COMPOSITION COMPRISING A HYDROPHOBIC POLYIONIC COMPLEX PARTICLE
Patent Information
- Application Number
- FR2022000444
- Authority / Receiving Office
- FR · FR
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2022-01-19
- Publication Date
- 2025-03-14
- Estimated Expiration
- 2042-01-19
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Abstract
Description
Title of the invention: COMPOSITION COMPRISING A HYDRO-PHOBIZED POLYIONIC COMPLEX PARTICLE Technical field
[0001] The present invention relates to a composition including hydrophobized polyionic complex particles, as well as to a cosmetic method using the composition, context of the art
[0002] A polyionic complex, which is formed with an anionic polymer and a cationic polymer, is already known.
[0003] For example, WO 2021 / 125069 discloses a composition useful for cosmetic treatments and comprising 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. WO 2021 / 125069 also discloses that the composition disclosed therein may include oil and may be in the form of an emulsion, disclosure of the invention
[0004] However, the composition disclosed in WO 2021 / 125069 has been found to be stable only when it includes a very limited amount of oil, such as 0.5% by weight relative to the total weight of the composition. When the composition disclosed in this document includes a relatively large amount of oil, it tends to be unstable.
[0005] Thus, an objective of the present invention is to provide a composition which comprises a polyionic complex particle and which is stable even when it comprises a relatively large amount of oil.
[0006] The above object of the present invention can be achieved by a composition, including:
[0007] (a) at least one particle, comprising
[0008] at least one cationic polymer
[0009] at least one anionic polymer, and
[0010] at least one non-polymeric acid having two or more pKa values or a salt thereof;
[0011] (b) at least one oil;
[0012] (c) at least one fatty acid; and
[0013] (d) water.
[0014] The (a) particle can be hydrophobized by the (c) fatty acid.
[0015] The cationic polymer may be 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 collagen, cationic cellulose polymers, chitosans and their salts.
[0016] The amount of cationic polymer(s) forming the (a) particle in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
[0017] The anionic polymer may be selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers, anionic (co)polyamino acids such as glutamic (co)polyacids, (meth)acrylic (co)polyacids, amic (co)polyacids, (co)polystyrene sulfonate, (co)poly(vinyl sulfates), dextran sulfate, chondroitin sulfate, maleic (co)polyacids, fumaric polyacids, maleic acid (co)polymers, and their salts.
[0018] The amount of anionic polymer(s) forming the (a) particle in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
[0019] The non-polymeric acid having two or more pKa values or a salt thereof may be an organic acid or a salt thereof, preferably a hydrophilic or water-soluble organic acid or a salt thereof, and more preferably phytic acid or a salt thereof.
[0020] The amount of the non-polymeric acid having two or more pKa values or a salt thereof in the composition according to the present invention may be 0.001% to 10% by weight, preferably 0.003% to 5% by weight, and more preferably 0.005% to 1% by weight, based on the total weight of the composition.
[0021] The amount of the (a) particle(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.
[0022] The amount of the (b) oil(s) in the composition according to the present invention may be from 1% to 45% by weight, preferably from 5% to 40% by weight, and more preferably from 10% to 35% by weight, relative to the total weight of the composition.
[0023] The amount of the (c) fatty acid(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.
[0024] The amount of (d) water in the composition according to the present invention may be from 50% to 95% by weight, preferably from 55% to 90% by weight, and more preferably from 60% to 85% by weight, relative to the total weight of the composition.
[0025] The composition according to the present invention may comprise fatty phases comprising (b) oil and (c) fatty acid, and an aqueous phase comprising (d) water, wherein the fatty phases are dispersed in the aqueous phase.
[0026] The present invention also relates to a cosmetic process for a keratinous substance such as skin, comprising the following steps
[0027] the application to the keratinous substance of the composition according to the present invention; and
[0028] drying the composition to form a cosmetic film on the keratinous substance.
[0029] The present invention also relates to a use of (c) at least one fatty acid in a composition, comprising:
[0030] (a) at least one particle, comprising
[0031] at least one cationic polymer,
[0032] at least one anionic polymer, and
[0033] at least one non-polymeric acid having two or more pKa values or a salt thereof;
[0034] (b) at least one oil; and
[0035] (d) water,
[0036] to increase the amount of (b) oil in the composition to be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the composition. Brief description of the drawings
[0037] Figure 1 shows schematic drawings showing the behaviors of the (a) particles around a fatty phase, such as an oil droplet, dispersed in an aqueous phase, and the examples of hydrophobization of the (a) particle, in one embodiment of the present invention.
[0038] [Fig. la] [Fig. la] shows a schematic drawing showing the behavior of (a) particles around a fatty phase, such as an oil droplet, dispersed in an aqueous phase, in the case where the fatty phase does not include (c) fatty acid.
[0039] [Fig.lb] [Fig.lb] shows a schematic drawing showing the behavior of (a) particles around a fatty phase, such as an oil droplet, dispersed in an aqueous phase, in the case where the fatty phase includes a (c) fatty acid.
[0040] [Fig. 1c] [Fig. 1c] shows a schematic drawing showing the example of the mechanism of hydrophobization of the (a) particle by the (c) fatty acid.
[0041] [Fig.2] [Fig.2] shows photomicrographs of the compositions according to the example 1 and comparative example 1. Best mode for carrying out the invention
[0042] After diligent research, the inventors have discovered that it is possible to provide a composition which comprises a polyionic complex particle and which is stable even when it comprises a relatively large amount of oil. Thus, the composition according to the present invention comprises:
[0043] (a) at least one particle, comprising
[0044] at least one cationic polymer
[0045] at least one anionic polymer, and
[0046] at least one non-polymeric acid having two or more pKa values or a salt thereof;
[0047] (b) at least one oil;
[0048] (c) at least one fatty acid; and
[0049] (d) water.
[0050] The composition according to the present invention may comprise an aqueous phase comprising (d) water.
[0051] The composition according to the present invention may comprise fatty phases comprising (b) oil, and (c) fatty acid.
[0052] The fatty phases can be dispersed in the aqueous phase.
[0053] The (a) particle may be present at the interface between the fatty phase and the aqueous phase.
[0054] The (a) particle is a polyionic complex particle. The polyionic complex particle (a) may be hydrophobized by the (c) fatty acid to stabilize the composition.
[0055] The composition according to the present invention is stable even when it comprises a relatively large amount of oil, for example up to 30% by weight relative to the total weight of the composition. Thus, the composition according to the present invention may comprise a relatively large amount of oil, such as up to 30% by weight relative to the total weight of the composition.
[0056] The composition according to the present invention is stable for a long period. In other words, phase separation of the composition according to the present invention can be avoided for a long period.
[0057] Accordingly, the composition according to the present invention can be stored for a long period of time.
[0058] Hereinafter, the present invention will be explained in more detail.
[0059] [Polyionic complex particle]
[0060] The composition according to the present invention includes (a) at least one particle which is a polyionic complex particle. Two or more different types of particles (a) may be used in combination. Thus, a single type of particle (a) or a combination of different types of particles (a) may be used.
[0061] The size of the polyionic complex particle may be between 5 nm and 100 qm, preferably between 100 nm and 50 qm, more preferably between 200 nm and 40 qm, and even more preferably between 500 nm and 30 qm. A particle size of less than 1 qm may be measured by a dynamic light scattering method, and a particle size of more than 1 qm may be measured by an optical microscope. This particle size may be based on the volume average diameter.
[0062] The amount of the (a) particle(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.
[0063] The amount of the (a) particle(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.
[0064] The amount of the (a) particle(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.
[0065] The (a) particle includes a combination of polymers. More specifically, the (a) particle includes: at least one cationic polymer and at least one anionic polymer. The cationic polymer and the anionic polymer may form a polyionic complex particle or polyionic complex particles.
[0066] (Cationic polymer)
[0067] The composition according to the present invention includes at least one cationic polymer. A single type of cationic polymer may be used, or two or more different types of cationic polymers may be used in combination.
[0068] A cationic polymer has a positive charge density. The charge density of the cationic polymer may be between 0.01 meq / g and 20 meq / g, preferably between 0.05 meq / g and 15 meq / g, and more preferably between 0.1 meq / g and 10 meq / g.
[0069] It may be preferable that the molecular weight of the cationic polymer is 1000 or more, preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more.
[0070] Unless otherwise defined in the descriptions, "molecular weight" means number average molecular weight.
[0071] The 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 "amino group" (primary) herein means a -NH2 group.
[0072] The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" means both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers which are obtained from three types of monomers.
[0073] The cationic polymer may be chosen from natural and synthetic cationic polymers, and preferably natural cationic polymers. Non-limiting examples of cationic polymers are as follows.
[0074] (1) Homopolymers and copolymers derived from acrylic or meth- esters and amides acrylics and comprising at least one motif chosen from the motifs of the following formulas:
[0075] in which:
[0076] R1 and R2, identical or different, are chosen from hydrogen and alkyl groups containing from 1 to 6 carbon atoms, for example methyl and ethyl groups;
[0077] R3, identical or different, are chosen from hydrogen and CH3 groups;
[0078] the symbols A, identical or different, are chosen from alkyl groups linear or branched 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;
[0079] R4, R5 and R6, identical or different, are chosen from 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
[0080] X is an anion derived from an inorganic or organic acid, such as methosulfate anions and halides, for example chloride and bromide.
