Composition containing cationic polymer and anionic polymer
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- LOREAL SA
- Filing Date
- 2023-04-18
- Publication Date
- 2026-04-28
AI Technical Summary
There is a need for transparent or translucent cosmetic compositions that can solubilize skin care active ingredients while incorporating environmentally compatible ingredients.
A composition comprising cationic and anionic polymers, fatty acids, and skin care active ingredients, with specific mass ratios and concentrations, forms nano-sized particles that enhance solubility and transparency, using ionic interactions and hydrophobicization to create a hydrophobic interior for skin care actives.
The composition effectively solubilizes skin care actives, improves penetration, and reduces environmental impact by using renewable and biodegradable materials, while maintaining transparency or translucency.
Abstract
Description
[Technical field]
[0001] The present invention relates to a composition comprising an anionic polymer and a cationic polymer, and a cosmetic method using said composition. [Background technology]
[0002] Environmentally compatible cosmetic formulations, designed and developed with environmental concerns in mind, have become a major goal in aiming to meet global challenges.
[0003] It is therefore essential to propose more sustainable compositions, methods of preparation and ingredients to address these environmental issues.
[0004] In this context, it is important to develop new cosmetic compositions with a better carbon footprint, in particular by promoting the use of renewable raw materials and / or materials with a good naturalness index and / or materials of natural origin, more particularly materials of plant origin, while at the same time reducing the use of compounds of petrochemical origin.
[0005] As is widely known, certain cosmetic and / or dermatological compositions, in particular for the preparation of cosmetics such as milks, creams, tonics, serums or lotions, as well as any other compositions, exist in the form of oil-in-water (O / W) or water-in-oil (W / O) emulsions. In particular, fine emulsions, such as O / W nano- or microemulsions, are particularly attractive in cosmetics due to their transparent or translucent appearance. [Prior art documents] [Patent documents]
[0006] [Patent Document 1] European Patent Application No. 0080976 [Patent Document 2] French Patent No. 2077143 [Patent Document 3] French Patent No. 2393573 [Patent Document 4] French Patent No. 1492597 [Patent Document 5] U.S. Patent No. 4,131,576 [Patent Document 6] U.S. Patent No. 3,589,578 [Patent Document 7] U.S. Patent No. 4,031,307 [Patent Document 8] French Patent No. 2162025 [Patent Document 9] French Patent No. 2280361 [Patent Document 10] French Patent No. 2252840 [Patent Document 11] French Patent No. 2368508 [Patent Document 12] French Patent No. 1,583,363 [Patent Document 13] U.S. Patent No. 3,227,615 [Patent Document 14] U.S. Patent No. 2,961,347 [Patent Document 15] French Patent No. 2080759 [Patent Document 16] French Patent No. 2320330 [Patent Document 17] French Patent No. 2270846 [Patent Document 18] French Patent No. 2316271 [Patent Document 19] French Patent No. 2336434 [Patent Document 20] French Patent No. 2413907 [Patent Document 21] U.S. Patent No. 2,273,780 [Patent Document 22] U.S. Patent No. 2,375,853 [Patent Document 23] U.S. Patent No. 2,388,614 [Patent Document 24] U.S. Patent No. 2,454,547 [Patent Document 25] U.S. Patent No. 3,206,462 [Patent Document 26] U.S. Patent No. 2,261,002 [Patent Document 27] U.S. Patent No. 2,271,378 [Patent Document 28] U.S. Patent No. 3,874,870 [Patent Document 29] U.S. Patent No. 4,001,432 [Patent Document 30] U.S. Patent No. 3,929,990 [Patent Document 31] U.S. Patent No. 3,966,904 [Patent Document 32] U.S. Patent No. 4,005,193 [Patent Document 33] U.S. Patent No. 4,025,617 [Patent Document 34] U.S. Patent No. 4,025,627 [Patent Document 35] U.S. Patent No. 4,025,653 [Patent Document 36] U.S. Patent No. 4,026,945 [Patent Document 37] U.S. Patent No. 4,027,020 [Patent Document 38] European Patent Application No. 0122324 [Patent Document 39] WO03 / 068824 [Patent Document 40] EP-A-0750899 [Patent Document 41] EP-A-1069172 [Patent Document 42] EP-A-0173109 [Patent Document 43] DE 4424530 [Patent Document 44] DE 4424533 [Patent Document 45] DE 4402929
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[0007] [Non-Patent Document 1] Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10-3694~3704 [Non-Patent Document 2] "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699-715 [Non-Patent Document 3] D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) pp. 2101-2127 [Non-Patent Document 4] Meylan and Howard, Atom / Fragment contribution method for estimating octanol-water partition coefficients, J. Pharm. Sci., 84: 83-92, 1995. [Non-Patent Document 5] Exploring QSAR: hydrophobic, electronic and steric constants (ACS professional reference book, 1995) [Non-Patent Document 6] http: / / esc.syrres.com / interkow / kowdemo.htm [Non-Patent Document 7] Downing, Journal of Lipid Research, Volume 35, pp. 2060-2068, 1994. Summary of the Invention [Problem to be solved by the invention]
[0008] There is a need for clear or translucent compositions that can solubilize skin care actives therein while including ingredients that are environmentally compatible.
[0009] Therefore, it is a first object of the present invention to provide a composition that can solubilize skin care actives in the composition, which may be transparent or translucent.
[0010] Additionally, a second object of the present invention is to provide a composition that may include at least one environmentally compatible ingredient. [Means for solving the problem]
[0011] The above object of the present invention is to (a) at least one cationic polymer; (b) at least one anionic polymer, and (c) at least one fatty acid This can be achieved by a composition, preferably a cosmetic composition, more preferably a skin cosmetic composition, comprising:
[0012] Compositions according to the present invention may further comprise (d) at least one skin care active, preferably having a logP of -1 or greater, more preferably 1 or greater, and even more preferably 2 or greater.
[0013] The composition according to the invention can meet the following requirements: the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, based on the total weight of the composition; the weight ratio of the amount of (a) cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.7, preferably less than 0.5, more preferably less than 0.3; the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.9, preferably less than 0.8, more preferably less than 0.7; and The weight ratio of the amount of (d) skin care active / the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.16, preferably less than 0.12, and more preferably less than 0.08.
[0014] The (a) cationic polymer may be hydrophobized with (c) a fatty acid.
[0015] (a) The cationic polymer may be selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine and chitosan, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof.
[0016] The molecular weight of the (a) cationic polymer may be less than 20,000, preferably less than 15,000, and more preferably less than 10,000.
[0017] The amount of the (a) cationic polymer in the composition according to the present invention may be 0.001% by mass to 15% by mass, preferably 0.005% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, relative to the total mass of the composition.
[0018] (b) The anionic polymer may be selected from the group consisting of polysaccharides such as carrageenan, alginic acid, hyaluronic acid, and cellulose polymers, anionic (co)polyamino acids such as (co)polyglutamic acid, (co)poly(meth)acrylic acid, (co)polyamic acid, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acid, polyfumaric acid, maleic acid (co)polymers, and salts thereof.
[0019] The amount of the anionic polymer (b) in the composition according to the present invention may be from 0.001% to 15% by mass, preferably from 0.005% to 10% by mass, and more preferably from 0.01% to 5% by mass, based on the total mass of the composition.
[0020] (c) Fatty acids are C4 to C 26 , preferably C6 to C 24 , more preferably C8 to C 22 They may be chosen from saturated and unsaturated straight-chain or branched fatty acids.
[0021] The amount of (c) fatty acid in the composition according to the present invention may be 0.001% by mass to 10% by mass, preferably 0.005% by mass to 5% by mass, and more preferably 0.01% by mass to 1% by mass, relative to the total mass of the composition.
[0022] The amount of the skin care active ingredient (d) in the composition according to the present invention may be from 0.001% to 10% by mass, preferably from 0.003% to 5% by mass, and more preferably from 0.005% to 1% by mass, relative to the total mass of the composition.
[0023] Preferably, the composition according to the present invention comprises (e) water.
[0024] The amount of (e) water in the composition according to the present invention may be 50% by mass to 99% by mass, preferably 55% by mass to 98% by mass, and more preferably 60% by mass to 97% by mass, based on the total mass of the composition.
[0025] The composition according to the invention may comprise at least one particle having a particle size of less than 1,000 nm, preferably less than 500 nm, more preferably less than 300 nm.
[0026] The composition according to the invention may not comprise a surfactant having at least one polyoxyethylene unit or it comprises a surfactant having at least one polyoxyethylene unit in an amount of less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, relative to the total weight of the composition.
[0027] In a preferred embodiment, the composition according to the invention comprises (a) at least one cationic polymer selected from chitosan; (b) at least one anionic polymer selected from polysaccharides such as carrageenan; (c) at least one fatty acid; (d) at least one skin care active selected from the group consisting of 2-N-oleoylaminooctadecane-1,3-diol, tocopherol, retinol, stearyl glycyrrhetinate, ascorbic acid, ascorbyl tetraisopalmitate, 2-N-stearoylaminooctadecane-1,3,4-triol, capryloyl salicylic acid, and mixtures thereof; and (e) water It may include, the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, based on the total weight of the composition; the weight ratio of the amount of (a) cationic polymer / the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.7, preferably less than 0.5, and more preferably less than 0.3; the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.9, preferably less than 0.8, more preferably less than 0.7; and The weight ratio of the amount of (d) skin care active / the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.16, preferably less than 0.12, and more preferably less than 0.08.
[0028] The present invention also provides a cosmetic method for keratinous materials, such as the skin, comprising the steps of: applying a composition according to the invention to a keratinous material; drying the composition to form a cosmetic film on the keratinous material; The present invention also relates to a method, comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] After extensive investigation, the inventors have discovered that it is possible to provide a composition in which skin care actives can be solubilized, which may be transparent or translucent, and which may include at least one environmentally compatible ingredient.
[0030] Therefore, the composition according to the invention (a) at least one cationic polymer; (b) at least one anionic polymer, and (c) at least one fatty acid Includes.
[0031] The composition according to the present invention is capable of solubilizing (d) at least one skin care active in the composition and may be transparent or translucent.
[0032] The (a) cationic polymer can form a complex with the (c) fatty acid through ionic interactions between the amino groups of the (a) cationic polymer and the carboxy groups of the (c) fatty acid. Thus, the (a) cationic polymer can be hydrophobized by the (c) fatty acid. The above complex, when present, can enhance the solubility of the (d) skin care active, especially lipophilic skin care active.
[0033] (b) Anionic polymers may also be included in the complex.
[0034] The components (a) to (c) in the composition according to the present invention can form particles. The particles may be hydrophobized with (c) a fatty acid.
[0035] Thus, the particles may be formed by (a) a cationic polymer, (b) an anionic polymer, and (c) a fatty acid, and may have a hydrophobized interior space in which (d) a skin care active may be included.
[0036] The size of the above particles may be small, at the nano level, i.e. less than 1,000 nm, so that the composition according to the invention may be transparent or translucent.
[0037] Additionally, the small size of the particles can improve penetration of the (d) skin care actives, if present, in the particles into the skin, particularly into the stratum corneum.
[0038] In addition, components (a)-(c) may originate from renewable and / or biodegradable materials, such as plants. Therefore, by selecting components (a)-(c) from such renewable materials, they may be environmentally compatible. Thus, the composition according to the present invention may include environmentally compatible components.
[0039] If the composition according to the present invention does not contain a surfactant having at least one polyoxyethylene unit or contains only a small amount of such a surfactant, the composition according to the present invention may be less irritating, and since most of such surfactants are not biodegradable, the composition according to the present invention may be more environmentally friendly.
[0040] The present invention will now be described in more detail.
[0041] [Composition] (cationic polymer) The composition according to the present invention comprises (a) at least one cationic polymer. A single type of cationic polymer may be used, but two or more different types of cationic polymers may also be used in combination.
[0042] The cationic polymer has a positive charge density. The charge density of the (a) cationic polymer can be from 0.01 meq / g to 20 meq / g, preferably from 0.05 meq / g to 15 meq / g, and more preferably from 0.1 meq / g to 10 meq / g.
[0043] It may be preferred that the molecular weight of the (a) cationic polymer is 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
[0044] Unless otherwise defined in the description, "molecular weight" means weight average molecular weight.
