Compositions containing a large amount of polyol

Abstract

To provide a composition capable of exhibiting reduced stickiness while containing a large amount, i.e., 10 mass% or more, of a polyol such as glycerin based on the total mass of the composition.SOLUTION: The present invention relates to a composition containing: (a) at least one cationic polymer; (b) at least one non-polymeric acid or a salt thereof having two or more pKa values; (c) at least one polyol; and (d) water, the amount of (c) polyol in the composition being 10 mass% or more based on the total mass of the composition. Although the composition according to the invention contains a large amount of a polyol such as glycerin, it can exhibit reduced stickiness.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compositions containing relatively large amounts of polyols and cosmetic methods of using the compositions. [Background technology]

[0002] Polyion complexes, which may be in the form of particles and which can be formed with cationic and anionic polymers, are already known.

[0003] For example, WO2021 / 125069 discloses a composition useful for cosmetic treatment, which in one embodiment comprises at least one cationic polymer, at least one hyaluronic acid-based anionic polymer, and at least one polyion complex particle comprising at least one non-polymeric acid or salt thereof having two or more pKa values. WO2021 / 125069 also discloses a specific composition comprising 5% by weight of glycerin.

[0004] For example, WO2022 / 131351 discloses a composition useful for cosmetic treatment, which in one embodiment comprises at least one cationic polymer, at least one anionic polymer, at least one non-polymeric acid or salt thereof having two or more pKa values, and at least one polyion complex particle containing at least one filler. WO2022 / 131351 also discloses a specific composition containing 5% by weight of glycerin.

[0005] Polyols such as glycerin are often used for cosmetic purposes on keratinous materials such as skin, however compositions containing large amounts of polyols such as glycerin, i.e., 10% by weight or more based on the total weight of the composition, tend to be sticky. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2021 / 125069 [Patent Document 2] WO2022 / 131351 [Patent Document 3] European Patent Application No. 0080976 [Patent Document 4] French Patent No. 2077143 [Patent Document 5] French Patent No. 2393573 [Patent Document 6] French Patent No. 1492597 [Patent Document 7] U.S. Patent No. 4,131,576 [Patent Document 8] U.S. Patent No. 3,589,578 [Patent Document 9] U.S. Patent No. 4,031,307 [Patent Document 10] French Patent No. 2162025 [Patent Document 11] French Patent No. 2280361 [Patent Document 12] French Patent No. 2252840 [Patent Document 13] French Patent No. 2368508 [Patent Document 14] French Patent No. 1,583,363 [Patent Document 15] U.S. Patent No. 3,227,615 [Patent Document 16] U.S. Patent No. 2,961,347 [Patent Document 17] French Patent No. 2080759 [Patent Document 18] French Patent No. 2320330 [Patent Document 19] French Patent No. 2270846 [Patent Document 20] French Patent No. 2316271 [Patent Document 21] French Patent No. 2336434 [Patent Document 22] French Patent No. 2413907 [Patent Document 23] U.S. Patent No. 2,273,780 [Patent Document 24] U.S. Patent No. 2,375,853 [Patent Document 25] U.S. Patent No. 2,388,614 [Patent Document 26] U.S. Patent No. 2,454,547 [Patent Document 27] U.S. Patent No. 3,206,462 [Patent Document 28] U.S. Patent No. 2,261,002 [Patent Document 29] U.S. Patent No. 2,271,378 [Patent Document 30] U.S. Patent No. 3,874,870 [Patent Document 31] U.S. Patent No. 4,001,432 [Patent Document 32] U.S. Patent No. 3,929,990 [Patent Document 33] U.S. Patent No. 3,966,904 [Patent Document 34] U.S. Patent No. 4,005,193 [Patent Document 35] U.S. Patent No. 4,025,617 [Patent Document 36] U.S. Patent No. 4,025,627 [Patent Document 37] U.S. Patent No. 4,025,653 [Patent Document 38] U.S. Patent No. 4,026,945 [Patent Document 39] U.S. Patent No. 4,027,020 [Patent Document 40] European Patent Application No. 0122324 [Patent Document 41] EP-A-0750899 [Patent Document 42] EP-A-1069172 [Patent Document 43] EP-A-0173109 [Non-patent literature]

[0007] [Non-Patent Document 1] "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering" - Macromolecules, 2000, Vol. 33, No. 10-3694~3704 [Non-patent document 2] "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006), pp. 699-715 [Non-patent document 3] D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) pp. 2101-2127 Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, an object of the present invention is to provide a composition that can exhibit reduced stickiness while containing a large amount of a polyol such as glycerin, i.e., 10% by weight or more relative to the total weight of the composition. [Means for solving the problem]

[0009] The above object of the present invention is to (a) at least one cationic polymer; (b) at least one non-polymeric acid or salt thereof having two or more pKa values; (c) at least one polyol, and (d) water A composition comprising: This can be achieved by a composition in which the amount of (c) polyol in the composition is 10% by mass or more relative to the total mass of the composition.

[0010] (a) The cationic polymer may be crosslinked with (b) a non-polymeric acid or salt thereof having two or more pKa values.

[0011] (a) The cationic polymer may have at least one positively charged and / or positively charged moiety selected from the group consisting of a primary, secondary, or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group, and a pyridyl group.

[0012] (a) The cationic polymer may be selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as chitosan and (co)polylysine, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof.

[0013] It may be more preferred that the (a) cationic polymer is selected from the group consisting of polylysine, chitosan, and mixtures thereof.

[0014] The amount of (a) cationic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0015] (b) The non-polymeric acid having two or more pKa values ​​or a salt thereof may be an organic acid or a salt thereof, preferably a hydrophilic or water-soluble organic acid or a salt thereof, more preferably phytic acid or a salt thereof, terephthalylidene dicamphorsulfonic acid or a salt thereof, or a mixture thereof.

[0016] The amount of (b) the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0017] (c) It may be preferred that the polyol is glycerin.

[0018] The amount of (c) polyol in the composition according to the present invention may be 95% by weight or less, based on the total weight of the composition.

[0019] The composition according to the present invention may further comprise (e) at least one anionic polymer.

[0020] (e) The anionic polymer may be selected from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and mixtures thereof, more preferably hyaluronic acid and its salts, carboxymethylcellulose and its salts, and mixtures thereof.

[0021] The amount of (e) anionic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0022] The composition according to the present invention may be a cosmetic composition, preferably a care cosmetic composition, more preferably a skin care or hair care cosmetic composition.

[0023] The present invention also provides a cosmetic method for keratinous materials, comprising: applying a composition according to the invention to keratinous materials; and drying the composition to form a cosmetic film on keratinous materials. DETAILED DESCRIPTION OF THE INVENTION

[0024] As a result of extensive research, the present inventors have discovered that it is possible to provide a composition that can exhibit reduced stickiness while containing a large amount of polyol such as glycerin, i.e., 10% by mass or more based on the total mass of the composition.

[0025] Therefore, the composition according to the present invention (a) at least one cationic polymer; (b) at least one non-polymeric acid or salt thereof having two or more pKa values; (c) at least one polyol, and (d) water Including, The amount of (c) polyol in the composition is 10% by mass or more based on the total mass of the composition.

[0026] Compositions according to the present invention can exhibit reduced stickiness despite containing large amounts of polyols such as glycerin.

[0027] The stickiness of the composition according to the present invention is less than the stickiness of a composition containing component (c) in an amount of 10% by mass or more based on the total mass of the composition and not containing components (a) and (b).

[0028] Thus, the compositions according to the present invention can provide improved texture, such as a smoother feel.

[0029] Polyols such as glycerin are hydrophilic and therefore can be easily washed off the surface of keratinous materials with water. However, components (a) and (b) in the composition according to the present invention can form a gel film or coacervate that better retains the polyol on keratinous materials such as skin.

[0030] Thus, the compositions according to the present invention may also provide enhanced cosmetic benefits derived from polyols, such as enhanced moisturizing benefits.

[0031] The compositions and methods according to the present invention will be described in more detail below.

[0032] (cationic polymer) The composition according to the present invention comprises (a) at least one cationic polymer.

[0033] (a) There is no limitation on the type of cationic polymer. Two or more different types of cationic polymers may be used in combination. Therefore, a single type of cationic polymer or a combination of different types of cationic polymers may be used.

[0034] The cationic polymer has a positive charge density. (a) The charge density of the cationic polymer may be 0.01 meq / g to 20 meq / g, preferably 0.05 to 15 meq / g, and more preferably 0.1 to 10 meq / g.