[0081] The copolymers of family (1) 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 by C1-C4 lower alkyl groups, groups derived from acrylic or methacrylic acids and esters thereof, vinyllactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.
[0082] Examples of copolymers of family (1) include, but are not limited to:
[0083] copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide,
[0084] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in European patent application No. 0 080 976,
[0085] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate,
[0086] quaternized or non-quatemized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, described for example in French patents Nos. 2,077,143 and 2,393,573,
[0087] dimethylaminoethyl methacrylate / vinylca-prolactam / vinylpyrrolidone terpolymers,
[0088] vinylpyrrolidone / methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymers, and
[0089] crosslinked polymers of methacryloyloxy alkyl (C1-C4) tri alkyl (C1-C4) ammonium 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 homopolymerization or copolymerization being followed by a crosslinking with an olefinically unsaturated compound, for example methylenebisacrylamide.
[0090] (2) Cationic polymers of cellulose such as cellulose ether derivatives having quaternary ammonium groups are 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 which have reacted with an epoxide substituted by a trimethylammonium group.
[0091] It is preferable that the cationic cellulose polymer has at least one quaternary ammonium group, preferably a trialkyl quaternary ammonium group, and more preferably a trimethyl quaternary ammonium group.
[0092] The quaternary ammonium group may be present in a group containing a quaternary ammonium group which may be represented by the following chemical formula (I): OH
[0093] in which
[0094] each of R1 and R2 represents a C1-3 alkyl group, preferably a methyl or ethyl group, and more preferably a methyl group,
[0095] R3 represents a C 24 alkyl group, preferably a methyl or ethyl group, and more preferably a methyl group,
[0096] X represents an anion, preferably a halide, and more preferably a chloride,
[0097] n denotes an integer from 0 to 30, preferably from 0 to 10, and more preferably 0, and
[0098] R4 represents a Cw alkylene group, preferably an ethylene or propylene group.
[0099] The leftmost ether bond (-O-) in chemical formula (I) above can attach to the sugar ring of the polysaccharide.
[0100] It is preferable that the group containing the quaternary ammonium group is -O-CH2-CH(OH)-CH2-N+(CH3)3.
[0101] (3) Cationic polymers of cellulose such as copolymers of cellulose and cellulose derivatives are grafted with a water-soluble quaternary ammonium monomer and described, for example, in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, e.g., hydroxymethyl-, hy- droxyethyl-, and hydroxypropylcelluloses grafted, for example, with a salt selected from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, and dimethyldiallylammonium salts.
[0102] Commercial products corresponding to these polymers include, for example, products sold under the name “Celquat® L 200” and “Celquat® H 100” by the company National Starch.
[0103] (4) The non-cellulosic cationic polysaccharides described in the patent 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, e.g., chloride, of 2,3-epoxypropyltrimethylammonium (guar hydroxypropyltrimonium chloride) may also be used.
[0104] Such products are sold, for example, under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17, and JAGUAR® C162 by the company MEYHALL.
[0105] (5) Polymers comprising piperazinyl units and alkylene or hy- groups Divalent droxyalkylene polymers comprising straight or branched chains, optionally interrupted by at least one entity selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, as well as the oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French patents Nos. 2,162,025 and 2,280,361.
[0106] (6) Water-soluble polyaminoamides prepared, for example, by polycon densification of an acidic compound with a polyamine; these polyaminoamides being able to be crosslinked with an entity chosen from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bis-unsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacyidiamines; bisalkyl halides; oligomers resulting from the reaction of a difunctional compound which is reactive with an entity chosen from bishalohydrins, bisazetidiniums, bishaloacyidiamines, bisalkyl halides, epihalohydrins, diepoxides and bisunsaturated derivatives; the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mole per amine group of the polyaminoamide; these polyaminoamides being optionally alkylated or, if they comprise at least one tertiary amine function, they can be quaternized. Such polymers are described, for example, in French patents Nos. 2,252,840 and 2,368,508.
[0107] (7) Polyaminoamide derivatives resulting from the condensation of polyalkylene po- lyamines with polycarboxylic acids, followed by alkylation with di-functional agents, e.g., 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. Such polymers are described, for example, in French patent No. 1,583,363. In at least one embodiment, these derivatives may be chosen from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.
[0108] (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 range from 0.8:1 to 1.4:1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine group of the polyaminoamide ranging from 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Patent Nos. 3,227,615 and 2,961,347.
[0109] (9) Alkyldiallylamine cyclopolymers and dialkyldiallyl- cyclopolymers ammonium, such as homopolymers and copolymers comprising, as the main constituent of the chain, at least one unit chosen from the units of formulae (Ia) and (Ib): ........ (there) ..................ÇWsî) .........OH?.......
[0110] in which:
[0111] k and t, identical or different, are equal to 0 or 1, the sum k+t being equal to 1;
[0112] Rn is chosen from hydrogen and methyl groups;
[0113] Rio and Rn, identical or different, are chosen 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, amidoalkyl groups (in CrC4) lower, or Rio and Rn may form, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl and morpholinyl; and
[0114] 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.
[0115] In one embodiment, R10 and Ru, identical or different, are chosen from alkyl groups comprising from 1 to 4 carbon atoms.
[0116] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chloride such as the homopolymer of dimethyldial-lylammonium chloride sold under the name "MERQUAT® 100" by CALGON (and its low weight average molecular weight counterparts) and copolymers of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".
[0117] Quaternary diammonium polymers comprising at least one repeating unit of formula (II):
[0118] in which:
[0119] Rn, Ru, Rb, and R16, which may be identical or different, are selected from aliphatic, alicyclic, and arylaliphatic groups comprising from 1 to 20 carbon atoms and lower aliphatic hydroxyalkyl groups, or Rn, Ru, R[5, and R[6 may form, jointly or separately, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second heteroatom other than nitrogen, or Rn, Rm, R[5 and R[6, which may be identical or different, are selected from linear or branched C1-C6 alkyl groups substituted by at least one group selected from nitrile groups, ester groups, acyl groups, amide groups, -CO-O-Rp -E groups and -CO-NH-R17-E groups, in which Rn is an alkylene group and E is a quaternary ammonium group;
[0120] Ai and Bb, 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 cycles, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups, ester groups, and
[0121] X is an anion derived from an inorganic or organic acid;
[0122] Ai, R13 and Rn can form, together with the two nitrogen atoms to which they are attached, a piperazine ring;
[0123] if Ai is chosen from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B1 can be chosen from:
[0124] -(CH2)n-CO-E'-OC-(CH2)n-
[0125] in which E' is chosen from:
[0126] a) glycol residues of formula -OZO-, in which Z is chosen from linear or branched hydrocarbon groups and groups of the following formulas:
[0127] -(CH2-CH2-O)X-CH2-CH2-
[0128] -[CH2-CH(CH3)-O]y-CH2-CH(CH3)-
[0129] in which x and y, identical or different, are chosen from the integers ranging from 1 to 4, which represent a defined and unique degree of polymerization, and the numbers ranging from 1 to 4, which represent an average degree of polymerization;
[0130] b) a bis-secondary diamine residue such as piperazine derivatives;
[0131] 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 -CH2 -CH2-SS-CH2-CH2-; and
[0132] d) ureylene groups of formula -NH-CO-NH-.
[0133] In at least one embodiment, X is an anion such as chloride or bromide.
[0134] 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 American 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.
[0135] Non-limiting examples of such polymers include those comprising at least one repeating unit of formula (III): (HD Rts J; § E — H— Ru Ris
[0136] in which
[0137] Rn, Ru, Rn and R[6, identical or different, are chosen from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbon atoms, n and p, identical or different, are integers ranging from 2 to 20, and X is an anion derived from an inorganic or organic acid.
[0138] (11) Polyquaterary ammonium polymers comprising units of formula (IV): (IV) - GO- x | | X"
[0139] in which:
[0140] R18, R19, R2o, and R2i, identical or different, are chosen from hydrogen, methyl groups, ethyl groups, propyl groups, [3-hydroxyethyl groups, [3-hydroxypropyl groups, -CH2CH2(OCH2CH2)POH groups, in which p is chosen from integers ranging from 0 to 6, provided that R[8, R19, R20, and R2[ are not simultaneously hydrogen,
[0141] r and s, identical or different, are chosen from the integers ranging from 1 to 6,
[0142] q is chosen from the integers ranging from 0 to 34,
[0143] X is an anion such as a halide, and
[0144] A is chosen from dihalide radicals and —CH2-CH2-O-CH2-CH2-.
[0145] Such compounds are described, for example, in European patent application No. 0 122 324.
[0146] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0147] 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, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives.
[0148] According to one embodiment of the present invention, the at least one cationic polymer is chosen from cellulose ether derivatives comprising quaternary ammonium groups, such as the products sold under the name "JR 400" by the company UNION CARBIDE CORPORATION, cationic cyclopolymers, for example, homopolymers and copolymers of dimethyldiallylammonium chloride sold under the names MERQUAT® 100, MERQUAT® 550, MERQUAT® S by the company CALGON, guar gums modified with a 2,3-epoxypropyltrimethylammonium salt, quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0149] (13) Polyamines
[0150] 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 the polymer or in a side group, if present, of the (co)poly amines.
