl ester having an HLB value of 4.0 to 8.0, preferably of 4.5 to 8.0 and, more preferably, of 5.0 to 8.0;

[0528] at least a second fatty acid polyglyceryl ester having an HLB value of 12.0 to 16.0, preferably 12.0 to 15.5 and, more preferably, 12.0 to 15.0; and

[0529] and a mixture of these.

[0530] The quantity of the (d) surfactant(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.01% by weight or more and, more preferably, 0.1% by weight or more, relative to the total weight of the composition.

[0531] Furthermore, the quantity of the (d) surfactant(s) in the composition according to the present invention may be less than or equal to 20% by weight, preferably less than or equal to 15% by weight and more preferably less than or equal to 10% by weight relative to the total weight of the composition.

[0532] The quantity of the (d) surfactant(s) in the composition according to the present invention may be from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, and more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.

[0533] [pH]

[0534] The pH of the composition according to the present invention can be from 2.0 to 9.0, preferably from 2.5 to 8.5 and, more preferably, from 3.0 to 8.0.

[0535] At a pH between 2.0 and 9.0, the (a) polyionic complex can be very stable.

[0536] The pH of the composition according to the present invention can be corrected by adding at least one alkali and / or at least one acid, other than a non-polymer acid having two or more pKa values ​​or salt(s) thereof, or a non-polymer base having two or more pKb values, or salt(s) thereof, to be incorporated into (a) the polyionic complex. The pH of the composition according to the present invention can also be corrected by adding at least one buffering agent.

[0537] (Alkaline agent)

[0538] The composition according to the present invention may comprise at least one alkali agent. Two or more alkali agents may be used in combination. Thus, a only one type of alkaline agent or a combination of different types of alkaline agents may be used.

[0539] The alkali agent may be an inorganic alkali agent. It is possible that the inorganic alkali agent may be chosen 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.

[0540] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. Sodium hydroxide is preferable as an inorganic alkali metal.

[0541] The alkali agent may be an organic alkali agent. Preferably, the organic alkali agent should be chosen 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.

[0542] Examples of organic alkali-aggregate agents include alkanolamines such as mono-, di- and tri-ethanolamine, 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:

[0543] in which R denotes an alkylene such as propylene optionally substituted with a hydroxyl or a Ci-C4 alkyl radical, and Rb R2, R3 and R4 independently denote a hydrogen atom, an alkyl radical or a Ci-C4 hydroxyalkyl radical, such as may be exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferred.

[0544] The alkali agent(s) may be used in an amount 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.

[0545] (Acid)

[0546] 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.

[0547] As an acid, mention may be made of all inorganic or organic acids, preferably inorganic, that are commonly used in cosmetic products. A monovalent acid and / or a polyvalent acid may be used. A monovalent acid such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) may be used. HCl is preferable.

[0548] 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.

[0549] (Buffer agent)

[0550] 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 be used.

[0551] As buffering agents, 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 (4-(2-hydroxyethyl)-l-pipeineethanesulfonic acid).

[0552] [Optional Additions]

[0553] The composition according to the present invention may include, in addition to the aforementioned components, components generally used in cosmetics, specifically oils such as ester oils and hydrocarbon oils, hydrophilic or lipophilic UV filters, hydrophilic or lipophilic thickeners, volatile or non-volatile organic solvents such as glycerin, glycols and ethanol, silicones and silicone derivatives, natural extracts derived from animals or plants, waxes and others, within a range that does not compromise the effects of the present invention.

[0554] The composition according to the present invention may include 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.

[0555] [Composition]

[0556] 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 keratinous fiber. By keratinous substance, we mean Here, a material containing keratin as its main constituent is used, for example, skin, scalp, lips, hair, and the like. Preferably, the cosmetic composition according to the present invention should be used for a cosmetic process involving keratin fibers, particularly skin.

[0557] Thus, the composition according to the present invention can 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.

[0558] The composition according to the present invention can be prepared by mixing the essential and optional ingredients above according to any of the processes which are well known to the person skilled in the art.