[0035] It may be preferable that the molecular weight of the (a) cationic polymer is 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.

[0036] Unless otherwise defined in the description, "molecular weight" means number average molecular weight.

[0037] (a) The cationic polymer may have at least one positively charged moiety selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups. The term "(primary) amino group" as used herein means an -NH group.

[0038] (a) The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and terpolymers obtained from more than two types of monomers, for example from three types of monomers.

[0039] The (a) cationic polymer may be selected from natural and synthetic cationic polymers. Non-limiting examples of (a) cationic polymers are:

[0040] (1) Homopolymers and copolymers are composed of units of the formula:

[0041] [ka]

[0042] (In the formula: R1 and R2 may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups; R3 may be the same or different and is selected from hydrogen and CH3; the symbols A may be the same or different and are selected from linear or branched alkyl groups containing 1 to 6 carbon atoms, for example 2 to 3 carbon atoms, and hydroxyalkyl groups containing 1 to 4 carbon atoms; R4, R5 and R6 may be the same or different and are selected from alkyl groups containing 1 to 18 carbon atoms, and benzyl groups, and in at least one embodiment alkyl groups containing 1 to 6 carbon atoms; X is derived from esters and amides of acrylic or methacrylic acid containing at least one unit selected from anions derived from inorganic or organic acids, such as methosulfate anion, and halide ions such as chloride and bromide.

[0043] The copolymers of the above family (1) may also contain at least one unit derived from a comonomer, which may be chosen from acrylamide, methacrylamide, diacetone acrylamide, acrylamides and methacrylamides whose nitrogen atoms are substituted with (C1-C4) lower alkyl groups, groups derived from acrylic or methacrylic acid and their esters, vinyl lactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.

[0044] Examples of family (1) copolymers include, but are not limited to: Copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halides, such as the copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described in European Patent Application No. 0 080 976, copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers described in French Patents Nos. 2 077 143 and 2 393 573, dimethylaminoethyl methacrylate / vinyl caprolactam / vinyl Examples include pyrrolidone terpolymers, vinylpyrrolidone / methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymers, and crosslinked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salt polymers, such as a polymer obtained by homopolymerizing dimethylaminoethyl methacrylate quaternized with methyl chloride, or copolymerizing acrylamide and dimethylaminoethyl methacrylate quaternized with methyl chloride, followed by crosslinking with a compound containing olefinic unsaturation, such as methylenebisacrylamide.

[0045] (2) Cationic cellulose polymers, such as cellulose ether derivatives containing one or more quaternary ammonium groups, as described in French Patent No. 1 492 597, such as the 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 quaternary ammonium derivatives of hydroxyethyl cellulose reacted with epoxides substituted with trimethylammonium groups.

[0046] It is preferred that the cationic cellulose polymer has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group, more preferably a quaternary trimethylammonium group.

[0047] The quaternary ammonium group has the following chemical formula (I):

[0048] [ka]

[0049] (In the formula, R1 and R2 each represent a C1-C3 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; R3 is C1~C 24 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; X- represents an anion, preferably a halide ion, more preferably a chloride ion; n represents an integer of 0 to 30, preferably 0 to 10, and more preferably 0; R4 may be present in a quaternary ammonium group-containing group which may be represented by a C1-C4 alkylene group, preferably an ethylene group or a propylene group.

[0050] The leftmost ether bond (-O-) in the above chemical formula (I) can be attached to the sugar ring of a polysaccharide.

[0051] The quaternary ammonium group-containing group is -O-CH2-CH(OH)-CH2-N + It is preferably (CH3)3.

[0052] (3) Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with quaternary ammonium water-soluble monomers, e.g., as described in U.S. Pat. No. 4,131,576, e.g., hydroxyalkyl celluloses, e.g., hydroxymethyl-, hydroxyethyl-, and hydroxypropyl celluloses grafted with salts selected from methacryloylethyltrimethylammonium salts, methacrylamidepropyltrimethylammonium salts, and dimethyldiallylammonium salts.

[0053] Commercially available products corresponding to these polymers include, for example, those sold under the names "Celquat® L 200" and "Celquat® H 100" by National Starch.

[0054] (4) Non-cellulosic cationic polysaccharides, such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid, and dextran hydroxypropyltrimonium chloride, as described in U.S. Patent Nos. 3,589,578 and 4,031,307. Guar gum modified with a salt, such as 2,3-epoxypropyltrimethylammonium chloride (guar hydroxypropyltrimonium chloride), can also be used.

[0055] Such products are sold, for example, by the company MEYHALL under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162.

[0056] (5) Polymers containing piperazinyl units and divalent alkylene or hydroxyalkylene groups containing linear or branched chains optionally interrupted by at least one entity selected from oxygen, sulfur, nitrogen, aromatic rings and heterocycles, and also the oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French Patents Nos. 2,162,025 and 2,280,361.

[0057] (6) Water-soluble polyaminoamides, for example, prepared by polycondensation of acidic compounds with polyamines, which polyaminoamides may be crosslinked with an entity selected from epihalohydrins, diepoxides, dianhydrides, unsaturated dianhydrides, bisunsaturated derivatives, bishalohydrins, bisazetidiniums, bishaloacyldiamines, bisalkylhalides, or oligomers obtained by reacting bifunctional compounds reactive with entities selected from bishalohydrins, bisazetidiniums, bishaloacyldiamines, bisalkylhalides, epihalohydrins, diepoxides, and bisunsaturated derivatives; the crosslinking agent is used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may optionally be alkylated or, if they contain at least one tertiary amine function, may be quaternized. Such polymers are described, for example, in French Patents Nos. 2,252,840 and 2,368,508.

[0058] (7) Polyaminoamide derivatives obtained by condensing polyalkylenepolyamines with polycarboxylic acids followed by alkylation with bifunctional agents, such as adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers, in which 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 ethylene groups. Such polymers are described, for example, in French Patent No. 1,583,363. In at least one embodiment, these derivatives can be selected from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.

[0059] (8) Polymers obtained by reacting a polyalkylenepolyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of polyalkylenepolyamine to dicarboxylic acid may be in the range of 0.8:1 to 1.4:1, and the resulting polyaminoamide is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups of the polyaminoamide in the range of 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Patents 3,227,615 and 2,961,347.

[0060] (9) Cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, for example, having as the main chain building blocks the formulae (Ia) and (Ib):

[0061] [ka]

[0062] (In the formula: k and t may be identical or different and are equal to 0 or 1, the sum k+t is equal to 1; R 12 is selected from hydrogen and a methyl group; R 10 and R 11 may be the same or different and are selected from alkyl groups containing 1 to 6 carbon atoms, hydroxyalkyl groups where the alkyl group contains, for example, 1 to 5 carbon atoms, and lower (C1-C4) amidoalkyl groups, or R 10 and R 11 may, together with the nitrogen atom to which they are attached, form a heterocyclic group, such as piperidinyl and morpholinyl; Homopolymers and copolymers containing at least one unit chosen from units of anions (Y' is an anion, for example bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate). These polymers are described, for example, in French Patent No. 2 080 759 and its Addition No. 2 190 406.

[0063] 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.

[0064] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chlorides, such as the dimethyldiallylammonium chloride homopolymer (Polyquaternium-6) sold under the name "MERQUAT® 100" by CALGON (and its homologs with lower weight average molecular weights), and the copolymer of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550."

[0065] (10) Formula (II):

[0066] [ka]

[0067] (In the formula: R 13 , R 14 , R 15 and R 16 are the same or different and are selected from aliphatic, alicyclic and arylaliphatic groups containing 1 to 20 carbon atoms, and lower hydroxyalkylaliphatic groups; or R 13 , R 14 , R 15 and R 16may together with or separately from the nitrogen atom to which they are attached form a heterocycle optionally containing a second heteroatom other than nitrogen, or R 13 , R 14 , R 15 and R 16 may be the same or different and may be a nitrile group, an ester group, an acyl group, an amide group, -CO-OR 17 -E group and -CO-NH-R 17 -E group (in the formula, R 17 is an alkylene group, and E is a quaternary ammonium group), A1 and B1 may be identical or different and are selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked 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; X - is an anion derived from an inorganic or organic acid, A1, R 13 and R 15 may be taken together with the two nitrogen atoms to which they are attached to form a piperazine ring; When A1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B1 can be selected from the following: -(CH2) n -CO-E'-OC-(CH2) n - wherein E′ is one of the following: a) glycol residues of the formula -OZO-, where Z is a linear or branched hydrocarbon-based group and -(CH2-CH2-O) x -CH2-CH2- -[CH2-CH(CH3)-O] y -CH2-CH(CH3)- (wherein x and y may be the same or different and are selected from integers ranging from 1 to 4 representing a defined unique degree of polymerization and numbers ranging from 1 to 4 representing an average degree of polymerization). selected from the group b) bis-secondary diamine residues, such as piperazine derivatives; c) bis-primary diamine residues of the formula -NH-Y-NH-, where Y is selected from linear or branched hydrocarbon-based groups and the divalent group -CH-CH-SS-CH-CH-, and d) a ureylene group of the formula -NH-CO-NH- A quaternary diammonium polymer comprising at least one repeating unit of the formula (which may be selected from the group consisting of:

[0068] In at least one embodiment, X - is an anion, such as chloride or bromide.