[0151] Examples of (co)polyamines include chitosan, (co)polyallylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polydimethylaminoethylenemethacrylates, (co)polyvinylpyridines such as (co)poly-1-methyl-2-vinylpyridines, (co)polyimines such as (co)polyethyleneimines, (co)polypyridines such as (co)poly(quaternary pyridines), (co)polybiguanides such as (co)polyaminopropyl biguanides, (co)polylysines, (co)polyornithines, (co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinyl acetals, and salts thereof.
[0152] As (co)polyamines, it is preferable to use (co)polylysines. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine which can be produced by bacterial fermentation. For example, polylysine can be e-poly-L-lysine, typically used as a natural preservative in food products. Polylysine is a polyelectrolyte which is soluble in polar solvents such as water, propylene glycol and glycerol. Polylysine is commercially available in different forms, such as poly D-lysine and poly L-lysine. Polylysine can be in salt and / or solution form.
[0153] (14) Cationic polyamino acids
[0154] As the cationic polymer, it is 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.
[0155] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, hydroxyprolyl stear-dimonium hydrolyzed wheat protein, hydroxypropyl cocodimonium hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, hydroxypropyl steardimonium hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydrolyzed soy protein, and the like.
[0156] The following descriptions relate to preferable embodiments of the cationic polymer.
[0157] It may be preferable for the cationic polymer to be chosen from cationic starches.
[0158] Examples of cationic starches include starches modified with a 2,3-epoxypropyltrimethylammonium salt (e.g. chloride), such as the product known as starch hydroxypropyltrimonium chloride according to the INC1 nomenclature and sold under the name SENSOMER Cl-50 from Ondeo or PencareTM DP 1015 from Ingredion.
[0159] It may also be preferable for the cationic polymer to be chosen from cationic gums.
[0160] The gums may be, for example, selected from the group consisting of cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum and gum arabic.
[0161] Examples of cationic gum include cationic polygalac-tomannan derivatives such as guar gum derivatives and cassia gum derivatives, e.g., CTFA: guar hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride, and cassia hydroxypropyltrimonium chloride. Guar hydroxypropyltrimonium chloride is commercially available under the Jaguar™ family of trade names from Rhodia Inc. and the N-Hance family of trade names from Ashland Inc. Cassia hydroxypropyltrimonium chloride is commercially available under the trademarks Sensomer™ CT-250 and Sensomer™ CT-400 from Lubrizol Advanced Materials, Inc. or ClearHance™ from Ashland Inc.
[0162] It may also be preferable for the cationic polymer to be chosen from chitosans.
[0163] It may be further preferred that the cationic polymer is selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldial-lylammonium cyclopolymers such as (co)polydiallyldialkylammonium chloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as cationized collagen, cationic cellulose polymers, chitosans and their salts.
[0164] It may be even more preferable that the cationic polymer is selected from the group consisting of polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, polylysine, chitosan and a mixture thereof.
[0165] The amount of cationic polymer(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.
[0166] The amount of 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.
[0167] The amount of cationic polymer(s) in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
[0168] (Anionic polymer)
[0169] The composition according to the present invention includes at least one anionic polymer. A single type of anionic polymer may be used, or two or more different types of anionic polymers may be used in combination.
[0170] 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 meq / g to 15 meq / g, and more preferably from 4 meq / g 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.
[0171] It may be preferable that the molecular weight of the anionic polymer is 1,000 or more, preferably 2,000 or more, even more preferably 5,000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, and even more preferably 1,000,000 or more.
[0172] Unless otherwise defined in the descriptions, "molecular weight" may mean number average molecular weight.
[0173] The 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.
[0174] The anionic polymer may be a homopolymer or a copolymer. By "copolymer" is meant both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.
[0175] The anionic polymer may be chosen from natural and synthetic anionic polymers, and preferably from natural anionic polymers.
[0176] The anionic polymer may comprise at least one hydrophobic chain.
[0177] The anionic polymer, which may comprise at least one hydrophobic chain, may be obtained by copolymerization of a monomer (a) chosen from carboxylic acids comprising an α,[3-monoethylenic unsaturation (monomer a') and 2-acrylamido-2-methylpropanesulfonic acid (monomer a”) with a non-surfactant monomer (b) comprising an ethylenic unsaturation different from (a) and / or a monomer (c) comprising an ethylenic unsaturation resulting from the reaction of an acrylic monomer comprising an α,[3-monoethylenic unsaturation or of an isocyanate monomer comprising a monoethylenic unsaturation with a monohydric nonionic amphiphilic component or with a primary or secondary fatty amine.
[0178] Thus, the anionic polymer comprising at least one hydrophobic chain can be obtained by two synthesis routes:
[0179] - either by copolymerization of the monomers (a1) and (c), or (a1), (b) and (c), or (a”) and (c), or (a”), (b) and (c),
[0180] - either by modification (and in particular esterification or amidation) of a copolymer formed from monomers (a1) or monomers (a1) and (b), or (a”) and (b), by a non-ionic monohydric amphiphilic compound or a primary or secondary fatty amine.
[0181] Mention may be made in particular, as copolymers of 2-acrylamido-methylpropanesulfonic acid, of those disclosed in the article "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10 - 3694 to 3704" and in applications EP A 0 750 899 and EP A 1 069 172.
[0182] The carboxylic acid comprising an α,[3-monoethylenic unsaturation constituting the monomer (a1) can be chosen from numerous acids and in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. It is preferably acrylic or methacrylic acid.
[0183] The copolymer may comprise a monomer (b) comprising monoethylenic unsaturation which does not exhibit a surfactant property. Preferred monomers are those which give water-insoluble polymers when homopolymerized. They may be chosen, for example, from C1-C4 alkyl acrylates and methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. The most particularly preferred monomers are methyl acrylate and ethyl acrylate. Other monomers which may be used are, for example, styrene, vinyltoluene, vinyl acetate, acrylonitrile and vinylidene chloride. Preferred are non-reactive monomers, these monomers being those in which the only ethylenic group is the only reactive group under the polymerization conditions. However, monomers that have groups that react under heat effect, such as hydroxyethyl acrylate, may optionally be used.
[0184] The monomer (c) is obtained by reacting an acrylic monomer comprising an α,[3-monoethylenic unsaturation, such as (a), or an isocyanate monomer comprising a monoethylenic unsaturation with a monohydric non-ionic amphiphilic compound or a primary or secondary fatty amine.
[0185] Monohydric nonionic amphiphilic compounds or primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. Monohydric nonionic 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, compounds in which a carbon chain comprising at least six carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.
[0186] The preferred monohydric nonionic amphiphilic compounds are compounds corresponding to the following formula (V):
[0187] R-(OCH2CHR')m-(OCH2CH2)n-OH (V)
[0188] 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.
[0189] 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.
[0190] Preferred primary and secondary fatty amines are composed of one or two alkyl chains comprising from 6 to 30 carbon atoms.
[0191] The monomer used to form the non-ionic urethane monomer (c) may be chosen from a wide variety of compounds. Any compound comprising copolymerizable unsaturation, such as acrylic, methacrylic or allylic unsaturation, may be used. The monomer (c) may be obtained in particular from an isocyanate comprising monoethylenic unsaturation, such as, in particular, α,α-dimethyl-m isopropenylbenzyl isocyanate.
[0192] The monomer (c) may be chosen in particular from oxyethylenated (1 to 50 EO) C6-C3o fatty alcohol acrylates, methacrylates or itaconates, such as steareth 20 methacrylate, oxyethylenated (25 EO) behenyl methacrylate, oxyethylenated (20 EO) monocetyl itaconate, oxyethylenated (20 EO) monostearyl itaconate or acrylate modified with polyoxyethylenated C12-C24 alcohols (25 EO) and with oxyethylenated C6-C30 fatty alcohol dimethyl-m-isopropenylbenzyl isocyanates (11 50 EO), such as in particular oxyethylenated behenyl alcohol dimethyl-m-isopropenylbenzyl isocyanate.
[0193] According to a specific embodiment of the present invention, the anionic polymer is selected from acrylic terpolymers obtained from (a) a carboxylic acid comprising α,[3-ethylenic unsaturation, (b) a non-surfactant monomer comprising ethylenic unsaturation other than (a), and (c) a non-ionic urethane monomer which is the reaction product of a monohydric non-ionic amphiphilic compound with an isocyanate comprising monoethylenic unsaturation.
[0194] Mention may in particular be made, as anionic polymers comprising at least one hydrophobic chain, of the acrylic acid / ethyl acrylate / alkyl acrylate terpolymer, such as the product in 30% aqueous dispersion sold under the name Acusol 823 by Rohm & Haas; the acrylates / steareth-20 methacrylate copolymer, such as the product sold under the name Aculyn 22 by Rohm & Haas; the (meth)acrylic acid / ethyl acrylate / oxyethylenated behenyl methacrylate (25 EO) terpolymer, such as the product in aqueous emulsion sold under the name Aculyn 28 by Rohm & Haas; acrylic acid / oxyethylenated monocetyl itaconate copolymer (20 EO), such as the 30% aqueous dispersion product sold under the name Structure 3001 by National Starch; acrylic acid / oxyethylenated monostearyl itaconate copolymer (20 EO), such as the 30% aqueous dispersion product sold under the name Structure 2001 by National Starch;acrylates / acrylates modified with a copolymer of polyoxyethylenated C12-C24 alcohols (25 EO), such as the 30 to 32% copolymer latex sold under the name Synthalen W2000 by 3V SA; or the terpolymer of methacrylic acid / methyl acrylate / dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylated behenyl alcohol, 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.;
[0195] The anionic polymers may also be Polyester-5, such as the product sold as Eastman AQ™ 55S Polymer by EASTMAN CHEMICAL having a chemical formula below.
