COMPOSITION COMPRISING CATIONIC AND ANIONIC POLYMERS
A composition of cationic and anionic polymers with fatty acids forms transparent, environmentally friendly particles to solubilize active skincare ingredients, addressing the need for sustainable cosmetic formulations.
Patent Information
- Application Number
- FR2023005130
- Authority / Receiving Office
- FR · FR
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2023-05-24
- Publication Date
- 2026-02-20
- Estimated Expiration
- 2043-05-24
AI Technical Summary
There is a need for transparent or translucent cosmetic compositions that can solubilize active skincare ingredients while incorporating environmentally friendly ingredients, particularly those derived from renewable materials, and minimize the use of petrochemical compounds.
A composition comprising cationic and anionic polymers, along with fatty acids, is formulated to solubilize active skincare ingredients, forming particles with a hydrophobic interior that are environmentally friendly and transparent or translucent, using renewable materials and minimizing surfactants with polyoxyethylene motifs.
The composition effectively solubilizes active skincare ingredients, enhances skin penetration, and reduces environmental impact by using biodegradable materials, while maintaining transparency and minimizing irritation.
Abstract
Description
Title of the invention: COMPOSITION COMPRISING CATIONIC AND ANIONIC POLYMERS Technical field
[0001] The present invention relates to a composition including anionic and cationic polymers, as well as a cosmetic process using the composition. STATE OF THE ART
[0002] The formulation of environmentally friendly cosmetic products, which are designed and developed taking environmental issues into account, is becoming a major objective in an effort to meet global challenges.
[0003] It is therefore essential to offer more sustainable compositions, preparation processes and ingredients to address these environmental concerns.
[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 and, more particularly, materials of plant origin while reducing the use of compounds of petrochemical origin.
[0005] As is widely known, certain cosmetic and / or dermatological compositions, and indeed all other compositions, are present in an oil-in-water (O / W) or water-in-oil (W / O) emulsion form, particularly for the preparation of cosmetic products such as lotions, creams, toners, serums, or eau de toilette. In particular, a fine emulsion such as a nano- or micro-O / W emulsion is especially desirable in cosmetic products because of its transparent or translucent appearance. DISCLOSURE OF THE INVENTION
[0006] There is a need for a transparent or translucent composition that can solubilize an active skincare ingredient in the composition, while including one or more environmentally friendly ingredients.
[0007] Thus, a first objective of the present invention is to propose a composition which can solubilize an active skin care ingredient in the composition, and can be transparent or translucent.
[0008] Furthermore, a second objective of the present invention is to propose a composition which can include at least one environmentally friendly ingredient.
[0009] The above objectives of the present invention can be achieved by a composition, preferably a cosmetic composition, and more preferably a cosmetic composition for the skin, comprising a. at least one cationic polymer; b. at least one anionic polymer and c. at least one fatty acid.
[0010] The composition according to the present invention may further comprise (d) at least one active skin care ingredient, preferably with a logP of -1 or more, more preferably of 1 or more, and even more preferably of 2 or more.
[0011] The composition according to the present invention can satisfy the following conditions:
[0012] the total quantity of (a) cationic polymer, (b) anionic polymer, (c) acid fatty and of (d) skin care active ingredient is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, relative to the total weight of the composition;
[0013] the weight ratio between the quantity of (a) cationic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is less than 0.7, preferably less than 0.5, and more preferably less than 0.3;
[0014] the weight ratio between the quantity of (b) anionic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7; and
[0015] the weight ratio between the quantity of (d) skin care active ingredient and the total quantity 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.
[0016] The (a) cationic polymer can be hydrophobicized by the (c) fatty acid.
[0017] The (a) cationic polymer can be chosen from the group consisting of cyclo alkyldiallylamine polymers and dialkyldiallylammonium cyclopolymers such as (co)diallydialkylammonium polychloride, (co)polyamines such as (co)polylysines and chitosans, (co)cationic amino acids such as collagen, cationic cellulose polymers and salts thereof.
[0018] The (a) cationic polymer may have a molecular weight less than 20,000, preferably less than 15,000 and more preferably less than 10,000.
[0019] The quantity of the (a) cationic polymer(s) in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
[0020] The (b) anionic polymer can be selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulosic polymers, anionic (co)polyamino acids such as (co)glutamic (co)polyacids, (co)poly(meth)acrylic (co)polyacids, (co)polyamic (co)sulfonate of (co)polystyrene, (co)poly(vinyl)sulfates, dextran sulfate, chondroitin sulfate, (co)polymaleic (co)polyacids, (co)fumaric (co)polymers of maleic acid and salts thereof.
[0021] The quantity of the (b) anionic polymer(s) in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
[0022] The (c) fatty acid can be chosen from C4-C26 fatty acids, preferably C6-C24, more preferably C8-C22 saturated and unsaturated, linear or branched.
[0023] The quantity of the (c) fatty acid(s) in the composition according to the present invention can be from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, and more preferably from 0.01% to 1% by weight, relative to the total weight of the composition.
[0024] The quantity of the (d) active skin care ingredient(s) in the composition according to the present invention may be from 0.001% to 10% by weight, preferably from 0.003% to 5% by weight, and more preferably from 0.005% to 1% by weight, relative to the total weight of the composition.
[0025] Preferably, the composition according to the present invention comprises (e) water.
[0026] The quantity of (e) water in the composition according to the present invention can be from 50% to 99% by weight, preferably from 55% to 98% by weight and, more preferably, from 60% to 97% by weight, relative to the total weight of the composition.
[0027] The composition according to the present invention may include at least one particle with a particle size less than 1000 nm, preferably less than 500 nm, and more preferably less than 300 nm.
[0028] The composition according to the present invention may include no surfactant having at least one polyoxyethylene motif or includes a surfactant having at least one polyoxyethylene motif in an amount of less than 1% by weight, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight, relative to the total weight of the composition.
[0029] In a preferred embodiment, the composition according to the present invention may include
[0030] (a) at least one cationic polymer selected from chitosans;
[0031] (b) at least one anionic polymer selected from polysaccharides such as car- raghénane;
[0032] (c) at least one fatty acid;
[0033] (d) at least one active skincare ingredient selected from the group consisting of 2-N-oleoylaminooctadecane-l,3-diol, tocopherol, retinol, stearyl glycyrrhetinate, ascorbic acid, ascorbyl tetraisopalmitate, 2-N-stearoylaminooctadecane-l,3,4-triol, capryloyl salicylic acid and a mixture thereof; and
[0034] (e) water,
[0035] in which
[0036] the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, relative to the total weight of the composition;
[0037] the weight ratio between the quantity of (a) cationic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is less than 0.7, preferably less than 0.5, and more preferably less than 0.3;
[0038] the weight ratio between the quantity of (b) anionic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7; and
[0039] the weight ratio between the quantity of (d) skin care active ingredient and the total quantity 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.
[0040] The present invention also relates to a cosmetic process for a keratinous substance such as skin, comprising
[0041] the application to the keratinous substance of the composition according to the present invention; and
[0042] drying the composition to form a cosmetic film on the keratinous substance. Best embodiment of the invention
[0043] After careful research, the inventors discovered that it is possible to propose a composition that can solubilize an active skincare ingredient in the composition, can be transparent or translucent, and can include at least one environmentally friendly ingredient.
[0044] Thus, the composition according to the present invention comprises:
[0045] (a) at least one cationic polymer;
[0046] (b) at least one anionic polymer and
[0047] (c) at least one fatty acid.
[0048] The composition according to the present invention can solubilize (d) at least one active skincare ingredient in the composition, and can be transparent or translucent.
[0049] The (a) cationic polymer can form a complex with the (c) fatty acid through ionic interaction between the amino groups of the (a) cationic polymer and the carboxy groups of the (c) fatty acid. The (a) cationic polymer can be hydrophobicated by the (c) fatty acid. The above complex can enhance the solubility, where applicable, of the (d) skincare active ingredient, particularly a lipophilic skincare active ingredient.
[0050] The (b) anionic polymer can also be included in the complex.
[0051] The ingredients (a) to (c) in the composition according to the present invention can form a particle. The particle can be hydrophobicated by the fatty acid (c).
[0052] Thus, the above particle can be formed by the (a) cationic polymer, the (b) anionic polymer and the (c) fatty acid, and can have a hydrophobic interior space in which the (d) active skin care ingredient can be included.
[0053] The size of the above particle is small and can be at the nanometer level, i.e. less than 1000 nm. Thus, the composition according to the present invention can be transparent or translucent.
[0054] Furthermore, given that the particle size is small, the penetration of the (d) active skincare ingredient, if any, into the skin, particularly into the stratum corneum, can be improved.
[0055] Furthermore, ingredients (a) to (c) can be derived from renewable materials such as plants and / or biodegradable materials. Thus, by selecting ingredients (a) to (c) from these renewable materials, they can be environmentally friendly. Therefore, the composition according to the present invention can include an environmentally friendly ingredient.
[0056] If the composition according to the present invention does not include any surfactant having at least one polyoxyethylene unit or a small amount of such surfactant(s), the composition according to the present invention may be less irritating. Also, since most of these surfactants are not biodegradable, the composition according to the present invention may be more environmentally friendly.
[0057] The composition according to the present invention will be explained in more detail below. [Composition]
[0058] (Cationic polymer)
[0059] The composition according to the present invention comprises (a) at least one cationic polymer. Only one type of cationic polymer may be used, but two or more different types of cationic polymers may be used in combination.
[0060] A cationic polymer has a positive charge density. The charge density of (a) the cationic polymer can be from 0.01 meq / g to 20 meq / g, preferably from 0.05 to 15 meq / g and, more preferably, from 0.1 to 10 meq / g.
[0061] It may be preferable that the molecular weight of the (a) cationic polymer be 1000 or more, preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more.
[0062] Unless otherwise defined in the descriptions, "molecular weight" means an average molecular weight by weight.
[0063] The (a) cationic polymer may have at least one positively chargeable and / or positively charged fraction selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group. The term "amino group" (main) here refers to a -NH2 group.
[0064] The (a) cationic polymer can be a homopolymer or a copolymer. The term "copolymer" is intended to refer to both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.
[0065] The (a) cationic polymer may be chosen from natural and synthetic cationic polymers, and preferably from natural cationic polymers. Non-limiting examples of cationic polymers are as follows.
[0066] (1) Homopolymers and copolymers derived from acrylic esters and amides or me- thacryliques and including at least one motif chosen from the motifs of the following formulas: O 0 W § IX AA TO i! ---Rs Rf' ''R; | R;' ' Rv Rs R; -------Q------. 0^0 NH X' HAS R$--R'—R§ RS
[0067] in which:
[0068] Ri and R2, which may be identical or different, are chosen from hydrogen and alkyl groups comprising 1 to 6 carbon atoms, for example, methyl and ethyl groups;
[0069] R3, which may be identical or different, is chosen from hydrogen and CH3;
[0070] the symbols A, which may be identical or different, are chosen from linear or branched alkyl groups comprising from 1 to 6 carbon atoms, for example from 2 to 3 carbon atoms and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;
[0071] R4, R5 and R6, which may be identical or different, are chosen from groups alkyl groups comprising from 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment, alkyl groups comprising from 1 to 6 carbon atoms; and
[0072] X is an anion derived from an inorganic or organic acid, such as methosulfate anions and halides, for example chloride and bromide.
[0073] The copolymers of family (1) may also comprise at least one motif derived from comonomers which may be selected from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen atom by lower alkyl groups in C1-C4, groups derivatives of acrylic or methacrylic acids and esters thereof, vinyl-lactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.
[0074] Examples of copolymers of family (1) include, but are not limited to:
[0075] acrylamide and dimethylaminoethyl methacrylate copolymers quaternized with dimethyl sulfate or with a dimethyl halide,
[0076] acrylamide and methacryloyloxyethyltrimethylammonium chloride copolymers described, for example, in European patent application no. 0 080 976,
[0077] acrylamide and methacryloyloxyethyltrimethylammonium methosulfate copolymers, quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers described, for example, in French patents no. 2 077 143 and 2 393 573,
[0078] dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers,
[0079] vinylpyrrolidone / methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymers and
[0080] crosslinked polymers of methacryloyloxy(Ci-C4)alkyltri(Ci-C4)alkylammonium salts such as polymers obtained by homopolymerization of quaternized dimethylaminoethyl methacrylate with methyl chloride, or by copolymerization of acrylamide with quaternized dimethylaminoethyl methacrylate with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with a compound containing an olefinic unsaturation, in particular methylenebisacrylamide.
