Composition containing hyaluronic acid-based polyion complex and lipophilic antioxidant

Abstract

To provide a composition that has less stickiness, and can bring about long-lasting antioxidant effect.SOLUTION: A composition contains: (a) at least one kind of complex containing at least one kind of cationic polymer and at least one kind of anionic polymer, at least one kind of cationic polymer and at least one kind of amphoteric polymer, at least one kind of anionic polymer and at least one kind of amphoteric polymer, or at least one kind of amphoteric polymer, and at least one kind of non-polymeric acid having two or more pKa values or a salt thereof, or at least one kind of non-polymeric base having two or more pKb values or a salt thereof; (b) at least one kind of lipophilic antioxidant; and (c) water, where the anionic polymer is selected from hyaluronic acid, a salt thereof and derivative thereof, and the amphoteric polymer is selected from cationized hyaluronic acid and a salt thereof. The composition has less stickiness, and can bring about long-lasting antioxidant effect.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition comprising a polyion complex, a film of the polyion complex, a method for preparing a film by using the polyion complex, and a cosmetic method using the polyion complex. [Background technology]

[0002] Hyaluronic acid is the main glycosaminoglycan found in the skin. Therefore, fibroblasts mainly synthesize collagen, non-collagenous matrix glycoproteins (fibronectin, laminin), proteoglycans and elastin. Keratinocytes, for their part, mainly synthesize sulfated glycosaminoglycans and hyaluronic acid. Hyaluronic acid is also called hyaluronan (HA).

[0003] Hyaluronic acid is present in free form in the epidermis and dermis and is responsible for the turgor of the skin. This polysaccharide can actually hold a large volume of water, up to 1000 times its mass. In this sense, hyaluronic acid plays an important role in increasing the amount of water bound in tissues, and also in the mechanical properties of the skin and wrinkle formation.

[0004] Hyaluronic acid has been widely used as a cosmetic ingredient due to its high moisturizing effect.

[0005] However, aqueous solutions of hyaluronic acid are sticky, which can result in an unpleasant texture, and the hyaluronic acid film that forms when an aqueous solution of hyaluronic acid dries on the skin is also sticky, which can also result in an unpleasant texture.

[0006] WO2021 / 125069 discloses reducing stickiness caused by hyaluronic acid by forming polyion complex particles having a cationic polymer and hyaluronic acid as an anionic polymer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] WO2021 / 125069 [Patent Document 2] European Patent Application No. 0080976 [Patent Document 3] French Patent No. 2077143 [Patent Document 4] French Patent No. 2393573 [Patent Document 5] French Patent No. 1492597 [Patent Document 6] U.S. Patent No. 4,131,576 [Patent Document 7] U.S. Patent No. 3,589,578 [Patent Document 8] U.S. Patent No. 4,031,307 [Patent Document 9] French Patent No. 2162025 [Patent Document 10] French Patent No. 2280361 [Patent Document 11] French Patent No. 2252840 [Patent Document 12] French Patent No. 2368508 [Patent Document 13] French Patent No. 1583363 [Patent Document 14] U.S. Patent No. 3,227,615 [Patent Document 15] U.S. Patent No. 2,961,347 [Patent Document 16] French Patent No. 2080759 [Patent Document 17] Additional Patent No. 2190406 of French Patent No. 2080759 [Patent Document 18] French Patent No. 2320330 [Patent Document 19] French Patent No. 2270846 [Patent Document 20] French Patent No. 2316271 [Patent Document 21] French Patent No. 2336434 [Patent Document 22] French Patent No. 2413907 [Patent Document 23] U.S. Patent No. 2,273,780 [Patent Document 24] U.S. Patent No. 2,375,853 [Patent Document 25] U.S. Patent No. 2,388,614 [Patent Document 26] U.S. Patent No. 2,454,547 [Patent Document 27] U.S. Patent No. 3,206,462 [Patent Document 28] U.S. Patent No. 2261002 [Patent Document 29] U.S. Patent No. 2,271,378 [Patent Document 30] U.S. Patent No. 3,874,870 [Patent Document 31] U.S. Patent No. 4001432 [Patent Document 32] U.S. Patent No. 3,929,990 [Patent Document 33] U.S. Patent No. 3,966,904 [Patent Document 34] U.S. Patent No. 4,005,193 [Patent Document 35] U.S. Patent No. 4,025,617 [Patent Document 36] U.S. Patent No. 4,025,627 [Patent Document 37] U.S. Patent No. 4,025,653 [Patent Document 38] U.S. Patent No. 4,026,945 [Patent Document 39] U.S. Patent No. 4027020 [Patent Document 40] European Patent Application No. 0122324 [Patent Document 41] Patent FR2608150 [Patent Document 42] Patent application FR699818 [Patent Document 43] Patent application FR2706478 [Patent Document 44] Patent application FR2907339 [Patent Document 45] Patent application FR2814943 [Patent Document 46] Patent application FR2873026 [Patent Document 47] U.S. Patent No. 4,698,360 [Patent Document 48] U.S. Patent No. 6,372,266 [Patent Document 49] U.S. Patent No. 5,720,956 [Patent Document 50] Patent application FR2908769 [Patent Document 51] Patent application FR2704754 [Patent Document 52] Patent application FR2877004 [Patent Document 53] Patent application FR2854160 [Patent Document 54] Patent application EP0511118 [Patent Document 55] Patent application WO94 / 11338 [Patent Document 56] Patent application FR2698095 [Patent Document 57] Patent application FR2737205 [Patent Document 58] Patent application EP0755925 [Patent Document 59] Patent application FR2825920 [Patent Document 60] U.S. Patent No. 2,528,378 [Patent Document 61] U.S. Patent No. 2,781,354

Patent Document 62

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Patent Document 64

Patent Document 65

Non-Patent Document

[0008]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Non-Patent Document 5

Non-Patent Document 6

Non-Patent Document 7

Summary of the Invention

[0009] There is a need for compositions containing hyaluronic acid-based polyion complexes that are less sticky and can provide long-lasting antioxidant effects.

[0010] Therefore, a first object of the present invention is to provide a composition that is less sticky and can provide a long-lasting antioxidant effect.

[0011] The above object of the present invention is to (a) 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 or salt thereof having two or more pKa values; or At least one non-polymeric base or salt thereof having two or more pKb values Including, At least one polyion complex; (b) at least one lipophilic antioxidant; and (c) Water and A composition comprising: The anionic polymer is selected from hyaluronic acid, its salts, and its derivatives; and This can be achieved by a composition in which the amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0012] The cationized hyaluronic acid may have at least one quaternary ammonium group-containing group, and has a degree of cationization of 0.05 to 0.6, preferably 0.1 to 0.5, and more preferably 0.15 to 0.4.

[0013] The cationic polymer may have at least one positive charge and / or have moieties that have a positive charge selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups.

[0014] The cationic polymer may be selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof.

[0015] The total amount of cationic and / or anionic and / or amphoteric polymers in the composition according to the present invention may be from 0.01% by mass to 15% by mass, preferably from 0.03% by mass to 10% by mass, and more preferably from 0.05% by mass to 5% by mass, relative to the total mass of the composition.

[0016] The non-polymeric acid or salt thereof having two or more pKa values ​​may be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof, and more preferably phytic acid or a salt thereof.

[0017] The amount of the non-polymeric acid or salt thereof having two or more pKa values, or the non-polymeric base or salt thereof having two or more pKb values ​​in the composition according to the present invention may be 0.001% by mass to 15% by mass, preferably 0.005% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, based on the total mass of the composition.

[0018] (b) The 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.

[0019] The amount of the (b) lipophilic antioxidant in the composition according to the present invention may be 0.001% by mass to 15% by mass, preferably 0.005% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, relative to the total mass of the composition.

[0020] The amount of (c) water in the composition according to the present invention may be 10% by mass to 99% by mass, preferably 30% by mass to 97% by mass, and more preferably 50% by mass to 95% by mass, based on the total mass of the composition.

[0021] The composition according to the invention may further comprise (d) at least one surfactant, preferably chosen from non-ionic surfactants, more preferably chosen from polyglyceryl fatty acid esters.

[0022] A second object of the present invention is to provide a method for preparing a coating which is less sticky and can provide long-lasting antioxidant effects.

[0023] The above object of the present invention is a method for preparing a film, preferably a cosmetic film, comprising the steps of: applying a composition according to the invention onto a substrate, preferably a keratin material; drying the composition; This can be achieved by a method comprising:

[0024] A third object of the present invention is to provide a coating which is less sticky and can provide a long-lasting antioxidant effect.

[0025] The above object of the present invention is to (1) on a substrate, preferably a keratinous material, applying a composition according to the present invention; drying the composition; a film, preferably a cosmetic film, prepared by a process comprising: or (2)(a) 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 or salt thereof having two or more pKa values; or At least one non-polymeric base or salt thereof having two or more pKb values Including, at least one polyion complex, (b) at least one lipophilic antioxidant; and Optionally, (d) at least one surfactant, preferably selected from nonionic surfactants, more preferably selected from polyglyceryl fatty acid esters. A film, preferably a cosmetic film, comprising: the anionic polymer is selected from hyaluronic acid, its salts, and its derivatives; This can be achieved by a coating, preferably a cosmetic coating, in which the amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0026] The present invention also provides a cosmetic method for keratinous materials, such as the skin, comprising the steps of: applying a composition according to the invention to a keratinous material; drying the composition to form a cosmetic film on the keratinous material; The present invention also relates to a cosmetic method including: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] As a result of intensive research, the present inventors have found that it is possible to provide a composition that is less sticky and can provide a long-lasting antioxidant effect. (a) 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 or salt thereof having two or more pKa values; or At least one non-polymeric base or salt thereof having two or more pKb values Including, At least one polyion complex; (b) at least one lipophilic antioxidant; (c) Water and Including, 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.

[0028] Furthermore, the inventors have found that it is possible to provide a method for preparing a film which is less sticky and which is able to provide a long-lasting antioxidant effect. Therefore, the method according to the invention is a method for preparing a film, preferably a cosmetic film, comprising the steps of: applying a composition according to the invention onto a substrate, preferably a keratin material; drying the composition; The method includes:

[0029] Furthermore, the present inventors have discovered that it is possible to provide a coating that is less sticky and can provide a long-lasting antioxidant effect. (1) on a substrate, preferably a keratinous material, applying a composition according to the present invention; drying the composition; a film, preferably a cosmetic film, prepared by a process comprising: Or, (2)(a) 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 or salt thereof having two or more pKa values; or At least one non-polymeric base or salt thereof having two or more pKb values At least one polyion complex comprising (b) at least one lipophilic antioxidant; and Optionally, (d) at least one surfactant, preferably selected from nonionic surfactants, more preferably selected from polyglyceryl fatty acid esters; A film, preferably a cosmetic film, comprising: the anionic polymer is selected from hyaluronic acid, its salts, and its derivatives; The amphoteric polymer is selected from cationized hyaluronic acid and its salts; A coating, preferably a cosmetic coating.

[0030] The stickiness of the composition according to the present invention can be reduced as compared to a composition containing hyaluronic acid that does not form a polyion complex.

[0031] Compositions and coatings according to the present invention can provide long-lasting antioxidant benefits.

[0032] Thus, the present invention may be useful for protecting the skin from damage caused by peroxidation of unsaturated lipids, such as sebum, which may be alterations in desquamation, squalene loss, acne and blackheads, dullness of the skin, and ageing, such as the formation of wrinkles and / or fine lines.

[0033] Furthermore, the compositions according to the invention may provide long-lasting cosmetic benefits and / or improved moisturizing textures based on hyaluronic acid or cationized hyaluronic acid.

[0034] Additionally, compositions and films according to the present invention can be transparent or translucent.

[0035] By applying the composition onto a substrate, preferably onto keratinous materials such as skin and hair, more preferably onto skin, and drying the composition, it is possible to easily prepare a film containing a polyion complex, which may contain at least one surfactant.

[0036] The stickiness of the film according to the present invention can be reduced as compared to a film of hyaluronic acid that does not form a polyion complex.

[0037] The coating according to the invention may be porous. The surface of the coating according to the invention may be uneven or rough.

[0038] The coating according to the invention can have various cosmetic functions, for example, the coating can provide a moisturizing effect based on hyaluronic acid or cationized hyaluronic acid in a polyion complex.

[0039] A film according to the present invention can trap sebum, impart a matte appearance to keratinous materials such as skin, absorb or adsorb malodors, and / or protect keratinous materials from, for example, dirt or pollutants.

[0040] When the film contains at least one cosmetic active ingredient such as oil, the film can also have a cosmetic effect provided by the cosmetic active ingredient. For example, when the polyion complex film contains at least one cosmetic active ingredient selected from a UV shielding agent, (b) an anti-aging agent other than a lipophilic antioxidant, a sebum suppressing agent, a deodorant agent, an antiperspirant, a whitening agent, and a mixture thereof, the film can shield UV rays, treat skin aging, absorb sebum on the skin, control odor on the skin, control sweat on the skin, and / or whiten the skin.

[0041] Coatings according to the present invention may be transparent or translucent and therefore may be difficult to perceive, even when the coating is relatively thick.

[0042] Furthermore, the film according to the invention is water resistant, so that the film can remain on the keratinous material, such as the skin, even when the surface of the keratinous material is wet, for example due to sweat or rain.

[0043] Furthermore, the film according to the present invention can be easily removed from keratinous materials such as skin under alkaline conditions. Thus, the film according to the present invention is difficult to remove with water, but can be easily removed with soap that can provide alkaline conditions.

[0044] Therefore, when the film according to the present invention contains a hydrophilic or water-soluble UV blocking agent, the film according to the present invention can be resistant to water (waterproof) and exhibit a long-lasting UV blocking effect, but can be easily removed with a soap that can provide alkaline conditions.

[0045] Hereinafter, the compositions, methods, coatings, etc. according to the invention will be described in more detail.

