COMPOSITION COMPRISING A LARGE QUANTITY OF POLYOL

Abstract

COMPOSITION COMPRISING A LARGE AMOUNT OF POLYOL The present invention relates to a composition comprising: (a) at least one cationic polymer, (b) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof; (c) at least one polyol; and (d) water, wherein the amount of (c) polyol(s) in the composition is 10% or more by weight, based on the total weight of the composition. The composition according to the present invention may exhibit reduced adhesion despite comprising a large amount of polyol such as glycerin. Figure for abstract: none

Description

Title of the invention: COMPOSITION COMPRISING A LARGE QUANTITY OF POLYOL Technical field

[0001] The present invention relates to a composition including a relatively large amount of polyol, as well as to a cosmetic process using the composition. CONTEXT OF ART

[0002] A polyionic polymer is already known, which can be in the form of a particle and can be formed with a cationic polymer and an anionic polymer.

[0003] For example, WO 2021 / 125069 discloses a composition that is useful for cosmetic treatments and comprises, in one embodiment, at least one polyionic complex particle comprising at least one cationic polymer, at least one anionic hyaluronic acid-based polymer, and at least one non-polymeric acid having two or more pKa values. WO 2021 / 125069 also discloses a specific composition that includes 5% by weight of glycerin.

[0004] For example, WO 2022 / 131351 discloses a composition that is useful for cosmetic treatments and comprises, in one embodiment, at least one polyionic complex particle comprising at least one cationic polymer, at least one anionic polymer and at least one non-polymeric acid having two or more pKa values ​​or a salt thereof, and at least one filler. WO 2022 / 131351 also discloses specific compositions that include 5% by weight of glycerin. DISCLOSURE OF THE INVENTION

[0005] A polyol such as glycerin is often used for cosmetic purposes for a keratinous substance such as skin. However, a composition comprising a large amount, i.e., 10% or more by weight relative to the total weight of the composition, of polyol such as glycerin tends to be sticky.

[0006] Thus, an object of the present invention is to provide a composition which can exhibit reduced adhesion, while including a large amount, i.e., 10% or more by weight relative to the total weight of the composition, of polyol such as glycerin.

[0007] The above objective of the present invention can be achieved by a composition, comprising:

[0008] (a) of at least one cationic polymer,

[0009] (b) at least one non-polymeric acid having two or more pKa values or salt(s) thereof;

[0010] (c) at least one polyol; and

[0011] (d) water,

[0012] in which

[0013] the quantity of the (c) polyol(s) in the composition is equal to or greater than 10% by weight relative to the total weight of the composition.

[0014] The cationic polymer may be crosslinked with the non-polymeric acid b) having two or more pKa values ​​or salt(s) thereof.

[0015] The (a) cationic polymer may have at least one positively chargeable 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.

[0016] The (a) cationic polymer may be selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as chitosans and (co)polylysines, cationic (co)polyamino acids such as collagen, cationic cellulose polymers and their salts.

[0017] It may be preferable that the (a) cationic polymer is selected from the group consisting of polylysines, chitosans and mixtures thereof.

[0018] The amount of the (a) cationic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition.

[0019] The (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof may be an organic acid or salts thereof, preferably a hydrophilic or water-soluble organic acid or salt(s) thereof and, more preferably, phytic acid or salts thereof, terephthalylidene dicamphor sulfonic acid or salts thereof, or a mixture thereof.

[0020] The amount of the (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition.

[0021] It may be preferable that the (c) polyol is glycerin.

[0022] Furthermore, the amount of the (c) polyol in the composition according to the present invention may be 95% by weight or less, relative to the total weight of the composition.

[0023] The composition according to the present invention may further comprise (e) at least one anionic polymer.

[0024] The anionic polymer (e) may be chosen from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and a mixture thereof, and more preferably hyaluronic acid and its salts, carboxymethylcellulose and its salts, and a mixture thereof.

[0025] The amount of the anionic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition.

[0026] The composition according to the present invention may be a cosmetic composition, preferably a cosmetic care composition and more preferably a cosmetic skin care or hair care composition.

[0027] The present invention also relates to a cosmetic process for caring for keratinous material, comprising

[0028] the application to the keratinous substance of the composition according to the present invention; and

[0029] drying the composition to form a cosmetic film on the keratinous substance. Best mode for carrying out the invention

[0030] After diligent research, the inventors have discovered that it is possible to provide a composition which can exhibit reduced adhesion, while including a large amount, i.e., 10% or more by weight relative to the total weight of the composition, of polyol such as glycerin.

[0031] Thus, the composition according to the present invention comprises:

[0032] (a) of at least one cationic polymer,

[0033] (b) at least one non-polymeric acid having two or more pKa values or salt(s) thereof;

[0034] (c) at least one polyol; and

[0035] (d) water,

[0036] in which

[0037] the quantity of the (c) polyol(s) in the composition is equal to or greater than 10% by weight relative to the total weight of the composition.

[0038] The composition according to the present invention may exhibit reduced adhesion although it comprises a large amount of polyol such as glycerin.

[0039] The adhesion of the composition according to the present invention is lower than that of the composition comprising ingredient (c) in an amount of 10% by weight or more, relative to the total weight of the composition, without ingredients (a) and (b).

[0040] Thus, the composition according to the present invention can provide an improved texture such as a smoother feel to the touch.

[0041] The polyol such as glycerin is hydrophilic and can therefore be easily removed with water on the surface of a keratinous substance. However, the ingredients (a) and (b) in the composition according to the present invention can form a gel film or coacervate which can well maintain the polyol on a keratinous substance such as the skin.

[0042] Thus, the composition according to the present invention can also provide improved cosmetic effects derived from the polyol, such as enhanced moisturizing effects.

[0043] The composition, process and other properties according to the present invention will be described in more detail hereinafter.

[0044] (Cationic polymer)

[0045] The composition according to the present invention may comprise (a) at least one cationic polymer.

[0046] There is no limit on the type of the (a) cationic polymer. Two or more different types of cationic polymers may be used in combination. Thus, a single type of cationic polymer or a combination of different types of cationic polymers may be used.

[0047] A cationic polymer has a positive charge density. The charge density of the (a) cationic polymer may be between 0.01 meq / g and 20 meq / g, preferably between 0.05 and 15 meq / g and, more preferably, between 0.1 and 10 meq / g.

[0048] It may be preferable that the molecular weight of the (a) cationic polymer is equal to or greater than 1,000, preferably equal to or greater than 2,000, more preferably equal to or greater than 3,000, and even more preferably equal to or greater than 4,000.

[0049] Unless otherwise indicated in the descriptions, "molecular weight" means an average molecular weight number.

[0050] The (a) cationic polymer may have at least one positively chargeable 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. The term "(primary) amino group" herein means a -NH2 group.

[0051] The (a) cationic polymer may be a homopolymer or a copolymer. By "copolymer" is meant both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.

[0052] The (a) cationic polymer may be selected from natural and synthetic cationic polymers. Non-limiting examples of the (a) cationic polymers are as follows.

[0053] (1) Homopolymers and copolymers derived from acrylic esters and amides or methacrylic and comprising at least one unit chosen from the units of the formulas following: R,

[0054] in which:

[0055] R1 and R2, which may be identical or different, are chosen from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms, for example methyl and ethyl groups;

[0056] R3, which may be the same or different, is chosen from hydrogen and CH3;

[0057] the symbols A, which may be identical or different, are chosen from linear or branched alkyl groups comprising from 1 to 6 carbon atoms, for example from 2 to 3 carbon atoms and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;

[0058] R4, R5 and R6, which may be the same or different, are chosen from groups alkyl groups comprising from 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment, alkyl groups comprising from 1 to 6 carbon atoms and

[0059] X is an anion derived from an inorganic or organic acid, such as methosulfate anions and halides, for example chloride and bromide.

[0060] The copolymers of family (1) above may also comprise at least one unit derived from comonomers which may be chosen from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen atom with (C1-C4) lower alkyl groups, groups derived from acrylic or methacrylic acids and their esters, vinyl lactams such as vinylpyrrolidone and vinylcaprolactam and vinyl esters.

[0061] Here are some examples of copolymers of family (1):

[0062] copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide,

[0063] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in European Patent Application No. 0 080 976,

[0064] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate,

[0065] copolymers of vinylpyrrolidone / dialkylaminoalkyl methacrylate or acrylate, quaternized or not, described, for example, in French Patents Nos. 2,077,143 and 2,393,573,

[0066] dimethylaminoethyl methacrylate / vinylca-prolactam / vinylpyrrolidone terpolymers,

[0067] vinylpyrrolidone / methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymers and

[0068] crosslinked polymers of methacryloyloxy(Ci-C4)alkyltri(Ci-C4)alkylammonium salts such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with a compound containing olefinic unsaturation, in particular methylenebisacrylamide.

[0069] (2) Cationic cellulose polymers such as cellulose ether derivatives comprising one or more quaternary ammonium groups described, for example, in French Patent No. 1,492,597, such as the polymers sold under the names “JR” (JR 400, JR 125, JR 30M) or “LR” (LR 400, LR 30M) by the company Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose reacted with an epoxide substituted by a trimethylammonium group.

[0070] It is preferable that the cationic cellulosic polymer has at least one quaternary ammonium group, preferably a trialkyl quaternary ammonium group and, more preferably, a trimethyl quaternary ammonium group.