[0045] (a) The cationic polymer may have at least one positively charged and / or positively charged moiety selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. The term (primary) "amino group" as used herein means an -NH2 group.
[0046] (a) The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, for example terpolymers resulting from three types of monomers.
[0047] (a) The cationic polymer may be selected from natural and synthetic cationic polymers, preferably natural cationic polymers. Non-limiting examples of cationic polymers are:
[0048] (1) Derived from esters and amides of acrylic or methacrylic acid, having the following formula:
[0049] [ka]
[0050] (In the formula, R1 and R2 may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups; R3, which may be the same or different, is selected from hydrogen and CH3; the symbols A may be the same or different and are selected from linear or branched alkyl groups containing 1 to 6 carbon atoms, for example 2 to 3 carbon atoms, and hydroxyalkyl groups containing 1 to 4 carbon atoms, R4, R5 and R6 may be the same or different and are selected from alkyl groups containing 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment alkyl groups containing 1 to 6 carbon atoms; X is an anion derived from an inorganic or organic acid, such as methosulfate, or an anion derived from a halide, such as chloride and bromide. Homopolymers and copolymers comprising at least one unit selected from the units:
[0051] The copolymers of family (1) may also contain at least one unit derived from a comonomer, which may be selected from acrylamide, methacrylamide, diacetone acrylamide, acrylamides and methacrylamides whose nitrogen atoms are substituted with (C1-C4) lower alkyl groups, groups derived from acrylic or methacrylic acid and their esters, vinyl lactams such as vinyl pyrrolidone and vinyl caprolactam, and vinyl esters.
[0052] Examples of family (1) copolymers include, but are not limited to, the following: Copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halides; Copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, such as those described in European Patent Application No. 0080976; Copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, such as those described in French Patents Nos. 2 077 143 and 2 393 573; Dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymer, Vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymer, quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymer, and Crosslinked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salt polymers, for example those obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or by copolymerization of acrylamide and dimethylaminoethyl methacrylate quaternized with methyl chloride, followed by crosslinking with a compound containing olefinic unsaturation, for example methylenebisacrylamide.
[0053] (2) Cationic cellulose polymers, such as cellulose ether derivatives containing one or more quaternary ammonium groups, as described in French Patent No. 1 492 597, such as the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation, which are also defined in the CTFA dictionary as quaternary ammonium of hydroxyethylcellulose reacted with epoxides substituted with trimethylammonium groups.
[0054] It is preferred that the cationic cellulose polymer has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group, more preferably a quaternary trimethylammonium group.
[0055] The quaternary ammonium group has the following chemical formula (I):
[0056] [ka]
[0057] (In the formula, Each of R1 and R2 is C 1~3 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; R3 is C 1~24 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; X - represents an anion, preferably a halide ion, more preferably a chloride ion, n represents an integer of 0 to 30, preferably 0 to 10, and more preferably 0; R4 is C 1~4 represents an alkylene group, preferably an ethylene group or a propylene group) The quaternary ammonium group may be present in a group containing a quaternary ammonium group, which may be represented by the formula:
[0058] The left-most ether linkage (-O-) in the above chemical formula (I) can be attached to a sugar ring of a polysaccharide.
[0059] The quaternary ammonium group-containing group is -O-CH2-CH(OH)-CH2-N + It is preferably (CH3)3.
[0060] (3) Cationic cellulose polymers, such as cellulose copolymers and cellulose derivatives grafted with water-soluble quaternary ammonium monomers, such as those described in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses grafted with salts selected from methacryloylethyltrimethylammonium salts, methacrylamidepropyltrimethylammonium salts, and dimethyldiallylammonium salts, such as hydroxymethyl-, hydroxyethyl-, and hydroxypropylcellulose.
[0061] Commercially available products corresponding to these polymers include, for example, the products sold under the names "Celquat® L 200" and "Celquat® H 100" by National Starch.
[0062] (4) Non-cellulosic cationic polysaccharides such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid and dextran hydroxypropyltrimonium chloride, as described in U.S. Patents 3,589,578 and 4,031,307. Guar gum modified with salts such as 2,3-epoxypropyltrimethylammonium chloride (guar hydroxypropyltrimonium chloride) can also be used.
[0063] Such products are, for example, sold by the company MEYHALL under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162.
[0064] (5) Polymers containing piperazinyl units and divalent alkylene or hydroxyalkylene groups, optionally containing linear or branched chains, optionally interrupted by at least one element selected from oxygen, sulfur, nitrogen, aromatic rings and heterocycles, and also the oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French Patents Nos. 2 162 025 and 2 280 361.
[0065] (6) Water-soluble polyaminoamides, for example prepared by polycondensation of acidic compounds with polyamines, which may be crosslinked with elements selected from epihalohydrins, diepoxides, dianhydrides, unsaturated dianhydrides, bisunsaturated derivatives, bishalohydrins, bisazetidiniums, bishaloacyldiamines, bisalkylhalides, oligomers obtained by reaction of bifunctional compounds reactive with elements selected from bishalohydrins, bisazetidiniums, bishaloacyldiamines, bisalkylhalides, epihalohydrins, diepoxides and bisunsaturated derivatives, the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide, these polyaminoamides being optionally alkylated or, if they contain at least one tertiary amine function, quaternized. Such polymers are described, for example, in French Patents Nos. 2252840 and 2368508.
[0066] (7) Polyaminoamide derivatives obtained by condensation of polyalkylenepolyamines with polycarboxylic acids followed by alkylation with bifunctional agents, such as adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers, in which the alkyl groups contain 1 to 4 carbon atoms, for example methyl, ethyl or propyl, and the alkylene groups contain 1 to 4 carbon atoms, for example ethylene. Such polymers are described, for example, in French Patent No. 1,583,363. In at least one embodiment, these derivatives may be selected from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.
[0067] (8) Polymers obtained by reacting polyalkylenepolyamines containing two primary amine groups and at least one secondary amine group with dicarboxylic acids selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of polyalkylenepolyamine to dicarboxylic acid may range from 0.8:1 to 1.4:1, and the polyaminoamides obtained therefrom are reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups of polyaminoamide ranging from 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Pat. Nos. 3,227,615 and 2,961,347.
[0068] (9) Cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallyl-ammonium, for example those having, as main chain building blocks, the formulae (Ia) and (Ib):
[0069] [ka]
[0070] [In the formula, k and t may be the same or different and are equal to 0 or 1, the sum k+t being equal to 1; R 12 is selected from hydrogen and a methyl group; R 10 and R 11 may be the same or different and are selected from alkyl groups containing 1 to 6 carbon atoms, hydroxyalkyl groups, the alkyl group containing, for example, 1 to 5 carbon atoms, and lower (C1 to C4) amidoalkyl groups, or R 10 and R 11 may, together with the nitrogen atom to which they are attached, form a heterocyclic group, such as piperidinyl and morpholinyl; Y' is an anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are described, for example, in French Patent No. 2 080 759 and its addition No. 2 190 406.
[0071] In one embodiment, R 10 and R 11 may be the same or different and are selected from alkyl groups containing 1 to 4 carbon atoms.
[0072] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chlorides, such as the dimethyldiallylammonium chloride homopolymer sold under the name "MERQUAT® 100" by CALGON (and its lower weight average molecular weight homologues), and the copolymer of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".
[0073] (10) Formula (II):
[0074] [ka]
[0075] [In the formula, R 13 , R 14 , R 15 and R 16 are the same or different and are selected from aliphatic, alicyclic and arylaliphatic groups containing 1 to 20 carbon atoms, and lower hydroxyalkyl aliphatic groups; or R 13 , R 14 , R 15 and R 16may be taken together with the nitrogen atom to which they are attached or separately form a heterocycle which optionally contains a second heteroatom other than nitrogen, or R 13 , R 14 , R 15 and R 16 may be the same or different, and may be a nitrile group, an ester group, an acyl group, an amide group, -CO-OR 17 -E group and -CO-NH-R 17 -E group (in the formula, R 17 is an alkylene group, and E is a quaternary ammonium group); A1 and B1 may be identical or different and are selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked or inserted in the main chain, at least one element selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups and ester groups; X - is an anion derived from an inorganic or organic acid, A1, R 13 and R 15 may form a piperazine ring together with the two nitrogen atoms to which they are attached; When A1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B1 is -(CH2) n -CO-E'-OC-(CH2) n - wherein E′ is a) a glycol residue of the formula -OZO-, where Z is selected from linear or branched hydrocarbon-based groups and groups of the formula: -(CH2-CH2-O) x -CH2-CH2- -[CH2-CH(CH3)-O] y -CH2-CH(CH3)- where x and y may be the same or different and are selected from integers ranging from 1 to 4 representing a unique defined degree of polymerization, and numbers ranging from 1 to 4 representing an average degree of polymerization, b) bis-secondary diamine residues, such as piperazine derivatives; c) bis-primary diamine residues of the formula -NH-Y-NH-, where Y is selected from linear or branched hydrocarbon-based radicals and the divalent radical -CH-CH-SS-CH-CH-, and d) a ureylene group of the formula -NH-CO-NH- selected from Select from A quaternary diammonium polymer comprising at least one repeat unit of:
[0076] In at least one embodiment, X - is an anion, for example chloride or bromide.
[0077] Polymers of this type are described, for example, in French Patents Nos. 2320330, 2270846, 2316271, 2336434 and 2413907, and in U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,000, and 2,372,411. 2, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945, and 4,027,020.
[0078] Non-limiting examples of such polymers include those of formula (III):
[0079] [ka]
[0080] (In the formula, R13 , R 14 , R 15 and R 16 are the same or different and are selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms, n and p are the same or different and are integers ranging from 2 to 20, and X - is an anion derived from an inorganic or organic acid. Examples of the repeating unit include those containing at least one repeating unit of the formula:
[0081] (11) Formula (IV):
[0082] [ka]
[0083] [In the formula, R 18 , R 19 , R 20 and R 21 may be the same or different and are hydrogen, methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl, -CH2CH2(OCH2CH2) p OH group (wherein p is selected from an integer ranging from 0 to 6), provided that R 18 , R 19 , R 20 and R 21 is not hydrogen at the same time, r and s may be the same or different and are selected from integers ranging from 1 to 6; q is selected from an integer ranging from 0 to 34; X - is an anion, for example a halide ion, A is selected from dihalides and -CH2-CH2-O-CH2-CH2- groups. A polyquaternary ammonium polymer comprising units of
[0084] Such compounds are described, for example, in European Patent Application No. 0122324.
[0085] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole. 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 units and vinylpyridinium units, condensates of polyamines with epichlorohydrin, quaternary polyureylenes, and chitin derivatives.
[0086] According to one embodiment of the present invention, the (a) cationic polymer is selected from cellulose ether derivatives containing quaternary ammonium groups, such as the product sold under the name "JR 400" by UNION CARBIDE CORPORATION, cationic cyclopolymers, such as the homopolymers and copolymers of dimethyldiallylammonium chloride sold under the names MERQUAT® 100, MERQUAT® 550 and MERQUAT® S by CALGON, guar gum modified with 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0087] (13) Polyamines As (a) cationic polymer it is also possible to use (co)polyamines, which may be homopolymers or copolymers, having a plurality of amino groups. The amino groups may be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone of the (co)polyamine or, if present, in pendant groups.
[0088] Examples of (co)polyamines include chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate, (co)polyvinylpyridine such as (co)poly-1-methyl-2-vinylpyridine, (co)polyimines such as (co)polyethylenimine, (co)polypyridines such as (co)poly(quaternary pyridine), (co)polybiguanides such as (co)polyaminopropyl biguanide, (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinyl acetal, and salts thereof.
[0089] As the (co)polyamine, it may be preferred to use (co)polylysine. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine can be ε-poly-L-lysine, which is typically used as a natural preservative in food. Polylysine is a polyelectrolyte that is soluble in polar solvents, such as water, propylene glycol and glycerol. Polylysine is commercially available in various forms, such as poly-D-lysine and poly-L-lysine. Poly-L-lysine is preferred. Polylysine can be in the form of a salt and / or a solution.