[0081] (2) Cationic cellulose polymers such as cellulose ether derivatives comprising one or more quaternary ammonium groups described, for example, in French patent no. 1,492,597, such as the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammonium compounds of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.
[0082] It is preferable that the cationic cellulose polymer has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group and more preferably, a quaternary trimethylammonium group.
[0083] The quaternary ammonium group may be present in a quaternary ammonium group which can be represented by the following chemical formula (I): OH
[0084] in which
[0085] each of Ri and R2 designates an alkyl group in Ci.3, preferably a methyl or ethyl group, and more preferably a methyl group,
[0086] R3 designates an alkyl group at C, 24, preferably a methyl or ethyl group, and more preferably a methyl group,
[0087] X- denotes an anion, preferably a halide, and more preferably a chloride,
[0088] n denotes an integer from 0 to 30, preferably from 0 to 10 and more preferably 0, and
[0089] R4 designates an alkylene group at C1.4, preferably an ethylene or propylene group.
[0090] The leftmost ether bond (-O-) in the chemical formula (I) above can attach to the sugar ring of the polysaccharide.
[0091] It is preferable that the group containing the quaternary ammonium group be -O-CH2-CH(OH)-CH2-N+(CH3)3.
[0092] (3) Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and described, for example, in US Patent No. 4,131,576, such as hydroxy-alkylcelluloses, for example, hydroxymethyl-, hydroxyethyl- and hydroxypropyl-celluloses grafted, for example, with a salt selected from the salts of methacryloyl-ethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium.
[0093] Commercial products corresponding to these polymers include, for example, products marketed under the names "Celquat® L 200" and "Celquat® H 100" by the company National Starch.
[0094] (4) Non-cellulosic cationic polysaccharides described in US patents Numbers 3,589,578 and 4,031,307, such as guar gums containing cationic tri-kylammonium groups, cationic hyaluronic acid, and hydroxypropyltrimonium dextran chloride. Guar gums modified with a salt, for example, 2,3-epoxypropyltrimethylammonium chloride (hydroxypropyltrimonium guar chloride), may also be used.
[0095] These products are sold, for example, under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162 by the company MEYHALL.
[0096] (5) Polymers comprising piperazinyl motifs and alkylene or hy- groups Divalent droxyalkylene polymers comprising straight or branched chains, optionally interrupted with at least one entity selected from oxygen, sulfur, nitrogen, aromatic rings, and heterocyclic rings, as well as the oxidation and / or quaternization products of these polymers. These polymers are described, for example, in French patents no. 2,162,025 and 2,280,361.
[0097] (6) Water-soluble polyaminoamides prepared, for example, by polycondensation of an acidic compound with a polyamine; these polyaminoamides being optionally crosslinked with an entity selected from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bisunsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacyidiamines; bisalkyl halides; oligomers resulting from the reaction of a difunctional compound that is reactive with an entity selected from bishalohydrins; bisazetidiniums, bishaloacyldiamines, bisalkyl halides; epihalohydrins; diepoxides and bisunsaturated derivatives; the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mole per amine group of the polyamino amide; these polyamino amides being optionally alkylated or, if they comprise at least one tertiary amine function, they may be quaternized.These polymers are described, for example, in French patents No. 2,252,840 and 2,368,508.
[0098] (7) Polyaminoamide derivatives resulting from the condensation of polyamines of poly- Alkylene with polycarboxylic acids, followed by alkylation with difunctional agents, for example, adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, and the alkylene group comprises 1 to 4 carbon atoms, such as an ethylene group. These polymers are described, for example, in French patent No. 1,583,363. In at least one embodiment, these derivatives may be selected from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.
[0099] (8) Polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid selected from diglycolic acid and saturated dicarboxylic aliphatic acids comprising 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid may range from 0.8:1 to 1.4:1; the resulting polyaminoamide is reacted with epichlorohydrin in a molar ratio between the epichlorohydrin and the secondary amine group of the polyaminoamide ranging from 0.5:1 to 1.8:1. These polymers are described, for example, in US patent Nos. 3,227,615 and 2,961,347.
[0100] (9) Alkyldiallylamine cyclopolymers and dialkyldiallyl- cyclopolymers ammonium, such as homopolymers and copolymers comprising, as the main constituent of the chain, at least one motif from among the motifs of formulas (la) and (Ib): <Ia) -(CH^t—0Rî2 XÇ(R^) —CHr-- H^CX ...,.^2 XN*'"' y~ / \ \ Rw Ru (Ib) KM — CRu xç(?W ■—GHg— H?OX. ,CHg ' \r<
[0101] in which:
[0102] k and t, which can be identical or different, are equal to 0 or 1, the sum k+t being equal to 1;
[0103] Rn is chosen from among the hydrogen and methyl groups;
[0104] Rio and Rn, which may be identical or different, are selected from alkyl groups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group comprises, for example, from 1 to 5 carbon atoms, and lower (Ci-C4)alkylamido groups, or R10 and Rn may form, with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl and morpholinyl; and
[0105] Y1 is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate. These polymers are described, for example, in French patent no. 2,080,759 and in its certificate of addition 2,190,406.
[0106] In one embodiment, Rio and Rn, which may be identical or different, are chosen from alkyl groups comprising 1 to 4 carbon atoms.
[0107] Among these polymers, we can mention, but not be limited to, (co)polydiallyldialkyl ammonium chloride such as the dimethylidiethylammonium chloride homopolymer sold under the name "MERQUAT® 100" by the company CALGON (and its low weight average molecular mass homologues) and the copolymers of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".
[0108] Quaternary diammonium polymers comprising at least one repeating motif of formula (II): Rn Rw (ll) .......N"......Ai.....N*.......B:......... IX | X Rw
[0109] in which:
[0110] Rn, Ru, Rb and Ri6, which may be identical or different, are selected from aliphatic, alicyclic and arylaliphatic groups comprising from 1 to 20 carbon atoms and lower hydroxyalkyl aliphatic groups, or Rn, R14, Ri5 and R16, together or separately, with the nitrogen atoms to which they are attached, heterocycles alternatively comprising a second heteroatom other than nitrogen, or R13, R14, R15, and R16, which may be identical or different, are selected from linear or branched Ci-C6 alkyl groups substituted by at least one group selected from alkyl groups, ester groups, acyl groups, amide groups, -CO-O-Rp-E groups and -CO-NH-Rp-E groups, where R17 is an alkylene group and E is an ammonium group quaternary;
[0111] Ai and Bb, which may be identical or different, are selected from polymethylene groups comprising from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may include, bonded or intercalated in the main chain, at least one entity selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups and ester groups, and
[0112] X designates an anion derived from an inorganic or organic acid;
[0113] Ai, Rn and Rb can form, in conjugation with the two nitrogen atoms to which they are attached, a piperazine ring;
[0114] If Ai is chosen from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, Bi can be chosen from:
[0115] -(CH2)n-CO-E'-OC-(CH2)n-
[0116] in which E' is chosen from:
[0117] a) glycolic residues of formula -OZO-, in which Z is selected from linear or branched hydrocarbon-based groups and groups of the following formulas:
[0118] -(CH2-CH2-O)X-CH2-CH2-
[0119] -[CH2-CH(CH3)-O]y-CH2-CH(CH3)-
[0120] in which x and y, which may be identical or different, are chosen from integers from 1 to 4, which represent a defined and unique degree of polymerization, and numbers from 1 to 4, which represent an average degree of polymerization;
[0121] b) a bis-secondary diamine residue such as piperazine derivatives;
[0122] c) bis-primary diamine residues of formula -NH-Y-NH-, wherein Y is selected from linear or branched hydrocarbon-based groups and the divalent group -CH2-CH2-SS-CH2-CH2-. and
[0123] d) ureylene groups of formula -NH-CO-NH-.
[0124] In at least one embodiment, X is an anion such as chloride or bromide.
[0125] Polymers of this type are described, for example, in French patents Nos. 2,320,330; 2,270,846; 2,316,271; 2,336,434; and 2,413,907 and in US patents Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261,002; 2,271,378; 3,874,870; 4,001,432; 3,929,990; 3,966,904; 4,005,193; 4,025,617; 4,025,627; 4,025,653; 4,026,945 and 4,027,020.
[0126] Non-limiting examples of these polymers include those comprising at least one repeating motif of formula (III): Rts Ris (ni)
[0127] in which
[0128] Rn, Ru, Rb and R[6, which may be identical or different, are selected from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbon atoms, n and p, which may be identical or different, are integers from 2 to 20, and X is an anion derived from an inorganic or organic acid.
[0129] (1 l) Polyquaterary ammonium polymers comprising formula motifs (IV):
[0130] in which:
[0131] Ri8, Rw, R2o and R2i, which may be identical or different, are chosen from hydrogen, methyl, ethyl, propyl, [3-hydroxyethyl, [3-hydroxypropyl, -CH groups 2CH2(OCH2CH2)pOH, in which p is chosen from integers from 0 to 6, provided that R[8, R19, R20 and R2[ are not simultaneously hydrogen,
[0132] r and s, which may be identical or different, are chosen from integers from 1 to 6,
[0133] q is chosen from integers ranging from 0 to 34,
[0134] X is an anion, such as a halide, and
[0135] A is chosen from dihalide radicals and -CH2-CH2-O-CH2-CH2-.
[0136] These compounds are described, for example, in European patent application No. 0 122 324.
[0137] (12)Quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0138] Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers comprising motifs selected from vinylpyridine and vinylpyridinium motifs, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.
[0139] According to one embodiment of the present invention, the (a) cationic polymer is selected from cellulose ether derivatives comprising quaternary ammonium groups, such as the products sold under the name "JR 400" by UNION CARBIDE CORPORATION, cationic cyclopolymers, for example, dimethyldiallylammonium chloride homopolymers and copolymers sold under the names MERQUAT® 100, MERQUAT® 550, and MERQUAT® S by CALGON, guar gums modified with a 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0140] (13)Polyamines
[0141] As a (a) cationic polymer, it is also possible to use (co)polyamines, which may be homopolymers or copolymers, with a plurality of amino groups. The amino group may be a primary, secondary, tertiary, or quaternary amino group. The amino group may be present in the polymer backbone or as a pendant group, as appropriate, of the (co)polyamines.
[0142] Examples of (co)polyamines include chitosans, (co)polyallylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polymethacrylates of dimethylaminoethylene, (co)polyvinylpyridines such as (co)poly-l-methyl-2-vinylpyridines, (co)polyimines such as (co)polyethyleneimines, (co)polypyridines such as (co)poly(quaternary pyridines), (co)polybiguanides such as (co)polyaminopropyl biguanides, (co)polylysines, (co)polyornithines, (co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinylacetals and their salts.
[0143] As with (co)polyamines, it may be preferable to use (co)polylysines. 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, typically used as a natural preservative in food products. Polylysine is a polyelectrolyte that is soluble in polar solvents such as water, propylene glycol, and glycerol. Polylysine is commercially available in various forms, such as poly-D-lysine and poly-L-lysine. Poly-L-lysine is preferable. Polylysine can be in the form of a salt and / or a solution.
[0144] (14)Cationic polyamino acids
[0145] As (a) a cationic polymer, it may be possible to use cationic polyamino acids, which may be homopolymers or cationic copolymers, with a plurality of amino groups and carboxyl groups. The amino group may be a primary, secondary, tertiary, or quaternary amino group. The amino group may be present in a polymer backbone or a pendant group, as appropriate, of the cationic polyamino acids. The carboxyl group may be present in a pendant group, as appropriate, of the cationic polyamino acids.
[0146] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, hydroxypropyl stear-dimonium hydrolyzed wheat protein, hydroxypropyl cocodimonium hydrolyzed wheat protein, hydroxypropyl trimonium hydrolyzed conchiolin protein, hydroxypropyl stear-dimonium hydrolyzed soy protein, hydroxypropyl trimonium hydrolyzed soy protein, hydroxypropyl cocodimonium hydrolyzed soy protein, and the like.
[0147] The following descriptions relate to preferred embodiments of the cationic polymer.
[0148] It is preferable that the (a) cationic polymer be chosen from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)diallyldialkyl ammonium polychloride, (co)polyamines such as (co)polylysines, (co)polyamino acids cationic such as collagen, cationic cellulose polymers and salts thereof.
