Compositions comprising hyaluronic acid-based polyionic complexes and hydrophilic or lipophilic antioxidants

Abstract

The present invention relates to a composition comprising: (a) at least one complex comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer, or at least one amphoteric polymer, and at least one non-polymeric acid or salt (s) thereof having two or more pKa values, or at least one non-polymeric base or salt (s) thereof having two or more pKb values; (b) at least one hydrophilic or lipophilic antioxidant; and (c) water wherein the anionic polymer is selected from hyaluronic acids, salts thereof, and derivatives thereof, and the amphoteric polymer is selected from cationized hyaluronic acids and salts thereof. The composition according to the present invention may be transparent or translucent, or less tacky, and may provide a lasting antioxidant effect.

Description

Technical Field

[0001] The present invention relates to a composition containing a polyion complex and 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 Art

[0002] Hyaluronic acid is the main glycosaminoglycan present in the skin. Therefore, fibroblasts mainly synthesize collagen, matrix glycoproteins other than collagen (fibronectin, laminin), proteoglycans, and elastin. In the case of keratinocytes, they mainly synthesize sulfated glycosaminoglycans and hyaluronic acid. Hyaluronic acid is also known as hyaluronic acid (HA).

[0003] Hyaluronic acid exists in a free state in the epidermis and dermis and causes skin swelling. This polysaccharide can actually retain a large amount of water, up to 1000 times its weight. In this sense, hyaluronic acid plays an important role in increasing the amount of water bound in tissues and the mechanical properties and wrinkle formation of the skin.

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

[0005] However, the aqueous solution of hyaluronic acid is viscous, and this may result in an uncomfortable texture. In addition, the hyaluronic acid film formed when the aqueous solution of hyaluronic acid dries on the skin is viscous, and this film may also result in an uncomfortable texture.

[0006] WO 2021 / 125069 discloses reducing the viscosity caused by hyaluronic acid by forming polyion complex particles with a cationic polymer and hyaluronic acid as an anionic polymer. Summary of the Invention

[0007] There is a need for a composition containing a hyaluronic acid-based polyion complex, which can be transparent or translucent and can provide a long-lasting antioxidant effect.

[0008] There is also a need for a composition containing a hyaluronic acid-based polyion complex, which can have lower viscosity and can provide a long-lasting antioxidant effect.

[0009] Therefore, the first object of the present invention is to provide a composition, which can be transparent or translucent, or have lower viscosity, and at the same time the composition can provide a long-lasting antioxidant effect. The above object of the present invention can be achieved by a composition containing:

[0010] (a) at least one polyion complex, which contains

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

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

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

[0014] at least one amphoteric polymer,

[0015] and

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

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

[0018] (b) at least one hydrophilic or lipophilic antioxidant, and

[0019] (c) water,

[0020] wherein

[0021] the anionic polymer is selected from hyaluronic acid, its salts, and its derivatives, and

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

[0023] In the composition according to the invention, the component (b) can be at least one hydrophilic antioxidant or at least one lipophilic antioxidant.

[0024] The cationized hyaluronic acid can have at least one group containing a quaternary ammonium 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.

[0025] The cationic polymer can have at least one positively chargeable and / or positively charged moiety selected from primary amino, secondary amino or tertiary amino, quaternary ammonium, guanidine, biguanidine, imidazole, imino and pyridyl groups.

[0026] The cationic polymer can be selected from cyclic polymers of alkyldiallylamines and cyclic polymers of dialkyldiallylammonium such as (co)polydiallyldialkylammonium chloride, (co)polyamines such as (co)polylysine, cationic (co)polyamino acids such as collagen, cationic cellulose polymers, and their salts.

[0027] In the composition according to the invention, the total amount of the cationic polymer and / or the anionic polymer and / or the amphoteric polymer(s) can be from 0.01% to 15% by weight, preferably 0.03% to 10% by weight, and more preferably 0.05% to 5% by weight, based on the total weight of the composition.

[0028] A non-polymeric acid having two or more pKa values or a salt thereof (one or more) can be an organic acid or a salt thereof (one or more), and is preferably a hydrophilic or water-soluble organic acid or a salt thereof (one or more), and more preferably phytic acid or a salt thereof.

[0029] In the composition according to the invention, the amount of the non-polymeric acid having two or more pKa values or a salt thereof (one or more) or the non-polymeric base having two or more pKb values or a salt thereof (one or more) can be from 0.001% by weight to 15% by weight, preferably from 0.005% by weight to 10% by weight, and more preferably from 0.01% by weight to 5% by weight, based on the total weight of the composition.

[0030] (b) The hydrophilic antioxidant can be selected from ascorbic acid, its derivatives, its salts, and mixtures thereof.

[0031] In the composition according to the invention, the amount of (b) the hydrophilic antioxidant can be from 0.01% by weight to 30% by weight, preferably from 0.05% by weight to 25% by weight, and more preferably from 0.1% by weight to 20% by weight, based on the total weight of the composition.

[0032] (b) The lipophilic antioxidant can be selected from pentaerythritol tetra(2,6-di-tert-butyl-4-hydroxyhydrocinnamate), nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxyanisole, ascorbyl palmitate, tocopherol, and mixtures thereof.

[0033] In the composition according to the invention, the amount of (b) the lipophilic antioxidant can be from 0.001% by weight to 15% by weight, preferably from 0.005% by weight to 10% by weight, and more preferably from 0.01% by weight to 5% by weight, based on the total weight of the composition.

[0034] A second object of the present invention is to provide a method for preparing a film capable of providing a long-lasting antioxidant effect.

[0035] The above object of the present invention can be achieved by a method for preparing a film, preferably a cosmetic film, which method comprises:

[0036] applying the composition according to the invention to a substrate, preferably a keratinous material; and

[0037] drying the composition.

[0038] A third object of the present invention is to provide a film capable of providing a long-lasting antioxidant effect.

[0039] The above object of the present invention can be achieved by the following means:

[0040] (1) A film, preferably a cosmetic film, which is prepared by a method comprising:

[0041] Applying a composition according to the invention to a substrate, preferably a keratinous material; and

[0042] Drying the composition,

[0043] Or

[0044] (2) A film, preferably a cosmetic film, which comprises:

[0045] (a) At least one polyion complex, said polyion complex comprising

[0046] At least one cationic polymer and at least one anionic polymer,

[0047] At least one cationic polymer and at least one amphoteric polymer,

[0048] At least one anionic polymer and at least one amphoteric polymer, or

[0049] At least one amphoteric polymer, and

[0050] At least one non-polymeric acid having two or more pKa values or its (one or more) salts, or

[0051] At least one non-polymeric base having two or more pKb values or its (one or more) salts;

[0052] (b) At least one hydrophilic or lipophilic antioxidant;

[0053] And

[0054] Optionally (d) at least one surfactant, which is preferably selected from non-ionic surfactants, and more preferably selected from polyglycerol fatty acid esters,

[0055] Wherein

[0056] The anionic polymer is selected from hyaluronic acid, its salts, and its derivatives; and

[0057] The amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0058] The present invention also relates to a cosmetic method for keratinous materials such as skin, which comprises:

[0059] Applying a composition according to the invention to the keratinous material; and

[0060] Drying the composition to form a cosmetic film on the keratinous material.

[0061] Best mode for carrying out the invention

[0062] After diligent research, the inventors have found that it is possible to provide a composition that is transparent or translucent, or has lower viscosity, while the composition can provide a lasting antioxidant effect. Thus, the composition according to the invention comprises:

[0063] (a) at least one polyionic complex, which comprises

[0064] at least one cationic polymer and at least one anionic polymer,

[0065] at least one cationic polymer and at least one amphoteric polymer,

[0066] at least one anionic polymer and at least one amphoteric polymer, or

[0067] at least one amphoteric polymer,

[0068] and

[0069] at least one non-polymeric acid having two or more pKa values or its (one or more) salts, or

[0070] at least one non-polymeric base having two or more pKb values or its (one or more) salts;

[0071] (b) at least one hydrophilic or lipophilic antioxidant; and

[0072] (c) water,

[0073] wherein

[0074] the anionic polymer is selected from hyaluronic acid, its salts, and its derivatives, and

[0075] the amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0076] In addition, the inventors have found that it is possible to provide a method for preparing a film that can provide a lasting antioxidant effect. Thus, the method according to the invention is a method for preparing a film (preferably a cosmetic film), which method comprises:

[0077] applying the composition according to the invention onto a substrate, preferably a keratinous material; and

[0078] drying the composition.

[0079] In addition, the inventors have found that it is possible to provide a film that can provide a lasting antioxidant effect.

[0080] Thus, the film according to the invention is

[0081] (1) a film, preferably a cosmetic film, which is prepared by a method comprising the following:

[0082] Apply the composition according to the present invention to a substrate, preferably a keratinous material; and

[0083] Dry the composition,

[0084] Or

[0085] (2) A film, preferably a cosmetic film, comprising:

[0086] (a) At least one polyion complex comprising

[0087] At least one cationic polymer and at least one anionic polymer,

[0088] At least one cationic polymer and at least one amphoteric polymer,

[0089] At least one anionic polymer and at least one amphoteric polymer, or

[0090] At least one amphoteric polymer, and

[0091] At least one non-polymeric acid having two or more pKa values or its salt(s), or

[0092] At least one non-polymeric base having two or more pKb values or its salt(s);

[0093] (b) At least one hydrophilic or lipophilic antioxidant;

[0094] And

[0095] Optionally (d) at least one surfactant, preferably selected from nonionic surfactants, and more preferably selected from polyglycerol fatty acid esters,

[0096] Wherein

[0097] The anionic polymer is selected from hyaluronic acid, its salts, and its derivatives; and

[0098] The amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0099] If at least one hydrophilic antioxidant is used as component (b), the composition and film according to the present invention can be transparent or translucent.

[0100] On the other hand, if at least one lipophilic antioxidant is used as component (b), the viscosity of the composition according to the present invention can be reduced compared to a composition comprising hyaluronic acid that does not form a polyion complex.

[0101] The composition and film according to the present invention can provide a long-lasting antioxidant effect.

[0102] Thus, the present invention can be used to protect the skin from damage caused, for example, by the peroxidation of unsaturated lipids such as sebum, where said damage can be desquamative alterations, squalene reduction, acne and blackheads, skin dullness and aging (such as the formation of wrinkles and / or fine lines).

[0103] Furthermore, the compositions and films according to the present invention can provide long-lasting cosmetic effects and / or improved moisturizing textures based on hyaluronic acid or cationized hyaluronic acid.

[0104] Films comprising polyion complexes can be easily prepared, where the film can include at least one surfactant, by applying the composition to a substrate (preferably a keratinous material such as skin and hair, and more preferably skin) and drying the composition.

[0105] Compared to films of hyaluronic acid that do not form polyion complexes, the stickiness of the films according to the present invention can be reduced.

[0106] The films according to the present invention can be porous. The surface of the films according to the present invention can not be flat, but can be rough.

[0107] The films according to the present invention can have various cosmetic functions. For example, the film can provide a moisturizing effect based on hyaluronic acid or cationized hyaluronic acid in the polyion complex.

[0108] The films according to the present invention are capable of trapping sebum, matting the appearance of keratinous materials (such as skin), absorbing or adsorbing odors and / or protecting keratinous materials from, for example, dirt or contaminants.

[0109] If the film includes at least one cosmetic active ingredient such as (one or more) oils, the film can also have cosmetic effects provided by the (one or more) cosmetic active ingredients. For example, if the polyion complex film contains at least one cosmetic active ingredient selected from UV filters, anti-aging agents other than (b) hydrophilic or lipophilic antioxidants, sebum-control agents, deodorants, antiperspirants, skin-whitening agents, and mixtures thereof, the film can filter ultraviolet rays, treat skin aging, absorb sebum on the skin, control the odor on the skin, control sweating on the skin, and / or whiten the skin.

[0110] The films according to the present invention can be transparent or translucent and thus not easily noticeable even when the film is relatively thick.

[0111] Furthermore, the films according to the present invention are water-resistant and thus can remain on keratinous materials such as skin even if the surface of the keratinous material is wet due to, for example, sweat or rain.

[0112] In addition, the film according to the present invention can be easily removed from keratinous substances such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, but can be easily removed using soap that can provide alkaline conditions.

[0113] Therefore, if the film according to the present invention contains a hydrophilic or water-soluble UV filter, the film according to the present invention can exhibit water resistance (waterproof) and a durable UV shielding effect, but can be easily removed using soap that can provide alkaline conditions.

[0114] Hereinafter, the composition, method, film, etc. according to the present invention will be described in more detail.

[0115] [Polyion complex]

[0116] The composition according to the present invention contains (a) at least one polyion complex. Two or more different types of (a) polyion complexes can be used in combination. Therefore, a single type of (a) polyion complex or a combination of different types of (a) polyion complexes can be used.

[0117] The size of the (a) polyion complex can be from 5 nanometers to 100 micrometers, preferably from 100 nanometers to 50 micrometers, more preferably from 200 nanometers to 40 micrometers, and even more preferably from 500 nanometers to 30 micrometers. Sizes less than 1 micrometer can be measured by dynamic light scattering, and sizes greater than 1 micrometer can be measured by optical microscopy. This size can be based on the number average diameter.

[0118] The amount of the (a) polyion complex(es) in the composition according to the present invention can 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.

[0119] The amount of the (a) polyion complex(es) in the composition according to the present invention can be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less based on the total weight of the composition.

[0120] The amount of the (a) polyion complex(es) in the composition according to the present invention can be from 0.01% by weight to 15% by weight, preferably from 0.05% by weight to 10% by weight, and more preferably from 0.1% by weight to 5% by weight based on the total weight of the composition.

[0121] The (a) polyion complex includes at least one polymer or a combination of polymers. Specifically, the (a) polyion complex includes:

[0122] (1) at least one cationic polymer and at least one anionic polymer;

[0123] (2) At least one cationic polymer and at least one amphoteric polymer;

[0124] (3) At least one anionic polymer and at least one amphoteric polymer; or

[0125] (4) At least one amphoteric polymer.

[0126] There is no restriction on the type of the cationic polymer. Two or more different types of cationic polymers can be used in combination. Therefore, a single type of cationic polymer or a combination of different types of cationic polymers can be used.

[0127] In the above (1), the ratio of the amount (e.g., chemical equivalent) of (one or more) cationic polymer / (one or more) anionic polymer can be 0.05 - 18, preferably 0.1 - 10, and more preferably 0.5 - 5.0. In particular, it can be preferred that the number of cationic groups of (one or more) cationic polymers / the number of anionic groups of (one or more) anionic polymers is 0.05 - 18, more preferably 0.1 - 10, and even more preferably 0.5 - 5.0.

[0128] In the above (2), the ratio of the amount (e.g., chemical equivalent) of (one or more) cationic polymer / (one or more) amphoteric polymer can be 0.05 - 18, preferably 0.1 - 10, and more preferably 0.5 - 5.0. In particular, it can be preferred that the number of cationic groups of (one or more) cationic polymers / the number of cationic and anionic groups of (one or more) amphoteric polymers is 0.05 - 18, more preferably 0.1 - 10, and even more preferably 0.5 - 5.0.