[0196] HO-GAGAGAGAGAGAGAGAG-OH
[0197] 11
[0198] SO3 Na+ SO3 Na+
[0199] A: dicarboxylic acid fragment
[0200] G: glycol fragment
[0201] SO3 Na+: sodium sulfo group
[0202] OH: hydroxyl group
[0203] It may be preferable that the anionic polymer is selected from the group consisting of polysaccharides such as alginic acid (algin), hyaluronic acid and cellulose polymers (e.g., carboxymethylcellulose), anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polyfumaric acids, (co)polymers of maleic acid and salts thereof.
[0204] 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.
[0205] Thus, the term "maleic acid copolymer" means 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 totally hydrolyzed. Hydrophilic polymers will preferably be used, i.e. polymers having a solubility in water greater than or equal to 2 g / L.
[0206] 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 and more preferably between 0.4 and 0.9.
[0207] 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.
[0208] It is preferable that the maleic acid copolymer is a styrene / maleic acid copolymer, and more preferably a styrene / sodium maleic acid copolymer.
[0209] A copolymer of styrene and maleic acid in a ratio of 50 / 50 will preferably be used.
[0210] It will be possible to use, for example, the styrene / maleic acid copolymer (50 / 50), in the form of ammonium salt at 30% in water, sold under the reference SMA1000H ® by Cray Valley or the styrene / maleic acid copolymer (50 / 50), in the form of sodium salt at 40% in water, sold under the reference SMAlOOOHNa® by Cray Valley.
[0211] The use of styrene / maleic acid copolymer such as styrene / sodium maleic acid copolymer can improve the wettability of a film prepared by the composition according to the present invention.
[0212] In a preferable embodiment, the anionic polymer may be selected from hyaluronic acid, its salts (e.g., sodium hyaluronate), and its derivatives.
[0213] Hyaluronic acid can be represented by the following chemical formula.
[0214] In the context of the present invention, the term "hyaluronic acid" covers in particular the basic unit of hyaluronic acid of formula:
[0215] It is the smallest fraction of hyaluronic acid comprising a dimer of di-saccharide, namely D-glucuronic acid and N-acetylglucosamine.
[0216] 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 to the chain by alternating [3(1,4) and [3(1,3)] glycosidic bonds, having a molecular weight (MW) which can vary between 380 and 13,000,000 daltons. This molecular weight depends largely on the source from which the hyaluronic acid is obtained and / or the preparation methods.
[0217] The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, hyaluronic acid salts. Examples of salts include alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.
[0218] 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.
[0219] Thus, the term “hyaluronic acid and its derivatives” includes all fractions or subunits of hyaluronic acid having a molecular weight in particular in the molecular weight range recalled above.
[0220] In the context of the present invention, hyaluronic acid fractions which do not exhibit inflammatory activity are preferably used.
[0221] As an illustration of the different fractions of hyaluronic acid, one can refer to the document “Hyaluronan fragments: an information-rich System”, R. Stem et al, European Journal of Cell Biology 58 (2006) 699-715, which reviews the listed biological activities of hyaluronic acid according to its molecular weight.
[0222] According to a preferred embodiment of the present invention, the hyaluronic acid fractions suitable for the use targeted by the present invention have a molecular weight 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, we speak of high molecular weight hyaluronic acid.
[0223] Alternatively, the hyaluronic acid fractions which may also be suitable for the use targeted by the present invention have a molecular weight of between 50,000 and 400,000 Da. In this case, we speak of hyaluronic acid of intermediate molecular weight.
[0224] Alternatively, the hyaluronic acid fractions which may also be suitable for the use contemplated by the present invention have a molecular weight of less than 50,000 Da. In this case, we speak of low molecular weight hyaluronic acid.
[0225] 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 by alkyl or oxyethylenated alcohols, comprising 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 ranging from 0.5 to 50%.
[0226] Mention may be made in particular of the 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.
[0227] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or one of its salts.
[0228] The molecular weights indicated above are also valid for hyaluronic acid esters.
[0229] The hyaluronic acid may in particular be the 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. Lûmes. 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).
[0230] The amount of the anionic polymer(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.
[0231] 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.
[0232] The amount of the anionic polymer(s) in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
[0233] (Non-polymeric acid having two or more acid dissociation constants)
[0234] The composition according to the present invention includes at least one non-polymeric acid having two or more pKa values or a salt thereof, i.e. at least one non-polymeric acid having two or more acid dissociation constants or a salt thereof. The pKa value (acid dissociation constant) is well known to those skilled in the art, and must be determined at a constant temperature such as 25°C.
[0235] The non-polymeric acid having two or more pKa values or a salt thereof may be included in the (a) particle. The non-polymeric acid having two or more pKa values may function as a crosslinking agent for the cationic polymer and / or the anionic polymer, particularly the cationic polymer.
[0236] The term "non-polymeric" herein means that the acid is not obtained by polymerization of two or more monomers. Thus, non-polymeric acid does not correspond to an acid obtained by polymerization of two or more monomers, such as polyacrylic acid.
[0237] It is preferable that the molecular weight of the non-polymeric acid having two or more pKa values or a salt thereof is 1000 or less, preferably 800 or less, and more preferably 700 or less.
[0238] There is no limit to the type of non-polymeric acid having two or more pKa values or a salt 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.
[0239] The term "salt" herein refers to a salt formed by the addition of one or more suitable bases 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. Examples of salts include 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.
[0240] The non-polymeric acid having two or more pKa values or a salt thereof may be an organic acid or a salt thereof, and preferably a hydrophilic or water-soluble organic acid or a salt thereof.
[0241] The 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.
[0242] The non-polymeric acid having two or more pKa values may be a non-polymeric polyvalent acid.
[0243] The non-polymeric acid having two or more pKa values may be selected from the group consisting of dicarboxylic acids, disulfonic acids and diphosphoric acids, and a mixture thereof.
[0244] The (c) 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 salts thereof; aspartic acid, glutamic acid and salts thereof; terephthalylidene dicamphor sulfonic acid or salts thereof (Mexoryl SX), benzophenone-9; phytic acid and salts thereof;Red 2 (Amaranth), Red 102 (New Coccine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brilliant Blue FCF), Blue 2 (Indigo Carminé), Red 201 (Lithol Rubine B), Red 202 (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 (Naphtol Green B), Green 402 (Guinea Green B), et Black 401 (Naphtol Blue Black) ; acide folique, acide ascorbique, acide érythorbique et des sels de ceux-ci ; cystine et des sels de celle-ci ; EDTA et des ; salts thereof; glycyrrhizin and salts thereof; and a mixture thereof.
[0245] It may be preferable that the non-polymeric acid having two or more pKa values or a salt thereof 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.
[0246] The non-polymeric acid having two or more pKa values or a salt thereof may be an organic acid or a salt thereof, preferably a hydrophilic or water-soluble organic acid or a salt thereof, and more preferably phytic acid or a salt thereof.
[0247] The amount of non-polymeric acid having two or more pKa values or a salt thereof in the composition according to the present invention may be 0.001 wt% or more, preferably 0.003 wt% or more, and more preferably 0.005 wt% or more, based on the total weight of the composition.
[0248] The amount of the non-polymeric acid having two or more pKa values or a salt thereof in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and more preferably 1% by weight or less, based on the total weight of the composition.
[0249] The amount of the non-polymeric acid having two or more pKa values or a salt thereof in the composition according to the present invention may be from 0.001% to 10% by weight, preferably from 0.003% to 5% by weight, and more preferably from 0.005% to 1% by weight, based on the total weight of the composition.
[0250] [Oil]
[0251] The composition according to the present invention comprises (b) at least one oil. If two (b) or more oils are used, they may be the same or different.
[0252] By "oil" is meant here a fatty compound or substance which is in the form of a liquid or a paste (not solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As oils, those generally used in cosmetics can be used alone or in combination. These oils can be volatile or non-volatile.
[0253] The oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a vegetable or animal oil and an ester oil or an ether oil; or a mixture thereof.
[0254] The oil may be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.
[0255] Examples of vegetable oils include, for example, apricot oil, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame, soybean oil, peanut oil, and mixtures thereof.
[0256] Examples of animal oils include, for example, squalene and squalane.
[0257] Examples of synthetic oils include alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.
[0258] The ester oils are preferably liquid esters of linear or branched, saturated or unsaturated, C1-C26 aliphatic monoacids or polyacids and linear or branched, saturated or unsaturated, C1-C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
[0259] Preferably, for the monoalcohol esters, at least one of the alcohol and the acid from which the esters of the present invention are derived is branched.
[0260] Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.
[0261] Esters of C4-C22 dicarboxylic or tricarboxylic acids and C1-C22 alcohols may also be used, as well as esters of monocarboxylic, dicarboxylic or tricarboxylic acids and C4-C26 non-sugar dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols.