[0149] It is more preferable that the (a) cationic polymer be chosen from among the chitosans.
[0150] Preferably the chitosan should have a molecular weight (Da) of 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 can be a low molecular weight chitosan.
[0151] The molecular weight (Da) of chitosan may be greater than 1000, preferably greater than 1500, and more preferably greater than 2000.
[0152] Thus, the molecular weight (Da) of chitosan can be greater than 1000 and less than 20,000, preferably greater than 1500 and less than 15,000, and more preferably greater than 2000 and less than 10,000.
[0153] Unless otherwise defined in the descriptions, "molecular weight" means an average molecular weight by weight. The molecular weight may be measured or determined by gel permeation chromatography, for example, in accordance with ASTM D5296-19.
[0154] Chitosan is very rare in nature. It is only reported in the exoskeletons of certain insects such as termite queens and in the cell walls of a particular class of fungi, the zygomycetes.
[0155] Chitosan can be obtained by deacetylation of chitin. Chitin is a polysaccharide composed of several N-acetyl-D-glucosamine motifs linked together by a [3(1,4) type bond.
[0156] The ideal chemical structure of chitosan is a sequence of [3-D-glucosamine] monomers linked by a glycosidic bond (1—>4).
[0157] The "chitosan" according to the present invention refers to any copolymer formed from constituent N-acetyl-D-glucosamine and D-glucosamine motifs, 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 motifs (deacetylated motifs) and N-acetyl-D-glucosamine motifs (acetylated motifs) linked together by [3(1,4)] type bonds and is a Poly(N-acetyl-D-glucosamine)-poly(D-glucosamine) polymer.
[0158] More preferably, the degree of acetylation of chitosan is less than or equal to 40%, preferably less than or equal to 35%, preferably less than or equal to 25%, preferably less than or equal to 15%, and preferably less than or equal to 10%.
[0159] The degree of acetylation is the percentage of acetylated motifs relative to the total number of motifs; it can be determined by Fourier transform infrared spectroscopy (FTIR) or by titration with a strong base.
[0160] The chitosan of the present invention is preferably a polysaccharide prepared from a fungal origin. In particular, it is extracted and purified from safe and abundant foods or from biotechnological fungal sources such as Agaricus bisporus or Aspergillus niger.
[0161] The chitosan of the present invention is preferably derived from the mycelium of an Ascomycete fungus, and in particular Aspergillus niger, and / or from a Basidiomycete fungus, and in particular Lentinula edodes (shiitake) and / or Agaricus bisporus. Preferably, the fungus is Aspergillus niger.
[0162] Chitosan may be of genetically modified organism (GMO) origin, but preferably of non-GMO origin.
[0163] The chitosan according to the present invention is native, that is to say, it is not modified. In particular, it contains no chemical modification.
[0164] One method for preparing chitosan is that described in WO03 / 068824.
[0165] Preferably, the chitosan used in the present invention is in powder form. It is marketed by Glentham Life Science under the name GU3511.
[0166] The amount of the (a) cationic polymer(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.
[0167] The quantity of the (a) cationic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
[0168] The quantity of the (a) cationic polymer(s) in the composition according to the present invention can be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.
[0169] (Anionic polymer)
[0170] The composition according to the present invention comprises (b) at least one anionic polymer. Only one type of anionic polymer may be used, or two or more different types of anionic polymers may be used in combination.
[0171] An anionic polymer has a negative charge density. The charge density of (b) anionic polymer can be from 0.1 meq / g to 20 meq / g, preferably from 1 meq / g to 15 meq / g, and more preferably from 4 meq / g to 10 meq / g if (b) anionic polymer is a synthetic anionic polymer, and the average degree of substitution of (b) anionic polymer can be from 0.1 to 3.0, preferably from 0.2 to 2.7, and more preferably from 0.3 to 2.5 if (b) anionic polymer is a natural anionic polymer.
[0172] In one embodiment, the (d) anionic polymer may have a charge density of 2.04 mmol / g or more, preferably of 3.00 mmol / g or more, and more preferably of 4.00 mmol / g or more.
[0173] It may be preferable that the molecular weight of the (b) anionic polymer be 1000 or more, preferably 2000 or more, even more preferably 5000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000, and even more preferably 1,000,000 or more.
[0174] Unless otherwise defined in the descriptions, "molecular weight" may refer to an average molecular weight by weight.
[0175] The (b) anionic polymer may have at least one negatively chargeable and / or negatively charged fraction selected from the group consisting of a sulfuric group, a sulfate group, a sulfonic group, a sulfonate group, a phosphoric group, a phosphate group, a phosphonic group, a phosphonate group, a carboxylic group and a carboxylate group.
[0176] The (b) anionic polymer may be a homopolymer or a copolymer. The term "copolymer" includes both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.
[0177] The (b) anionic polymer can be chosen from natural and synthetic anionic polymers, and preferably from natural anionic polymers.
[0178] The (b) anionic polymer may comprise at least one hydrophobic chain.
[0179] The (b) anionic polymer, which may comprise at least one hydrophobic chain, can be obtained by copolymerization of a monomer (a) selected from carboxylic acids comprising an α,[3-ethylenic unsaturation (monomer α') and a 2-acrylamido-2-methylpropanesulfonic acid (monomer α") with a surface-inactive monomer (b) comprising an ethylenic unsaturation other than (α) and / or a monomer (c) comprising an ethylenic unsaturation resulting from the reaction of an acrylic monomer comprising an α,[3-monoethylenic unsaturation or of an isocyanate monomer comprising a monoethylenic unsaturation with a nonionic amphiphilic monohydric component or with a primary or secondary fatty amine.
[0180] Thus, the (b) anionic polymer with at least one hydrophobic chain can be obtained by two synthetic routes: • either by copolymerization of monomers (a1) and (c), or (a1), (b) and (c), or (a") and (c), or (a"), (b) and (c), • either by modification (and in particular by esterification or amidation) of a copolymer formed from monomers (a1) or monomers (a1) and (b), or (a") and (b), by a non-ionic amphiphilic monohydric compound or a primary or secondary fatty amine.
[0181] Examples of 2-acrylamido-2-methylpropanesulfonic acid copolymers include those disclosed in the article "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10 - 3694-3704" and in applications EP-A-0 750 899 and EP-A-1 069 172.
[0182] The carboxylic acid comprising an α,[3-monoethylenic unsaturation constituting the monomer (α1) can be chosen from many acids and, in particular, acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. Preferably, it is acrylic or methacrylic acid.
[0183] The copolymer may include a (b) monomer comprising a monoethylenic unsaturation that has no surfactant properties. Preferred monomers are those that give water-insoluble polymers when homopolymerized. They may be selected, for example, from the Ci-C4 alkyl acrylates and methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, or the corresponding methacrylates. The most preferred monomers are methyl acrylate and ethyl acrylate. Other monomers that may be used are, for example, styrene, vinyltoluene, vinyl acetate, acrylonitrile, and vinylidene chloride. Non-reactive monomers are preferred, these monomers being those in which the single ethylenic group is the only reactive group under the polymerization conditions.However, monomers that include groups that react under the effect of heat, such as hydroxyethyl acrylate, may be used optionally.
[0184] Monomer (c) is obtained by reacting an acrylic monomer comprising the α,[3-monoethylenic unsaturation, such as (a), or an isocyanate monomer comprising a monoethylenic unsaturation with a nonionic amphiphilic monohydric compound or a primary or secondary fatty amine.
[0185] The nonionic amphiphilic monohydric compounds or the primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. The nonionic amphiphilic monohydric compounds are generally hydrophobic alkoxylated compounds comprising an alkylene oxide forming the hydrophilic portion of the molecule. The hydrophobic compounds are generally composed of an aliphatic alcohol or an alkylphenol, in which a carbon chain comprising at least six carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.
[0186] Preferred amphiphilic non-ionic monohydric compounds are compounds corresponding to the following formula (V):
[0187] R-(OCH2CHR')m-(OCH2CH2)n-OH (V)
[0188] wherein R is selected from alkyl or alkylene groups comprising 6 to 30 carbon atoms and alkylaryl groups having alkyl radicals comprising 8 to 30 carbon atoms, R' is selected from alkyl groups comprising 1 to 4 carbon atoms, n is an average number from approximately 1 to 150 and m is an average number from approximately 0 to 50, provided that n is at least as large as m.
[0189] Preferably, in compounds of formula (V), the R group is chosen from alkyl groups comprising 12 to 26 carbon atoms and al-kylphenyl groups in which the alkyl group is C8-Ci3; the R' group is the methyl group; m = 0 and n = 125.
[0190] Preferred primary and secondary fatty amines are composed of one or two alkyl chains comprising 6 to 30 carbon atoms.
[0191] The monomer used to form the nonionic urethane monomer (c) can be chosen from a wide variety of compounds. Any compound comprising a copolymerizable unsaturation, such as an acrylic, methacrylic, or allylic unsaturation, can be used. Monomer (c) can be obtained in particular from an isocyanate comprising a monoethylenic unsaturation, such as, in particular, α,α-dimethyl-m-isopropenylbenzyl isocyanate.
[0192] Monomer (c) may be selected, in particular, from acrylates, methacrylates or oxyethylenated fatty alcohol itaconates (1 to 50 EO) C6-C3o, such as steareth-20 methacrylate, oxyethylenated behenyl methacrylate (25 EO), oxyethylenated monocetyl itaconate (20 EO), oxyethylenated monostearyl itaconate (20 EO) or polyoxyethylenated alcohol-modified acrylate (25 EO) Ci2-C24 and from dimethyl-m-isopropenylbenzyl isocyanates of oxyethylenated fatty alcohol (1 to 50 EO) C6-C30, such, in particular, dimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenyl alcohol.
[0193] According to a specific embodiment of the present invention, the (b) anionic polymer is selected from acrylic terpolymers obtained from (a) a carboxylic acid comprising an α,[3-ethylenic unsaturation, (b) a surface-nonactive monomer comprising an ethylenic unsaturation other than (a), and (c) a nonionic urethane monomer that is the reaction product of an amphiphilic nonionic monohydric compound with an isocyanate comprising a monoethylenic unsaturation.
[0194] In particular, examples of anionic polymers comprising at least one hydrophobic chain include the acrylic acid / ethyl acrylate / alkyl acrylate terpolymer, such as the product in the form of a 30% aqueous dispersion sold under the name Acusol 823 by Rohm & Haas; the acrylates / steareth-20 methacrylate copolymer, such as the product sold under the name Aculyn 22 by Rohm & Haas; the (meth)acrylic acid / ethyl acrylate / oxyethylenated behenyl methacrylate (25 EO) terpolymer, such as the product in the form of an aqueous emulsion sold under the name Aculyn-28 by Rohm & Haas; the acrylic acid / oxyethylenated monocetyl itaconate (20 EO) copolymer, such as the product in the form of a 30% aqueous dispersion sold under the name Structure 3001 by National Starch; acrylic acid / oxyethylenated monostearyl itaconate copolymer (20°EO), such as the product under 30% aqueous dispersion form sold under the name Structure 2001 by National Starch; acrylates / acrylate modified by polyoxyethylenated alcohol copolymer (25 OE) Ci2-C24, such as the 30-32% latex copolymer sold under the name Synthalen W2000 by 3V SA; or methacrylic acid / methyl acrylate / dimethyl-meta-isopropenylbenzyl ethoxylated behenyl alcohol terpolymer, such as the product in 24% aqueous dispersion form and comprising 40 ethylene oxide groups disclosed in document EP-A-0 173 109.
[0195] The (b) anionic polymers may also be Polyester-5, such as the product sold under the name Eastman AQ™ 55S Polymer by EASTMAN CHEMICAL corresponding to a chemical formula below. HO-GAGAGAGAGAGAGAGAG-OH SOrNa+ . SO3-Na+
[0196] A: dicarboxylic acid fraction
[0197] G: glycol fraction
[0198] SO3 Na+: sodium sulfo group
[0199] OH: hydroxyl group
[0200] It may be preferable that the (b) anionic polymer be chosen from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (for example, carboxymethylcellulose and carrageenan), anionic (co)polyamino acids such as (co)glutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polyfumaric acids, (co)polymers of maleic acid and salts thereof.
[0201] The maleic acid copolymer may comprise one or more maleic acid comonomers, and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising 2 to 20 carbon atoms and styrene.