[0069] Polymers of this type are described, for example, in French Patents Nos. 2320330, 2270846, 2316271, 2336434 and 2413907, and in U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,0 ... Nos. 2, 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.

[0070] Non-limiting examples of such polymers include those of formula (III):

[0071] [ka]

[0072] (In the formula, R 13, R 14 , R 15 and R 16 are the same or different and are selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms; n and p are the same or different and are integers ranging from 2 to 20; X - is an anion derived from an inorganic acid or an organic acid).

[0073] (11) Formula (IV):

[0074] [ka]

[0075] (In the formula: R 18 , R 19 , R 20 and R 21 may be the same or different and are hydrogen, methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl, -CH2CH2(OCH2CH2) p OH group (wherein p is selected from an integer ranging from 0 to 6), provided that R 18 , R 19 , R 20 and R 21 and hydrogen at the same time, r and s may be the same or different and are selected from integers ranging from 1 to 6; q is selected from an integer ranging from 0 to 34; X - is an anion, for example a halide ion, A is selected from the group consisting of dihalides and -CH2-CH2-O-CH2-CH2-.

[0076] Such compounds are described, for example, in European Patent Application No. 0122324.

[0077] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0078] Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines such as polyethyleneimine, polymers comprising units selected from vinylpyridine units and vinylpyridinium units, condensates of polyamines with epichlorohydrin, quaternary polyureylenes, and chitin derivatives.

[0079] According to one embodiment of the present invention, the (a) cationic polymer is selected from cellulose ether derivatives containing quaternary ammonium groups, such as the product sold under the name "JR 400" by UNION CARBIDE CORPORATION, cationic cyclopolymers, such as the homopolymers and copolymers of dimethyldiallylammonium chloride sold under the names MERQUAT® 100, MERQUAT® 550 and MERQUAT® S by CALGON, guar gum modified with 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0080] (13) Polyamines As the (a) cationic polymer, it is also possible to use (co)polyamines, which may be homopolymers or copolymers having multiple amino groups. The amino groups may be primary, secondary, tertiary, or quaternary amino groups. The amino groups may be present in the polymer backbone of the (co)polyamine or, if present, in pendant groups.

[0081] Examples of (co)polyamines include chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate, (co)polyvinylpyridines such as (co)poly-1-methyl-2-vinylpyridine, (co)polyimines such as (co)polyethyleneimine, (co)polypyridines such as (co)poly(quaternary pyridine), (co)polybiguanides such as (co)polyaminopropylbiguanide, (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinyl acetal, and salts thereof.

[0082] It may be preferred that the (a) cationic polymer is selected from chitosan.

[0083] In some cases it may be preferred that the (a) cationic polymer is selected from (co)polylysine.

[0084] Polylysine is well known. Polylysine may be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine may be α-poly-L-lysine and ε-poly-L-lysine, which are typically used as natural preservatives 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 may be in the form of a salt and / or a solution.

[0085] (14) Cationic polyamino acids (a) As the cationic polymer, it may be possible to use a cationic polyamino acid, which may be a cationic homopolymer or copolymer having a plurality of amino and carboxyl groups. The amino groups may be primary, secondary, tertiary, or quaternary amino groups. The amino groups may be present in the polymer backbone of the cationic polyamino acid or, if present, in pendant groups. The carboxyl groups may be present in pendant groups of the cationic polyamino acid, if present.

[0086] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, steardimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, and cocodimonium hydroxypropyl hydrolyzed soy protein.

[0087] The following description relates to preferred embodiments of (a) the cationic polymer.

[0088] It may be preferred that the (a) cationic polymer is selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as chitosan and (co)polylysine, cationic (co)polyamino acids, such as cationized collagen, cationic cellulose polymers, and salts thereof.

[0089] It may be more preferred that the (a) cationic polymer is selected from the group consisting of polylysine, chitosan, and mixtures thereof.

[0090] The amount of (a) cationic polymer in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, relative to the total weight of the composition.

[0091] The amount of (a) cationic polymer in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, relative to the total weight of the composition.

[0092] The amount of (a) cationic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0093] (anionic polymer) The composition according to the present invention may also comprise (e) at least one anionic polymer.

[0094] When the composition according to the present invention contains (e) anionic polymer, (a) cationic polymer can form a polyion complex with (e) anionic polymer.

[0095] (e) There is no limitation on the type of anionic polymer. Two or more different types of anionic polymers may be used in combination. Therefore, a single type of anionic polymer or a combination of different types of anionic polymers may be used.

[0096] The anionic polymer has a positive charge density. (e) When the anionic polymer is a synthetic anionic polymer, the charge density of the anionic polymer may be 0.1 meq / g to 20 meq / g, preferably 1 to 15 meq / g, and more preferably 4 to 10 meq / g, and (e) when the anionic polymer is a natural anionic polymer, the average degree of substitution of the anionic polymer may be 0.1 to 3.0, preferably 0.2 to 2.7, and more preferably 0.3 to 2.5.

[0097] (e) It may be preferred that the molecular weight of the anionic polymer is 1,000 or more, preferably 3,000 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.

[0098] Unless otherwise defined in the description, "molecular weight" can mean number average molecular weight.

[0099] (e) The anionic polymer may have at least one negatively charged and / or negatively charged moiety selected from the group consisting of sulfate groups, sulfate groups, sulfonic acid groups, sulfonate groups, phosphoric acid groups, phosphate groups, phosphonic acid groups, phosphonate groups, carboxylic acid groups, and carboxylate groups.

[0100] (e) The anionic polymer may be a homopolymer or a copolymer, the term "copolymer" being understood to mean both copolymers obtained from two types of monomers and terpolymers obtained from more than two types of monomers, for example from three types of monomers.

[0101] (e) The anionic polymer can be selected from natural and synthetic anionic polymers.

[0102] (e) The anionic polymer may include at least one hydrophobic chain.

[0103] Anionic polymers which may comprise at least one hydrophobic chain can be obtained by copolymerizing a monomer (a) chosen from a carboxylic acid containing α,β-ethylenic unsaturation (monomer a′) and 2-acrylamido-2-methylpropanesulfonic acid (monomer a″) with a non-surface-active monomer containing ethylenic unsaturation other than (a) (b) and / or a monomer (c) containing ethylenic unsaturation obtained by reacting an acrylic monomer containing α,β-monoethylenic unsaturation or an isocyanate monomer containing monoethylenic unsaturation with a monovalent nonionic amphiphilic component or a primary or secondary fatty amine.

[0104] Therefore, anionic polymers with at least one hydrophobic chain can be synthesized via two synthetic routes: - copolymerization of the monomers (a') and (c), or (a'), (b) and (c), or (a'') and (c), or (a''), (b) and (c), or modification (e.g. esterification or amidation) of the monomer (a') or of a copolymer formed from the monomers (a') and (b) or (a'') and (b) with a monovalent nonionic amphiphilic compound or with a primary or secondary fatty amine, It can be obtained by either

[0105] As 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made in particular of those disclosed in the article "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10, pp. 3694-3704" and in the applications EP-A-0750899 and EP-A-1069172.

[0106] The carboxylic acid containing α,β-monoethylenic unsaturation constituting the monomer (a′) can be chosen from a large number of acids, in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid, and is preferably acrylic acid or methacrylic acid.