[0262] Mention may in particular be made of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol dii-sononanoate.
[0263] As ester oils, sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids can be used. It is recalled that the term "sugar" designates oxygenated hydrocarbon compounds comprising several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.
[0264] Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and their derivatives, including alkyl derivatives, such as methyl derivatives, for example methylglucose.
[0265] The fatty acid sugar esters may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched, saturated or unsaturated fatty acids, C6-C30 and preferably C[2-C22. If they are unsaturated, these compounds may contain one to three conjugated or unconjugated carbon-carbon double bonds.
[0266] The esters according to this variant can also be chosen from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.
[0267] These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, in particular, mixed esters of oleopalmitate, oleostearate and palmitostearate, as well as pentaerythrityl tetraethyl hexanoate.
[0268] More particularly, monoesters and diesters are used, and in particular mono- or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates of sucrose, glucose or methylglucose.
[0269] An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
[0270] Examples of preferable ester oils include, for example, dii-isopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate / caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, Isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.
[0271] Examples of artificial triglycerides include, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate / caprylate) and glyceryl tri(caprate / caprylate / linolenate).
[0272] Examples of silicone oils include, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and the like; and mixtures thereof.
[0273] Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
[0274] These silicone oils can also be organomodified. Organo-silicones modified oils usable according to the present invention are silicone oils as defined above and comprise in their structure one or more organo-functional groups attached via a hydrocarbon group.
[0275] Organopolysiloxanes are further defined in Walter Noll's Chemistry and Technology of Silicones (1968), Academy Press. They may be volatile or non-volatile.
[0276] When they are volatile, the silicones are more particularly chosen from those having a boiling point between 60°C and 260°C, and even more particularly from:
[0277] (i) Cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecame-ethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the di-methylsiloxane / methylalkylsiloxane type, such as Silicone Volatile® FZ 3109 sold by the company Union Carbide, of formula: r— Dw — D' ---------G" - D? ■---1 CH. ।1 CH, with D!ï: with C': S-* v
[0278] Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis(2,2,2',2',3,3'-hexatrimethylsilyloxy)neopentane; and
[0279] (ii) volatile linear polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity less than or equal to 5x106 m2 / s at 25°C. Examples include decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of silicones is measured at 25°C according to ASTM 445 Annex C.
[0280] Non-volatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may mainly be made of polydimethylsiloxanes containing groups trimethylsilyl terminals.
[0281] Among these polydialkylsiloxanes, the following commercial products may be mentioned, without limitation:
[0282] - Silbione® oils from the 47 and 70 047 range or Mirasil® oils commercially available marketed by Rhodia, for example oil 70 047 V 500 000;
[0283] - oils from the Mirasil® range sold by the company Rhodia;
[0284] - oils from the 200 range of the Dow Corning company, such as DC200 with a viscosity of 60,000 mmVs; and
[0285] - Viscasil® oils from General Electric and certain oils from the range SF (SF 96, SF 18) of the General Electric company.
[0286] Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known as dimethiconol (CTFA), such as the oils of the 48 range from the company Rhodia.
[0287] Among the silicones with aryl groups, mention may be made of polydiarylsiloxanes, in particular polydiphenylsiloxanes and polyalkylarylsiloxanes such as a phenyl silicone oil.
[0288] The phenylsilicone oil can be chosen from phenylsilicones of the following formula:
[0289] in which
[0290] Ri to Rio, independently of each other, are C1-C30 hydrocarbon radicals, saturated or unsaturated, linear, cyclic or branched, preferably C1-C12 hydrocarbon radicals, and more preferably C1-C6 hydrocarbon radicals, in particular methyl, ethyl, propyl or butyl radicals, and
[0291] m, n, p and q are, independently of each other, integers from 0 to 900 inclusive, preferably from 0 to 500 inclusive, and more preferably from 0 to 100 inclusive,
[0292] provided that the sum n+m+q is different from 0.
[0293] Examples include products sold under the following names:
[0294] - Silbione® oils from the 70 641 range from Rhodia;
[0295] - oils from the Rhodorsil® 70 633 and 763 range from Rhodia;
[0296] - Dow Corning 556 Cosmetic Grade Fluid oil from Dow Corning;
[0297] - silicones from the Bayer PK range, such as the PK20 product;
[0298] - certain oils from the General Electric SF range, such as SF 1023, SF 1154, SF 1250 and SF 1265.
[0299] As phenyl silicone oil, phenyl trimethicone (R1 to R10 are methyl groups; p, qetn = 0; m=l in the above formula) is preferable.
[0300] Organomodified liquid silicones may in particular contain poly-ethyleneoxy and / or polypropyleneoxy groups. Examples include silicone KF-6017 offered by Shin-Etsu, and Silwet® L722 and L77 oils from Union Carbide.
[0301] The hydrocarbon oils can be chosen from:
[0302] - lower C6-Ci6 alkanes, linear or branched, optionally cyclic. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, e.g., isohexadecane, isododecane, and isodecane; and
[0303] - linear or branched hydrocarbons containing more than 16 carbon atoms, such as such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam, and squalane.
[0304] Preferable examples of hydrocarbon oils include, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, petrolatum or petroleum jelly, naphthalenes and the like; hydrogenated polyisobutene, isoeicosane and decene / butene copolymer; and mixtures thereof.
[0305] The term "fatty" in fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols that have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms fall within the scope of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.
[0306] The fatty alcohol may have the structure R-OH in which R is selected from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be selected from C12-C20 alkyl and C12-C20 alkenyl groups. R may or may not be substituted by at least one hydroxyl group.
[0307] Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenic alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonic alcohol, erucic alcohol and mixtures thereof.
[0308] It is preferable that the fatty alcohol is a saturated fatty alcohol.
[0309] Thus, the fatty alcohol can be chosen from linear or branched C6-C3o alcohols, saturated or unsaturated, preferably linear or branched, saturated C6-C30 alcohols, and more preferably linear or branched, saturated C12-C20 alcohols.
[0310] The term "saturated fatty alcohol" herein refers to an alcohol having a long saturated aliphatic carbon chain. It is preferable that the saturated fatty alcohol is selected from all linear or branched C6-C30 saturated fatty alcohols. Among the linear or branched C6-C30 saturated fatty alcohols, linear or branched C12-C20 saturated fatty alcohols may be preferably used. All linear or branched C16-C20 saturated fatty alcohols may be more preferably used. Branched C16-C20 fatty alcohols may be more preferably used.
[0311] Examples of saturated fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenic alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol), as well as behenyl alcohol, may be used as the saturated fatty alcohol.
[0312] According to at least one embodiment, the fatty alcohol used in the composition according to the present invention is preferably chosen from octyldodecanol, hexyldecanol and their mixtures.
[0313] It is preferable that the (b) oil is selected from vegetable oils, synthetic ester oils and mixtures thereof, and preferably from vegetable oils.
[0314] According to the present invention, the (b) oil may be surrounded by a plurality of particles (a) or the (b) oil may be present in the hollow of a capsule formed by the (a) particles. In other words, the (b) oil may be covered by the (a) particles, or a capsule formed by the (a) particles includes the (b) oil in the hollow of the capsule.
[0315] The (b) oil which is surrounded by the (a) particles or present in the hollow of the capsule formed by the (a) particles cannot come into direct contact with a keratinous substance such as the skin. Thus, even if the (b) oil has a sticky or greasy feeling in use, the composition according to the present invention will not give a sticky or greasy feeling in use.
[0316] The amount of the (b) oil(s) in the composition according to the present invention may be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the composition.
[0317] The amount of the (b) oil(s) in the composition according to the present invention may be 45% by weight or less, preferably 40% by weight or less, and more preferably 35% by weight or less, relative to the total weight of the composition.
[0318] The amount of the (b) oil(s) in the composition according to the present invention may be from 1% to 45% by weight, preferably from 5% to 40% by weight, and more preferably from 10% to 35% by weight, relative to the total weight of the composition.
[0319] [Fatty acid]
[0320] The composition according to the present invention comprises (c) at least one fatty acid. If two or more fatty acids are used, they may be the same or different.
[0321] The term “fatty acid” herein refers to a long-chain aliphatic carbon carboxylic acid.
[0322] The (c) fatty acid comprises at least 4 carbon atoms, preferably at least 6 carbon atoms, and more preferably at least 8 carbon atoms. The (c) fatty acid may comprise up to 24 carbon atoms, preferably up to 22 carbon atoms, and more preferably up to 20 carbon atoms. It is preferable that the (c) fatty acid is selected from C6-C24 fatty acids, more preferably from C8-C22 fatty acids, and even more preferably from C10-C20 fatty acids.
[0323] The (c) fatty acid may be chosen from saturated or unsaturated, linear or branched fatty acids. Thus, the (c) fatty acid may be chosen from saturated and unsaturated, linear or branched, C4-C24, preferably C6-C22, more preferably C8-C20 fatty acids.
[0324] As unsaturated, linear or branched fatty acids, monounsaturated, linear or branched fatty acids or polyunsaturated, linear or branched fatty acids may be used. As the unsaturated fraction of unsaturated, linear or branched fatty acids, a carbon-carbon double bond or a carbon-carbon triple bond may be mentioned.