[0202] Thus, "maleic acid copolymer" means any polymer obtained by copolymerization of one or more maleic acid comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic acid comonomers being optionally partially or completely hydrolyzed. Hydrophilic polymers, namely polymers having a water solubility greater than or equal to 2 g / L, are preferred.
[0203] In an advantageous aspect of the present invention, the maleic acid copolymer may have a mole fraction of maleic acid motifs between 0.1 and 1, more preferentially between 0.4 and 0.9.
[0204] The average molar mass by weight of the maleic acid copolymer can be between 1000 and 500,000 and preferably between 1000 and 50,000.
[0205] It is preferable that the maleic acid copolymer be a styrene / maleic acid copolymer, and more preferably a styrene / maleic acid copolymer.
[0206] A 50 / 50 copolymer of styrene and maleic acid will preferably be used.
[0207] For example, styrene / maleic acid copolymer (50 / 50), in the form of 30% ammonium salt in water, sold under the reference SMA1000H® by Cray Valley, or styrene / maleic acid copolymer (50 / 50), in the form of 40% sodium salt in water, sold under the reference SMAlOOOHNa® by Cray Valley, may be used.
[0208] The use of styrene / maleic acid copolymer such as sodium styrene / maleic acid copolymer can improve the wettability of a film prepared by the composition according to the present invention.
[0209] In a preferred embodiment, the (b) anionic polymer can be selected from hyaluronic acid, its salts (e.g., sodium hyaluronate) and its derivatives.
[0210] Hyaluronic acid can be represented by the following chemical formula.
[0211] In the context of the present invention, the term "hyaluronic acid" covers in particular the basic unit of hyaluronic acid of formula:
[0212] This is the smallest fraction of hyaluronic acid comprising a di-saccharide dimer, namely D-glucuronic acid and N-acetylglucosamine.
[0213] The expression "hyaluronic acid and its derivatives" also includes, in the In the context of the present invention, the linear polymer comprising the polymeric motif described above, linked together in the chain by alternating [3(1,4) and [3(1,3)] glycosidic bonds, having a molecular weight (MW) that can vary between 380 and 13,000,000 daltons. This molecular weight depends largely on the source from which the hyaluronic acid is obtained and / or the preparation processes.
[0214] The expression "hyaluronic acid and its derivatives" also includes, in the context of the present invention, hyaluronic acid salts. Examples of salts include alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.
[0215] In its natural state, hyaluronic acid is present in pericellular gels, in the basic substance of connective tissues of vertebrate organs such as the dermis and epithelial tissues and, in particular, in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord and in the crista galli apophysis.
[0216] Thus, the expression "hyaluronic acid and its derivatives" includes all fractions or sub-motifs of hyaluronic acid having a molecular weight in particular within the molecular weight range recalled above.
[0217] In the context of the present invention, hyaluronic acid fractions that do not have inflammatory activity are preferably used.
[0218] As an illustration of the various fractions of hyaluronic acid, reference may be made to the paper "Hyaluronan fragments: an information-rich System", R. Stem et al., European Journal of Cell Biology 58 (2006) 699-715, which reviews the listed biological activities of hyaluronic acid according to its molecular weight.
[0219] According to a preferred embodiment of the present invention, the hyaluronic acid fractions suitable for the use covered by the present invention have a molecular weight between 50,000 and 5,000,000, in particular between 100,000 and 5,000,000, especially between 400,000 and 5,000,000 Da. In this case, the expression used is high molecular weight hyaluronic acid.
[0220] Alternatively, the hyaluronic acid fractions that may also be suitable for the use covered by the present invention have a molecular weight between 50,000 and 400,000 Da. In this case, the expression used is hyaluronic acid of intermediate molecular weight.
[0221] Alternatively, the hyaluronic acid fractions suitable for the use covered by the present invention have a molecular weight of less than 50,000 Da. In this case, the expression used is low molecular weight hyaluronic acid.
[0222] Finally, the expression "hyaluronic acid and its derivatives" also includes hyaluronic acid esters, in particular those in which all or part of the carboxylic groups of the acid functions are esterified with oxyethylenated alkyls or alcohols, containing from 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%.
[0223] Examples include methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. These esters were described in particular in D. Campoccia et al. “Semisynthetic resorbable materials from hyaluronan esterification”, Biomaterials 19 (1998) 2101-2127.
[0224] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.
[0225] The molecular weights indicated above are also valid for hyaluronic acid esters.
[0226] Hyaluronic acid may in particular be hyaluronic acid supplied by the company Hyactive under the trade name CPN (PM: 10 to 150 kDa), by the company Soliance under the trade name Cristalhyal (PM: 1.1 times 106), by the company Bioland under the name Nutra HA (PM: 820,000 Da), by the company Bioland under the name Nutra AF (PM: 69,000 Da), by the company Bioland under the name Oligo HA (PM: 6100 Da) or by the company Vam Farmacos Metica under the name D Factor (PM: 380 Da).
[0227] In a preferred embodiment, the (b) anionic polymer may be selected from the group consisting of carrageenan such as i-carrageenan and A-carrageenan, algin, chondroitin sulfate, pectin and a mixture thereof.
[0228] It may be more preferable for the (b) anionic polymer to be chosen from the group consisting of carrageenan, pectin and a mixture thereof.
[0229] It may be even more preferable that the (b) anionic polymer be chosen from among the carrageenans.
[0230] The quantity of the (b) anionic polymer(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.
[0231] The quantity of the (b) anionic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
[0232] The quantity of the (b) anionic polymer(s) in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, relative to the weight total composition. [Fatty acid]
[0233] The composition according to the present invention comprises (c) at least one fatty acid. If two or more fatty acids are used, they may be identical or different.
[0234] The term "fatty acid" here refers to a carboxylic acid with a long aliphatic carbon chain.
[0235] The (c) fatty acid has at least 4 carbon atoms, preferably at least 6 carbon atoms and, more preferably, at least 8 carbon atoms. The (c) fatty acid may comprise up to 26 carbon atoms, preferably up to 24 carbon atoms and, more preferably, up to 22 carbon atoms. Preferably, the (c) fatty acid is selected from the C4-C26 fatty acid, more preferably from the C6-C24 fatty acid, and even more preferably from the C8-C22 fatty acid.*
[0236] 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-C26 fatty acids, preferably C6-C24, more preferably C8-C22, saturated and unsaturated, linear or branched.
[0237] Monounsaturated fatty acids, linear or branched, or polyunsaturated fatty acids, linear or branched, may be used as unsaturated fatty acids. A carbon-carbon double bond or a carbon-carbon triple bond may be cited as the unsaturated fraction of unsaturated fatty acids, linear or branched.
[0238] Examples of saturated fatty acids include caprylic acid (C8), pelargonic acid (C9), capric acid (C10), lauric acid (C12), myristic acid (C14), pentadecanoic acid (C15), palmitic acid (C16), heptadecanoic acid (C17), stearic acid (C18), isostearic acid (C18), nonadecanoic acid (C19), arachidic acid (C20), behenic acid (C22) and lignoceric acid (C24).
[0239] Examples of unsaturated fatty acids include myristoleic acid (Ci4), palmitoleic acid (Ci6), oleic acid (Ci8), linoleic acid (Ci8), linolenic acid (Ci8), elaidic acid (Ci8), arachidonic acid (C20), eicosenoic acid (C20), erucic acid (C22) and nervonic acid (C24).
[0240] It is preferable that the (c) fatty acid be chosen from among the saturated or unsaturated fatty acids, linear or branched in C8-Ci8, and more preferably from the group consisting of caprylic acid, capric acid, oleic acid, linoleic acid, stearic acid, isostearic acid and mixtures thereof.
[0241] The (c) fatty acid may be in the form of a free acid or in the form of a salt thereof. Examples of salts of the fatty acid include an inorganic salt such as an alkali metal salt (a sodium salt, a potassium salt, or the like) and an alkali- metal salt. earthy (a magnesium salt, a calcium salt, or similar); and an organic salt such as an ammonium salt (a quaternary ammonium salt or similar) and an amine salt (a triethanolamine salt, a triethylamine salt, or similar). Only one type of fatty acid salt or a combination of different types of fatty acid salts may be used. In addition, a combination of one or more fatty acids in free acid form and one or more fatty acids in salt form may be used, in which one or more types of salts may also be used.
[0242] The quantity of the (c) fatty acid(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.
[0243] Furthermore, the quantity of the (c) fatty acid(s) in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the composition.
[0244] Accordingly, the quantity of the (c) fatty acid(s) in the composition according to the present invention can range from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, and more preferably from 0.01% to 1% by weight, relative to the total weight of the composition.
[0245] (Skin care active ingredient)
[0246] The composition according to the present invention may comprise (d) at least one skincare active ingredient. Only one type of (c) skincare active ingredient may be used, but two or more different types of (c) skincare active ingredients may be used in combination.
[0247] It is preferable that the (d) active skincare ingredient has a logP value of -1 or more, more preferably of 1 or more, and even more preferably of 2 or more.
[0248] Thus, the (d) skincare active ingredient may be hydrophilic or lipophilic, and preferably lipophilic. A lipophilic skincare active ingredient means that the partition coefficient of the lipophilic skincare active ingredient between n-butanol and water is > 1, more preferably > 10, and even more preferably > 100.
[0249] A log P value is a base-ten logarithm value of the apparent octan-l-ol / water partition coefficient. Log P values are known and are determined by a standard test that determines the concentration of the active skincare ingredient in octan-l-ol and water. Log P can be calculated (clogP) according to the method described in the article by Meylan and Howard: Atom / Fragment contribution method for estimating octanol-water partition coefficients, J. Pharm. Sci., 84: 83-92, 1995. This The value can also be calculated using numerous commercially available software packages that determine log P based on a molecule's structure. For example, the United States Environmental Protection Agency's Epiwin software can be cited.
[0250] The values can be calculated using the ACD (Advanced Chemistry Development) Solaris V4.67 software; they can also be obtained from Exploring QSAR: hydrophobia, electronic and steric constants (ACS professional reference book, 1995). There is also a website that provides estimated values (address: http: / / esc.syrres.com / interkow / kowdemo.htm).
[0251] The (d) active skin care ingredient may be in the form of a salt. Salts of the (d) active skin care ingredient include conventional non-toxic salts of said compounds, such as those formed from an acid or a base.
[0252] It is preferable that the (d) skin care active ingredient be a cosmetic skin care active ingredient and more preferably, a skin emollient or moisturizer, or an anti-aging skin ingredient such as an antioxidant or anti-wrinkle ingredient.
[0253] As (d) active skin care ingredient, ceramide compounds may be mentioned.
[0254] According to the present invention, the expression "ceramide compound" means natural or synthetic ceramides and / or glycoceramides and / or pseudo-ceramides and / or neoceramides.
[0255] 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.
[0256] Ceramide compounds that can be used according to the present invention include, and in fact preferentially correspond to, the general formula (I): n ® O C..- TS C / RT r4 r5
[0257] in which
[0258] Ri designates: • either a saturated or unsaturated, linear or branched hydrocarbon radical in the C1-C50 configuration, preferably in C5-C50, this hydrocarbon radical being able to be substituted by one or more hydroxyl groups optionally esterified by an acid R7COOH, R7 being a hydrocarbon radical optionally mono- or polyhydroxylated, saturated or unsaturated and linear or branched in Ci-C35, it is possible that the hydroxyl or hydroxyls of the radical R7 are esterified by a fatty acid in Ci_c35 optionally mono- or polyhydroxylated, saturated or unsaturated and linear or branched; • or a radical R"-(NR-CO)-R', in which R designates a hydrogen atom or a mono- or polyhydroxylated hydrocarbon radical, preferably mono- or polyhydroxylated, in Ci-C20, R' and R" are hydrocarbon radicals, whose sum of carbon atoms is between 9 and 30, R' being a divalent radical; • or a radical R8-O-CO-(CH2)P, in which R8 denotes a hydrocarbon radical in CrC2o and p is an integer ranging from 1 to 12;
[0259] R2 is selected from a hydrogen atom, a saccharide-type radical, in particular a (glycosyl)n, (galactosyl)m radical or a sulphogalactosyl radical, a sulfate or phosphate residue, a phosphorylethylamine radical and a phosphorylethylammonium radical, in which n is an integer from 1 to 4 and m is an integer from 1 to 8;
[0260] R3 designates a hydrogen atom or a hydrocarbon radical in the form of Ci-C33, hydroxylated or non-hydroxylated and saturated or unsaturated. It is possible to esterify the hydroxyl or hydroxyls with an inorganic acid or an acid R7COOH, R7 having the same meaning as above, and it is possible to etherify the hydroxyl or hydroxyls with a radical (glycosyl)n, (galactosyl)m, sulphogactosyl, phosphorylethylamine or phosphorylethylammonium, in which n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8. It is also possible to substitute R3 with one or more alkyl radicals in the form of CrCi4;
[0261] R4 denotes a hydrogen atom, a methyl or ethyl radical, a C3-C5o hydrocarbon radical optionally hydroxylated, saturated or unsaturated and linear or branched, or a -CH2-CHOH-CH2-O-R6 hydrocarbon radical, in which R6 denotes a Ci0-C26 hydrocarbon radical, or an R8-O-CO-(CH2)P radical, in which R8 denotes a CrC2o hydrocarbon radical and p is an integer from 1 to 12;
[0262] R 5 designates a hydrogen atom or a C rC30 hydrocarbon radical optionally mono- or polyhydroxylated, saturated or unsaturated and linear or branched, it is possible to etherify the hydroxyl or hydroxyls with a hydrocarbon radical (glycosyl)n, (galactosyl)m, sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium, in which n is an integer from 1 to 4 and m is an integer from 1 to 8; provided that, where R3 and R5 designate hydrogen or where R3 designates hydrogen and R5 designates methyl, then R4 does not designate a hydrogen atom or a methyl or ethyl radical.