[0129] In the above (3), the ratio of the amount (e.g., chemical equivalent) of (one or more) anionic polymer / (one or more) amphoteric polymer can be 0.05 - 18, preferably 0.1 - 10, and more preferably 0.5 - 5.0. In particular, it can be preferred that the number of anionic groups of (one or more) anionic polymers / the number of cationic and anionic groups of (one or more) amphoteric polymers is 0.05 - 18, more preferably 0.1 - 10, and even more preferably 0.5 - 5.0.

[0130] In the composition according to the present invention, the total amount of (one or more) polymers according to any one of the above (1) to (4) can be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more based on the total weight of the composition.

[0131] In the composition according to the invention, the total amount of the (one or more) polymers according to any one of (1) to (4) above may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0132] In the composition according to the invention, the total amount of the (one or more) polymers according to any one of (1) to (4) above may be from 0.01% by weight to 15% by weight, preferably from 0.03% by weight to 10% by weight, and more preferably from 0.05% by weight to 5% by weight, based on the total weight of the composition.

[0133] (Cationic polymer)

[0134] The cationic polymer has a positive charge density. The charge density of the cationic polymer may be from 0.01 meq / g to 20 meq / g, preferably from 0.05 to 15 meq / g, and more preferably from 0.1 to 10 meq / g.

[0135] 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.

[0136] Unless otherwise defined in the specification, "molecular weight" refers to the number average molecular weight.

[0137] The cationic polymer may have at least one positively chargeable and / or positively charged moiety selected from primary amino, secondary amino or tertiary amino, quaternary ammonium, guanidine, biguanidine, imidazole, imine and pyridine groups. Here, the term (primary) "amino" refers to the -NH2 group.

[0138] The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean copolymers obtained from two monomers and copolymers obtained from more than two monomers, such as terpolymers obtained from three monomers.

[0139] The cationic polymer may be selected from natural and synthetic cationic polymers. Non-limiting examples of cationic polymers are as follows:

[0140] (1) Homopolymers and copolymers derived from acrylic acid or methacrylate and amide and containing at least one unit selected from the units of the following formula:

[0141]

[0142] Wherein:

[0143] R1 and R2, which may be the same or different, are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups;

[0144] R3, which may be the same or different, is selected from hydrogen and CH3;

[0145] The symbol A, which may be the same or different, is selected from straight-chain or branched alkyl groups containing 1 to 6 carbon atoms (e.g., 2 to 3 carbon atoms) and hydroxyalkyl groups containing 1 to 4 carbon atoms;

[0146] R4, R5, and R6, which may be the same or different, are selected from alkyl groups containing 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment, are selected from alkyl groups containing 1 to 6 carbon atoms; and

[0147] X is an anion derived from an inorganic acid or an organic acid, such as a methyl sulfate anion and halogen ions, such as chloride ions and bromide ions.

[0148] The copolymer of family (1) may further comprise at least one unit derived from a comonomer, which may be selected from acrylamide, methacrylamide, diacetone acrylamide, acrylamide and methacrylamide (substituted on the nitrogen atom by (C1-C4) lower alkyl groups), groups derived from acrylic acid or methacrylic acid and their esters, vinyl lactams (such as vinyl pyrrolidone and vinyl caprolactam), and vinyl esters.

[0149] Examples of the copolymer of family (1) include, but are not limited to:

[0150] Copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide;

[0151] Copolymers of acrylamide and methacryloyloxyethyl trimethylammonium chloride as described, for example, in European Patent Application No. 0080976,

[0152] Copolymers of acrylamide and methacryloyloxyethyl trimethyl methyl sulfate;

[0153] Quaternized or non-quaternized copolymers of vinyl pyrrolidone / dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate, such as those described in French Patents Nos. 2077143 and 2393573,

[0154] Dimethylaminoethyl methacrylate / vinyl caprolactam / vinyl pyrrolidone terpolymers,

[0155] Copolymers of vinyl pyrrolidone / methacrylamidopropyl dimethylamine, quaternized copolymers of vinyl pyrrolidone / dimethylaminopropyl methacrylamide, and

[0156] Crosslinked methacryloyloxy (C1-C4) alkyl tri (C1-C4) alkyl ammonium salt polymers, such as polymers obtained by homopolymerizing dimethylaminoethyl methacrylate (quaternized with chloromethane) or copolymerizing acrylamide with dimethylaminoethyl methacrylate (quaternized with chloromethane), and crosslinked with a compound containing ethylenic unsaturation (such as methylene bisacrylamide) after homopolymerization or copolymerization.

[0157] (2) Cationic cellulose polymers, such as cellulose ether derivatives containing one or more quaternary ammonium groups, such as those described in French Patent No. 1492597, such as polymers sold by Union Carbide Corporation under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as the quaternary ammonium of hydroxyethyl cellulose that has reacted with an epoxide substituted with a trimethylammonium group.

[0158] Preferably, the cationic cellulose polymer has at least one quaternary ammonium group, preferably a trialkylammonium group, and more preferably a trimethylammonium group.

[0159] The quaternary ammonium group may be present in a quaternary ammonium group-containing group represented by the following chemical formula (I):

[0160]

[0161] where

[0162] R1 and R2 each represent a C 1-3 alkyl group, preferably a methyl or ethyl group, and more preferably a methyl group,

[0163] R3 represents a C 1-24 alkyl group, preferably a methyl or ethyl group, and more preferably a methyl group, X- represents an anion, preferably a halide ion, and more preferably a chloride ion,

[0164] n represents an integer from 0 to 30, preferably from 0 to 10, and more preferably 0, and

[0165] R4 represents a C 1-4 alkylene group, preferably an ethylene or propylene group.

[0166] The leftmost ether bond (-O-) in the above chemical formula (I) can be connected to the sugar ring of the polysaccharide.

[0167] Preferably, the quaternary ammonium group-containing group is -O-CH2-CH(OH)-CH2-N + (CH3)3.

[0168] (3) Cationic cellulose polymers, such as cellulose copolymers and cellulose derivatives grafted with water-soluble monomers of quaternary ammonium, and described, for example, in U.S. Patent No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl-, hydroxyethyl- and hydroxypropyl celluloses grafted with salts selected from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium salts.

[0169] Commercial products corresponding to these polymers include, for example, those sold by National Starch under the names “ L 200” and “ H 100”.

[0170] (4) Non-cellulose-based cationic polysaccharides described in U.S. Patent Nos. 3,589,578 and 4,031,307, such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid and dextran hydroxypropyltrimethylammonium chloride. Guar gum modified with salts such as 2,3-epoxypropyltrimethylammonium chloride (guar hydroxypropyltrimethylammonium chloride) can also be used.

[0171] These products are sold, for example, by MEYHALL under the trade names C13 S, C 15, C17 and C162.

[0172] (5) Polymers containing piperazinyl units and containing a straight-chain or branched divalent alkylene or hydroxyalkylene group, optionally interrupted by at least one entity selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, and oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French Patent Nos. 2162025 and 2280361.

[0173] (6) Water-soluble polyaminoamides, which are prepared, for example, by polycondensation of acidic compounds with polyamines; these polyaminoamides can be crosslinked with entities selected from the following: epihalohydrin; diepoxides; dianhydrides; unsaturated dianhydrides; bisunsaturated derivatives; dihalohydrins; bisazetidiniums; dihaloacyl diamides; dialkyl halides; oligomers resulting from the reaction of bifunctional compounds resulting from the reaction with entities selected from dihalohydrins, bisazetidiniums, dihaloacyl diamides, dialkyl halides, epihalohydrin, diepoxides and bisunsaturated derivatives; the crosslinking agent is used in an amount of 0.025 to 0.35 moles per amine group of the polyaminoamide; these polyaminoamides are optionally alkylated, or, if they contain at least one tertiary amine functional group, they can be quaternized. Such polymers are described, for example, in French Patent Nos. 2252840 and 2368508.

[0174] (7) Polyaminoamide derivatives, which are produced by condensation of polyalkylene polyamines with polycarboxylic acids and then alkylation with bifunctional reagents, such as adipic acid / dialkylamino hydroxyalkyl diethylene triamine polymers, where the alkyl groups contain 1 to 4 carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene groups contain 1 to 4 carbon atoms, such as the ethylene group. Such polymers are described, for example, in French Patent No. 1583363. In at least one embodiment, these derivatives can be selected from adipic acid / dimethylamino hydroxypropyl diethylene triamine polymers.

[0175] (8) Polymers obtained by reacting a polyalkylene polyamine containing two primary amino groups and at least one secondary amino group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of the polyalkylene polyamine to the dicarboxylic acid can be in the range of 0.8:1 to 1.4:1; the resulting polyaminoamide is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amino groups of the polyaminoamide of 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Patent Nos. 3,227,615 and 2,961,347.

[0176] (9) Cyclic polymers of alkyldiallylamines and cyclic polymers of dialkyldiallyl-ammonium, such as homopolymers and copolymers, which contain at least one unit selected from the units of formula (Ia) and (Ib) as the main component of the chain:

[0177]

[0178] where:

[0179] k and t, which can be the same or different, are equal to 0 or 1, and the sum of k + t is equal to 1;

[0180] R 12 Selected from hydrogen and methyl groups;

[0181] R 10 and R 11 , which may be the same or different, are selected from alkyl groups containing 1 to 6 carbon atoms, hydroxyalkyl groups (wherein the alkyl group contains, for example, 1 to 5 carbon atoms), and lower (C1-C4) amidoalkyl groups, or R 10 and R 11 may together with the nitrogen atom to which they are attached form a heterocyclic group (such as piperidyl and morpholinyl); and

[0182] Y' is an anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, and phosphate. Such polymers are described, for example, in French Patent No. 2080759 and its supplementary certificate 2190406.

[0183] 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.

[0184] Examples of such polymers include, but are not limited to, (co)poly(diallyldialkylammonium chloride), such as the homopolymer of dimethyldiallylammonium chloride (and its homologues of low weight-average molecular weight) sold by CALGON Corporation under the name " 100" and the copolymer of diallyldimethylammonium chloride and acrylamide sold under the name " 550".

[0185] (10) A quaternary ammonium polymer comprising at least one repeating unit of formula (II):

[0186]

[0187] Wherein:

[0188] 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 hydroxyalkylaliphatic groups, or alternatively R 13 、R 14 、R 15 and R 16 may together with the nitrogen atom to which they are attached or individually form a heterocycle which optionally contains a second heteroatom other than nitrogen, or alternatively R 13 、R 14 、R15 and R 16 , which may be the same or different, are selected from linear or branched C1-C6 alkyl groups substituted by at least one group selected from cyano, ester, acyl, amide, -CO-O-R 17 -E groups and -CO-NH-R 17 -E groups, where R 17 is an alkylene group and E is a quaternary ammonium group;

[0189] A1 and B1, which may be the same or different, are selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, be linked to, or inserted in the main chain at least one entity 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, and

[0190] X - is an anion derived from an inorganic or organic acid;

[0191] A1, R 13 and R 15 may together with the two nitrogen atoms to which they are attached form a piperazine ring;

[0192] If A1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, then B1 may be selected from:

[0193] -(CH2) n -CO-E'-OC-(CH2) n -

[0194] where E' is selected from:

[0195] a) a diol residue of the formula -OZO-, where Z is selected from linear or branched, hydrocarbon-based groups and groups of the following formula:

[0196] -(CH2-CH2-O) x -CH2-CH2-

[0197] -[CH2-CH(CH3)-O] y -CH2-CH(CH3)-

[0198] where x and y, which may be the same or different, are selected from integers from 1 to 4, which represent a definite and unique degree of polymerization, and numbers in the range from 1 to 4, which represent an average degree of polymerization;

[0199] b) a bis-secondary diamine residue, such as a piperazine derivative;

[0200] c) a double primary diamine residue of the formula -NH-Y-NH-, where Y is selected from straight-chain or branched, hydrocarbon-based groups and the divalent group -CH2-CH2-S-S-CH2-CH2-; and

[0201] d) a urea group of the formula -NH-CO-NH-.

[0202] In at least one embodiment, X - is an anion, such as chloride or bromide.

[0203] Polymers of this type are described, for example, in French Patent Nos. 2320330; 2270846; 2316271; 2336434; and 2413907 and U.S. Patent Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261,002; 2,271,378; 3,874,870; 4,001,432; 3,929,990; 3,966,904; 4,005,193; 4,025,617; 4,025,627; 4,025,653; 4,026,945; and 4,027,020.

[0204] Non-limiting examples of such polymers include those containing at least one repeating unit of formula (III):

[0205]

[0206] where

[0207] R 13 、R 14 、R 15 and R 16 , which may be the same or different, are selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms, n and p, which may be the same or different, are integers from 2 to 20, and X - is an anion derived from an inorganic or organic acid.

[0208] (11) Polyquaternary ammonium polymers containing units of formula (IV):

[0209]

[0210] where:

[0211] R 18 、R 19 、R 20 and R 21, which may be the same or different, and are selected from hydrogen, methyl group, ethyl group, propyl group, β - hydroxyethyl group, β - hydroxypropyl group, -CH2CH2(OCH2CH2) p OH groups, where p is an integer selected from 0 to 6, provided that R 18 、R 19 、R 20 and R 21 are not simultaneously hydrogen,

[0212] r and s may be the same or different and are selected from integers from 1 to 6,

[0213] q is an integer selected from 0 to 34,

[0214] X - is an anion, such as a halide ion, and

[0215] A is selected from groups of dihalides and -CH2-CH2-O-CH2-CH2-.

[0216] For example, such compounds are described in European Patent Application No. 0122324.

[0217] (12) Quaternary polymer of vinylpyrrolidone and vinylimidazole.

[0218] Other examples of suitable cationic polymers include, but are not limited to, cationic protein hydrolysates and cationic protein hydrolysates, polyalkyleneimines such as polyethyleneimine, polymers containing units selected from vinylpyridine and vinylpyridinium units, condensates of polyamine and epichlorohydrin, quaternary polyurea and chitin derivatives.

[0219] According to one embodiment of the present invention, the at least one cationic polymer is selected from cellulose ether derivatives containing quaternary ammonium groups, such as the product sold by UNION CARBIDE CORPORATION under the name "JR400", cationic cyclic polymers, such as those sold by CALGON under the name 100, 550 and S, homopolymers and copolymers of dimethyldiallylammonium chloride, guar gum modified with 2,3 - epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0220] (13) Polyamine

[0221] As a cationic polymer, a (co)polyamine can also be used, which can be a homopolymer or copolymer having a plurality of amino groups. The amino groups can be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone or side groups (if any) of the (co)polyamine.

[0222] As examples of the (co)polyamine, chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)poly(dimethylaminoethyl methacrylate), (co)polyvinylpyridine (such as (co)poly-1-methyl-2-vinylpyridine), (co)polyimine (such as (co)polyethyleneimine), (co)polypyridine (such as (co)poly(quaternary pyridine)), (co)polybiguanide (such as (co)polyaminopropyl biguanide), (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminoglucan, aminocellulose, amino (co)polyvinyl acetal, and salts thereof can be mentioned.

[0223] As the (co)polyamine, (co)polylysine is preferably used. 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, such as ε-poly-L-lysine, which is commonly used as a natural preservative in foods. 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 solution.