[0107] The copolymer may also contain a monomer (b) containing monoethylenic unsaturation that does not have surfactant properties. Preferred monomers are those that, when homopolymerized, result in a water-insoluble polymer. These can be selected, for example, from acrylic acid and alkyl (C1-C4) methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, or the corresponding methacrylates. More particularly preferred monomers are methyl acrylate and ethyl acrylate. Other monomers that can be used are, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile, and vinylidene chloride. Non-reactive monomers are preferred, and these monomers are those in which a single ethylenic group is the only group reactive under the polymerization conditions. However, monomers containing a group that reacts under the action of heat, such as hydroxyethyl acrylate, can optionally be used.

[0108] Monomer (c) is obtained by reacting an acrylic monomer containing α,β-monoethylenic unsaturation, such as (a), or an isocyanate monomer containing monoethylenic unsaturation, with a monovalent nonionic amphiphilic compound or a primary or secondary fatty amine.

[0109] The monovalent nonionic amphiphilic compounds or primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. The monovalent nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds containing alkylene oxides that form the hydrophilic portion of the molecule. The hydrophobic compounds are generally composed of aliphatic alcohols or alkylphenols, in which a carbonaceous chain containing at least 6 carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.

[0110] Preferred monovalent nonionic amphiphilic compounds have the following formula (V): R-(OCH2CHR') m -(OCH2CH2) n -OH (V) wherein R is selected from alkyl or alkylene groups containing 6 to 30 carbon atoms and alkylaryl groups having alkyl groups containing 8 to 30 carbon atoms; R' is selected from alkyl groups containing 1 to 4 carbon atoms; n is an average number ranging from approximately 1 to 150; and m is an average number ranging from approximately 0 to 50, with the proviso that n is at least as large as m.

[0111] Preferably, in the compounds of formula (V), the R group is an alkyl group containing 12 to 26 carbon atoms and the alkyl group is a C8-C 13 wherein R' is a methyl group, m=0, and n=1 to 25.

[0112] Preferred primary and secondary fatty amines are composed of one or two alkyl chains containing from 6 to 30 carbon atoms.

[0113] The monomers used to form the nonionic urethane monomer (c) can be selected from a wide variety of compounds. Any compound containing copolymerizable unsaturation, such as acrylic, methacrylic, or allylic unsaturation, may be used. Monomer (c) can be derived, in particular, from isocyanates containing monoethylenic unsaturation, such as, in particular, α,α-dimethyl-m-isopropenylbenzyl isocyanate.

[0114] Monomer (c) is in particular an oxyethylenated (1 to 50 EO) C-C 30 Acrylates, methacrylates or itaconates of fatty alcohols, such as steareth-20 methacrylate, oxyethylenated (25EO) behenyl methacrylate, oxyethylenated (20EO) monocetyl itaconate, oxyethylenated (20EO) monostearyl itaconate or polyoxyethylenated (25EO) C 12~C 24 From alcohol-modified acrylates and oxyethylenated (1 to 50EO) C6 to C 30 They may also be selected from the dimethyl-m-isopropenylbenzyl isocyanates of fatty alcohols, such as the dimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenyl alcohol in particular.

[0115] According to certain embodiments of the present invention, the (e) anionic polymer is selected from an acrylic terpolymer obtained from (a) a carboxylic acid containing α,β-ethylenic unsaturation, (b) a non-surface-active monomer containing ethylenic unsaturation other than (a), and (c) a nonionic urethane monomer that is the reaction product of a monovalent nonionic amphiphilic compound with an isocyanate containing monoethylenic unsaturation.

[0116] Examples of anionic polymers comprising at least one hydrophobic chain include, in particular, acrylic acid / ethyl acrylate / alkyl acrylate terpolymers, such as the product sold as a 30% aqueous dispersion under the name Acusol 823 by Rohm & Haas; acrylates / steareth-20 methacrylate copolymers, such as the product sold as an aqueous emulsion under the name Aculyn 22 by Rohm & Haas; (meth)acrylic acid / ethyl acrylate / oxyethylated (25EO) behenyl methacrylate terpolymers, such as the product sold as an aqueous emulsion under the name Aculyn 28 by Rohm & Haas; acrylic acid / oxyethylated (20EO) monocetyl itaconate copolymers, such as the product sold as a 30% aqueous dispersion under the name Structure 3001 by National Starch; acrylic acid / oxyethylated (20EO) monostearyl itaconate copolymers, such as the product sold as a 30% aqueous dispersion under the name Structure 3001 by National Starch. Product sold as a 30% aqueous dispersion in 2001; Acrylate / Polyoxyethylenated (25EO)C 12 ~C 24Mention may be made of copolymers of alcohol-modified acrylates, such as the 30-32% copolymer latex sold under the name Synthalen W2000 by the company 3V SA; or the terpolymer of methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol with dimethyl-meta-isopropenylbenzyl isocyanate, such as the product disclosed in document EP-A-0 173 109 as a 24% aqueous dispersion containing 40 ethylene oxide groups.

[0117] (e) The anionic polymer may also be polyester-5, such as the product sold by Eastman Chemical Company under the name Eastman AQ™ 55S Polymer, having the following chemical formula:

[0118] [ka]

[0119] A: Dicarboxylic acid moiety G: glycol moiety SO3 - Na + : Sodium sulfo group OH: hydroxyl group

[0120] (e) It may be preferred that the anionic polymer is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (e.g., carboxymethylcellulose and cellulose gum), anionic (co)polyamino acids such as (co)polyglutamic acid, (co)poly(meth)acrylic acid, (co)polyamine acid, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acid, (co)polyfumaric acid, maleic acid (co)polymers, and salts thereof.

[0121] The maleic acid copolymer may comprise one or more maleic acid comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing from 2 to 20 carbon atoms, and styrene.

[0122] Thus, "maleic acid copolymer" is understood to mean any polymer obtained by copolymerization of one or more maleic acid comonomers with one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic acid comonomers optionally being partially or completely hydrolyzed. Preferably, hydrophilic polymers are used, i.e. polymers with a water solubility of 2 g / l or more.

[0123] In an advantageous embodiment of the invention, the maleic acid copolymer may have a mole fraction of maleic acid units between 0.1 and 1, more preferably between 0.4 and 0.9.

[0124] The weight average molar mass of the maleic acid copolymers can be between 1,000 and 500,000, preferably between 1,000 and 50,000.

[0125] It is preferred that the maleic acid copolymer is a styrene / maleic acid copolymer, more preferably sodium styrene / maleic acid copolymer.

[0126] Preferably, a copolymer of styrene and maleic acid in a 50 / 50 ratio is used.

[0127] For example, a styrene / maleic acid (50 / 50) copolymer in the form of its ammonium salt at 30% in water sold under the reference SMA1000H® by Cray Valley, or a styrene / maleic acid (50 / 50) copolymer in the form of its sodium salt at 40% in water sold under the reference SMA1000HNa® by Cray Valley, may be used.

[0128] The use of styrene / maleic acid copolymers, such as sodium styrene / maleic acid copolymer, can improve the wettability of films prepared with compositions according to the present invention.

[0129] According to one embodiment of the present invention, (e) the anionic polymer is preferably selected from hyaluronic acid and its derivatives.

[0130] Hyaluronic acid can be represented by the following chemical formula:

[0131] [ka]

[0132] In the context of the present invention, the term "hyaluronic acid" specifically refers to a compound of the formula:

[0133] [ka]

[0134] It includes the basic unit of hyaluronic acid.

[0135] It is the smallest part of hyaluronic acid, containing a disaccharide dimer, namely D-glucuronic acid and N-acetylglucosamine.

[0136] The term "hyaluronic acid and its derivatives" in the context of the present invention also includes linear polymers comprising the above polymer units linked together in a chain via alternating β(1,4) and β(1,3) glycosidic bonds, with a molecular weight (MW) that can range between 380 and 13,000,000 daltons, which depends primarily on the source from which the hyaluronic acid is obtained and / or the preparation method.

[0137] The term "hyaluronic acid and its derivatives" in the context of the present invention also includes hyaluronic acid salts, which may include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

[0138] In nature, hyaluronic acid is found in the percellular gel in the matrix of connective tissues of vertebrate organs, such as the dermis and epithelial tissues, specifically in the epidermis, synovial fluid of joints, vitreous humor, human umbilical cord, and crest process.

[0139] Therefore, the term "hyaluronic acid and its derivatives" includes all fractions or subunits of hyaluronic acid, especially those having molecular weights within the range of molecular weights envisaged above.

[0140] In the context of the present invention, it is preferred to use hyaluronic acid fractions that do not have inflammatory activity.

