Composition containing hyaluronic acid-based polyion complex and lipophilic antioxidant

Abstract

To provide a composition that can be transparent or translucent, and can bring about long-lasting antioxidant effect.SOLUTION: A composition contains: (a) at least one kind of polyion 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 can be transparent or translucent, 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 large volumes 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 in 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] Its additional patent no. 2190406 [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

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Non-licensed literature

[0008] [Non-licensed document 1] CTFA Dictionary [Non-licensed document 2] "Hyaluronan fragments: an information-rich system", R. Stern, European Journal of Cell Biology 58 (2006) pp. 699~715 [Non-licensed document 3] D. Campoccia, "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) pp. 2101~2127

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Non-licensed Document 7

[0009] There is a need for compositions containing hyaluronic acid-based polyion complexes that can be transparent or translucent and can provide long-lasting antioxidant benefits.

[0010] Therefore, it is a first object of the present invention to provide a composition that can be transparent or translucent and can provide long-lasting antioxidant benefits.

[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 At least one polyion complex comprising (b) at least one hydrophilic antioxidant; (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 hydrophilic antioxidant may be selected from ascorbic acid, its derivatives, its salts, and mixtures thereof.

[0019] The amount of the hydrophilic antioxidant (b) in the composition according to the present invention may be 0.01% by mass to 30% by mass, preferably 0.05% by mass to 25% by mass, and more preferably 0.1% by mass to 20% 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 that 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 that can provide long-lasting antioxidant effects.

[0025] The above object of the present invention is to (1) applying to a substrate, preferably a keratinous material, 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 hydrophilic 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. This can be achieved by:

[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 discovered that it is possible to provide a composition that can be transparent or translucent 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 At least one polyion complex comprising (b) at least one hydrophilic 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 capable of providing 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 inventors have discovered that it is possible to provide a coating that can provide long-lasting antioxidant benefits. (1) applying a composition according to the invention onto a substrate, preferably a keratinous material; 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 hydrophilic antioxidant; 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; and The amphoteric polymer is selected from cationized hyaluronic acid and its salts; A coating, preferably a cosmetic coating.

[0030] Compositions and films according to the present invention can be transparent or translucent.

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

[0032] Thus, the present invention may be useful, for example, to protect 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, compositions and films according to the present invention may be based on hyaluronic acid or cationized hyaluronic acid to provide long-lasting cosmetic benefits and / or improved moisturizing texture.

[0034] Furthermore, 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.

[0035] A film containing a polyion complex, which film may contain at least one surfactant, can be easily prepared by applying the composition onto a substrate, preferably a keratinous material such as skin and hair, more preferably onto skin, and allowing the composition to dry.

[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 the cosmetic effect provided by the cosmetic active ingredient. For example, when the polyion complex film contains at least one cosmetic active ingredient selected from UV shielding agent, (b) anti-aging agent other than hydrophilic antioxidant, sebum suppressing agent, deodorant agent, antiperspirant, whitening agent, and mixtures 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 can 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 and therefore can remain on keratinous materials such as 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 particle size 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 -NH 2 means a 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 may 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 formula:

[0067] [ka]

[0068] (In the formula, R 1 and R 2 are the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, for example methyl and ethyl groups; R 3 may be the same or different, and are hydrogen and CH 3 Selected from 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, R 4 , R 5 and R 6 are 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 acrylamide, methacrylamide, diacetone acrylamide, or a copolymer in which the nitrogen atom is (C 1 ~C 4 ) Acrylamides and methacrylamides substituted with 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 (C 1 ~C 4 )Alkyltri(C 1 ~C 4) Alkylammonium salt polymers, for example those obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or by copolymerization of acrylamide with 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, R 1 and R 2 Each of the C 1~3 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; R 3 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; R 4 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-CH 2 -CH(OH)-CH 2 -N + (CH 3 ) 3 It is preferable that:

[0078] (3) Cationic cellulose polymers, such as cellulose copolymers and cellulose derivatives grafted with water-soluble quaternary ammonium monomers, such as those described in U.S. Pat. No. 4,131,576, for example hydroxyalkylcelluloses, such as hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted with salts selected from the group consisting of 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) can 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, 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 may 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 include alkyl groups having 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group has, for example, 1 to 5 carbon atoms, and lower (C 1 ~C 4 ) 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 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, 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), 1 ~C 6 selected from alkyl groups, A 1 and B. 1 are selected from polymethylene groups, which may be the same or different and contain from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked or inserted in the backbone, 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, A 1 , R 13 and R 15 may be taken together with the two nitrogen atoms to which they are attached to form a piperazine ring, A 1 is selected from linear or branched, saturated or unsaturated alkylene groups or hydroxyalkylene groups, B 1 You can choose from the following: -(CH 2 ) n --CO-E'-OC-(CH 2 ) 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: -(CH 2 -CH 2 -O) x -CH 2 -CH 2 - -[CH 2 -CH(CH 3 )-O] y -CH 2 -CH(CH 3 )- (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) a group of the formula -NH-Y-NH-, where Y is a linear or branched hydrocarbon group or a divalent group -CH 2 -CH 2 -SS-CH 2 -CH 2 -), 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 16 may 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) A polyquaternary ammonium polymer 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, a methyl group, an ethyl group, a propyl group, a β-hydroxyethyl group, a β-hydroxypropyl group, -CH 2 CH 2 (OCH 2 CH 2 ) 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 a dihalide and -CH 2 -CH 2 -O-CH 2 -CH 2 - selected from the group

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

[0103] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0104] 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.

[0105] 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.

[0106] (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.

[0107] 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.

[0108] 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.

[0109] (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.

[0110] 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.

[0111] The following description relates to preferred embodiments of the cationic polymer.

[0112] It may be preferred that the cationic polymer is selected from cationic starches.

[0113] 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.

[0114] It may also be preferred that the cationic polymer is selected from cationic gums.

[0115] 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.

[0116] 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 under the trade name Jaguar series from Rhodia Inc. and under the trade name N-Hance series from Ashland Inc. Cassia hydroxypropyltrimonium chloride is commercially available under the trade names Sensomer CT-250 and Sensomer CT-400 from Lubrizol Advanced Materials, Inc. or ClearHance from Ashland Inc.

[0117] It may also be preferred that the cationic polymer is selected from chitosan.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] (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.

[0124] 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.

[0125] Unless otherwise defined in the description, "molecular weight" may mean number average molecular weight.

[0126] According to the invention, the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives.

[0127] Hyaluronic acid has the chemical formula:

[0128] [ka]

[0129] It can be expressed as:

[0130] In the context of the present invention, the term "hyaluronic acid" refers specifically to a compound of the formula:

[0131] [ka]

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

[0133] The term "derivative" of hyaluronic acid, in the context of the present invention, 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 present 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 publication "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 examples 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 of the D-glucuronic acid level 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 are 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), supplied by Bioland under the name Nutra AF (MW: 69,000 Da), supplied by Bioland under the name Oligo HA (MW: 6100 Da), or supplied 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 is 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 shown 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 salt used as the raw material (hereinafter referred to as "raw material hyaluronic acid and / or its salt") with the 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 salt 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 salt 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 2.3-epoxypropyltrialkylammonium halide as shown in the following general formula (3) and 3-halogeno-2-hydroxypropyltrialkylammonium halide as shown in the following general formula (4).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 the 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 a quaternary ammonium group-containing group) can be calculated by the following formula: Degree of cationization (x) = [(N S -N N )×401.3] / [1400-129.5 * (N S -N N )]

[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 included in 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 polymers 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 acids or their salts 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 acids or their salts 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 No. 2 (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 (Lithol Rubin B), Red No. 202 (Lithol Rubin BCA), Red No. 204 (Lake Red CBA), Red No. 206 (Lithol Red CA), Red No. 207 (Lithol Red BA), Red No. 208 (Lisol 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 405 No. 502 (Ponceau 3R), No. 503 (Ponceau R), No. 504 (Ponceau SX), No. 401 (Naphthol Green B), No. 402 (Guinea Green B) and 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 a salt thereof having two or more pKb values ​​can be included in 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 polymers 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 means a salt formed by adding a suitable acid to a non-polymeric base having a pKb value of two or more, which can be obtained by reacting a non-polymeric base having a pKb value of two or more with an acid according to methods known to those skilled in the art. As salts, ammonium salts, such as HCl and HNO 3 and the like, as well as 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 base or salt 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] [Hydrophilic antioxidant] The composition according to the present invention comprises (b) at least one hydrophilic antioxidant. Two or more hydrophilic antioxidants may be used in combination. Thus, a single type of hydrophilic antioxidant or a combination of different types of hydrophilic antioxidants may be used.

[0218] According to the present invention, antioxidants are compounds or substances capable of scavenging the various radical forms that may be present in the skin, preferably they simultaneously scavenge all the various radical forms present.

[0219] (b) By hydrophilic antioxidant is meant that the partition coefficient of the antioxidant between n-butanol and water is <1, more preferably <0.5, and even more preferably <0.1.