[0046] [Polyion complex] The composition according to the present invention comprises at least one type of polyion complex (a). Two or more different types of polyion complexes (a) may be used in combination. Thus, a single type of polyion complex (a) or a combination of different types of polyion complexes (a) may be used.

[0047] (a) The polyion complex may be in the form of particles.

[0048] The diameter of the polyion complex particles may be 5 nm to 100 μm, preferably 100 nm to 50 μm, more preferably 200 nm to 40 μm, and even more preferably 500 nm to 30 μm. Particle sizes less than 1 μm can be measured by dynamic light scattering, and particle sizes greater than 1 μm can be measured by optical microscopy. The particle size can be based on the number average diameter.

[0049] The amount of the (a) polyion complex in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, based on the total weight of the composition.

[0050] The amount of the (a) polyion complex in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition.

[0051] The amount of the (a) polyion complex in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0052] The (a) polyion complex comprises at least one polymer or combination of polymers. Specifically, the (a) polyion complex comprises: (1) at least one cationic polymer and at least one anionic polymer; (2) at least one cationic polymer and at least one amphoteric polymer; (3) at least one anionic polymer and at least one amphoteric polymer, or (4) at least one amphoteric polymer Includes.

[0053] There is no limitation on the type of cationic polymer. Two or more different types of cationic polymers may be used in combination. Therefore, a single type of cationic polymer or a combination of different types of cationic polymers may be used.

[0054] In the above (1), the amount of cationic polymer / anionic polymer, for example, the ratio of chemical equivalents, may be 0.05 to 18, preferably 0.1 to 10, and more preferably 0.5 to 5.0. In detail, it may be preferable that the number of cationic groups in the cationic polymer / the number of anionic groups in the anionic polymer is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5 to 5.0.

[0055] In the above (2), the amount of cationic polymer / ampholytic polymer, for example, the ratio of chemical equivalents, may be 0.05 to 18, preferably 0.1 to 10, more preferably 0.5 to 5.0. In detail, it may be preferable that the number of cationic groups in the cationic polymer / the number of cationic groups and anionic groups in the ampholytic polymer is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5 to 5.0.

[0056] In the above (3), the amount of anionic polymer / ampholytic polymer, for example, the ratio of chemical equivalents, may be 0.05 to 18, preferably 0.1 to 10, and more preferably 0.5 to 5.0. In detail, it may be preferable that the number of anionic groups in the anionic polymer / the number of cationic groups and anionic groups in the ampholytic polymer is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5 to 5.0.

[0057] The total amount of the polymer according to any one of the above (1) to (4) in the composition according to the present invention may be 0.01 mass % or more, preferably 0.03 mass % or more, and more preferably 0.05 mass % or more, based on the total mass of the composition.

[0058] The total amount of the polymer according to any one of the above (1) to (4) in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the composition.

[0059] The total amount of the polymer according to any one of the above (1) to (4) in the composition according to the present invention may be 0.01 mass % to 15 mass %, preferably 0.03 mass % to 10 mass %, and more preferably 0.05 mass % to 5 mass %, relative to the total mass of the composition.

[0060] (cationic polymer) The cationic polymer has a positive charge density of 0.01 meq / g to 20 meq / g, preferably 0.05 to 15 meq / g, and more preferably 0.1 to 10 meq / g.

[0061] It may be preferred that the molecular weight of the cationic polymer is 500 or more, preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more.

[0062] Unless otherwise defined in the description, "molecular weight" means number average molecular weight.

[0063] The cationic polymer may have at least one positive charge and / or a moiety having a positive charge selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups. The term (primary) "amino group" as used herein means an -NH2 group.

[0064] The cationic polymers may be homopolymers or copolymers. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.

[0065] The cationic polymer can be selected from natural and synthetic cationic polymers. Non-limiting examples of cationic polymers are:

[0066] (1) Homopolymers and copolymers derived from esters and amides of acrylic or methacrylic acid and containing at least one unit selected from units of the following formulae:

[0067] [ka]

[0068] [In the formula, R1 and R2 may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups; R3, which may be the same or different, is selected from hydrogen and CH3; the symbols A may be the same or different and are selected from linear or branched alkyl groups containing 1 to 6 carbon atoms, for example 2 to 3 carbon atoms, and hydroxyalkyl groups containing 1 to 4 carbon atoms, R4, R5 and R6 may be the same or different and are selected from alkyl groups containing 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment alkyl groups containing 1 to 6 carbon atoms; X - are anions derived from inorganic or organic acids, such as methosulfate anion, and halide ions, such as chloride and bromide.

[0069] The copolymers of family (1) may also contain at least one unit derived from a comonomer, which may be chosen from acrylamide, methacrylamide, diacetone acrylamide, acrylamides and methacrylamides whose nitrogen atoms are substituted with (C1-C4) lower alkyl groups, groups derived from acrylic or methacrylic acid and their esters, vinyl lactams such as vinyl pyrrolidone and vinyl caprolactam, and vinyl esters.

[0070] Examples of family (1) copolymers include, but are not limited to, the following: Copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halides; Copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, such as those described in European Patent Application No. 0080976; Copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, Quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, such as those described in French Patents Nos. 2 077 143 and 2 393 573; Dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymer, Vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymer, quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymer, and Crosslinked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salt polymers, for example those obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or by copolymerization of acrylamide and dimethylaminoethyl methacrylate quaternized with methyl chloride, followed by crosslinking with a compound containing olefinic unsaturation, for example methylenebisacrylamide.

[0071] (2) Cationic cellulose polymers, such as the cellulose ether derivatives containing one or more quaternary ammonium groups described in French Patent No. 1 492 597, such as the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation, which are also defined in the CTFA dictionary as quaternary ammonium of hydroxyethylcellulose reacted with epoxides substituted with trimethylammonium groups.

[0072] It is preferred that the cationic cellulose polymer has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group, more preferably a quaternary trimethylammonium group.

[0073] The quaternary ammonium group has the following chemical formula (I):

[0074] [ka]

[0075] [In the formula, Each of R1 and R2 is C 1~3 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; R3 is C 1~24 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; X - represents an anion, preferably a halide ion, more preferably a chloride ion, n represents an integer of 0 to 30, preferably 0 to 10, and more preferably 0; R4 is C 1~4 represents an alkylene group, preferably an ethylene group or a propylene group. The quaternary ammonium group may be present in a group containing a quaternary ammonium group which may be represented by:

[0076] The left-most ether linkage (-O-) in the above chemical formula (I) can be attached to a sugar ring of a polysaccharide.

[0077] The quaternary ammonium group-containing group is -O-CH2-CH(OH)-CH2-N + It is preferably (CH3)3.

[0078] (3) Cationic cellulose polymers, such as cellulose copolymers and cellulose derivatives grafted with water-soluble quaternary ammonium monomers and described, for example, in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for example hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted with salts selected from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium salts.

[0079] Commercially available products corresponding to these polymers include, for example, the products sold under the names "Celquat® L 200" and "Celquat® H 100" by National Starch.

[0080] (4) Non-cellulosic cationic polysaccharides such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid and dextran hydroxypropyltrimonium chloride, as described in U.S. Patents 3,589,578 and 4,031,307. Guar gum modified with salts such as 2,3-epoxypropyltrimethylammonium chloride (guar hydroxypropyltrimonium chloride) may also be used.

[0081] Such products are, by way of example, sold by the company MEYHALL under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162.

[0082] (5) Polymers containing piperazinyl units and divalent alkylene or hydroxyalkylene groups, containing linear or branched chains optionally interrupted by at least one element selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, and also the oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French Patents Nos. 2 162 025 and 2 280 361.

[0083] (6) Water-soluble polyaminoamides, for example prepared by polycondensation of acidic compounds with polyamines, which may be crosslinked with an element selected from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bisunsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacyldiamines; bisalkylhalides; oligomers obtained by reaction of bifunctional compounds reactive with elements selected from bishalohydrins, bisazetidiniums, bishaloacyldiamines, bisalkylhalides, epihalohydrins, diepoxides and bisunsaturated derivatives; the crosslinking agent is used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may be optionally alkylated or, if they contain at least one tertiary amine function, they may be quaternized. Such polymers are described, for example, in French patents nos. 2,252,840 and 2,368,508.

[0084] (7) Polyaminoamide derivatives obtained by condensation of polyalkylenepolyamines with polycarboxylic acids followed by alkylation with bifunctional agents, such as adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl groups contain from 1 to 4 carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene groups contain from 1 to 4 carbon atoms, such as ethylene groups. Such polymers are described, by way of example, in French Patent No. 1 583 363. In at least one embodiment, these derivatives can be chosen from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.

[0085] (8) Polymers obtained by reacting polyalkylenepolyamines containing two primary amine groups and at least one secondary amine group with dicarboxylic acids selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of polyalkylenepolyamine to dicarboxylic acid may range from 0.8:1 to 1.4:1, and the polyaminoamides obtained therefrom are reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups of polyaminoamide ranging from 0.5:1 to 1.8:1. Such polymers are described, for example, in US Pat. Nos. 3,227,615 and 2,961,347.

[0086] (9) Cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallyl-ammonium, for example homopolymers and copolymers which contain, as main chain building blocks, at least one unit selected from units of formulae (Ia) and (Ib) below:

[0087] [ka]

[0088] [In the formula, k and t may be the same or different and are equal to 0 or 1, the sum k+t being equal to 1; R 12 is selected from hydrogen and a methyl group; R 10 and R 11 may be the same or different and are selected from alkyl groups containing 1 to 6 carbon atoms, hydroxyalkyl groups, where the alkyl group contains, for example, 1 to 5 carbon atoms, and lower (C1 to C4) amidoalkyl groups, or R 10 and R 11 may, together with the nitrogen atom to which they are attached, form a heterocyclic group, such as piperidinyl and morpholinyl; 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 addition no. 2 190 406.

[0089] In one embodiment, R 10 and R 11 may be the same or different and are selected from alkyl groups containing 1 to 4 carbon atoms.

[0090] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chlorides, such as the dimethyldiallylammonium chloride homopolymer sold under the name "MERQUAT® 100" by CALGON (and its homologs of lower weight average molecular weight), and the copolymer of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".

[0091] (10) A quaternary diammonium polymer comprising at least one repeat unit of formula (II):

[0092] [ka]

[0093] {In the formula, R 13 , R 14 , R 15 and R 16 may be the same or different and are selected from aliphatic, alicyclic and arylaliphatic groups containing 1 to 20 carbon atoms, and lower hydroxyalkyl aliphatic groups; or R 13 , R 14 , R 15 and R 16may be taken together with the nitrogen atom to which they are attached or separately form a heterocycle which optionally contains a second heteroatom other than nitrogen, or R 13 , R 14 , R 15 and R 16 may be the same or different, and may be a nitrile group, an ester group, an acyl group, an amide group, -CO-OR 17 -E group and -CO-NH-R 17 -E group (in the formula, R 17 is an alkylene group, and E is a quaternary ammonium group); A1 and B1 may be the same or different and are selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked or inserted in the main chain, at least one element selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups and ester groups; X - is an anion derived from an inorganic or organic acid, A1, R 13 and R 15 may be taken together with the two nitrogen atoms to which they are attached to form a piperazine ring, When A1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B1 can be selected from: -(CH2) n --CO-E'-OC-(CH2) n - [In the formula, E' is a) a compound of the formula -OZO-, where Z is a linear or branched hydrocarbon-based group and a group of the formula: -(CH2-CH2-O) x -CH2-CH2- -[CH2-CH(CH3)-O] y -CH2-CH(CH3)- (wherein x and y may be the same or different and are selected from integers ranging from 1 to 4 representing a unique defined degree of polymerization and numbers ranging from 1 to 4 representing an average degree of polymerization). a glycol residue selected from b) bis-secondary diamine residues, such as piperazine derivatives; c) bis-primary diamine residues of the formula -NH-Y-NH-, where Y is selected from linear or branched hydrocarbon-based radicals and the divalent radical -CH-CH-SS-CH-CH-, and d) a ureylene group of the formula -NH-CO-NH- selected from

[0094] In at least one embodiment, X - is an anion, for example chloride or bromide.

[0095] Polymers of this type are described, for example, in French Patents Nos. 2320330, 2270846, 2316271, 2336434 and 2413907, and in U.S. Pat. Nos. 2273780, 2375853, 2388614, 2454547, 3206462, 3206463 and 3206464. Nos. 2261002, 2271378, 3874870, 4001432, 3929990, 3966904, 4005193, 4025617, 4025627, 4025653, 4026945 and 4027020.

[0096] Non-limiting examples of such polymers include those of formula (III):

[0097] [ka]

[0098] [In the formula, R 13 , R 14 , R 15 and R 16may be the same or different and are selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms, n and p may be the same or different and are integers ranging from 2 to 20, and X - is an anion derived from an inorganic or organic acid. Examples of the repeating unit include those containing at least one of the following repeating units:

[0099] (11) Polyquaternary ammonium polymers comprising units of formula (IV):

[0100] [ka]

[0101] [In the formula, R 18 , R 19 , R 20 and R 21 may be the same or different and are hydrogen, methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl, -CH2CH2(OCH2CH2) p OH group (wherein p is an integer selected from 0 to 6), with the proviso that R 18 , R 19 , R 20 and R 21 is not hydrogen at the same time, r and s may be the same or different and are selected from integers ranging from 1 to 6; q is selected from an integer ranging from 0 to 34; X - is an anion, for example a halide ion, A is selected from a dihalide group and a -CH2-CH2-O-CH2-CH2- group.

[0102] Such compounds are described, by way of example, in European Patent Application No. 0122324.

[0103] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole. Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimine, polymers containing units selected from vinylpyridine units and vinylpyridinium units, condensates of polyamines with epichlorohydrin, quaternary polyureylenes, and chitin derivatives.