[0141] Reference can be made to the article "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006), pp. 699-715, which provides an overview of the listed biological activities of hyaluronic acid according to its molecular weight through examples of various hyaluronic acid fractions.

[0142] According to a preferred embodiment of the present invention, the hyaluronic acid fraction suitable for use in the present invention has a molecular weight of between 50,000 and 5,000,000, in particular between 100,000 and 5,000,000, and especially between 400,000 and 5,000,000 Da, in which case the term used is high molecular weight hyaluronic acid.

[0143] Alternatively, hyaluronic acid fractions that may also be suitable for use within the present invention have a molecular weight between 50,000 and 400,000 Da, in which case the term used is intermediate molecular weight hyaluronic acid.

[0144] Additionally or alternatively, hyaluronic acid fractions that may be suitable for use within the present invention have a molecular weight of less than 50,000 Da, in which case the term used is low molecular weight hyaluronic acid.

[0145] Finally, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid esters, in particular those in which all or part of the carboxylic acid groups of the acid functions are esterified with oxyethylenated alkyls or alcohols, containing 1 to 20 carbon atoms, in particular with a degree of substitution at the level of D-glucuronic acid of hyaluronic acid ranging from 0.5 to 50%.

[0146] Mention may in particular be made of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid, which are described in detail in D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) pp. 2101-2127.

[0147] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.

[0148] The molecular weights shown above are also valid for hyaluronic acid esters.

[0149] Hyaluronic acid is available, in particular, from Hyactive under the trade name CPN (MW: 10-150 kDa) and from Soliance under the trade name Cristalhyal (MW: 1.1 x 10 6 ), hyaluronic acid supplied by Bioland under the name Nutra HA (MW: 820 000 Da), by Bioland under the name Nutra AF (MW: 69 000 Da), by Bioland under the name Oligo HA (MW: 6100 Da) or by Vam Farmacos Metica under the name D Factor (MW: 380 Da).

[0150] (e) It may be preferred that the anionic polymer is selected from natural anionic polymers, more preferably polysaccharides.

[0151] (e) It may be even more preferred that the anionic polymer is selected from the group consisting of hyaluronic acid and its derivatives, cellulose polymers and their salts, such as carboxymethylcellulose and cellulose gum (sodium carboxymethylcellulose), and mixtures thereof.

[0152] Thus, (e) the anionic polymer may be selected from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and mixtures thereof, more preferably hyaluronic acid and its salts (e.g., sodium hyaluronate), carboxymethylcellulose and its salts, such as cellulose gum, and mixtures thereof.

[0153] The amount of (e) anionic polymer in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, relative to the total weight of the composition.

[0154] The amount of (e) anionic polymer in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, relative to the total weight of the composition.

[0155] The amount of (e) anionic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0156] The total amount of (a) cationic polymer and (e) anionic polymer in the composition according to the present invention may be 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, based on the total weight of the composition.

[0157] The total amount of (a) cationic polymer and (e) anionic polymer in the composition according to the present invention may be 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, based on the total weight of the composition.

[0158] The total amount of (a) cationic polymer and (e) anionic polymer in the composition according to the present invention may be 0.1% by mass to 20% by mass, preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass, relative to the total mass of the composition.

[0159] The amount of (a) cationic polymer / (e) anionic polymer, for example, the ratio of chemical equivalents, may be 0.05 to 18, preferably 0.1 to 10, and more preferably 0.5 to 5.0. Specifically, it may be preferable that the ratio of the number of cationic groups in (a) cationic polymer / the number of anionic groups in (e) anionic polymer is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5 to 5.0.

[0160] (Non-polymeric acids with two or more acid dissociation constants) The composition according to the present invention comprises (b) at least one non-polymeric acid or salt thereof having two or more pKa values, i.e., at least one non-polymeric acid or salt thereof having two or more acid dissociation constants. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined at a certain temperature, for example, 25°C.

[0161] The (b) non-polymeric acid having two or more pKa values ​​can function as a crosslinker for the (a) cationic polymer. The (a) cationic polymer may be ionically crosslinked by the (b) non-polymeric acid or salt thereof having two or more pKa values.

[0162] The term "non-polymeric" as used herein means that the acid is not obtained by polymerizing two or more monomers, and therefore does not correspond to acids obtained by polymerizing two or more monomers, such as polycarboxylic acids.

[0163] (b) The molecular weight of the non-polymeric acid or salt thereof having two or more pKa values ​​is preferably 1,000 or less, more preferably 800 or less, and even more preferably 700 or less.

[0164] (b) There is no limitation on the type of non-polymeric acid or salt thereof having two or more pKa values. Two or more different types of non-polymeric acids or salts thereof having two or more pKa values ​​may be used in combination. Therefore, a single type of non-polymeric acid or salt thereof having two or more pKa values, or a combination of different types of non-polymeric acids or salts thereof having two or more pKa values, may be used.

[0165] The term "salt" as used herein refers to a salt formed by adding a suitable 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 base according to a method known to those skilled in the art. The salt can include metal salts, such as salts with alkali metals such as Na and K and salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

[0166] (b) The non-polymeric acid or salt thereof having two or more pKa values ​​may be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof.

[0167] (b) The non-polymeric acid having two or more pKa values ​​can have at least two acid groups selected from the group consisting of carboxylic acid groups, sulfate groups, sulfonic acid groups, phosphate groups, phosphonic acid groups, phenolic hydroxyl groups, and mixtures thereof.

[0168] (b) The non-polymeric acid having two or more pKa values ​​may be a non-polymeric polyacid.

[0169] (b) The non-polymeric acid having two or more pKa values ​​can be selected from the group consisting of dicarboxylic acids, disulfonic acids, and diphosphoric acids, and mixtures thereof.

[0170] (b) Non-polymeric acids or salts thereof having two or more pKa values ​​include 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 salts thereof; aspartic acid, glutamic acid, and salts thereof; terephthalylidene dicamphorsulfonic acid, and salts thereof (Mexoryl SX), Benzophenone-9; Phytic Acid and Its Salts; Red No. 2 (Amaranth), Red No. 102 (New Coccine), Yellow No. 5 (Tartrazine), Yellow No. 6 (Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Red No. 201 (Lithol Rubin B), Red No. 202 (Lithol Rubin BCA), Red No. 204 (Lake Red CBA), Red No. 206 (Lithol Red CA), Red No. 207 (Lithol Red BA), Red No. 208 (Lithol Red SR), Red No. 219 (Brilliant Lake Red R), Red No. 220 (Deep Maroon), Red No. 227 (Fast Acid Magenta), Yellow No. 203 (Quinoline Yellow W) S), Green No. 201 (Alizanin Cyanine Green F), Green No. 204 (Pyranine Concentrate), Green No. 205 (Light Green SF Yellow), Blue No. 203 (Patent Blue CA), Blue No. 205 (Alphazurine FG), Red No. 401 (Violamin R), Red No. 405 (Permanent Red F5R), Red No. 502 (Ponceau 3R), Red No. 503 (Ponceau R), Red No. 504 (Ponceau SX), Green No. 401 (Naphthol Green B), Green No. 402 (Guinea Green B) and Black No. 401 (Naphthol Blue Black); folic acid, ascorbic acid, erythorbic acid and salts thereof; cystine and salts thereof; EDTA and salts thereof; glycyrrhizin and salts thereof; and mixtures thereof.

[0171] (b) It may be preferred that the non-polymeric acid or salt thereof having two or more pKa values ​​is selected from the group consisting of terephthalylidene dicamphorsulfonic acid and its salts (Mexoryl SX), Yellow No. 6 (Sunset Yellow FCF), ascorbic acid, phytic acid, and salts thereof, and mixtures thereof.

[0172] (b) It may be more preferred that the non-polymeric acid or salt thereof having two or more pKa values ​​is selected from the group consisting of terephthalylidene dicamphorsulfonic acid and its salts (Mexoryl SX), phytic acid and their salts, and mixtures thereof.

[0173] The amount of (b) the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, based on the total weight of the composition.

[0174] The amount of (b) the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the composition.

[0175] The amount of (b) the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0176] [Polyol] The composition according to the present invention comprises (c) at least one polyol. When two or more polyols are used, they may be the same or different.

[0177] The term "polyol" as used herein refers to an alcohol having two or more hydroxy groups and does not include sugars or their derivatives. Sugar derivatives include sugar alcohols obtained by reducing one or more carbonyl groups of a sugar, and sugars or sugar alcohols in which the hydrogen atom in one or more of the hydroxy groups has been replaced with at least one substituent, such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group, or a carbonyl group.