[0559] The composition according to the present invention can be prepared by simple or easy mixing with a conventional mixing means such as a stirrer. Consequently, there is no need for vigorous shearing, for example using a homogenizer. Furthermore, heating is not required.

[0560] The composition according to the present invention can be used to easily prepare a film.

[0561] Thus, the present invention also relates to a process for preparing a film, preferably a cosmetic film, optionally with a thickness of 0.1 µm or more, more preferably of 0.5 µm or more, and even more preferably of 1 µm or more, comprising:

[0562] the application to a substrate, preferably a keratinous substance, more preferably the skin, of the composition according to the present invention; and

[0563] the drying of the composition.

[0564] The upper limit of the thickness of the film according to the present invention is not limited. Thus, for example, the thickness of the film according to the present invention can be 1 mm or less, preferably 500 sqm or less, more preferably 300 sqm or less, and even more preferably 100 sqm or less.

[0565] Since the process for preparing the film according to the present invention comprises the steps of applying the composition according to the present invention onto a substrate, preferably a keratinous substance, and more preferably skin, and drying the composition, the process according to the present invention does not require any deposition by spinning or spraying, and it is therefore even possible to easily prepare a relatively thick film. Thus, the process for preparing a film according to the present invention can prepare a relatively thick film without any special equipment such as deposition spinning wheels and spraying machines.

[0566] The film according to the invention may be less sticky although it comprises a hyaluronic acid-based polymer.

[0567] The film according to the invention can be transparent or translucent and can produce antioxidant effects that can be long-lasting.

[0568] Even though the film according to the present invention is relatively thick, it is still thin and may be transparent, and therefore may not be easily perceptible. Thus, the film according to the present invention can preferably be used as a cosmetic film.

[0569] 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 all cases, it is preferable that the substrate be flexible or elastic.

[0570] If the substrate is not a keratinous substance, it is preferable that the substrate be water-soluble, since it is possible to leave the film according to the present invention by washing the substrate with water. Examples of water-soluble materials include polyacids (methacrylic acids), polyethylene glycols, polyacrylamides, polyvinyl alcohol (PVA), starch, cellulose acetates, and the like. PVA is preferable.

[0571] 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 invention, in order to facilitate the 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.

[0572] It is preferable that the film according to the present invention be able to be released from the non-keratinous substrate. The method of release is not limited. Therefore, the film according to the present invention can be peeled off the non-keratinous substrate, or released by dissolving the substrate sheet in a solvent such as water.

[0573] The present invention also relates to:

[0574] (1) A film, preferably cosmetic, preferably of a thickness of greater than 0.1 pm, more preferably greater than 0.5 pm, and even more preferably greater than 1 pm, prepared by a process comprising:

[0575] the application to a substrate, preferably a keratinous substance, and more preferably to the skin, of the composition according to the present invention; and

[0576] drying of the composition,

[0577] and

[0578] (2) A film, preferably a cosmetic film, optionally of a thickness preferably greater than 0.1 pm, more preferably greater than 0.5 pm, and even more preferably greater than 1 pm, comprising:

[0579] (a) at least one polyionic complex, comprising

[0580] at least one cationic polymer and at least one anionic polymer,

[0581] at least one cationic polymer and at least one amphoteric polymer,

[0582] at least one anionic polymer and at least one amphoteric polymer, or

[0583] at least one amphoteric polymer,

[0584] at least one non-polymer acid having two or more pKa values ​​or salt(s) thereof, or at least one non-polymer base having two or more pKb values ​​or salt(s) thereof;

[0585] (b) at least one lipophilic antioxidant;

[0586] and

[0587] optionally (d) at least one surfactant, preferably selected from non-ionic surfactants, and more preferably selected from fatty acid polyglyceryl esters,

[0588] in which

[0589] the anionic polymer is selected from hyaluronic acid and its salts; and

[0590] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

[0591] The above explanations concerning the cationic, anionic and amphoteric polymers and the lipophilic antioxidant and surfactant above can be applied to those of the films (1) and (2) above.