[0104] According to one embodiment of the present invention, the at least one cationic polymer is chosen from cellulose ether derivatives containing quaternary ammonium groups, such as the product sold under the name "JR 400" by UNION CARBIDE CORPORATION, cationic cyclopolymers, such as the homopolymers and copolymers of dimethyldiallylammonium chloride sold under the names MERQUAT® 100, MERQUAT® 550 and MERQUAT® S by CALGON, guar gum modified with 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0105] (13) Polyamines It is also possible to use as cationic polymers (co)polyamines, which may be homopolymers or copolymers, having multiple amino groups. The amino groups may be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone of the (co)polyamine or, if present, in pendant groups.

[0106] Examples of (co)polyamines include chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate, (co)polyvinylpyridine such as (co)poly-1-methyl-2-vinylpyridine, (co)polyimines such as (co)polyethylenimine, (co)polypyridines such as (co)poly(quaternary pyridine), (co)polybiguanides such as (co)polyaminopropyl biguanide, (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinyl acetal, and salts thereof.

[0107] As the (co)polyamine, it is preferred to use (co)polylysine. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. Polylysine can be α-polylysine or ε-polylysine. For example, polylysine can be ε-polylysine, e.g. ε-poly-L-lysine, which is typically used as a natural preservative in food. 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.

[0108] (14) Cationic polyamino acids As cationic polymers, it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers having multiple amino and carboxyl groups. The amino groups may be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone of the cationic polyamino acid or in pendant groups, if present. The carboxyl groups may be present in pendant groups of the cationic polyamino acid, if present.

[0109] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, steardimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed soy protein, and the like.

[0110] The following description relates to preferred embodiments of the cationic polymer.

[0111] It may be preferred that the cationic polymer is selected from cationic starches.

[0112] As examples of cationic starches, mention may be made of starches modified with 2,3-epoxypropyltrimethylammonium salts (e.g. chloride), such as the product known by the INCI name Starch Hydroxypropyltrimonium Chloride, sold under the name SENSOMER Cl-50 by the company Ondeo, or Pencare™ DP 1015 by the company Ingredion.

[0113] It may also be preferred that the cationic polymer is selected from cationic gums.

[0114] The gum may, for example, be selected from the group consisting of cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum and gum arabic.

[0115] Examples of cationic gums include cationic polygalactomannan derivatives, such as guar gum derivatives and cassia gum derivatives, such as CTFA: guar hydroxypropyltrimonium chloride, hydroxypropyl guar hydroxypropyltrimonium chloride and cassia hydroxypropyltrimonium chloride. Guar hydroxypropyltrimonium chloride is commercially available from Rhodia Inc. under the trade name Jaguar series and from Ashland Inc. under the trade name N-Hance series. Cassia hydroxypropyltrimonium chloride is commercially available from Lubrizol Advanced Materials, Inc. under the trade name Sensomer CT-250 and Sensomer CT-400, or from Ashland Inc. under ClearHance .

[0116] It may also be preferred that the cationic polymer is selected from chitosan.

[0117] It may be more preferred that the cationic polymer is selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine, cationic (co)polyamino acids, such as cationized collagen, cationic cellulose polymers, and salts thereof.

[0118] It may even be more preferred that the cationic polymer is selected from the group consisting of polylysine, polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan, and mixtures thereof.

[0119] The amount of cationic polymer in the composition according to the invention may be at least 0.01% by weight, preferably at least 0.03% by weight, more preferably at least 0.05% by weight, relative to the total weight of the composition.

[0120] The amount of cationic polymer in the composition according to the invention may be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, relative to the total weight of the composition.

[0121] The amount of cationic polymer in the composition according to the present invention may be from 0.01% to 15% by mass, preferably from 0.03% to 10% by mass, and more preferably from 0.05% to 5% by mass, based on the total mass of the composition.

[0122] (anionic polymer) The anionic polymer has a positive charge density. When the anionic polymer is a synthetic anionic polymer, the charge density of the anionic polymer may be 0.1 meq / g to 20 meq / g, preferably 1 to 15 meq / g, more preferably 4 to 10 meq / g, and when the anionic polymer is a natural anionic polymer, the average degree of substitution of the anionic polymer may be 0.1 to 3.0, preferably 0.2 to 2.7, more preferably 0.3 to 2.5.

[0123] It may be preferred that the molecular weight of the anionic polymer is 300 or more, preferably 1,000 or more, even more preferably 5,000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, even more preferably 1,000,000 or more.

[0124] Unless otherwise defined in the description, "molecular weight" may mean number average molecular weight.

[0125] According to the invention, the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives.

[0126] Hyaluronic acid has the chemical formula:

[0127] [ka]

[0128] It can be expressed as:

[0129] In the context of the present invention, the term "hyaluronic acid" refers specifically to a compound of the formula:

[0130] [ka]

[0131] It includes the basic unit of hyaluronic acid.

[0132] This is the smallest fraction of hyaluronic acid that contains the disaccharide dimer, namely D-glucuronic acid and N-acetylglucosamine.

[0133] The term "derivative" of hyaluronic acid, in the context of the present invention, also includes linear polymers comprising the above-listed polymer units linked together in a chain via alternating β(1,4) and β(1,3) glycosidic bonds, with a molecular weight (MW) that can range between 380 and 13,000,000 daltons, which depends mainly on the source from which the hyaluronic acid is obtained and / or on the method of preparation.

[0134] The term "salt" of hyaluronic acid, in the context of the present invention, includes any salt of hyaluronic acid, including alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

[0135] In nature, hyaluronic acid is found in the percellular gel in the matrix of connective tissues of vertebrate organs, such as the dermis and epithelial tissues, specifically in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord, and in the crest process.

[0136] The term "hyaluronic acid" therefore includes all fractions or subunits of hyaluronic acid having molecular weights especially within the molecular weight ranges recalled above.

[0137] In the context of the present invention, hyaluronic acid fractions that do not have inflammatory activity are preferably used.

[0138] Reference may be made to the article "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699-715, which reviews the enumerated biological activities of hyaluronic acid according to its molecular weight through the illustration of various hyaluronic acid fractions.

[0139] According to a preferred embodiment of the present invention, the hyaluronic acid fraction suitable for use in the present invention has a molecular weight between 50 kDa and 5,000 kDa, in particular between 100 kDa and 5,000 kDa, and more particularly between 400 kDa and 5,000 kDa, in which case the term used is high molecular weight hyaluronic acid.

[0140] Alternatively, hyaluronic acid fractions that may also be suitable for use within the present invention have a molecular weight between 50 kDa and 400 kDa, in which case the term used is intermediate molecular weight hyaluronic acid.

[0141] Again, alternatively, hyaluronic acid fractions that may be suitable for use within the present invention have a molecular weight of less than 50 kDa, in which case the term used is low molecular weight hyaluronic acid.

[0142] It may be preferable to use a combination of two or more types of hyaluronic acid or its salt, for example, a combination of a high molecular weight hyaluronic acid or its salt with a medium molecular weight hyaluronic acid or its salt, a combination of a high molecular weight hyaluronic acid or its salt with a low molecular weight hyaluronic acid or its salt, and a combination of a medium molecular weight hyaluronic acid or its salt with a low molecular weight hyaluronic acid or its salt.

[0143] Finally, the term "derivatives" of hyaluronic acid also includes hyaluronic acid esters, in particular those in which all or part of the carboxylic acid groups of the acid functions are esterified with oxyethylated alkyls or alcohols containing 1 to 20 carbon atoms, in particular those in which the degree of substitution at the level of D-glucuronic acid of hyaluronic acid ranges from 0.5 to 50%.

[0144] Mention may in particular be made of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. Such esters have been described in detail in D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) pp. 2101-2127.

[0145] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.

[0146] The molecular weights given above are also valid for hyaluronic acid esters.

[0147] Specifically, hyaluronic acid is sold by Hyactive under the trade name CPN (MW: 10-150 kDa) and by Soliance under the trade name Cristalhyal (MW: 1.1×10 6 ), supplied by Bioland under the name Nutra HA (MW: 820,000 Da), by Bioland under the name Nutra AF (MW: 69,000 Da), by Bioland under the name Oligo HA (MW: 6100 Da), or by Vam Farmacos Metica under the name D Factor (MW: 380 Da).

[0148] The amount of anionic polymer in the composition according to the invention may be greater than or equal to 0.01% by weight, preferably greater than or equal to 0.03% by weight, more preferably greater than or equal to 0.05% by weight, relative to the total weight of the composition.

[0149] The amount of anionic polymer in the composition according to the invention may be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, relative to the total weight of the composition.

[0150] The amount of anionic polymer in the composition according to the present invention may be from 0.01% to 15% by mass, preferably from 0.03% to 10% by mass, more preferably from 0.05% to 5% by mass, based on the total mass of the composition.

[0151] (Amphoteric polymer) Amphoteric polymers have both positive and negative charge densities.

[0152] The positive charge density of the amphoteric polymer may be from 0.01 to 20 meq / g, preferably from 0.05 to 15 meq / g, and more preferably from 0.1 to 10 meq / g.

[0153] The negative charge density of the amphoteric polymer may be from 0.01 to 20 meq / g, preferably from 0.05 to 15 meq / g, and more preferably from 0.1 to 10 meq / g.

[0154] It may be preferred that the molecular weight of the amphoteric polymer is 500 or more, preferably 1,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more.

[0155] It may be preferred that the molecular weight of the amphoteric polymer be 1,000,000 or less, preferably 900,000 or less, more preferably 800,000 or less.

[0156] Unless otherwise defined in the description, "molecular weight" may mean number average molecular weight.

[0157] According to the invention, the amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0158] Cationized hyaluronic acid contains at least one cationic group, such as an ammonium group, in its molecule, which does not exhibit a counter cation of the salt, since there is no counter cation in the hyaluronic acid molecule.

[0159] Salts may include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

[0160] The cationized hyaluronic acid may have at least one quaternary ammonium group-containing group.

[0161] The cationized hyaluronic acid and / or a salt thereof may be represented by the following general formula (1):

[0162] [ka]

[0163] [In the formula, R 4 ~R 9 are each independently a hydrogen atom or a quaternary ammonium group-containing group (R 4 ~R 9 represents a hydrogen atom), and n represents an integer of 2 to 5,000. The compound may have a structure represented by:

[0164] In the above general formula (1), R 4 ~R 9 Examples of quaternary ammonium group-containing groups represented by the following general formula (2):

[0165] [ka]

[0166] [In the formula, R 1 ~R 3 each represents a hydrocarbon group; X - represents a monovalent anion] Examples of the groups include those represented by the following formula:

[0167] In the above general formula (2), R 1 ~R 3 Examples of the hydrocarbon group represented by include linear or branched alkyl groups, unsaturated hydrocarbon groups, and aromatic hydrocarbon groups. Among these, alkyl groups are preferred. Examples of the alkyl groups include alkyl groups having 1 to 30 (preferably 1 to 6) carbon atoms. R 1 ~R 3 It is more preferable that the hydrocarbon group represented by the following formula: is an alkyl group having 1 to 3 carbon atoms.

[0168] In the above general formula (2), X - Examples of monovalent anions represented by include halogen ions such as fluoride, bromide, chloride, and iodide.

[0169] The quaternary ammonium group-containing group can be introduced by replacing the hydrogen atom of the carboxyl group contained in the hyaluronic acid and / or its salts used as raw materials (hereinafter referred to as "raw material hyaluronic acid and / or its salts") with a quaternary ammonium group-containing group. In this case, the quaternary ammonium group-containing group is bonded to the oxygen atom of the (-C(-O)O-) group contained in the cationized hyaluronic acid and / or its salts according to this embodiment. The fact that the quaternary ammonium group-containing group is bonded to the oxygen atom of the (-C(-O)O-) group contained in the cationized hyaluronic acid and / or its salts according to this embodiment can be seen by nuclear magnetic resonance ( 13 The presence of a peak attributable to the carbon atom of the -C(-O)O- group to which the quaternary ammonium group-containing group is bonded via an oxygen atom can be confirmed by analyzing the chemical shifts in the C NMR spectrum.

[0170] Specifically, the quaternary ammonium group-containing group can be obtained by reacting the carboxyl group (and / or hydroxyl group) of raw material hyaluronic acid and / or its salt with a cationizing agent containing a quaternary ammonium group.Preferably, the cationizing agent is at least one of the following general formula (3): 2,3-epoxypropyltrialkylammonium halide and the following general formula (4): 3-halogeno-2-hydroxypropyltrialkylammonium halide.The reaction of raw material hyaluronic acid and / or its salt with a cationizing agent is described in the preparation method hereinafter.

[0171] [ka]

[0172] [In the formula, R 1 ~R 3 is the same as defined for general formula (2), and X represents a halogen atom.

[0173] [ka]

[0174] [In the formula, R 1 ~R 3 is the same as defined for general formula (2), and X and Y each represent a halogen atom.

[0175] Examples of halogen atoms represented by X and Y in the above general formulas (3) and (4) include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.

[0176] The cationized hyaluronic acid may have at least one quaternary ammonium group-containing group, and has a degree of cationization of 0.05 to 0.6, preferably 0.1 to 0.5, and more preferably 0.15 to 0.4.

[0177] The degree of cationization of the cationized hyaluronic acid and / or its salt according to the present embodiment (i.e., the degree of substitution with a quaternary ammonium group-containing group) can be determined by calculating the nitrogen content of the raw material sodium hyaluronate and the nitrogen content of the cationized hyaluronic acid by the semi-micro Kjeldahl method, and calculating the degree of cationization according to the following formula based on the increase in nitrogen content:

[0178] The nitrogen content of the raw material sodium hyaluronate is N N The nitrogen content of the cationized hyaluronic acid having a degree of cationization of (x) is referred to as N S When referring to the increase in nitrogen content (N S -N N The relationship between the degree of cationization (x) and the amount of cationization (x) is given by the following formula: N S -N N (%) = [14x / (molecular weight of disaccharide unit of cationized hyaluronic acid)] × 100 = [14x / (molecular weight of disaccharide unit of raw material sodium hyaluronate) + 129.5x] x 100 =[14x / (401.3+129.5x)]×100 As shown by:

[0179] Therefore, the degree of cationization (i.e., the degree of substitution with quaternary ammonium group-containing groups) can be calculated by the following formula: Degree of cationization (x) = [(N S -N N )×401.3] / [1400-129.5*(N S -N N )] Thus, it can be calculated.