[0178] The polyols used in the present invention are liquid at room temperature, such as 25° C., under atmospheric pressure (760 mmHg or 105 Pa).

[0179] (c) The polyol is a C hydroxyl group containing at least two hydroxyl groups, preferably 2 to 5 hydroxyl groups. 2~24 Polyol, preferably C 2~9 It may also be a polyol.

[0180] (c) The polyol may be a natural or synthetic polyol. The polyol may have a linear, branched, or cyclic molecular structure.

[0181] (c) The polyol may be selected from glycerin and its derivatives, and glycols and their derivatives. The polyol may be glycerin, diglycerin, polyglycerin, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, C6 to C8 24 It may be selected from the group consisting of polyethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol.

[0182] (c) The polyol is preferably glycerin.

[0183] The amount of (c) polyol in the composition used in the present invention is 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more, based on the total mass of the composition.

[0184] On the other hand, the amount of (c) polyol in the composition used in the present invention may be 95% by mass or less, preferably 60% by mass or less, more preferably 30% by mass or less, based on the total mass of the composition.

[0185] The amount of (c) polyol in the composition used in the present invention may be in the range of 10% by mass to 95% by mass, preferably 10% by mass to 60% by mass, and more preferably 10% by mass to 30% by mass, relative to the total mass of the composition.

[0186] [water] The composition according to the present invention comprises (d) water.

[0187] (d) The amount of water may be 1% 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.

[0188] (d) The amount of water may be 90% by weight or less, preferably 50% by weight or less, and more preferably 10% by weight or less, based on the total weight of the composition.

[0189] The amount of (d) water may be 1% by mass to 90% by mass, preferably 30% by mass to 90% by mass, and more preferably 50% by mass to 90% by mass, relative to the total mass of the composition.

[0190] [pH] The pH of the composition according to the present invention may be 9.0 or less, preferably 8.5 or less, more preferably 8.1 or less.

[0191] The pH of the composition according to the present invention may be 3.0 or higher, preferably 3.3 or higher, more preferably 3.5 or higher.

[0192] The pH of the composition according to the present invention may be 3.0 to 9.0, preferably 3.3 to 8.5, and more preferably 3.5 to 8.1.

[0193] At a pH of 3.0 to 9.0, the composition according to the present invention can be very stable.

[0194] The pH of the composition according to the present invention can be adjusted by adding at least one alkaline agent and / or at least one acid other than (b) a non-polymeric acid or a salt thereof having two or more pKa values. The pH of the composition according to the present invention can also be adjusted by adding at least one buffering agent.

[0195] (Alkaline agent) The composition according to the present invention may contain at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

[0196] The alkaline agent may be an inorganic alkaline agent, preferably selected from the group consisting of ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates and monohydrogen phosphates, such as sodium phosphate or sodium monohydrogen phosphate.

[0197] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. Sodium hydroxide is preferred as the inorganic alkaline agent.

[0198] The alkaline agent may be an organic alkaline agent, which is preferably selected from the group consisting of monoamines and derivatives thereof, diamines and derivatives thereof, polyamines and derivatives thereof, basic amino acids and derivatives thereof, oligomers of basic amino acids and derivatives thereof, polymers of basic amino acids and derivatives thereof, urea and derivatives thereof, and guanidine and derivatives thereof.

[0199] Examples of organic alkaline agents include alkanolamines, such as mono-, di-, and tri-ethanolamine, and isopropanolamine; urea, guanidine, and derivatives thereof; basic amino acids, such as lysine, ornithine, or arginine; and diamines, such as those having the following structure:

[0200] [ka]

[0201] (wherein R represents an alkylene group such as propylene optionally substituted with a hydroxyl group or a C1-C4 alkyl group, and R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group, or a C1-C4 hydroxyalkyl group), and examples thereof include 1,3-propanediamine and its derivatives. Arginine, urea, and monoethanolamine are preferred.

[0202] The alkaline agent can be used in a total amount of 0.01% by mass to 15% by mass, preferably 0.02% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass, relative to the total mass of the composition, depending on the solubility thereof.

[0203] (acid) The compositions according to the present invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.

[0204] The acid may be any inorganic or organic acid commonly used in cosmetics, preferably an inorganic acid. Monobasic and / or polybasic acids may be used. Monobasic acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid, and hydrochloric acid (HCl) may be used. HCl is preferred.

[0205] Depending on their solubility, acids can be used in a total amount of 0.01% by mass to 15% by mass, preferably 0.02% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass, relative to the total mass of the composition.

[0206] (buffering agent) The compositions according to the present invention may contain at least one buffering agent. Two or more buffering agents may be used in combination. Thus, a single type of buffering agent or a combination of different types of buffering agents may be used.

[0207] Buffers can include acetate buffers (e.g., acetic acid plus sodium acetate), phosphate buffers (e.g., sodium dihydrogen phosphate plus disodium hydrogen phosphate), citrate buffers (e.g., citric acid plus sodium citrate), borate buffers (e.g., boric acid plus sodium borate), tartrate buffers (e.g., tartaric acid plus sodium tartrate dihydrate), Tris buffers (e.g., tris(hydroxymethyl)aminomethane), and Hepes buffer (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[0208] [Optional ingredients] In addition to the aforementioned essential components (components (a) to (d)), the composition according to the present invention may contain optional components, such as (e) anionic polymers, as well as components typically used in cosmetics, specifically surfactants (particularly nonionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or nonvolatile solvents other than component (c), hydrophilic or hydrophobic UV filters, silicones and silicone derivatives, natural extracts derived from animals or plants, oils, waxes, etc., within ranges that do not impair the effects of the present invention.

[0209] The composition according to the present invention may contain the above-mentioned optional components in an amount of 0.01% to 50% by mass, preferably 0.05% to 30% by mass, and more preferably 0.1% to 10% by mass, relative to the total mass of the composition.

[0210] The composition according to the invention may be free of surfactants or may contain limited amounts of surfactants, for example less than 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight, relative to the total weight of the composition.

[0211] [Preparation] The compositions according to the present invention can be prepared by mixing the essential and optional ingredients described above in a conventional manner.

[0212] For example, the composition according to the present invention comprises: (a) at least one cationic polymer; (b) at least one non-polymeric acid or salt thereof having two or more pKa values; (c) at least one polyol, and (d) water wherein the amount of (c) polyol in the composition is 10% by mass or more based on the total mass of the composition.

[0213] Any of the optional ingredients may be further incorporated, for example, (e) at least one anionic polymer.

[0214] The mixing can be carried out at any temperature, such as room temperature (e.g., 25°C), preferably without heating. The compositions according to the present invention can be prepared without any heating step, which may make them environmentally friendly.

[0215] It is preferred that the cosmetic composition according to the present invention is in liquid form at room temperature (eg 25°C).

[0216] [Coating] The composition according to the present invention can be used to easily prepare a coating.

[0217] The present invention therefore also relates to a method for preparing a film, preferably a cosmetic film, optionally having a thickness of preferably at least 10 nm, more preferably at least 50 nm, even more preferably at least 100 nm, comprising: applying a composition according to the invention to a substrate, preferably keratinous materials, more preferably skin and hair; and drying the composition.

[0218] There is no upper limit to the thickness of the coating. Therefore, for example, the thickness of the coating may be 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less.

[0219] Therefore, the present invention also provides a film, preferably a cosmetic film, comprising: (a) at least one cationic polymer; (b) at least one non-polymeric acid or salt thereof having two or more pKa values, and (c) at least one polyol The present invention also relates to a coating comprising:

[0220] The coating may further comprise (d) water.

[0221] The film, preferably the cosmetic film, is resistant to water having a pH of 7 or less and is removable by water having a pH of more than 7, preferably 8 or more, more preferably 9 or more.

[0222] In other words, the film, preferably the cosmetic film, may be water-resistant under neutral or acidic conditions, such as a pH of 7 or less, preferably in the range of 6 or more and 7 or less, more preferably in the range of 5 or more and 7 or less, while the film, preferably the cosmetic film, may be removed under alkaline conditions, such as a pH of more than 7, preferably 8 or more, more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11.

[0223] Accordingly, the film, preferably the cosmetic film, can be water-resistant, and therefore can remain on keratinous materials such as skin and hair, even when the surface of the keratinous material is wet, for example, by sweat or rain. On the other hand, the film, preferably the cosmetic film, can be easily removed from keratinous materials under alkaline conditions. Therefore, although the film, preferably the cosmetic film, is difficult to remove with water, it can be easily removed, for example, using a soap that can create alkaline conditions.

[0224] Furthermore, the above-mentioned films may have cosmetic benefits such as absorbing or adsorbing malodors, changing the appearance of keratinous materials such as skin and hair, changing the feel of keratinous materials, and / or protecting keratinous materials from, for example, dirt or pollutants, due to the properties of the film, even if the film does not contain any cosmetic active ingredients.

[0225] When the above-mentioned film contains (c) at least one polyol such as glycerin, the film can have the cosmetic effect, for example, moisturizing effect, brought about by the (c) polyol.

[0226] [Cosmetic uses and cosmetic methods] The composition according to the present invention may be used as a cosmetic composition, preferably a care cosmetic composition, more preferably a skin care or hair care cosmetic composition.

[0227] Therefore, the cosmetic composition according to the present invention may be intended for application to a keratinous substance. The keratinous substance may be a keratinous fiber. In this specification, the term "keratinous fiber" refers to a fiber containing keratin as a main component, and examples thereof include hair, eyelashes, eyebrows, etc. On the other hand, the keratinous substance may be skin or a mucous membrane such as the lips.

[0228] The compositions according to the invention can preferably be used as leave-on or rinse-off cosmetic compositions for keratinous materials such as skin and hair.

[0229] "Leave-on" as used herein means that the composition according to the present invention is not removed from keratinous materials such as skin and hair after being applied onto the keratinous materials.

[0230] "Rinse-off" as used herein means that the composition according to the present invention is removed from keratinous materials such as skin and hair by rinsing after being applied thereto. Water can be used for rinsing. Even after rinsing off, the composition according to the present invention can remain and form a film or coating on keratinous materials such as skin and hair.

[0231] The present invention also provides a method for treating keratinous materials such as skin and hair, applying a composition according to the invention to keratinous materials; drying the composition to form a cosmetic film on the keratinous material; A beauty method including the For preparing a film, preferably a cosmetic film, applying a composition according to the invention onto keratinous materials such as skin and hair; and drying the composition.

[0232] Cosmetic method means herein a non-therapeutic cosmetic method for caring for keratinous materials such as skin and hair and / or styling keratinous fibers such as hair.

[0233] The present invention may also relate to the use of a composition according to the invention for the preparation of a cosmetic film on keratinous materials such as the skin and hair.

[0234] The present invention also provides (a) at least one cationic polymer; (b) at least one non-polymeric acid or salt thereof having two or more pKa values; For keratinous materials such as skin and hair, (c) at least one polyol, and (d) water The present invention may also relate to use of the polyol (c) in a cosmetic composition comprising the composition to reduce stickiness of the composition, wherein the amount of the polyol (c) in the composition is 10% by mass or more relative to the total mass of the composition.

[0235] The use according to the present invention can reduce stickiness of a composition comprising components (c) and (d) by combining components (a) and (b) optionally with component (e), wherein the amount of component (c) in the composition is 10% by mass or more relative to the total mass of the composition.

[0236] The explanations regarding components (a) to (e) in the composition according to the present invention can be applied to the explanations regarding the use according to the present invention. [Example]

[0237] The present invention will now be described in a more detailed manner by means of examples, which should not, however, be construed as limiting the scope of the present invention.

[0238] (Examples 1 to 4 and Comparative Examples 1 to 4) [Preparation] Each of the compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 was prepared by mixing the components shown in Table 1 at room temperature (25°C). All numerical values ​​for the amounts of components in Table 1 are based on "mass %" of the raw materials.

[0239] [Table 1]

[0240] [evaluation] (gel film formation) A 10 g amount of each of the compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0241] Five experts evaluated the formation of the gel film in the Petri dishes according to the following grading scale: 5: A uniform gel film was formed (the gel film was uniformly distributed on the Petri dish) 4: A gel film was formed, but it was not uniform (the gel film was unevenly distributed on the Petri dish). 3: A slight gel film was formed 2: Very little gel film formed 1: No gel film formed

[0242] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0243] The results are shown in Table 1.

[0244] (texture) A 10 g amount of each of the compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0245] Five experts evaluated the texture on the Petri dish according to the following ratings: 5: Non-sticky (very smooth) 4: Very slight stickiness (smooth) 3: Slightly sticky 2: Sticky 1: Very sticky

[0246] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0247] The results are shown in Table 1.

[0248] (Summary) The compositions according to Examples 1 to 4 formed a gel film. The compositions according to Examples 1 and 2 formed a better gel film than the compositions according to Examples 3 and 4.

[0249] The compositions according to Comparative Examples 1 to 4 were unable to form gels at all.

[0250] The compositions according to Comparative Examples 2 and 4 did not contain glycerin, and therefore the texture of the compositions was not evaluated.

[0251] It has been demonstrated that cationic polymers (polylysine and chitosan), crosslinkers (phytic acid or terephthalylidene dicamphorsulfonic acid) and glycerin can form a gel film (coacervate), reducing the stickiness inherent in glycerin.

[0252] (Examples 5 to 6 and Comparative Examples 5 to 6) [Preparation] Each of the compositions according to Examples 5 and 6 and Comparative Examples 5 and 6 was prepared by mixing the components shown in Table 2 at room temperature (25°C). All numerical values ​​for the amounts of components in Table 2 are based on "mass %" of the raw materials.

[0253] [Table 2]

[0254] [evaluation] (gel film formation) A 10 g amount of each of the compositions according to Examples 5-6 and Comparative Examples 5-6 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0255] Five experts evaluated the formation of the gel film in the Petri dishes according to the following grading scale: 5: A uniform gel film was formed (the gel film was uniformly distributed on the Petri dish) 4: A gel film was formed, but it was not uniform (the gel film was unevenly distributed on the Petri dish). 3: A slight gel film was formed 2: Very little gel film formed 1: No gel film formed

[0256] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0257] The results are shown in Table 2.

[0258] (texture) A 10 g amount of each of the compositions according to Examples 5-6 and Comparative Examples 5-6 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0259] Five experts evaluated the texture on the Petri dish according to the following ratings: 5: Non-sticky (very smooth) 4: Very slight stickiness (smooth) 3: Slightly sticky 2: Sticky 1: Very sticky

[0260] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0261] The results are shown in Table 2.

[0262] (Summary) The compositions according to Examples 5 and 6 formed a uniform gel film that spread over the entire surface of the Petri dish.

[0263] The compositions of Comparative Examples 5 and 6 were unable to form gels at all.

[0264] Since the composition according to Comparative Example 5 did not contain glycerin, the stickiness of the composition was not evaluated.

[0265] It has been demonstrated that anionic polymers (sodium hyaluronate and cellulose gum) can be added to a cationic polymer (polylysine), a cross-linker (phytic acid) and glycerin to form a gel film (coacervate), and that the gel film thus formed is more favorable (more uniform).

[0266] (Examples 7 to 8 and Comparative Examples 7 to 8) [Preparation] Each of the compositions according to Examples 7 to 8 and Comparative Examples 7 to 8 was prepared by mixing the components shown in Table 3 at room temperature (25°C). All numerical values ​​for the amounts of components in Table 3 are based on "mass %" of the raw materials.

[0267] [Table 3]

[0268] [evaluation] (gel film formation) A 10 g amount of each of the compositions according to Examples 7-8 and Comparative Examples 7-8 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0269] Five experts evaluated the formation of the gel film in the Petri dishes according to the following grading scale: 5: A uniform gel film was formed (the gel film was uniformly distributed on the Petri dish) 4: A gel film was formed, but it was not uniform (the gel film was unevenly distributed on the Petri dish). 3: A slight gel film was formed 2: Very little gel film formed 1: No gel film formed

[0270] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0271] The results are shown in Table 3.

[0272] (texture) A 10 g amount of each of the compositions according to Examples 7-8 and Comparative Examples 7-8 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0273] Five experts evaluated the texture on the Petri dish according to the following ratings: 5: Non-sticky (very smooth) 4: Very slight stickiness (smooth) 3: Slightly sticky 2: Sticky 1: Very sticky

[0274] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0275] The results are shown in Table 3.

[0276] (Summary) The compositions according to Examples 7-8 formed gels.

[0277] The compositions of Comparative Examples 7 and 8 were unable to form gels at all.

[0278] It was demonstrated that large amounts of glycerin can be used to form a gel film (coacervate).