[0224] (14) Cationic polyamino acid

[0225] As a cationic polymer, a cationic polyamino acid may be used, which can be a cationic homopolymer or copolymer having a plurality of amino groups and carboxyl groups. The amino groups can be primary amino groups, secondary amino groups, tertiary amino groups or quaternary amino groups. The amino groups may be present in the polymer backbone or side groups (if any) of the cationic polyamino acid. The carboxyl groups may be present in the side groups (if any) of the cationic polyamino acid.

[0226] As examples of the cationic polyamino acid, cationized collagen, cationized gelatin, steardimonium hydroxyprolyl hydrolyzed wheat protein, coco dimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyl trimonium hydrolyzed conchiolin, steardimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyl trimonium hydrolyzed soy protein, coco dimonium hydroxypropyl hydrolyzed soy protein, etc. can be mentioned.

[0227] The following description relates to preferred embodiments of cationic polymers.

[0228] Preferably, the cationic polymer is selected from cationic starches.

[0229] As an example of a cationic starch, mention may be made of starch modified with 2,3-epoxypropyltrimethylammonium salts (such as chlorides), such as starch hydroxypropyltrimethylammonium chloride according to INCI nomenclature and sold by Ondeo under the name SENSOMER Cl-50 or by Ingredion under the name Pencare TM DP 1015.

[0230] Also preferably, the cationic polymer is selected from cationic gums.

[0231] For example, the gum may be selected from cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, gum arabic and acacia gum.

[0232] Examples of cationic gums include cationic polygalactomannan derivatives, such as guar gum derivatives and cassia gum derivatives, such as CTFA: guar gum hydroxypropyltrimethylammonium chloride, hydroxypropyl guar gum hydroxypropyltrimethylammonium chloride and cassia gum hydroxypropyltrimethylammonium chloride. Guar gum hydroxypropyltrimethylammonium chloride is commercially available from Rhodia Inc. under the Jaguar TM product name series and from Ashland Inc. under the N-Hance product name series. Cassia gum hydroxypropyltrimethylammonium chloride is commercially available from Lubrizol Advanced Materials, Inc under the Sensomer TM CT-250 and Sensomer TM CT-400 trademarks or from Ashland Inc. under the ClearHance TM trade name.

[0233] Also preferably, the cationic polymer is selected from chitosan.

[0234] More preferably, the cationic polymer is selected from cyclic polymers of alkyldiallylamines and cyclic polymers of dialkyldiallylammonium such as (co)poly(diallyldialkylammonium chloride), (co)polyamines such as (co)polylysine, cationic (co)polyamino acids such as cationized collagen, cationic cellulose polymers and their salts.

[0235] Even more preferably, the cationic polymer is selected from polylysine, polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimethyl ammonium chloride, cinnamyl hydroxypropyltrimethyl ammonium chloride, chitosan, and mixtures thereof.

[0236] In the composition according to the present invention, the amount of the (one or more) cationic polymer may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, based on the total weight of the composition.

[0237] In the composition according to the present invention, the amount of the (one or more) cationic polymer may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0238] In the composition according to the present invention, the amount of the (one or more) cationic polymer may be from 0.01% by weight to 15% by weight, preferably from 0.03% by weight to 10% by weight, and more preferably from 0.05% by weight to 5% by weight, based on the total weight of the composition.

[0239] (anionic polymer)

[0240] The anionic polymer has a positive charge density. If the anionic polymer is a synthetic anionic polymer, the charge density of the anionic polymer may be from 0.1 meq / g to 20 meq / g, preferably from 1 to 15 meq / g, and more preferably from 4 to 10 meq / g; and if the anionic polymer is a natural anionic polymer, the average degree of substitution of the anionic polymer may be from 0.1 to 3.0, preferably from 0.2 to 2.7, and more preferably from 0.3 to 2.5.

[0241] Preferably, 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, and even more preferably 1,000,000 or more.

[0242] Unless otherwise defined in the specification, "molecular weight" may refer to the number average molecular weight.

[0243] According to the present invention, the anionic polymer is selected from hyaluronic acid, its salts, and derivatives thereof.

[0244] Hyaluronic acid can be represented by the following chemical formula.

[0245]

[0246] In the context of the present invention, the term "hyaluronic acid" particularly encompasses the basic units of hyaluronic acid of the following formula:

[0247]

[0248] This is the smallest part of hyaluronic acid containing disaccharide dimers (i.e., D-glucuronic acid and N-acetylglucosamine).

[0249] In the context of the present invention, the term "derivatives" of hyaluronic acid includes linear polymers containing the above-mentioned polymerization units, linked together in the chain by alternating β(1,4) and β(1,3) glycosidic bonds, having a molecular weight (MW) between 380 and 13,000,000 daltons. This molecular weight depends to a large extent on the source from which the hyaluronic acid is obtained and / or the preparation method.

[0250] In the context of the present invention, the term "salts" of hyaluronic acid includes any salts of hyaluronic acid. As salts, alkali metal salts (such as sodium salts and potassium salts), alkaline earth metal salts (such as magnesium salts, ammonium salts), and mixtures thereof can be cited.

[0251] In its natural state, hyaluronic acid is present in the pericellular gel, the ground substance of connective tissues of vertebrate organs (such as dermis and epithelial tissues), and particularly in the epithelium, synovial fluid of joints, vitreous body, in the human umbilical cord, and in the crista galli apophysis of chickens.

[0252] Therefore, the term "hyaluronic acid" encompasses all fractions or subunits of hyaluronic acid having a molecular weight particularly within the above-mentioned molecular weight range.

[0253] In the context of the present invention, hyaluronic acid fractions without inflammatory activity are preferably used.

[0254] For the description of various hyaluronic acid fractions, reference can be made to the document "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) 699 - 715, which reviews the biological activities of hyaluronic acid listed according to its molecular weight.

[0255] According to a preferred embodiment of the present invention, the hyaluronic acid fraction suitable for the uses covered by the present invention has a molecular weight of 50 kDa to 5000 kDa, particularly 100 kDa to 5000 kDa, especially 400 kDa to 5000 kDa. In this case, the term used is high molecular weight hyaluronic acid.

[0256] Alternatively, a hyaluronic acid fraction suitable for the uses covered by the present invention has a molecular weight of from 50 kDa to 400 kDa. In this case, the term used is hyaluronic acid of medium molecular weight.

[0257] Alternatively, a hyaluronic acid fraction suitable for the uses covered by the present invention has a molecular weight of less than 50 kDa. In this case, the term used is hyaluronic acid of low molecular weight.

[0258] It may be preferred to use a combination of two or more hyaluronic acids or salts thereof, such as a combination of high molecular weight hyaluronic acid or a salt thereof with medium molecular weight hyaluronic acid or a salt thereof; a combination of high molecular weight hyaluronic acid or a salt thereof with low molecular weight hyaluronic acid or a salt thereof; and a combination of medium molecular weight hyaluronic acid or a salt thereof with low molecular weight hyaluronic acid or a salt thereof.

[0259] Finally, the term "derivatives" of hyaluronic acid also includes hyaluronic acid esters, in particular those in which all or some of the acid-functional carboxyl groups are esterified with oxyethylated alkyl or alcohols containing from 1 to 20 carbon atoms, especially with a degree of substitution at the level of D-glucuronic acid of hyaluronic acid of from 0.5% to 50%.

[0260] Methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid may be mentioned in particular. Such esters are described in particular in D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) 2101-2127.

[0261] Hyaluronic acid derivatives may be, for example, acetylated hyaluronic acid or a salt thereof.

[0262] The molecular weights indicated above are also valid for hyaluronic acid esters.

[0263] Hyaluronic acid may be in particular hyaluronic acid provided by Hyactive under the trade name CPN (MW: 10 to 150 kDa), by Soliance under the trade name Cristalhyal (MW: 1.1×10 6 )), by Bioland under the name Nutra HA (MW: 820000 Da), by Bioland under the name Nutra AF (MW: 69000 Da), by Bioland under the name Oligo HA (MW: 6100 Da) or by VamFarmacos Metica under the name D Factor (MW: 380 Da).

[0264] In the composition according to the invention, the amount of the (one or more) anionic polymer(s) can be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, based on the total weight of the composition.

[0265] In the composition according to the invention, the amount of the (one or more) anionic polymer(s) can be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0266] In the composition according to the invention, the amount of the (one or more) anionic polymer(s) can be from 0.01% by weight to 15% by weight, preferably from 0.03% by weight to 10% by weight, and more preferably from 0.05% by weight to 5% by weight, based on the total weight of the composition.

[0267] (Amphoteric polymer)

[0268] The amphoteric polymer has both a positive charge density and a negative charge density.

[0269] The positive charge density of the amphoteric polymer can be from 0.01 meq / g to 20 meq / g, preferably from 0.05 to 15 meq / g, and more preferably from 0.1 to 10 meq / g.

[0270] The negative charge density of the amphoteric polymer can be from 0.01 meq / g to 20 meq / g, preferably from 0.05 to 15 meq / g, and more preferably from 0.1 to 10 meq / g.

[0271] It can be preferred that the molecular weight of the amphoteric polymer is 500 or greater, preferably 1,000 or greater, more preferably 10,000 or greater, and even more preferably 100,000 or greater.

[0272] It can be preferred that the molecular weight of the amphoteric polymer is 1,000,000 or less, preferably 900,000 or less, and more preferably 800,000 or less.

[0273] Unless otherwise defined in the specification, "molecular weight" can refer to the number-average molecular weight.

[0274] According to the invention, the amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0275] Cationized hyaluronic acid contains at least one cationic group, such as an ammonium group, in its molecule. The cationic group does not indicate the counter cation of the salt, as the counter cation is not in the molecule of hyaluronic acid.

[0276] As salts, mention may be made of alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

[0277] The cationized hyaluronic acid may have at least one quaternary ammonium group-containing group.

[0278] The cationized hyaluronic acid and / or its salt may have a structure represented by the following general formula (1):

[0279]

[0280] wherein

[0281] R 4 -R 9 each represent a hydrogen atom or a quaternary ammonium group-containing group (excluding the case where all of R 4 to R 9 represent hydrogen atoms), and n represents an integer from 2 to 5000.

[0282] In the above general formula (1), examples of the quaternary ammonium group-containing group represented by R 4 to R 9 include a group represented by the following general formula (2):

[0283]

[0284] wherein

[0285] R 1 to R 3 each represent a hydrocarbon group, and X - represents a monovalent anion.

[0286] In the above general formula (2), examples of the hydrocarbon group represented by R 1 to R 3 include linear or branched alkyl groups, unsaturated hydrocarbon groups, and aromatic hydrocarbon groups. Among these, alkyl groups are preferred. Examples of the alkyl group include an alkyl group having 1 to 30 (preferably 1 to 6) carbon atoms. More preferably, the hydrocarbon group represented by R 1 to R 3 is an alkyl group having 1 to 3 carbon atoms.

[0287] In the above general formula (2), examples of the monovalent anion represented by X - include halogen ions such as fluoride ion, bromide ion, chloride ion, and iodide ion.

[0288] The quaternary ammonium group-containing group can be introduced by substituting the hydrogen atom of the carboxyl group included in the hyaluronic acid and / or its salt (hereinafter may be referred to as "raw material hyaluronic acid and / or its salt") used as a raw material with a quaternary ammonium group-containing group. In this case, the quaternary ammonium group-containing group binds to the oxygen atom of the group (-C(=O)O-) included in the cationized hyaluronic acid and / or its salt according to the present embodiment. The fact that the quaternary ammonium group-containing group binds to the oxygen atom of the group (-C(=O)O-) included in the cationized hyaluronic acid and / or its salt according to the present embodiment can be confirmed by the presence of a peak attributed to the carbon atom of the -C(=O)O- group (the quaternary ammonium group-containing group binds to it through an oxygen atom), which is determined by analyzing the chemical shift of the nuclear magnetic resonance ( 13 C NMR) spectrum.

[0289] Specifically, the quaternary ammonium group-containing group can be obtained by reacting the carboxyl group (and / or hydroxyl group) of the 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 represented by the following general formula (3) and 3-halo-2-hydroxypropyltrialkylammonium halide represented by the following general formula (4). The reaction of the raw material hyaluronic acid and / or its salt with the cationizing agent is described in the following manufacturing method.

[0290]

[0291] Wherein

[0292] R 1 to R 3 are the same as those defined in the general formula (2), and X represents a halogen atom.

[0293]

[0294] Wherein

[0295] R 1 to R 3 are the same as those defined in the general formula (2), and X and Y each represent a halogen atom.

[0296] 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.

[0297] The cationized hyaluronic acid can have at least 1 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.

[0298] The degree of cationization of the cationized hyaluronic acid and / or its salt according to the present embodiment (i.e., the degree of substitution of the quaternary ammonium group-containing group) can be determined as follows: Calculate 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 calculate the degree of cationization based on the increase in nitrogen content through the following expression.

[0299] When the nitrogen content of the raw material sodium hyaluronate is denoted as N N (%), and the nitrogen content of the cationized hyaluronic acid with a degree of cationization (x) is denoted as N S (%), the relationship between the increase in nitrogen content (N S -N N ) and the degree of cationization (x) is represented by the following expression.

[0300] N S -N N (%)

[0301] =[14x / (molecular weight of the disaccharide unit of the cationized hyaluronic acid)]×100

[0302] =[14x / (molecular weight of the disaccharide unit of the raw material sodium hyaluronate)+129.5x]×100

[0303] =[14x / (401.3+129.5x)]×100

[0304] Therefore, the degree of cationization (i.e., the degree of substitution of the quaternary ammonium group-containing group) can be calculated by the following expression.

[0305] Degree of cationization (x)=[(N S -N N )×401.3] / [1400-129.5*(N S -N N )].

[0306] Assuming that the raw material sodium hyaluronate is sodium hyaluronate with a purity of 99% or higher, the degree of cationization of the cationized hyaluronic acid when the raw material hyaluronic acid is unknown can be calculated by the above expression.

[0307] It is possible that 1% or more, preferably 5% or more, and more preferably 10% or more and / or 50% or less, preferably 40% or less, and more preferably 30% or less of the anionic groups in the hyaluronic acid are substituted by cationic groups, preferably quaternary ammonium group-containing groups, and more preferably quaternary ammonium group-containing groups represented by the above general formula (2).

[0308] As the cationized hyaluronic acid, mention may be made of hydroxypropyltrimethylammonium hyaluronic acid sold by Kewpie of Japan under the names Hyaloveil and Hyaloveul-MPF.

[0309] In the composition according to the invention, the amount of the (one or more) amphoteric polymers may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, based on the total weight of the composition.

[0310] In the composition according to the invention, the amount of the (one or more) amphoteric polymers may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0311] In the composition according to the invention, the amount of the (one or more) amphoteric polymers may be from 0.01% by weight to 15% by weight, preferably from 0.03% by weight to 10% by weight, and more preferably from 0.05% by weight to 5% by weight, based on the total weight of the composition.

[0312] (Non-polymeric acid having two or more acid dissociation constants)

[0313] The composition according to the invention may comprise at least one non-polymeric acid having two or more pKa values or its (one or more) salts, i.e., at least one non-polymeric acid having two or more acid dissociation constants or its (one or more) salts. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be measured at a constant temperature such as 25°C.