[0263] Preference is given, among compounds of formula (I), to ceramides and / or to glycoceramides according to the structure described by Downing in Journal of Lipid Research, Vol. 35, 2060-2068, 1994, or those disclosed in French patent application FR-2 673 179.
[0264] It is preferable that, in the formula (I) above, R3 denotes a Ci5-C26 α-hydroxyalkyl radical, the hydroxyl group being optionally esterified by a Ci6-C30 α-hydroxacid.
[0265] The ceramide compounds that are most particularly preferred according to the present invention are compounds of formula (I) for which Ri denotes an optionally hydroxylated and saturated or unsaturated alkyl group derived from C14-C22 fatty acids; R2 denotes a hydrogen atom; and R3 denotes a Cn-Ci7 radical and preferably a Ci3-Ci5 radical that is optionally hydroxylated and linear. R3 preferably denotes an α-hydroxyketyl radical, and R2, R4, and R5 denote hydrogen atoms.
[0266] It is preferable that the ceramide compound be 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-palmitoylaminooctadecane-1,3-diol, and mixtures thereof.
[0267] It is also preferable that the (b) ceramide compound be selected from bis(N-hydroxyethyl-N-cetyl)malonamide, N-(2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxypropyl)acetyl acid amide and N-docosanoyl-N-methyl-D-glucamine.
[0268] Mixtures of ceramide compounds can also be used, such as, for example, mixtures of ceramide(s) 2 and ceramide(s) 5 according to the Downing classification.
[0269] In particular, compounds of formula (I) may also be used where R denotes a saturated or unsaturated alkyl radical derived from C12-C22 fatty acids; R2 denotes a galactosyl or sulphogalactosyl radical and R3 denotes a saturated or unsaturated hydrocarbon radical in C12-C22 and preferably a -CH=CH-(CH 2)12-CH3 group.
[0270] One can cite, by way of example, the product composed of a mixture of glycoceramides sold under the trade name Glycocer by Waitaki International Biosciences.
[0271] The 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.
[0272] These compounds include, for example, Questamide H (bis(N-hydroxyethyl-N-cetyl)malonamide), sold by Quest, or cetyl acid N-(2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxypropyl)amide.
[0273] N-docosanoyl-N-methyl-D-glucamine, disclosed in patent application WO 94 / 24097, can also be used.
[0274] It is of course possible to use mixtures of the various ceramide compounds in the compositions of the present invention.
[0275] As an example of (d) active skin care ingredient, one can cite retinoid.
[0276] The retinoid can be retinol (vitamin A), retinal (vitamin A aldehyde), of retinoic acid (vitamin A acid), or an ester of retinol and a C2 20- acid such as retinol propionate, acetate, linoleate or palmitate (retinol palmitate).
[0277] Among the retinoids, references may be made to retinol, retinal, retinoic acid, in particular all-trans retinoic acid and 13-cis retinoic acid, retinol derivatives, such as retinyl acetate, propionate or palmitate, and the retinoids described in the following patent applications: FR 2 370 377, EP 0 199 636, EP 0 325 540 and EP 0 402 072:
[0278] According to a preferred embodiment of the present invention, the retinoid is retinol or proretinol.
[0279] The term "retinol" is meant to refer to all isomers of retinol, i.e. any trans retinol, 13-cis retinol, 11-cis retinol, 9-cis retinol and 3,4-didehydro retinol.
[0280] Retinyl palmitate can be cited as a representative of pro-retinol.
[0281] It is preferable that the retinoid be retinol.
[0282] Examples of (d) active skin care ingredients include lipophilic antioxidants.
[0283] According to the present invention, antioxidant agents are compounds or substances that can trap the various forms of radicals that may be present in the skin; preferably, they simultaneously trap all the various forms of radicals present.
[0284] The lipophilic antioxidant means that the partition coefficient of the antioxidant between n-butanol and water is > 1, more preferably > 10 and even more preferably > 100.
[0285] The lipophilic antioxidant agent is hydrophobic, and is not a hydrophilic antioxidant such as ascorbic acid or glutathione.
[0286] As a lipophilic antioxidant, phenolic antioxidants may be cited, which have a hindered phenol structure or a semi-hindrained phenol structure within the molecule. Specific examples of such compounds include 3,5-bis(l,l-dimethylethyl)-4-hydroxybenzenepropanoic acid (INCI name pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate), 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-1,1bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecyl propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionato]methane, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] of triethylene glycol, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, l,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] of 1,6-hexanediol, l,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-l,3,5-triazine-2,4,6-trione, 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-l,3,5-triazine, acrylate of 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl, 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-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate].
[0287] Examples of lipophilic antioxidants include BHA (butylated hydroxyanisole) and BHT (butylated hydroxytoluene), vitamin E (or tocopherols and tocotrienol) and their derivatives, such as the phosphate derivative, for example TPNA® sold by Showa Denko, coenzyme Q10 (or ubiquinone), idebenone, certain carotenoids such as lutein, astaxanthin, beta-carotene, polyphenols, phenolic acids and derivatives (for example, chlorogenic acid) and flavonoids, which represent the main subgroup of polyphenols.
[0288] Among the flavonoids, mention may be made in particular of chalcones, hydroxylated chalcones and their reduced derivatives (as described in particular in patent FR 2 608 150), for example phloretin, neohesperidin, phloridzin, aspalathin, etc., flavanones, for example hesperetin and naringin, flavonols, for example quercetin, rutin, flavanols, for example catechin, EGCG, flavones, for example apigenidin, and finally anthocyanins. Tannins may also be mentioned. Reference may also be made to the compounds described in patent applications FR 2 699 818, FR 2 706 478, FR 2 907 339, FR 2 814 943 and FR 2 873 026.
[0289] Polyphenol compounds can notably be derived from plant extracts chosen from extracts of green tea, apple, hops, guava, cocoa, or woods such as chestnut, oak, horse chestnut, or hazel. It is also possible to use an extract of maritime pine bark, for example, obtained according to the processes described in US Patent No. 4,698,360, US Patent No. 6,372,266, and US Patent No. 5,720,956. Examples of such extracts include the compound referenced by the INCI name Pinus pinaster (bark extract) and by the CTFA name Pinus pinaster (pine bark extract). This includes, in particular, the maritime pine bark extract marketed under the name PYCNOGENOL® by BIOLANDES AROMES and / or HORPHAG Research. Pine bark extracts (maritime) from LAYN Natural Ingredients, Pine Bark from Blue California and also Oligopin® from DRT (Les Dérivés Résiniques et Ter-péniques) can also be mentioned.
[0290] In the context of the present invention, the expression "polyphenol compound" therefore also covers the plant extract itself, which is rich in these polyphenol compounds.
[0291] Lipophilic antioxidant agents that may also be cited include di-thiolanes, for example asparagusic acid, or their derivatives, for example siliceous dithiolane derivatives, in particular those described in patent application FR 2 908 769.
[0292] Lipophilic antioxidants that may also be mentioned include:
[0293] glutathione and its derivatives (GSH and / or GSHOEt), such as alkyl esters of glutathione (such as those described in patent applications FR 2 704 754 and FR 2 908 769); and
[0294] 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 FR 2 877 004 and FR 2 854 160; and
[0295] ferulic acid and its derivatives (esters, salts, etc.). In particular, esters of ferulic acid and C1-C30 alcohols may be mentioned, especially methyl ferulate, ethyl ferulate, isopropyl ferulate, octyl ferulate, and oryzanyl ferulate;
[0296] certain enzymes for defense against oxidative stress, such as catalase, superoxide dismutase (SOD), lactoperoxidase, glutathione peroxidase and quinone reductases;
[0297] benzylcyclanones; substituted naphthalenones; pidolates (as described in particular in patent application EP 0 511 118); caffeic acid and its derivatives, gamma-oryzanol; melatonin, sulforaphane and extracts containing it (excluding cress);
[0298] the diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, as described in particular in patent applications WO 94 / 11338, FR 2 698 095, FR 2 737 205 or EP 0 755 925; And
[0299] deferoxamine (or desferal) as described in patent application FR 2 825 920.
[0300] The lipophilic antioxidant agents that are preferentially used are chalcones, more particularly phloretin or neohesperidin, diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, or a maritime pine bark extract such as PYCNOGENOL®.
[0301] Examples of the lipophilic antioxidant agent include pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, propyl gallate, butylated hydroxytoluene, butylated hydroxyanisole, ascorbyl palmitate, tocopherol and mixtures thereof.
[0302] The lipophilic antioxidant agent may be at least one tocopherol selected from the group consisting of α-tocopherol, γ-tocopherol, γ-tocopherol, β-tocopherol and a mixture thereof. Vitamin E may also be used as a lipophilic antioxidant agent.
[0303] Examples of (d) active skin care ingredients include anti-inflammatory or soothing agents.
[0304] Examples of anti-inflammatory or soothing agents that may be used in the composition according to the present invention include: pentacyclic triterpenes and plant extracts (e.g., Glycyrrhiza glabra) containing these, for example, 3-glycyrrhetinic acid and its salts and / or derivatives (glycyrrhetinic acid monoglucuronide, stearyl glycyrrhetinate, 3-stearyloxyglycyrrhetic acid), ursolic acid and its salts, oleanolic acid and its salts, betulinic acid and its salts, bisabolol, an extract of Paeonia suffruticosa and / or lactiflora, phycosaccharides from the Codif company, an extract of Laminaria saccharina, canola oil, bisabolol and chamomile extracts, allantoin, Sepivital EPC (phosphoric diester of vitamins E and C) from Seppic, unsaturated omega-3 oils such as rosehip oil, blackcurrant oil, ecchium oil, fish oil, plankton extracts,capryloyl glycine, Seppicalm VG (sodium palmitoylproline and Nymphaea alba) from Seppic, an extract of Pygeum, an extract of Boswellia serrata, an extract of Centipeda cunninghami, an extract of Helianthus annuus, an extract of Linum usitatissimum, tocotrienols, extracts of Cola nitida, Centella asiatica, piperonal, clove extract, Epilobium an-gustifolium extract, aloe vera, Bacopa monieri extract, phytosterols, nia-cinamide, cortisone, hydrocortisone, indomethacin and betamethasone. ,
[0305] The preferred anti-inflammatory agents to be used in the present invention are extracts of Centella asiatica, [3-glycyrrhetinic acid and its salts, α-bisabolol and niacinamide.
[0306] As (d) an active skin care ingredient, examples include hy- antioxidants Drophiles such as ascorbic acid and its derivatives.
[0307] Ascorbic acid is generally in L form, since it is usually extracted from natural products.
[0308] Because of 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 chosen, for example, from ascorbic acid saccharide esters or phosphoryl ascorbic acid metal salts, alkali metal salts, esters and sugars.