[0180] When the raw material hyaluronic acid is unknown, the degree of cationization of the cationized hyaluronic acid can be calculated by the above formula on the assumption that the raw material sodium hyaluronate is sodium hyaluronate having a purity of 99% or more.

[0181] It is possible for 1% or more, preferably 5% or more, more preferably 10% or more, and / or 50% or less, preferably 40% or less, more preferably 30% or less of the anionic groups in hyaluronic acid to be replaced with cationic groups, preferably with quaternary ammonium group-containing groups, more preferably with quaternary ammonium group-containing groups represented by the above general formula (2).

[0182] Cationic hyaluronic acids include hydroxypropyltrimonium hyaluronate, commercially available as Hyaloveil and Hyaloveul-MPF by Kewpie Corporation, Japan.

[0183] The amount of amphoteric polymer in the composition according to the invention may be greater than or equal to 0.01% by weight, preferably greater than or equal to 0.03% by weight, more preferably greater than or equal to 0.05% by weight, relative to the total weight of the composition.

[0184] The amount of amphoteric polymer in the composition according to the invention may be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, relative to the total weight of the composition.

[0185] The amount of amphoteric polymer in the composition according to the present invention may be from 0.01% to 15% by mass, preferably from 0.03% to 10% by mass, more preferably from 0.05% to 5% by mass, based on the total mass of the composition.

[0186] (Non-polymeric acids with two or more acid dissociation constants) The composition according to the present invention may comprise at least one non-polymeric acid or salt thereof having two or more pKa values, i.e., at least one non-polymeric acid or salt thereof having two or more acid dissociation constants. pKa values ​​(acid dissociation constants) are well known to those skilled in the art and should be determined at a constant temperature, such as 25°C.

[0187] A non-polymeric acid or salt thereof having two or more pKa values ​​can be incorporated into the (a) polyion complex. A non-polymeric acid having two or more pKa values ​​can function as a crosslinker, specifically an anionic crosslinker for cationic and / or amphoteric polymers.

[0188] It is preferred that a non-polymeric acid or salt thereof having two or more pKa values ​​be used in conjunction with the cationic and anionic polymers.

[0189] The term "non-polymeric" as used herein means that the acid is not obtained by polymerizing two or more monomers, and thus does not correspond to acids obtained by polymerizing two or more monomers, such as polycarboxylic acids.

[0190] It is preferred that the molecular weight of the non-polymeric acid or salt thereof having two or more pKa values ​​is 1000 or less, preferably 800 or less, and more preferably 700 or less.

[0191] There is no limitation on the type of non-polymeric acid or its salt having two or more pKa values. Two or more different types of non-polymeric acid or its salt having two or more pKa values ​​may be used in combination. Therefore, a single type of non-polymeric acid or its salt having two or more pKa values, or a combination of different types of non-polymeric acid or its salt having two or more pKa values ​​may be used.

[0192] The term "salt" as used herein means a salt formed by adding a suitable base to a non-polymeric acid having two or more pKa values, which can be obtained from the reaction of a non-polymeric acid having two or more pKa values ​​with a base according to methods known to those skilled in the art. The salt can include metal salts, such as salts with alkali metals such as Na and K, and salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

[0193] The non-polymeric acid or salt thereof having two or more pKa values ​​may be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof.

[0194] The non-polymeric acid having two or more pKa values ​​can have at least two acid groups selected from the group consisting of carboxylic acid groups, sulfate groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, phenolic hydroxyl groups, and mixtures thereof.

[0195] A non-polymeric acid having two or more pKa values ​​may be a non-polymeric polyacid.

[0196] The non-polymeric acids having two or more pKa values ​​can be selected from the group consisting of dicarboxylic acids, disulfonic acids, and diphosphoric acids, and mixtures thereof.

[0197] Non-polymeric acids or their salts having two or more pKa values ​​are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid, and their salts; aspartic acid, glutamic acid, and their salts; terephthalylidene dicamphorsulfonic acid or its salts (Megizolyl SX), benzophenone-9; phytic acid and its salts; Red 2. No. (Amaranth), Red No. 102 (New Coccine), Yellow No. 5 (Tartrazine), Yellow No. 6 (Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Red No. 201 (Risorubin B), Red No. 202 (Risorubin BCA), Red No. 204 (Lake Red CBA), Red No. 206 (Risoru Red CA), Red No. 207 (Risoru Red BA), Red No. 208 (Risorubin BCA), Sole Red SR), Red No. 219 (Brilliant Lake Red R), Red No. 220 (Deep Maroon), Red No. 227 (Fast Acid Magenta), Yellow No. 203 (Quinoline Yellow WS), Green No. 201 (Alizanine Cyanine Green F), Green No. 204 (Pyranine Conc), Green No. 205 (Light Green SF Yellow), Blue No. 203 (Patent Blue CA), Blue No. 205 (Alphazuline FG), Red No. 401 (Violamin R), Red 40 Red No. 5 (Permanent Red F5R), Red No. 502 (Ponceau 3R), Red No. 503 (Ponceau R), Red No. 504 (Ponceau SX), Green No. 401 (Naphthol Green B), Green No. 402 (Guinea Green B) and Black No. 401 (Naphthol Blue Black); folic acid, ascorbic acid, erythorbic acid, and salts thereof; cystine and its salts; EDTA and its salts; glycyrrhizin and its salts; and mixtures thereof.

[0198] It may be preferred that the non-polymeric acid or salt thereof having two or more pKa values ​​is selected from the group consisting of terephthalylidene dicamphorsulfonic acid and its salts (Megizolil SX), Yellow No. 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and their salts, and mixtures thereof.

[0199] The amount of the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, based on the total weight of the composition.

[0200] The amount of non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition.

[0201] The amount of the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 0.001% by mass to 15% by mass, preferably 0.005% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, based on the total mass of the composition.

[0202] (Non-polymeric bases with two or more base dissociation constants) The composition according to the invention may comprise at least one non-polymeric base or salt thereof having a pKb value of at least two, i.e. at least one non-polymeric base or salt thereof having a base dissociation constant of at least two. pKb values ​​(base dissociation constants) are well known to those skilled in the art and should be determined at a constant temperature, such as 25°C.

[0203] A non-polymeric base or salt thereof having two or more pKb values ​​can be incorporated into the (a) polyion complex. A non-polymeric base having two or more pKb values ​​can function as a crosslinker, specifically a cationic crosslinker for anionic and / or amphoteric polymers.

[0204] It is preferred that a non-polymeric base or salt thereof having a pKb value of two or more be used in conjunction with the cationic and anionic polymers.

[0205] The term "non-polymeric" means herein that the base is not obtained by polymerizing two or more monomers. Thus, the non-polymeric base does not correspond to a base obtained by polymerizing two or more monomers, such as polyallylamine.

[0206] It is preferred that the molecular weight of the non-polymeric base or salt thereof having two or more pKb values ​​is 1000 or less, preferably 800 or less, and more preferably 700 or less.

[0207] There is no limitation on the type of non-polymeric base or its salt having two or more pKb values. Two or more different types of non-polymeric bases or their salts having two or more pKb values ​​may be used in combination. Therefore, a single type of non-polymeric base or its salt having two or more pKb values, or a combination of different types of non-polymeric bases or their salts having two or more pKb values ​​may be used.

[0208] The term "salt" as used herein refers to a salt formed by adding a suitable acid to a non-polymeric base having two or more pKb values, which can be obtained by reacting a non-polymeric base having two or more pKb values ​​with an acid according to methods known to those skilled in the art.Salts can include ammonium salts, for example, salts with inorganic acids such as HCl and HNO3, and salts with organic acids such as carboxylic acids and sulfonic acids.

[0209] The non-polymeric base or salt thereof having two or more pKb values ​​may be an organic base or salt thereof, preferably a hydrophilic or water-soluble organic base or salt thereof.

[0210] The non-polymeric base having two or more pKb values ​​can have at least two basic groups selected from the group consisting of amino groups, guanidine groups, biguanide groups, imidazole groups, imino groups, pyridyl groups, and mixtures thereof.

[0211] The non-polymeric base having two or more pKb values ​​can be selected from the group consisting of non-polymeric diamines, such as ethylenediamine, propylenediamine, pentanediamine, hexanediamine, urea and its derivatives, and guanidine and its derivatives, non-polymeric polyamines, such as spermine and spermidine, basic amino acids, and mixtures thereof.

[0212] The non-polymeric base or salt thereof having two or more pKb values ​​can be selected from the group consisting of arginine, lysine, histidine, cysteine, cystine, tyrosine, tryptophan, ornithine, and mixtures thereof.

[0213] It may be preferred that the non-polymeric base or salt thereof having two or more pKb values ​​is selected from the group consisting of arginine, lysine, histidine, and mixtures thereof.

[0214] The amount of the non-polymeric base or salt thereof having two or more pKb values ​​in the composition according to the invention may be 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, based on the total weight of the composition.

[0215] The amount of non-polymeric bases or salts thereof having two or more pKb values ​​in the composition according to the invention may be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, based on the total weight of the composition.

[0216] The amount of the non-polymeric base or salt thereof having two or more pKb values ​​in the composition according to the present invention may be from 0.001% to 15% by mass, preferably from 0.005% to 10% by mass, more preferably from 0.01% to 5% by mass, based on the total mass of the composition.

[0217] [Lipophilic antioxidant] The composition according to the invention comprises (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.

[0218] According to the present invention, an antioxidant is a compound or substance capable of scavenging the various radical forms that may be present in the skin, preferably the antioxidant simultaneously scavenges all of the various radical forms present.

[0219] (b) Lipophilic antioxidant means that the partition coefficient of the antioxidant between n-butanol and water is >1, more preferably >10, and even more preferably >100.

[0220] (b) A lipophilic antioxidant is hydrophobic and is not a hydrophilic antioxidant, such as ascorbic acid or glutathione.

[0221] (b) As the lipophilic antioxidant, there can be mentioned a phenolic antioxidant having a hindered phenol structure or a semi-hindered phenol structure in the molecule. Specific examples of such compounds include 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid (having the INCI name pentaerythrityl tetra-di-t-butylhydroxyhydrocinnamate), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono- or 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, 2,5-di-tert-amylhydroquinone, tris[N-(3, 5-di-tert-butyl-4-hydroxybenzyl)]isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, butylidene-1,1 bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], octadecyl 3-(3,5-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-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6-trione, 2,4-bis(n-octylthio)-6-(4-hydroxyphenyl)propionate Examples of the hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,6-bis[(octylthio)methyl]-o-cresol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] can be mentioned.

[0222] (b) Lipophilic antioxidants include BHA (butylated hydroxyl anisole) and BHT (butylated hydroxyl toluene), vitamin E (or tocopherols and tocotrienols) and their derivatives, such as the phosphate derivatives, e.g. TPNA® sold by Showa Denko KK, coenzyme Q10 (or ubiquinone), idebenone, certain carotenoids, such as lutein, astaxanthin, β-carotene, polyphenols, phenolic acids and derivatives (e.g. chlorogenic acid), and flavonoids, which represent a major subgroup of polyphenols.

[0223] Among the flavonoids, mention may be made in particular of chalcones, hydroxylated chalcones and their reduced derivatives (especially those described in patent FR2608150), such as phloretin, neohesperidin, phloridzin, aspalathin, etc., flavanones, such as hesperetin and naringin, flavonols, such as quercetin, rutin, flavanols, such as catechin, EGCG, flavones, such as apigenidin, and finally anthocyans.Tannins may also be mentioned.Furthermore, reference may be made to the compounds described in patent applications FR699818, FR2706478, FR2907339, FR2814943 and FR2873026.

[0224] The polyphenolic compounds may be derived from a plant extract, selected from among green tea, apple, hops, guava, cocoa, or wood extracts such as chestnut, oak, horse chestnut or hazel.It is also possible to use an extract of Pinus maritime bark, obtained, for example, according to the method described in US Patent No. 4,698,360, US Patent No. 6,372,266 and US Patent No. 5,720,956.As an example of such an extract, the compound with the INCI name Pinus maritime (bark extract) and the CTFA name Pinus maritime bark extract can be cited.It may in particular be the extract of Pinus maritime bark marketed under the name PYCNOGENOL® by BIOLANDES AROMES and / or HORPHAG Research. Extracts of pine bark (Maritime) from LAYN Natural Ingredients, Pine Bark from Blue California and also Oligopin® from DRT (Les Derives Resiniques et Terpeniques) can also be cited.

[0225] In the context of the present invention, the term "polyphenolic compounds" thus also encompasses the plant extracts themselves which are rich in these polyphenolic compounds.

[0226] (b) Lipophilic antioxidants that may also be mentioned are dithiolanes, such as asparagusic acid or its derivatives, such as siliceous dithiolane derivatives, especially those described, for example, in patent application FR 2 908 769.

[0227] (b) Lipophilic antioxidants that may also be mentioned are: Glutathione and its derivatives (GSH and / or GSHOEt), such as glutathione alkyl esters (e.g., those described in patent applications FR2704754 and FR2908769); and 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 FR2877004 and FR2854160; and Ferulic acid and its derivatives (esters, salts, etc.). Particular mention may be made of esters of ferulic acid with C1-C30 alcohols, in particular methyl ferulate, ethyl ferulate, isopropyl ferulate, octyl ferulate and oryzanyl ferulate; Certain enzymes to protect against oxidative stress, such as catalase, superoxide dismutase (SOD), lactoperoxidase, glutathione peroxidase and quinone reductase; benzylcyclanones; substituted naphthalenones; pidolates (among others those described in patent application EP 0511118); caffeic acid and its derivatives, gamma oryzanol; melatonin, sulforaphane and extracts containing same (except for cress); diisopropyl esters with N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, especially those described in patent applications WO 94 / 11338, FR 2 698 095, FR 2 737 205 or EP 0 755 925, and Deferoxamine (or Desferal), described in patent application FR2825920.