[0314] The non-polymeric acid having two or more pKa values or its (one or more) salts may be included in (a) polyion complex. The non-polymeric acid having two or more pKa values may act as a crosslinking agent for the cationic polymer and / or the amphoteric polymer, particularly an anionic crosslinking agent.

[0315] Preferably, the non-polymeric acid having two or more pKa values or its (one or more) salts is used together with the cationic polymer and the anionic polymer.

[0316] The term "non-polymeric" as used herein means that the acid is not obtained by polymerizing two or more monomers. Thus, the non-polymeric acid does not correspond to an acid obtained by polymerizing two or more monomers, such as a polycarboxylic acid.

[0317] Preferably, the non-polymeric acid having two or more pKa values or its (one or more) salts has a molecular weight of 1000 or less, preferably 800 or less, and more preferably 700 or less.

[0318] There is no limitation on the type of non-polymeric acid having two or more pKa values or its (one or more) salts. Two or more different types of non-polymeric acids having two or more pKa values or their salts can be used in combination. Thus, a single type of non-polymeric acid having two or more pKa values or its salt, or a combination of different types of non-polymeric acids having two or more pKa values or their salts can be used.

[0319] The term "salt" as used herein refers to a salt formed by adding a suitable (one or more) base to a non-polymeric acid having two or more pKa values, which can be obtained by reacting a non-polymeric acid having two or more pKa values with a (one or more) base according to methods known to those skilled in the art. As salts, mention may be made of 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.

[0320] The non-polymeric acid having two or more pKa values or its (one or more) salts can be an organic acid or its (one or more) salts, and is preferably a hydrophilic or water-soluble organic acid or its (one or more) salts.

[0321] The non-polymeric acid having two or more pKa values can have at least two acid groups selected from carboxyl, sulfate, sulfonic acid, phosphoric acid, phosphonic acid, phenolic hydroxyl, and mixtures thereof.

[0322] The non-polymeric acid having two or more pKa values can be a non-polymeric polyvalent acid.

[0323] The non-polymeric acid having two or more pKa values can be selected from dicarboxylic acids, disulfonic acids, and diphosphoric acids, and mixtures thereof.

[0324] The non-polymeric acid having two or more pKa values or its (one or more) salts may be selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid, and their salts; aspartic acid, glutamic acid, and their salts; terephthalylidene dicamphor sulfonic acid or its salt (Mexoryl SX), benzophenone-9; phytic acid and its salts; Red 2 (Amaranth), Red102 (New Coccine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brilliant Blue FCF), Blue 2 (Indigo Carmine), Red 201 (Lithol Rubine B), Red 202 (Lithol Rubine BCA), Red 204 (Lake Red CBA), Red206 (Lithol Red CA), Red207 (Lithol Red BA), Red 208 (Lithol Red SR), Red219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 227 (Fast Acid Magenta), Yellow 203 (Quinoline Yellow WS), Green201 (Alizanine Cyanine Green F), Green 204 (Pyranine Conc), Green 205 (Light Green SF Yellowish), Blue 203 (Patent Blue CA), Blue 205 (Alfazurine FG), Red 401 (Violamine R), Red 405 (Permanent Re F5R), Red502 (Ponceau 3R), Red503 (Ponceau R), Red 504 (Ponceau SX), Green401 (Naphtol Green B), Green402 (Guinea Green B) and Black401 (Naphtol Blue Black); folic acid, ascorbic acid, isoascorbic acid and their salts; cystine and its salts; EDTA and its salts; glycyrrhizin and its salts; and mixtures thereof.

[0325] Preferably, the non-polymeric acid having two or more pKa values or its (one or more) salts are selected from terephthalylidene dicamphor sulfonic acid and its salts (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salts, and mixtures thereof.

[0326] In the composition according to the invention, the amount of the non-polymeric acid having two or more pKa values or its (one or more) salts may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, based on the total weight of the composition.

[0327] In the composition according to the invention, the amount of the non-polymeric acid having two or more pKa values or its (one or more) salts may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0328] In the composition according to the invention, the amount of the non-polymeric acid having two or more pKa values or its salts may be 0.001% by weight to 15% by weight, preferably 0.005% by weight to 10% by weight, and more preferably 0.01% by weight to 5% by weight, based on the total weight of the composition.

[0329] (Non-polymeric base having two or more base dissociation constants)

[0330] The composition according to the invention may comprise at least one non-polymeric base having two or more pKb values or its (one or more) salts, i.e., at least one non-polymeric base having two or more base dissociation constants or its (one or more) salts. The pKb value (base dissociation constant) is well known to those skilled in the art and should be measured at a constant temperature such as 25 °C.

[0331] The non-polymeric base having two or more pKb values or its (one or more) salts may be included in (a) polyion complex. The non-polymeric base having two or more pKb values may act as a crosslinking agent for anionic polymers and / or amphoteric polymers, especially a cationic crosslinking agent.

[0332] Preferably, the non-polymeric acid having two or more pKb values or its (one or more) salts is used together with a cationic polymer and an anionic polymer.

[0333] The term "non-polymeric" herein means 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).

[0334] Preferably, the non-polymeric base having two or more pKb values or its (one or more) salts have a molecular weight of 1000 or less, preferably 800 or less, and more preferably 700 or less.

[0335] There is no limitation on the type of non-polymeric base having two or more pKb values or its (one or more) salts. Two or more different types of non-polymeric bases having two or more pKb values or their salts can be used in combination. Thus, a single type of non-polymeric base having two or more pKb values or its salt or a combination of different types of non-polymeric bases having two or more pKb values or their salts can be used.

[0336] The term "salt" as used herein refers to a salt formed by adding a suitable (one or more) acid to a non-polymeric base having two or more pKb values, which can be obtained by reacting the non-polymeric base having two or more pKb values with the (one or more) acid according to methods known to those skilled in the art. As salts, ammonium salts can be mentioned, such as salts with inorganic acids such as HCl and HNO3, and salts with organic acids such as carboxylic acids and sulfonic acids.

[0337] The non-polymeric base having two or more pKb values or its (one or more) salts can be an organic base or its (one or more) salts, and preferably a hydrophilic or water-soluble organic base or its (one or more) salts.

[0338] The non-polymeric base having two or more pKb values can have at least two basic groups selected from amino, guanidino, biguanidino, imidazolyl, imino, pyridyl, and mixtures thereof.

[0339] The non-polymeric base having two or more pKb values can be selected from non-polymeric diamines such as ethylenediamine, propylenediamine, pentamethylenediamine, hexamethylenediamine, urea and its derivatives, and guanidine and its derivatives, non-polymeric polyamines such as spermine and spermidine, basic amino acids, and mixtures thereof.

[0340] The non-polymeric base having two or more pKb values or its (one or more) salts can be selected from arginine, lysine, histidine, cysteine, cystine, tyrosine, tryptophan, ornithine, and mixtures thereof.

[0341] It can be preferred that the non-polymeric base having two or more pKb values or its (one or more) salts are selected from arginine, lysine, histidine, and mixtures thereof.

[0342] The amount of the non-polymeric base having two or more pKb values or its (one or more) salts in the composition according to the present invention can be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more based on the total weight of the composition.

[0343] The amount of the non-polymeric base having two or more pKb values or its (one or more) salts in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0344] The amount of the non-polymeric base having two or more pKb values or its (one or more) salts in the composition according to the present invention may be from 0.001% by weight to 15% by weight, preferably from 0.005% by weight to 10% by weight, and more preferably from 0.01% by weight to 5% by weight, based on the total weight of the composition.

[0345] [Hydrophilic antioxidant]

[0346] The composition according to the present invention may include, as component (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.

[0347] According to the present invention, an antioxidant is a compound or substance capable of scavenging various free radical forms that may be present in the skin; preferably, they scavenge all the various free radical forms present simultaneously.

[0348] (b) A hydrophilic antioxidant means that the partition coefficient of the antioxidant between n-butanol and water is <1, more preferably <0.5, and even more preferably <0.1.

[0349] Preferably, (b) the hydrophilic antioxidant is selected from ascorbic acid, its derivatives, its salts, and mixtures thereof.

[0350] As a derivative of ascorbic acid, for example, ascorbyl glucoside may be mentioned. The term "ascorbyl glucoside" should be understood to mean a condensation product of glucose in the D configuration (i.e., α- or β-glucopyranose or α- or β-fructofuranose configuration) or L configuration with ascorbic acid (preferably in the L configuration). L-ascorbic acid 2-O-α-D-glucopyranoside may be preferably used in the present invention. It is particularly available from Hayashibara.

[0351] As an example of a derivative of ascorbic acid, ethers of ascorbic acid may also be mentioned. The ether of ascorbic acid may be an alkyl ether of ascorbic acid, such as ethyl ascorbic acid, especially 3-O-ethyl ascorbic acid.

[0352] As a salt of ascorbic acid, metal salts of ascorbic acid may be mentioned, such as sodium ascorbate, magnesium ascorbyl phosphate, and sodium ascorbyl phosphate.

[0353] Preferably, (b) the hydrophilic antioxidant is selected from ascorbic acid, ascorbyl glucoside, ethyl ascorbic acid, sodium ascorbate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, and mixtures thereof.

[0354] In the composition according to the invention, the amount of (one or more) hydrophilic antioxidants (b) can 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.

[0355] In the composition according to the invention, the amount of (one or more) hydrophilic antioxidants (b) can be 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less, based on the total weight of the composition.

[0356] In the composition according to the invention, the amount of (one or more) hydrophilic antioxidants (b) can be from 0.01% by weight to 30% by weight, preferably from 0.05% by weight to 25% by weight, and more preferably from 0.1% by weight to 20% by weight, based on the total weight of the composition.

[0357] [Lipophilic antioxidant]

[0358] The composition according to the invention can include, as component (b), at least one lipophilic antioxidant. Two or more lipophilic antioxidants can be used in combination. Thus, a single type of lipophilic antioxidant or a combination of different types of lipophilic antioxidants can be used.

[0359] According to the invention, antioxidants are compounds or substances capable of scavenging various free radical forms that may be present in the skin; preferably, they scavenge all the various free radical forms present simultaneously.

[0360] (b) A lipophilic antioxidant means that the partition coefficient of the antioxidant between n-butanol and water is >1, more preferably >10, and even more preferably >100.

[0361] (b) Lipophilic antioxidants are hydrophobic, as opposed to hydrophilic antioxidants such as ascorbic acid or glutathione.

[0362] As (b) lipophilic antioxidants, phenolic antioxidants can be mentioned, which have a hindered phenol structure or a semi-hindered phenol structure within the molecule. As specific examples of such compounds, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, whose INCI name is pentaerythritol tetra(2,6-di-tert-butyl-4-methylhydrocinnamate), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono- or di- or tri-(α-methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tris[N-(3,5-di-tert-butyl-4-hydroxybenzyl)]isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, butylene-1,1-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)]-1,3,5-triazine-2,4,6-trione, 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate, 4,6-bis[(octylthio)methyl]-o-cresol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] can be mentioned.

[0363] As (b) lipophilic antioxidants, BHA (butylated hydroxyanisole) and BHT (butylated hydroxytoluene), vitamin E (or tocopherols and tocotrienols) and their derivatives (such as phosphate derivatives, such as those sold by Showa Denko KK under ) can be mentioned, coenzyme Q10 (or ubiquinone), idebenone, certain carotenoids (such as lutein, astaxanthin, β-carotene), polyphenols, phenolic acids and derivatives (such as chlorogenic acid) and flavonoid compounds, which represent the main subclasses of polyphenols.

[0364] Among the flavonoid compounds, mention may be made in particular of chalcones, hydroxylated chalcones and their reduced derivatives (such as those described in particular in patent FR2608150), such as phloretin, neohesperidin, phloridzin, aspalathin, etc.; flavanones, such as hesperetin and naringin; flavonols, such as quercetin, rutin; flavanols, such as catechin, EGCG; flavones, such as apigenin; and finally anthocyanins. Mention may also be made of tannins. Reference may also be made to the compounds described in patent applications FR2699818, FR2706478, FR2907339, FR2814943 and FR2873026.

[0365] The polyphenol compounds may in particular be derived from plant extracts selected from green tea, apple, hops, guava, cocoa, or extracts of wood (such as chestnut, oak, horse chestnut or hazel). Extracts of pinaster bark may also be used (such as those obtained according to the methods described in US Patent No. 4,698,360, US Patent No. 6,372,266 and US Patent No. 5,720,956). As examples of such extracts, mention may be made of the compounds designated by the INCI name Pinus pinaster (bark extract) and the CTFA name Pine (Pinus pinaster) bark extract. In particular, it may be a pinaster bark extract sold by BIOLANDES AROMES and / or HORPHAG Research under name. Mention may also be made of (coastal) pine bark extracts from LAYN Natural Ingredients, pine bark extracts from Blue California and also from D.R.T. (Les Derives Resiniques et Terpeniques)

[0366] Thus, in the context of the present invention, the term "polyphenol compound" also encompasses the plant extracts themselves which are rich in these polyphenol compounds.

[0367] Also mentionable (b) lipophilic antioxidants include dithiolanes, such as asparagusic acid, or derivatives thereof, such as silicon-containing dithiolane derivatives, especially those described in patent application FR 2908769.

[0368] Also mentionable (b) lipophilic antioxidants include:

[0369] Glutathione and its derivatives (GSH and / or GSHOEt), such as glutathione alkyl esters (such as those described in patent applications FR2704754 and FR 2908769); and

[0370] Cysteine and its derivatives, such as N-acetylcysteine or L-2-oxothiazolidine-4-carboxylic acid. Reference can also be made to the cysteine derivatives described in patent applications FR 2877004 and FR 2854160; and

[0371] Ferulic acid and its derivatives (esters, salts, etc.). Especially mentionable are the esters of ferulic acid with C1-C30 alcohols, especially methyl ferulate, ethyl ferulate, isopropyl ferulate, octyl ferulate and oryzanol ferulate;

[0372] Certain enzymes for defense against oxidative stress, such as catalase, superoxide dismutase (SOD), lactoperoxidase, glutathione peroxidase and quinone reductase;

[0373] Benzylcycloketones; substituted naphthones; pidolates (as described especially in patent application EP 0511118); caffeic acid and its derivatives, γ-oryzanol; melatonin, sulforaphane and extracts containing it (excluding watercress);

[0374] The diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, especially as described in patent applications WO 94 / 11338, FR 2698095, FR 2737205 or EP 0755925; and

[0375] Deferoxamine (or desferrioxamine), as described in patent application FR 2825920.

[0376] Preferred (b) lipophilic antioxidants to be used are chalcones, more specifically phloretin or neohesperidin, the diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, or a maritime pine bark extract, such as

[0377] As examples of (b) lipophilic antioxidants, mention may be made of pentaerythritol tetra(di-tert-butylhydroxyhydrocinnamate), nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxyanisole, ascorbyl palmitate, tocopherols, and mixtures thereof.

[0378] In the composition according to the invention, the amount of (b) one or more lipophilic antioxidants may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, based on the total weight of the composition.