[0220] (b) The hydrophilic antioxidant is preferably selected from ascorbic acid, its derivatives, its salts, and mixtures thereof.

[0221] Derivatives of ascorbic acid can include, for example, ascorbyl glucoside. The term "ascorbyl glucoside" is understood to mean a condensation product of glucose in D-form, i.e. in α- or β-glucopyranose or α- or β-furanose form, or in L-form with ascorbic acid, preferably in L-form. L-ascorbic acid 2-O-α-D-glucopyranoside may be preferred for use in the present invention. It is available, in particular, from Hayashibara Co., Ltd.

[0222] Examples of derivatives of ascorbic acid include ethers of ascorbic acid, which may be alkyl ethers of ascorbic acid, such as ethyl ascorbic acid, in particular 3-O-ethyl ascorbic acid.

[0223] Salts of ascorbic acid include metal salts of ascorbic acid, such as sodium ascorbate, magnesium ascorbyl phosphate, and sodium ascorbyl phosphate.

[0224] (b) It may be preferred that the hydrophilic antioxidant is selected from the group consisting of ascorbic acid, ascorbyl glycosides, ethyl ascorbic acid, sodium ascorbate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, and mixtures thereof.

[0225] The amount of (b) the hydrophilic antioxidant in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, based on the total weight of the composition.

[0226] The amount of (b) the hydrophilic antioxidant in the composition according to the present invention may be 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less, relative to the total weight of the composition.

[0227] The amount of the hydrophilic antioxidant (b) in the composition according to the present invention may be 0.01% by mass to 30% by mass, preferably 0.05% by mass to 25% by mass, and more preferably 0.1% by mass to 20% by mass, relative to the total mass of the composition.

[0228] [water] The composition according to the present invention comprises (c) water.

[0229] 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.

[0230] (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.

[0231] 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.

[0232] [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.

[0233] The surfactant used in the present invention may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants and nonionic surfactants.

[0234] (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.

[0235] The anionic surfactant is (C 6 ~C 30 ) alkyl sulfates, (C 6 ~C 30 ) alkyl ether sulfates, (C 6 ~C 30 ) Alkyl amide ether sulfates, alkyl aryl polyether sulfates, monoglyceride sulfates; (C 6 ~C 30 ) alkylsulfonates, (C 6 ~C 30 ) alkylamide sulfonate, (C 6 ~C 30 ) alkylarylsulfonates, α-olefinsulfonates, paraffin sulfonates; (C 6 ~C 30 ) alkyl phosphate; (C 6 ~C 30 ) alkyl sulfosuccinate, (C 6 ~C 30 ) alkyl ether sulfosuccinate, (C 6 ~C 30 ) alkylamide sulfosuccinate; (C 6 ~C 30 ) alkyl sulfoacetate; (C 6 ~C 24 ) acyl sarcosinate; (C 6~C 24 ) acyl glutamate; (C 6 ~C 30 ) alkyl polyglycoside carboxyl ether; (C 6 ~C 30 ) alkyl polyglycoside sulfosuccinate; (C 6 ~C 30 ) alkyl sulfosuccinate; (C 6 ~C 24 ) acyl isethionate;N-(C 6 ~C 24 ) Acyl taurate; C 6 ~C 30 Fatty acid salts; coconut oil salts or hydrogenated coconut oil salts; (C 8 ~C 20 ) acyl lactate; (C 6 ~C 30 ) Alkyl-D-galactosiduronic acid salts; Polyoxyalkylenated (C 6 ~C 30 ) Alkyl ether carboxylates; Polyoxyalkylenated (C 6 ~C 30 ) alkyl aryl ether carboxylates; and polyoxyalkylenated (C 6 ~C 30 ) alkyl amide ether carboxylates; and the corresponding acid forms.

[0236] In at least one embodiment, the anionic surfactant is in the form of a salt, such as an alkali metal salt, for example sodium salt; an alkaline earth metal salt, for example magnesium salt; an ammonium salt; an amine salt; and an amino alcohol salt. Under some conditions, the anionic surfactant may also be in the form of an acid.

[0237] The anionic surfactant is (C 6 ~C 30 ) alkyl sulfates, (C 6 ~C 30 ) alkyl ether sulfates, or chlorinated or non-chlorinated polyoxyalkylenated (C 6 ~C 30) salts of alkyl ether carboxylic acids.

[0238] (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.

[0239] 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).

[0240] The amphoteric surfactant may preferably be selected from the group consisting of betaines and amidoamine carboxylated derivatives.

[0241] Preferably, the amphoteric surfactant is selected from betaine type surfactants.