[0592] The film thus obtained can be self-supporting. The term “self-supporting” here means that the film can be in the form of a sheet and can be handled as an independent sheet without the assistance of a substrate or support. Thus, the term “self-supporting” can have the same meaning as “self-supporting”.

[0593] It is preferable that the film according to the present invention be hydrophobic.

[0594] In this descriptive document, the term “hydrophobic” means that the solubility The polymer content in water (preferably 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 be insoluble in water.

[0595] If the film according to the present invention is hydrophobic, the film can have water-resistant properties and, consequently, can 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 according to the present invention provides a cosmetic effect, the cosmetic effect can last a long time.

[0596] On the other hand, the film according to the present invention can be easily removed from a keratinous substance such as skin under alkaline conditions such as a pH from 8 to 12, preferably from 9 to 11. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap that can provide such alkaline conditions.

[0597] The film according to the present invention may comprise at least one layer of biocompatible and / or biodegradable polymer. 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.

[0598] The term “biocompatible” polymer in this specification means that the polymer does not have excessive interaction between the polymer and the cells of the living body, including the skin, and that the polymer is not recognized by the living body as a foreign material.

[0599] The term "biodegradable" polymer in this specification means that the polymer can be degraded or broken down in a living organism due to, for example, the metabolism of the living organism itself, or the metabolism of microorganisms that may be present in the living organism. Furthermore, the biodegradable polymer can be degraded by hydrolysis.

[0600] If the film according to the present invention comprises a biocompatible and / or biodegradable polymer, it is less irritating or non-irritating to the skin and does not cause any skin rash. Furthermore, due to the use of a biocompatible and / or biodegradable polymer, the cosmetic sheet according to the present invention can adhere well to the skin.

[0601] The film according to the present invention can be used for cosmetic treatments of keratinous substances, preferably the skin, particularly the face. The film according to the present invention can take any shape. For example, it can be used as a full-face mask sheet or as a patch for a part of the face such as the cheek, nose, and around the eyes.

[0602] If the film according to the present invention comprises at least one hydrophilic or water-soluble UV filter, it can provide UV-blocking effects derived from the hydrophilic or water-soluble UV filter. Normally, a hydrophilic or water-soluble UV filter can be removed from the surface of a keratinous substrate such as skin by water, such as perspiration and rain. However, since the hydrophilic or water-soluble UV filter is included in the film according to the present invention, it is difficult to remove the hydrophilic or water-soluble UV filter with water, resulting in long-lasting UV-blocking effects.

[0603] [Cosmetic process and use]

[0604] The present invention also relates to:

[0605] a cosmetic process for a keratinous substance such as skin, comprising: applying the composition according to the present invention to the keratinous substance; and drying the composition to form a cosmetic film on the keratinous substance; and

[0606] a use of the composition according to the present invention for the preparation of a cosmetic film on a keratinous substance such as skin.

[0607] The cosmetic process here refers to a non-therapeutic cosmetic process for the care and / or makeup of the surface of a keratinous substance such as the skin.

[0608] In both the above process and use, the above cosmetic film is resistant to water of a pH less than or equal to 7, and can be removed with water of a pH greater than 7, preferably 8 or more and preferably 9 or more.

[0609] 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 greater than 7, preferably 8 or more, and more preferably 9 or more. The upper limit of pH is preferably 13, more preferably 12, and even more preferably 11.

[0610] Consequently, the above-mentioned cosmetic film can be water-resistant and can therefore 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. On the other hand, the above-mentioned cosmetic film can be easily removed from a keratinous substance such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, whereas it can be easily removed with a soap that can provide alkaline conditions.

[0611] If the above cosmetic film includes a UV filter which may be present in the composition according to the present invention, the above cosmetic film can protect a keratinous substance such as skin from UV rays, thus limiting skin darkening, improving color and evenness of complexion, and / or treating skin aging.

[0612] In addition, the above cosmetic film can have cosmetic effects such as sebum capture, mattifying the appearance of a keratin substrate such as skin, absorption or odor absorption, and / or protection of the keratinous substance against, for example, dirt or pollutants, due to the properties of the polyionic complex in the cosmetic film, even if the cosmetic film does not contain any active cosmetic ingredients.