[0379] In the composition according to the invention, the amount of (b) one or more lipophilic antioxidants may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0380] In the composition according to the invention, the amount of (b) one or more lipophilic antioxidants may be from 0.001% by weight to 15% by weight, preferably from 0.005% by weight to 10% by weight, and more preferably from 0.01% by weight to 5% by weight, based on the total weight of the composition.

[0381] [Water]

[0382] The composition according to the invention comprises (c) water.

[0383] 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.

[0384] The amount of (c) water may be 99% by weight or less, preferably 97% by weight or less, and more preferably 95% by weight or less, based on the total weight of the composition.

[0385] The amount of (c) water may be from 10% by weight to 99% by weight, preferably from 30% by weight to 97% by weight, and more preferably from 50% by weight to 95% by weight, based on the total weight of the composition.

[0386] [Surfactant]

[0387] The composition according to the 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.

[0388] The surfactants used in the present invention may be selected from anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.

[0389] [Anionic surfactant]

[0390] The composition according to the present invention may comprise at least one anionic surfactant. Two or more anionic surfactants may be used in combination.

[0391] Preferably, the anionic surfactant is selected from (C6-C 30 ) alkyl sulfates, (C6-C 30 ) alkyl ether sulfates, (C6-C 30 ) alkyl amide ether sulfates, alkyl aryl polyether sulfates, monoglyceride sulfates; (C6-C 30 ) alkyl sulfonates, (C6-C 30 ) alkyl amide sulfonates, (C6-C 30 ) alkyl aryl sulfonates, α-olefin sulfonates, paraffin sulfonates; (C6-C 30 ) alkyl phosphates; (C6-C 30 ) alkyl sulfosuccinates, (C6-C 30 ) alkyl ether sulfosuccinates, (C6-C 30 ) alkyl amide sulfosuccinates; (C6-C 30 ) alkyl sulfonacetates; (C6-C 24 ) acyl sarcosinates; (C6-C 24 ) acyl glutamates; (C6-C 30 ) alkylpolyglycoside carboxylic ethers; (C6-C 30 ) alkylpolyglycoside sulfosuccinates; (C6-C 30 ) alkyl sulfosuccinamates; (C6-C 24 ) acyl hydroxyethyl sulfonates; N-(C6-C 24 ) acyl taurates; C6-C 30 fatty acid salts; coconut oil salts or hydrogenated coconut oil salts; (C8-C 20 ) acyl lactates; (C6-C 30 ) alkyl-D-galactoside uronates; polyoxyalkylenated (C6-C 30 ) alkyl ether carboxylates; polyoxyalkylenated (C6-C 30 ) alkyl aryl ether carboxylates; and polyoxyalkylenated (C6-C 30 ) alkyl amide ether carboxylates; and the corresponding acid forms.

[0392] In at least one embodiment, the anionic surfactant is in the form of a salt, such as a salt of an alkali metal such as sodium; a salt of an alkaline earth metal such as magnesium; an ammonium salt; an amine salt; and an amino alcohol salt. Optionally, they may also be in the form of an acid.

[0393] More preferably, the anionic surfactant is selected from (C6-C 30 ) alkyl sulfates, (C6-C 30 ) alkyl ether sulfates or polyoxyalkylenated (C6-C 30 ) alkyl ether carboxylic acids, either in salt form or non-salted form.

[0394] (Amphoteric surfactant)

[0395] The composition according to the invention may comprise at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.

[0396] The amphoteric or zwitterionic surfactant may be, for example (non-limiting list), amine derivatives such as aliphatic secondary or tertiary amines, and optionally quaternized amine derivatives, wherein the aliphatic group is a straight or branched chain comprising 8 to 22 carbon atoms and contains at least one water-soluble anionic group (e.g., carboxylate, sulfonate, sulfate, phosphate or phosphonate).

[0397] The amphoteric surfactant may preferably be selected from betaines and amidoamine carboxylated derivatives.

[0398] Preferably, the amphoteric surfactant is selected from betaine-type surfactants.

[0399] The betaine-type amphoteric surfactant is preferably selected from alkyl betaines, alkylamidoalkyl betaines, sulfobetaines, phosphobetaines and alkylamidoalkyl sulfobetaines, especially (C8-C 24 ) alkyl betaines, (C8-C 24 ) alkylamido (C1-C8) alkyl betaines, sulfobetaines and (C8-C 24 ) alkylamido (C1-C8) alkyl sulfobetaines. In one embodiment, the betaine-type amphoteric surfactant is selected from (C8-C 24 ) alkyl betaines, (C8-C 24 ) alkylamido (C1-C8) alkyl sulfobetaines, sulfobetaines and phosphobetaines.

[0400] Non-limiting examples that may be mentioned include compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook (15th Edition, 2014) under the names: cocamidopropyl betaine, lauryl betaine, cetyl betaine, cocamidopropyl / oleamidopropyl betaine, cocamidopropyl betaine, palmamidopropyl betaine, stearamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl hydroxysultaine, oleamidopropyl hydroxysultaine, cocohydroxysultaine, lauryl hydroxysultaine, and cocosultaine, either alone or as a mixture.

[0401] The betaine-type amphoteric surfactants are preferably alkyl betaines and alkylamidoalkyl betaines, especially cocamidopropyl betaine and lauryl betaine.

[0402] Among the amidoamine carboxylation derivatives, mention may be made of products sold under the name Miranol, as described in U.S. Patent Nos. 2,528,378 and 2,781,354 and classified in the CTFA Dictionary, 3rd Edition, 1982 (the disclosure of which is incorporated herein by reference) under the names Amphocarboglycinates and Amphocarbopropionates, having the corresponding structures:

[0403] R1-CONHCH2CH2-N + (R2)(R3)(CH2COO - )M + X - (B1)

[0404] Wherein:

[0405] R1 represents an alkyl group of the acid R1-COOH present in hydrolyzed coconut oil, a heptyl group, a nonyl group, or an undecyl group,

[0406] R2 represents a β-hydroxyethyl group,

[0407] R3 represents a carboxymethyl group,

[0408] M + represents a cation derived from an alkali metal (such as sodium); an ammonium ion; or an ion derived from an organic amine;

[0409] X - represents an organic or inorganic anion, such as a halide ion, acetate, phosphate, nitrate, alkyl (C1-C4) sulfate, alkyl (C1-C4)- or alkyl (C1-C4) arylsulfonate, especially methyl sulfate and ethyl sulfate; or M + and X - are absent;

[0410] R1'-CONHCH2CH2-N(B)(C)(B2)

[0411] wherein:

[0412] R1' represents the alkyl group of the acid R1'-COOH present in coconut oil or hydrolyzed linseed oil, such as C7, C9, C 11 or C 13 alkyl group, C 17 alkyl group and its isomers, or an unsaturated C 17 alkyl group of the group,

[0413] B represents -CH2CH2OX',

[0414] C represents -(CH2) z -Y', where z = 1 or 2,

[0415] X' represents a -CH2-COOH group, -CH2-COOZ', -CH2CH2-COOH, -CH2CH2-COOZ' or a hydrogen atom, and

[0416] Y' represents a -COOH, -COOZ', -CH2-CHOH-SO3Z', -CH2-CHOH-SO3H group or a -CH2-CH(OH)-SO3-Z' group,

[0417] where Z' represents an ion of an alkali metal or alkaline earth metal such as sodium, an ion derived from an organic amine or ammonium ion;

[0418] and

[0419] R a” -NH-CH(Y”)-(CH2) n -C(O)-NH-(CH2) n’ -N(Rd)(Re) (B’2)

[0420] wherein:

[0421] Y” represents -C(O)OH, -C(O)OZ”, -CH2-CH(OH)-SO3H or -CH2-CH(OH)-SO3-Z”, where Z” represents a cation derived from an alkali metal or alkaline earth metal such as sodium, an ion derived from an organic amine or ammonium ion;

[0422] Rd and Re represent C1-C4 alkyl or C1-C4 hydroxyalkyl groups;

[0423] R a” represents C from the acid 10 -C 30an alkyl group or an alkenyl group, and

[0424] n and n' independently represent an integer from 1 to 3.

[0425] Preferably, the zwitterionic surfactants of formulae B1 and B2 are selected from (C8-C 24 ) alkyl amphoacetates, (C8-C 24 ) alkyl amphodiacetates, (C8-C 24 ) alkyl amphopropionates and (C8-C 24 ) alkyl amphodipropionates.

[0426] These compounds are classified in the CTFA Dictionary (5th Edition, 1993) under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium capryloamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, sodium lauroamphopropionate, disodium capryloamphodipropionate, lauroamphodipropionate and cocoamphodipropionate.

[0427] By way of example, mention may be made of cocoamphodiacetate sold by Rhodia Chimie under the trade name C2M CONCENTRATE.

[0428] Among the compounds of formula (B'2), mention may be made of sodium diethylaminopropyl cocoaspartamide (CTFA) sold by CHIMEX under the name CHIMEXANE HB.

[0429] (Cationic surfactant)

[0430] The composition according to the invention may comprise at least one cationic surfactant. Two or more cationic surfactants may be used in combination.

[0431] The cationic surfactant may be selected from optionally polyoxyalkylated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

[0432] Examples of quaternary ammonium salts that may be mentioned include, but are not limited to:

[0433] Those of the following general formula (B3):

[0434]

[0435] where

[0436] R1, R2, R3 and R4 may be the same or different and are selected from straight-chain or branched-chain aliphatic groups comprising from 1 to 30 carbon atoms and optionally comprising heteroatoms (such as oxygen, nitrogen, sulfur and halogen). The aliphatic groups may be selected from, for example, alkyl, alkoxy, C2-C6 polyoxyalkylene, alkylamide, (C12 -C 22 )alkylamido (C2-C6) alkyl, (C 12 -C 22 )alkyl acetate and hydroxyalkyl group; and aromatic group (such as aryl and alkylaryl); and X - is selected from halide ion, phosphate, acetate, lactate, (C2-C6) alkyl sulfate and alkyl sulfonate or alkylaryl sulfonate;

[0437] Quaternary ammonium salts of imidazoline, such as those of formula (B4):

[0438]

[0439] wherein:

[0440] R5 is selected from alkenyl and alkyl groups including 8 to 30 carbon atoms, such as fatty acid derivatives of tallow or coconut;

[0441] R6 is selected from hydrogen, C1-C4 alkyl groups, and alkenyl and alkyl groups including 8 to 30 carbon atoms;

[0442] R7 is selected from C1-C4 alkyl groups;

[0443] R8 is selected from hydrogen and C1-C4 alkyl groups; and

[0444] X - is selected from halide, phosphate, acetate, lactate, alkyl sulfate, alkyl sulfonate and alkylaryl sulfonate. In one embodiment, R5 and R6 are a mixture of groups selected from alkenyl and alkyl groups including 12 to 21 carbon atoms, such as fatty acid derivatives of tallow, R7 is methyl, and R8 is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA1997) and Quaternium-83 (CTFA1997), which are sold by Witco Corporation under the names of W75, W90, W75PG and W75HPG;

[0445] di- or triquaternary ammonium salts of formula (B5):

[0446]

[0447] wherein:

[0448] R9 is selected from aliphatic groups including 16 to 30 carbon atoms;

[0449] R 10 is selected from hydrogen or alkyl groups including 1 to 4 carbon atoms or the group -(CH2)3(R 16a )(R 17a )(R18a )N + X- - ;

[0450] R 11 、R 12 、R 13 、R 14 、R 16a 、R 17a and R 18a may be the same or different and are selected from hydrogen and alkyl groups having 1 to 4 carbon atoms; and

[0451] X - is selected from halide ions, acetate, phosphate, nitrate, ethyl sulfate, and methyl sulfate.

[0452] An example of such a bisquaternary ammonium salt is FINETEX (Quaternium-89) or FINQUAT CT-P of FINQUAT CT (Quaternium-75);

[0453] and

[0454] quaternary ammonium salts comprising at least one ester functionality, such as those of formula (B6):

[0455]

[0456] wherein:

[0457] R 22 is selected from C1-C6 alkyl groups and C1-C6 hydroxyalkyl and dihydroxyalkyl groups;

[0458] R 23 is selected from:

[0459] the following groups:

[0460]

[0461] linear and branched, saturated and unsaturated C1-C 22 hydrocarbon-based group R 27 , and

[0462] hydrogen,

[0463] R 25 is selected from:

[0464] the following groups:

[0465]

[0466] linear and branched, saturated and unsaturated C1-C6 hydrocarbon-based group R 29 , and

[0467] Hydrogen,

[0468] R 24 , R 26 and R 28 , which may be the same or different and are selected from linear and branched, saturated and unsaturated, C7-C 21 hydrocarbon-based groups;

[0469] r, s, and t, which may be the same or different and are selected from integers from 2 to 6;

[0470] Each of r1 and t1, which may be the same or different, is 0 or 1, and r2 + r1 = 2r and t1 + 2t = 2t;

[0471] y is selected from integers from 1 to 10;

[0472] x and z, which may be the same or different, are selected from integers from 0 to 10;

[0473] X - is selected from simple and complex, organic and inorganic anions; provided that the sum of x + y + z is from 1 to 15, and when x is 0, R 23 represents R 27 , and when z is 0, R 25 represents R 29 . R 22 may be selected from linear or branched alkyl groups. In one embodiment, R 22 is selected from linear alkyl groups. In another embodiment, R 22 is selected from methyl, ethyl, hydroxyethyl, and dipropylol groups, such as methyl and ethyl groups. In one embodiment, the sum of x + y + z is from 1 to 10. When R 23 is a hydrocarbon-based group R 27 , it may be a long chain and include 12 to 22 carbon atoms, or a short chain and include 1 to 3 carbon atoms. When R 25 is a hydrocarbon-based group R 29 , it may include, for example, 1 to 3 carbon atoms. By way of non-limiting example, in one embodiment, R 24 , R 26 and R 28 (which may be the same or different) are selected from linear and branched, saturated and unsaturated C 11 -C 21 hydrocarbon-based groups, such as linear and branched, saturated and unsaturated C 11 -C 21Alkyl and alkenyl groups. In another embodiment, x and z (which may be the same or different) are 0 or 1. In one embodiment, y equals 1. In another embodiment, r, s, and t (which may be the same or different) equal 2 or 3, for example equal 2. The anion X - may be selected from, for example, halide ions such as chloride, bromide, and iodide ions; and C1-C4 alkyl sulfates such as methyl sulfate. However, mesylate, phosphate, nitrate, tosylate, anions derived from organic acids (such as acetate and lactate), and any other anions compatible with ammonium (including ester functional groups) are other non-limiting examples of anions that can be used according to the present invention. In one embodiment, the anion X - is selected from chloride and methyl sulfate.

[0474] In another embodiment, an ammonium salt of formula (B6) can be used, wherein:

[0475] R 22 is selected from methyl and ethyl groups,

[0476] x and y equal 1;

[0477] z equals 0 or 1;

[0478] r, s, and t equal 2;

[0479] R 23 is selected from:

[0480] the following groups:

[0481]

[0482] methyl, ethyl, and C 14 -C 22 hydrocarbon-based groups, and hydrogen;

[0483] R 25 is selected from:

[0484] the following groups:

[0485]

[0486] and hydrogen;

[0487] R 24 、R 26 and R 28 (which may be the same or different) are selected from straight-chain and branched-chain, saturated and unsaturated, C 13 -C 17 hydrocarbon-based groups, such as from straight-chain and branched-chain, saturated and unsaturated, C 13 -C 17 alkyl and alkenyl groups.