[0242] 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, (C 8 ~C 24 ) alkyl betaine, (C 8 ~C 24 ) Alkylamide (C 1 ~C 8 ) alkylbetaines, sulfobetaines and (C 8 ~C 24 ) Alkylamide (C 1 ~C 8 In one embodiment, the betaine type amphoteric surfactant is selected from the group consisting of (C 8 ~C 24 ) alkyl betaine, (C 8 ~C 24) Alkylamide (C 1 ~C 8 ) selected from alkylsulfobetaines, sulfobetaines and phosphobetaines.

[0243] Non-limiting examples that may be mentioned include the compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th Edition, 2014, under 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.

[0244] The betaine type amphoteric surfactants are preferably the alkyl betaines and alkylamidoalkyl betaines, in particular coco betaine and cocamidopropyl betaine.

[0245] 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, the respective structures of which are as follows: R 1 -CONHCH 2 CH 2 -N + (R 2 )(R 3 )(CH 2 COO - )M + X - (B1) [In the formula, R 1 is the acid R present in hydrolyzed coconut oil. 1-COOH alkyl group, heptyl group, nonyl group or undecyl group, R 2 indicates a beta-hydroxyethyl group, R 3 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 - is an organic or inorganic anion, such as a halide, acetate, phosphate, nitrate, alkyl (C 1 ~C 4 ) sulfate ion, alkyl (C 1 ~C 4 )- or alkyl(C 1 ~C 4 ) arylsulfonates, especially methylsulfate and ethylsulfate, or M + and X - does not exist] R 1 '-CONHCH 2 CH 2 -N(B)(C) (B2) [In the formula, R 1 ' is the acid R present in coconut oil or hydrolyzed linseed oil. 1 Alkyl group of -COOH, C 7 , C 9 , C 11 Or C 13 Alkyl group, C 17 Alkyl groups and their isoforms, or unsaturated C 17 represents a group, B is -CH 2 CH 2 OX', C is -(CH 2 ) z -Y' (wherein z=1 or 2), X' is -CH 2 -COOH group, -CH 2 -COOZ', -CH 2 CH 2 -COOH, -CH2 CH 2 -COOZ' or a hydrogen atom, Y' is -COOH, -COOZ', -CH 2 -CHOH-SO 3 Z', -CH 2 -CHOH-SO 3 H group or CH 2 -CH(OH)-SO 3 represents a -Z' group, In these formulas, Z' represents an ion of an alkali metal or alkaline earth metal, such as a sodium ion, an ion derived from an organic amine, or an ammonium ion. and R a'' -NH-CH(Y'')-(CH 2 ) n -C(O)-NH-(CH 2 ) n' -N(Rd)(Re) (B'2) [In the formula, Y'' is -C(O)OH, -C(O)OZ'', -CH 2 -CH(OH)-SO 3 H or -CH 2 -CH(OH)-SO 3 -Z'' (wherein Z'' represents a cationic ion derived from an alkali metal or alkaline earth metal, such as a sodium ion, an ion derived from an organic amine, or an ammonium ion), Rd and Re are C 1 ~C 4 Alkyl group or C 1 ~C 4 represents a 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' are independently an integer of 1 to 3.

[0246] The amphoteric surfactant having the formula B1 and B2 is 8 ~C 24 )-Alkyl amphomonoacetates, (C 8 ~C 24) alkyl amphodiacetate, (C 8 ~C 24 ) alkyl amphoteric monopropionates and (C 8 ~C 24 ) alkyl amphodipropionates.

[0247] 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.

[0248] Mention may be made, by way of example, of cocoamphodiacetate sold under the trade name Miranol® C2M concentrate by the company Rhodia Chimie.

[0249] 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.

[0250] (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.

[0251] 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.

[0252] Examples of quaternary ammonium salts that may be mentioned include, but are not limited to: Of the general formula (B3) below:

[0253] [ka]

[0254] [In the formula, R 1 , R 2 , R 3 and R 4 are 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 groups, alkoxy groups, C 2 ~C 6 Polyoxyalkylene group, alkylamide group, (C 12 ~C 22 ) Alkylamide (C 2 ~C 6 ) alkyl group, (C 12 ~C 22 ) alkyl acetate groups and hydroxyalkyl groups; and aromatic groups, such as aryl and alkylaryl; X - are halide ions, phosphate ions, acetate ions, lactate ions, (C 2 ~C 6 ) alkyl sulfate ions, and alkyl sulfonate ions or alkylaryl sulfonate ions; Quaternary ammonium salts of imidazolines, such as those of formula (B4):

[0255] [ka]