[0071] The quaternary ammonium group may be present in a quaternary ammonium group which may be represented by the following chemical formula (I):

[0072] in which

[0073] each of the groups R 1 and R 2 denotes a C 1 -C 3 alkyl group, preferably a methyl or ethyl group and, more preferably, a methyl group,

[0074] R3 denotes a Cr C24 alkyl group, preferably a methyl or ethyl group and, more preferably, a methyl group,

[0075] X- denotes an anion, preferably a halide and, more preferably, a chloride,

[0076] n denotes an integer between 0 and 30, preferably between 0 and 10 and, more preferably, equal to 0, and

[0077] R4 denotes a Cr C4> alkylene group, preferably an ethylene or propylene group.

[0078] The leftmost ether bond (-O-) in the above chemical formula (I) can attach to the sugar ring of the polysaccharide.

[0079] It is preferable that the group containing the quaternary ammonium is -O-CH2 -CH(OH)-CH2-N+(CH3)3.

[0080] (3) Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and described, for example, in U.S. Patent No. 4,131,576, such as hydroxyalkylcelluloses, for example, hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted with, for example, a salt selected from methacryloyl-ethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium salts.

[0081] Commercial products corresponding to these polymers include, for example, products sold under the names “Celquat® L 200” and “Celquat® H 100” by the company National Starch.

[0082] (4) Non-cellulosic cationic polysaccharides described in US patents Nos. 3,589,578 and 4,031,307, such as guar gums comprising cationic trialkylammonium groups, cationic hyaluronic acid and dextran hydroxypropyl trimonium chloride. Guar gums modified with a salt, for example the chloride, of 2,3-epoxypropyltrimethylammonium (guar hydroxypropyltrimonium chloride) may also be used.

[0083] These products are sold, for example, under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162 by the company MEYHALL.

[0084] (5) Polymers comprising piperazinyl units and alkylene groups or divalent hydroxyalkylene polymers comprising straight or branched chains, optionally interrupted with at least one entity selected from oxygen, sulfur, nitrogen, aromatic and heterocyclic rings, as well as the oxidation and / or quaternization products of these polymers. These polymers are described, for example, in French patents Nos. 2,162,025 and 2,280,361.

[0085] (6) Water-soluble polyamino-amides prepared, for example, by polycon densification of an acidic compound with a polyamine; these polyamino-amides being optionally crosslinked with an entity selected from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; biunsaturated derivatives; bishalo-hydrins; bisazetidiniums; bishaloacyl-diamines; bisalkyl halides; oligomers resulting from the reaction of a difunctional compound which is reactive with an entity selected from bishalohydrins; bisazetidiniums, bishaloacyl-diamines, bisalkyl halides; epihalohydrins; dihydroxides and bisunsaturated derivatives; the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mole per amine group of polyaminoamides; these polyaminoamides being optionally alkylated or, if they comprise at least one tertiary amine function, they can be quaternized. These polymers are described, for example, in French patents Nos. 2,252,840 and 2,368,508.

[0086] (7) Polyamino-amide derivatives resulting from the condensation of polyamines of po- lyalkylene with polycarboxylic acids, followed by alkylation with di-functional agents, for example, adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises from 1 to 4 carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene group comprises from 1 to 4 carbon atoms, such as an ethylene group. These polymers are described, for example, in French patent No. 1,583,363. In at least one embodiment, these derivatives may be selected from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.

[0087] (8) Polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids comprising from 3 to 8 carbon atoms. The molar ratio of polyalkylene polyamine to dicarboxylic acid may vary from 0.8:1 to 1.4:1; the polyamino amide resulting from this reaction with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine group of the polyamino amide ranging from 0.5:1 to 1.8:1. These polymers are described, for example, in U.S. Patent Nos. 3,227,615 and 2,961,347.

[0088] (9) Alkyldiallylamine cyclopolymers and dialkyldiallyl- cyclopolymers ammonium, such as homopolymers and copolymers comprising, as main constituent of the chain, at least one motif chosen from the motifs of formulas (Ia) and (Ib): fCHJk (Ia) ..HAS \ CSR HR

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] --(OHg)t — ÇW XÛ(R^)--CHA— HgCk .CHg X. XH""" Rio in which: k and t, which may be the same or different, are equal to 0 or 1, the sum k+t being equal to 1; R12 is selected from hydrogen and methyl groups; Rio and Rn, which may be the same or different, are selected from alkyl groups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group comprises, for example, from 1 to 5 carbon atoms and lower amidoalkyl groups (Ci-C4), or R10 and Ru may form, with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl and morpholinyl and Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate. These polymers are described, for example, in French patent No. 2,080,759 and in its certificate of addition 2,190,406. In one embodiment, Rio and Ru, which may be the same or different, are selected from alkyl groups comprising from 1 to 4 carbon atoms. Among these polymers, mention may be made, in particular, of (co)polydiallyldialkyl ammonium chloride such as the homopolymer of dimethyldiethylammonium chloride (polyquaternium-6) marketed under the name “MERQUAT® 100” by the company CALGON (and its low-weight medium molecular weight counterparts) and the copolymers of diallyldimethylammonium chloride and acrylamide com- marketed under the name “MERQUAT® 550”.

[0096] Quaternary diammonium polymers comprising at least one repeating unit of formula (II): Ra (ll) | x" | r Rh Ru

[0097] in which:

[0098] Rn, Ru, Ri5 and Ri6, which may be the same or different, are selected from aliphatic, alicyclic and aliphatic aryl groups comprising from 1 to 20 carbon atoms and lower aliphatic hydroxyalkyl groups, or Rn, Rm, Ri5 and R i6, together or separately, with the nitrogen atoms to which they are attached, heterocycles alternatively comprising a second heteroatom other than nitrogen, or R13, R14, R15, and R16 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 alkyl groups, ester groups, acyl groups, amide groups, -CO-O-Rp-E groups and -CO-NH-R17-E groups, where R17 is an alkylene group and E is an ammonium group quaternary;

[0099] Ai and Bb which may be identical or different, are chosen from polymethylene groups comprising from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may comprise, linked or intercalated in the main chain, at least one entity chosen 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

[0100] X denotes an anion derived from an inorganic or organic acid;

[0101] it being understood that Ab Rn and Ri5 can form, with the two nitrogen atoms to which they are attached, a piperazine cycle;

[0102] if Ai is chosen from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, Bi can be chosen from:

[0103] -(CH2)n-CO-E'-OC-(CH2)n-

[0104] where E' is chosen from:

[0105] a) glycolic residues of formula -OZO-, where Z is chosen from linear or branched hydrocarbon groups and groups of the following formulas:

[0106] -(CH2-CH2-O)X-CH2-CH2-

[0107] -[CH2-CH(CH3)-O]y-CH2-CH(CH3)-

[0108] where x and y, which may be the same or different, are chosen from integers ranging from 1 to 4, which represent a defined and unique degree of polymerization, and numbers ranging from 1 to 4, which represent an average degree of polymerization;

[0109] b) a bissecondary diamine residue such as piperazine derivatives;

[0110] c) bis-primary diamine residues of formula -NH-Y-NH-, in which Y is selected from linear or branched hydrocarbon groups and the divalent group -CH 2 -CH2 -SS -CH2 -CH 2 -CH2 -. and

[0111] d) ureylene groups of formula -NH-CO-NH-.

[0112] In at least one embodiment, X is an anion such as chloride or bromide.

[0113] Polymers of this type are described, for example, in French patents Nos. 2,320,330; 2,270,846; 2,316,271; 2,336,434; and 2,413,907 and in US patents Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261,002; 2,271,378; 3,874,870; 4,001,432; 3,929,990; 3,966,904; 4,005,193; 4,025,617; 4,025,627; 4,025,653; 4,026,945 and 4,027,020.

[0114] Among the non-limiting examples of these polymers are those comprising at least one repeating unit of formula (III):

[0115] in which Rn, RM, Ri5 and R[6, which may be the same or different, are chosen from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbon atoms, n and p, which may be the same or different, are integers ranging from 2 to 20, and X is an anion derived from an inorganic or organic acid.

[0116] (11) polyquaternary ammonium polymers comprising units of formula (IV): — MMGHgVNH-OOHCHg)——A— Rts X" Rst

[0117] in which:

[0118] Ri8, Rw, R2o and R2i, which may be the same or different, are chosen from hydrogen, methyl, ethyl, propyl, [3-hydroxyethyl, [3-hydroxypropyl, -CH 2CH2(OCH2CH2)POH] groups, where p is chosen from integers between 0 and 6, under provided that R[8, Ri9, R20 and R2i are not simultaneously hydrogen,

[0119] r and s, which may be identical or different, are chosen from integers ranging from 1 to 6,

[0120] q is chosen from integers ranging from 0 to 34,

[0121] - X denotes an anion, such as a halide and

[0122] A is chosen from dihalide radicals and -CH2-CH2-O-CH2-CH2-.

[0123] These compounds are described, for example, in European patent application No. 0 122 324.

[0124] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0125] Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers comprising units selected from vinylpyridine and vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.