[0228] The (b) lipophilic antioxidant preferably used is a chalcone, more particularly phloretin or neophesperidin, the diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, or an extract of maritime pine bark such as PYCNOGENOL®.

[0229] (b) Examples of lipophilic antioxidants include pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxylanisole, ascorbyl palmitate, tocopherol, and mixtures thereof.

[0230] The amount of (b) lipophilic antioxidant in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, relative to the total weight of the composition.

[0231] The amount of (b) lipophilic antioxidant in the composition according to the present invention may be not more than 15% by weight, preferably not more than 10% by weight, more preferably not more than 5% by weight, relative to the total weight of the composition.

[0232] The amount of the (b) lipophilic antioxidant in the composition according to the present invention may be 0.001% by mass to 15% by mass, preferably 0.005% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, relative to the total mass of the composition.

[0233] [water] The composition according to the present invention comprises (c) water.

[0234] The amount of (c) water may be 10% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight or more, based on the total weight of the composition.

[0235] (c) The amount of water may be up to 99% by weight, preferably up to 97% by weight, and more preferably up to 95% by weight, based on the total weight of the composition.

[0236] The amount of (c) water may be from 10% to 99% by mass, preferably from 30% to 97% by mass, and more preferably from 50% to 95% by mass, based on the total mass of the composition.

[0237] [Surfactants] The composition according to the present invention may further comprise (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.

[0238] The surfactant used in the present invention may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants and nonionic surfactants.

[0239] (anionic surfactant) The composition according to the invention may comprise at least one anionic surfactant. Two or more anionic surfactants may be used in combination.

[0240] The anionic surfactant is (C6-C 30 ) Alkyl sulfate, (C6-C 30 ) Alkyl ether sulfates, (C6-C 30 ) Alkyl amide ether sulfates, alkyl aryl polyether sulfates, monoglyceride sulfates; (C6-C 30 ) Alkyl sulfonates, (C6-C 30 ) Alkyl amidosulfonate, (C6-C 30 ) Alkylarylsulfonates, α-olefinsulfonates, paraffin sulfonates; (C6-C 30 ) Alkyl phosphate;(C6-C 30 ) Alkyl sulfosuccinate, (C6-C 30 ) Alkyl ether sulfosuccinate, (C6-C 30 ) Alkylamide sulfosuccinate; (C6-C 30 ) Alkyl sulfoacetate; (C6-C 24 ) Acyl sarcosinate; (C6-C24 ) Acyl glutamate; (C6-C 30 ) Alkyl polyglycoside carboxylic acid ether; (C6-C 30 ) Alkyl polyglycoside sulfosuccinate; (C6-C 30 ) Alkyl sulfosuccinate; (C6-C 24 )Acyl isethionate;N-(C6-C 24 ) Acyl taurate; C6~C 30 Fatty acid salts; coconut oil salts or hydrogenated coconut oil salts; (C8-C 20 ) Acyl lactate; (C6-C 30 ) Alkyl-D-galactosiduronic acid salts; Polyoxyalkylenated (C6-C 30 ) Alkyl ether carboxylate; Polyoxyalkylenated (C6-C 30 ) alkyl aryl ether carboxylates; and polyoxyalkylenated (C6-C 30 ) alkyl amide ether carboxylates; and the corresponding acid forms.

[0241] In at least one embodiment, the anionic surfactant is in the form of a salt, such as an alkali metal, e.g., sodium salt; an alkaline earth metal, e.g., magnesium salt; an ammonium salt; an amine salt; and an amino alcohol salt. Under some conditions, the anionic surfactant may be in the form of an acid.

[0242] The anionic surfactant is (C6-C 30 ) Alkyl sulfate, (C6-C 30 ) alkyl ether sulfates, or chlorinated or non-chlorinated polyoxyalkylenated (C6-C 30 ) salts of alkyl ether carboxylic acids.

[0243] (Amphoteric surfactant) The composition according to the invention may comprise at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.

[0244] The amphoteric or zwitterionic surfactants can be, for example (non-limiting list), amine derivatives, such as aliphatic secondary or tertiary amines, and optionally quaternized, where the aliphatic group is linear or branched, containing 8 to 22 carbon atoms and at least one water-solubilizing anionic group (e.g., carboxylate, sulfonate, sulfate, phosphate, or phosphonate).

[0245] The amphoteric surfactant may preferably be selected from the group consisting of betaines and amidoamine carboxylated derivatives.

[0246] Preferably, the amphoteric surfactant is selected from betaine type surfactants.

[0247] The betaine type amphoteric surfactant is preferably an alkyl betaine, an alkyl amido alkyl betaine, a sulfo betaine, a phospho betaine, or an alkyl amido alkyl sulfo betaine, specifically, (C8 to C 24 ) Alkyl betaine, (C8-C 24 ) Alkylamide (C1-C8) alkyl betaine, sulfobetaine and (C8-C 24 In one embodiment, the betaine type amphoteric surfactant is selected from the group consisting of (C8-C) alkylamide (C1-C8) alkylsulfobetaines. 24 ) Alkyl betaine, (C8-C 24 ) alkylamide (C1-C8) alkyl sulfobetaines, sulfobetaines and phosphobetaines.

[0248] Non-limiting examples that may be mentioned include the compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th Edition, 2014, by the names coco betaine, lauryl betaine, cetyl betaine, coco / oleamidopropyl betaine, cocamidopropyl betaine, palmitamidopropyl betaine, stearamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl hydroxysultaine, oleamidopropyl hydroxysultaine, coco hydroxysultaine, lauryl hydroxysultaine and coco sultaine, alone or in mixtures.

[0249] The betaine-type amphoteric surfactants are preferably alkyl betaines and alkylamidoalkyl betaines, particularly coco betaine and cocamidopropyl betaine.

[0250] Among the amidoamine carboxylated derivatives, mention may be made of the products sold under the name Miranol, which are described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and which are classified in the CTFA Dictionary, Third Edition, 1982, the disclosures of which are incorporated herein by reference, under the names amphocarboxyglycinates and amphocarboxypropionates, whose respective structures are as follows: R1-CONHCH2CH2-N + (R2)(R3)(CH2COO - )M + X - (B1) [In the formula, R1 represents the alkyl, heptyl, nonyl or undecyl group of the acid R1-COOH present in the hydrolyzed coconut oil; R2 represents a beta-hydroxyethyl group; R3 represents a carboxymethyl group; M + represents a cationic ion derived from an alkali metal such as sodium; an ammonium ion; or an ion derived from an organic amine, X -denotes an organic or inorganic anion, such as a halide, acetate, phosphate, nitrate, alkyl(C1-C4)sulfate, alkyl(C1-C4)- or alkyl(C1-C4)aryl-sulfonate, in particular methylsulfate and ethylsulfate; or M + and X - does not exist] R1'-CONHCH2CH2-N(B)(C) (B2) [In the formula, R1' is the alkyl group of the acid R1'-COOH present in coconut oil or hydrolyzed linseed oil, C7, C9, C 11 Or C 13 Alkyl group, C 17 Alkyl groups and their isoforms, or unsaturated C 17 represents a group, B represents -CH2CH2OX'; C is -(CH2) z -Y' (wherein z=1 or 2), X' represents a -CH2-COOH group, -CH2-COOZ', -CH2CH2-COOH, -CH2CH2-COOZ', or a hydrogen atom; Y' represents a -COOH, -COOZ', -CH2-CHOH-SO3Z', -CH2-CHOH-SO3H group or a -CH2-CH(OH)-SO3-Z' group; In these formulas, Z' represents an ion of an alkali metal or alkaline earth metal such as sodium, an ion derived from an organic amine, or an ammonium ion. and R a'' -NH-CH(Y'')-(CH2) n -C(O)-NH-(CH2) n' -N(Rd)(Re) (B'2) [In the formula, Y″ represents —C(O)OH, —C(O)OZ″, —CH2—CH(OH)—SO3H, or —CH2—CH(OH)—SO3-Z″ (wherein Z″ represents a cationic ion derived from an alkali metal such as sodium or an alkaline earth metal, an ion derived from an organic amine, or an ammonium ion); Rd and Re each represent a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group; R a'' is C from the acid 10 ~C 30 represents an alkyl group or an alkenyl group represented by the formula: n and n' independently represent an integer of 1 to 3.

[0251] The amphoteric surfactant having the formula B1 and B2 is (C8-C 24 )-Alkyl amphomonoacetate, (C8-C 24 ) Alkyl amphodiacetate, (C8-C 24 ) Alkyl amphomonopropionate and (C8-C 24 ) alkyl amphodipropionates.

[0252] These compounds are classified in the CTFA Dictionary, 5th Edition, 1993 under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphopropionate, disodium caprylamphodipropionate, lauroamphodipropionic acid, and cocoamphodipropionic acid.

[0253] Mention may be made, by way of example, of cocoamphodiacetate sold under the trade name Miranol® C2M concentrate by the company Rhodia Chimie.

[0254] Among the compounds of formula (B'2), mention may be made of sodium diethylaminopropyl cocoaspartamide (CTFA), sold under the name CHIMEXANE HB by the company CHIMEX.

[0255] (Cationic Surfactant) The composition according to the present invention may comprise at least one cationic surfactant. Two or more cationic surfactants may be used in combination.

[0256] The cationic surfactant may be selected from the group consisting of optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

[0257] Examples of quaternary ammonium salts that may be mentioned include, but are not limited to: Of the following general formula (B3):

[0258] [ka]

[0259] [In the formula, R1, R2, R3 and R4 may be the same or different and are selected from linear and branched aliphatic groups containing 1 to 30 carbon atoms and optionally containing heteroatoms such as oxygen, nitrogen, sulfur and halogens. Aliphatic groups include, for example, alkyl, alkoxy, C2-C6 polyoxyalkylene, alkylamide, (C 12 ~C 22 ) alkylamide (C2-C6) alkyl, (C 12 ~C 22 ) alkyl acetate and hydroxyalkyl groups; and aromatic groups, such as aryl and alkylaryl; X - is selected from a halide ion, a phosphate ion, an acetate ion, a lactate ion, a (C2-C6) alkyl sulfate ion, and an alkyl sulfonate ion or an alkylaryl sulfonate ion. Quaternary ammonium salts of imidazolines, such as those of formula (B4):

[0260] [ka]

[0261] [In the formula, R5 is selected from alkenyl and alkyl groups containing 8 to 30 carbon atoms, such as fatty acid derivatives of tallow or coconut oil; R6 is selected from hydrogen, C1-C4 alkyl groups, and alkenyl and alkyl groups containing 8 to 30 carbon atoms; R7 is selected from C1 to C4 alkyl groups; R8 is selected from hydrogen and C1-C4 alkyl groups; X - is selected from a halide ion, a phosphate ion, an acetate ion, a lactate ion, an alkyl sulfate ion, an alkyl sulfonate ion, and an alkylaryl sulfonate ion. In one embodiment, R5 and R6 are, for example, a mixture of radicals selected from alkenyl and alkyl radicals containing 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R7 is methyl and R8 is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), sold by Witco under the names "Rewoquat®" W75, W90, W75PG and W75HPG; Di- or tri-quaternary ammonium salts of formula (B5):

[0262] [ka]

[0263] [In the formula, R9 is selected from an aliphatic group containing 16 to 30 carbon atoms; R 10 is hydrogen, an alkyl group containing 1 to 4 carbon atoms, or -(CH2)3(R 16a )(R 17a )(R 18a )N + X-groups, R 11 , R 12 , R 13 , R 14 , R 16a , R 17a and R 18aare the same or different and are selected from hydrogen and alkyl groups containing 1 to 4 carbon atoms; X - is selected from the group consisting of halide ions, acetate ions, phosphate ions, nitrate ions, ethyl sulfate ions and methyl sulfate ions.

[0264] An example of such a diquaternary ammonium salt is FINQUAT CT-P (quaternium-89) or FINQUAT CT (quaternium-75) from FINETEX; and Quaternary ammonium salts containing at least one ester functional group, such as those of formula (B6):

[0265] [ka]

[0266] [In the formula, R 22 is selected from C1 to C6 alkyl groups, and C1 to C6 hydroxyalkyl groups and dihydroxyalkyl groups; R 23 teeth, The following groups:

[0267] [ka]

[0268] , linear and branched, saturated and unsaturated C1-C 22 Hydrocarbon group R 27 and hydrogen; R 25 teeth, The following groups:

[0269] [ka]

[0270] , linear and branched, saturated and unsaturated C1-C6 hydrocarbon radicals R29 and hydrogen; R 24 , R 26 and R 28 may be the same or different, and are linear or branched, saturated or unsaturated, C7-C 21 selected from hydrocarbon groups, r, s and t may be the same or different and are selected from integers ranging from 2 to 6; Each of r1 and t1 may be the same or different and is 0 or 1, r2+r1=2r and t1+2t=2t; y is selected from an integer ranging from 1 to 10; x and z may be the same or different and are selected from integers ranging from 0 to 10; X - are selected from simple and complex organic and inorganic anions, with the proviso that the sum x+y+z is in the range of 1 to 15, and if x is 0, then R 23 is R 27 If z is 0, R 25 is R 29 R 22 can be selected from linear and branched alkyl groups. In one embodiment, R 22 is selected from linear alkyl groups. 22 is selected from methyl, ethyl, hydroxyethyl and dihydroxypropyl groups, for example, methyl and ethyl groups. In one embodiment, the sum x+y+z is in the range of 1 to 10. R 23 is a hydrocarbon group R 27 When R is a cyclic alkyl group, it may be a long chain containing 12 to 22 carbon atoms, or a short chain containing 1 to 3 carbon atoms. 25 is a hydrocarbon group R 29 When R is, it may contain, for example, 1 to 3 carbon atoms. 24 , R 26 and R 28 may be the same or different, linear and branched, saturated and unsaturated C 11~C 21 Selected from hydrocarbon groups, for example linear and branched, saturated and unsaturated C 11 ~C 21 In another embodiment, x and z are the same or different and are equal to 0 or 1. In one embodiment, y is equal to 1. In another embodiment, r, s and t are the same or different and are equal to 2 or 3, for example, equal to 2. The anion X - can be selected from, for example, halides, such as chloride, bromide and iodide; and C1-C4 alkyl sulfates, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, anions derived from organic acids, such as acetate and lactate, and any other anion compatible with ammonium containing an ester function, 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 ion and methyl sulfate ion.