[0090] (14) Cationic polyamino acids (a) As cationic polymer it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers having multiple amino and carboxyl groups. The amino groups may be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone of the cationic polyamino acid or in pendant groups, if present. The carboxyl groups may be present in pendant groups, if present, of the cationic polyamino acid.
[0091] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, steardimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed soy protein, and the like.
[0092] The following description relates to preferred embodiments of the cationic polymer.
[0093] The (a) cationic polymer is preferably selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine and chitosan, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof.
[0094] More preferably, the (a) cationic polymer is selected from chitosan.
[0095] It is preferred that the molecular weight (Da) of the chitosan is less than 20,000, more preferably less than 15,000, and even more preferably less than 10,000. In other words, the (a) cationic polymer may be a low molecular weight chitosan.
[0096] The molecular weight (Da) of chitosan may be greater than 1,000, preferably greater than 1,500, more preferably greater than 2,000.
[0097] Therefore, the molecular weight (Da) of chitosan may be greater than 1,000 and less than 20,000, preferably greater than 1,500 and less than 15,000, more preferably greater than 2,000 and less than 10,000.
[0098] Unless otherwise defined in the description, "molecular weight" means weight average molecular weight. Molecular weight can be measured or determined, for example, by gel permeation chromatography according to ASTM D5296-19.
[0099] Chitosan is not commonly found in nature: it has only been reported in the exoskeletons of certain insects, such as termite queens, and in the cell walls of a certain class of fungi, the Zygomycetes.
[0100] Chitosan can be obtained by deacetylation of chitin, a polysaccharide composed of several N-acetyl-D-glucosamine units linked together by β-type bonds (1,4).
[0101] The idealized chemical structure of chitosan is a sequence of β-D-glucosamine monomers linked by glycosidic bonds (1→4).
[0102] "Chitosan" according to the present invention means any copolymer formed from the building blocks N-acetyl-D-glucosamine and D-glucosamine, the degree of acetylation of which is less than 90%, preferably less than 80%, preferably less than 70%, preferably less than 60%, preferably less than 50%. Chitosan consists of glucosamine sugar units (deacetylated units) and N-acetyl-D-glucosamine units (acetylated units) linked together by β-type bonds (1,4), and is a polymer of the poly(N-acetyl-D-glucosamine)-poly(D-glucosamine) type.
[0103] More preferably, the degree of acetylation of chitosan is not more than 40%, preferably not more than 35%, preferably not more than 25%, preferably not more than 15%, preferably not more than 10%.
[0104] The degree of acetylation is the percentage of acetylated units relative to the total number of units and can be determined by Fourier transform infrared spectroscopy (FT-IR) or by titration with a strong base.
[0105] The chitosan of the present invention is preferably a polysaccharide prepared from fungal origin, in particular, it is extracted and purified from safe and abundant food or biotechnological fungal sources, such as mushroom (Agaricus bisporus) or Aspergillus niger.
[0106] The chitosan of the present invention is preferably derived from the mycelium of a fungus of the Ascomycota type, in particular Aspergillus niger and / or a fungus of the Basidiomycota type, in particular Lentinula edodes (shiitake mushroom) and / or Agaricus bisporus. Preferably, the fungus is Aspergillus niger.
[0107] The chitosan may be of genetically modified organism (GMO) origin, but is preferably of non-GMO origin.
[0108] The chitosan according to the invention is natural, i.e. unmodified, in particular it does not contain any chemical modification.
[0109] One method for preparing chitosan is the method described in WO03 / 068824.
[0110] Preferably, the chitosan used in the present invention is in the form of a powder. It is commercially available from Glentham Life Sciences under the name GU3511.
[0111] The amount of (a) cationic polymer in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, based on the total weight of the composition.
[0112] The amount of (a) cationic polymer in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition.
[0113] The amount of the (a) cationic polymer in the composition according to the present invention may be 0.001% by mass to 15% by mass, preferably 0.005% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, relative to the total mass of the composition.
[0114] (anionic polymer) The composition according to the present invention comprises (b) at least one anionic polymer. A single type of anionic polymer may be used, but two or more different types of anionic polymers may also be used in combination.
[0115] The anionic polymer has a negative charge density. When the (b) anionic polymer is a synthetic anionic polymer, the charge density of the (b) anionic polymer may be 0.1 meq / g to 20 meq / g, preferably 1 meq / g to 15 meq / g, and more preferably 4 meq / g to 10 meq / g, and when the (b) anionic polymer is a natural anionic polymer, the average degree of substitution of the (b) anionic polymer may be 0.1 to 3.0, preferably 0.2 to 2.7, and more preferably 0.3 to 2.5.
[0116] In one embodiment, the charge density of (b) the anionic polymer may be 2.04 mmol / g or more, preferably 3.00 mmol / g or more, and more preferably 4.00 mmol / g or more.
[0117] (b) It may be preferred 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.
[0118] Unless otherwise defined in the description, "molecular weight" may mean weight average molecular weight.
[0119] (b) The anionic polymer may have at least one negative charge and / or a negatively charged moiety selected from the group consisting of sulfate groups, sulfate groups, sulfonic acid groups, sulfonate groups, phosphoric acid groups, phosphate groups, phosphonic acid groups, phosphonate groups, carboxylic acid groups, and carboxylate groups.
[0120] (b) The anionic polymer may be a homopolymer or a copolymer, the term "copolymer" being understood to mean both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.
[0121] (b) The anionic polymer may be selected from natural and synthetic anionic polymers, preferably natural anionic polymers.
[0122] (b) The anionic polymer may comprise at least one hydrophobic chain.
[0123] The (b) anionic polymer, which may comprise at least one hydrophobic chain, can be obtained by copolymerizing a monomer (a) selected from a carboxylic acid containing α,β-ethylenic unsaturation (monomer a′) and 2-acrylamido-2-methylpropanesulfonic acid (monomer a″) with a non-surface-active monomer containing ethylenic unsaturation other than (a) (b) and / or a monomer (c) containing ethylenic unsaturation resulting from reacting an acrylic monomer containing α,β-monoethylenic unsaturation or an isocyanate monomer containing monoethylenic unsaturation with a monovalent nonionic amphiphilic component or a primary or secondary fatty amine.
[0124] Thus, the (b) anionic polymer having at least one hydrophobic chain can be obtained by two synthetic routes, namely: - copolymerization of the monomers (a') and (c), or (a'), (b) and (c), or (a''), (c), or (a''), (b) and (c), or modification (e.g. esterification or amidation) of monomer (a'), or of copolymers formed from monomers (a') and (b), or (a'') and (b), with monovalent non-ionic amphiphilic compounds or with primary or secondary fatty amines.
[0125] As 2-acrylamido-2-methylpropanesulfonate copolymers, mention may be made in particular of those disclosed in the article "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10, pp. 3694 to 3704" and in applications EP-A-0750899 and EP-A-1069172.
[0126] The carboxylic acid containing α,β-monoethylenic unsaturation constituting monomer (a′) can be chosen from a large number of acids, in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid, and is preferably acrylic acid or methacrylic acid.
[0127] The copolymer may also comprise a monomer (b) containing monoethylenic unsaturation that does not have surfactant properties. Preferred monomers are those which, when homopolymerized, result in a water-insoluble polymer. These can be selected, for example, from acrylic acid and alkyl methacrylates (C1-C4), such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. Particularly preferred monomers are methyl acrylate and ethyl acrylate. Other monomers which may be used are, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile and vinylidene chloride. Non-reactive monomers are preferred, these monomers being those in which the single ethylenic group is the only group which is reactive under the polymerization conditions. However, monomers containing groups which react under the action of heat, such as hydroxyethyl acrylate, can optionally be used.
[0128] Monomer (c) is obtained by reacting an acrylic monomer containing α,β-monoethylenic unsaturation, such as (a), or an isocyanate monomer containing monoethylenic unsaturation, with a monovalent nonionic amphiphilic compound or a primary or secondary fatty amine.
[0129] The monovalent nonionic amphiphilic compounds or primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. The monovalent nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds with alkylene oxides forming the hydrophilic portion of the molecule. The hydrophobic compounds are generally composed of aliphatic alcohols or alkylphenols, in which the carbonaceous chain containing at least 6 carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.
[0130] Preferred monovalent nonionic amphiphilic compounds have the following formula (V): R-(OCH2CHR') m -(OCH2CH2) n -OH (V) wherein R is selected from alkyl or alkylene groups containing 6 to 30 carbon atoms, and alkylaryl groups having an alkyl group containing 8 to 30 carbon atoms; R' is selected from alkyl groups containing 1 to 4 carbon atoms; n is an average number ranging from about 1 to 150; and m is an average number ranging from about 0 to 50, with the proviso that n is at least as large as m. It is a compound having the formula:
[0131] Preferably, in the compound of formula (V), the R group is an alkyl group containing 12 to 26 carbon atoms and the alkyl group is a C8 to C 13 wherein R′ is a methyl group, m=0, and n=1-25.
[0132] Preferred primary and secondary fatty amines are composed of one or two alkyl chains containing from 6 to 30 carbon atoms.
[0133] The monomers used to form the nonionic urethane monomer (c) can be selected from a wide variety of compounds. Any compound containing copolymerizable unsaturation, such as acrylic, methacrylic or allylic unsaturation, may be used. Monomer (c) can be obtained in particular from isocyanates containing monoethylenic unsaturation, such as in particular α,α-dimethyl-m-isopropenyl benzyl isocyanate.
[0134] The monomers (c) are in particular oxyethylenated (1 to 50 EO) C6-C 30 Acrylates, methacrylates or itaconates of fatty alcohols, such as steareth-20 methacrylate, oxyethylenated (25EO) behenyl methacrylate, oxyethylenated (20EO) monocetyl itaconate, oxyethylenated (20EO) monostearyl itaconate or polyoxyethylenated (25EO) C 12 ~C 24 From alcohol modified acrylates and oxyethylenated (1 to 50 EO) C6 to C 30It may be selected from the dimethyl-m-isopropenyl benzyl isocyanates of aliphatic alcohols, such as in particular the dimethyl-m-isopropenyl benzyl isocyanate of oxyethylenated behenyl alcohol.
[0135] According to a particular embodiment of the present invention, the (b) anionic polymer is selected from an acrylic terpolymer obtained from (a) a carboxylic acid containing α,β-ethylenic unsaturation, (b) a non-surface active monomer containing ethylenic unsaturation other than (a), and (c) a nonionic urethane monomer which is the reaction product of a monovalent nonionic amphiphilic compound with an isocyanate containing monoethylenic unsaturation.
[0136] Examples of anionic polymers comprising at least one hydrophobic chain include, in particular, acrylic acid / ethyl acrylate / alkyl acrylate terpolymers, such as the product sold as a 30% aqueous dispersion under the name Acusol 823 by Rohm & Haas; acrylates / steareth-20 methacrylate copolymers, such as the product sold as a 30% aqueous dispersion under the name Aculyn 22 by Rohm & Haas; (meth)acrylic acid / ethyl acrylate / oxyethylated (25EO) behenyl methacrylate terpolymers, such as the product sold as an aqueous emulsion under the name Aculyn 28 by Rohm & Haas; acrylic acid / oxyethylated (20EO) monocetyl itaconate copolymers, such as the product sold as a 30% aqueous dispersion under the name Structure 3001 by National Starch; acrylic acid / oxyethylated (20EO) monostearyl itaconate copolymers, such as the product sold as a 30% aqueous dispersion under the name Structure 3001 by National Starch. Product sold in 2001 as a 30% aqueous dispersion; Acrylate / Polyoxyethylenated (25EO)C 12 ~C 24Mention may be made of copolymers of acrylates modified with alcohols, such as the 30-32% copolymer latex sold under the name Synthalen W2000 by the company 3V SA; or the terpolymers of methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol with dimethyl-meta-isopropenylbenzyl isocyanate, such as the product disclosed in document EP-A-0173109 as a 24% aqueous dispersion containing 40 ethylene oxide groups.