[0256] [In the formula, R 5 is selected from alkenyl and alkyl groups containing 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or coconut oil, R 6 is hydrogen, C 1 ~C 4 alkyl groups, and alkenyl and alkyl groups containing 8 to 30 carbon atoms; R 7 is C 1 ~C 4 selected from alkyl groups, R 8 is hydrogen and C 1 ~C 4 selected from alkyl groups, X - is selected from the group consisting of halides, phosphate ions, acetate ions, lactate ions, alkyl sulfate ions, alkyl sulfonate ions and alkylaryl sulfonate ions. In one embodiment, R 5 and R 6 is, for example, a mixture of radicals selected from alkenyl and alkyl radicals containing 12 to 21 carbon atoms, for example a fatty acid derivative of tallow, R 7 is methyl, R 8 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):

[0257] [ka]

[0258] [In the formula, R 9 is selected from aliphatic groups containing 16 to 30 carbon atoms; R 10 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, or (CH 2 ) 3 (R 16a )(R 17a )(R 18a )N + X-groups, R 11 , R 12 , R 13 , R 14 , R 16a , R17a and R 18a are 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.

[0259] 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) below:

[0260] [ka]

[0261] [In the formula, R 22 is C 1 ~C 6 Alkyl groups, and C 1 ~C 6 selected from hydroxyalkyl groups and dihydroxyalkyl groups; R 23 teeth, Under the following criteria:

[0262] [ka]

[0263] , linear and branched, saturated and unsaturated C 1 ~C 22 Hydrocarbon group R 27 and hydrogen; R 25 teeth, Under the following criteria:

[0264] [ka]

[0265] , linear and branched, saturated and unsaturated C 1 ~C 6 Hydrocarbon group R 29 and hydrogen; R 24 , R 26 and R 28 may be the same or different, linear or branched, saturated or unsaturated C 7 ~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 - is 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 , 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 29When R 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 - are, for example, halide ions, such as chloride, bromide and iodide ions; and C 1 ~C 4 The anion X may be selected from 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.

[0266] 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, Under the following criteria:

[0267] [ka]

[0268] , methyl, ethyl and C 14 ~C 22 selected from hydrocarbon radicals and hydrogen; R 25 teeth, Under the following criteria:

[0269] [ka]

[0270] 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 groups, such as linear and branched, saturated and unsaturated C 13 ~C 17 It is selected from an alkyl group and an alkenyl group.

[0271] In one embodiment, the hydrocarbon-based group is linear.

[0272] 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.

[0273] 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.

[0274] 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".

[0275] 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 US Pat. Nos. 4,874,554 and 4,137,180.

[0276] 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.

[0277] 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.

[0278] (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.

[0279] 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 esters of alcohols, alpha-diols, alkylphenols and fatty acids, which compounds can be ethoxylated, propoxylated or glycerolized and have at least one fatty chain containing, for example, 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 (C 6 ~C 24 Polyethoxylated fatty acid mono- or diesters of N-(C) alkyl polyglycosides; 6 ~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.

[0280] 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.

[0281] Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned are: Monooxyalkylenated or polyoxyalkylenated (C 8 ~C 24 ) alkylphenols, Saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C 8 ~C 30 alcohol, Saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C 8 ~C 30 Amides, Saturated or unsaturated, linear or branched C 8 ~C 30 esters of acids and polyalkylene glycols; Saturated or unsaturated, linear or branched C 8 ~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.

[0282] 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).

[0283] Polyoxyethylated saturated fatty alcohols (or C 8 ~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.

[0284] Polyoxyethylenated unsaturated fatty alcohols (or C 8 ~C 30Examples 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.

[0285] Examples of monoglycerolated or polyglycerolated nonionic surfactants include monoglycerolated or polyglycerolated C 8 ~C 40 Alcohol is preferably used.

[0286] In particular, monoglycerolized or polyglycerolized C 8 ~C 40 The alcohol has the formula: RO-[CH 2 -CH(CH 2 OH)-O] m -H, or RO-[CH(CH 2 OH)-CH 2 O] m -H (Wherein, R is a linear or branched C 8 ~C 40 , preferably C 8 ~C 30 represents an alkyl group or an alkenyl group, and m represents a number ranging from 1 to 30, preferably from 1.5 to 10. is equivalent to.

[0287] 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.

[0288] Just as the value of m represents a statistical value, the alcohol may represent a mixture of alcohols, which means that several types of polyglycerolized fatty alcohols may coexist in the form of a mixture in a commercial product.