[0325] As saturated fatty acid, mention may be made, for example, of caprylic acid (C8), pelargonic acid (C9), capric acid (Ci0), lauric acid (Ci2), myristic acid (CM), pentadecanoic acid (Ci5), palmitic acid (Ci6), heptadecanoic acid (Ci7), stearic acid (Ci8), isostearic acid (Ci8), nonadecanoic acid (Ci9), arachidic acid (C20), behenic acid (C22) and lignoceric acid (C24).
[0326] As unsaturated fatty acid, mention may be made, for example, of myristoleic acid (Ci4), palmitoleic acid (Ci6), oleic acid (Ci8), linoleic acid (Ci8), linolenic acid (Ci8), elaidic acid (Ci8), arachidonic acid (C20), eicosenoic acid (C20), erucic acid (C22) and nervonic acid (C24).
[0327] It is preferable that the (c) fatty acid is selected from saturated or unsaturated, linear or branched C12-C22 fatty acids, and more preferably from the group consisting of caprylic acid, capric acid, oleic acid, linoleic acid, stearic acid, isostearic acid and mixtures thereof.
[0328] The (c) fatty acid may be in the form of a free acid or in the form of a salt thereof. As the salt of the fatty acid, there may be mentioned an inorganic salt such as an alkali metal salt (a sodium salt, a potassium salt or the like) and an alkaline earth metal salt (a magnesium salt, a calcium salt or the like); and an organic salt such as an ammonium salt (a quaternary ammonium salt or the like) and an amine salt (a triethanolamine salt, a triethylamine salt or the like). A single type of fatty acid salt or a combination of different types of fatty acid salts may be used. Furthermore, a combination of one or more fatty acids in the form of a free acid and one or more fatty acids in the form of a salt may be used, in which one or more types of salts may also be used.
[0329] The amount of the (c) fatty acid(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. It may be even more preferable that the amount of the (c) fatty acid(s) in the composition according to the present invention is 0.5% by weight or more, relative to the total weight of the composition.
[0330] On the other hand, the amount of the (c) fatty acid(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. It may be even more preferable that the amount of the (c) fatty acid(s) in the composition according to the present invention is 3% by weight or less, relative to the total weight of the composition.
[0331] Therefore, the amount of the (c) fatty acid(s) in the composition according to the present invention may range 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. It may be even more preferable that the amount of the (c) fatty acid(s) in the composition according to the present invention is from 0.5% to 3% by weight, relative to the total weight of the composition.
[0332] [Water]
[0333] The composition according to the present invention comprises (d) water.
[0334] The amount of (d) water may be 50% by weight or more, preferably 55% by weight or more, and more preferably 60% by weight or more, relative to the total weight of the composition.
[0335] The amount of (d) water may be 95% by weight or less, preferably 90% by weight or less, and more preferably 85% by weight or less, relative to the total weight of the composition.
[0336] The amount of (d) water may be from 50% to 95% by weight, preferably from 55% to 90% by weight, and more preferably from 60% to 85% by weight, relative to to the total weight of the composition.
[0337] [pH]
[0338] The pH of the composition according to the present invention may be from 3 to 9, preferably from 3.5 to 8.5, and more preferably from 3.5 to 8.
[0339] At a pH ranging from 3 to 9, the (a) particle can be very stable.
[0340] The pH of the composition according to the present invention may be adjusted by adding at least one alkaline agent and / or at least one acid, other than (c) non-polymeric acid having two or more pKa values or salt thereof, to be incorporated into the (a) particle. The pH of the composition according to the present invention may also be adjusted by adding at least one buffering agent.
[0341] (Alkaline agent)
[0342] 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.
[0343] The alkaline agent may be an inorganic alkaline agent. It is preferable 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.
[0344] 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 alkaline agent, sodium hydroxide is preferable.
[0345] 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 derivatives thereof; diamines and derivatives thereof; polyamines and derivatives thereof; basic amino acids and derivatives thereof; oligomers of basic amino acids and derivatives thereof; polymers of basic amino acids and derivatives thereof; urea and derivatives thereof; and guanidine and derivatives thereof.
[0346] 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 NRN R2 Z R4
[0347] wherein R denotes an alkylene such as propylene optionally substituted 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 C1-C4 hydroxyalkyl radical which can be exemplified by 1,3-propanediamine and derivatives thereof. Arginine, urea and monoethanolamine are preferable.
[0348] The alkaline agent(s) may be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, more preferably 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.
[0349] (Acid)
[0350] The composition according to the present invention may comprise at least one acid other than the (d) acid to be incorporated into the (a) particle. 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.
[0351] As the acid, mention may be made of all inorganic or organic acids, preferably inorganic acids, 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. Lactic acid may be preferable.
[0352] The acid(s) may be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, more preferably 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.
[0353] (Buffering agent)
[0354] 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.
[0355] As buffering agent, mention may be made of an acetate buffer (for example, acetic acid + sodium acetate), a phosphate buffer (for example, sodium dihydrogen phosphate + disodium hydrogen phosphate), a citrate buffer (for example, citric acid + sodium citrate), a borate buffer (for example, boric acid + sodium borate), a tartrate buffer (for example, tartaric acid + sodium tartrate dihydrate), a Tris buffer (e.g., tris(hydroxymethyl)aminomethane), a Hepes buffer (4-(2-hydroxyethyl)-l-piperazineethanesulfonic acid).
[0356] [Optional additives]
[0357] The composition according to the present invention may comprise, in addition to the aforementioned components, components typically used in cosmetics, in particular surfactants / emulsifiers, hydrophilic or lipophilic thickeners, derived for example from synthetic polymers other than the cationic and anionic polymers to be used for the (a) particle, from volatile or non-volatile organic solvents, from silicones and silicone derivatives other than the (b) oil, from natural extracts derived from animals or plants, from waxes, and others, in a range which does not alter the effects of the present invention.
[0358] The composition according to the present invention may comprise the above optional additive(s) in an amount of 0.01% to 30% by weight, preferably 0.05% to 20% by weight, and more preferably 0.1% to 10% by weight, relative to the total weight of the composition.
[0359] The composition according to the present invention may include a very limited quantity of surfactant(s) / emulsifier(s) and / or synthetic thickener(s) and / or organic solvent(s) in the interests of respect for the environment.
[0360] The amount of surfactant(s) / emulsifier(s) and / or synthetic thickener(s) and / or organic solvent(s) in the composition according to the present invention may be less than or equal to 1% by weight, preferably less than or equal to 0.1% by weight, and more preferably less than or equal to 0.01% by weight, relative to the total weight of the composition. It is particularly preferable that the composition according to the present invention does not include any surfactant / emulsifier or synthetic thickener or organic solvent.
[0361] [Preparation]
[0362] The composition according to the present invention can be prepared by mixing the essential ingredient(s) as explained above, and the optional ingredient(s), if necessary, as explained above.
[0363] The method and means for mixing the above essential and optional ingredients are not limited. Any conventional method and means can be used for mixing the above essential and optional ingredients to prepare the composition according to the present invention.
[0364] The composition according to the present invention can be prepared by simple or easy mixing with a conventional mixing means such as a stirrer and a homogenizer. In addition, heating may not be necessary. Therefore, the method of preparing the composition according to the present invention can be environmentally friendly.
[0365] [Cosmetic composition]
[0366] The composition according to the present invention may be intended to be used as a cosmetic composition. Thus, the cosmetic composition according to the present invention may be intended to be applied to a keratinous substance. By keratinous substance is meant here a material containing keratin as a main constituent element, and by way of example, it may include the skin, the scalp, the nails, the lips, the hair, and the like. Thus, it is preferable that the cosmetic composition according to the present invention is used for a cosmetic process of the keratinous substance, in particular the skin.
[0367] Thus, the cosmetic composition according to the present invention may be a cosmetic composition for the skin, preferably a skin care composition or a skin makeup composition, and more preferably a skin care composition.
[0368] [Shape]
[0369] In the composition according to the present invention, the (b) oil can form fatty phases, (d) water can form an aqueous phase, and the fatty phases can be dispersed in the aqueous phase. Thus, the aqueous phase can function as a continuous phase, and the fatty phase can function as a dispersed phase.
[0370] Thus, the composition according to the present invention may be in the form of an O / W dispersion such as an O / W emulsion. If the composition according to the present invention is of the O / W type, it may provide a sensation of freshness thanks to (d) the water which constitutes the external phase.
[0371] [Mechanism]
[0372] Figure 1 shows schematic drawings showing the behaviors of the (a) particles around a fatty phase, such as an oil droplet, dispersed in an aqueous phase, and the examples of hydrophobization of the (a) particle, in one embodiment of the present invention.
[0373] A plurality of particles (a) may be present at the interface between the fatty phase and the aqueous phase. Thus, the (a) particles may form an emulsion without the aid of any conventional surfactant or emulsifier. The emulsion formed by the (a) particles may be similar to a so-called Pickering emulsion.
[0374] Alternatively, a plurality of particles (a) may form a capsule having a hollow. The (b) oil may be present in the hollow. In other words, the (b) oil may be incorporated into the capsule. The wall of the capsule may be composed of a continuous layer or film formed from the (a) particles. Without wishing to theorize, it is believed that the (a) particles may rearrange at the interface of the (b) oil and (d) water to spontaneously form a capsule having a hollow to include the (b) oil. For example, a continuous aqueous phase comprising (d) water and dispersed phases comprising the (b) oil in the capsule may form an O / W emulsion which can also be similar to a so-called Pickering emulsion.
[0375] The above means that the (a) particle itself is amphiphilic and insoluble in oil or water.
[0376] The fatty phase comprises the (c) fatty acid. The (c) fatty acid in the fatty phase can hydrophobize the (a) particle in situ. Figure 1 shows a scheme of hydrophobization of the (a) particle by the (c) fatty acid.
[0377] Figure 1A shows a schematic drawing showing the behavior of (a) particles around a fatty phase, such as an oil droplet, dispersed in an aqueous phase, in the case where the fatty phase does not include a (c) fatty acid.
[0378] In Figure 1A, the (a) particles have insufficient hydrophobicity. Therefore, the affinity between the (a) particle and the fatty phase including the (b) oil is limited. Thus, the emulsification of the fatty phase in the aqueous phase is less stable.
[0379] On the other hand, Figure 1B shows a schematic drawing showing the behavior of (a) particles around a fatty phase, such as an oil droplet, dispersed in an aqueous phase, in the case where the fatty phase includes (c) a fatty acid.
[0380] In Figure 1B, the carboxylic group of the (c) fatty acid in the fat phase can ionically interact with the cationic or cationizable group, such as the ammonium group or the amino group, in the cationic polymer of the (a) particle, as shown in Figure 1C. Therefore, the (a) particle is ionically hydrophobic and can have sufficient hydrophobicity. Therefore, the affinity between the (a) particle and the fat phase including the (b) oil is improved. Thus, the emulsification of the fat phase in the aqueous phase is stable.
[0381] The composition according to the present invention can be used to easily prepare a film. The (a) particles can aggregate and integrate into a continuous film.
[0382] Thus, the present invention may also relate to a process for preparing a film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.5 qm, more preferably 1.0 qm or more, and even more preferably 1.5 qm or more, comprising:
[0383] applying to a substrate, preferably a keratinous substance, more preferably the skin, the composition according to the present invention; and
[0384] drying the composition.
[0385] The upper limit of the thickness of the film according to the present invention is not limited. Thus, for example, the thickness of the film according to the present invention may be less than or equal to 1 mm, preferably less than or equal to 500 qm, more preferably less than or equal to 300 qm, and even more preferably less than or equal to 100 qm.
[0386] Since the method of preparing a film according to the present invention includes the steps of applying the composition according to the present invention to a substrate, preferably a keratinous substance, and more preferably the skin, and drying the composition, the method according to the present invention does not require spin coating or spraying, and therefore it is possible to easily prepare even a relatively thick film. Thus, the method for preparing a film according to the present invention can prepare a relatively thick film without any special equipment such as spin coaters and spraying machines.
[0387] Even though the film according to the present invention is relatively thick, it is still thin and may be transparent, and therefore, may not be easy to perceive. Thus, the film according to the present invention can be preferably used as a cosmetic film.
[0388] If the substrate is not a keratinous substance such as skin, the composition according to the present invention may be applied to a substrate made of any material other than keratin. The materials of the non-keratinous substrate are not limited. Two or more materials may be used in combination. Thus, a single type of material or a combination of different types of materials may be used. In any case, it is preferable that the substrate be soft or elastic.
[0389] If the substrate is not a keratinous substance, it is preferable that the substrate is water-soluble, since it is possible to leave the film according to the present invention by washing the substrate with water. Examples of water-soluble materials include poly(meth)acrylic acids, polyethylene glycols, polyacrylamides, polyvinyl alcohol (PVA), starch, cellulose acetates, and the like. PVA is preferable.
[0390] If the non-keratinous substrate is in the form of a sheet, it may have a thickness greater than that of the film according to the present invention, in order to facilitate handling of the film attached to the substrate sheet. The thickness of the non-keratinous substrate sheet is not limited, but may be between 1 μm and 5 mm, preferably between 10 μm and 1 mm, and more preferably between 50 and 500 μm.
[0391] It is more preferable that the film according to the present invention is releasable from the non-keratinous substrate. The mode of release is not limited. Thus, the film according to the present invention can be peeled off from the non-keratinous substrate, or released by dissolving the substrate sheet in a solvent such as water.
[0392] The present invention may also relate to:
[0393] (1) A film, preferably a cosmetic film, optionally with a thickness of preferably greater than 0.5 pm, more preferably 1.0 pm or more, and even more preferably 1.5 pm or more, prepared by a process comprising:
[0394] applying to a substrate, preferably a keratinous substance, and more preferably the skin, the composition according to the present invention; and.
[0395] drying the composition,
[0396] and
[0397] (2) A film, preferably a cosmetic film, optionally with a thickness of preferably greater than 0.5 qm, more preferably 1.0 pm or more, and even more preferably 1.5 pm or more, comprising:
[0398] at least one cationic polymer and at least one anionic polymer,
[0399] at least one non-polymeric acid having two or more pKa values or a salt of this one,
[0400] at least one oil, and
[0401] at least one fatty acid.
[0402] The above explanations regarding cationic and anionic polymers, and non-polymeric acid having two or more pKa values or a salt thereof, as well as the above oil and fatty acid can be applied to those of films (1) and (2) above.
[0403] The film thus obtained above may be self-supporting. The term "self-supporting" herein means that the film may be in the form of a sheet and may be handled as an independent sheet without the aid of a substrate or support. Thus, the term "self-supporting" may have the same meaning as "self-supporting".
[0404] It is preferable that the film according to the present invention is hydrophobic.
[0405] The term "hydrophobic" in this specification means that the solubility of the film in water (preferably with a volume of 1 liter) at a temperature of 20 to 40°C, preferably 25 to 40°C, and more preferably 30 to 40°C is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, based on the total weight of the film. Preferably, the film is not soluble in water.
[0406] If the film according to the present invention is hydrophobic, the film can have water-resistant properties, and therefore, it can remain on a keratinous substance such as skin even if the surface of the keratinous substance is wet due to, for example, sweat and rain. Thus, when the film according to the present invention provides any cosmetic effect, the cosmetic effect can last for a long time.
[0407] On the other hand, the film according to the present invention can be easily removed from a keratinous substance such as skin under alkaline conditions such as a pH of 8 to 12, preferably 9 to 11. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can create such alkaline conditions.
[0408] The film according to the present invention may comprise at least one layer of biocompatible and / or biodegradable polymer. Two or more biocompatible and / or biodegradable polymers biocompatible and / or biodegradable polymers can be used in combination. Thus, a single type of biocompatible and / or biodegradable polymer or a combination of different types of biocompatible and / or biodegradable polymers can be used.
[0409] The term "biocompatible" polymer in this specification means that the polymer does not exhibit excessive interaction between the polymer and cells of the living body, including the skin, and that the polymer is not recognized by the living body as a foreign material.
[0410] The term "biodegradable" polymer in this specification means that the polymer can be degraded or broken down in a living body due to, for example, the metabolism of the living body itself or the metabolism of microorganisms that may be present in the living body. Similarly, the biodegradable polymer can be degraded by hydrolysis.
[0411] If the film according to the present invention includes a biocompatible and / or biodegradable polymer, it is less irritable or non-irritable to the skin, and does not cause a rash. In addition, by using a biocompatible and / or biodegradable polymer, the cosmetic sheet according to the present invention can adhere well to the skin.
[0412] The film according to the present invention can be used for cosmetic treatments of keratinous substances, preferably of the skin, in particular of the face. The film according to the present invention can be of any shape. For example, it can be used as a mask sheet for the entire face, or a patch for a part of the face such as the cheek, the nose, and the eye contour.
[0413] If the film according to the present invention includes at least one hydrophilic or water-soluble UV filter, it can provide UV protection effects derived from the hydrophilic or water-soluble UV filter. Normally, a hydrophilic or water-soluble UV filter can be removed from the surface of a keratinous substrate such as skin by water, such as sweat and rain. However, since the hydrophilic or water-soluble UV filter is included in the film according to the present invention, it is difficult for the hydrophilic or water-soluble UV filter to be removed by water, thereby achieving long-lasting UV protection effects.
[0414] [Cosmetic process and use]
[0415] The present invention also relates to:
[0416] a cosmetic process for a keratinous substance such as skin, comprising: applying to the keratinous substance the composition according to the present invention; and drying the composition to form a cosmetic film on the keratinous substance; or
[0417] 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.
[0418] By cosmetic process is meant here a non-therapeutic cosmetic process for caring for and / or making up the surface of a keratinous substance such as the skin.
[0419] In the above method and use, the above cosmetic film is resistant to water with a pH of 7 or less, and can be removed with water with a pH of more than 7, preferably 8 or more, and more preferably 9 or more.
[0420] In other words, the above 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 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.
[0421] Accordingly, the above cosmetic film can be water-resistant, and thus, it can remain on a keratinous substance such as skin even if the surface of the keratinous substance is wet due to, for example, sweat and rain. On the other hand, the above cosmetic film can be easily removed from a keratinous substance such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can create alkaline conditions.
[0422] If the above cosmetic film includes a UV filter which may be present in the composition according to the present invention, the above cosmetic film can protect a keratinous substance such as skin from UV rays, thereby limiting the darkening of the skin, improving the color and uniformity of the complexion, and / or treating the aging of the skin.