[0613] Furthermore, the above cosmetic film can immediately change or alter the appearance of the skin by modifying the reflection of light on the skin and other factors, even if The cosmetic film contains no active cosmetic ingredients. Therefore, it is possible that the above-mentioned cosmetic film may conceal skin imperfections such as pores or wrinkles. Furthermore, the above-mentioned cosmetic film may immediately change or alter the skin's feel by modifying its surface roughness and similar properties. In addition, the above-mentioned cosmetic film may immediately protect the skin by covering its surface and acting as a barrier against environmental stressors such as pollutants, contaminants, and other aggressors.

[0614] The above cosmetic effects can be adjusted or controlled by changing the chemical composition, thickness and / or surface roughness of the above cosmetic film.

[0615] If the above cosmetic film contains at least one additional cosmetic active ingredient such as an oil, the cosmetic film may have cosmetic effects provided by the additional cosmetic active ingredient(s). For example, if the cosmetic film contains at least one cosmetic active ingredient selected from among anti-aging agents other than (b) lipophilic antioxidant, sebum-regulating agents, deodorizing agents, antiperspirant agents, whitening agents, and a mixture thereof, the cosmetic film may treat skin aging, absorb sebum on the skin, control odors on the skin, control perspiration on the skin, and / or whiten the skin.

[0616] It is also possible to apply a cosmetic makeup composition to the cosmetic film or sheet according to the present invention after its application to the skin. EXAMPLES

[0617] The present invention will be described in more detail with the aid of examples. However, these examples shall not be construed as limiting the scope of the present invention. [Examples 1 to 2 and Comparative Examples 1 to 2]

[0618] [Preparation]

[0619] Each of the compositions according to Examples 1 to 2 and Comparative Examples 1 to 2 was prepared by mixing the ingredients listed in Table 1. The numerical values ​​of the quantities of ingredients in Table 1 are all based on a '% by weight' of raw materials.

[0620] [Tables 1] Ex. 1 Ex. 2 Ex. comp. 1 Ex. comp. 2 Water q.s. 100 q.s. 100 q.s. 100 q.s. 100 q.s. 100 Tocopherol 0.10 0.10 - 0.10 Polyglyceryl-4 Caprate - 3.12 3.12 - Polyglyceryl-2 Isostearate - 0.05 0.05 - Phytic Acid 0.14 0.14 0.14 - Polyepsilon-Lysine 0.10 0.10 0.10 - Sodium Hydroxide 0.03 0.03 0.03 - Sodium Hyaluronate (MW 20-50 kDa) 1.00 1.00 1.00 1.00 Sodium Hyaluronate (MW 1000-1400 kDa) 0.50 0.50 0.50 0.50 Ethanol 3.00 3.00 3.00 3.00 Glycerin 3.00 3.00 3.00 3.00 Betaine 1.00 1.00 1.00 1.00 Ammonium Polyacryloyldimethyl Taurate 0.40 0.40 0.40 0.40 Isopropyl Myristate 0.32 0.32 0.32 0.32 Isononyl Isononanoate 0.32 0.32 0.32 0.32 Trisodium Ethylenediamine Disuccinate 0.25 0.25 0.25 0.25 Hydroxypropyl Methylcellulose 0.10 0.10 0.10 0.10 Preservative qsqsqsqs Stickiness Very Good Good Poor Good Duration of Effect antioxidant Good Very good Very bad Bad

[0621] [Evaluations]

[0622] (Sticky character)

[0623] Three panelists evaluated the texture, in terms of stickiness, of each of the compositions according to Examples 1-2 and Comparative Examples 1-2 at the time of and after application of the composition. More specifically, each panelist Each product was applied to her hand and spread to assess the feeling of hydration, and rated from 1 (low) to 5 (high). It was then classified into the following three categories based on the average rating:

[0624] Very good: 4 to 5 (non-sticky)

[0625] Good: 3 to less than 4 (slightly sticky)

[0626] Bad: more than 2 and less than 3 (sticky)

[0627] Very bad: 1 to 2 (very sticky)

[0628] The results are shown in Table 1.