[0137] (b) The anionic polymer may also be polyester-5, for example the product sold under the name Eastman AQ™ 55S Polymer by EASTMAN CHEMICAL, having the following chemical formula:
[0138] [ka]
[0139] (In the formula, A: Dicarboxylic acid moiety G: glycol moiety SO3 - Na + : Sodium sulfo group OH: hydroxyl group)
[0140] (b) It may be preferred that the anionic polymer is selected from the group consisting of polysaccharides such as carrageenan, alginic acid, hyaluronic acid, and cellulose polymers (e.g. carboxymethylcellulose and carrageenan), anionic (co)polyamino acids such as (co)polyglutamic acid, (co)poly(meth)acrylic acid, (co)polyamic acid, (co)polystyrenesulfonate, (co)poly(vinylsulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acid, (co)polyfumaric acid, maleic acid (co)polymers, and salts thereof.
[0141] The maleic acid copolymers may comprise one or more maleic acid comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing from 2 to 20 carbon atoms, and styrene.
[0142] Thus, "maleic copolymer" is understood to mean any polymer obtained by copolymerization of one or more maleic comonomers with one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic comonomers being optionally partially or completely hydrolyzed. Preferably, hydrophilic polymers are used, i.e. polymers with a water solubility of 2 g / l or more.
[0143] In an advantageous embodiment of the invention, the maleic copolymer may have a molar fraction of maleic units between 0.1 and 1, more preferably between 0.4 and 0.9.
[0144] The weight average molar mass of the maleic acid copolymers may be between 1,000 and 500,000, preferably between 1,000 and 50,000.
[0145] It is preferred that the maleic acid copolymer is a styrene / maleic acid copolymer, more preferably a sodium styrene / maleic acid copolymer.
[0146] Preferably, a 50 / 50 copolymer of styrene and maleic acid is used.
[0147] For example, a styrene / maleic acid (50 / 50) copolymer in the form of its ammonium salt at 30% in water sold under the reference SMA1000H® by the company Cray Valley, or a styrene / maleic acid (50 / 50) copolymer in the form of its sodium salt at 40% in water sold under the reference SMA1000HNa® by the company Cray Valley, may be used.
[0148] The use of styrene / maleic acid copolymers, such as sodium styrene / maleic acid copolymer, can improve the wettability of films prepared with the compositions according to the invention.
[0149] In a preferred embodiment, (b) the anionic polymer may be selected from hyaluronic acid, its salts (eg, sodium hyaluronate), and its derivatives.
[0150] Hyaluronic acid has the following chemical formula:
[0151] [ka]
[0152] It can be expressed as:
[0153] In the context of the present invention, the term "hyaluronic acid" refers specifically to a compound having the following formula:
[0154] [ka]
[0155] It includes the basic unit of hyaluronic acid.
[0156] It is the smallest portion of hyaluronic acid that contains a disaccharide dimer, namely D-glucuronic acid and N-acetylglucosamine.
[0157] The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, linear polymers comprising the above polymer units linked together in a chain via alternating β(1,4) and β(1,3) glycosidic bonds, with a molecular weight (MW) that can range between 380 and 13,000,000 daltons, which depends mainly on the source from which the hyaluronic acid is obtained and / or on the method of preparation.
[0158] The term "hyaluronic acid and its derivatives" in the context of the present invention also includes hyaluronic acid salts, which may include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.
[0159] In nature, hyaluronic acid is found in the percellular gel in the matrix of connective tissues of vertebrate organs, such as the dermis and epithelial tissues, specifically in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord, and in the crest process.
[0160] Thus, the term "hyaluronic acid and its derivatives" includes all fractions or subunits of hyaluronic acid having molecular weights especially within the molecular weight ranges envisaged above.
[0161] In the context of the present invention, hyaluronic acid fractions that do not have inflammatory activity are preferably used.
[0162] As an example of various hyaluronic acid fractions, reference may be made to the publication "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699-715, which outlines the enumerated biological activities of hyaluronic acid according to its molecular weight.
[0163] According to a preferred embodiment of the present invention, the hyaluronic acid fraction suitable for use in the present invention has a molecular weight between 50,000 Da and 5,000,000 Da, in particular between 100,000 Da and 5,000,000 Da, and more particularly between 400,000 Da and 5,000,000 Da, in which case the term used is high molecular weight hyaluronic acid.
[0164] Alternatively, hyaluronic acid fractions that may be suitable for use within the present invention have a molecular weight between 50,000 Da and 400,000 Da, in which case the term used is intermediate molecular weight hyaluronic acid.
[0165] Additionally or alternatively, hyaluronic acid fractions that may be suitable for use within the present invention have a molecular weight of less than 50,000 Da, in which case the term used is low molecular weight hyaluronic acid.
[0166] Finally, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid esters, in particular those in which all or part of the carboxylic acid groups of the acid functions are esterified with oxyethylenated alkyls or alcohols, containing 1 to 20 carbon atoms, in particular with a degree of substitution at the level of D-glucuronic acid of hyaluronic acid ranging from 0.5 to 50%.
[0167] Mention may in particular be made of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. Such esters are described in detail in D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) pp. 2101-2127.
[0168] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.
[0169] The molecular weights given above are also valid for hyaluronic acid esters.
[0170] Specifically, hyaluronic acid is sold by Hyactive under the trade name CPN (MW: 10-150 kDa) and by Soliance under the trade name Cristalhyal (MW: 1.1×10 6 ), supplied by Bioland under the name Nutra HA (MW: 820,000 Da), by Bioland under the name Nutra AF (MW: 69,000 Da), by Bioland under the name Oligo HA (MW: 6100 Da), or by Vam Farmacos Metica under the name D Factor (MW: 380 Da).
[0171] In a preferred embodiment, (b) the anionic polymer may be selected from the group consisting of carrageenans, such as iota-carrageenan and Λ-carrageenan, algins, chondroitin sulfate, pectin, and mixtures thereof.
[0172] It may be more preferred that the (b) anionic polymer is selected from the group consisting of carrageenan, pectin, and mixtures thereof.
[0173] It may even be more preferred that the (b) anionic polymer is selected from carrageenan.
[0174] The amount of (b) anionic polymer in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, based on the total weight of the composition.
[0175] The amount of (b) anionic polymer in the composition according to the present invention may be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, relative to the total weight of the composition.
[0176] The amount of the anionic polymer (b) in the composition according to the present invention may be from 0.001% to 15% by mass, preferably from 0.005% to 10% by mass, and more preferably from 0.01% to 5% by mass, based on the total mass of the composition.
[0177] (fatty acid) The composition according to the invention comprises (c) at least one fatty acid. When two or more fatty acids are used, they may be the same or different.
[0178] As used herein, the term "fatty acid" refers to a carboxylic acid having a long chain of aliphatic carbons.
[0179] (c) The fatty acid has at least 4 carbon atoms, preferably at least 6 carbon atoms, more preferably at least 8 carbon atoms. (c) The fatty acid may contain up to 26 carbon atoms, preferably up to 24 carbon atoms, more preferably up to 22 carbon atoms. (c) The fatty acid may be C4-C 26 Fatty acids, preferably C6-C 24 Fatty acids, even more preferably C8-C 22 It is preferably selected from fatty acids.
[0180] The (c) fatty acid may be selected from saturated or unsaturated, linear or branched fatty acids. Thus, the (c) fatty acid may be selected from C4 to C 26 , preferably C6 to C 24 , more preferably C8 to C 22 They can be chosen from saturated and unsaturated, straight-chain or branched fatty acids.
[0181] As the unsaturated linear or branched fatty acid, monounsaturated linear or branched fatty acid or polyunsaturated linear or branched fatty acid may be used. The unsaturated portion of the unsaturated linear or branched fatty acid may include a carbon-carbon double bond or a carbon-carbon triple bond.
[0182] Saturated fatty acids include, for example, caprylic acid (C8), pelargonic acid (C9), and capric acid (C10 ), lauric acid (C 12 ), myristic acid (C 14 ), pentadecanoic acid (C 15 ), palmitic acid (C 16 ), heptadecanoic acid (C 17 ), stearic acid (C 18 ), Isostearic acid (C 18 ), nonadecanoic acid (C 19 ), arachidic acid (C 20 ), behenic acid (C 22 ), and lignoceric acid (C 24 ) can be mentioned.
[0183] Examples of unsaturated fatty acids include myristoleic acid (C 14 ), palmitoleic acid (C 16 ), oleic acid (C 18 ), linoleic acid (C 18 ), linoleic acid (C 18 ), elaidic acid (C 18 ), arachidonic acid (C 20 ), eicosenoic acid (C 20 ), erucic acid (C 22 ), and nervonic acid (C 24 ) can be mentioned.
[0184] (c) Fatty acids are C8 to C 18 It is preferred to select from saturated or unsaturated, straight or branched chain fatty acids, more preferably from the group consisting of caprylic acid, capric acid, oleic acid, linoleic acid, stearic acid, isostearic acid and mixtures thereof.
[0185] (c) The fatty acid may be in the form of its free acid or its salt. The salt of the fatty acid may include inorganic salts, such as alkali metal salts (sodium salt, potassium salt, etc.) and alkaline earth metal salts (magnesium salt, calcium salt, etc.), as well as organic salts, such as ammonium salts (quaternary ammonium salts, etc.) and amine salts (triethanolamine salt, triethylamine salt, etc.). 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 free acid and one or more fatty acids in the form of salt may be used, and one or more types of salt may be used.
[0186] The amount of (c) fatty acid in the composition according to the present invention may be 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, based on the total mass of the composition.
[0187] On the other hand, the amount of (c) fatty acid in the composition according to the present invention may be 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the composition.
[0188] Accordingly, the amount of (c) fatty acid in the composition according to the present invention may be in the range of 0.001% by mass to 10% by mass, preferably 0.005% by mass to 5% by mass, and more preferably 0.01% by mass to 1% by mass, relative to the total mass of the composition.
[0189] (Active skin care ingredient) The composition according to the present invention may comprise at least one skin care active ingredient (d). A single type of skin care active ingredient (d) may be used, or two or more different types of skin care active ingredients (d) may be used in combination.
[0190] (d) It is preferred that the skin care active has a logP value of -1 or greater, more preferably 1 or greater, and even more preferably 2 or greater.
[0191] Thus, (d) the skin care active may be hydrophilic or lipophilic, preferably lipophilic. By lipophilic skin care active, it is meant that the partition coefficient of the lipophilic skin care active between n-butanol and water is greater than 1, more preferably greater than 10, and even more preferably greater than 100.
[0192] The log P value is the base 10 logarithm of the apparent partition coefficient of octan-1-ol / water. The log P value is known and determined by standard tests that determine the concentration of (d) skin care actives in octan-1-ol and water. The log P can be calculated by the method described in Meylan and Howard, Atom / Fragment contribution method for estimating octanol-water partition coefficients, J. Pharm. Sci., 84: 83-92, 1995 (clogP). This value may be calculated using a number of commercially available software packages that determine the log P as a function of the structure of the molecule. An example is the Epiwin software from the United States Environmental Protection Agency.
[0193] This value can be calculated using, inter alia, ACD (Advanced Chemistry Development) Solaris software V4.67, and it can also be obtained from Exploring QSAR: hydrophobic, electronic and steric constants (ACS professional reference book, 1995). There is also an internet site that provides approximate values (address: http: / / esc.syrres.com / interkow / kowdemo.htm).
[0194] (d) The skin care actives may be in the form of salts. Salts of (d) the skin care actives include the conventional non-toxic salts of such compounds formed, for example, from acids or bases.
[0195] (d) The skin care active is preferably a skin care cosmetic active, more preferably a skin emollient or moisturizer, or a skin anti-aging ingredient such as an antioxidant or anti-wrinkle ingredient.
[0196] (d) Examples of skin care active ingredients include ceramide compounds.
[0197] According to the invention, the term "ceramide compounds" is understood to mean natural or synthetic ceramides and / or glycoceramides and / or pseudoceramides and / or neoceramides.
[0198] Ceramide compounds are disclosed, for example, in patent applications DE 4424530, DE 4424533, DE 4402929, DE 4420736, WO 95 / 23807, WO 94 / 07844, EP-A-0 646 572, WO 95 / 16665, FR-2 673 179, EP-A-0 227 994, WO 94 / 07844, WO 94 / 24097 and WO 94 / 10131, the teachings of which are incorporated herein by reference.