[0126] According to one embodiment of the present invention, the (a) cationic polymer is selected from cellulose ether derivatives comprising quaternary ammonium groups, such as the products marketed under the name "JR 400" by the company UNION CARBIDE CORPORATION, cationic cyclopolymers, for example, homopolymers and copolymers of dimethyldiallyl chloride marketed under the names MERQUAT® 100, MERQUAT® 550, and MERQUAT® S by the company CALGON, guar gums modified with a 2,3-epoxypropyltrimethylammonium salt and quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0127] (13) Polyamines

[0128] As (a) cationic polymer, it is also possible to use (co)polyamines, which may be homopolymers or copolymers, with a plurality of amino groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in the backbone of a polymer or in a pendant group, if present, of the (co)polyamines.

[0129] Examples of (co)polyamines include chitosan, (co)polylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polydimethylaminoethylenemethacrylates, (co)polyvinylpyridines such as (co)poly-1-methyl-2-vinylpyridines, (co)polyimines such as (co)polyimines, (co)polypyridines such as (co)poly(quaternary pyridines), (co)polybiguanides such as (co)polyaminopropyl biguanides, (co)polylysines, (co)polyomithines, (co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinylacetals and their salts.

[0130] It may be preferable to choose the (a) cationic polymer to be chosen from the chitosans.

[0131] It may also be preferable to choose the (a) cationic polymer to be chosen from (co)polylysines.

[0132] 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, typically used as a natural preservative in food products. Polylysine is a polyelectrolyte that is soluble in polar solvents such as water, propylene glycol, and glycerol. Polylysine is commercially available in various forms, such as poly D-lysine and poly L-lysine. Polylysine may be in the form of a salt and / or a solution.

[0133] (14) Cationic polyamino acids

[0134] As (a) the cationic polymer, it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers, with a plurality of amino groups and carboxyl groups. The amino group may be a primary, secondary, tertiary, or quaternary amino group. The amino group may be present in the backbone of a polymer or in a pendant group, if present, of the cationic polyamino acids. The carboxyl group may be present in a pendant group, if present, of the cationic polyamino acids.

[0135] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, hydroxypropyl stear-dimonium hydrolyzed wheat protein, hydroxypropyl cocodimonium hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, hydroxypropyltrimonium steardimonium hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydrolyzed soy protein, and the like.

[0136] The following descriptions relate to preferable embodiments of the (a) cationic polymer.

[0137] It may be preferable that (a) the cationic polymer is selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkylammonium chloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as cationized collagen, cationic cellulose polymers and their salts.

[0138] It may be preferable that the (a) cationic polymer is selected from the group consisting of polylysines, chitosans and mixtures thereof.

[0139] The amount of the (a) cationic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more and, more preferably, 0.1% by weight or more, relative to the total weight of the composition.

[0140] The amount of the (a) cationic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and, more preferably, 5% by weight or less, relative to the total weight of the composition.

[0141] The amount of the (a) cationic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition.

[0142] (Anionic polymer)

[0143] The composition according to the present invention may include (e) at least one anionic polymer.

[0144] If the composition according to the present invention comprises the anionic polymer(s), the cationic polymer(s) may form one or more polyionic complexes with the anionic polymer(s).

[0145] There is no limit on the type of (e) anionic polymer. Two or more different types of anionic polymers may be used in combination. Thus, a single type of anionic polymer or a combination of different types of anionic polymers may be used.

[0146] An anionic polymer has a positive charge density. 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 if the anionic polymer is a synthetic anionic polymer, and 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 if the anionic polymer is a natural anionic polymer.

[0147] It may be preferable that the molecular weight of the (e) anionic polymer is greater than or equal to 1,000, preferably greater than or equal to 3,000, even more preferably equal to or greater than 5,000, even more preferably greater than or equal to 10,000, even more preferably greater than or equal to 50,000 and, even more preferably greater than or equal to 100,000, greater than or equal to 1,000,000 or more.

[0148] Unless otherwise indicated in the descriptions, "molecular weight" means a number average molecular mass.

[0149] The (e) anionic polymer may have at least one negatively chargeable and / or negatively charged moiety selected from the group consisting of a sulfuric group, a sulfate group, a sulfonic group, a sulfonate group, a phosphoric group, a phosphate group, a phosphonic group, a phosphonate group, a carboxylic group and a carboxylate group.

[0150] The anionic polymer may be a homopolymer or a copolymer. For "copolymer" means both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.

[0151] The anionic polymer may be chosen from natural and synthetic anionic polymers.

[0152] The anionic polymer may comprise at least one hydrophobic chain.

[0153] The anionic polymer, which may comprise at least one hydrophobic chain, may be obtained by copolymerization of a monomer (a) selected from carboxylic acids comprising α,[3-ethylenic unsaturation (monomer a') and a 2-acrylamido-2-methylpropanesulfonic acid (monomer a") with a non-surface-active monomer (b) comprising ethyl unsaturation other than (a) and / or a monomer (c) comprising ethyl unsaturation resulting from the reaction of an acrylic monomer comprising α,[3-monoethylenic unsaturation or a monomer comprising monoethylenic unsaturation with a non-ionic amphiphilic monohydric component or with a primary or secondary amine.

[0154] Thus, the anionic polymer with at least one hydrophobic chain can be obtained by two synthetic routes:

[0155] - either by copolymerization of the monomers (a1) and (c), or (a1), (b) and (c), or (a") and (c), or (a"), (b) and (c),

[0156] - either by modification (and in particular by esterification or amidation) of a co polymer formed from monomers (a1) or monomers (a'") and (b), or (a) and (b), by an amphiphilic non-ionic monohydric compound or a primary or secondary fatty amine.

[0157] Mention may in particular be made, as copolymers of 2-acrylamido-2-methylpropanesulfonic acid, of those mentioned in the article "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10 -3694-3704" and in applications EP-A-0 750 899 and EP-A-1 069 172.

[0158] The carboxylic acid comprising an α,[3-monoethylenic unsaturation constituting the monomer (a1) can be chosen from numerous acids and, in particular, acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. Preferably it is acrylic or methacrylic acid.

[0159] The copolymer may comprise a (b) monomer comprising monoethylenic unsaturation which has no surfactant property. Preferred monomers are those which give water-insoluble polymers when homopolymerized. They may be chosen, for example, from alkyl acrylates and Cr C4> methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or metha corresponding acrylates. The most preferred monomers are methyl acrylate and ethyl acrylate. Other monomers that may be used are, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile, and vinylidene chloride. Non-reactive monomers are preferred, these monomers being those in which the single ethylenic group is the only reactive group under the polymerization conditions. However, monomers that include groups that react under heat, such as hydroxyethyl acrylate, may be used as an option.

[0160] Monomer (c) is obtained by reacting an acrylic monomer comprising α,[3-monoethylenic unsaturation, such as (a), or an isocyanate monomer comprising monoethylenic unsaturation with a non-ionic monohydric amphiphilic compound or a primary or secondary fatty amine.

[0161] Nonionic monohydric amphiphilic compounds or primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. Nonionic monohydric amphiphilic compounds are generally alkoxylated hydrophobic compounds comprising an alkylene oxide forming the hydrophilic portion of the molecule. Hydrophobic compounds are generally composed of an aliphatic alcohol or an alkylphenol, in the compounds of which a carbon chain comprising at least six carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.

[0162] The preferred non-ionic monohydric amphiphilic compounds are compounds corresponding to the following formula (V):

[0163] R-(OCH2CHR')m-(OCH2CH2)n-OH (V)

[0164] wherein R is selected from alkyl or alkylene groups comprising from 6 to 30 carbon atoms and alkylaryl groups having alkyl radicals comprising from 8 to 30 carbon atoms, R' is selected from alkyl groups comprising from 1 to 4 carbon atoms, n is an average number ranging from about 1 to 150 and m is an average number ranging from about 0 to 50, provided that n is at least as large as m.

[0165] Preferably, in the compounds of formula (V), the group R is chosen from alkyl groups comprising from 12 to 26 carbon atoms and alkylphenyl groups in which the alkyl group is C8-Ci3; the group R' is the methyl group; m = 0 and n = 1 to 25.

[0166] Preferred primary and secondary fatty amines are composed of one or two alkyl chains comprising from 6 to 30 carbon atoms.

[0167] The monomer used to form the nonionic urethane monomer (c) may be chosen from a wide variety of compounds. Any compound comprising copolymerizable unsaturation, such as acrylic, methacrylic or allylic. Monomer (c) can be obtained in particular from an isocyanate comprising monoethylenic unsaturation such as, in particular, α,α-dimethyl-m-isopropenylbenzyl isocyanate.

[0168] The monomer (c) may be chosen, in particular, from acrylates, methacrylates or itaconates of oxyethylated alcohol (1 to 50 EO) C6-C30> such as steareth-20 methacrylate, oxyethylated behenyl methacrylate (25 EO), oxyethylenic monocetyl itaconate (20 EO), oxyethylethylated monostearyl itaconate (20 EO) or acrylate modified with polyoxyethylenic alcohols (25 EO) C12-C24 and from isocyanates of dimethyl-m-isopropenylbenzyl of ethylated alcohol (1 to 50 EO) C6 -C30> such as, in particular, dimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenyl alcohol.

[0169] According to a specific embodiment of the present invention, the (e) anionic polymer is selected from acrylic terpolymers obtained from (a) a carboxylic acid comprising α,[3-ethylenic unsaturation, (b) a non-surface-active monomer comprising ethylenic unsaturation other than (a), and (c) a non-ionic urethane monomer which is the reaction product of a non-ionic monohydric amphiphilic compound with an isocyanate comprising monoethylenic unsaturation.

[0170] Mention may in particular be made, as anionic polymers comprising at least one hydrophobic chain of the following compounds: acrylic acid / ethyl acrylate / alkyl acrylate terpolymer, such as the product in the form of a 30% aqueous dispersion marketed under the name Acusol 823 by Rohm & Haas; acrylate / steareth-20 methacrylate copolymer, such as the product sold under the name Aculyn 22 by Rohm & Haas; (meth)acrylic acid / ethyl acrylate / oxyethylenated behenyl methacrylate (25 EO) terpopolymer, such as the product in the form of an aqueous emulsion marketed under the name Aculyn-28 by Rohm & Haas; acrylic acid / monocetyl oxyethylenated itaconate (20 EO) copolymer, such as the 30% aqueous dispersion product marketed as Structure 3001 by National Starch;acrylic acid / oxyethylenated monostearyl itaconate copolymer (20°EO), such as the product in the form of a 30% aqueous dispersion marketed under the name Structure 2001 by National Starch; acrylates / acrylate modified with polyoxyethylated (25 EO) C[2 -C24 alcohol copolymer, such as the 30-32% copolymer latex marketed under the name Synthalen W2000 by 3V SA; or methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol dimethyl-isopropenylbenzyl isocyanate terpolymer, such as the product in the form of a 24% aqueous dispersion and comprising 40 ethylene oxide groups disclosed in EP -A-0 173 109. ;

[0171] The anionic (e) polymers may also be Polyester-5, such as product sold under the name Eastman AQ™ 55S Polymer by EASTMAN CHEMICAL having the chemical formula below.

[0172] HO-GAGAGAGAGAGAGAGAG-OH

[0173] 11

[0174] SO3 Na+ SO3 Na+

[0175] A: dicarboxylic acid fraction

[0176] G: glycol fraction

[0177] SO3 Na+: sodium sulfo group

[0178] OH: hydroxyl group

[0179] It may be preferable that the anionic polymer is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulosic polymers (e.g., carboxymethylcellulose), anionic (co)polyamino acids such as glutamic (co)polyacids, (co)poly(meth)acrylic acids, (co)polyamic acids, styrene (co)polysulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, maleic (co)polyacids, fumaric (co)polyacids, maleic acid (co)polymers and their salts.

[0180] The maleic acid copolymer may comprise one or more maleic acid comonomers, and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms and styrene.

[0181] By "maleic acid copolymer" is meant any polymer obtained by copolymerization of one or more maleic acid comonomers and one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic acid comonomers being optionally partially or completely hydrolyzed. Hydrophilic polymers will preferably be used, i.e. polymers having a solubility in water greater than or equal to 2 g / L.

[0182] In an advantageous aspect of the present invention, the maleic acid copolymer may have a molar fraction of maleic acid units of between 0.1 and 1, more preferably between 0.4 and 0.9.

[0183] The weight average molar mass of the maleic acid copolymer may be between 1,000 and 500,000 and, preferably, between 1,000 and 50,000.

[0184] It is preferable that the maleic acid copolymer is a styrene / maleic acid copolymer and, more preferably, a styrene / maleic acid copolymer.

[0185] A copolymer of styrene and maleic acid in a 50 / 50 ratio will preferably be used.

[0186]

[0187]

[0188]

[0189]

[0190]

[0191] For example, styrene / maleic acid copolymer (50 / 50) in the form of 30% ammonium salt in water, sold under the reference SMA1000H® by Cray Valley, or styrene / maleic acid copolymer (50 / 50) in the form of 40% sodium salt in water, sold under the reference SMAlOOOHNa® by Cray Valley, can be used. The use of styrene / maleic acid copolymer such as sodium styrene / maleic acid copolymer can improve the wettability of a film prepared by the composition according to the present invention. According to one embodiment of the present invention, it is preferable that the anionic polymer is selected from hyaluronic acid and its derivatives. Hyaluronic acid can be represented by the following chemical formula. In the context of the present invention, the term "hyaluronic acid" covers in particular the basic unit of hyaluronic acid of formula:

[0192]

[0193]

[0194] It is the smallest fraction of hyaluronic acid comprising a dimer disaccharide, namely D-glucuronic acid and N-acetylglucosamine. The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, the linear polymer comprising the polymeric unit described above, linked together in the chain via alternating glycosidic bonds [3(1,4) and [3(1,3), having a molecular weight (MW) which can vary between 380 and 13,000,000 daltons. This molecular mass depends largely on the source from which the hyaluronic acid is obtained and / or the preparation methods. The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, salts of hyaluronic acid. As salts, mention may be made of alkali metal salts such as sodium and potassium salts, salts of alkaline earth metal such as magnesium salts, ammonium salts and their mixtures.

[0195] In its natural state, hyaluronic acid is present in pericellular gels, in the basic substance of connective tissues of vertebrate organs such as the dermis and epithelial tissues and, in particular, in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord and in the crista galli apophysis.

[0196] Thus, the term “hyaluronic acid and its derivatives” includes all fractions or subunits of hyaluronic acid having a molecular mass in particular in the molecular mass range recalled above.

[0197] In the context of the present invention, hyaluronic acid fractions which do not have inflammatory activity are preferably used.

[0198] As an illustration of the different hyaluronic acid fractions, reference may be made to the document “Hyaluronan fragments: an information-rich System”, R. Stem et al., European Journal of Cell Biology 58 (2006) 699-715, which examines the listed biological activities of hyaluronic acid as a function of its molecular mass.

[0199] According to a preferred embodiment of the present invention, the hyaluronic acid fractions suitable for the use covered by the present invention have a molecular mass of between 50,000 and 5,000,000, in particular between 100,000 and 5,000,000, in particular between 400,000 and 5,000,000 Da. In this case, the term used is high molecular mass hyaluronic acid.

[0200] Alternatively, hyaluronic acid fractions which may also be suitable for the use covered by the present invention have a molecular mass of between 50,000 and 400,000 Da. In this case, the term used is intermediate molecular mass hyaluronic acid.

[0201] As a further alternative, the hyaluronic acid fractions which may be suitable for the use covered by the present invention have a molecular mass of less than 50,000 Da. In this case, the term used is low molecular mass hyaluronic acid.

[0202] Finally, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid esters, in particular, those in which all or part of the carboxylic groups of the acid functions are esterified with oxyethylated alkyls or alcohols, containing from 1 to 20 carbon atoms, in particular with a degree of substitution at the level of the D-glucuronic acid of the hyaluronic acid of between 0.5 and 50%.

[0203] Mention may in particular be made of methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. These esters have in particular been described in D. Campoccia et al. “Semisynthetic resorbable materials from hyaluronan esterification”, Biomaterials 19 (1998) 2101-2127.

[0204] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.

[0205] The molecular masses indicated above are also valid for hyaluronic acid esters.

[0206] The hyaluronic acid may in particular be hyaluronic acid supplied by the company Hyactive under the trade name CPN (MW: 10 to 150 kDa), by the company Soliance under the trade name Cristalhyal (MW: 1.1 times 106), by the company Bioland under the name Nutra HA (MW: 820,000 Da), by the company Bioland under the name Nutra AF (MW: 69,000 Da), by the company Bioland under the name Oligo HA (MW: 6100 Da) or by the company Vam Farmacos Metica under the name D Factor (MW: 380 Da).

[0207] It may be preferable for the (e) anionic polymer to be chosen from natural anionic polymers, and more preferably from polysaccharides.

[0208] It may be even more preferable that the (e) 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.

[0209] Thus, the (e) anionic polymer may be chosen from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and a mixture thereof, and more preferably hyaluronic acid and its salts (for example, sodium hyaluronate), carboxymethylcellulose and its salts such as cellulose gum, and a mixture thereof.

[0210] The amount of the anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more and, more preferably, 0.1% by weight or more, relative to the total weight of the composition.

[0211] Furthermore, the amount of the anionic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and, more preferably, 5% by weight or less, relative to the total weight of the composition.

[0212] The amount of the anionic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition.

[0213] The total amount of the (a) cationic polymer(s) and the (e) anionic polymer(s) in the composition according to the present invention may be 0.1% by weight or more, preferably 0.5% by weight or more and, more preferably, 1% by weight or more, relative to the total weight of the composition.

[0214] The total amount of the (a) cationic polymer(s) and the (e) anionic polymer(s) in the composition according to the present invention may be 20% by weight or less, preferably 15% by weight or less and, more preferably, 10% by weight or less, relative to the total weight of the composition.

[0215] The total amount of the (a) cationic polymer(s) and the (e) anionic polymer(s) in the composition according to the present invention may be between 0.1% and 20% by weight, preferably between 0.5% and 15% by weight and, more preferably, between 1% and 10% by weight, relative to the total weight of the composition.

[0216] The ratio of the amount, for example the chemical equivalent, of the (a) cationic polymer(s) / the anionic polymer(s) may be 0.05-18, preferably 0.1-10 and, more preferably, 0.5-5.0. In particular, it may be preferable that the number of cationic groups of the (a) cationic polymer(s) / the number of anionic groups of the (e) anionic polymer(s) is 0.05-18, more preferably 0.1-10, and even more preferably 0.5-5.0.

[0217] (Non-polymeric acid having two or more acid dissociation constants)

[0218] The composition according to the present invention comprises (b) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof, i.e. at least one non-polymeric acid having two or more acid dissociation constants or salt(s) thereof. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined at a constant temperature such as 25°C.

[0219] The (b) non-polymeric acid having two or more pKa values ​​may act as a crosslinker for the (a) cationic polymer. The (a) cationic polymer(s) may be ionically crosslinked by the (b) non-polymeric acid(s) having two or more pKa values ​​or salt(s) thereof.

[0220] The term "non-polymeric" herein means that the acid is not obtained by polymerization of two or more monomers. Therefore, non-polymeric acid does not correspond to an acid obtained by polymerizing two or more monomers such as a polycarboxylic acid.

[0221] It is preferable that the molecular weight of the (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof is less than or equal to 1,000, preferably less than or equal to 800 and, more preferably, less than or equal to 700.

[0222] There is no limit to the type of the (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof. Two or more different types of non-polymeric acids having two or more pKa values ​​or their salts may be used in combination. Thus, a single type of non-polymeric acid having two or more pKa values ​​or a salt thereof or a combination of different types of non-polymeric acids having two or more pKa values ​​or salts thereof may be used.

[0223] Herein, the term "salt" means a salt formed by the addition of suitable base(s) to the non-polymeric acid having two or more pKa values, which can be obtained from a reaction with the non-polymeric acid having two or more pKa values ​​with the base(s) according to methods known to those skilled in the art. As a salt, mention may be made of metal salts, for example alkali metal salts such as Na and K and alkaline earth metal salts such as Mg and Ca and ammonium salts.

[0224] The (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof may be an organic acid or salt(s) thereof, and preferably a hydrophilic or water-soluble organic acid or salt(s) thereof.

[0225] The (b) non-polymeric acid having two or more pKa values ​​may have at least two acid groups selected from the group consisting of a carboxylic group, a sulfuric group, a sulfonic group, a phosphoric group, a phosphonic group, a phenolic hydroxyl group and a mixture thereof.

[0226] The (b) non-polymeric acid having two or more pKa values ​​may be a non-polymeric polyvalent acid.

[0227] The (b) non-polymeric acid having two or more pKa values ​​may be selected from the group consisting of dicarboxylic acids, disulfonic acids and diphosphoric acids, as well as a mixture thereof.

[0228] The (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid and their salts; aspartic acid, glutamic acid and their salts; sulfonic terephthalylidene dicamphor acid or their salts (Mexoryl SX), Benzophenone-9; phytic acid and its salts;Red 2 (Amaranth), Red 102 (New Coccine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brillant blue FCF), Blue 2 (Indigo Carminé), Red 201 (Lithol Rubine B), (Lithol Rubine BCA), Red 204 (Lake Red CBA), Red 206 (Lithol Red CA), Red 207 (Lithol Red BA), Red 208 (Lithol Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 227 (Fast Acid Magenta), Yellow 203 (Quinoline Yellow WS), Green 201 (Alizanine Cyanine Green F), Green 204 (Pyranine Conc), Green 205 (Light Green SF Yellowish), Blue 203 (Patent Blue CA), Blue 205 (Alfazurine FG), Red 401 (Violamine R), Red 405 (Permanent Re F5R), Red 502 (Ponceau 3R), Red ; 503 (Ponceau R), Red 504 (Ponceau SX), Green 401 (Naphthol Green B), Green 402 (Guinea Green B), and Black 401 (Naphthol Blue Black); acide folique, acide ascorbique, acide erythorbique et sels de ces derniers; cystine et ses sels, EDTA et ses sels; glycyrrhizine et ses sels et un mélange de ceux-ci.

[0229] It may be preferable that the (b) non-polymeric acid having two or more pKa values ​​or one or more of its salts is selected from the group consisting of terephthalylidene dicamphor sulfonic acid and its salts (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salts, and a mixture thereof.

[0230] It may be preferable that the (b) non-polymeric acid having two or more pKa values ​​or one or more of its salts is selected from the group consisting of terephthalylidene dicamphor sulfonic acid and its salts (Mexoryl SX), phytic acid and its salts, and a mixture thereof.

[0231] The amount of the (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more and, more preferably, 0.1% by weight or more, relative to the total weight of the composition.

[0232] The amount of the (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.

[0233] The amount of (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight and, more preferably, from 0.1% to 5% by weight, relative to the total weight of the composition.

[0234] [Polyol]

[0235] The composition according to the present invention includes (c) at least one polyol. If two or more polyols are used, they may be the same or different.

[0236] The term "polyol" herein refers to an alcohol having two or more hydroxy groups and does not include a saccharide or a derivative thereof. The derivative of a saccharide includes a sugar alcohol obtained by reducing one or more carbonyl groups of a saccharide, as well as a saccharide or a sugar alcohol in which the hydrogen atom(s) in one or more hydroxy groups thereof has been replaced by at least one substituent such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group or a carbonyl group.

[0237] The polyols used in the present invention are liquid at room temperature, for example 25°C under atmospheric pressure (760 mmHg or 105 Pa).

[0238] The (c) polyol may be a C2-24 polyol, preferably a C2-9 polyol, comprising at least 2 hydroxy groups, and preferably 2 to 5 hydroxy groups.

[0239] The (c) polyol may be a natural or synthetic polyol. The polyol may have a linear, branched or cyclic molecular structure.

[0240] The (c) polyol may be selected from glycerins and their derivatives, as well as glycols and their derivatives. The polyol may be selected from the group consisting of glycerin, diglycerin, polyglycerin, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, C6-C24 polyethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol.

[0241] It is preferable that the (c) polyol is glycerin.

[0242] The amount of the (c) polyol(s) in the composition used in the present invention is 10% by weight or more, preferably 15% by weight or more, and more preferably 20% by weight or more, relative to the total weight of the composition.

[0243] Furthermore, the amount of the (c) polyol(s) in the composition according to the present invention may be 95% by weight or less, preferably 60% by weight or less, and more preferably 30% by weight or less, relative to the total weight of the composition.

[0244] The amount of the (c) polyol(s) in the composition according to the present invention may be from 10% to 95% by weight, preferably from 10% to 60% by weight, and more preferably from 10% to 30% by weight, relative to the total weight of the composition.

[0245] [Water]

[0246] The composition according to the present invention comprises (d) water.

[0247] The amount (d) of water in the composition according to the present invention may be 1% by weight or more, preferably 30% by weight or more and, more preferably, 50% by weight or more, relative to the total weight of the composition.

[0248] Furthermore, the amount (d) of water may be 90% by weight or less, preferably 50% by weight or less and, more preferably, 10% by weight or less, relative to the total weight of the composition.

[0249] The quantity (d) of water may be from 1% to 90% by weight, preferably from 30% to 90% by weight and, more preferably, from 50% to 90% by weight, relative to the total weight of the composition.

[0250] [pH]

[0251] The pH of the composition according to the present invention may be less than or equal to 9.0, preferably less than or equal to 8.5, and more preferably less than or equal to 8.1.

[0252] The pH of the composition according to the present invention may be greater than or equal to 3.0, preferably greater than or equal to 3.3, and more preferably greater than or equal to 3.5.

[0253] The pH of the composition according to the present invention may be from 3.0 to 9.0, preferably from 3.3 to 8.5 and, more preferably, from 3.5 to 8.1.

[0254] At a pH between 3.0 and 9.0, the composition according to the present invention can be very stable.

[0255] The pH of the composition according to the present invention may be corrected by adding at least one alkaline agent and / or at least one acid, other than (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof. The pH of the composition according to the present invention may also be corrected by adding at least one buffering agent.

[0256] (Alkaline agent)

[0257] The composition according to the present invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

[0258] The alkaline agent may be an inorganic alkaline agent. It is possible that the inorganic alkaline agent is 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.

[0259] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. As an inorganic alkali agent, sodium hydroxide is preferable.

[0260] The alkaline agent may be an organic alkaline agent. It is preferable that the organic alkaline agent is selected from the group consisting of monoamines and their derivatives; diamines and their derivatives; polyamines and their derivatives; basic amino acids and their derivatives; oligomers of basic amino acids and their derivatives; polymers of basic amino acids and their derivatives; urea and its derivatives and guanidine and its derivatives.

[0261] Examples of organic alkaline agents include alkanolamines such as mono-, di- and triethanolamine, and isopropanolamine; urea, guanidine and their derivatives; basic amino acids such as lysine, ornithine or arginine and diamines such as those described in the structure below: R1 R3 NRW R2 Z R4

[0262] in which R denotes an alkylene such as optionally substituted propylene by a hydroxyl or a C1-C4 alkyl radical, and Rh R2, R3 and R4 independently denote a hydrogen atom, an alkyl radical or a CrC4 hydroxyalkyl radical, as exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferable.

[0263] The alkaline agent(s) may be used in an amount ranging from 0.01% to 15% by weight, preferably from 0.02% to 10% by weight, and more preferably from 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.

[0264] (Acid)

[0265] The composition according to the present invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.