[0289] Among monoglycerolated or polyglycerolated alcohols, C containing 1 mol of glycerol 8 / C 10 Alcohol, C containing 1 mol glycerol 10 / C 12 C containing alcohol and 1.5 mol of glycerol 12 It is preferred to use alcohol.

[0290] Monoglycerolized or polyglycerolized C 8 ~C 40 The fatty ester has the following formula: R'O-[CH 2 -CH(CH 2 OR''')-O] m -R”, or R'O-[CH(CH 2 OR''')-CH 2 O] m -R” (wherein R', R" and R'" are each independently a hydrogen atom or a linear or branched C 8~C 40 , preferably C 8 ~C 30 represents an alkyl-CO- or 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.

[0291] Examples of polyoxyethylenated fatty esters that may be mentioned are the ethylene oxide adducts of lauric, palmitic, stearic or behenic esters and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurates (CTFA names: PEG-9 laurate to PEG-50 laurate), PEG-9 to PEG-50 palmitates (CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearates (CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenates (CTFA names: PEG-9 behenate to PEG-50 behenate); Polyethylene glycol 100 EO monostearate (CTFA name: PEG-100 stearate); and mixtures thereof.

[0292] 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 C 8 ~C 24 , preferably C 12 ~C 22 and polyoxyalkylenated derivatives thereof, preferably containing 10 to 200, more preferably 10 to 100 oxyalkylene units; 8 ~C 24 , preferably C12 ~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; 8 ~C 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 C 8 ~C 24 , preferably C 12 ~C 22 with aliphatic alcohols; and mixtures thereof.

[0293] 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 polyoxyalkylenated derivatives thereof, 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).

[0294] Mixtures of these surfactants can also be used, such as the product containing glyceryl stearate and PEG-100 stearate sold by Uniqema under the name ARLACEL 165, and the product containing glyceryl stearate (mono- and distearate) and potassium stearate sold by Goldschmidt under the name TEGIN (CTFA name: Glyceryl Stearate SE).

[0295] C 8 ~C 24 The 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 sold under the name Span 60 by the company ICI (CTFA name: sorbitan stearate), sorbitan monopalmitate sold under the name Span 40 by the company ICI (CTFA name: sorbitan palmitate) 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.

[0296] Esters of fatty acids with glucose or alkyl glucose: glucose palmitate, alkyl glucose sesquistearates, e.g. methyl glucose sesquistearate, alkyl glucose palmitates, e.g. methyl glucose or ethyl glucose palmitate, methyl glucoside fatty esters, diesters of methyl glucoside with oleic acid (CTFA name: methyl glucose dioleate), mixed esters of methyl glucoside with a mixture of oleic acid / hydroxystearic acid (CTFA name: methyl glucose dioleate / hydroxystearate), esters of methyl glucoside with isostearic acid (CTFA name: methyl glucose isostearate), esters of methyl glucoside with lauric acid (CTFA name: methyl glucose laurate), mixtures of mono- and diesters of methyl glucoside and isostearic acid (CTFA name: methyl glucose sesqui-isostearate), mixtures of mono- and diesters of methyl glucoside and stearic acid (CTFA name: Mention may be made of methylglucose sesquistearate), and in particular the product sold under the name Glucate SS by the company AMERCHOL, and mixtures thereof.

[0297] 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 methylglucose 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.

[0298] As sucrose esters there may be mentioned, for example, saccharose palmito-stearate, saccharose stearate and saccharose monolaurate.

[0299] 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.

[0300] Mixtures of alkoxylated vegetable oil glycerides may also be mentioned, such as a mixture of ethoxylated (200 EO) palm and copra (7 EO) glycerides.

[0301] 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.

[0302] 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(C 2 H 4 O) a (C 3 H 6 O) b (C 2 H 4 O) 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.

[0303] According to one embodiment of the invention, the non-ionic surfactant may be chosen from silicone surfactants, including, but not limited to, those disclosed in documents US-A-5364633 and US-A-5411744.

[0304] The silicone surfactant preferably has the formula (I):

[0305] [ka]

[0306] [In the formula, R 1 , R 2 and R 3 are, independently of each other, C 1 ~C 6 Alkyl group or -(CH 2 ) x -(OCH2 CH 2 ) y -(OCH 2 CH 2 CH 2 ) z -OR 4 group, and at least one R 1 Group, R 2 Group or R 3 The group is not an alkyl group, but an R 4 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; z is an integer ranging from 0 to 5. The compound may be:

[0307] 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.