[0309] The saccharide esters of ascorbic acid that can be used in the present invention include, in particular, glycosylated, mannosyl, fructosyl, fucosyl, galactosyl, N-acetylucosamine, and N-acetylmuramic derivatives of ascorbic acid, and mixtures thereof, and more particularly ascorbyl glucoside such as ascorbyl-2 glucoside, 2-OaD-glucopyranosyl L-ascorbic acid, or 6-O-[3-D-galactopyranosyl L-ascorbic acid. These latter compounds and the processes for their preparation are described in particular in documents EP-A-0 487 404, EP-A-0 425 066, and JP 05 213 736.
[0310] As regards the metallic salt of phosphoryl ascorbic acid, it may be chosen from alkali metals and in particular sodium, ascorbyl phosphates, alkaline earth metal ascorbyl phosphates and transition metal ascorbyl phosphates.
[0311] It is also possible to use ascorbic acid precursors such as active agent amides and active agent saccharide derivatives, which respectively involve proteases or peptidases and glycosidases as enzymes to release ascorbic acid in situ. These compounds are described in patent EP 0 667 145.
[0312] The active agent saccharide derivatives are specially selected from C3 to C6 saccharide derivatives. They are particularly selected from glucosyl, mannosyl, fructosyl, fucosyl, N-acetylglucosamine, galactosyl and N-acetylgalactosamine derivatives, N-acetylmuramic acid derivatives and sialic acid derivatives, and a mixture of these derivatives.
[0313] The second precursors of ascorbic acid can be selected from derivatives that are hydrolyzed by other enzymes, for example, esterases, phosphatases, sulfatases, etc. According to the present invention, the second precursors of the active agent can be selected, for example, from phosphates, sulfates, palmitates, acetates, propionates, ferulates, and, in general, alkyl or acyl esters, alkyl or acyl ethers of the active agent. The acyl and alkyl radicals, in particular, contain from 1 to 30 carbon atoms. As an active ingredient in skincare, one can cite ascorbic acid. 3-O-ethyl ascorbic acid.
[0314] In particular, the second precursor may be an ester derived from the reaction with a mineral acid such as a sulfate or a phosphate to react with a sulfatase or a phosphatase on contact with the skin, and the second precursor may be an acyl or alkyl ester derived from the reaction with an organic acid, for example palmitic acid, acetic acid, propionic acid, nicotinic acid, 1,2,3-propanetricarboxylic acid or ferulic acid to react with a specific skin esterase.
[0315] Other derivatives are described, for example, in patent EP 1 430 883.
[0316] Ascorbic acid analogues are more particularly its salts, especially alkali metal salts, for example sodium ascorbate, its esters, especially its acetic, propionic or palmitic esters, especially ascorbyl tetraisopalmitate, or its sugars, especially glycosyl ascorbic acid.
[0317] As (d) an active skin care ingredient, salicylic acid and its derivatives may be cited. Salicylic acid derivatives may be represented by formula (I) or its salt:
[0318] in which:
[0319] Ri represents hydrogen or a saturated, linear, branched or cyclized aliphatic hydrocarbon group or an alkoxy, ester or ketoxy group, or an unsaturated group having at least one conjugated or non-conjugated double bond, where these groups may contain from 1 to 22 carbon atoms and may be substituted by at least one substituent selected from halogen atoms, trifluoromethyl groups and hydroxyl groups in a free form or esterified by an acid having from 1 to about 6 carbon atoms;
[0320] R2 represents a hydroxyl radical or an ester of formula (II): -oc-r4 (II)
[0321] where
[0322] R4 represents a saturated aliphatic hydrocarbon group or an alkenyl group having from 1 to 18 carbon atoms; and
[0323] R 3 represents hydrogen or a saturated or unsaturated aliphatic hydrocarbon group, linear or branched having from 2 to 30 carbon atoms, optionally containing one or more substituents such as those listed above.
[0324] As R3, alkyl and alkenyl radicals containing 2 to 30 carbon atoms are suitable and are optionally substituted.
[0325] The preferred substituent is a hydroxyl radical.
[0326] When R3 is hydrogen, salts of compounds of formula (I) can be used, in particular salts obtained by reaction with a base. Suitable bases include alkali metal hydroxides (sodium and potassium hydroxides), 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.
[0327] According to a preferred embodiment of the present invention, the compositions are prepared using derivatives of formula (I) where Ri contains at least 4 carbon atoms. For example, Ri may be a saturated linear alkyl or alkoxy radical having from 4 to 11 carbon atoms.
[0328] Derivatives of formula (I) in which R2 is hydroxyl and R3 is hydrogen, include 5-n-octanoylsalicylic acid (CTFA name: Capryloyl Salicylic 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 a base.
[0329] Where Ri represents hydrogen and R2 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 alcohols, or esters of butyl, propyl, and ethyl alcohols, 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.
[0330] It is even more preferable that the (d) active skin care ingredient be selected from the group consisting of 2-N-oleoylaminooctadecane-l,3-diol (2-oleamide-l,3-octadecanediol), tocopherol, retinol, stearyl glycyrrhetinate, ascorbic acid, ascorbyl tetraisopalmitate, 2-N-stearoylaminooctadecane-l,3,4-triol (ceramide NP), capryloyl salicylic acid and a mixture of these.
[0331] The quantity of the (d) active skincare ingredient(s) in the composition according to the present invention may be 0.001% by weight or more, preferably of 0.003% by weight or more, and more preferably 0.005% by weight or more, relative to the total weight of the composition.
[0332] Furthermore, the quantity of the (d) active skin care ingredient(s) in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the composition.
[0333] Thus, the quantity of the (d) active skin care ingredient(s) in the composition according to the present invention can range from 0.001% to 10% by weight, preferably from 0.003% to 5% by weight, more preferably from 0.005% to 1% by weight, relative to the total weight of the composition.
[0334] (Particle)
[0335] The (a) cationic polymer and the (b) anionic polymer, with or without the (c) fatty acid, may form at least one particle. Thus, the composition according to the present invention may include at least one particle. The (c) fatty acid may hydrophobicize the particle.
[0336] The above particle may be a polyionic complex particle that may be formed by the (a) cationic polymer and the (b) anionic polymer. The (c) fatty acid may hydrophobize the polyionic complex particle.
[0337] The particle may include, where appropriate, the (d) active skincare ingredient. Thus, the (d) active skincare ingredient may be solubilized by the particle.
[0338] The particle size can be less than 1000 nm. Thus, the particle can be of nanometric size.
[0339] A particle size can be measured by a dynamic light scattering method. This particle size can be based on the volume-average diameter.
[0340] The particle size in the composition according to the present invention may be less than 500 nm, preferably less than 400 nm, and more preferably less than 300 nm.
[0341] The particle size in the composition according to the present invention may be 10 nm or more, preferably 30 nm or more, and more preferably 50 nm or more.
[0342] The particle size can be from 10 nm to 500 nm, preferably from 30 nm to 400 nm, and more preferably from 50 nm to 300 nm.
[0343] (Conditions)
[0344] According to the present invention, the following conditions (1) to (4) can be satisfied for the composition according to the present invention. 1. The total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably profitability less than 0.5% by weight, relative to the total weight of the composition; 2. The weight ratio of the amount of (a) cationic polymer / total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient 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 ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7; and 4. The weight ratio of the quantity of (d) skin care active ingredient / the total quantity 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.
[0345] It may be preferable that the composition according to the present invention also satisfy any one, preferably all, of the following conditions (5) to (8).
[0346] (5) The total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is greater than 0.01% by weight, preferably greater than 0.05% by weight, and more preferably greater than 0.1% by weight, relative to the total weight of the composition;
[0347] (6) The weight ratio of the quantity of (a) cationic polymer to the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is greater than 0.01, preferably greater than 0.05 and more preferably greater than 0.1;
[0348] (7) The weight ratio of the quantity of (b) anionic polymer to the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is greater than 0.3, preferably greater than 0.4 and more preferably, greater than 0.5; and
[0349] (8) The weight ratio between the quantity of (d) skin care active ingredient / the the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is greater than 0.005, preferably greater than 0.01, and more preferably greater than 0.05.
[0350] (Water)
[0351] The composition according to the present invention may include (e) water.
[0352] The quantity of (e) water may be 50% by weight or more, preferably of 55% by weight or more, and more preferably 60% by weight or more, relative to the total weight of the composition.
[0353] Furthermore, the quantity of (e) water may be 99% by weight or less, preferably 98% by weight or less, and more preferably 97% by weight or less, relative to the total weight of the composition.
[0354] The quantity of (e) water may be from 50% to 99% by weight, preferably from 55% to 98% by weight, and more preferably from 60% to 97% by weight, relative to the total weight of the composition.
[0355] (pH)
[0356] The pH of the composition according to the present invention can be from 3 to 9, preferably from 3.3 to 8.5 and, more preferably, from 3.5 to 8.
[0357] At a pH of 3 to 9, the above particle, which may be a polyionic complex particle that may be formed by the (a) cationic polymer and the (b) anionic polymer, in which the (c) fatty acid can hydrophobize the polyionic complex particle, may be very stable.
[0358] The pH of the composition according to the present invention can be corrected by the addition of at least one alkali and / or at least one acid. The pH of the composition according to the present invention can also be corrected by the addition of at least one buffering agent.
[0359] (Alkaline agent)
[0360] The composition according to the present invention may comprise at least one alkali agent. Two or more alkali agents may be used in combination. Thus, a single type of alkali agent or a combination of different types of alkali agents may be used.
[0361] The alkali agent may be an inorganic alkali agent. Preferably, the inorganic alkali agent should be chosen 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.
[0362] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. Sodium hydroxide is preferable as an inorganic alkali metal.
[0363] The alkali agent may be an organic alkali agent. Preferably, the organic alkali agent should be chosen 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.
[0364] Examples of organic alkali-aggregate agents include alkanolamines such as mono-, di- and triethanolamine, and isopropanolamine; urea, guanidine and their derivatives; basic amino acids such as lysine, ornithine or arginine and diamines such as those described in the structure below: R1 R3 NRN R2 Z X R4
[0365] in which R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a C1-C4 alkyl radical, and Rh R2, R3 and R4 independently denote a hydrogen atom, an alkyl radical or a CrC4 hydroxyalkyl radical, an example of which may be 1,3-propanediamine and its derivatives.
[0366] The alkali agent or agents may be used in an amount from 0.001% to 15% by weight, preferably from 0.002% to 10% by weight, and more preferably from 0.003% to 5% by weight, relative to the total weight of the composition, depending on their solubility.
[0367] (Acid)
[0368] The composition according to the present invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.
[0369] As an acid, any inorganic or organic acids, preferably inorganic, that are commonly used in cosmetic products may be mentioned. A monovalent acid and / or a polyvalent acid may be used. A monovalent acid such as citric acid, lactic acid, sulfuric acid, phosphoric acid, and hydrochloric acid (HCl) may be used. Lactic acid may be preferred.
[0370] The acid(s) may be used in an amount ranging from 0.001% to 15% by weight, preferably from 0.002% to 10% by weight, more preferably from 0.003% to 5% by weight, relative to the total weight of the composition, depending on their solubility.
[0371] (Optional ingredient)
[0372] The composition according to the present invention may comprise, in addition to the aforementioned ingredients, one or more optional ingredients typically used in cosmetics, specifically, oils; UV filters; surfactants / emulsifiers; hydrophilic or lipophilic thickeners, derived, for example, from synthetic polymers other than (a) cationic polymers or (b) anionic polymers; volatile or non-volatile organic solvents; amphoteric polymers; non-ionic 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; and the like, in a beach which does not alter the effects of the present invention.
[0373] The composition according to the present invention may comprise the above optional ingredient(s) in an amount of 0.01% to 30% by weight, preferably 0.05% to 20% by weight, and more preferably 0.1% to 10% by weight, relative to the total weight of the composition.
[0374] The composition according to the present invention does not comprise a surfactant having at least one polyoxyethylene unit or at least one surfactant having at least one polyoxyethylene unit in an amount of 1% by weight or less, preferably 0.1% by weight or less, and more preferably 0.01% by weight or less, relative to the total weight of the composition. It is particularly preferable that the composition according to the present invention not include any surfactant / emulsifier having at least one polyoxyethylene unit.
[0375] The composition according to the present invention may include a very limited amount of synthetic thickener(s) and / or organic solvent(s) in order to be environmentally friendly.