[0279] (Example 9 and Comparative Example 9) [Preparation] Each of the compositions according to Example 9 and Comparative Example 9 was prepared by mixing the components shown in Table 4 at room temperature (25°C). All figures for the amounts of components in Table 4 are based on "mass %" of the raw materials.

[0280] [Table 4]

[0281] [evaluation] (gel film formation) A 10 g amount of each of the compositions according to Example 9 and Comparative Example 9 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0282] Five experts evaluated the formation of the gel film in the Petri dishes according to the following grading scale: 5: A uniform gel film was formed (the gel film was uniformly distributed on the Petri dish) 4: A gel film was formed, but it was not uniform (the gel film was unevenly distributed on the Petri dish). 3: A slight gel film was formed 2: Very little gel film formed 1: No gel film formed

[0283] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0284] The results are shown in Table 4.

[0285] (texture) A 10 g amount of each of the compositions according to Example 9 and Comparative Example 9 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0286] Five experts evaluated the texture on the Petri dish according to the following ratings: 5: Non-sticky (very smooth) 4: Very slight stickiness (smooth) 3: Slightly sticky 2: Sticky 1: Very sticky

[0287] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0288] The results are shown in Table 4.

[0289] (Summary) The composition according to Example 9 formed a gel.

[0290] The composition according to Comparative Example 9 was unable to form any gel.

[0291] It has been demonstrated that a gel film (coacervate) can be formed using large amounts of cationic polymer and / or large amounts of crosslinker.

[0292] (Examples 10 to 16) [Preparation] Each of the compositions according to Examples 10 to 16 was prepared by mixing the ingredients shown in Table 5 at room temperature (25°C). All figures for the amounts of ingredients in Table 5 are based on "mass %" of the ingredients.

[0293] [Table 5]

[0294] [evaluation] (gel film formation) A 10 g amount of each of the compositions according to Examples 10-16 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0295] Five experts evaluated the formation of the gel film in the Petri dishes according to the following grading scale: 5: A uniform gel film was formed (the gel film was uniformly distributed on the Petri dish) 4: A gel film was formed, but it was not uniform (the gel film was unevenly distributed on the Petri dish). 3: A slight gel film was formed 2: Very little gel film formed 1: No gel film formed

[0296] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0297] The results are shown in Table 5.

[0298] (texture) A 10 g amount of each of the compositions according to Examples 10-16 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0299] Five experts evaluated the texture on the Petri dish according to the following ratings: 5: Non-sticky (very smooth) 4: Very slight stickiness (smooth) 3: Slightly sticky 2: Sticky 1: Very sticky

[0300] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0301] The results are shown in Table 5.

[0302] (Summary) The compositions according to Examples 10 to 16 formed gels.

[0303] It was demonstrated that the amount of cross-linker to form the gel film (coacervate) can be varied.

[0304] (Example 17 and Comparative Examples 10 to 14) [Preparation] Each of the compositions according to Example 17 and Comparative Examples 10 to 14 was prepared by mixing the components shown in Table 6 at room temperature (25°C). All numerical values ​​for the amounts of components in Table 6 are based on "mass %" of the raw materials.

[0305] [Table 6]

[0306] [evaluation] (gel film formation) A 10 g amount of each of the compositions according to Example 17 and Comparative Examples 10 to 14 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0307] Five experts evaluated the formation of the gel film in the Petri dishes according to the following grading scale: 5: A uniform gel film was formed (the gel film was uniformly distributed on the Petri dish) 4: A gel film was formed, but it was not uniform (the gel film was unevenly distributed on the Petri dish). 3: A slight gel film was formed 2: Very little gel film formed 1: No gel film formed

[0308] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0309] The results are shown in Table 6.

[0310] (texture) A 10 g amount of each of the compositions according to Example 17 and Comparative Examples 10 to 14 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0311] Five experts evaluated the texture on the Petri dish according to the following ratings: 5: Non-sticky (very smooth) 4: Very slight stickiness (smooth) 3: Slightly sticky 2: Sticky 1: Very sticky

[0312] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0313] The results are shown in Table 6.

[0314] (Summary) The composition according to Example 17 formed a gel.

[0315] The compositions of Comparative Examples 10 to 14 were unable to form gels at all.

[0316] It was demonstrated that the use of a monovalent acid (HCl) failed to form a gel film (coacervate). It can be seen that the use of a polyvalent cross-linking agent (e.g., phytic acid) is essential.

[0317] (Examples 18 to 23) [Preparation] Each of the compositions according to Examples 18 to 23 was prepared by mixing the ingredients shown in Table 7 at room temperature (25°C). All figures for the amounts of ingredients in Table 7 are based on "mass %" of the ingredients.

[0318] [Table 7]

[0319] [evaluation] (gel film formation) A 10 g amount of each of the compositions according to Examples 18-23 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0320] Five experts evaluated the formation of the gel film in the Petri dishes according to the following grading scale: 5: A uniform gel film was formed (the gel film was uniformly distributed on the Petri dish) 4: A gel film was formed, but it was not uniform (the gel film was unevenly distributed on the Petri dish). 3: A slight gel film was formed 2: Very little gel film formed 1: No gel film formed

[0321] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0322] The results are shown in Table 7.

[0323] (texture) A 10 g amount of each of the compositions according to Examples 18-23 was placed in a Petri dish and dried at 45° C. for 24 hours.

[0324] Five experts evaluated the texture on the Petri dish according to the following ratings: 5: Non-sticky (very smooth) 4: Very slight stickiness (smooth) 3: Slightly sticky 2: Sticky 1: Very sticky

[0325] They were then classified into the following categories based on the average rating: 5: Very good 4: Good 3: Normal 2: Bad 1: Very poor

[0326] The results are shown in Table 7.

[0327] (Summary) The compositions according to Examples 18 to 23 formed gels.

[0328] It has been demonstrated that gel films can be formed at least at a pH below 8.1.

Claims

1. (a) at least one cationic polymer; (b) at least one non-polymeric acid or salt thereof having two or more pKa values; (c) at least one polyol, and (d) water A composition comprising: A composition, wherein the amount of (c) polyol in the composition is 10% by mass or more relative to the total mass of the composition.

2. 2. The composition of claim 1, wherein the (a) cationic polymer is crosslinked with the (b) non-polymeric acid or salt thereof having two or more pKa values.

3. 2. The composition of claim 1, wherein the (a) cationic polymer has at least one moiety that can have a positive charge and / or has a positive charge selected from the group consisting of a primary, secondary, or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group, and a pyridyl group.

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

5. 2. The composition of claim 1, wherein the (a) cationic polymer is selected from the group consisting of polylysine, chitosan, and mixtures thereof.

6. 2. The composition according to claim 1, wherein the amount of the (a) cationic polymer in the composition is 0.01% by weight to 15% by weight, preferably 0.05% by weight to 10% by weight, and more preferably 0.1% by weight to 5% by weight, relative to the total weight of the composition.

7. The composition according to claim 1, wherein the (b) non-polymeric acid having two or more pKa values ​​or a salt thereof is an organic acid or a salt thereof, preferably a hydrophilic or water-soluble organic acid or a salt thereof, more preferably phytic acid or a salt thereof, terephthalylidene dicamphorsulfonic acid or a salt thereof, or a mixture thereof.

8. The composition according to claim 1, wherein the amount of the (b) non-polymeric acid or salt thereof having two or more pKa values ​​in the composition is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

9. The composition of claim 1, wherein the (c) polyol is glycerin.

10. The composition according to claim 1, wherein the amount of the (c) polyol in the composition is 95% by mass or less, based on the total mass of the composition.

11. 10. The composition of claim 1, further comprising: (e) at least one anionic polymer.

12. The composition according to claim 11, wherein the (e) anionic polymer is selected from polysaccharides, preferably hyaluronic acid and derivatives thereof, cellulose polymers and salts thereof, and mixtures thereof, more preferably hyaluronic acid and salts thereof, carboxymethylcellulose and salts thereof, and mixtures thereof.

13. The composition according to claim 11, wherein the amount of the (e) anionic polymer in the composition is 0.01% to 15% by weight, preferably 0.05% to 10% by weight, and more preferably 0.1% to 5% by weight, relative to the total weight of the composition.

14. 2. The composition according to claim 1, which is a cosmetic composition, preferably a care cosmetic composition, more preferably a skin care or hair care cosmetic composition.

15. A cosmetic method for keratinous materials, comprising: applying a composition according to any one of claims 1 to 14 to the keratinous material; and drying the composition to form a cosmetic film on the keratinous material.