[0271] In another embodiment, an ammonium salt of formula (B6) can be used, wherein R 22 is selected from a methyl group and an ethyl group, x and y are equal to 1, z is equal to 0 or 1, r, s and t are equal to 2, R 23 teeth, The following groups:

[0272] [ka]

[0273] , methyl, ethyl and C 14 ~C 22 selected from hydrocarbon radicals and hydrogen; R 25 teeth, The following groups:

[0274] [ka]

[0275] and hydrogen; R 24 , R 26 and R 28 may be the same or different, linear and branched, saturated and unsaturated C 13 ~C 17 Hydrocarbon-based groups, such as linear and branched, saturated and unsaturated C 13 ~C 17 It is selected from an alkyl group and an alkenyl group.

[0276] In one embodiment, the hydrocarbon-based group is linear.

[0277] Non-limiting examples of compounds of formula (B6) that may be mentioned include salts such as the chlorides and methylsulfates of diacyloxyethyl-dimethylammonium, diacyloxyethyl-hydroxyethyl-methylammonium, monoacyloxyethyl-dihydroxyethyl-methylammonium, triacyloxyethyl-methylammonium, monoacyloxyethyl-hydroxyethyl-dimethyl-ammonium, and mixtures thereof. In one embodiment, the acyl group may contain 14 to 18 carbon atoms and may be derived, for example, from vegetable oils, such as palm oil and sunflower oil. When the compound contains several acyl groups, these groups may be the same or different.

[0278] These products can be obtained, for example, by direct esterification of optionally oxyalkylenated triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine with fatty acids or with mixtures of fatty acids of vegetable or animal origin, or by transesterification of their methyl esters, which can be followed by quaternization using an alkylating agent selected from alkyl halides, such as methyl and ethyl halides; dialkyl sulfates, such as dimethyl and diethyl sulfate; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrins; and glycerol chlorohydrins.

[0279] Such compounds are sold, for example, by the company Cognis under the name Dehyquart®, by the company Stepan under the name Stepanquat®, by the company Ceca under the name Noxamium® and by the company Rewo-Goldschmidt under the name "Rewoquat® WE 18".

[0280] Other non-limiting examples of ammonium salts that may be used in the compositions according to the present invention include ammonium salts containing at least one ester functional group, as described in U.S. Pat. Nos. 4,874,554 and 4,137,180.

[0281] The above-mentioned quaternary ammonium salts that may be used in the compositions according to the invention include, but are not limited to, those corresponding to formula (I), such as tetraalkylammonium chlorides, such as dialkyldimethylammonium chloride and alkyltrimethylammonium chlorides, where the alkyl group contains from about 12 to 22 carbon atoms, such as behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride and benzyldimethylstearylammonium chloride, palmitylamidopropyltrimethylammonium chloride, and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk.

[0282] According to one embodiment, the cationic surfactants that may be used in the compositions according to the invention are chosen from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, quaternium-83, quaternium-87, quaternium-22, behenylamidopropyl-2,3-dihydroxypropyldimethylammonium chloride, palmitylamidopropyltrimethylammonium chloride and stearamidopropyldimethylamine.

[0283] (Nonionic surfactant) The composition according to the invention may comprise at least one non-ionic surfactant. Two or more non-ionic surfactants may be used in combination.

[0284] Nonionic surfactants are well known compounds in themselves or in themselves (see, for example, in this respect, "Handbook of Surfactants", MR Porter, Blackie & Son, Glasgow and London, 1991, pp. 116-178). Thus, the nonionic surfactants can be chosen, for example, from alcohols, alpha-diols, alkylphenols and esters of fatty acids, which compounds can be ethoxylated, propoxylated or glycerolized and have at least one fatty chain, for example containing 8 to 30 carbon atoms, the number of ethylene oxide or propylene oxide groups ranging from 2 to 50 and the number of glycerol groups ranging from 1 to 30. Mention can also be made of maltose derivatives. Also included, but not limited to, are copolymers of ethylene oxide and / or propylene oxide; condensates of ethylene oxide and / or propylene oxide with fatty alcohols; polyethoxylated fatty amides, for example containing 2 to 30 moles of ethylene oxide; polyglycerolated fatty amides, for example containing 1.5 to 5, for example 1.5 to 4 glycerol groups; ethoxylated fatty acid esters of sorbitan, containing 2 to 30 moles of ethylene oxide; ethoxylated oils of vegetable origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; glycerol (C6 to C7 24 ) alkyl polyglycosides, polyethoxylated fatty acid monoesters or diesters; N-(C6-C 24 ) alkylglucamine derivatives; (C 10 ~C 14 ) alkylamine oxide or N-(C 10 ~C 14 ) amine oxides such as acylaminopropylmorpholine oxide; silicone surfactants; and mixtures thereof.

[0285] The non-ionic surfactants may preferably be chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or polyglycerolated non-ionic surfactants, the oxyalkylene units being more particularly oxyethylene or oxypropylene units or combinations thereof, preferably oxyethylene units.

[0286] Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned are: Monooxyalkylenated or polyoxyalkylenated (C8-C 24 ) alkylphenols, Saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C8-C 30 alcohol, Saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C8-C 30 Amides, Saturated or unsaturated, linear or branched, C8-C 30 esters of acids and polyalkylene glycols; Saturated or unsaturated, linear or branched, C8-C 30 Monooxyalkylenated or polyoxyalkylenated esters of acids with sorbitol, Saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated vegetable oils, Especially the condensation products of ethylene oxide and / or propylene oxide, either alone or in mixtures.

[0287] The surfactant preferably contains a number of moles of ethylene oxide and / or propylene oxide between 1 and 100, most preferably between 2 and 50. According to one embodiment of the invention, the polyoxyalkylenated nonionic surfactant is selected from polyoxyethylenated fatty alcohols (polyethylene glycol ethers of fatty alcohols) and polyoxyethylenated fatty esters (polyethylene glycol esters of fatty acids).

[0288] Polyoxyethylenated saturated fatty alcohols (or C8-C 30 Examples of the ethylene oxide adducts of lauryl alcohol, especially those containing 5 to 50 oxyethylene units, more especially those containing 7 to 12 oxyethylene units (CTFA names Laureth-7 to Laureth-12); ethylene oxide adducts of behenyl alcohol, especially those containing 9 to 50 oxyethylene units (CTFA names Beheneth-9 to Beheneth-50); ethylene oxide adducts of cetearyl alcohol (mixtures of cetyl alcohol and stearyl alcohol), especially those containing 10 to 50 oxyethylene units (CTFA names Ceteareth-10 to ethylene oxide adducts of cetyl alcohol, especially those containing 10 to 50 oxyethylene units (CTFA names Ceteth-10 to Ceteth-50); ethylene oxide adducts of stearyl alcohol, especially those containing 10 to 50 oxyethylene units (CTFA names Steareth-10 to Steareth-50, e.g. Steareth-20); ethylene oxide adducts of isostearyl alcohol, especially those containing 10 to 50 oxyethylene units (CTFA names Isosteareth-10 to Isosteareth-50); and mixtures thereof.

[0289] Polyoxyethylenated unsaturated fatty alcohols (or C8-C 30 Examples of ethylene oxide adducts of oleyl alcohol include those containing 2 to 50 oxyethylene units, more particularly those containing 10 to 40 oxyethylene units (CTFA names oleth-10 to oleth-40); and mixtures thereof.

[0290] Examples of monoglycerolated or polyglycerolated nonionic surfactants include monoglycerolated or polyglycerolated C8-C 40 Alcohol is preferably used.

[0291] In particular, monoglycerolized or polyglycerolized C8-C 40 The alcohol has the formula: RO-[CH2-CH(CH2OH)-O] m -H, or RO-[CH(CH2OH)-CH2O] m -H [In the formula, R is a linear or branched C8-C 40 , preferably C8 to C 30 represents an alkyl group or an alkenyl group, and m represents a number in the range of 1 to 30, preferably 1.5 to 10. is equivalent to.

[0292] Examples of compounds that are suitable in the context of the present invention include 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.

[0293] Just as the value of m represents a statistical value, the alcohol may represent a mixture of alcohols, which means that several types of polyglycerolated fatty alcohols may coexist in the form of a mixture in a commercial product.

[0294] C8 / C containing 1 mol of glycerol in monoglycerated or polyglycerated alcohols 10 Alcohol, C containing 1 mol glycerol 10 / C 12 C containing alcohol and 1.5 mol of glycerol 12It is preferred to use alcohol.

[0295] Monoglycerolized or polyglycerolized C8-C 40 The fatty ester has the following formula: R'O-[CH2-CH(CH2OR''')-O] m -R'', or R'O-[CH(CH2OR''')-CH2O] m -R'' [In the formula, R', R'' and R''' each independently represent a hydrogen atom or a linear or branched C8-C 40 , preferably C8 to C 30 an alkyl-CO- group or an alkenyl-CO- group, with the proviso that at least one of R', R'' and R''' is not a hydrogen atom, and m represents a number ranging from 1 to 30, preferably from 1.5 to 10. It can be equivalent to.

[0296] Examples of polyoxyethylenated fatty esters that may be mentioned are the ethylene oxide adducts of the esters of lauric acid, palmitic acid, stearic acid or behenic acid and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (CTFA name: PEG-9 laurate to PEG-50 laurate), PEG-9 to PEG-50 palmitate (CTFA name: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA name: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (CTFA name: PEG-9 behenate to PEG-50 behenate); Polyethylene glycol 100 EO monostearate (CTFA name: PEG-100 stearate); and mixtures thereof.

[0297] According to one embodiment of the invention, the nonionic surfactants are esters of polyols with fatty acids having a saturated or unsaturated chain containing, for example, 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and their polyoxyalkylenated derivatives, preferably containing 10 to 200, more preferably 10 to 100 oxyalkylene units, for example one or more C8 to C9 oxyalkylene units. 24 , preferably C 12 ~C 22 and polyoxyalkylenated derivatives thereof, preferably containing 10 to 200, more preferably 10 to 100 oxyalkylene units; 24 , preferably C 12 ~C 22 sorbitol esters of fatty acids of the formula (I) and their polyoxyalkylenated derivatives, preferably containing 10 to 200, more preferably 10 to 100 oxyalkylene units; 24 , preferably C 12 ~C 22 and polyoxyalkylenated derivatives thereof, preferably containing 10 to 200, more preferably 10 to 100 oxyalkylene units; ethers of fatty alcohols; sugars and one or more C8 to C 24 , preferably C 12 ~C 22 and mixtures thereof.

[0298] As glyceryl esters of fatty acids, mention may be made of glyceryl stearate (mono-, di- and / or tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate, as well as mixtures thereof, and as their polyoxyalkylenated derivatives, mono-, di- or triesters of fatty acids and polyoxyalkylenated glycerol (mono-, di- or triesters of fatty acids and polyalkylene glycol ethers of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di- and / or tristearate), such as PEG-20 glyceryl stearate (mono-, di- and / or tristearate).

[0299] Mixtures of these surfactants can also be used, such as the product containing glyceryl stearate and PEG-100 stearate sold under the name ARLACEL 165 by the company Uniqema, and the product containing glyceryl stearate (mono- and distearate) and potassium stearate sold under the name TEGIN by the company Goldschmidt (CTFA name: Glyceryl Stearate SE).

[0300] C8~C 24The sorbitol esters of fatty acids and their polyoxyalkylenated derivatives can be chosen from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate and esters of fatty acids with alkoxylated sorbitans, for example containing 20 to 100 EOs, such as sorbitan monostearate (CTFA name: sorbitan stearate) sold under the name Span 60 by the company ICI, sorbitan monopalmitate (CTFA name: sorbitan palmitate) sold under the name Span 40 by the company ICI, and sorbitan tristearate 20 EO (CTFA name: polysorbate 65) sold under the name Tween 65 by the company ICI, polyethylene sorbitan trioleate (polysorbate 85), or the compounds sold under the trade names Tween 20 or Tween 60 by the company Uniqema.

[0301] As esters of fatty acids with glucose or alkylglucose, there are, in particular, glucose palmitate, alkylglucose sesquistearates, such as methylglucose sesquistearate, alkylglucose palmitates, such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters, diesters of methylglucoside with oleic acid (CTFA name: methylglucose dioleate), mixed esters of methylglucoside with a mixture of oleic acid / hydroxystearic acid (CTFA name: methylglucose dioleate / hydroxystearate), esters of methylglucoside with isostearic acid (CTFA name: methylglucose isostearate), esters of methylglucoside with lauric acid (CTFA name: methylglucose laurate), mixtures of mono- and diesters of methylglucoside and isostearic acid (CTFA name: methylglucose sesqui-isostearate), mixtures of mono- and diesters of methylglucoside and stearic acid (CTFA name: methylglucose sesquistearate) and in particular those under the name Glucate by the company AMERCHOL. Citation may be made to the products commercially available under SS, as well as mixtures thereof.

[0302] As ethoxylated ethers of fatty acids with glucose or alkylglucose, there may be mentioned, for example, ethoxylated ethers of fatty acids with methylglucose, in particular the polyethylene glycol ether of a diester of methylglucose with about 20 moles of ethylene oxide and of stearic acid (CTFA name: PEG-20 methylglucose distearate), for example the product sold under the name Glucam E-20 distearate by the company AMERCHOL, polyethylene glycol ethers of mixtures of mono- and diesters of methyl-glucose with about 20 moles of ethylene oxide and of stearic acid (CTFA name: PEG-20 methylglucose sesquistearate), in particular the product sold under the name Glucamate SSE-20 by the company AMERCHOL, and the product sold under the name Grillocose PSE-20 by the company GOLDSCHMIDT, and mixtures thereof.