[0376] The amount of synthetic thickener(s) or organic solvent(s) in the composition according to the present invention may be 1% by weight or less, preferably 0.1% by weight or less, and more preferably 0.01% by weight or less, relative to the total weight of the composition. It is particularly preferable that the composition according to the present invention include neither synthetic thickener nor organic solvent. [Preparation]
[0377] The composition according to the present invention can be prepared by mixing the essential ingredient(s) as explained above, and the optional ingredient(s), if necessary, as explained above.
[0378] The method and means for mixing the above essential and optional ingredients are not limited. Any conventional method and means can be used to mix the above essential and optional ingredients to prepare the composition according to the present invention.
[0379] The composition according to the present invention can be prepared by simple or easy mixing with a conventional mixing means such as a stirrer and homogenizer. Furthermore, heating may not be necessary. Therefore, the process of preparing the composition according to the present invention can be environmentally friendly. [Cosmetic application]
[0380] The composition according to the present invention may be intended for use as a cosmetic composition. Thus, the cosmetic composition according to the present The invention may be intended for application to a keratinous substance. Here, "keratinous substance" refers to a material containing keratin as its principal constituent, and examples include skin, scalp, lips, hair, and the like. Therefore, it is preferable that the cosmetic composition according to the present invention be used for a cosmetic process on keratinous substances, particularly skin.
[0381] Thus, the cosmetic composition according to the present invention can be a cosmetic composition for the skin, preferably a cosmetic skin care composition or a skin makeup composition, and more preferably a cosmetic skin care composition. [Shape]
[0382] The composition according to the present invention may be in any form.
[0383] For example, if the composition according to the present invention includes oil, the oil can form oily phases, (e) water can form an aqueous phase, and the oily phases can be dispersed in the aqueous phase. Thus, the aqueous phase can function as a continuous phase, and the oily phase can function as a dispersed phase. In other words, the composition according to the present invention can be in the form of an oil-in-water (O / W) dispersion such as an oil-in-water emulsion. If the composition according to the present invention is of the oil-in-water type, it can provide a cooling sensation due to (e) the water that forms its outer phase.
[0384] The composition according to the present invention may have a transparent or translucent appearance, preferably a transparent appearance.
[0385] Transparency can be measured by measuring turbidity (for example, with the HACH 2100Q portable turbidimeter). The turbidity of the composition according to the present invention can be less than 400 NTU (translucent), preferably less than 350 NTU, more preferably less than 300 NTU (transparent). [ Movie ]
[0386] The composition according to the present invention can be used to easily prepare a film.
[0387] If ingredients (a) and (b), with or without ingredient (c), form particles, the particles can aggregate and integrate into a continuous film.
[0388] Thus, the present invention may also relate to a process for preparing a film, preferably a cosmetic film, optionally with a thickness of 0.5 pm or more, more preferably of 1.0 pm or more, and even more preferably of 1.5 pm or more, comprising:
[0389] application to a substrate, preferably a keratinous substance, more pre- differentially the skin, of the composition according to the present invention; and
[0390] the drying of the composition.
[0391] The upper limit of the thickness of the film according to the present invention is not limited. Thus, for example, the thickness of the film according to the present invention can be 1 mm or less, preferably 500 pm or less, more preferably 300 pm or less, and even more preferably 100 pm or less.
[0392] Since the process for preparing a film according to the present invention comprises the steps of applying the composition according to the present invention onto a substrate, preferably a keratinous substance, and more preferably skin, and drying the composition, the process according to the present invention does not require deposition on a turntable or spraying, and it is therefore possible to easily prepare a relatively thick film. Thus, the process for preparing a film according to the present invention can prepare a relatively thick film without any special equipment such as deposition turntables and spraying machines.
[0393] Even though the film according to the present invention is relatively thick, it remains thin and may be transparent, and therefore may not be easily perceptible. Thus, the film according to the present invention can preferably be used as a cosmetic film.
[0394] If the substrate is not a keratinous substance such as skin, the composition according to the present invention can be applied to a substrate made of any material other than keratin. The materials of the non-keratinous substrate are not limited. Two or more materials can be used in combination. Thus, a single type of material or a combination of different types of materials can be used. In all cases, it is preferable that the substrate be flexible or elastic.
[0395] If the substrate is not a keratinous substance, it is preferable that the substrate be water-soluble, since it is possible to leave the film according to the present invention by washing the substrate with water. Examples of water-soluble materials include polyacids (methacrylic acids), polyethylene glycols, polyacrylamides, polyvinyl alcohol (PVA), starch, cellulose acetates, and the like. PVA is preferable.
[0396] If the non-keratinous substrate is in the form of a sheet, it may have a thickness greater than that of the film according to the present invention, in order to facilitate the handling of the film attached to the substrate sheet. The thickness of the non-keratinous substrate sheet is not limited, but may be from 1 µm to 5 mm, preferably from 10 µm to 1 mm, and more preferably from 50 to 500 µm.
[0397] It is preferable that the film according to the present invention be able to be released from the non-keratinous substrate. The method of release is not limited. Therefore, the film according to the present invention can be peeled from the non-keratinous substrate, or released by dissolving the substrate sheet in a solvent such as water.
[0398] The present invention may also relate to:
[0399] (1) A film, preferably a cosmetic film, optionally of a thickness preferably greater than 0.5 qm, more preferably 1.0 qm or more, and even more preferably 1.5 qm or more, prepared by a process comprising:
[0400] the application to a substrate, preferably a keratinous substance, and more preferably the skin, of the composition according to the present invention; and
[0401] drying of the composition,
[0402] and
[0403] (2) A film, preferably a cosmetic film, optionally of a thickness preferably greater than 0.5 sq m, more preferably 1.0 sq m or more, even more preferably 1.5 sq m or more, comprising:
[0404] (a) at least one cationic polymer;
[0405] (b) at least one anionic polymer;
[0406] (c) at least one fatty acid; and
[0407] (d) at least one active skin care ingredient,
[0408] in which
[0409] the weight ratio between the quantity of (a) cationic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 0.7, preferably less than 0.5, and more preferably less than 0.3,
[0410] the weight ratio between the quantity of (b) anionic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7, and
[0411] the weight ratio between the quantity of (d) skin care active ingredient and the total quantity 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.
[0412] The above explanations concerning (a) cationic polymer, (b) anionic polymers, (c) fatty acid, and (d) skin care active ingredient can be applied to those of films (1) and (2) above.
[0413] The film thus obtained can be self-supporting. The term “self-supporting” here means that the film can be in the form of a sheet and can be handled as an independent sheet without the assistance of a substrate or support. Thus, the term “self-supporting” can have the same meaning as “self-supporting”.
[0414] It is preferable that the film according to the present invention be hydrophobic.
[0415] In this descriptive document, the term “hydrophobic” means that the solubility of the film in water (preferably with a volume of 1 liter) at 20 to 40 °C, preferably The film's water content, ideally between 25 and 40 °C, and more preferably between 30 and 40 °C, is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, relative to the total weight of the film. It is highly preferable that the film not be water-soluble.
[0416] If the film according to the present invention is hydrophobic, the film can have water-resistant properties and, consequently, can remain on a keratinous substance such as skin, even if the surface of the keratinous substance is wet due to, for example, perspiration or rain. Thus, when the film according to the present invention provides a cosmetic effect, the cosmetic effect can last a long time.
[0417] On the other hand, the film according to the present invention can be easily removed from a keratinous substance such as skin under alkaline conditions such as a pH of 8 to 12, preferably 9 to 11. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap that can provide such alkaline conditions.
[0418] The film according to the present invention may comprise at least one layer of biocompatible and / or biodegradable polymer. Two or more biocompatible and / or biodegradable polymers 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.
[0419] The term “biocompatible” polymer in this specification means that the polymer does not have excessive interaction between the polymer and the cells of the living body including the skin, and that the polymer is not recognized by the living body as a foreign material.
[0420] The term "biodegradable" polymer in this specification means that the polymer can be degraded or broken down in a living organism due to, for example, the metabolism of the living organism itself or the metabolism of microorganisms that may be present in the living organism. Furthermore, the biodegradable polymer can be degraded by hydrolysis.
[0421] If the film according to the present invention includes a biocompatible and / or biodegradable polymer, it is less irritating or non-irritating to the skin and / or it may not contaminate environments.
[0422] In fact, the film according to the present invention may include (a) at least one cationic polymer which may be selected from chitosans, and / or (b) at least one anionic polymer which may be selected from polysaccharides, such as carrageenan, which are biodegradable polymers.
[0423] Furthermore, due to the use of a biocompatible and / or biodegradable polymer, the cosmetic sheet according to the present invention can adhere well to the skin.
[0424] The film according to the present invention can be used for cosmetic treatments of keratinous substances, preferably the skin, particularly the face. The film according to the present invention can be in any form. For example, it can be used as a mask sheet for the entire face or as a patch for a part of the face such as the cheek, nose, and around the eyes. [Cosmetic process and use]
[0425] The present invention also relates to:
[0426] a cosmetic process for a keratinous substance such as skin, comprising: applying the composition according to the present invention to the keratinous substance; and drying the composition to form a cosmetic film on the keratinous substance; or
[0427] a use of the composition according to the present invention for the preparation of a cosmetic film on a keratinous substance such as skin.
[0428] The cosmetic process here refers to a non-therapeutic cosmetic process of care and / or makeup of the surface of a keratinous substance such as the skin.
[0429] In both the above process and use, the above cosmetic film is resistant to water of a pH of 7 or less, and can be removed with water of a pH greater than 7, preferably 8 or more, and more preferably 9 or more.
[0430] In other words, the above cosmetic film can be water-resistant under neutral or acidic conditions such as a pH of 7 or less, preferably within a range of 6 or more and 7 or less, and more preferably within a range of 5 or more and 7 or less, while the above cosmetic film can be removed under alkaline conditions such as a pH greater than 7, preferably 8 or more, and more preferably 9 or more. The upper limit of pH is preferably 13, more preferably 12, and even more preferably 11.
[0431] Consequently, the above-mentioned cosmetic film can be water-resistant and can therefore remain on a keratinous substance such as skin even if the surface of the keratinous substance is wet due to, for example, perspiration and rain. On the other hand, the above-mentioned cosmetic film can be easily removed from a keratinous substance such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, whereas it can be easily removed with a soap that can provide alkaline conditions.
[0432] In addition, the above cosmetic film may have cosmetic effects such as sebum capture, mattifying the appearance of a keratinous substance such as skin, absorbing or neutralizing an unpleasant odor, and / or protecting the keratinous substance against, for example, dirt or pollutants, due to the properties of the complex in the cosmetic film, even if the cosmetic film does not include any sebum-controlling, deodorizing, or protective agents.
[0433] Furthermore, the above cosmetic film can immediately change or alter the appearance of the skin by changing the reflection of light on the skin and similar effects, even if the cosmetic film does not include any active cosmetic ingredients. Therefore, it may be possible for the above cosmetic film to conceal skin defects such as pores or wrinkles. In addition, the above cosmetic film can immediately change or alter the feel of the skin by changing the surface roughness of the skin and similar effects. Furthermore, the above cosmetic film can immediately protect the skin by covering its surface and protecting it, like a barrier, against environmental aggressors such as pollutants, contaminants, and the like.
[0434] The above cosmetic effects can be adjusted or regulated by changing the chemical composition, thickness and / or surface roughness of the above cosmetic film.
[0435] Since the above cosmetic film includes (d) at least one active skin-care ingredient, the cosmetic film may have cosmetic effects provided by the (d) active skin-care ingredient(s). For example, if the cosmetic film includes at least one active skin-care ingredient selected from anti-aging agents, such as antioxidants, the cosmetic film may treat skin aging.
[0436] It is also possible to apply a cosmetic makeup composition to the cosmetic film or sheet according to the present invention after its application to the skin.
[0437] The present invention may also relate to a use of: a. at least one cationic polymer; b. at least one anionic polymer and c. at least one fatty acid, in a composition comprising: d. at least one active skincare ingredient; and e. water,
[0438] in which
[0439] the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, relative to the total weight of the composition,
[0440] the weight ratio between the quantity of (a) cationic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 0.7, preferably less than 0.5, and more preferably less than 0.3,
[0441] 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 ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7, and
[0442] the weight ratio between the quantity of (d) skin care active ingredient and the total quantity 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,
[0443] in order to solubilize the (d) active skin care ingredient in the composition.