[0308] Examples of silicone surfactants of formula (I) include those of formula (II):

[0309] [ka]

[0310] (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.) Compounds of the formula:

[0311] Examples of silicone surfactants of formula (I) include those of formula (III): H-(OCH 2 CH 2 ) y -(CH 2 ) 3 -[(CH 3 )2 SiO] A' -(CH 2 ) 3 -(OCH 2 CH 2 ) y -OH (III) (In the formula, A' and y are integers ranging from 10 to 20.) Mention may also be made of compounds of the formula:

[0312] 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) where 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.

[0313] The compound Q4-3667 is a compound of formula (III) (wherein A is 15 and y is 13).

[0314] (d) The surfactant is preferably selected from nonionic surfactants.

[0315] More preferably, the (d) surfactant is selected from polyglyceryl fatty acid esters.

[0316] The polyglyceryl fatty acid ester may have a polyglyceryl 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.

[0317] 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.

[0318] It is preferred that the (d) surfactant is selected from polyglyceryl saturated or unsaturated fatty acid monoesters.

[0319] 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.

[0320] Polyglyceryl fatty acid esters include PG-2 stearate (HLB: 5.0), PG-2 isostearate (HLB: 5.5), PG-2 oleate (HLB: 6.5), PG-2 caprate (HLB: 9.5), PG-2 laurate (HLB: 8.5), PG-4 oleate (HLB: 8.8), PG-4 laurate (HLB: 10.4), PG-4 isostearate (HLB: 8.2), PG-5 laurate (HLB: 15.8), PG-6 isostearate (HLB: 10.8), PG-3 coconut oil fatty acid (HLB: 12.0), PG-3 caprate (HLB: 10.0), PG-4 caprylate (HLB: 14), PG-4 caprate (HLB: 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.

[0321] 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.

[0322] It is preferred that the composition according to the invention comprises at least two polyglyceryl fatty acid esters.

[0323] (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:

[0324] 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.

[0325] 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.

[0326] 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.

[0327] [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.

[0328] At a pH of 2.0 to 9.0, the (a) polyion complex can be very stable.

[0329] 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.

[0330] (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.

[0331] 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.

[0332] 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.

[0333] 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.

[0334] 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:

[0335] [ka]

[0336] (Wherein, R is a hydroxyl group or C 1 ~C 4 R represents an alkylene, such as propylene, optionally substituted with an alkyl group; 1 , R 2 , R 3 and R 4 are independently a hydrogen atom, an alkyl group or C 1 ~C 4represents a hydroxyalkyl group, which can be exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferred.

[0337] 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.

[0338] (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.

[0339] 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.

[0340] Depending on their solubility, the acids may be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, more preferably 0.03% to 5% by weight, based on the total weight of the composition.

[0341] (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.

[0342] 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).

[0343] [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 ranges that do not impair the effects of the present invention.

[0344] 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.

[0345] [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 to a keratinous material. In this specification, a keratinous material means a material that contains keratin as a main component, and examples thereof include skin, scalp, nails, lips, hair, etc. Therefore, it is preferable that the cosmetic composition according to the present invention is used in a cosmetic method for a keratinous material, particularly for the skin.

[0346] 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.

[0347] 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.

[0348] 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 strong shear, for example with a homogenizer, is required, and no heating is required.

[0349] [Coating] The composition according to the present invention can be used to easily prepare a coating.

[0350] 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:

[0351] 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.

[0352] Since the method for preparing a 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 a film according to the present invention can prepare a relatively thick film without using any special equipment such as a spin coater or a spray machine.

[0353] The presently claimed coatings may be transparent or translucent and may provide long-lasting antioxidant benefits.

[0354] Even when the film according to the invention is relatively thick, it can still be thin and transparent and therefore difficult to perceive, so that the film according to the invention can preferably be used as a cosmetic film.

[0355] The presently claimed coating may be less sticky even though it contains a hyaluronic acid based polymer.

[0356] If the substrate is not a keratinous material such as skin, the composition according to the present invention can be applied onto a 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.

[0357] 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.

[0358] 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.

[0359] 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.

[0360] 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 hydrophilic antioxidant; 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 A film, preferably a cosmetic film, in which the amphoteric polymer is selected from cationized hyaluronic acid and its salts. Also relates to.

[0361] The above comments regarding the cationic, anionic and amphoteric polymers, and the hydrophilic antioxidants and surfactants described above, can be applied to coatings (1) and (2) above.

[0362] The film thus obtained above 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. Therefore, the term "self-supporting" can have the same meaning as "self-supporting".

[0363] It is preferred that the coating according to the present invention is hydrophobic.

[0364] The term "hydrophobic" as used herein 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.