[0303] As sucrose esters there may be mentioned, for example, sucrose palmito-stearate, sucrose stearate and sucrose monolaurate.

[0304] As sugar ethers, alkyl polyglucosides can be used, such as decyl glucoside, for example the product sold under the name MYDOL 10 by Kao Corporation, the product sold under the name PLANTAREN 2000 by Henkel and the product sold under the name ORAMIX NS 10 by Seppic; caprylyl / capryl glucoside, for example the product sold under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF; lauryl glucoside, for example the products sold under the name PLANTAREN 1200 N and PLANTACARE 1200 by Henkel; coco-glucoside, for example the product sold under the name PLANTACARE 818 / UP by Henkel; cetostearyl glucoside, possibly mixed with cetostearyl alcohol, for example the product sold under the name MONTANOV by Seppic. Mention may in particular be made of those sold under the names TEGO-CARE CG90 by the company Goldschmidt and EMULGADE KE3302 by the company Henkel; arachidyl glucoside, for example in the form of a mixture of arachidyl and behenyl alcohol and arachidyl glucoside sold under the name MONTANOV 202 by the company Seppic; cocoyl ethyl glucoside, for example in the form of a mixture of cetyl and stearyl alcohol (35 / 65) sold under the name MONTANOV 82 by the company Seppic, and mixtures thereof.

[0305] Mixtures of alkoxylated vegetable oil glycerides may also be mentioned, such as a mixture of ethoxylated (200 EO) palm and copra (7 EO) glycerides.

[0306] The nonionic surfactant according to the present invention is preferably an alkenyl or branched C 12 ~C 22 More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

[0307] According to one of the embodiments of the invention, the nonionic surfactant is a copolymer of ethylene oxide and propylene oxide, specifically having the following formula: HO(C2H4O) a (C3H6O) b (C2H4O) c H [wherein a, b, and c are integers such that a+c is in the range of 2 to 100, and b is in the range of 14 to 60] and copolymers thereof, as well as mixtures thereof.

[0308] According to one of the embodiments of the invention, the non-ionic surfactant may be chosen from silicone surfactants, non-limiting examples of which may be mentioned are those disclosed in documents US-A-5364633 and US-A-5411744.

[0309] The silicone surfactant preferably has the formula (I):

[0310] [ka]

[0311] [In the formula, R1, R2 and R3 are each independently a C1 to C6 alkyl group or -(CH2) x -(OCH2CH2) y -(OCH2CH2CH2) z represents an -OR group, where at least one R, R or R group is not an alkyl group, and R is hydrogen, an alkyl group or an acyl group; A is an integer ranging from 0 to 200; B is an integer in the range of 0 to 50, with the condition that A and B are not equal to 0 at the same time; x is an integer ranging from 1 to 6; y is an integer ranging from 1 to 30, and z is an integer ranging from 0 to 5. The compound may be:

[0312] According to a preferred embodiment of the present invention, in the compound of formula (I), the alkyl group is a methyl group, x is an integer in the range of 2-6, and y is an integer in the range of 4-30.

[0313] Examples of silicone surfactants of formula (I) that may be mentioned are those of formula (II):

[0314] [ka]

[0315] [In the formula, A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10, and y is an integer ranging from 10 to 20] It is a compound of the formula:

[0316] As examples of silicone surfactants of formula (I), mention may also be made of those of formula (III): H-(OCH2CH2) y -(CH2)3-[(CH3)2SiO] A' -(CH2)3-(OCH2CH2) y -OH (III) [In the formula, A′ and y are integers ranging from 10 to 20] It is a compound of the formula:

[0317] Compounds of the 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. Compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II) in which A is 22, B is 2, y is 12; A is 103, B is 10, y is 12; A is 27, B is 3, y is 12, respectively.

[0318] The compound Q4-3667 is a compound of formula (III) wherein A is 15 and y is 13.

[0319] (d) The surfactant is preferably selected from nonionic surfactants.

[0320] More preferably, the (d) surfactant is selected from polyglyceryl fatty acid esters.

[0321] The polyglyceryl fatty acid ester may have a polyglycerol moiety derived from 2 to 10 glycerols, preferably 2 to 8 glycerols, more preferably 2 to 6 glycerols. In other words, the polyglyceryl fatty acid ester may contain 2 to 10 polyglyceryl units, preferably 2 to 8 polyglyceryl units, more preferably 2 to 6 polyglyceryl units. When all the polyglyceryl fatty acid esters have short polyglyceryl chains (e.g., less than 10 polyglyceryl units, preferably less than 8 polyglyceryl units, more preferably less than 6 polyglyceryl units), the stability of the composition according to the present invention may be enhanced.

[0322] The polyglyceryl fatty acid esters may be selected from mono-, di- and triesters of linear or branched, saturated or unsaturated, preferably saturated, fatty acids containing from 4 to 32 carbon atoms, preferably from 8 to 26 carbon atoms, 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.

[0323] (d) The surfactant is preferably selected from saturated or unsaturated polyglyceryl fatty acid monoesters.

[0324] The polyglyceryl fatty acid ester may have an HLB (hydrophilic-lipophilic balance) value of 4.0 to 16.0, preferably 4.5 to 15.5, more preferably 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. When two or more polyglyceryl fatty acid esters are used, the HLB value is determined by the weighted average of the HLB values ​​of all the polyglyceryl fatty acid esters.

[0325] Polyglyceryl fatty acid esters are 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), coconut oil and fat. PG-3 fatty acid (HLB: 12.0), PG-3 capric acid (HLB: 10.0), PG-4 caprylic acid (HLB: 14), PG-4 capric acid (HLB: 14.0), PG-5 myristic acid (HLB: 15.4), PG-5 stearate (HLB: 15.0), PG-5 oleic acid (HLB: 14.9), PG-6 caprylic acid (HLB: 14.6), PG-6 capric acid (HLB: 13.1), PG-6 lauric acid (HLB: 14.5), and mixtures thereof.

[0326] It may be preferred that the (d) surfactant is selected from the group consisting of PG-4 caprate (HLB: 14.0), PG-2 isostearate (HLB: 5.5), and mixtures thereof.

[0327] It is preferred that the composition according to the invention comprises at least two polyglyceryl fatty acid esters.

[0328] (d) the surfactant is at least one first polyglyceryl fatty acid ester having an HLB value of 4.0 to 8.0, preferably 4.5 to 8.0, more preferably 5.0 to 8.0; At least one second polyglyceryl fatty acid ester having an HLB value of 12.0 to 16.0, preferably 12.0 to 15.5, more preferably 12.0 to 15.0; and Mixtures of these It is preferably selected from:

[0329] The amount of the (d) surfactant in the composition according to the present invention may be 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

[0330] The amount of the (d) surfactant in the composition according to the present invention may be 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total mass of the composition.

[0331] The amount of the surfactant (d) in the composition according to the present invention may be 0.001% by mass to 20% by mass, preferably 0.01% by mass to 15% by mass, and more preferably 0.1% by mass to 10% by mass, relative to the total mass of the composition.

[0332] [pH] The pH of the composition according to the present invention may be from 2.0 to 9.0, preferably from 2.5 to 8.5, and more preferably from 3.0 to 8.0.

[0333] At a pH of 2.0 to 9.0, the (a) polyion complex can be very stable.

[0334] The pH of the composition according to the invention can be adjusted by adding at least one alkaline agent and / or at least one acid other than the non-polymeric acid or its salt having two or more pKa values ​​or the non-polymeric base or its salt having two or more pKb values ​​to be incorporated into the polyion complex (a).The pH of the composition according to the invention can also be adjusted by adding at least one buffering agent.

[0335] (Alkaline agent) The composition according to the present invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

[0336] The alkaline agent may be an inorganic alkaline agent, preferably selected from the group consisting of ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates and monohydrogen phosphates, such as sodium phosphate or sodium monohydrogen phosphate.

[0337] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. As the inorganic alkaline agent, sodium hydroxide is preferred.

[0338] The alkaline agent may be an organic alkaline agent, which is preferably selected from the group consisting of monoamines and their derivatives, diamines and their derivatives, polyamines and their derivatives, basic amino acids and their derivatives, oligomers of basic amino acids and their derivatives, polymers of basic amino acids and their derivatives, urea and its derivatives, and guanidine and its derivatives.

[0339] Examples of organic alkaline 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 having the following structures:

[0340] [ka]

[0341] [wherein R represents an alkylene, such as propylene, optionally substituted with a hydroxyl group or a C1-C4 alkyl group; and R1, R2, R3 and R4 independently represent a hydrogen atom, an alkyl group or a C1-C4 hydroxyalkyl group, which may be exemplified by 1,3-propanediamine and its derivatives] Arginine, urea and monoethanolamine are preferred.

[0342] The alkaline agents can be used in a total amount of 0.01% to 15% by mass, preferably 0.02% to 10% by mass, and more preferably 0.03% to 5% by mass, based on the total mass of the composition, depending on their solubility.

[0343] (acid) The composition according to the 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.

[0344] The acid may include any inorganic or organic acid commonly used in cosmetics, preferably inorganic acid. Monobasic and / or polybasic acids may be used. Monobasic acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) may be used. HCl is preferred.

[0345] Depending on their solubility, the acids may be used in a total amount of 0.01% to 15% by mass, preferably 0.02% to 10% by mass, and more preferably 0.03% to 5% by mass, based on the total mass of the composition.

[0346] (Buffer) The compositions according to the 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.

[0347] Buffers can include acetate buffers (e.g., acetic acid+sodium acetate), phosphate buffers (e.g., sodium dihydrogen phosphate+disodium hydrogen phosphate), citrate buffers (e.g., citric acid+sodium citrate), borate buffers (e.g., boric acid+sodium borate), tartrate buffers (e.g., tartaric acid+sodium tartrate dihydrate), Tris buffers (e.g., tris(hydroxymethyl)aminomethane), and Hepes buffers (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[0348] [Optional Additives] In addition to the above-mentioned components, the composition according to the present invention may contain components typically used in cosmetics, specifically, oils such as ester oils and hydrocarbon oils, hydrophilic or lipophilic UV screening agents, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents such as glycerin, glycol, and ethanol, silicones and silicone derivatives, natural extracts derived from animals or plants, waxes, etc., within the range that does not impair the effects of the present invention.

[0349] The composition according to the present invention may contain the above-mentioned optional additives in an amount of 0.01% by mass to 50% by mass, preferably 0.05% by mass to 30% by mass, more preferably 0.1% by mass to 10% by mass, relative to the total mass of the composition.

[0350] [Composition] The composition according to the present invention may be intended to be used as a cosmetic composition. Therefore, the cosmetic composition according to the present invention may be intended to be applied onto keratinous materials. Keratinous materials herein mean materials that contain keratin as a main component, examples of which include skin, scalp, nails, lips, hair, etc. Therefore, it is preferred that the cosmetic composition according to the present invention is used in a cosmetic method for keratinous materials, particularly skin.

[0351] Therefore, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin make-up composition, more preferably a skin care composition.

[0352] The composition according to the present invention can be prepared by mixing the above essential and optional ingredients according to any of the methods well known to those skilled in the art.

[0353] The compositions according to the present invention can be prepared by simple or easy mixing using conventional mixing means such as a stirrer, so that no high shear, for example with a homogenizer, is required, and no heating is required.

[0354] [Coating] The composition according to the present invention can be used to easily prepare a coating.

[0355] Therefore, the present invention also relates to a method for preparing a film, preferably a decorative film, optionally having a thickness of more than 0.1 μm, more preferably 0.5 μm or more, even more preferably 1 μm or more, comprising: applying a composition according to the invention onto a substrate, preferably a keratinous material, more preferably the skin; drying the composition; The present invention also relates to a method, comprising:

[0356] The upper limit of the thickness of the coating according to the present invention is not limited. Therefore, for example, the thickness of the coating according to the present invention may be 1 mm or less, preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less.

[0357] Since the method for preparing the film according to the present invention includes a step of applying the composition according to the present invention to a substrate, preferably a keratinous material, more preferably the skin, and a step of drying the composition, the method according to the present invention does not require any spin coating or spraying, and therefore even a relatively thick film can be easily prepared. Therefore, the method for preparing the film according to the present invention can prepare a relatively thick film without using any special equipment such as a spin coater and a spray machine.

[0358] The presently claimed coating may be less sticky even though it contains hyaluronic acid based polymers.

[0359] The presently claimed coatings may be transparent or translucent and may provide long-lasting antioxidant benefits.

[0360] Even when the film according to the invention is relatively thick, the film can still be thin and transparent and therefore not easily perceived, so that the film according to the invention can preferably be used as a cosmetic film.

[0361] If the substrate is not a keratinous material such as skin, the composition according to the present invention can be applied onto the substrate made of any material other than keratin. The material of the non-keratinous substrate is not limited. Two or more materials may be used in combination. Thus, a single type of material or a combination of different types of materials can be used. In any case, it is preferred that the substrate is flexible or elastic.

[0362] If the substrate is not a keratinous material, it is preferred that the substrate is water-soluble, since it is possible to leave the film according to the invention by washing the substrate with water. Examples of water-soluble materials include poly(meth)acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate, etc. PVA is preferred.

[0363] When the non-keratin substrate is in the form of a sheet, the substrate may have a thickness greater than that of the coating according to the present invention in order to facilitate handling of the coating attached to the substrate sheet. The thickness of the non-keratin substrate sheet is not limited, but may be 1 μm to 5 mm, preferably 10 μm to 1 mm, more preferably 50 to 500 μm.

[0364] It is more preferred that the film according to the present invention is removable from the non-keratin substrate. The manner of removal is not limited. Thus, the film according to the present invention may be peeled off from the non-keratin substrate, or may be removed by dissolving the substrate sheet in a solvent such as water.

[0365] The present invention also provides (1) A film, preferably a decorative film, optionally having a thickness of preferably more than 0.1 μm, more preferably 0.5 μm or more, even more preferably 1 μm or more, applying a composition according to the invention onto a substrate, preferably a keratinous material, more preferably the skin; drying the composition; A film, preferably a cosmetic film, prepared by a process comprising: and (2) A film, preferably a decorative film, optionally having a thickness of preferably more than 0.1 μm, more preferably 0.5 μm or more, even more preferably 1 μm or more, (a) 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, At least one non-polymeric acid or salt thereof having two or more pKa values; or At least one non-polymeric base or salt thereof having two or more pKb values At least one polyion complex comprising (b) at least one lipophilic antioxidant; and Optionally, (d) at least one surfactant, preferably selected from nonionic surfactants, more preferably selected from polyglyceryl fatty acid esters; Including, The anionic polymer is selected from hyaluronic acid and its salts; and The amphoteric polymer is selected from cationized hyaluronic acid and its salts; It also relates to a film, preferably a decorative film.

[0366] The above statements regarding the cationic, anionic and amphoteric polymers, as well as the lipophilic antioxidants and surfactants described above, can be applied to the statements made in coatings (1) and (2) above.

[0367] The film thus obtained can be self-supporting. The term "self-supporting" as used herein means that the film can be in the form of a sheet and can be handled as an independent sheet without the aid of a substrate or support. Thus, the term "self-supporting" can have the same meaning as "self-supporting".

[0368] It is preferred that the coating according to the present invention is hydrophobic.

[0369] The term "hydrophobic" in this specification means that the solubility of the polymer in water (preferably in a volume of 1 liter) at 20-40° C., preferably 25-40° C., more preferably 30-40° C. is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, based on the total weight of the polymer. Most preferably, the polymer is not soluble in water.

[0370] When the film according to the invention is hydrophobic, the film can have water-resistant properties and therefore can remain on the keratinous material, such as the skin, even when the surface of the keratinous material is wet, for example, by sweat or rain, so that when the film according to the invention provides any cosmetic benefit, the cosmetic benefit can last for a long time.

[0371] On the other hand, the film according to the invention can be easily removed from keratinous materials such as skin under alkaline conditions, such as a pH of 8 to 12, preferably 9 to 11. Thus, the film according to the invention is difficult to remove with water, whereas the film can be easily removed with soaps capable of providing such alkaline conditions.

[0372] The coating according to the present invention may comprise at least one biocompatible and / or biodegradable polymer layer. Two or more biocompatible and / or biodegradable polymers may be used in combination. Thus, a single type of biocompatible and / or biodegradable polymer or a combination of different types of biocompatible and / or biodegradable polymers may be used.

[0373] As used herein, the term "biocompatible" polymer means that the polymer does not have excessive interactions between the polymer and cells in the body, including the skin, and that the polymer is not recognized as foreign by the body.

[0374] As used herein, the term "biodegradable" polymer means that the polymer can be broken down or broken down in vivo, for example by the metabolism of the organism itself or by the metabolism of microorganisms that may be present in the organism. Biodegradable polymers can also be broken down by hydrolysis.

[0375] When the coating according to the present invention comprises a biocompatible and / or biodegradable polymer, it causes little or no irritation to the skin and does not cause any rash. In addition, the use of a biocompatible and / or biodegradable polymer allows the decorative sheet according to the present invention to adhere well to the skin.

[0376] The film according to the present invention can be used for the cosmetic treatment of keratinous materials, preferably skin, especially face.The film according to the present invention can be in any shape or form.For example, the film can be used as a full face mask sheet, or a patch for a part of the face, such as cheeks, nose, and around the eyes.

[0377] When the film according to the present invention comprises at least one hydrophilic or water-soluble UV blocking agent, the film can provide UV blocking effect derived from the hydrophilic or water-soluble UV blocking agent.Normally, the hydrophilic or water-soluble UV blocking agent can be removed from the surface of keratin substrate such as skin by water such as sweat and rain.However, since the hydrophilic or water-soluble UV blocking agent is contained in the film according to the present invention, the hydrophilic or water-soluble UV blocking agent is difficult to be removed by water, thereby providing a long-lasting UV blocking effect.

[0378] [Cosmetic methods and uses] The present invention also provides A cosmetic method for keratinous materials, such as the skin, comprising the steps of applying a composition according to the present invention to a keratinous material and drying the composition to form a cosmetic film on the keratinous material, and Use of the composition according to the invention for preparing a cosmetic film on a keratinous material such as the skin Also relates to.

[0379] Cosmetic method means herein a non-therapeutic cosmetic method for caring for and / or making up the surfaces of keratinous materials such as the skin.

[0380] In both the above method and use, the above decorative film is resistant to water having a pH of 7 or less and is removable with water having a pH of greater than 7, preferably 8 or more, more preferably 9 or more.

[0381] In other words, the decorative film can be water-resistant under neutral or acidic conditions, such as a pH of 7 or less, preferably in the range of ≧6 to ≦7, more preferably in the range of ≧5 to ≦7, while the decorative film can be removed under alkaline conditions, such as a pH of more than 7, preferably more than 8, more preferably more than 9. The upper limit of pH is preferably 13, more preferably 12, even more preferably 11.

[0382] Accordingly, the cosmetic film can be water-resistant, and therefore can remain on the keratinous material, such as the skin, even when the surface of the keratinous material is wet, for example due to sweat or rain. On the other hand, the cosmetic film can be easily removed from the keratinous material, such as the skin, under alkaline conditions. Thus, although the film according to the present invention is difficult to remove with water, the film can be easily removed with a soap that can provide alkaline conditions.

[0383] When said cosmetic film comprises a UV filter, which may be present in the composition according to the invention, said cosmetic film can protect keratinous materials such as skin from UV radiation, thereby reducing skin darkening, improving skin tone and evenness, and / or treating skin aging.

[0384] Furthermore, the above-mentioned cosmetic films can have cosmetic effects such as trapping sebum, imparting a matte appearance to keratinous substrates such as skin, absorbing or adsorbing malodors, and / or protecting keratinous materials from, for example, dirt or pollutants, due to the properties of the polyion complexes in the cosmetic films, even when the cosmetic films do not contain any cosmetic active ingredients.

[0385] In addition, the cosmetic film can instantly change or modify the appearance of the skin, such as by changing the light reflection on the skin, even if the cosmetic film does not contain any cosmetic active ingredient. Thus, the cosmetic film may be able to hide skin defects such as pores or wrinkles. Furthermore, the cosmetic film can instantly change or modify the feel of the skin, such as by changing the surface roughness on the skin. Furthermore, the cosmetic film can instantly protect the skin from environmental stresses, such as pollutants, impurities, etc., by covering the surface of the skin as a barrier and shielding the skin.

[0386] The cosmetic benefits can be adjusted or controlled by varying the chemical composition, thickness and / or surface roughness of the cosmetic film.

[0387] When the cosmetic film includes at least one additional cosmetic active ingredient such as oil, the cosmetic film can have a cosmetic effect brought about by the additional cosmetic active ingredient. For example, when the cosmetic film includes at least one cosmetic active ingredient selected from (b) an anti-aging agent other than a lipophilic antioxidant, a sebum suppressant, a deodorant agent, an antiperspirant, a whitening agent, and a mixture thereof, the cosmetic film can treat skin aging, absorb sebum on the skin, control odor on the skin, control sweat on the skin, and / or whiten the skin.

[0388] It is also possible to apply the make-up cosmetic composition according to the invention after the cosmetic film or sheet has been applied onto the skin. EXAMPLES

[0389] The present invention will now be described in more detail by means of examples, which should not, however, be construed as limiting the scope of the present invention.

[0390] (Examples 1-2 and Comparative Examples 1-2) [Preparation] Each of the compositions according to Examples 1-2 and Comparative Examples 1-2 was prepared by mixing the components shown in Table 1. All figures for the amounts of components in Table 1 are based on "mass %" of the active material.

[0391] [Table 1]

[0392] [evaluation] (sticky) Three panelists evaluated the texture of each of the compositions according to Examples 1-2 and Comparative Examples 1-2 in terms of stickiness during and after application of the composition. In detail, each panelist applied each composition onto their hands, spread it, evaluated the moisturizing sensation, and rated it from 1 (low) to 5 (high). It was then classified into the following four categories based on the average of the ratings: Very good: 4~5 (not sticky) Good: 3 to less than 4 (slightly sticky) Poor: More than 2 and less than 3 (sticky) Very bad: 1~2 (very sticky)

[0393] The results are shown in Table 1.

[0394] (Sustained antioxidant effect) 0.6 g of a β-carotene solution (solvent: caprylic / capric triglyceride) having a concentration of 0.05% by mass was mixed with 0.2 g of each of the compositions according to Examples 1-2 and Comparative Examples 1-2 to obtain mixtures.

[0395] 0.4 g of the above mixture was applied onto a filter (glass microfiber filter).

[0396] The filter was rinsed off with tap water (300 mL, 23-27°C).

[0397] The filters were exposed to UV light having a wavelength of 365 nm for 30 minutes to oxidize β-carotene.

[0398] When β-carotene is oxidized, the original yellow color derived from β-carotene fades.

[0399] The b* values ​​in the L*a*b* (CIE 1976) space before and after UV exposure of the filters (b*(T=0) and b*(T=30 min), respectively) were measured by a spectrophotometer (Konica Minolta CM-700d) and the difference between the b*(T=0) and b*(T=30 min) values ​​was determined as Δb*. It is noted that the b*(T=0) values ​​of the filters before rinse-off were between 45 and 65.

[0400] The Δb* value and the b*(T=30 min) value were evaluated according to the following criteria. Very good: Δb*<10 and b*(T=30 minutes)>30 Good: Δb*<10 and 30>b*(T=30 minutes)>20 Defective: Δb*<10 and 20>b* (T=30 minutes) Very poor: Δb*>10

[0401] The results are shown in Table 1.

[0402] (overview) The compositions according to Examples 1 and 2 can provide good or very good stickiness and good or very good long-lasting antioxidant benefits.

[0403] From the comparison between Example 1 and Comparative Example 2, it is clear that the use of polyion complex can reduce stickiness and prolong the antioxidant effect.

[0404] From the comparison between Example 2 and Comparative Example 1, it is clear that the use of tocopherol can not only enhance the antioxidant effect but also improve stickiness.

[0405] From the comparison between Example 1 and Example 2, it is clear that the use of surfactants such as polyglyceryl fatty acid esters can further extend the antioxidant effect, even under rinse-off conditions.

Claims

1. (a) 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 anionic polymer; and at least one non-polymeric acid or salt thereof having two or more pKa values; or At least one non-polymeric base or salt thereof having two or more pKb values Including, at least one polyion complex; (b) at least one lipophilic antioxidant; and (c) Water and A composition comprising: The anionic polymer is selected from hyaluronic acid, its salts, and its derivatives; and The amphoteric polymer is selected from cationized hyaluronic acid and salts thereof. composition.

2. 2. The composition according to claim 1, wherein the cationized hyaluronic acid has at least one quaternary ammonium group-containing group and a degree of cationization of 0.05 to 0.6, preferably 0.1 to 0.5, and more preferably 0.15 to 0.

4.

3. 2. The composition of claim 1, wherein the cationic polymer has at least one positively charged moiety 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.

4. 2. The composition of claim 1, wherein the cationic polymer is selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof.

5. 2. The composition according to claim 1, wherein the total amount of cationic and / or anionic and / or amphoteric polymers in the composition is from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.

6. 2. The composition of claim 1, wherein the non-polymeric acid or salt thereof having two or more pKa values ​​is an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof, more preferably phytic acid or salt thereof.

7. 2. The composition according to claim 1, wherein the amount of the non-polymeric acid or salt thereof having two or more pKa values, or the non-polymeric base or salt thereof having two or more pKb values ​​in the composition is 0.001% to 15% by weight, preferably 0.005% to 10% by weight, more preferably 0.01% to 5% by weight, relative to the total weight of the composition.

8. 2. The composition of claim 1, wherein (b) the lipophilic antioxidant is selected from the group consisting of pentaerythrityl tetra-di-t-butylhydroxyhydrocinnamate, nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxyanisole, ascorbyl palmitate, tocopherol, and mixtures thereof.

9. 2. The composition according to claim 1, wherein the amount of (b) lipophilic antioxidant in the composition is 0.001% to 15% by weight, preferably 0.005% to 10% by weight, and more preferably 0.01% to 5% by weight, relative to the total weight of the composition.

10. The composition according to claim 1, wherein the amount of (c) water in the composition is 10% by mass to 99% by mass, preferably 30% by mass to 97% by mass, and more preferably 50% by mass to 95% by mass, relative to the total mass of the composition.

11. 2. The composition of claim 1, further comprising (d) at least one surfactant, preferably selected from nonionic surfactants, more preferably selected from polyglyceryl fatty acid esters.

12. 1. A method for preparing a film, preferably a cosmetic film, comprising: applying a composition according to any one of claims 1 to 11 onto a substrate, preferably a keratin material; drying the composition; Including, method.

13. applying a composition according to any one of claims 1 to 11 onto a substrate, preferably a keratin material; drying the composition; 1. A film, preferably a cosmetic film, prepared by a method comprising:

14. (a) 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 or salt thereof having two or more pKa values; or At least one non-polymeric base or salt thereof having two or more pKb values At least one polyion complex comprising: (b) at least one lipophilic antioxidant; and Optionally, (d) at least one surfactant, preferably selected from nonionic surfactants, more preferably selected from polyglyceryl fatty acid esters; Including, A film, preferably a cosmetic film, the anionic polymer is selected from hyaluronic acid, its salts, and its derivatives; The amphoteric polymer is selected from cationized hyaluronic acid and salts thereof. A film, preferably a cosmetic film.

15. A cosmetic method for keratinous materials such as skin, comprising: applying to keratinous materials a composition according to any one of claims 1 to 11; drying the composition to form a cosmetic film on the keratinous material; Including, Beauty method.