[0488] In one embodiment, the hydrocarbon-based group is linear.

[0489] Non-limiting examples of compounds of formula (B6) that may be mentioned include salts of diacyloxyethyl dimethyl ammonium, diacyloxyethyl hydroxyethyl methyl ammonium, monoacyloxyethyl dihydroxyethyl methyl ammonium, triacyloxyethyl methyl ammonium, monoacyloxyethyl hydroxyethyl dimethyl ammonium (e.g., chlorides and methyl sulfates), and mixtures thereof. In one embodiment, the acyl group may include 14 to 18 carbon atoms and may be derived from, for example, vegetable oils such as palm oil and sunflower oil. When the compound includes several acyl groups, these groups may be the same or different.

[0490] These products can be obtained, for example, by directly esterifying optionally oxyalkylated triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine onto fatty acids or mixtures of fatty acids of vegetable or animal origin, or by transesterification of their methyl esters. The esterification reaction may then be followed by quaternization using an alkylating agent selected from: alkyl halides such as methyl halide and ethyl halide; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; methyl methanesulfonate; methyl p-toluenesulfonate; glycol chlorohydrin; and glycerol chlorohydrin.

[0491] Such compounds are, for example, sold by Cognis under the name, by Stepan under the name, by Ceca under the name, and by Rewo-Goldschmidt under the name “ WE 18”.

[0492] Other non-limiting examples of ammonium salts used in the compositions according to the invention include ammonium salts comprising at least one ester functionality as described in U.S. Patent Nos. 4,874,554 and 4,137,180.

[0493] The above-mentioned quaternary ammonium salts that can be used in the compositions according to the invention include, but are not limited to, those corresponding to formula (I), such as tetraalkyl ammonium chlorides, such as dialkyldimethyl ammonium chloride and alkyltrimethyl ammonium chloride, wherein the alkyl group includes about 12 to 22 carbon atoms, such as behenyltrimethyl ammonium chloride, distearyldimethyl ammonium chloride, cetyltrimethyl ammonium chloride, and benzyl dimethyl stearyl ammonium chloride; palmamidopropyltrimethyl ammonium chloride; and stearamidopropyldimethyl (myristoyl acetate) ammonium chloride, sold by Van Dyk under the name “ 70”.

[0494] According to one embodiment, the cationic surfactants that can be used in the compositions according to the invention are selected from behenyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, Quaternium-83, Quaternium-87, Quaternium-22, behenylamidopropyl-2,3-dihydroxypropyl dimethyl ammonium chloride, palmitylamidopropyl trimethyl ammonium chloride and stearamidopropyl dimethyl amine.

[0495] (Non-ionic surfactant)

[0496] The compositions according to the invention may comprise at least one non-ionic surfactant. Two or more non-ionic surfactants may be used in combination.

[0497] Non-ionic surfactants themselves are well-known compounds (in this regard, for example, see "Handbook of Surfactants" by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pages 116-178). Thus, they may be selected, for example, from esters of alcohols, α-diols, alkylphenols and fatty acids, which are ethoxylated, propoxylated or glycerolated and have at least one fatty chain containing, for example, 8 to 30 carbon atoms, with the number of ethylene oxide or propylene oxide groups possibly being 2 to 50 and the number of glycerol groups being 1 to 30. Maltose derivatives may also be mentioned. Also non-limitingly mentioned are copolymers of ethylene oxide and / or propylene oxide; condensates of ethylene oxide and / or propylene oxide with fatty alcohols; polyethoxylated fatty amides (containing, for example, 2 to 30 mol of ethylene oxide); polyglycerolized fatty amides (containing, for example, 1.5 to 5 glycerol groups, for example 1.5 to 4); ethoxylated fatty acid esters of sorbitan (containing 2 to 30 mol of ethylene oxide); ethoxylated oils of plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; glycerol (C6-C 24 ) polyethoxylated fatty acid mono- or diesters of alkyl polyglycosides; N-(C6-C 24 ) alkyl glucamine derivatives; amine oxides, such as (C 10 -C 14 ) alkyl amine oxides or N-(C 10 -C 14 ) acylaminopropyl morpholine oxides; silicone surfactants; and mixtures thereof.

[0498] The non-ionic surfactant may preferably be selected from mono-oxyalkylated, poly-oxyalkylated, mono-glycerolated or poly-glycerolated non-ionic surfactants. More specifically, the alkylene oxide units are ethylene oxide or propylene oxide units, or a combination thereof, and are preferably ethylene oxide units.

[0499] Examples of mono- or polyoxyalkylenated nonionic surfactants that may be mentioned include:

[0500] Mono- or polyoxyalkylenated (C8-C 24 ) alkylphenols,

[0501] Saturated or unsaturated, straight-chain or branched-chain, mono- or polyoxyalkylenated C8-C 30 alcohols,

[0502] Saturated or unsaturated, straight-chain or branched-chain, mono- or polyoxyalkylenated C8-C 30 amides,

[0503] Saturated or unsaturated, straight-chain or branched-chain, C8-C 30 esters of acids with polyalkylene glycols,

[0504] Saturated or unsaturated, straight-chain or branched-chain, C8-C 30 mono- or polyoxyalkylenated esters of acids with sorbitol,

[0505] Saturated or unsaturated, mono- or polyoxyalkylenated vegetable oils,

[0506] Condensates of ethylene oxide and / or propylene oxide, especially alone or as a mixture.

[0507] The surfactant preferably contains a molar amount of ethylene oxide and / or propylene oxide between 1 and 100, and most preferably between 2 and 50. According to one embodiment of the present 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).

[0508] Polyoxyethylenated saturated fatty alcohols (or C8-C 30Examples of ethylene oxide (including ethylene oxide) include adducts of ethylene oxide with lauryl alcohol, especially those containing 5 to 50 ethylene oxide units, and more specifically those containing 7 to 12 ethylene oxide units (Laureth-7 to Laureth-12 as CTFA names); adducts of ethylene oxide with behenyl alcohol, especially those containing 9 to 50 ethylene oxide units (Beheneth-9 to Beheneth-50 as CTFA names); adducts of ethylene oxide with cetearyl alcohol (a mixture of cetyl alcohol and stearyl alcohol), especially those containing 10 to 50 ethylene oxide units (Ceteareth-10 to Ceteareth-50 such as Ceteareth-6). adducts of ethylene oxide with stearyl alcohol, in particular those containing 10 to 50 oxyethylene units (Steareth-10 to Steareth-50, for example Steareth-20, as CTFA names); adducts of ethylene oxide with isostearyl alcohol, in particular those containing 10 to 50 oxyethylene units (Isosteareth-10 to Isosteareth-50, as CTFA names); and mixtures thereof.

[0509] Mention may be made of polyoxyethylene unsaturated fatty alcohols (or C8-C 30 Examples of ethylene oxide (Oleth-10 to Oleth-40, as CTFA names) include adducts of ethylene oxide with oleyl alcohol, particularly those containing from 2 to 50 ethylene oxide units, and more particularly those containing from 10 to 40 ethylene oxide units (Oleth-10 to Oleth-40, as CTFA names); and mixtures thereof.

[0510] As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C8-C 40 alcohol.

[0511] Specifically, monoglycerolated or polyglycerolated C8-C 40 The alcohol corresponds to the following formula:

[0512] RO-[CH2-CH(CH2OH)-O] m -H or RO-[CH(CH2OH)-CH2O] m -H

[0513] Where R represents a straight or branched C8-C 40 Alkyl or alkenyl group, preferably C8-C 30 An alkyl or alkenyl group, and m represents a value of 1 to 30, and preferably 1.5 to 10.

[0514] As examples of the compounds in the context suitable for the present invention, mention may be made of 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, cetostearyl alcohol containing 6 mol of glycerol and stearyl alcohol containing 6 mol of glycerol.

[0515] Alcohols can represent mixtures of alcohols in the same way as the m value represents a statistical value, which means that in commercial products, several polyglycerolated fatty alcohols can coexist in the form of a mixture.

[0516] Among monoglycerolated or polyglycerolated alcohols, it is preferred to use C8 / C alcohol containing 1 mol of glycerol, C alcohol containing 1 mol of glycerol, 10 C alcohol containing 1 mol of glycerol, 10 / C 12 C alcohol containing 1.5 mol of glycerol, 12 and C alcohol containing 1.5 mol of glycerol.

[0517] Monoglycerolated or polyglycerolated C8-C 40 fatty esters may correspond to the following formula:

[0518] R’O-[CH2-CH(CH2OR”’)-O] m -R” or R’O-[CH(CH2OR”’)-CH2O] m -R”

[0519] where each of R’, R” and R”’ independently represents a hydrogen atom, or a straight-chain or branched C8-C 40 and preferably C8-C 30 alkyl-CO- or alkenyl-CO- group, provided that at least one of R’, R” and R”’ is not a hydrogen atom, and m represents a number from 1 to 30 and preferably from 1.5 to 10.

[0520] Examples of polyoxyethylenated fatty acid esters that may be mentioned include adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (CTFA name: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA name: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA name: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (CTFA name: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG-100 stearate); and mixtures thereof.

[0521] According to one embodiment of the invention, the nonionic surfactant may be selected from esters of polyols with fatty acids having saturated or unsaturated chains containing, for example, from 8 to 24 carbon atoms, preferably from 12 to 22 carbon atoms, preferably containing from 10 to 200, and more preferably from 10 to 100, oxyalkylene units, such as C8-C 24 Preferably C 12 -C 22 Preferably C 24 -C 12 -C 22 Preferably C 24 -C 12 -C 22 glycerol esters of fatty acids or acids and their polyoxyalkylated derivatives, preferably containing from 10 to 200, and more preferably from 10 to 100, oxyalkylene units; sorbitan esters of C8-C 24 Preferably C 12 -C 22 fatty acids or acids and their polyoxyalkylated derivatives, preferably containing from 10 to 200, and more preferably from 10 to 100, oxyalkylene units; sugar (sucrose, maltose, glucose, fructose and / or alkyl glucoside) esters of C8-C

[0522] As glycerol esters of fatty acids, glyceryl stearates (mono-, di- and / or tri-stearates) (CTFA name: glyceryl stearate), examples include glyceryl laurate or glyceryl ricinoleate and mixtures thereof, and as their polyoxyalkylene derivatives, examples include mono-, di- or tri-esters of fatty acids with polyoxyalkylated glycerol (mono-, di- or tri-esters of fatty acids with polyalkylene glycol ethers of glycerol), preferably polyoxyethylated glyceryl stearates (mono-, di- and / or tri-stearates), such as PEG-20 glyceryl stearate (mono-, di- and / or tri-stearate).

[0523] Mixtures of these surfactants can also be used, for example, products containing glyceryl stearate and PEG-100 stearate sold by Uniqema under the name ARLACEL 165, and products containing glyceryl stearate (monoglyceryl stearate and diglyceryl stearate) and potassium stearate sold by Goldschmidt under the name TEGIN (CTFA name: glyceryl stearate SE).

[0524] C8-C 24 Sorbitan esters of fatty acids and their polyoxyalkylene derivatives can be selected from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate and esters of fatty acids with alkoxylated sorbitan, which contain, for example, 20 to 100 EO, such as sorbitan monostearate (CTFA name: sorbitan stearate) sold by ICI under the name Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate) sold by ICI under the name Span 40, and sorbitan tristearate 20EO (CTFA name: polysorbate 65), polyethylene sorbitan trioleate (polysorbate 85) sold by ICI under the name Tween 65, or compounds sold by Uniqema under the trade names Tween 20 or Tween 60.

[0525] Examples of esters of fatty acids with glucose or alkyl glucosides include: glucose palmitate, alkyl glucoside sesquistearates (e.g., methyl glucoside sesquistearate), alkyl glucoside palmitates (e.g., methyl glucoside palmitate or ethyl glucoside palmitate), methyl glucoside fatty esters, diesters of methyl glucoside and oleic acid (CTFA name: methyl glucose dioleate), mixed esters of methyl glucoside and a mixture of oleic acid / hydroxy stearic acid (CTFA name: methyl glucose dioleate / hydroxystearate), esters of methyl glucoside and isostearic acid (CTFA name: methyl glucose isostearate), esters of methyl glucoside and lauric acid (CTFA name: methyl glucose laurate), mixtures of mono- and diesters of methyl glucoside and isostearic acid (CTFA name: methyl glucose sesquisostearate), mixtures of mono- and diesters of methyl glucoside and stearic acid (CTFA name: methyl glucose sesquistearate), and in particular the product sold by AMERCHOL under the name Glucate SS, and mixtures thereof.

[0526] Examples of ethoxylated ethers of fatty acids and glucose or alkyl glucosides include, for example, ethoxylated ethers of fatty acids and methyl glucoside, and in particular polyethylene glycol ethers of diesters of methyl glucoside and stearic acid with approximately 20 moles of ethylene oxide (CTFA name: PEG - 20 methyl glucose distearate), such as the product sold by AMERCHOL under the name Glucam E - 20 distearate, polyethylene glycol ethers of mixtures of mono- and diesters of methyl glucoside and stearic acid with approximately 20 moles of ethylene oxide (CTFA name: PEG - 20 methyl glucose sesquistearate), and in particular the product sold by AMERCHOL under the name Glucamate SSE - 20 and the product sold by GOLDSCHMIDT under the name Grillocose PSE - 20, and mixtures thereof.

[0527] Examples of sucrose esters include sucrose palmitate - stearate, sucrose stearate, and sucrose monolaurate.

[0528] As the sugar ether, alkyl polyglucosides can be used, and specifically, for example, decyl glucoside, such as the product sold by Kao Chemicals under the name MYDOL 10, the product sold by Henkel under the name PLANTAREN 2000, and the product sold by Seppic under the name ORAMIX NS10; octanoyl / decoyl glucoside, such as the product sold by Seppic under the name ORAMIX CG 110 or the product sold by BASF under the name LUTENSOL GD 70; lauryl glucoside, such as the products sold by Henkel under the names PLANTAREN 1200N and PLANTACARE 1200; coconut glucoside, such as the product sold by Henkel under the name PLANTACARE 818 / UP; cetearyl glucoside (possibly mixed with cetearyl alcohol), for example, sold by Seppic under the name MONTANOV 68, sold by Goldschmidt under the name TEGO-CARE CG90, and sold by Henkel under the name EMULGADE KE3302; arachidyl glucoside, for example, in the form of a mixture of arachidyl alcohol and behenyl alcohol, and the arachidyl glucoside sold by Seppic under the name MONTANOV 202; coconut ethyl glucoside, for example, in the form of a mixture of cetyl alcohol and stearyl alcohol (35 / 65), sold by Seppic under the name MONTANOV 82, and their mixtures.

[0529] Mixtures of glycerol esters of alkoxylated vegetable oils can also be mentioned, for example, a mixture of ethoxylated (200 EO) palm oil glyceride and coconut oil (copra) (7 EO) glyceride.