[0423] Furthermore, the above cosmetic film may have cosmetic effects such as capturing sebum, matting the appearance of a keratinous substrate such as skin, absorbing or adsorbing malodors, and / or protecting the keratinous substance from, for example, dirt or pollutants, due to the properties of the polyionic complex particles in the cosmetic film, even if the cosmetic film does not include any cosmetic active ingredient.
[0424] Furthermore, the above-mentioned cosmetic film can immediately change or modify the appearance of the skin by changing the reflection of light on the skin and the like, even if the cosmetic film does not include any cosmetic active ingredient. Therefore, it may be possible for the above cosmetic film to conceal skin defects such as pores or wrinkles. In addition, the above cosmetic film can immediately change or modify the touch feeling of the skin by changing the roughness of the skin surface and the like. Furthermore, the above-mentioned cosmetic film can immediately protect the skin by covering the skin surface and protecting the skin, as a barrier, against environmental aggressions such as pollutants, contaminants and others.
[0425] The above cosmetic effects can be adjusted or controlled by changing the chemical composition, thickness and / or surface roughness of the above cosmetic film.
[0426] If the above cosmetic film includes at least one additional cosmetic active ingredient other than (b) oil, the cosmetic film may have cosmetic effects provided by the additional cosmetic active ingredient(s). For example, if the cosmetic film includes at least one cosmetic active ingredient selected from anti-aging agents, anti-sebum agents, deodorant agents, anti-perspirant agents, whitening agents, and a mixture thereof, the cosmetic film may treat skin aging, absorb sebum on the skin, control odor on the skin, control perspiration on the skin, and / or whiten the skin.
[0427] It is also possible to apply a cosmetic makeup composition to the cosmetic film or sheet according to the present invention after it has been applied to the skin.
[0428] The present invention also relates to a use of (c) at least one fatty acid in a composition, comprising:
[0429] (a) at least one particle, comprising
[0430] at least one cationic polymer,
[0431] at least one anionic polymer, and
[0432] at least one non-polymeric acid having two or more pKa values or a salt thereof;
[0433] (b) at least one oil; and
[0434] (d) water,
[0435] to increase the amount of (b) oil in the composition to be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the composition.
[0436] The above explanations regarding the cationic and anionic polymers as well as the above oil and fatty acid can be applied to those of the above use.
[0437] The above use according to the present invention can improve the stability of the composition even if the composition comprises a relatively large amount of oil, such as 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the composition. Therefore, phase separation of the composition can be prevented for a long time. EXAMPLES
[0438] The present invention will be described in more detail with the aid of examples. However, they should not be construed as limiting the scope of the present invention. Examples 1-5 and comparative example 1
[0439] [Preparations]
[0440] (Example 1)
[0441] Two grams of an aqueous solution (25% by weight) of polyepsilon-lysine were added to water, then 20 g of zea mays (corn) germ oil and 1.7 g of oleic acid were added with stirring. Then, 1 g of sodium hyaluronate was added with stirring. Then, 0.55 g of an aqueous solution (50% by weight) of phytic acid was added with stirring. Thus, a composition comprising polyionic complex gel particles (PGP) was prepared. The preparation was carried out at room temperature without heating.
[0442] The ingredients used to prepare the PGP dispersion according to Example 1 are shown in Table 1. The units of the ingredient amounts shown in Table 1 are all "grams".
[0443] (Examples 2-5)
[0444] The procedures according to Example 1 were repeated provided that the ingredients shown in Table 1 were used to prepare stable PGP dispersions according to Examples 2-5.
[0445] The ingredients used to prepare the PGP dispersion according to Examples 2-5 are shown in Table 1. The units of the ingredient amounts shown in Table 1 are all "grams".
[0446] (Comparative Example 1)
[0447] In Comparative Example 1, the preparation of the composition according to Example 1 was repeated provided that oleic acid was not added.
[0448] The ingredients used to prepare the PGP dispersion according to Comparative Example 1 are shown in Table 1. The units of the ingredient amounts shown in Table 1 are all "grams".
[0449] [Tables 1] Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 1 Comp. Water qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 qsp 100 Sodium Hyaluronate 1 1 1 1 1 1 Polyepsilon-Lysine (25% aqueous solution) 2 2 2 2 2 2 Zea Mays (Corn) Germ Oil 20 20 20 30 30 30 Oleic Acid 1.7 - - 1.7 1.7 - Linoleic Acid - 1.7 - - - - Isostearic Acid - - 1.7 - - - Phytic Acid (50% aqueous solution) 0.55 0.55 0.55 0.55 0.01 0.55 Stability Good Good Good Good Good Poor
[0450] [Evaluations]
[0451] (Microscopic observation)
[0452] The composition according to Example 1 and the composition according to Comparative Example 1 were subjected to microscopic observation. The photomicrographs of the compositions according to Example 1 and Comparative Example 1 are shown in [Fig.2].
[0453] The size of the oil droplets in the composition according to Example 1 was small, and the oil droplets were uniformly dispersed, whereas the size of the oil droplets in the composition according to Comparative Example 1 varies, and the oil droplets were not uniformly dispersed, forming some agglomerates.
[0454] (Stability)
[0455] Each of the compositions according to Examples 1 to 5 and Comparative Example 1 was stored in a transparent container at room temperature for one week. The stability of the compositions was observed visually and evaluated according to the following criteria.
[0456] Good: The uniformity of the composition was maintained.
[0457] Bad: Composition uniformity was not maintained.
[0458] The results are shown in Table 1.
[0459] The compositions according to Examples 1 to 5 were stable to maintain a uniform emulsified appearance, without phase separation, while the composition according to Comparative Example 1 was not stable because phase separation was observed. Example 6 and Comparative Example 2
[0460] [Preparations]
[0461] (Example 6)
[0462] Two grams of chitosan were dissolved in water by adding 1 g of lactic acid to the water, followed by adding 20 g of zea mays (corn) germ oil and 0.5 g of oleic acid with stirring. Then, 0.01 g of sodium hyaluronate was added with stirring. Then, 0.01 g of an aqueous solution (50% by weight) of phytic acid was added with stirring. Thus, a composition comprising polyionic complex gel particles (PGP) was prepared.
[0463] The ingredients used to prepare the PGP dispersion according to Example 6 are shown in Table 2. The units of the ingredient amounts shown in Table 2 are all "grams".
[0464] (Comparative Example 2)
[0465] In Comparative Example 2, the preparation of the composition according to Example 6 was repeated provided that oleic acid was not added.
[0466] The ingredients used to prepare the PGP dispersion according to Comparative Example 2 are shown in Table 2. The units of the ingredient amounts shown in Table 2 are all "grams".
[0467] [Tables2] Ex. 6 Ex. Comp. 2 Water qsp 100 qsp 100 Sodium hyaluronate 0.01 0.01 Chitosan 2 2 Zea Mays (corn) germ oil 20 20 Oleic acid 0.5 - Phytic acid (50% aqueous solution) 0.01 0.01 Lactic acid 1 1 Stability Good Poor
[0468] [Evaluations]
[0469] (Stability)
[0470] The compositions according to Example 6 and Comparative Example 2 were stored separately in transparent containers at room temperature for one week. The stability of the composition was observed visually and evaluated according to the following criteria.
[0471] Good: The uniformity of the composition was maintained.
[0472] Bad: Composition uniformity was not maintained.
[0473] The results are shown in Table 2.
[0474] The composition according to Example 6 was stable to maintain a uniform emulsified appearance, without phase separation, whereas the composition according to Comparative Example 2 was not stable because phase separation was observed.
Claims
Claims
1. A composition, comprising: (a) at least one 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; (b) from 5% to 45% by weight of at least one oil; (c) at least one fatty acid; and (d) water, based on the total weight of the composition.
2. The composition of claim 1, wherein 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 collagen, cationic cellulose polymers, chitosans, and their salts.
3. A composition according to claim 1 or claim 2, wherein the amount of cationic polymer(s) forming the (a) particle in the composition is from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
4. A composition according to any one of claims 1 to 3, wherein the anionic polymer is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers, anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl sulfates), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, polyfumaric acids, (co)polymers of maleic acid, and their salts.
5. A composition according to any one of claims 1 to 4, wherein the non-polymeric acid having two or more pKa values or a salt thereof is an organic acid or a salt thereof, preferably a hydrophilic or water-soluble organic acid or a salt thereof, and more preferably phytic acid or a salt thereof.
6. A composition according to any one of claims 1 to 5, wherein the amount of the non-polymeric acid having two or more pKa values or a salt thereof in the composition is 0.001% to 10% by weight, preferably 0.003% to 5% by weight, and more preferably 0.005% to 1% by weight, based on the total weight of the composition.
7. A composition according to any one of claims 1 to 6, wherein the composition comprises fatty phases comprising (b) oil and (c) fatty acid, and an aqueous phase comprising (d) water, wherein the fatty phases are dispersed in the aqueous phase.
8. A cosmetic process for a keratinous substance such as skin, comprising the following steps: 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.
9. Use of (c) at least one fatty acid in a composition, comprising: (a) at least one 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; (b) at least one oil; and (d) water, to increase the amount of (b) oil in the composition to be from 5% to 45% by weight, based on the total weight of the composition.