[0199] The ceramide compounds that can be used according to the present invention have the general formula (I):
[0200] [ka]
[0201] [In the formula, R1 is, - Saturated or unsaturated, linear or branched, C1-C 50 , preferably C5 to C 50 Hydrocarbon radicals, which may be substituted by one or more hydroxyl groups, optionally esterified by an acid R7COOH, R7 being optionally mono- or polyhydroxylated, saturated or unsaturated, linear or branched C1-C 35is a hydrocarbon group, wherein one or more hydroxyls of the R7 group are optionally mono- or polyhydroxylated, saturated or unsaturated, linear or branched C1-C 35 may be esterified with a fatty acid), or - an R"-(NR-CO)-R' group, where R is a hydrogen atom or a mono- or polyhydroxylated, preferably monohydroxylated C1-C 20 R′ and R″ are hydrocarbon groups having a total of between 9 and 30 carbon atoms, and R′ is a divalent group; or - R8-O-CO-(CH2) p Group (wherein R8 is a C1-C 20 represents a hydrocarbon group, and p is an integer ranging from 1 to 12. Indicates either R2 is a hydrogen atom, a saccharide-type group, especially (glycosyl) n , (galactosyl) m or a sulfogalactosyl group, a sulfate or phosphate residue, a phosphorylethylamine group, and a phosphorylethylammonium group, where n is an integer varying from 1 to 4 and m is an integer varying from 1 to 8; R3 is a hydrogen atom or a hydroxylated or non-hydroxylated, saturated or unsaturated C1-C 33 represents a hydrocarbon group, one or more of the hydroxyls may be esterified by an inorganic acid or an acid R7COOH, R7 having the same meaning as above, one or more of the hydroxyls may be (glycosyl) n , (galactosyl) m , sulfogalactosyl, phosphorylethylamine or phosphorylethylammonium groups, where n is an integer varying from 1 to 4, m is an integer varying from 1 to 8, and R3 is one or more C1-C 14 It may also be substituted by an alkyl group. R4 is a hydrogen atom, a methyl or ethyl group, an optionally hydroxylated, saturated or unsaturated, linear or branched C3-C 50 represents a hydrocarbon group or a -CH2-CHOH-CH2-O-R6 group, where R6 is C 10 ~C 26 Hydrocarbon group, or R8-O-CO-(CH2) p R8 represents a C1-C 20 represents a hydrocarbon group, and p is an integer ranging from 1 to 12; R5 is a hydrogen atom or a saturated or unsaturated, linear or branched C1-C aryl group, optionally mono- or polyhydroxylated. 30 represents a hydrocarbon group, one or more hydroxyls being (glycosyl) n , (galactosyl) m , sulfogalactosyl, phosphorylethylamine or phosphorylethylammonium groups, where n is an integer varying from 1 to 4 and m is an integer varying from 1 to 8, with the proviso that when R3 and R5 represent hydrogen, or when R3 represents hydrogen and R5 represents methyl, R4 does not represent a hydrogen atom, a methyl group or an ethyl group. and in fact preferably corresponds to general formula (I):
[0202] Among the compounds of formula (I), preference is given to ceramides and / or glycoceramides having the structure described in Downing, Journal of Lipid Research, Vol. 35, pp. 2060-2068, 1994, or as disclosed in French patent application FR-2 673 179, the teachings of which are incorporated herein by reference.
[0203] In the above formula (I), R3 is C 15 ~C 26 α-hydroxyalkyl group, the hydroxyl group optionally being C 16 ~C 30 It is preferably esterified with an alpha-hydroxy acid.
[0204] Particularly preferred ceramide compounds according to the invention are compounds of formula (I), wherein R1 is C 14 ~C 22 R2 represents a hydrogen atom; and R3 represents a linear C alkyl group, optionally hydroxylated, derived from a fatty acid. 11 ~C 17 Group, preferably C 13 ~C 15 R3 preferably represents an α-hydroxycetyl group, and R2, R4 and R5 preferably represent hydrogen atoms.
[0205] It is preferred that the ceramide compound is selected from the group consisting of 2-N-linoleoylaminooctadecane-1,3-diol, 2-N-oleoylaminooctadecane-1,3-diol, 2-N-palmitoylaminooctadecane-1,3-diol, 2-N-stearoylaminooctadecane-1,3-diol, 2-N-behenoylaminooctadecane-1,3-diol, 2-N-[2-hydroxypalmitoyl]aminooctadecane-1,3-diol, 2-N-stearoylaminooctadecane-1,3,4-triol, 2-N-palmitoylaminohexadecane-1,3-diol, and mixtures thereof.
[0206] It is also preferred that the (b) ceramide compound is selected from bis(N-hydroxyethyl-N-cetyl)malonamide, N-(2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxypropyl)amide of cetylic acid, and N-docosanoyl-N-methyl-D-glucamine.
[0207] Mixtures of ceramide compounds may also be used, such as a mixture of ceramide 2 and ceramide 5 according to the Downing classification.
[0208] Particularly usable are also compounds of formula (I) in which R1 is 12 ~C 22R2 represents a galactosyl group or a sulfogalactosyl group; R3 represents a saturated or unsaturated C 12 ~C 22 Hydrocarbon groups, preferably -CH=CH-(CH2) 12 Indicates the -CH3 group.
[0209] By way of example, mention may be made of the product consisting of a mixture of glycoceramides sold under the trade name Glycocer by the company Waitaki International Biosciences.
[0210] Compounds of formula (I) disclosed in patent applications EP-A-0 227 994, EP-A-0 647 617, EP-A-0 736 522 and WO 94 / 07844 may also be used.
[0211] Such compounds include, for example, Questamide H (bis(N-hydroxyethyl-N-cetyl)malonamide) sold by Quest, or the N-(2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxy-propyl)amide of cetylic acid.
[0212] N-docosanoyl-N-methyl-D-glucamine, which is disclosed in patent application WO 94 / 24097, may also be used.
[0213] Of course, it is possible to use mixtures of different ceramide compounds in the compositions of the present invention.
[0214] (d) Skin care actives can include retinoids.
[0215] Retinoids are retinol (vitamin A), retinal (vitamin A aldehyde), retinoic acid (vitamin A acid), or retinol and C 2~20It may also be an ester with an acid, for example the propionate, acetate, linoleate, or palmitate ester of retinol (retinyl palmitate).
[0216] Among the retinoids, mention may be made of retinol, retinal, retinoic acid, in particular all-trans retinoic acid and 13-cis retinoic acid, retinol derivatives such as retinyl acetate, retinyl propionate or retinyl palmitate, and the retinoids described in the following patent applications: FR2370377, EP0199636, EP0325540, and EP0402072.
[0217] According to one preferred embodiment of the present invention, the retinoid is retinol or pro-retinol.
[0218] The term "retinol" is intended to mean all isomers of retinol, i.e., all-trans retinol, 13-cis retinol, 11-cis retinol, 9-cis retinol, and 3,4-didehydroretinol.
[0219] A representative example of pro-retinol is retinyl palmitate.
[0220] Preferably, the retinoid is retinol.
[0221] (d) Skin care actives can include lipophilic antioxidants.
[0222] According to the present invention, antioxidants are compounds or substances capable of scavenging the various radical forms that may be present in the skin, and preferably, they simultaneously scavenge all of the various radical forms present.
[0223] By lipophilic antioxidant is meant that the partition coefficient of the antioxidant between n-butanol and water is greater than 1, more preferably greater than 10, even more preferably greater than 100.
[0224] Lipophilic antioxidants are hydrophobic, as opposed to hydrophilic antioxidants such as ascorbic acid or glutathione.
[0225] The lipophilic antioxidants include phenolic antioxidants having a hindered phenol structure or a semi-hindered phenol structure in the molecule. Specific examples of such compounds include 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid (having the INCI name tetra(di-t-butylhydroxyhydrocinnamate) pentaerythrityl), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono- or di- or tri-(α-methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tris[N-(3, 5-di-tert-butyl-4-hydroxybenzyl)]isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, butylidene-1,1 bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionato]methane, triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6-trione, 2,4-bis(n-octylthio)-6-(4-hydroxyphenyl)propionate Examples of the hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,6-bis[(octylthio)methyl]-o-cresol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] can be mentioned.
[0226] Lipophilic antioxidants include BHA (butylated hydroxyl anisole) and BHT (butylated hydroxyl toluene), vitamin E (or tocopherols and tocotrienols) and derivatives thereof, such as phosphate derivatives, e.g. TPNA® sold by Showa Denko KK, coenzyme Q10 (or ubiquinone), idebenone, certain carotenoids, such as lutein, astaxanthin, β-carotene, polyphenols, phenolic acids and derivatives (e.g. chlorogenic acid), and flavonoids, which represent a major subgroup of polyphenols.
[0227] Among the flavonoids, particular mention may be made of chalcones, hydroxylated chalcones and their reduced derivatives (especially those described in FR2608150), such as phloretin, neohesperidin, phloridzin, aspalathin, etc., flavanones, such as hesperetin and naringin, flavonols, such as quercetin, rutin, flavanols, such as catechin, EGCG, flavones, such as apigenidin, and finally anthocyans.Tannins may also be mentioned.Furthermore, reference may be made to the compounds described in patent applications FR2699818, FR2706478, FR2907339, FR2814943 and FR2873026.
[0228] The polyphenolic compounds may be derived from plant extracts selected from among green tea, apple, hops, guava, cocoa, or extracts of trees such as chestnut, oak, horse chestnut or hazel. It is also possible to use an extract of pinaster bark, obtained for example according to the methods described in US Patent No. 4,698,360, US Patent No. 6,372,266 and US Patent No. 5,720,956. As an example of such an extract, one can cite the compound with the INCI name Pinus maritime (extract of bark) and the CTFA name Extract of bark of Pinus maritime (Pinus maritime). It may in particular be an extract of pinaster bark marketed under the name PYCNOGENOL® by the BIOLANDES AROMES firm and / or HORPHAG Research. There may also be mentioned (Maritime) pine bark extract from the company LAYN Natural Ingredients, Pine Bark from the company Blue California and also Oligopin® from the company DRT (Les Derives Resiniques et Terpeniques).
[0229] Thus, in the context of the present invention, the term "polyphenolic compounds" also encompasses the plant extracts themselves which are rich in these polyphenolic compounds.
[0230] Lipophilic antioxidants which may further be mentioned include dithiolanes, such as asparagusic acid or its derivatives, such as siliceous dithiolane derivatives, especially those described, for example, in patent application FR 2 908 769.
[0231] Lipophilic antioxidants that may also be mentioned include: Glutathione and its derivatives (GSH and / or GSHOEt), such as glutathione alkyl esters (such as those described in patent applications FR2704754 and FR2908769), and Cysteine and its derivatives, such as N-acetylcysteine or L-2-oxothiazolidine-4-carboxylic acid. Reference may also be made to the cysteine derivatives described in patent applications FR2877004 and FR2854160, as well as Ferulic acid and its derivatives (esters, salts, etc.). Particular mention may be made of esters of ferulic acid with C1-C30 alcohols, specifically methyl ferulate, ethyl ferulate, isopropyl ferulate, octyl ferulate and oryzanyl ferulate; Specific enzymes to protect against oxidative stress, such as catalase, superoxide dismutase (SOD), lactoperoxidase, glutathione peroxidase and quinone reductase; benzylcyclanones; substituted naphthalenones; pidolates (among others those described in patent application EP 0511118); caffeic acid and its derivatives, gamma oryzanol; melatonin, sulforaphane and extracts containing same (except for cress); diisopropyl esters of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, in particular those described in patent applications WO 94 / 11338, FR 2 698 095, FR 2 737 205 or EP 0 755 925; and Deferoxamine (or Desferal), as described in FR2825920 It is.
[0232] Preferably, the lipophilic antioxidant used is a chalcone, more particularly phloretin or neophesperidin, the diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, or an extract of pine bark, such as PYCNOGENOL®.
[0233] Examples of lipophilic antioxidants include pentaerythrityl tetra(di-t-butyl hydroxyhydrocinnamate), nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxylanisole, ascorbyl palmitate, tocopherol, and mixtures thereof.
[0234] The lipophilic antioxidant may be at least one tocopherol selected from the group consisting of α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof. Vitamin E may also be used as a lipophilic antioxidant.
[0235] (d) Skin care actives may include anti-inflammatory or analgesic agents.
[0236] Anti-inflammatory or analgesic agents which may be used in the compositions according to the invention include pentacyclic triterpenes and plant extracts containing them (e.g. Glycyrrhiza glabra), such as β-glycyrrhetinic acid and its salts and / or derivatives (glycyrrhetinic acid monoglucuronide, stearyl glycyrrhetinate, 3-stearoyloxyglycyrrhetinic acid), ursolic acid and its salts, oleanolic acid and its salts, betulinic acid and its salts, bisabolol, extracts of Paeonia suffruticosa and / or Paeonia lactiflora, Phycosaccharides from Codif, extracts of Laminaria saccharina, rapeseed oil, bisabolol and chamomile extracts, allantoin, Sepivital from Seppic. EPC (phosphate diesters of vitamins E and C), omega-3 unsaturated oils such as musk rose oil, black currant oil, echium oil, fish oil, plankton extracts, capryloyl glycine, Seppic Seppicalm VG (Sodium Palmitoyl Proline and Water Lily (Nymphaea alba)), Pygeum extracts, Boswellia Serrata extracts, Centipeda cunninghami extracts, Sunflower extracts (Helianthus annuus), Linum usitatissimum extracts, tocotrienols, Cola nitida extracts, Centella asiatica extracts, Piperonal, Clove extracts, Epilobium Examples of suitable anti-inflammatory agents include extracts of (Angustifolium), aloe vera, extracts of Bacopa monieri, phytosterols, niacinamide, cortisone, hydrocortisone, indomethacin, and betamethasone.
[0237] Preferred anti-inflammatory agents for use in the present invention are extracts of Centella asiatica, β-glycyrrhetinic acid and its salts, α-bisabolol, and niacinamide.
[0238] (d) Skin care actives can include hydrophilic antioxidants such as ascorbic acid and its derivatives.
[0239] Ascorbic acid is generally in the L form, as it is usually extracted from natural products.
[0240] Due to its chemical structure (α-keto lactone), which makes it very sensitive to certain environmental parameters, such as light, heat and aqueous media, it may be advantageous to use ascorbic acid in the form of a derivative or analogue, for example selected from sugar esters of ascorbic acid, or metal salts, alkali metal salts, esters and sugars of phosphoryl ascorbic acid.
[0241] Sugar esters of ascorbic acid which may be used in the present invention are, inter alia, the glycosyl, mannosyl, fructosyl, fucosyl, galactosyl, N-acetylglucosamine and N-acetylmuramin derivatives of ascorbic acid, and mixtures thereof, in particular ascorbyl glucosides, such as ascorbyl-2-glucoside, 2-O-α-D-glucopyranosyl L-ascorbic acid or 6-O-β-D-galactopyranosyl L-ascorbic acid. The latter compounds and methods for their preparation are described, inter alia, in documents EP-A-0 487 404, EP-A-0 425 066 and JP-A-05-213 736.
[0242] As regards the metal salt of phosphoryl ascorbic acid, it may be chosen from alkali metal salts of ascorbyl phosphate, especially sodium ascorbyl phosphate, alkaline earth metal salts of ascorbyl phosphate and transition metal salts of ascorbyl phosphate.
[0243] It is also possible to use ascorbic acid precursors, such as activator amides and activator sugar derivatives, which require proteases or peptidases and glycosidases, respectively, as enzymes to release ascorbic acid in situ. Such compounds are described in patent EP 0 667 145.
[0244] The active agent sugar derivative is in particular selected from C3-C6 sugar derivatives, in particular selected from glucosyl, mannosyl, fructosyl, fucosyl, N-acetylglucosamine, galactosyl and N-acetylgalactosamine derivatives, N-acetylmuramic acid derivatives and sialic acid derivatives, and mixtures thereof.
[0245] The second ascorbic acid precursor may be selected from derivatives hydrolyzed by other enzymes, such as esterases, phosphatases, sulfatases, etc. According to the invention, the second active agent precursor may be selected from, for example, phosphate esters, sulfate esters, palmitate esters, acetate esters, propionate esters, ferulate esters, generally active agent alkyl or acyl esters, acyl or alkyl ethers. The acyl and alkyl groups contain, in particular, 1 to 30 carbon atoms. The skin care active may include 3-O-ethyl ascorbic acid.
[0246] In particular, the second precursor may be an ester derived from reaction with a mineral acid, such as a sulfate or phosphate ester, which reacts with sulfatases or phosphatases on contact with the skin, or the second precursor may be an acyl or alkyl ester derived from reaction with an organic acid, such as palmitic acid, acetic acid, propionic acid, nicotinic acid, 1,2,3-propanetricarboxylic acid, or ferulic acid, which reacts with certain skin esterases.
[0247] Further derivatives are described, for example, in patent EP 1 430 883.
[0248] Ascorbic acid analogues are more particularly salts thereof, especially alkali metal salts such as sodium ascorbate, esters thereof, especially acetates, propionates or palmitates, especially ascorbyl tetraisopalmitate, or sugars thereof, especially glycosyl ascorbic acids.
[0249] (d) Skin care active ingredients include salicylic acid and its derivatives. Derivatives of salicylic acid are represented by the following formula (I):
[0250] [ka]
[0251] [In the formula, R1 represents hydrogen or a saturated linear, branched or cyclic aliphatic hydrocarbon group, or an alkoxy, ester or ketoxy group, or an unsaturated group having at least one conjugated or non-conjugated double bond, which may contain from 1 to 22 carbon atoms and may be substituted with at least one substituent selected from halogen atoms, trifluoromethyl groups and hydroxyl groups in free form or esterified by an acid having from 1 to about 6 carbon atoms; R2 is a hydroxyl group or a group of formula (II):
[0252] [ka]
[0253] (In the formula, R4 represents a saturated aliphatic hydrocarbon group or an alkenyl group having 1 to 18 carbon atoms. represents an ester of; R3 represents hydrogen or a saturated or unsaturated, linear or branched aliphatic hydrocarbon group having 2 to 30 carbon atoms and optionally containing one or more substituents such as those listed above. or a salt thereof.
[0254] Suitable R3 groups are alkyl and alkenyl groups containing 2 to 30 carbon atoms, which are optionally substituted.
[0255] A preferred substituent is the hydroxyl group.
[0256] When R3 is hydrogen, salts of the compound of formula (I) can be used, particularly salts obtained by reaction with a base. Suitable bases include alkali metal hydroxides (sodium and potassium hydroxide), ammonium hydroxide, organic bases such as primary, secondary, tertiary or cyclic organic amines, and amino acids. Specific examples of bases include glycine, taurine, alanine, valine, cysteine, trihydroxymethylaminomethane (TRISTA) and triethanolamine.
[0257] According to a preferred embodiment of the present invention, the composition is prepared using a derivative of formula (I), where R1 contains at least 4 carbon atoms. For example, R1 may be a saturated linear alkyl or alkoxy group having 4 to 11 carbon atoms.
[0258] Derivatives of formula (I), where R2 is hydroxyl and R3 is hydrogen, include 5-n-octanoylsalicylic acid (CTFA name: capryloylsalicylic acid), 5-n-decanoylsalicylic acid, 5-n-dodecanoylsalicylic acid, 5-n-octylsalicylic acid, 5-n-heptyloxysalicylic acid, 5-tert-octylsalicylic acid, 5-butoxysalicylic acid, 5-ethoxysalicylic acid, 5-methoxysalicylic acid, 5-propoxysalicylic acid, 5-methylsalicylic acid, 5-ethylsalicylic acid and 5-propylsalicylic acid, optionally treated with base.
[0259] When R1 represents hydrogen and R2 represents a hydroxyl group, the derivative of formula (I) is a salicylic acid ester.Preferred compounds include esters of fatty alcohols such as dodecyl, hexadecyl, stearyl, cetyl, myristyl, linoleyl, octyl, oleyl and tridecyl alcohol, or esters of butyl, propyl and ethyl alcohol, or esters of polyols such as propylene glycol, butylene glycol, ethylene glycol or glycerol, or mixtures of these esters.Specific examples include cetyl salicylate, dodecyl salicylate and tridecyl salicylate.
[0260] It is even more preferred that (d) the skin care active is selected from the group consisting of 2-N-oleoylaminooctadecane-1,3-diol (2-oleamido-1,3-octadecanediol), tocopherol, retinol, stearyl glycyrrhetinate, ascorbic acid, ascorbyl tetraisopalmitate, 2-N-stearoylaminooctadecane-1,3,4-triol (ceramide NP), capryloyl salicylic acid, and mixtures thereof.
[0261] The amount of (d) skin care active in the composition according to the present invention may be 0.001% by weight or more, preferably 0.003% by weight or more, more preferably 0.005% by weight or more, based on the total weight of the composition.
[0262] On the other hand, the amount of (d) skin care active in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, based on the total weight of the composition.
[0263] Therefore, the amount of (d) skin care active ingredient in the composition according to the present invention may be in the range of 0.001% to 10% by mass, preferably 0.003% to 5% by mass, and more preferably 0.005% to 1% by mass, relative to the total mass of the composition.
[0264] (particle) (a) cationic polymer and (b) anionic polymer can form at least one type of particle with or without (c) fatty acid. Therefore, the composition according to the present invention can include at least one type of particle. (c) fatty acid can hydrophobize the particle.
[0265] The particles may be polyion complex particles which may be formed by (a) a cationic polymer and (b) an anionic polymer, and (c) a fatty acid which may hydrophobize the polyion complex particles.
[0266] The particles, when present, can include (d) a skin care active, such that the (d) skin care active can be solubilized by the particles.
[0267] The size of the particles may be less than 1,000 nm, so the particles may be nano-sized particles.
[0268] Particle size can be measured by dynamic light scattering and can be based on volume average diameter.
[0269] The size of the particles in the composition according to the invention may be less than 500 nm, preferably less than 400 nm, more preferably less than 300 nm.
[0270] The size of the particles in the composition according to the invention may be 10 nm or more, preferably 30 nm or more, more preferably 50 nm or more.
[0271] The size of the particles may be from 10 nm to 500 nm, preferably from 30 nm to 400 nm, more preferably from 50 nm to 300 nm.
[0272] (conditions) According to the present invention, the following conditions (1) to (4) can be met for the composition according to the present invention. (1) the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, based on the total weight of the composition; (2) the weight ratio of the amount of (a) cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.7, preferably less than 0.5, and more preferably less than 0.3; (3) the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.9, preferably less than 0.8, and more preferably less than 0.7; and (4) The weight ratio of the amount of (d) skin care active to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.16, preferably less than 0.12, and more preferably less than 0.08.
[0273] It may also be preferred for the composition according to the present specification to satisfy any one, preferably all, of the following conditions (5) to (8): (5) the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is greater than 0.01% by weight, preferably greater than 0.05% by weight, and more preferably greater than 0.1% by weight, based on the total weight of the composition; (6) the weight ratio of the amount of (a) cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is greater than 0.01, preferably greater than 0.05, and more preferably greater than 0.1; (7) the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is greater than 0.3, preferably greater than 0.4, and more preferably greater than 0.5; and (8) The weight ratio of the amount of (d) skin care active to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is greater than 0.005, preferably greater than 0.01, and more preferably greater than 0.05.
[0274] (water) The composition according to the present invention may include (e) water.
[0275] The amount of (e) water may be 50% by weight or more, more preferably 55% by weight or more, more preferably 60% by weight or more, based on the total weight of the composition.
[0276] (e) The amount of water may be up to 99% by weight, preferably up to 98% by weight, and more preferably up to 97% by weight, based on the total weight of the composition.
[0277] The amount of (e) water may be 50% to 99% by mass, preferably 55% to 98% by mass, and more preferably 60% to 97% by mass, based on the total mass of the composition.
[0278] (pH) The pH of the composition according to the present invention may be 3-9, preferably 3.3-8.5, and more preferably 3.5-8.
[0279] At pH 3-9, the particles, which may be polyion complex particles formed by (a) a cationic polymer and (b) anionic polymer, may be very stable, where (c) a fatty acid can hydrophobize the polyion complex particles.
[0280] The pH of the composition according to the invention can be adjusted by adding at least one alkaline agent and / or at least one acid. The pH of the composition according to the invention can also be adjusted by adding at least one buffering agent.
[0281] (Alkaline agent) The composition according to the present invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.
[0282] The alkaline agent may be an inorganic alkaline agent, preferably selected from the group consisting of ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates and monohydrogen phosphates, such as sodium phosphate or sodium monohydrogen phosphate.
[0283] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. As the inorganic alkaline agent, sodium hydroxide is preferred.
[0284] The alkaline agent may be an organic alkaline agent, which is preferably selected from the group consisting of monoamines and their derivatives, diamines and their derivatives, polyamines and their derivatives, basic amino acids and their derivatives, oligomers of basic amino acids and their derivatives, polymers of basic amino acids and their derivatives, urea and its derivatives, and guanidine and its derivatives.
[0285] 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 ornithine, and diamines, such as those having the following structures:
[0286] [ka]
[0287] (wherein R represents an alkylene, such as propylene, optionally substituted with a hydroxyl group or a C1-C4 alkyl group; and R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group, or a C1-C4 hydroxyalkyl group). and can be exemplified by 1,3-propanediamine and its derivatives.
[0288] The alkaline agents can be used in a total amount of 0.001% by mass to 15% by mass, preferably 0.002% by mass to 10% by mass, and more preferably 0.003% by mass to 5% by mass, based on the total mass of the composition, depending on their solubility.
[0289] (acid) The composition according to the invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.
[0290] The acid may include any inorganic or organic acid commonly used in cosmetics, preferably inorganic acid. Monobasic and / or polybasic acids may be used. Monobasic acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid, and hydrochloric acid (HCl) may be used. Lactic acid may be preferred.
[0291] The acids can be used in a total amount of 0.001% by mass to 15% by mass, preferably 0.002% by mass to 10% by mass, and more preferably 0.003% by mass to 5% by mass, based on the total mass of the composition, depending on their solubility.
[0292] (Optional Ingredients) In addition to the above-mentioned components, the composition according to the present invention may contain optional components typically used in cosmetics, particularly oils, UV screening agents, surfactants / emulsifiers, hydrophilic or lipophilic thickeners derived from synthetic polymers other than (a) cationic polymers or (b) anionic polymers, volatile or non-volatile organic solvents, amphoteric polymers, nonionic polymers such as beta-glucan, silicones and silicone derivatives, natural extracts derived from animals or plants other than (a) cationic polymers or (b) anionic polymers, waxes, etc., within a range that does not impair the effects of the present invention.
[0293] The composition according to the present invention may contain the above optional components in an amount of 0.01% by mass to 30% by mass, preferably 0.05% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass, relative to the total mass of the composition.
[0294] The composition according to the invention is free of surfactants having at least one polyoxyethylene unit or contains at least one surfactant having at least one polyoxyethylene unit in an amount of at most 1% by weight, preferably at most 0.1% by weight, more preferably at most 0.01% by weight, relative to the total weight of the composition. It is particularly preferred that the composition according to the invention is free of surfactants / emulsifiers having at least one polyoxyethylene unit.
[0295] The composition according to the invention may contain very limited amounts of synthetic thickeners and / or organic solvents, taking into account environmental compatibility.
[0296] The amount of synthetic thickeners and / or organic solvents in the composition according to the invention may be up to 1% by weight, preferably up to 0.1% by weight, more preferably up to 0.01% by weight, relative to the total weight of the composition. It is particularly preferred that the composition according to the invention does not comprise any synthetic thickeners or organic solvents.
[0297] [Preparation] The composition according to the present invention can be prepared by mixing the essential components described above and, if necessary, the optional components described above.
[0298] The method and means for mixing the above essential components and optional components are not limited. Any conventional method and means can be used to mix the above essential components and optional components to prepare the composition according to the present invention.
[0299] The composition according to the present invention can be prepared by simple or easy mixing with conventional mixing means such as stirrers and homogenizers. Also, heating may not be required. Therefore, the preparation method of the composition according to the present invention can be environmentally friendly.
[0300] [Beauty use] 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 keratinous materials. Keratinous materials herein mean materials that contain keratin as a main component, examples of which include skin, scalp, nails, lips, hair, etc. Therefore, it is preferred that the cosmetic composition according to the present invention is used for a cosmetic method for keratinous materials, particularly skin.
[0301] Therefore, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin make-up composition, more preferably a skin care composition.
[0302] [form] The composition according to the present invention may be in any form.
[0303] For example, when the composition according to the present invention comprises oil, the oil can form a fatty phase, and (e) water can form an aqueous phase, and the fatty phase can be dispersed in the aqueous phase. Therefore, the aqueous phase can function as a continuous phase, and the fatty phase can function as a dispersed phase. In other words, the composition according to the present invention can be in the form of an O / W dispersion, such as an O / W emulsion. When the composition according to the present invention is an O / W type, it can provide a refreshing feeling due to (e) water forming its outer phase.
[0304] The composition according to the invention may have a transparent or translucent appearance, preferably a transparent appearance.
[0305] Clarity may be measured by measuring turbidity (e.g., with a HACH 2100Q Portable Turbidimeter). The turbidity of the compositions according to the invention may be less than 400 NTU (semi-transparent), preferably less than 350 NTU, more preferably less than 300 NTU (transparent).
[0306] [Coating] The composition according to the present invention can be used to easily prepare a coating.
[0307] When components (a) and (b) form particles with or without component (c), the particles may agglomerate and become incorporated into a continuous coating.
[0308] The present invention therefore also relates to a method for preparing a film, preferably a decorative film, optionally having a thickness of more than 0.5 μm, more preferably 1.0 μm or more, even more preferably 1.5 μm or more, comprising: applying a composition according to the invention onto a substrate, preferably a keratinous material, more preferably the skin; drying the composition; The present invention may also relate to a method, comprising:
[0309] The upper limit of the thickness of the coating according to the present invention is not limited. Thus, for example, the thickness of the coating according to the present invention may be 1 mm or less, preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less.
[0310] Since the method for preparing a film according to the present invention includes a step of applying the composition according to the present invention onto a substrate, preferably a keratinous material, more preferably onto the skin, and a step of drying the composition, the method according to the present invention does not require any spin coating or spraying, and therefore, even a relatively thick film can be easily prepared. Therefore, the method for preparing a film according to the present invention can prepare a relatively thick film without using any special equipment such as a spin coater or a spray machine.
[0311] Even if the film according to the invention is relatively thick, it can still be thin and transparent and therefore not easily perceptible, so that the film according to the invention can preferably be used as a cosmetic film.
[0312] If the substrate is not a keratinous material such as skin, the composition according to the present invention can be applied onto the substrate made of any material other than keratin. The material of the non-keratinous substrate is not limited. Two or more materials may be used in combination. Thus, a single type of material or a combination of different types of materials can be used. In any case, it is preferred that the substrate is flexible or elastic.
[0313] If the substrate is not a keratinous material, it is preferred that the substrate is water-soluble, since the coating according to the invention can be removed by washing the substrate with water. Examples of water-soluble materials include poly(meth)acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate, etc. PVA is preferred.
[0314] When the non-keratin substrate is in the form of a sheet, the substrate may have a thickness greater than that of the coating according to the present invention in order to facilitate handling of the coating attached to the substrate sheet. The thickness of the non-keratin substrate sheet is not limited, but may be 1 μm to 5 mm, preferably 10 μm to 1 mm, more preferably 50 to 500 μm.
[0315] It is more preferred that the film according to the present invention is removable from the non-keratin substrate. The manner of removal is not limited. Thus, the film according to the present invention may be peeled off from the non-keratin substrate, or may be removed by dissolving the substrate sheet in a solvent such as water.
[0316] The present invention also provides (1) A film, preferably a decorative film, optionally having a thickness of preferably more than 0.5 μm, more preferably 1.0 μm or more, even more preferably 1.5 μm or more, applying a composition according to the invention onto a substrate, preferably a keratinous material, more preferably the skin; drying the composition; A coating prepared by a method comprising: and (2) A coating, preferably a decorative coating, optionally having a thickness of preferably more than 0.5 μm, more preferably 1.0 μm or more, even more preferably 1.5 μm or more, (a) at least one cationic polymer; (b) at least one anionic polymer; (c) at least one fatty acid, and (d) at least one skin care active ingredient Including, the weight ratio of the amount of (a) cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.7, preferably less than 0.5, more preferably less than 0.3; the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.9, preferably less than 0.8, more preferably less than 0.7; and The present invention also relates to a coating in which the weight ratio of the amount of (d) skin care active ingredient to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active ingredient is less than 0.16, preferably less than 0.12, and more preferably less than 0.08.
[0317] The above descriptions regarding (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active are applicable to films (1) and (2) above.
[0318] The film thus obtained above may be self-supporting. The term "self-supporting" as used 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. Therefore, the term "self-supporting" may have the same meaning as "self-supporting".
[0319] Coatings according to the present invention are preferably hydrophobic.
[0320] The term "hydrophobic" in this specification means that the solubility of the film in water (preferably 1 liter volume) at 20 to 40° C., preferably 25 to 40° C., more preferably 30 to 40° C. is less than 10% by mass, preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.1% by mass relative to the total mass of the film at 20 to 40° C., preferably 25 to 40° C., and more preferably 30 to 40° C. It is most preferable that the film is not soluble in water.
[0321] When the film according to the present invention is hydrophobic, the film can have water-resistant properties and can therefore remain on the keratinous material, such as the skin, even when the surface of the keratinous material is wet, for example, from sweat and rain, so that when the film according to the present invention provides any cosmetic benefit, the cosmetic benefit can last for a long time.
[0322] On the other hand, the film according to the invention can be easily removed from keratinous materials such as skin under alkaline conditions, such as a pH of 8 to 12, preferably 9 to 11. Thus, while the film according to the invention is difficult to remove with water, it can be easily removed with soaps that can provide such alkaline conditions.
[0323] The coating according to the present invention may comprise at least one biocompatible and / or biodegradable polymer layer. Two or more biocompatible and / or biodegradable polymers may be used in combination. Thus, a single type of biocompatible and / or biodegradable polymer or a combination of different types of biocompatible and / or biodegradable polymers may be used.
[0324] As used herein, the term "biocompatible" polymer means that the polymer does not have excessive interactions between the polymer and cells in the body, including the skin, and the polymer is not recognized as foreign by the body.
[0325] As used herein, the term "biodegradable" polymer means that the polymer can be broken down or broken down in vivo, for example by the metabolism of the organism itself or by the metabolism of microorganisms that may be present in the organism. Biodegradable polymers can also be broken down by hydrolysis.
[0326] When the coating according to the present invention comprises a biocompatible and / or biodegradable polymer, the coating causes little or no irritation to the skin and / or does not pollute the environment.
[0327] Indeed, the coating according to the invention may comprise at least one cationic polymer, which may be selected from (a) chitosan, and / or (b) anionic polymer, which may be selected from polysaccharides such as carrageenan, which are biodegradable polymers.
[0328] In addition, the use of biocompatible and / or biodegradable polymers allows the cosmetic sheet according to the present invention to adhere well to the skin.
[0329] The film according to the present invention can be used for the cosmetic treatment of keratinous materials, preferably skin, especially face.The film according to the present invention can be in any shape or form.For example, the film can be used as a full face mask sheet, or a patch for a part of face, such as cheek, nose, and around the eyes.
[0330] [Cosmetic methods and uses] The present invention also provides A cosmetic method for keratinous materials such as the skin, comprising the steps of applying a composition according to the invention to the keratinous materials and drying the composition to form a cosmetic film on the keratinous materials, or Use of the composition according to the invention for preparing a cosmetic film on a keratinous material such as the skin Also relates to.
[0331] Cosmetic method means herein a non-therapeutic cosmetic method for caring for and / or making up the surfaces of keratinous materials such as the skin.
[0332] In both the above method and use, the above decorative film is resistant to water having a pH of 7 or less and is removable with water having a pH of greater than 7, preferably 8 or more, more preferably 9 or more.
[0333] In other words, the decorative film may be water-resistant under neutral or acidic conditions, such as a pH of 7 or less, preferably in the range of ≧6 and ≦7, more preferably in the range of ≧5 and ≦7, but the decorative film can be removed under alkaline conditions, such as a pH of more than 7, preferably ≧8, more preferably ≧9. The upper limit of the pH is preferably 13, more preferably 12, even more preferably 11.
[0334] Accordingly, the cosmetic film may be water-resistant, and therefore may remain on the keratinous material, such as the skin, even when the surface of the keratinous material is wet, for example, by sweat and rain. On the other hand, the cosmetic film may be easily removed from the keratinous material, such as the skin, under alkaline conditions. Thus, the film according to the present invention is difficult to remove with water, but on the other hand, the film may be easily removed with a soap that can provide alkaline conditions.
[0335] Furthermore, the cosmetic film described above may have cosmetic benefits such as trapping sebum, imparting a matte appearance to keratinous materials such as skin, absorbing or adsorbing malodors, and / or protecting keratinous materials from, for example, dirt or pollutants, due to the properties of the complexes in the cosmetic film, even if the cosmetic film does not contain any antisebum agents, deodorants, or protectants.
[0336] In addition, the cosmetic film can instantly change or modify the appearance of the skin by changing the light reflection on the skin, even if the cosmetic film does not contain any cosmetic active ingredient. Thus, the cosmetic film can be capable of hiding skin defects such as pores or wrinkles. Furthermore, the cosmetic film can instantly change or modify the feel of the skin by changing the surface roughness on the skin, etc. Furthermore, the cosmetic film can instantly protect the skin from environmental stresses, such as pollutants, impurities, etc., by covering the surface of the skin and shielding the skin as a barrier.
[0337] The cosmetic benefits can be adjusted or controlled by varying the chemical composition, thickness and / or surface roughness of the cosmetic coating.
[0338] Since the cosmetic film includes at least one skin care active ingredient (d), the cosmetic film can have the cosmetic effect provided by the skin care active ingredient (d). For example, when the cosmetic film includes at least one skin care active ingredient selected from anti-aging agents such as antioxidants, the cosmetic film can treat skin aging.
[0339] It is also possible to apply a make-up cosmetic composition onto the cosmetic film or cosmetic sheet according to the present invention after application onto the skin.
[0340] The present invention also provides a composition comprising: (d) a composition for solubilizing a skin care active in the composition; (d) at least one skin care active, and (e) water In a composition comprising (a) at least one cationic polymer; (b) at least one anionic polymer, and (c) at least one fatty acid The use of the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, based on the total weight of the composition; the weight ratio of the amount of (a) cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.7, preferably less than 0.5, more preferably less than 0.3; the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.9, preferably less than 0.8, more preferably less than 0.7; and The weight ratio of the amount of (d) skin care active ingredient to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active ingredient is less than 0.16, preferably less than 0.12, more preferably less than 0.08.
[0341] The present invention also provides a composition comprising: (d) at least one skin care active, and (e) water In a composition comprising (a) at least one cationic polymer; (b) at least one anionic polymer, and (c) at least one fatty acid The use of the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, based on the total weight of the composition; the weight ratio of the amount of (a) cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.7, preferably less than 0.5, more preferably less than 0.3; the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.9, preferably less than 0.8, more preferably less than 0.7; and the weight ratio of the amount of (d) skin care active to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.16, preferably less than 0.12, and more preferably less than 0.08; It may also relate to use.
[0342] The present invention also provides a composition comprising: (d) a composition for enhancing the penetration of a skin care active into the skin; (d) at least one skin care active, and (e) water In a composition comprising (a) at least one cationic polymer; (b) at least one anionic polymer, and (c) at least one fatty acid The use of the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, based on the total weight of the composition; the weight ratio of the amount of (a) cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.7, preferably less than 0.5, more preferably less than 0.3; the weight ratio of the amount of (b) anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.9, preferably less than 0.8, more preferably less than 0.7; and the weight ratio of the amount of (d) skin care active to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid, and (d) skin care active is less than 0.16, preferably less than 0.12, and more preferably less than 0.08; It may also relate to use.
[0343] The above statements regarding (a) cationic polymer, (b) anionic polymer, (c) fatty acid, (d) skin care active, and (e) water are applicable in the above uses. EXAMPLES
[0344] The present invention will now be described in a more detailed manner by means of examples, which should not, however, be construed as limiting the scope of the present invention.
[0345] (Example 1 and Comparative Examples 1 to 3) [Preparation] Each of the compositions according to Example 1 and Comparative Examples 1 to 3 was prepared by mixing the components shown in Table 1. All numerical values for the amounts of components in Table 1 are based on "mass %" of the active ingredient.
[0346] [Table 1]
[0347] [evaluation] (exterior) The appearance of each of the compositions according to Example 1 and Comparative Examples 1 to 3 was visually observed. The results of the visual observation were classified as follows. Good: Appearance was transparent or translucent Precipitation: The appearance was translucent, but precipitate was observed. Poor: Cloudy appearance
[0348] The results are shown in Table 1.
[0349] The compositions according to Example 1 and Comparative Examples 1 and 2 were transparent or translucent.
[0350] The composition according to Comparative Example 3 was cloudy.
[0351] (Solubility) The solubility of the ceramide (2-oleamido-1,3-octadecanediol) was visually observed in each of the compositions according to Example 1 and Comparative Examples 1 to 3. The results of the visual observation were classified as follows. Good: Ceramide was solubilized Poor: ceramide was not solubilized
[0352] The results are shown in Table 1.
[0353] Ceramide was solubilized in the compositions according to Example 1 and Comparative Example 2, but ceramide was not solubilized in the compositions according to Comparative Examples 1 and 3.
[0354] (particle size) Using a particle size analyzer (dynamic light scattering, ELSZ2000, Otsuka), the size of the particles in the compositions according to Example 1 and Comparative Examples 1-3 was determined at room temperature (25° C.).
[0355] The results are shown in Table 1.
[0356] The particle size of the particles in the composition according to Example 1 was small and nano-sized.
[0357] The particle size of the particles in the compositions according to Comparative Examples 2 and 3 was not small.
[0358] For the composition according to Comparative Example 1, the particle size could not be determined.
[0359] (Turbidity) The turbidity of each of the compositions according to Example 1 and Comparative Examples 1 to 3 was measured at room temperature (25° C.) using a turbidity meter (2100Q Portable, HACH Company).
[0360] The results are shown as "NTU" in Table 1. The lower the NTU value, the more transparent the composition.
[0361] The turbidity of the composition according to Comparative Example 3 was excessively high.
[0362] (Examples 2 to 12) [Preparation] Each of the compositions according to Examples 2-12 was prepared by mixing the ingredients shown in Table 2. All numerical values for the amounts of ingredients in Tables 2 and 3 are based on "mass %" of the active ingredient.
[0363] [Table 2]
[0364] [Table 3A]
[0365] [Table 3B]
[0366] [evaluation] (exterior) The appearance of each of the compositions according to Examples 2 to 12 was visually observed. The results of the visual observation were classified as follows. Good: Appearance was transparent or translucent Precipitation: The appearance was translucent, but precipitate was observed. Poor: Cloudy appearance
[0367] The results are shown in Tables 2 and 3.
[0368] The compositions according to Examples 2 to 12 were transparent or translucent.
[0369] (Solubility) The solubility of the ceramide (2-oleamido-1,3-octadecanediol) in each of the compositions according to Examples 2 to 5 was visually observed. The solubility of each of the various cosmetic active ingredients (d) in each of the compositions according to Examples 6 to 12 was also visually observed. The results of the visual observation were classified as follows: Good: Ceramide or cosmetic active ingredient is solubilized Poor: Ceramide or cosmetic active ingredient was not solubilized
[0370] The results are shown in Tables 2 and 3.
[0371] The ceramide or cosmetic active ingredient was solubilized in the compositions according to Examples 2-12.
[0372] (particle size) The size of the particles in the compositions according to Examples 2-12 was determined at room temperature (25° C.) using a particle size analyzer (Dynamic Light Scattering, ELSZ2000, Otsuka).
[0373] The results are shown in Tables 2 and 3.
[0374] The particle size of the particles in the compositions according to Examples 2 to 12 was small and was in the nano-size.
[0375] (Turbidity) The turbidity of each of the compositions according to Examples 2 to 12 was measured at room temperature (25° C.) by using a turbidity meter (2100Q Portable, Hach Company).
[0376] The results are shown as "NTU" in Tables 2 and 3. The lower the NTU value, the more transparent the composition.
[0377] Moreover, the compositions according to the present invention contain ingredients that are environmentally compatible.
Claims
1. A composition, a cosmetic composition, preferably a cosmetic composition for keratin substances, more preferably a skin cosmetic composition, (a) at least one cationic polymer, (b) at least one anionic polymer, and (c) at least one fatty acid A composition containing the following:
2. The composition according to claim 1, further comprising (d) at least one skincare active ingredient, preferably having a logP of -1 or higher, more preferably 1 or higher, and even more preferably 2 or higher.
3. The total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skincare active ingredient is less than 1.5% by mass, preferably less than 1.0% by mass, and more preferably less than 0.5% by mass, relative to the total mass of the composition. (a) The mass ratio of the amount of cationic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skincare active ingredients is less than 0.7, preferably less than 0.5, more preferably less than 0.
3. (b) The mass ratio of the amount of anionic polymer to the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skincare active ingredients is less than 0.9, preferably less than 0.8, more preferably less than 0.7, and The composition according to claim 1, wherein the mass ratio of (d) the amount of the skincare active ingredient to the total amount of (a) the cationic polymer, (b) the anionic polymer, (c) the fatty acid and (d) the skincare active ingredient is less than 0.16, preferably less than 0.12, and more preferably less than 0.
08.
4. The composition according to claim 1, wherein (a) a cationic polymer is hydrophobized by (c) a fatty acid.
5. (a) The composition according to 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)polylysine and chitosan, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof.
6. (a) The composition according to claim 1, wherein the molecular weight of the cationic polymer is less than 20,000, preferably less than 15,000, and more preferably less than 10,000.
7. The composition according to claim 1, wherein the amount of (a) cationic polymer in the composition is 0.001% to 15% by mass, preferably 0.005% to 10% by mass, and more preferably 0.01% to 5% by mass, based on the total mass of the composition.
8. (b) The composition according to claim 1, wherein the anionic polymer is selected from the group consisting of polysaccharides, such as carrageenan, alginic acid, hyaluronic acid, and cellulose polymers, anionic (co)polyamino acids, such as (co)polyglutamic acid, (co)poly(meth)acrylic acid, (co)polyamic acid, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acid, polyfumaric acid, maleic acid (co)polymer, and salts thereof.
9. The composition according to claim 1, wherein the amount of (b) anionic polymer in the composition is 0.001% to 15% by mass, preferably 0.005% to 10% by mass, and more preferably 0.01% to 5% by mass, based on the total mass of the composition.
10. (c) Fatty acids, C 4 ~C 26 Preferably C 6 ~C 24 , more C 8 ~C 22 The composition according to claim 1, selected from saturated and unsaturated linear or branched fatty acids.
11. The composition according to claim 1, wherein the amount of (c) fatty acid in the composition is 0.001% to 10% by mass, preferably 0.005% to 5% by mass, and more preferably 0.01% to 1% by mass, based on the total mass of the composition.
12. The composition according to claim 2, wherein the amount of (d) skincare active ingredient in the composition is 0.001% to 10% by mass, preferably 0.003% to 5% by mass, and more preferably 0.005% to 1% by mass, based on the total mass of the composition.
13. The composition according to claim 1, comprising at least one particle having a particle size of less than 1,000 nm, preferably less than 500 nm, and more preferably less than 300 nm.
14. The composition according to claim 1, which does not contain a surfactant having at least one polyoxyethylene unit, or contains a surfactant having at least one polyoxyethylene unit in an amount of less than 1% by mass, preferably less than 0.1% by mass, and more preferably less than 0.01% by mass, based on the total mass of the composition.
15. A cosmetic method for keratinous substances in the skin, etc. A step of applying the composition according to any one of claims 1 to 14 to a keratin substance, The process involves drying the composition to form a cosmetic film on the keratin material. Methods that include...