[0530] The nonionic surfactant according to the present invention preferably contains an alkenyl or branched C 12 -C 22 acyl chain, such as an oleyl or isostearyl group. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

[0531] According to one embodiment of the present invention, the nonionic surfactant can be selected from copolymers of ethylene oxide and propylene oxide, especially copolymers of the following formula:

[0532] HO(C2H4O) a (C3H6O) b (C2H4O) c H

[0533] where a, b, and c are integers such that the range of a + c is from 2 to 100, and the range of b is from 14 to 60, and their mixtures.

[0534] According to one embodiment of the present invention, the nonionic surfactant may be selected from silicone surfactants. Mention may be made, without limitation, of those disclosed in documents US-A-5364633 and US-A-5411744.

[0535] The silicone surfactant may preferably be a compound of the following formula (I):

[0536]

[0537] wherein:

[0538] R1, R2 and R3 independently of one another represent a C1-C6 alkyl group or the group -(CH2) x -(OCH2CH2) y -(OCH2CH2CH2) z -OR4, at least one of the groups R1, R2 or R3 not being an alkyl group; R4 being hydrogen, an alkyl group or an acyl group;

[0539] A is an integer from 0 to 200;

[0540] B is an integer from 0 to 50; provided that A and B are not both equal to zero;

[0541] x is an integer from 1 to 6;

[0542] y is an integer from 1 to 30; and

[0543] z is an integer from 0 to 5.

[0544] 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 from 2 to 6, and y is an integer from 4 to 30.

[0545] As an example of the silicone surfactant of formula (I), mention may be made of a compound of the following formula (II):

[0546]

[0547] where A is an integer from 20 to 105, B is an integer from 2 to 10, and y is an integer from 10 to 20.

[0548] As an example of the silicone surfactant of formula (I), mention may also be made of a compound of the following formula (III):

[0549] H-(OCH2CH2) y -(CH2)3-[(CH3)2SiO] A’ -(CH2)3-(OCH2CH2) y -OH (III)

[0550] Wherein A' and y are integers from 10 to 20.

[0551] Compounds of the present invention that can be used are those from Dow Corning under the names DC 5329, DC 7439-146, DC2-5695 and Q4-3667. Compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II), wherein respectively A is 22, B is 2 and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12.

[0552] Compound Q4-3667 is a compound of formula (III), wherein A is 15 and y is 13.

[0553] Preferably, (b) the surfactant is selected from nonionic surfactants.

[0554] More preferably, (b) the surfactant is selected from polyglycerol fatty acid esters.

[0555] The polyglycerol fatty acid ester may have a polyglycerol moiety derived from 2 to 10 glycerols, preferably 2 to 8 glycerols, and more preferably 2 to 6 glycerols. In other words, the polyglycerol fatty acid ester may contain 2 to 10 polyglycerol units, preferably 2 to 8 polyglycerol units, and more preferably 2 to 6 polyglycerol units. If all polyglycerol fatty acid esters have shorter polyglycerol chains (e.g., less than 10 polyglycerol units, preferably less than 8 polyglycerol units, and more preferably less than 6 polyglycerol units), the stability of the composition according to the present invention can be enhanced.

[0556] The polyglycerol fatty acid ester may be selected from monoesters, diesters and triesters of straight-chain or branched-chain, saturated or unsaturated fatty acids, preferably saturated fatty acids, which include 4 to 32 carbon atoms, preferably 8 to 26 carbon atoms, and more preferably 10 to 20 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid and myristic acid.

[0557] Preferably, (b) the surfactant is selected from polyglycerol saturated or unsaturated fatty acid monoesters.

[0558] The polyglycerol fatty acid ester may have an HLB (hydrophilic-lipophilic balance) value of 4.0 to 16.0, preferably 4.5 to 15.5, and 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 of the hydrophilic part to the lipophilic part in the molecule. If two or more polyglycerol fatty acid esters are used, the HLB value is determined by the weighted average of the HLB values of all polyglycerol fatty acid esters.

[0559] The polyglycerol fatty acid ester may be selected from PG-2 stearate (HLB: 5.0), PG-2 isostearate (HLB: 5.5), PG-2 oleate (HLB: 6.5), PG-2 caprate (HLB: 9.5), PG-2 laurate (HLB: 8.5), PG-4 oleate (HLB: 8.8), PG-4 laurate (HLB: 10.4), PG-4 isostearate (HLB: 8.2), PG-5 laurate (HLB: 15.8), PG-6 isostearate (HLB: 10.8), PG-3 cocoate (HLB: 12.0), PG-3 caprate (HLB: 10.0), PG-4 caprylate (HLB: 14), PG-4 caprate (HLB: 14.0), PG-5 myristate (HLB: 15.4), PG-5 stearate (HLB: 15.0), PG-5 oleate (HLB: 14.9), PG-6 caprylate (HLB: 14.6), PG-6 caprate (HLB: 13.1), PG-6 laurate (HLB: 14.5), and mixtures thereof.

[0560] It may be preferred that (d) the surfactant is selected from PG-4 caprate (HLB: 14.0), PG-2 isostearate (HLB: 5.5), and mixtures thereof.

[0561] Preferably, the composition according to the present invention comprises at least two polyglycerol fatty acid esters.

[0562] Preferably, (d) the surfactant is selected from

[0563] at least one first polyglycerol fatty acid ester having an HLB value of 4.0 to 8.0, preferably 4.5 to 8.0, and more preferably 5.0 to 8.0;

[0564] at least one second polyglycerol fatty acid ester having an HLB value of 12.0 to 16.0, preferably 12.0 to 15.5, and more preferably 12.0 to 15.0; and

[0565] mixtures thereof.

[0566] In the composition according to the present invention, the amount of the surfactant(s) (d) may be 0.001% by weight or more, preferably 0.01% by weight or more, and more preferably 0.1% by weight or more based on the total weight of the composition.

[0567] In the composition according to the present invention, the amount of the surfactant(s) (d) may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less based on the total weight of the composition.

[0568] In the composition according to the invention, the amount of the surfactant(s) (d) can be from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, and more preferably from 0.1% to 10% by weight, based on the total weight of the composition.

[0569] [pH]

[0570] The pH of the composition according to the invention can be from 2.0 to 9.0, preferably from 2.5 to 8.5, and more preferably from 3.0 to 8.0.

[0571] At a pH value from 2.0 to 9.0, the polyion complex (a) can be very stable.

[0572] The pH of the composition according to the invention can be adjusted by adding at least one basic agent and / or at least one acid, with the exception of non-polymeric acids or their salt(s) having two or more pKa values or non-polymeric bases or their salt(s) having two or more pKb values, in order to incorporate them into the polyion complex (a). The pH of the composition according to the invention can also be adjusted by adding at least one buffer.

[0573] (Basic agent)

[0574] The composition according to the invention can comprise at least one basic agent. Two or more basic agents can be used in combination. Thus, a single type of basic agent or a combination of different types of basic agents can be used.

[0575] The basic agent can be an inorganic basic agent. Preferably, the inorganic basic agent is selected from ammonia; alkali metal hydroxides; alkaline earth metal hydroxides; alkali metal phosphates and monohydrogen phosphates, such as sodium phosphate or monosodium hydrogen phosphate.

[0576] As examples of inorganic alkali metal hydroxides, sodium hydroxide and potassium hydroxide can be mentioned. As examples of alkaline earth metal hydroxides, calcium hydroxide and magnesium hydroxide can be mentioned. As the inorganic basic agent, sodium hydroxide is preferred.

[0577] The basic agent can be an organic basic agent. Preferably, the organic basic agent is selected from 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.

[0578] As examples of organic basic agents, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and isopropanolamine can be mentioned; urea, guanidine and their derivatives; basic amino acids such as lysine, ornithine or arginine; and diamines such as those described in the following structures:

[0579]

[0580] Wherein R represents an alkylene group, such as a propylene group, which is optionally substituted by a hydroxyl group or a C1-C4 alkyl group, and R1, R2, R3 and R4 independently represent a hydrogen atom, an alkyl group or a C1-C4 hydroxyalkyl group, which can be exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferred.

[0581] Relative to the total weight of the composition, the (one or more) basic agents can 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, depending on their solubility.

[0582] (Acid)

[0583] The composition according to the present invention can contain at least one acid. Two or more acids can be used in combination. Thus, a single type of acid or a combination of different types of acids can be used.

[0584] As the acid, any inorganic or organic acid commonly used in cosmetics can be mentioned, preferably an inorganic acid. Monovalent acids and / or polyvalent acids can be used. Monovalent acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) can be used. HCl is preferred.

[0585] Relative to the total weight of the composition, the (one or more) acids can 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, depending on their solubility.

[0586] (Buffer)

[0587] The composition according to the present invention can contain at least one buffer. Two or more buffers can be used in combination. Thus, a single type of buffer or a combination of different types of buffers can be used.

[0588] As the buffer, acetate buffer (e.g., acetic acid + sodium acetate), phosphate buffer (e.g., sodium dihydrogen phosphate + disodium hydrogen phosphate), citrate buffer (e.g., citric acid + sodium citrate), borate buffer (e.g., boric acid + sodium borate), tartrate buffer (e.g., tartaric acid + sodium tartrate dihydrate), Tris buffer (e.g., tris(hydroxymethyl)aminomethane) and Hepes buffer (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) can be mentioned.

[0589] [Optional additives]

[0590] In addition to the aforementioned components, the composition according to the present invention may contain components commonly used in cosmetics within the scope that does not impair the effects of the present invention. Specifically, oils (such as ester oils and hydrocarbon oils), hydrophilic or lipophilic UV filters, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents (such as glycerol, ethylene glycol, and ethanol), silicones and silicone derivatives, natural extracts derived from animals or plants, waxes, etc.

[0591] The composition according to the present invention may contain the above-mentioned optional additive(s) in an amount of 0.01% by weight to 50% by weight, preferably 0.05% by weight to 30% by weight, and more preferably 0.1% by weight to 10% by weight based on the total weight of the composition.

[0592] [Composition]

[0593] 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 keratinous substances. Keratinous substances herein refer to materials containing keratin as the main constituent element, and examples thereof include skin, scalp, nails, lips, hair, etc. Therefore, preferably, the cosmetic composition according to the present invention is used in a beauty method for keratinous substances (especially skin).

[0594] Therefore, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin makeup composition, and more preferably a skin care composition.

[0595] The composition according to the present invention can be prepared by mixing the above-mentioned essential and optional components by any method known to those skilled in the art.

[0596] The composition according to the present invention can be prepared by simple or easy mixing using a conventional mixing device such as a stirrer. Therefore, strong shear by, for example, a homogenizer is not necessary. In addition, heating is not necessary.

[0597] [Film]

[0598] The composition according to the present invention can be used to easily prepare a film.

[0599] Therefore, the present invention also relates to a method for preparing a film, preferably a cosmetic film, which optionally has a thickness preferably greater than 0.1 μm, more preferably 0.5 μm or greater, and even more preferably 1 μm or greater, the method comprising:

[0600] Applying the composition according to the present invention to a substrate, preferably a keratinous substance, more preferably the skin; and

[0601] Drying the composition.

[0602] There is no upper limit to the thickness of the film according to the present invention. Thus, for example, the thickness of the film 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.

[0603] Since the method for preparing the film according to the present invention includes applying the composition according to the present invention to a substrate, preferably a keratinous material, and more preferably the skin, and drying the composition, the method according to the present invention does not require any spin coating or spraying, and thus, even a relatively thick film can be easily prepared. Therefore, the method for preparing the film according to the present invention can prepare a relatively thick film without any special equipment such as a spin coater and a sprayer.

[0604] If a (b) hydrophilic antioxidant is used, the film according to the present claim can be transparent or translucent and can provide an antioxidant effect that can last.

[0605] Even if the film according to the present invention is relatively thick, it is still thin and can be transparent and thus can be not easily noticed. Therefore, the film according to the present invention can preferably be used as a cosmetic film.

[0606] If a (b) lipophilic antioxidant is used, although it contains a hyaluronic acid-based polymer, the film according to the present claim can be less viscous and can provide an antioxidant effect that can last.

[0607] If the substrate is not a keratinous material such as the skin, the composition according to the present invention can be applied to a substrate made of any material other than keratin. The material of the non-keratin substrate is not limited. Two or more materials can be used in combination. Thus, a single type of material or a combination of different types of materials can be used. In any case, it is preferred that the substrate is flexible or elastic.

[0608] If the substrate is not a keratinous material, it is preferred that the substrate is water-soluble because the film according to the present invention can be left by washing the substrate with water. As examples of water-soluble materials, poly(meth)acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate, etc. can be mentioned. PVA is preferred.

[0609] If the non-keratin substrate is in the form of a sheet, it can have a thickness greater than that of the film according to the present invention in order to easily handle the film attached to the substrate sheet. The thickness of the non-keratin substrate sheet is not limited, but can be 1 μm to 5 mm, preferably 10 μm to 1 mm, and more preferably 50 to 500 μm.

[0610] More preferably, the film according to the present invention is releasable from a non-keratin substrate. The manner of release is not limited. Thus, the film according to the present invention can be peeled off from the non-keratin substrate or released by dissolving the substrate sheet in a solvent such as water.

[0611] The present invention also relates to:

[0612] (1) A film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.1 μm, more preferably 0.5 μm or greater, and even more preferably 1 μm or greater, prepared by a method comprising the steps of:

[0613] applying the composition according to the present invention to a substrate, preferably a keratinous material, and more preferably the skin; and

[0614] drying the composition,

[0615] and

[0616] (2) A film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.1 μm, more preferably 0.5 μm or greater, and even more preferably 1 μm or greater, comprising:

[0617] (a) at least one polyion complex comprising

[0618] at least one cationic polymer and at least one anionic polymer,

[0619] at least one cationic polymer and at least one amphoteric polymer,

[0620] at least one anionic polymer and at least one amphoteric polymer, or

[0621] at least one amphoteric polymer;

[0622] at least one non-polymeric acid having two or more pKa values or its (one or more) salts, or at least one non-polymeric base having two or more pKb values or its (one or more) salts;

[0623] (b) at least one hydrophilic or lipophilic antioxidant;

[0624] and

[0625] optionally (d) at least one surfactant, preferably selected from nonionic surfactants, and more preferably selected from polyglycerol fatty acid esters,

[0626] wherein,

[0627] the anionic polymer is selected from hyaluronic acid and its salts; and

[0628] the amphoteric polymer is selected from cationized hyaluronic acid and its salts.

[0629] The above explanations regarding the cationic polymer, anionic polymer, and amphoteric polymer, and the above hydrophilic or lipophilic antioxidants and surfactants can be applied to those in the above membranes (1) and (2).

[0630] The membranes thus obtained can be self - standing. The term "self - standing" herein means that the membrane can be in the form of a sheet and can be handled as an independent sheet without the help of a substrate or support. Thus, the term "self - standing" can have the same meaning as "self - supporting".

[0631] Preferably, the membrane according to the present invention is hydrophobic.

[0632] The term "hydrophobic" in this specification means that the solubility of the polymer in water (preferably with a volume of 1 liter) at 20 to 40 °C, preferably 25 to 40 °C, and more preferably 30 to 40 °C is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, relative to the total weight of the polymer. Most preferably, the polymer is insoluble in water.

[0633] If the membrane according to the present invention is hydrophobic, the membrane can have water - resistant properties, and thus it can remain on keratinous substances such as the skin even if the surface of the keratinous substance is wet due to, for example, sweat and rain. Therefore, when the membrane according to the present invention provides any cosmetic effect, the cosmetic effect can last for a longer time.

[0634] On the other hand, the membrane according to the present invention can be easily removed from keratinous substances such as the skin under alkaline conditions (such as a pH of 8 to 12, preferably 9 to 11). Thus, the membrane according to the present invention is difficult to remove with water, while it can be easily removed with soap that can provide such alkaline conditions.

[0635] The membrane according to the present invention can comprise at least one biocompatible and / or biodegradable polymer layer. Two or more biocompatible and / or biodegradable polymers can 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 can be used.

[0636] In this specification, the term "biocompatible" polymer means that there is no excessive interaction between the polymer and cells in a living organism including the skin, and the polymer is not recognized by the living organism as a foreign substance.

[0637] In the present specification, the term "biodegradable" polymer means that the polymer can be degraded or decomposed in a living body due to, for example, the metabolism of the living body itself or the metabolism of microorganisms that may be present in the living body. In addition, the biodegradable polymer can be degraded by hydrolysis.

[0638] If the film according to the present invention contains a biocompatible and / or biodegradable polymer, it is less irritating or non-irritating to the skin and does not cause any rash. In addition, due to the use of a biocompatible and / or biodegradable polymer, the cosmetic sheet according to the present invention can adhere well to the skin.

[0639] The film according to the present invention can be used for the cosmetic treatment of keratinous substances (preferably the skin, especially the face). The film according to the present invention can be of any shape or form. For example, it can be used as a full-face mask or a patch for a part of the face such as the cheeks, nose, and around the eyes.

[0640] If the film according to the present invention contains at least one hydrophilic or water-soluble UV filter, it can provide a UV shielding effect derived from the hydrophilic or water-soluble UV filter. Generally, the hydrophilic or water-soluble UV filter can be removed from the surface of a keratinous substrate (such as the skin) by water (such as sweat and rain). However, due to the inclusion of the hydrophilic or water-soluble UV filter in the film according to the present invention, it is difficult to remove the hydrophilic or water-soluble UV filter with water, thereby producing a long-lasting UV shielding effect.

[0641] [Cosmetic methods and uses]

[0642] The present invention also relates to:

[0643] A cosmetic method for keratinous substances such as the skin, which comprises: applying the composition according to the present invention to the keratinous substance; and drying the composition to form a cosmetic film on the keratinous substance; and

[0644] The use of the composition according to the present invention for preparing a cosmetic film on a keratinous substance (such as the skin).

[0645] The cosmetic method herein refers to a non-therapeutic cosmetic method for caring for and / or making up the surface of keratinous substances (such as the skin).

[0646] In both of the above methods and uses, the above cosmetic film is resistant to water with a pH of 7 or lower and can be removed with water having a pH greater than 7, preferably 8 or higher, and more preferably 9 or higher.

[0647] In other words, the above cosmetic film can be water-resistant under neutral or acidic conditions such as a pH of 7 or lower, preferably in the range of 6 or higher to 7 or lower, and more preferably in the range of 5 or higher to 7 or lower; while the above cosmetic film can be removed under alkaline conditions such as a pH higher than 7, preferably 8 or higher, and more preferably 9 or higher. The upper limit value of the pH is preferably 13, more preferably 12, and even more preferably 11.

[0648] Therefore, the above cosmetic film can be water-resistant and thus can remain on a keratinous substance such as the skin even if the surface of the keratinous substance is wet due to, for example, sweat and rain. On the other hand, the above cosmetic film can be easily removed from a keratinous substance such as the skin under alkaline conditions. Thus, the film according to the present invention is difficult to remove with water, while it can be easily removed with soap that can provide an alkaline condition.

[0649] If the above cosmetic film contains a UV filter that can be present in the composition according to the present invention, the above cosmetic film can protect a keratinous substance (such as the skin) from ultraviolet rays, thereby restricting skin darkening, improving the color and uniformity of the skin color, and / or treating skin aging.

[0650] In addition, due to the nature of the polyelectrolyte complex in the cosmetic film, the above cosmetic film can have cosmetic effects such as trapping sebum, matting the appearance of a keratinous substance (such as the skin), absorbing or adsorbing odors, and / or protecting the keratinous substance from, for example, dirt or contaminants, even if the cosmetic film does not contain any cosmetic active ingredients.

[0651] In addition, the above cosmetic film can immediately change or modify the skin appearance by changing light reflection on the skin, etc., even if the cosmetic film does not contain any cosmetic active ingredients. Therefore, the above cosmetic film can hide skin defects such as pores or wrinkles. In addition, by changing the surface roughness on the skin, etc., the above cosmetic film can immediately change or modify the skin touch. In addition, the above cosmetic film can immediately protect the skin by covering the skin surface as a barrier and shielding the skin from environmental stresses such as contaminants, dirt, etc.

[0652] The above cosmetic effects can be adjusted or controlled by changing the chemical composition, thickness, and / or surface roughness of the above cosmetic film.

[0653] If the above cosmetic film contains at least one additional cosmetic active ingredient such as an oil, the cosmetic film may have a cosmetic effect provided by the additional (one or more) cosmetic active ingredients. For example, if the cosmetic film contains at least one cosmetic active ingredient selected from anti-aging agents, sebum-control agents, deodorants, antiperspirants, skin-whitening agents, and mixtures thereof, other than (b) hydrophilic or lipophilic antioxidants, the cosmetic film can treat skin aging, absorb sebum on the skin, control the odor on the skin, control sweating on the skin, and / or whiten the skin.

[0654] A cosmetic beauty composition can also be applied onto the skin after the cosmetic film or sheet according to the invention has been applied thereto. Examples

[0655] The present invention will be described in more detail by way of examples. However, they should not be construed as limiting the scope of the present invention.

[0656] [Examples 1A - 2A and Comparative Example 1A]

[0657] [Preparation]

[0658] The respective compositions according to Examples 1A - 2A and Comparative Example 1A were prepared by mixing the ingredients shown in Table 1A. The numerical values of the amounts of the ingredients in Table 1A are all based on "wt%" as the active substance.

[0659] Table 1A

[0660]

[0661]

[0662] [Evaluation]

[0663] (Transparency)

[0664] The appearance of the respective compositions according to Examples 1A - 2A and Comparative Example 1A was evaluated. Specifically, each composition was placed in a transparent cylindrical glass container, and the ease of observing the background through the container was evaluated. Also, each composition was dropped onto the hand, and the ease of observing the skin of the hand was evaluated according to the following criteria:

[0665] Very good: The background can be easily seen through the container (transparent)

[0666] Good: The background can be seen through the container, although slightly blurred (semi-transparent)

[0667] Fair: The background cannot be seen through the container, but the skin can be easily seen (semi-transparent)

[0668] Poor: The skin cannot be seen (opaque)

[0669] The results are shown in Table 1A.

[0670] (Persistence of antioxidant action)

[0671] 0.6 g of a β-carotene solution having a concentration of 0.05% by weight (solvent: triglyceride of caprylic / capric acid) and 0.2 g each of the compositions according to Examples 1A-2A and Comparative Example 1A were mixed to obtain a mixture.

[0672] 0.4 g of the above mixture was applied to a filter (glass microfiber filter).

[0673] The filter was rinsed with tap water (300 mL, 23 - 27 °C).

[0674] The above filter was exposed to ultraviolet light with a wavelength of 365 nm for 30 minutes to oxidize β-carotene.

[0675] If β-carotene is oxidized, the original yellow color derived from β-carotene fades.

[0676] The b* value (b*(T = 0) and b*(T = 30 minutes) respectively) of the filter in the L*a*b* (CIE1976) space before and after UV exposure was measured by a spectrocolorimeter (CM-700d manufactured by KONICA MINOLTA), and the difference between the b*(T = 0) value and the b*(T = 30 minutes) value was determined as Δb*. It should be noted that the b*(T = 0) value of the filter before rinsing was between 45 and 65.

[0677] The Δb* value and the b*(T = 30 minutes) value were evaluated according to the following criteria.

[0678] Very good: Δb* < 10 and b*(T = 30 minutes) > 30

[0679] Good: Δb* < 10 and 30 > b*(T = 30 minutes) > 20

[0680] Poor: Δb* < 10 and 20 > b*(T = 30 minutes)

[0681] Very poor: Δb* > 10

[0682] The results are shown in Table 1A.

[0683] (Summary)

[0684] The compositions according to Examples 1A and 2A may have a transparent or semi-transparent appearance.

[0685] It is apparent from the comparison between Examples 1A-2A and Comparative Example 1 that the use of polyion complexes can prolong the antioxidant effect.

[0686] It is apparent from the comparison between Example 1A and Example 2A that the use of a surfactant (such as polyglyceryl fatty acid ester) can further extend the antioxidant effect even under rinsing conditions.

[0687] [Examples 1B - 2B and Comparative Examples 1B - 2B]

[0688] [Preparation]

[0689] The respective compositions according to Examples 1B - 2B and Comparative Examples 1B - 2B were prepared by mixing the ingredients shown in Table 1B. The numerical values of the amounts of the ingredients in Table 1B are all based on "wt%" as the active substance.

[0690] Table 1B

[0691]

[0692]

[0693] [Evaluation]

[0694] (Viscosity)

[0695] Three reviewers evaluated the texture in terms of the viscosity of the respective compositions according to Examples 1B - 2B and Comparative Examples 1B - 2B during and after the application of the compositions. Specifically, each reviewer applied each composition on his / her hand and spread it to evaluate the moisturizing feeling, and rated it from 1 (low) to 5 (high). Then, based on the average score, it was classified into the following three categories:

[0696] Very good: 4 to 5 (not sticky)

[0697] Good: 3 to less than 4 (slightly sticky)

[0698] Poor: greater than 2 and less than 3 (sticky)

[0699] Very poor: 1 to 2 (very sticky)

[0700] The results are shown in Table 1B.

[0701] (Persistence of antioxidant effect)

[0702] 0.6 g of a β - carotene solution with a concentration of 0.05 wt% (solvent: triglyceride of caprylic / capric acid), and 0.2 g each of the compositions according to Examples 1B - 2B and Comparative Examples 1B - 2B were mixed to obtain a mixture.

[0703] 0.4 g of the above mixture was applied to a filter disc (glass microfiber filter disc).

[0704] The filter disc was rinsed with tap water (300 mL, 23 - 27 °C).

[0705] Expose the above-mentioned filter to ultraviolet light with a wavelength of 365 nm for 30 minutes to oxidize β-carotene.

[0706] If β-carotene is oxidized, the original yellow color derived from β-carotene fades.

[0707] Measure the b* value (b*(T = 0) and b*(T = 30 minutes) respectively) of the filter in the L*a*b* (CIE1976) space before and after UV exposure using a spectrophotometer (CM-700d manufactured by KONICA MINOLTA), and determine the difference between the b*(T = 0) value and the b*(T = 30 minutes) value as Δb*. It should be noted that the b*(T = 0) value of the filter before rinsing is between 45 and 65.

[0708] Evaluate the Δb* and b*(T = 30 minutes) values according to the following criteria.

[0709] Very good: Δb* < 10 and b*(T = 30 minutes) > 30

[0710] Good: Δb* < 10 and 30 > b*(T = 30 minutes) > 20

[0711] Poor: Δb* < 10 and 20 > b*(T = 30 minutes)

[0712] Very poor: Δb* > 10

[0713] The results are shown in Table 1B.

[0714] (Summary)

[0715] The compositions according to Examples 1B and 2B are good or very good in terms of viscosity and can provide good or very good long-lasting antioxidant effects.

[0716] It is obvious from the comparison between Example 1B and Comparative Example 2B that the use of polyion complexes can reduce viscosity and extend the antioxidant effect.

[0717] It is obvious from the comparison between Example 2B and Comparative Example 1B that the use of tocopherol can not only enhance the antioxidant effect but also improve the viscosity.

[0718] It is obvious from the comparison between Example 1B and Example 2B that the use of surfactants (such as polyglyceryl fatty acid esters) can further extend the antioxidant effect even under rinsing conditions.

Claims

1. A composition, comprising: (a) at least one polyion complex, said polyion complex comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer, or at least one amphoteric polymer, and at least one non-polymeric acid having two or more pKa values or one or more of its salts, or at least one non-polymeric base having two or more pKb values or one or more of its salts; (b) at least one hydrophilic or lipophilic antioxidant; and (c) water, wherein 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.

2. The composition according to claim 1, wherein the cationized hyaluronic acid has 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.

3. The composition according to claim 1 or 2, wherein the cationic polymer has at least one positively chargeable and / or positively charged moiety selected from primary amino, secondary amino or tertiary amino, quaternary ammonium, guanidine, biguanidine, imidazole, imine, and pyridyl.

4. The composition according to any one of claims 1 to 3, wherein the cationic polymer is selected from cyclic polymers of alkyldiallylamines and cyclic polymers of dialkyldiallylammonium such as (co)polydiallyldimethylammonium chloride, (co)polyamines such as (co)polylysine, cationic (co)polyamino acids such as collagen, cationic cellulose polymers, and their salts.

5. The composition according to any one of claims 1 to 4, wherein the total amount of the cationic polymer and / or anionic polymer and / or amphoteric polymer in the composition is 0.01% by weight to 15% by weight based on the total weight of the composition, preferably 0.03% by weight to 10% by weight, and more preferably 0.05% by weight to 5% by weight.

6. The composition according to any one of claims 1 to 5, wherein the non-polymeric acid having two or more pKa values or one or more of its salts is an organic acid or one or more of its salts, preferably a hydrophilic or water-soluble organic acid or one or more of its salts, and more preferably phytic acid or its salts.

7. The composition according to any one of claims 1 to 6, wherein the amount of the non-polymeric acid having two or more pKa values or one or more of its salts or the non-polymeric base having two or more pKb values or one or more of its salts in the composition is 0.001% by weight to 15% by weight based on the total weight of the composition, preferably 0.005% by weight to 10% by weight, and more preferably 0.01% by weight to 5% by weight.

8. The composition according to any one of claims 1 to 7, wherein the (b) hydrophilic antioxidant is selected from ascorbic acid, its derivatives, its salts, and mixtures thereof.

9. The composition according to any one of claims 1 to 8, wherein the amount of the (b) hydrophilic antioxidant in the composition is from 0.01% by weight to 30% by weight, preferably from 0.05% by weight to 25% by weight, and more preferably from 0.1% by weight to 20% by weight, based on the total weight of the composition.

10. The composition according to any one of claims 1 to 7, wherein the (b) lipophilic antioxidant is selected from pentaerythrityl tetra (di - tert - butylhydroxyhydrocinnamate), nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxyanisole, ascorbyl palmitate, tocopherol, and mixtures thereof.

11. The composition according to any one of claims 1 to 8, wherein the amount of the (b) lipophilic antioxidant in the composition is from 0.001% by weight to 15% by weight, preferably from 0.005% by weight to 10% by weight, and more preferably from 0.01% by weight to 5% by weight, based on the total weight of the composition.

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

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

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

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

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