[0444] The present invention may also relate to a use of: a. at least one cationic polymer; b. at least one anionic polymer and c. at least one fatty acid, in a composition comprising: d. at least one active skincare ingredient; and e. of water,
[0445] in which
[0446] the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, relative to the total weight of the composition,
[0447] the weight ratio between the quantity of (a) cationic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 0.7, preferably less than 0.5, and more preferably less than 0.3,
[0448] 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 ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7, and
[0449] the weight ratio between the quantity of (d) skin care active ingredient and the total quantity 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,
[0450] in order to make the composition transparent or translucent.
[0451] The present invention may also relate to a use of: a. at least one cationic polymer; b. at least one anionic polymer and c. at least one fatty acid, in a composition comprising: d. at least one active skincare ingredient; and e. of water,
[0452] in which
[0453] the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, relative to the total weight of the composition,
[0454] the weight ratio between the quantity of (a) cationic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 0.7, preferably less than 0.5, and more preferably less than 0.3,
[0455] the weight ratio between the quantity of (b) anionic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) skin care active ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7, and
[0456] the weight ratio between the quantity of (d) skin care active ingredient and the total quantity 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,
[0457] in order to improve skin penetration of (d) skin care active ingredient.
[0458] The above explanations concerning (a) cationic polymer, (b) anionic polymers, (c) fatty acid, (d) skin care active ingredient and (e) water may apply to those of the above uses. EXAMPLES
[0459] The present invention will be described in more detail with the aid of examples. However, these examples shall not be construed as limiting the scope of the present invention. [Example 1 and Comparative Examples 1 to 3] [Preparations]
[0460] Each of the compositions according to Example 1 and Comparative Examples 1 to 3 was prepared by mixing the ingredients shown in Table 1. The numerical values of the quantities of ingredients in Table 1 are all based on a "% by weight" of raw materials.
[0461] [Tables 1] Ex. 1 Ex. Comp. 1 Ex. Comp. 2 Ex. Comp. 3 Caprylyl Glycol 0.3 0.3 0.3 0.3 Chitosan (a) 0.027 0.027 0.027 - Water qsp 100 qsp 100 qsp 100 qsp 100 Carrageenan (b) 0.1 0.1 - 0.3 Glycerin 3 3 3 3 Oleic Acid (c) 0.018 - 0.018 0.054 2-Oleamide-1,3-Octadecanediol (d) 0.01 0.01 0.01 0.03 Pentylene Glycol 1 1 1 1 Lactic Acid qs. pH 5 qs. pH 5 qs. pH 5 qs. pH 5 (a)+(b)+(c)+(d) 0.155 0.137 0.055 0.384 (b) / [(a)+(b)+(c)+(d)] xlOO 64.5 73.0 - 78.1 (a) / [(a)+(b)+(c)+(d)] xlOO 17.4 19.7 49.1 - (c) / [(a)+(b)+(c)+(d)] xlOO 11.6 - 32.7 14.1 (d) / [(a)+(b)+(c)+(d)] xlOO 6.5 7.3 18.2 7.8 Appearance Good Good Good Poor Solubility Good Poor Good Poor Particle Size (nm) 92 NA >1000 >1000 Turbidity (NTU) 110 50 500 NA
[0462] nd: not available [Reviews]
[0463] (Aspect)
[0464] The appearance of each of the compositions according to Example 1 and the comparative examples Items 1 to 3 were observed visually. The results of the visual observation were classified as follows.
[0465] Good: the appearance was transparent or translucent
[0466] Precipitation: the appearance was translucent but precipitation was observed
[0467] Bad: the appearance was cloudy
[0468] The results are shown in Table 1.
[0469] The compositions according to Example 1 and Comparative Examples 1 and 2 were transparent or translucent.
[0470] The composition according to Comparative Example 3 was cloudy.
[0471] (Solubility)
[0472] The solubility of ceramide (2-oleamide-1,3-octadecanediol) in each of the compositions according to Example 1 and Comparative Examples 1 to 3 was observed visually. The results of the visual observation were classified as follows.
[0473] Good: the ceramide has been solubilized
[0474] Bad: the ceramide has not been solubilized
[0475] The results are shown in Table 1.
[0476] Ceramide was solubilized in the composition according to Example 1 and Comparative Example 2, whereas ceramide was not solubilized in the compositions according to Comparative Examples 1 and 3.
[0477] (Particle size)
[0478] A particle size analyzer (Dynamic Light Scattering, ELSZ2000, Otsuka) was used to determine the particle size in the compositions according to Example 1 and Comparative Examples 1 to 3 at room temperature (25 °C).
[0479] The results are shown in Table 1.
[0480] The particle size of the particles in the composition according to Example 1 was small so that it was of nanometric size.
[0481] The particle size of the particles in the composition according to Comparative Examples 2 and 3 was not small.
[0482] It was not possible to measure the particle size for the compositions according to Comparative Example 1.
[0483] (Turbidity)
[0484] 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 turbidimeter (2100Q portable, HACH company).
[0485] The results are shown in Table 1 as "NTU". The lower the NTU value, the more transparent the composition.
[0486] The turbidity of the compositions according to Comparative Example 3 was too high. Examples 2 to 12 [Preparations]
[0487] Each of the compositions according to Examples 2 to 12 was prepared by mixing the ingredients shown in Tables 2 and 3. The numerical values of the quantities of ingredients shown in Tables 2 and 3 are all based on "% by weight" of raw materials. Ex. 2 Ex. 3 Ex. 4 Ex. 5 Caprylyl Glycol 0.3 0.3 0.3 0.3 Chitosan (a) 0.027 0.027 0.027 0.027 Water q.s. 100 q.s. 100 q.s. 100 q.s. 100 q.s. 100 Carrageenan (b) 0.1 0.1 0.1 0.1 Glycerin 3 3 3 3 Stearic Acid (c) 0.018 - - - Isostearic Acid (c) - 0.018 - - Behenic Acid (c) - - 0.018 - Decanoic Acid (c) - - - 0.018 2-Oleamide-1,3-Octadecanediol (d) 0.01 0.01 0.01 0.01 Pentylene Glycol 1 1 1 1 Lactic acid qs. pH 5 qs. pH 5 qs. pH 5 qs. pH 5 (a)+(b)+(c)+(d) 0.155 0.155 0.155 0.155 (b) / [(a)+(b)+(c)+(d)] xlOO 64.5 64.5 64.5 64.5 (a) / [(a)+(b)+(c)+(d)] xlOO 17.4 17.4 17.4 17.4 (c) / [(a)+(b)+(c)+(d)] xlOO 11.6 11.6 11.6 11.6 (d) / [(a)+(b)+(c)+(d)] xlOO 6.5 6.5 6.5 6.5 Appearance Good Good Good Good Solubility Good Good Good Good Particle Size (nm) 478 75.7 292,135.2 Turbidity (NTU) 104,39.2,193,81 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Caprylyl Glycol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Chitosan (a) 0.027 0.027 0.027 0.027 0.027 0.027 0.027 Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 Carrageenan (b) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Glycerin 3 3 3 3 3 3 3 Oleic acid (c) 0.018 0.018 0.018 0.018 0.018 0.018 0.018 Tocopherol (d) 0.01 - - - - - - Retinol - 0.01 - - - - - Stearyl Glycyrrhetinate - - 0.01 - - - - Ascorbic Acid - - - 0.01 - - - Ascorbyl Tetraisopalmitate - - - - 0.01 - - Ceramide NP - - - - - 0.01 - Capryloyl Salicylic Acid - - - - - - 0.01 Pentylene Glycol 1 1 1 1 1 1 1 Lactic Acid qs. pH 5 qs. pH 5 qs. pH 5 qs. pH 5 qs. pH 5 qs. pH 5 qs.pH 5 (a)+(b)+(c)+(d) 0.155 0.155 0.155 0.155 0.155 0.155 0.155 (b) / [(a)+(b)+(c)+(d)] xlOO 64.5 64.5 64.5 64.5 64.5 64.5 64.5 (a) / [(a)+(b)+(c)+(d)] 11.6 (d) / [(a)+(b)+(c)+(d)] xlOO 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Aspect Good Good Good Good Good Good Good. Solubility Good Good Good Good Good Good Good Particle size (nm) 71.5 201.7 111.2 112.8 261.6 131.9 135.4 Turbidity (NTU) 28.3 192 62.2 33.6 265 43.3 20.7 [Reviews]
[0490] (Aspect)
[0491] The appearance of each of the compositions according to Examples 2 to 12 was observed visually. The results of the visual observation were classified as follows.
[0492] Good: the appearance was transparent or translucent
[0493] Precipitation: the appearance was translucent but precipitation was observed
[0494] Bad: the appearance was cloudy
[0495] The results are shown in Tables 2 and 3.
[0496] The compositions according to Examples 2 to 12 were stable.
[0497] (Solubility)
[0498] The solubility of ceramide (2-oleamide-1,3-octadecanediol) in each of the compositions according to Examples 2 to 5 was observed visually. In addition, the solubility of each of the various cosmetic active ingredients (d) in each of the compositions according to Examples 6 to 12 was observed visually. The results of the visual observation were classified as follows.
[0499] Good: the ceramide or cosmetic active ingredient has been solubilized
[0500] Bad: the ceramide or cosmetic active ingredient has not been solubilized
[0501] The results are shown in Tables 2 and 3.
[0502] The ceramide or cosmetic active ingredient has been solubilized in the composition according to Examples 2 to 12.
[0503] (Particle size)
[0504] A particle size analyzer (Dynamic Light Scattering, ELSZ2000, Otsuka) was used to determine the particle size in the compositions according to Examples 2 to 12 at room temperature (25 °C).
[0505] The results are shown in Tables 2 and 3.
[0506] The particle size of the particles in the composition according to Examples 2 to 12 was small so that it was of nanometric size.
[0507] (Turbidity)
[0508] The turbidity of each of the compositions according to Examples 2 to 12 was measured at room temperature (25 °C) using a turbidimeter (2100Q portable, Hach Company).
[0509] The results are shown in Tables 2 and 3 as "NTU". The lower the NTU value, the more transparent the composition.
[0510] Moreover, the compositions according to the present invention include one or more environmentally friendly ingredients.
Claims
Demands
1. Composition, preferably a cosmetic composition, more preferably a cosmetic composition for a keratinous substance, and more preferably a cosmetic composition for the skin, comprising: (a) at least one cationic polymer selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as diallyldialkyl ammonium (co)polychloride, (co)polyamines such as (co)polylysines and chitosans, cationic (co)polyamino acids such as collagen, cationic cellulose polymers and salts thereof; (b) at least one anionic polymer, (c) at least one fatty acid, and (d) at least one active skincare ingredient, in which the total amount of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient is less than 1.5% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight, relative to the total weight of the composition, the weight ratio between the quantity of (a) cationic polymer / the total quantity of (a) cationic polymer, (b) anionic polymer, (c) fatty acid and (d) active skin care ingredient 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 ingredient is less than 0.9, preferably less than 0.8, and more preferably less than 0.7, and the weight ratio of the amount of (d) skin care active ingredient / 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.
2. Composition according to claim 1, wherein (d) at least one active skincare ingredient has a logP of -1 or greater, preferably- tiellement of 1 or more, and more preferably of 2 or more.
3. Composition according to any one of claims 1 to 2, wherein the (a) cationic polymer is hydrophobicated by the (c) fatty acid.
4. Composition according to any one of claims 1 to 3, with a turbidity of less than 400 NTU, preferably less than 350 NTU, more preferably less than 300 NTU.
5. Composition according to any one of claims 1 to 4, wherein the (a) cationic polymer has a molecular weight of less than 20,000 Da, preferably less than 15,000 Da and more preferably less than 10,000 Da.
6. Composition according to any one of claims 1 to 5, wherein the (b) anionic polymer is selected from the group consisting of polysaccharides such as carrageenan, alginic acid, hyaluronic acid and cellulosic polymers, (co)polyamino acids anionic such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl sulfates), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, polyfumaric acids, (co)polymers of maleic acids and their salts.
7. Composition according to any one of claims 1 to 6, wherein (c) fatty acid is selected from saturated and unsaturated fatty acids, linear or branched in C4-C26, preferably C6-C24, more preferably C8-C22.
8. Composition according to any one of claims 1 to 7, wherein the composition comprises at least one particle of a particle size less than 1000 nm, preferably less than 500 nm, and more preferably less than 300 nm.
9. A cosmetic process for a keratinous substance such as skin, comprising applying to the keratinous substance the composition according to any one of claims 1 to 8; and drying the composition to form a cosmetic film on the keratinous substance.