[0629] (Durability of the antioxidant effect)

[0630] 0.6 g of a solution of [3-carotene (solvent: caprylic / capric triglyceride) with a concentration of 0.05% by weight, and 0.2 g of each of the compositions according to Examples 1-2 and Comparative Examples 1-2 were mixed to obtain a mixture.

[0631] 0.4 g of the above mixture was applied to a filter (glass microfiber filter).

[0632] The filter was rinsed with tap water (300 mL, 23-27 °C).

[0633] The above filter was exposed to UV rays with a wavelength of 365 nm for 30 minutes to oxidize the [3-carotene.

[0634] If [3-carotene is oxidized, the original yellow color derived from [3-carotene] fades.

[0635] The b* values ​​in the L*a*b* space (CIE1976) before and after UV exposure (b* (T=0) and b* (T=30 min), respectively) of the filter were measured by a spectrocolorimeter (CM-700d manufactured by KONICA MINOLTA), and the difference between the b* value (T=0) and the b* value (T=30 min) was determined as Ab*. It should be noted that the b* value (T=0) of the filter before rinsing was between 45 and 65.

[0636] The Ab* and b* values ​​(T=30 min) were evaluated according to the following criteria.

[0637] Very good: Ab* <10 and b* (T=30 min) >30

[0638] Good: Ab* <10 and 30 > b* (T=30 min) >20

[0639] Bad: Ab* <10 and 20 > b* (T=30 min)

[0640] Very bad: Ab* >10

[0641] The results are shown in Table 1.

[0642] (Summary)

[0643] The compositions according to Examples 1 and 2 are good or very good in terms of stickiness and can offer good or very good long-lasting antioxidant effects.

[0644] It is clear from the comparison between Example 1 and Comparative Example 2 that the use of a polyionic complex can reduce stickiness and prolong antioxidant effects.

[0645] It is clear from the comparison between Example 2 and Comparative Example 1 that the use of tocopherol can not only enhance the antioxidant effects, but also improve the stickiness.

[0646] It is clear from the comparison between Example 1 and Example 2 that the use of a surfactant such as a fatty acid polyglyceryl ester can further prolong the antioxidant effects, even under rinsing conditions.

Claims

Demands

1. Composition, comprising: (a) at least one polyionic complex, comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer, or at least one amphoteric polymer, and at least phytic acid or salts thereof; (b) at least tocopherol; (c) water; and (d) at least one surfactant selected from fatty acid polyglyceryl esters;in which the anionic polymer is selected from hyaluronic acid, its salts, and its derivatives, and the amphoteric polymer is selected from cationized hyaluronic acid and its salts in which the cationic polymer comprises at least one positively chargeable fraction and / or positively charged fraction selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group.;

2. Composition according to claim 1, wherein the cationic polymer is selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as diallyldialkyl ammonium (co)polychloride, (co)polyamines such as chitosans and (co)polylysines, cationic (co)polyamino acids such as collagen, cationic cellulose polymers and their salts.

3. A process for preparing a film, preferably a cosmetic film, comprising: the application to a substrate, preferably a keratinous substance, of the composition according to any one of claims 1 or 2; and the drying of the composition.

4. Film, preferably cosmetic film, prepared by a process comprising: applying to a substrate, preferably a keratinous substance, the composition according to any one of claims 1 or 2; and drying the composition.

5. Film, preferably a cosmetic film, comprising: (a) at least one polyionic complex comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer, or at least one amphoteric polymer, and at least phytic acid or salts thereof; (b) tocopherol; and (d) at least one surfactant selected from fatty acid polyglyceryl esters, wherein the anionic polymer is selected from hyaluronic acid, its salts and derivatives;and the amphoteric polymer is selected from cationized hyaluronic acid and its salts, wherein the cationic polymer comprises at least one positively chargeable fraction and / or a positively charged fraction selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group.;

6. A cosmetic process for a keratinous substance such as skin, comprising the application of the composition to the keratinous substance according to any one of claims 1 or 2; and the drying of the composition to form a cosmetic film on the keratinous substance.