[0266] As the acid, mention may be made of all inorganic or organic acids, preferably inorganic, which are commonly used in cosmetic products. A monovalent acid and / or a polyvalent acid may be used. A monovalent acid such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) may be used. HCl is preferable.

[0267] The acid(s) may be used in an amount ranging from 0.01% to 15% by weight, preferably from 0.02% to 10% by weight, and more preferably from 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.

[0268] (Buffering agent)

[0269] The composition according to the present invention may comprise at least one buffering agent. Two or more buffering agents may be used in combination. Thus, a single type of buffering agent or a combination of different types of buffering agents may be used.

[0270] As a buffering agent, there may be mentioned an acetate buffer (e.g., acetic acid + sodium acetate), a phosphate buffer (e.g., sodium dihydrogen phosphate + disodium hydrogen phosphate), a citrate buffer (e.g., citric acid + sodium citrate), a borate buffer (e.g., boric acid + sodium borate), a tartrate buffer (e.g., tartaric acid + sodium tartrate dihydrate), a Tris buffer (e.g., tris(hydroxymethyl)aminomethane) and a Hepes buffer (4-(2-hydroxyethyl)-l-pipeineethanesulfonic acid).

[0271] [Optional Ingredients]

[0272] The composition according to the present invention may comprise, in addition to the above-mentioned essential ingredients (ingredients (a) to (d)), optional ingredients such as the anionic polymer (e) and those typically used in cosmetics, specifically, surfactants (in particular, non-ionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, volatile or non-volatile organic solvents other than ingredient (c), hydrophilic or hydrophobic UV filters, silicones and silicone derivatives, natural extracts derived from animals or plants, oils, waxes, and the like, in a range which does not affect the effects of the present invention.

[0273] The composition according to the present invention may comprise the optional ingredient(s) in an amount of 0.01% to 50% by weight, preferably 0.05% to 30% by weight, and more preferably 0.1% to 10% by weight, relative to the total weight of the composition.

[0274] The composition according to the present invention may include no surfactant or include a limited amount of surfactant, for example, less than 0.1% by weight, preferably less than 0.01% by weight, and more preferably less than 0.001% by weight, relative to the total weight of the composition.

[0275] [Preparation]

[0276] The composition according to the present invention can be prepared by mixing the essential and optional ingredients described above in a conventional manner.

[0277] For example, the composition according to the present invention can be prepared by a process comprising the step of

[0278] mixture

[0279] (a) of at least one cationic polymer,

[0280] (b) at least one non-polymeric acid having two or more pKa values or salt(s) thereof,

[0281] (c) at least one polyol, and

[0282] (d) water,

[0283] in which

[0284] the amount of the (c) polyol(s) in the composition is equal to or greater than 10% by weight relative to the total weight of the composition.

[0285] It is possible to further mix any of the optional ingredients. For example, the at least one anionic polymer may be mixed.

[0286] The mixing can be carried out at any temperature, for example at room temperature (25°C), preferably without heating. The composition according to the present invention can be environmentally friendly because it can be prepared without any heating step.

[0287] It is preferable that the cosmetic composition according to the present invention is in the form of a liquid at room temperature (for example, 25°C).

[0288] The composition according to the present invention can be used to easily prepare a film.

[0289] Thus, the present invention may also relate to a preparation process of a film, preferably a cosmetic film, preferably with a thickness of 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, comprising:

[0290] the application to a substrate, preferably a keratinous substance, and more preferably to the skin and hair, of the composition according to the present invention; and

[0291] drying the composition.

[0292] The upper limit of the thickness of the above film is not limited. Thus, for example, the thickness of the above film 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.

[0293] Thus, the present invention may also relate to a film, preferably a cosmetic film, comprising:

[0294] (a) at least one cationic polymer;

[0295] (b) at least one non-polymeric acid having two or more pKa values or salt(s) thereof;

[0296] (c) at least one polyol.

[0297] The film may further contain (d) water.

[0298] The above film, preferably the cosmetic film, is resistant to water of a pH less than or equal to 7, and can be removed with water of a pH greater than 7, preferably 8 or more and, more preferably, 9 or more.

[0299] In other words, the above film, preferably the cosmetic film, can be water-resistant under neutral or acidic conditions such as a pH of 7 or less, preferably in a range of 6 or more and 7 or less, and more preferably in a range of 5 or more and 7 or less, while the above film, preferably the cosmetic film, can be removed under alkaline conditions such as a pH of more than 7, preferably 8 or more, and more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11.

[0300] Therefore, the above film can be water-resistant and therefore it can remain on a keratinous substance such as skin and hair even if the surface of the keratinous substance is wet due to, for example, perspiration or rain. On the other hand, the above film, the above film, can be easily removed from the keratinous substance under alkaline conditions. Therefore, the above film, preferably the cosmetic film, is difficult to remove with water, while it can be easily removed with, for example, a soap which can provide alkaline conditions.

[0301] In addition, the above film may have cosmetic effects such as absorption or the adsorption of unpleasant odors, the modification of the appearance of keratinous fibers such as skin and hair, the modification of the feel of the keratinous substance and / or the protection of the keratinous substance against, for example, dirt or pollutants, due to the properties of the film, even if the film does not contain any cosmetic active ingredients.

[0302] Since the above film includes (c) at least one polyol such as glycerin, the film may have cosmetic effects provided by the (c) polyol, for example, moisturizing effects.

[0303] [Cosmetic Use and Process]

[0304] The composition according to the present invention may be a cosmetic composition, preferably a cosmetic skin care composition and more preferably a cosmetic skin care or hair care composition.

[0305] Thus, the cosmetic composition according to the present invention may be intended to be applied to a keratinous fiber. The keratinous substance may be keratinous fibers. Keratinous fibers herein designate fibers containing keratin as the main constituent, and their examples include hair, eyelashes, eyebrows, and the like. On the other hand, the keratinous substance may be the skin and mucous membranes such as the lips.

[0306] The composition according to the present invention may preferably be used as a leave-in or rinse-out cosmetic composition for a keratinous substance such as skin or hair.

[0307] The expression "no rinsing" means here that the composition according to the present invention is not removed from a keratinous substance such as the skin or the hair after having been applied to the keratinous substance.

[0308] The expression "rinse-off" herein means that the composition according to the present invention is removed, by rinsing, from the keratinous substance such as skin or hair after being applied to the keratinous substance. Water may be used for rinsing. Even after rinsing, the composition according to the present invention may remain to form a film or coating on a keratinous substance such as skin or hair.

[0309] The present invention also relates to

[0310] a cosmetic process for a keratinous substance such as skin and hair, comprising:

[0311] the application to the keratinous substance of the composition according to the present invention; and

[0312] drying the composition to form a cosmetic film on the keratinous substance,

[0313] and

[0314] a process for preparing a film, preferably a cosmetic film, comprising:

[0315] the application to a keratinous substance such as skin and hair, of the composition according to the present invention; and

[0316] drying the composition.

[0317] The cosmetic process here designates a non-therapeutic cosmetic process for caring for a keratinous substance such as the skin or hair, and / or the styling of keratinous fibers such as the hair.

[0318] The present invention may also relate to a use of the composition according to the present invention for the preparation of a cosmetic film on a keratinous substance such as the skin.

[0319] The present invention may also relate to a use of:

[0320] (a) at least one cationic polymer; and

[0321] (b) at least one non-polymeric acid having two or more pKa values or salt(s) thereof,

[0322] in a cosmetic composition for a keratinous substance such as skin and hair, comprising:

[0323] (c) at least one polyol; and

[0324] (d) water,

[0325] in which

[0326] the amount of the (c) polyol(s) in the composition is equal to or greater than 10% by weight, relative to the total weight of the composition,

[0327] in order to reduce the adhesion of the composition.

[0328] The use according to the present invention can reduce the stickiness of a composition comprising ingredients (c) and (d) wherein the amount of ingredient (c) in the composition is 10% by weight or more, based on the total weight of the composition, by a combination of ingredients (a) and (b), optionally with ingredient (e).

[0329] The explanations concerning the ingredients (a) to (e) in the composition according to the present invention can be applied to those of the use according to the present invention. EXAMPLES

[0330] The present invention will be described in more detail with the aid of examples. However, these examples should not be construed as limiting the scope of the present invention. [Examples 1 to 4 and comparative examples 1 to 4] [0331 ] [Preparation]

[0332] Each of the compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 was prepared by mixing the ingredients shown in Table 1 at room temperature (25°C). The numerical values ​​of the ingredient amounts shown in Table 1 are all based on "% by weight" of raw materials.

[0333] [Tables 1] Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. Ex. 1 Ex. Ex. 2 Ex. Ex. 3 Ex. Ex. 4 Polylysine 2 2 - - 2 2 - - Chitosan - - 2 2 - - 2 2 Phytic acid 0.55 - 0.55 0 - 0.55 - 0.55 Terephthalylidene dicamphor sulfonic acid - 1 0 0.55 - - - - Glycerin 10 10 10 10 10 - 10 - Water qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 Gel film formation Good Good Fair Fair Very poor Very poor Very poor Very poor Texture Very good Very good Good Good Very poor NA Very bad e NA

[0334] [Evaluations]

[0335] (Gel film formation)

[0336] Each of the compositions according to Examples 1 to 4 and Comparative Examples 1 to 4, in an amount of 10 g, was poured into a Petri dish and dried at 45 °C for 24 hours.

[0337] Five experts evaluated the formation of a gel film in the Petri dish according to the following grade:

[0338] 5: A homogeneous gel film was formed (the gel film appeared uniformly on the Petri dish)

[0339] 4: A gel film formed, but it was not homogeneous (the gel film presented unevenly on the Petri dish)

[0340] 3: The gel film formed slightly

[0341] 2: The gel film formed very slightly

[0342] 1: The gel film had not formed

[0343] It was then classified into the following three categories based on the average of the rank.

[0344] 5: Very good

[0345] 4: Good

[0346] 3: Correct

[0347] 2: Bad

[0348] 1: Very bad

[0349] The results are shown in Table 1.

[0350] (Texture)

[0351] Each of the compositions according to Examples 1 to 4 and Comparative Examples 1 to 4, in an amount of 10 g, was poured into a Petri dish and dried at 45 °C for 24 hours.

[0352] Five experts evaluated the texture of the Petri dish according to the following grade:

[0353] 5: Non-sticky (very smooth)

[0354] 4: Very slightly sticky (smooth)

[0355] 3: Slightly sticky

[0356] 2: Sticky

[0357] 1: Very sticky

[0358] She was then classified into the following three categories based on the grade average.

[0359] 5: Very good

[0360] 4: Good

[0361] 3: Correct

[0362] 2: Bad

[0363] 1: Very bad

[0364] The results are shown in Table 1.

[0365] (Summary)

[0366] The compositions according to Examples 1 to 4 formed a gel film. The compositions according to Examples 1 and 2 formed a gel film better than the compositions according to Examples 3 and 4.

[0367] The compositions according to Comparative Examples 1-4 could not form a gel.

[0368] Since the compositions according to Comparative Examples 2 and 4 did not include glycerin, the texture of the compositions was not evaluated.

[0369] It is demonstrated that a cationic polymer (polylysine and chitosan), a crosslinker (physical acid or terephthalylidene dicamphor sulfonic acid) and glycerin can form a gel film (coacervate) and can reduce the adhesion which is inherent to glycerin. [Examples 5-6 and comparative examples 5-6]

[0370] [Preparation]

[0371] Each of the compositions according to Examples 5-6 and Comparative Examples 5-6 was prepared by mixing the ingredients shown in Table 2 at room temperature (25°C). The numerical values ​​of the ingredient amounts shown in Table 2 are all based on "% by weight" of raw materials.

[0372] [Tables2] Ex. 5 Ex. 6 Ex. Ex. 5 Ex. Ex. 6 Polylysine 2 2 2 2 Sodium hyaluronate 1 - - - Cellulose gum - 1 - 1 Phytic acid 0.55 0.55 0.55 - Glycerin 10 10 - 10 Water qsp 100 qsp 100 qsp 100 qsp 100 PH 6.9 7.4 6.5 9.8 Gel film formation Very good Very good Very bad Very bad Texture Very good Very good NA Very bad

[0373] [Evaluations]

[0374] (Gel film formation)

[0375] Each of the compositions according to Examples 5-6 and Comparative Examples 5-6, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0376] Five experts evaluated the formation of a gel film in the Petri dish according to the following grade:

[0377] 5: A homogeneous gel film was formed (the gel film appeared uniformly on the Petri dish)

[0378] 4: A gel film formed, but it was not homogeneous (the gel film presented unevenly on the Petri dish)

[0379] 3: The gel film formed slightly

[0380] 2: The gel film formed very slightly

[0381] 1: The gel film had not formed

[0382] She was then classified into the following three categories based on the grade average.

[0383] 5: Very good

[0384] 4: Good

[0385] 3: Correct

[0386] 2: Bad

[0387] 1: Very bad

[0388] The results are shown in Table 2.

[0389] (Texture)

[0390] Each of the compositions according to Examples 5-6 and Comparative Examples 5-6, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0391] Five experts evaluated the texture of the Petri dish according to the following grade:

[0392] 5: Non-sticky (very smooth)

[0393] 4: Very slightly sticky (smooth)

[0394] 3: Slightly sticky

[0395] 2: Sticky

[0396] 1: Very sticky

[0397] She was then classified into the following three categories based on the grade average.

[0398] 5: Very good

[0399] 4: Good

[0400] 3: Correct

[0401] 2: Bad

[0402] 1: Very bad

[0403] The results are shown in Table 2.

[0404] (Summary)

[0405] The compositions according to Examples 5 to 6 formed a homogeneous gel film. The gel film was spread over the entire surface of the Petri dish.

[0406] The compositions according to Comparative Examples 5-6 could not form a gel.

[0407] Since the composition according to Comparative Example 5 did not include glycerin, the adhesion of the composition was not evaluated.

[0408] It is demonstrated that an anionic polymer (sodium hyaluronate and cellulose gum) can be added to a cationic polymer (polylysine), a crosslinker (physical acid) and glycerin to form a gel film (coacervate) and that the gel film thus formed is more preferable (more homogeneous). [Examples 7-8 and comparative examples 7-8]

[0409] [Preparation]

[0410] Each of the compositions according to Examples 7-8 and Comparative Examples 7-8 was prepared by mixing the ingredients listed in Table 3 at room temperature (25°C). The numerical values ​​of the ingredient amounts shown in Table 3 are all based on "% by weight" of raw materials.

[0411] [T ableaux3 ] Ex. 7 Ex. 8 Comp. Ex. 7 Ex. Ex. 8 Polylysine 2 2 2 - Phytic acid 0.55 0.55 - - Glycerin 50 90 50 50 Water qsp 100 qsp 100 qsp 100 qsp 100 PH 6.5 6.5 9.7 5.7 Gel film formation Good Good Very bad Very bad Texture Very good Very good Very bad Very bad

[0412] [Evaluations]

[0413] (Gel film formation)

[0414] Each of the compositions according to Examples 7-8 and Comparative Examples 7-8, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0415] Five experts evaluated the formation of a gel film in the Petri dish according to the following grade:

[0416] 5: A homogeneous gel film was formed (the gel film appeared uniformly on the Petri dish)

[0417] 4: A gel film formed, but it was not homogeneous (the gel film presented unevenly on the Petri dish)

[0418] 3: The gel film formed slightly

[0419] 2: The gel film formed very slightly

[0420] 1: The gel film had not formed

[0421] It was then classified into the following three categories based on the average of the rank.

[0422] 5: Very good

[0423] 4: Good

[0424] 3: Correct

[0425] 2: Bad

[0426] 1: Very bad

[0427] The results are shown in Table 3.

[0428] (Texture)

[0429] Each of the compositions according to Examples 7-8 and Comparative Examples 7-8, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0430] Five experts evaluated the texture of the Petri dish according to the following grade:

[0431] 5: Non-sticky (very smooth)

[0432] 4: Very slightly sticky (smooth)

[0433] 3: Slightly sticky

[0434] 2: Sticky

[0435] 1: Very sticky

[0436] She was then classified into the following three categories based on the grade average.

[0437] 5: Very good

[0438] 4: Good

[0439] 3: Correct

[0440] 2: Bad

[0441] 1: Very bad

[0442] The results are shown in Table 3.

[0443] (Summary)

[0444] The compositions according to Examples 7-8 formed a gel.

[0445] The compositions according to Comparative Examples 7-8 could not form a gel.

[0446] It is demonstrated that a large amount of glycerin can be used to form a gel film (coacervate). [Example 9 and Comparative Example 9]

[0447] [Preparation]

[0448] Each of the compositions according to Example 9 and Comparative Example 9 was prepared by mixing the ingredients listed in Table 4 at room temperature (25°C). The numerical values ​​of the ingredient amounts shown in Table 4 are all based on "% by weight" of raw materials.

[0449] [Tables4] Ex. 9 Comp. Ex. 9 Polylysine 4 - Phytic acid 1,1 - Glycerin 10 10 Water qsp 100 qsp 100 PH 6.7 6.3 Gel film formation Good Very poor Texture Very good Very poor

[0450] [Evaluations]

[0451] (Gel film formation)

[0452] Each of the compositions of Example 9 and Comparative Example 9, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0453] Five experts evaluated the formation of a gel film in the Petri dish according to the following grade:

[0454] 5: A homogeneous gel film was formed (the gel film appeared uniformly on the Petri dish)

[0455] 4: A gel film formed, but it was not homogeneous (the gel film presented unevenly on the Petri dish)

[0456] 3: The gel film formed slightly

[0457] 2: The gel film formed very slightly

[0458] 1: The gel film had not formed

[0459] It was then classified into the following three categories based on the average of the rank.

[0460] 5: Very good

[0461] 4: Good

[0462] 3: Correct

[0463] 2: Bad

[0464] 1: Very bad

[0465] The results are shown in Table 4.

[0466] (Texture)

[0467] Each of the compositions of Example 9 and Comparative Example 9, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0468] Five experts evaluated the texture of the Petri dish according to the following grade:

[0469] 5: Non-sticky (very smooth)

[0470] 4: Very slightly sticky (smooth)

[0471] 3: Slightly sticky

[0472] 2: Sticky

[0473] 1: Very sticky

[0474] She was then classified into the following three categories based on the grade average.

[0475] 5: Very good

[0476] 4: Good

[0477] 3: Correct

[0478] 2: Bad

[0479] 1: Very bad

[0480] The results are shown in Table 4.

[0481] (Summary)

[0482] The composition according to Example 9 formed a gel.

[0483] The composition according to Comparative Example 9 could not form a gel.

[0484] It is demonstrated that a large amount of a cationic polymer and / or a large amount of a crosslinker can be used to form a gel film (coacervate). [Examples 10-16]

[0485] [Preparation]

[0486] Each of the compositions according to Examples 10-16 was prepared by mixing the ingredients listed in Table 5 at room temperature (25°C). The numerical values ​​of the amounts of ingredients shown in Table 5 are all based on "% by weight" of raw materials.

[0487] [Tables5] Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Polylysine 2 2 2 2 2 2 2 Phytic acid 0.55 0.60 0.68 0.73 0.78 0.90 1.00 Glycerin 10 10 10 10 10 10 10 Water qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 PH 6.5 6.14 5.07 4.50 4.05 3.05 2.58 Gel film formation Good Good Good Good Good Good Good Texture Very good Very good Very good Very good Very good Very good

[0488] [Evaluations]

[0489] (Gel film formation)

[0490] Each of the compositions according to Examples 10-16, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0491] Five experts evaluated the formation of a gel film in the Petri dish according to the following grade:

[0492] 5: A homogeneous gel film was formed (the gel film appeared uniformly on the Petri dish)

[0493] 4: A gel film formed, but it was not homogeneous (the gel film presented unevenly on the Petri dish)

[0494] 3: The gel film formed slightly

[0495] 2: The gel film formed very slightly

[0496] 1: The gel film had not formed

[0497] It was then classified into the following three categories based on the average of the rank.

[0498] 5: Very good

[0499] 4: Good

[0500] 3: Correct

[0501] 2: Bad

[0502] 1: Very bad

[0503] The results are shown in Table 5.

[0504] (Texture)

[0505] Each of the compositions according to Examples 10-16, in an amount of 10 g, was poured in a Petri dish and dried at 45°C for 24 hours.

[0506] Five experts evaluated the texture of the Petri dish according to the following grade:

[0507] 5: Non-sticky (very smooth)

[0508] 4: Very slightly sticky (smooth)

[0509] 3: Slightly sticky

[0510] 2: Sticky

[0511] 1: Very sticky

[0512] She was then classified into the following three categories based on the grade average.

[0513] 5: Very good

[0514] 4: Good

[0515] 3: Correct

[0516] 2: Bad

[0517] 1: Very bad

[0518] The results are shown in Table 5.

[0519] (Summary)

[0520] The compositions according to Examples 10-16 formed a gel.

[0521] It is demonstrated that the amount of a crosslinker can be varied to form a gel film (coacervate). Example 17 and Comparative Examples 10-14

[0522] [Preparation]

[0523] Each of the compositions according to Example 17 and Comparative Examples 10-14 was prepared by mixing the ingredients listed in Table 6 at room temperature (25°C). The numerical values ​​of the ingredient amounts shown in Table 6 are all based on "% by weight" of raw materials.

[0524]

[0525]

[0526]

[0527]

[0528]

[0529]

[0530]

[0531]

[0532]

[0533]

[0534]

[0535]

[0536]

[0537]

[0538]

[0539]

[0540]

[0541] [Tableauxô] Ex. 17 Ex. Ex. 10 Comp. Ex. 11 Comp. Ex. 12 Ex. Ex. 13 Ex. Ex. 14 Polylysine 2 2 2 2 2 2 Phytic acid 0.55 - - - - - 0.1 M HCl - 2.80 3.40 3.90 3.96 4.10 Glycerin 10 10 10 10 10 10 Water qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 PH 6.5 6.57 6.00 5.07 3.86 2.51 Gel film formation Good Very Very Very Very Very Very Texture Very ... [Evaluations] (Gel film formation) Each of the compositions of Example 17 and Examples 10-16, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours. Five experts evaluated the formation of a gel film in the Petri dish according to the following grade: 5: A homogeneous gel film was formed (the gel film appeared uniformly on the Petri dish) 4: A gel film formed, but it was not homogeneous (the gel film appeared unevenly on the Petri dish) 3: The gel film formed slightly 2: The gel film formed very slightly 1: The gel film had not formed She was then classified into the following three categories based on the grade average. 5: Very good 4: Good 3: Correct 2: Bad 1: Very bad The results are shown in Table 6. (Texture)

[0542] Each of the compositions of Example 17 and Examples 10-16, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0543] Five experts evaluated the texture of the Petri dish according to the following grade:

[0544] 5: Non-sticky (very smooth)

[0545] 4: Very slightly sticky (smooth)

[0546] 3: Slightly sticky

[0547] 2: Sticky

[0548] 1: Very sticky

[0549] She was then classified into the following three categories based on the grade average.

[0550] 5: Very good

[0551] 4: Good

[0552] 3: Correct

[0553] 2: Bad

[0554] 1: Very bad

[0555] The results are shown in Table 6.

[0556] (Summary)

[0557] The composition according to Example 17 formed a gel.

[0558] The compositions according to Comparative Examples 10-14 could not form a gel.

[0559] It has been shown that the use of a monovalent acid (HCl) could not form a gel film (coacervate). It can be understood that the use of a multivalent crosslinker (e.g., phytic acid) is necessary. Examples 18-23

[0560] [Preparation]

[0561] Each of the compositions according to Examples 18-23 was prepared by mixing the ingredients listed in Table 7 at room temperature (25°C). The numerical values ​​of the ingredient amounts shown in Table 7 are all based on "% by weight" of raw materials.

[0562] [Tables?] Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Polylysine 2 2 2 2 2 2 Terephthalylidene dicamphor sulfonic acid 1 1.25 1.5 2.0 2.5 3.0 Glycerin 10 10 10 10 10 10 Water qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 PH 8.1 8.0 7.9 7.6 7.3 5.7 Gel film formation Good Good Good Good Good Good Texture Very good Very good Very good Very good Very good

[0563] [Evaluations]

[0564] (Gel film formation)

[0565] Each of the compositions according to Examples 18-23, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0566] Five experts evaluated the formation of a gel film in the Petri dish according to the following grade:

[0567] 5: A homogeneous gel film was formed (the gel film appeared uniformly on the Petri dish)

[0568] 4: A gel film formed, but it was not homogeneous (the gel film presented unevenly on the Petri dish)

[0569] 3: The gel film formed slightly

[0570] 2: The gel film formed very slightly

[0571] 1: The gel film had not formed

[0572] It was then classified into the following three categories based on the average of the rank.

[0573] 5: Very good

[0574] 4: Good

[0575] 3: Correct

[0576] 2: Bad

[0577] 1: Very bad

[0578] The results are shown in Table 7.

[0579] (Texture)

[0580] Each of the compositions according to Examples 18-23, in an amount of 10 g, was poured into a Petri dish and dried at 45°C for 24 hours.

[0581] Five experts evaluated the texture of the Petri dish according to the following grade:

[0582] 5: Non-sticky (very smooth)

[0583] 4: Very slightly sticky (smooth)

[0584] 3: Slightly sticky

[0585] 2: Sticky

[0586] 1: Very sticky

[0587] She was then classified into the following three categories based on the grade average.

[0588] 5: Very good

[0589] 4: Good

[0590] 3: Correct

[0591] 2: Bad

[0592] 1: Very bad

[0593] The results are shown in Table 7.

[0594] (Summary)

[0595] The compositions according to Examples 18-23 formed a gel.

[0596] It is demonstrated that a gel film can form at a pH, at least, below 8.1.

Claims

Claims

1. A composition, comprising: (a) at least one cationic polymer selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as chitosans and (co)polylysines, cationic (co)polyamino acids such as collagen, cationic cellulose polymers and their salts, (b) at least one non-polymeric acid having two or more pKa values ​​or salt(s) thereof, selected from the group consisting of terephthalylidene dicamphor sulfonic acid and its salts, phytic acid and its salts, and a mixture thereof; (c) at least one polyol; and (d) water. wherein the amount of the (c) polyol(s) in the composition is equal to or greater than 10% by weight relative to the total weight of the composition.

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

3. A composition according to any one of claims 1 to 2, wherein the (a) cationic polymer is selected from the group consisting of polylysines, chitosans and mixtures thereof.

4. A composition according to any one of claims 1 to 3, wherein the (b) non-polymeric acid having two or more pKa values ​​or salt(s) thereof is an organic acid or salt(s) thereof, preferably a hydrophilic or water-soluble organic acid or salt(s) thereof, and more preferably phytic acid or salts thereof, terephthalylidene dicamphor sulfonic acid or salts thereof, or a mixture thereof.

5. A composition according to any one of claims 1 to 4, wherein the (c) polyol is glycerin.

6. A composition according to any one of claims 1 to 5, wherein the composition further comprises (e) at least one anionic polymer.

7. Composition according to claim 6, in which the (e) anionic polymer is selected from polysaccharides, preferably

8. hyaluronic acid and its derivatives, cellulose polymers and their salts, and a mixture thereof, and more preferably hyaluronic acid and its salts, carboxymethylcellulose and its salts, and a mixture thereof. A cosmetic process for keratinous substance, comprising applying to the keratinous substance the composition according to any one of claims 1 to 7; and drying the composition to form a cosmetic film on the keratinous substance.