[0365] When the film according to the present invention is hydrophobic, the film can have water-resistant properties, and therefore the film 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 present invention provides any cosmetic benefit, the cosmetic benefit can last for a long time.

[0366] 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.

[0367] 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.

[0368] 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 the polymer is not recognized as foreign by the body.

[0369] The term "biodegradable" polymer as used herein 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.

[0370] 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 rashes. 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.

[0371] 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.

[0372] 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 long-lasting UV blocking effect.

[0373] [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 the keratinous materials and drying the composition to form a cosmetic film on the keratinous materials, 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.

[0374] 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.

[0375] 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.

[0376] In other words, the decorative coating 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 coating 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.

[0377] 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, the film according to the present invention is difficult to remove with water, but can be easily removed with a soap that can provide alkaline conditions.

[0378] 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 rays, thereby reducing skin darkening, improving skin tone and evenness, and / or treating skin aging.

[0379] Furthermore, the above-mentioned cosmetic films may have cosmetic benefits 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.

[0380] 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 ingredients. Thus, the cosmetic film can be capable of hiding skin imperfections, 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 and shielding the skin as a barrier.

[0381] The cosmetic benefits can be adjusted or controlled by varying the chemical composition, thickness and / or surface roughness of the cosmetic film.

[0382] 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 hydrophilic 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.

[0383] After the cosmetic film or cosmetic sheet according to the present invention has been applied to the skin, it is also possible to apply a make-up cosmetic composition thereon. EXAMPLES

[0384] The present invention will now be described in a more detailed manner by means of examples, which should not, however, be construed as limiting the scope of the present invention.

[0385] (Examples 1 to 2 and Comparative Example 1) [Preparation] Each of the compositions according to Examples 1-2 and Comparative Example 1 was prepared by mixing the components shown in Table 1. All values ​​for the amounts of components in Table 1 are based on "mass %" of the active material.

[0386] [Table 1]

[0387] [evaluation] (transparency) The appearance of each of the compositions according to Examples 1 and 2 and Comparative Example 1 was evaluated. In detail, each composition was placed in a transparent cylindrical glass container, and the appearance was evaluated in terms of visibility of the background through the container, and each composition was dropped onto the hand, and the appearance was evaluated in terms of visibility of the skin of the hand, according to the following evaluation criteria: Very good: the background is easily visible through the container (transparent) Good: The background is visible through the container, but is slightly cloudy (semi-transparent) Normal: The background is not visible through the container, but the skin is easily visible (semi-transparent) Poor: Skin not visible (opaque)

[0388] The results are shown in Table 1.

[0389] (Sustained antioxidant effect) 0.6 g of a β-carotene solution (solvent: caprylic / capric triglyceride) having a concentration of 0.05% by mass and 0.2 g of each of the compositions according to Examples 1 and 2 and Comparative Example 1 were mixed to obtain mixtures.

[0390] 0.4 g of the above mixture was applied onto a filter (glass microfiber filter).

[0391] The filter was rinsed off with tap water (300 mL, 23-27°C).

[0392] The above filters were exposed to UV light having a wavelength of 365 nm for 30 minutes to oxidize β-carotene.

[0393] When β-carotene is oxidized, the original yellow color derived from β-carotene fades.

[0394] L before and after UV exposure of the filter * a * b * (CIE1976) b in space * value (b * (T=0) and b * (T = 30 min)) was measured using a spectrophotometer (CM-700d manufactured by Konica Minolta, Inc.), and b * (T=0) value and b * (T = 30 min) The difference between the value and Δb * The filter before rinse-off was determined as * Note that the (T=0) values ​​were between 45 and 65.

[0395] Δb * value and b * (T=30 min) values ​​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 bad: Δb * >10

[0396] The results are shown in Table 1.

[0397] (overview) The compositions according to Examples 1 and 2 can have a transparent or translucent appearance.

[0398] From the comparison between Examples 1 and 2 and Comparative Example 1, it is clear that the use of polyion complex can prolong the antioxidant effect.

[0399] From the comparison between Example 1 and Example 2, it is clear that the use of a surfactant such as polyglyceryl fatty acid ester 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 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 hydrophilic antioxidant; (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 hydrophilic antioxidant is selected from ascorbic acid, its derivatives, its salts, and mixtures thereof.

9. The composition according to claim 1, wherein the amount of (b) the hydrophilic antioxidant in the composition is 0.01% by weight to 30% by weight, preferably 0.05% by weight to 25% by weight, and more preferably 0.1% by weight to 20% 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; A method comprising:

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 Including, at least one polyion complex; (b) at least one hydrophilic antioxidant; 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; and 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; Beauty methods, including: