Composition comprising polyionic complex particles based on hyaluronic acid and a surfactant
Patent Information
- Application Number
- FR2022000464
- Authority / Receiving Office
- FR · FR
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2022-01-20
- Publication Date
- 2025-03-14
- Estimated Expiration
- 2042-01-20
Abstract
Description
Title of the invention: Composition comprising polyionic complex particles based on hyaluronic acid and a surfactant
[0001] CONTEXT Technical field
[0002] The present invention relates to a composition comprising polyionic complex particles and a film of polyionic complex particles, as well as a method for preparing a film using polyionic complex particles and a cosmetic method using polyionic complex particles. Prior art
[0003] Hyaluronic acid is a predominant glucosaminoglycan present in the skin. Thus, fibroblasts synthesize mainly collagens, matrix glycoproteins other than collagens (fibronectin, laminin), proteoglycans and elastin. Keratinocytes, for their part, synthesize mainly sulfated glycosaminoglycans and hyaluronic acid. Hyaluronic acid is also called hyaluronan (HA).
[0004] Hyaluronic acid is present in the free state in the epidermis and dermis and is responsible for the turgor of the skin. This polysaccharide can in fact retain a significant volume of water, corresponding to up to 1,000 times its weight. In this sense, hyaluronic acid plays an important role in increasing the quantities of water bound to tissues, as well as in the mechanical properties of the skin and in the formation of wrinkles.
[0005] Hyaluronic acid has been widely used as a cosmetic ingredient due to its high moisturizing effects.
[0006] However, an aqueous solution of hyaluronic acid is sticky, which can result in an uncomfortable texture. In addition, a hyaluronic acid film, which forms when an aqueous solution of hyaluronic acid dries on the skin, is sticky, and such a film can also result in an uncomfortable texture.
[0007] WO 2021 / 125069 describes the reduction of stickiness due to hyaluronic acid by forming a polyionic complex particle with a cationic polymer and hyaluronic acid as an anionic polymer. Disclosure of the invention
[0008] There has subsequently been a need for a composition which comprises a hyaluronic acid-based polyionic complex particle but which can provide long-lasting cosmetic effects and / or an improved moisturizing texture.
[0009] Thus, a first objective of the present invention is to provide a composition capable of providing hyaluronic acid-based cosmetic effects, while providing long-lasting cosmetic effects and / or an improved moisturizing texture.
[0010] The above objective of the present invention can be achieved by a composition, comprising:
[0011] (a) at least one particle, comprising
[0012] at least one cationic polymer and at least one anionic polymer,
[0013] at least one cationic polymer and at least one amphoteric polymer,
[0014] at least one anionic polymer and at least one amphoteric polymer or
[0015] at least one amphoteric polymer,
[0016] and at least one non-polymeric acid having two or more pKa values or salt(s) thereof or
[0017] at least one non-polymeric base having at least two pKb values or salt(s) thereof;
[0018] (b) at least one surfactant and
[0019] (c) water;
[0020] where
[0021] the anionic polymer is chosen from hyaluronic acid and its derivatives and
[0022] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.
[0023] The cationized hyaluronic acid may have at least one group containing a quaternary ammonium group and has a degree of cationization of 0.05 to 0.6, preferably 0.1 to 0.5, and more preferably 0.15 to 0.4.
[0024] The cationic polymer may have at least one positively chargeable and / or positively charged moiety selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group.
[0025] The cationic polymer may be selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkylammonium chloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as collagen, cationic cellulosic polymers and their salts.
[0026] The total amount of the cationic and / or anionic and / or amphoteric polymer(s) forming the particle (a) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, and better still from 0.05% to 5% by weight, relative to the total weight of the composition.
[0027] The non-polymeric acid having at least two pKa values or salt(s) thereof may be an organic acid or salt(s) thereof, and preferably a hydrophilic or water-soluble organic acid or salt(s) thereof, and more preferably a phytic acid or salts thereof.
[0028] The amount of non-polymeric acid having at least two pKa values or salt(s) thereof or non-polymeric base having two or more pKb values or salt(s) thereof in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005 to 10% by weight, and more preferably from 0.01 to 5% by weight, relative to the total weight of the composition.
[0029] The surfactant (b) may be chosen from non-ionic surfactants, preferably polyglyceryl fatty acid esters.
[0030] The amount of the (b) surfactant(s) in the composition according to the present invention may be from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, and better still from 0.1% to 10% by weight, relative to the total weight of the composition.
[0031] The amount of (c) water in the composition according to the present invention may be from 10 to 99% by weight, preferably from 30 to 97% by weight, and more preferably from 50 to 95% by weight, relative to the total weight of the composition.
[0032] The pH of the composition according to the present invention may be from 2.0 to 9.0, preferably from 2.5 to 8.5, and more preferably from 3.0 to 8.0.
[0033] The composition according to the present invention may further comprise (c) at least one oil.
[0034] A second objective of the present invention is to provide a method for preparing a hyaluronic acid-based film with long-lasting cosmetic effects and / or improved moisturizing texture.
[0035] The above objective of the present invention can be achieved by a method of preparing a film, preferably a cosmetic film, comprising:
[0036] the application to a substrate, preferably a keratin material, of the composition according to the present invention and
[0037] drying the composition.
[0038] A third objective of the present invention is to provide a hyaluronic acid-based film with long-lasting cosmetic effects and / or improved moisturizing texture.
[0039] The above objective of the present invention can be achieved with:
[0040] (1) A film, preferably a cosmetic film, prepared by a process comprising:
[0041] the application to a substrate, preferably a keratin material, of the composition according to the present invention and
[0042] drying the composition,
[0043] or
[0044] (2) A film, preferably a cosmetic film, comprising:
[0045] at least one cationic polymer and at least one anionic polymer,
[0046] at least one cationic polymer and at least one amphoteric polymer,
[0047] at least one anionic polymer and at least one amphoteric polymer or
[0048] at least one amphoteric polymer;
[0049] at least one non-polymeric acid having two or more pKa values or salt(s) of this one or
[0050] at least one non-polymeric base having at least two pKb values or salt(s) thereof;
[0051] at least one surfactant, preferably a non-ionic surfactant, and better still a polyglyceryl fatty acid ester;
[0052] and
[0053] optionally at least one oil,
[0054] where
[0055] the anionic polymer is chosen from hyaluronic acid and its derivatives and
[0056] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.
[0057] The present invention also relates to a cosmetic process for a keratin material such as skin, comprising
[0058] the application to the keratin material of the composition according to the present invention and
[0059] drying the composition to form a cosmetic film on the keratin material. Best mode for carrying out the invention
[0060] After diligent research, the inventors discovered that it was possible to provide a composition capable of providing cosmetic effects based on hyaluronic acid, while providing long-lasting cosmetic effects and / or an improved moisturizing texture. Thus, the composition according to the present invention comprises:
[0061] (a) at least one particle, comprising
[0062] at least one cationic polymer and at least one anionic polymer,
[0063] at least one cationic polymer and at least one amphoteric polymer,
[0064] at least one anionic polymer and at least one amphoteric polymer or
[0065] at least one amphoteric polymer,
[0066] and at least one non-polymeric acid having two or more pKa values or salt(s) thereof or
[0067] at least one non-polymeric base having at least two pKb values or salt(s) thereof;
[0068] (b) at least one surfactant and
[0069] (c) water;
[0070] where
[0071] the anionic polymer is chosen from hyaluronic acid and its derivatives and
[0072] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.
[0073] Furthermore, the inventors have discovered that it is possible to propose a method of preparation of a hyaluronic acid-based film with long-lasting cosmetic effects and / or an improved moisturizing texture. Thus, the method according to the present invention is a method for preparing a film, preferably a cosmetic film, the method comprising
[0074] the application to a substrate, preferably a keratin material, of the composition according to the present invention and
[0075] drying the composition.
[0076] Furthermore, the inventors have discovered that it is possible to provide a hyaluronic acid-based film with long-lasting cosmetic effects and / or an improved moisturizing texture. Thus, the film according to the present invention is
[0077] (1) A film, preferably a cosmetic film, prepared by a process comprising:
[0078] the application to a substrate, preferably a keratin material, of the composition according to the present invention and
[0079] drying the composition,
[0080] or
[0081] (2) A film, preferably a cosmetic film, comprising:
[0082] at least one cationic polymer and at least one anionic polymer,
[0083] at least one cationic polymer and at least one amphoteric polymer,
[0084] at least one anionic polymer and at least one amphoteric polymer or
[0085] at least one amphoteric polymer;
[0086] at least one non-polymeric acid having two or more pKa values or salt(s) thereof or
[0087] at least one non-polymeric base having at least two pKb values or salt(s) thereof;
[0088] at least one surfactant, preferably a non-ionic surfactant, and better still a polyglyceryl fatty acid ester;
[0089] and
[0090] optionally at least one oil,
[0091] where
[0092] the anionic polymer is chosen from hyaluronic acid and its derivatives and
[0093] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.
[0094] The composition according to the present invention can provide long-lasting cosmetic effects and / or an improved moisturizing texture based on hyaluronic acid or cationized hyaluronic acid.
[0095] The stickiness of the composition according to the present invention can be reduced compared to a composition comprising hyaluronic acid which does not form polyionic complex particle.
[0096] It is possible to readily prepare a film of a polyionic complex wherein the film may comprise at least one oil by applying the composition to a substrate, preferably a keratinous substance such as skin and hair, and more preferably skin, and drying the composition.
[0097] The stickiness of the film according to the present invention can be reduced compared to a hyaluronic acid film which does not form a polyionic complex.
[0098] The film according to the present invention may be porous. The surface of the film according to the present invention may not be flat but may be rough.
[0099] The polyionic complex film according to the present invention may have various cosmetic functions. For example, the polyionic complex film may provide moisturizing effects based on hyaluronic acid or cationized hyaluronic acid in the polyionic complex.
[0100] The film according to the present invention is capable of capturing sebum, mattifying the appearance of a keratin material such as skin, absorbing or adsorbing bad odors and / or protecting the keratin material from dirt or pollutants, for example.
[0101] If the polyionic complex comprises at least one oil, the film according to the present invention may also have cosmetic effects due to the oil(s). It is also possible to achieve a sustained release of the oil(s) from the film.
[0102] If the polyionic complex film comprises at least one cosmetic active ingredient other than the oil(s), the film may also have cosmetic effects provided by the cosmetic active ingredient(s). For example, if the polyionic complex film comprises at least one cosmetic active ingredient selected from UV filters, anti-aging agents, anti-sebum agents, deodorant agents, antiperspirant agents, whitening agents, and a mixture thereof, the film may filter UV rays, treat skin aging, absorb sebum on the skin, control odor on the skin, control perspiration on the skin, and / or whiten the skin.
[0103] The film according to the present invention may be transparent and, therefore, may not be easily perceived, even when the film is relatively thick.
[0104] In addition, the film according to the present invention is water resistant and, therefore, it can remain on a keratin substance such as skin even if the surface of the keratin substance is wet due to, for example, sweat and rain.
[0105] In addition, the film according to the present invention can be easily removed from a keratin material such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can provide alkaline conditions.
[0106] Thus, if the film according to the present invention comprises a hydrophilic or water-soluble UV filter, the film according to the present invention can exhibit UV protection effects that are water-resistant and can be durable, but can be easily removed with soap that can provide alkaline conditions.
[0107] Hereinafter, the composition, method, film and the like according to the present invention will be explained in more detail.
[0108] [Polyionic complex particle]
[0109] The composition according to the present invention comprises (a) at least one particle which is a polyionic complex particle. Two or more different types of particles (a) may be used in combination. Therefore, a single type of particle (a) or a combination of different types of particles (a) may be used.
[0110] The size of the polyionic complex particle may be from 5 nm to 100 pm, preferably from 100 nm to 50 pm, more preferably from 200 nm to 40 pm, and even more preferably from 500 nm to 30 pm. A particle size of less than 1 pm may be measured by a dynamic light scattering method, and a particle size of greater than 1 pm may be measured by an optical microscope. This particle size may be based on the number average diameter.
[0111] The amount of (a) the particle(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition.
[0112] The amount (a) of the particle(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
[0113] The amount (a) of the particle(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and better still from 0.1% to 5% by weight, relative to the total weight of the composition.
[0114] If the composition according to the present invention comprises (d) at least one oil explained below, several of the (a) particles may be present at the interface between the water (c) and the oil (d). Thus, the particles (a) may stabilize an emulsion. For example, if the water (c) constitutes a continuous phase and the oil (d) constitutes dispersed phases, the particles (a) may form an O / W emulsion which may be similar to a so-called Pickering emulsion.
[0115] Alternatively, a plurality of particles (a) may form a capsule having a hollow. Oil (d) may be present in the hollow. In other words, the oil (d) may be incorporated into the capsule. The wall of the capsule may be composed of a continuous layer or film formed from the particles (a). Without wishing to be bound by theory, it is believed that the particles (a) may rearrange at the interface of water (c) and oil (d) to spontaneously form a capsule having a hollow to include (d) oil. For example, a continuous phase consisting of water (c) and dispersed phases consisting of oil (d) in the capsule can form an O / W emulsion which can also be similar to a so-called Pickering emulsion.
[0116] The above would mean that particle (a) itself is amphiphilic and insoluble in oil or water.
[0117] The particle (a) comprises at least one polymer or a combination of polymers. More specifically, the particle (a) comprises:
[0118] (1) at least one cationic polymer and at least one anionic polymer,
[0119] (2) at least one cationic polymer and at least one amphoteric polymer,
[0120] (3) at least one anionic polymer and at least one amphoteric polymer or
[0121] (4) at least one amphoteric polymer.
[0122] There is no limit to the type of cationic polymers. Two or more different types of cationic polymers may be used in combination. Thus, a single type of cationic polymer or a combination of different types of cationic polymers may be used.
[0123] In (1) above, the ratio of the amount, for example, the chemical equivalent, of the cationic polymer(s) / the anionic polymer(s) may be 0.05 to 18, preferably 0.1 to 10, and more preferably 0.5 to 5.0. In particular, it may be preferable that the number of cationic groups of the cationic polymer(s) / number of anionic groups of the anionic polymer(s) is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5-5.0.
[0124] In (2) above, the ratio of the amount, for example, the chemical equivalent, of the cationic polymer(s) / the amphoteric polymer(s) may be 0.05 to 18, preferably 0.1 to 10, and more preferably 0.5 to 5.0. In particular, it may be preferable that the number of cationic groups of the cationic polymer(s) to the number of cationic and anionic groups of the amphoteric polymer(s) is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5-5.0.
[0125] In (3) above, the ratio of the amount, for example, the chemical equivalent, of the anionic polymer(s) / the amphoteric polymer(s) may be 0.05 to 18, preferably 0.1 to 10, and more preferably 0.5 to 5.0. In particular, it may be preferable that the number of anionic groups of the anionic polymer(s) to the number of cationic and anionic groups of the amphoteric polymer(s) is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5-5.0.
[0126] The total amount of the polymer(s) according to any one of (1) to (4) above in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.
[0127] The total amount of the polymer(s) according to any one of (1) to (4) above 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.
[0128] The total amount of the polymer(s) according to any one of (1) to (4) above in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, and more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.
[0129] (Cationic polymer)
[0130] A cationic polymer has a positive charge density. The charge density of the cationic polymer may 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.
[0131] It may be preferable that the molecular weight of the cationic polymer is 500 or more, preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more.
[0132] Unless otherwise defined in the descriptions, “molecular weight” means number average molecular weight.
[0133] The cationic polymer may have at least one positively chargeable and / or positively charged moiety selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group. The term "amino group" (primary) herein refers to a -NH2 group.
[0134] The cationic polymer may be a homopolymer or a copolymer. By "copolymer" is meant both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.
[0135] The cationic polymer may be chosen from natural and synthetic cationic polymers. Non-limiting examples of cationic polymers are as follows.
[0136] (1) Homopolymers and copolymers derived from acrylic or meth- esters and amides acrylics and comprising at least one unit chosen from the units of the following formulas:
[0137] where:
[0138] R1 and R2, identical or different, are chosen from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms such as methyl and ethyl groups;
[0139] R3, which may be the same or different, is chosen from hydrogen and CH3;
[0140] 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;
[0141] R4, R5 and R6, which may be identical or different, are chosen from the 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
[0142] X is an anion derived from an inorganic or organic acid, such as methsulfate anions and halides, for example, chloride and bromide.
[0143] The copolymers of family (1) may also comprise at least one unit derived from comonomers which may be chosen from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen atom by lower alkyl groups (CrC4), groups derived from acrylic or methacrylic acids and their esters, vinyl lactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.
[0144] Examples of copolymers of family (1) include, in particular:
[0145] copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide,
[0146] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in European patent application No. 0 080 976,
[0147] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methsulfate,
[0148] the copolymers of methacrylate or vinylpyrrolidone / dialkylaminoalkyl acrylate, quaternized or not, described, for example, in French patents Nos. 2,077,143 and 2,393,573,
[0149] dimethylaminoethyl methacrylate / vinylca-prolactam / vinylpyrrolidone terpolymers,
[0150] vinylpyrrolidone / methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymers, and
[0151] polymers of crosslinked methacryloyloxy(Ci-C4)alkyltri(Ci-C4)alkylammonium salts such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, for example, methylenebisacrylamide.
[0152] (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 marketed under the names “JR” (JR 400, JR 125, JR 30M) or “LR” (LR 400, LR 30M) by the company Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose having reacted with an epoxide substituted by a trimethylammonium group.
[0153] It is preferable that the cationic cellulosic polymer has at least one quaternary ammonium group, preferably a trialkyl quaternary ammonium group and, more preferably, a trimethyl quaternary ammonium group.
[0154] The quaternary ammonium group may be present in a group containing a quaternary ammonium group which may be represented by the following chemical formula (I): Rj (!) > . h h2 r —O”-VR4OTC—'Ç—C~N ™R3 » * i OH 1¾
[0155] where
[0156] each of R1 and R2 denotes a C1-3 alkyl group, preferably a methyl or ethyl group, and better still a methyl group,
[0157] R3 denotes a C, 23 alkyl group, preferably a methyl or ethyl group, and better still a methyl group,
[0158] X- denotes an anion, preferably a halide, and better still a chloride,
[0159] n denotes an integer from 0 to 30, preferably from 0 to 10, and better still 0, and
[0160] R4 denotes a C1-4 alkylene group, preferably an ethylene or propylene group.
[0161] The leftmost ether bond (-O-) in chemical formula (I) above can attach to the sugar ring of the polysaccharide.
[0162] It is preferable that the group containing a quaternary ammonium group is an O-CH2-CH(OH)-CH2-N+(CH3)3 group.
[0163] (3) Cationic cellulosic polymers such as cellulosic 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 hydroxyalkylcelluloses, for example, hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted, for example, with a salt selected from methacryloyl-ethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium salts.
[0164] The commercial products corresponding to these polymers are, for example, the products marketed under the names “Celquat® L 200” and “Celquat® H 100” by the company National Starch.
[0165] (4) The non-cellulosic cationic polysaccharides described in US patents Nos. 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups, cationic hyaluronic acid, dextran hydroxypropyl trimonium chloride. Guar gums modified with a salt, for example, 2,3-epoxypropyltrimethylammonium chloride (guar hydroxypropyltrimonium chloride), may also be used.
[0166] Such products are, for example, marketed under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162 by the company MEYHALL.
[0167] (5) Polymers comprising piperazinyl units and divalent groups alkylene or hydroxyalkylene with straight or branched chains, optionally interrupted by at least one entity chosen from oxygen, sulfur, nitrogen, aromatic rings, heterocyclic rings, as well as the oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French patents Nos. 2,162,025 and 2,280,361,
[0168] (6) Water-soluble polyaminoamides prepared, for example, by polycondensation of an acidic compound with a polyamine; these polyaminoamides being able to be crosslinked with an entity chosen from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bisunsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacyidiamines; bisalkyl halides; oligomers resulting from the reaction of a reactive difunctional compound with an entity chosen from bishalohydrins, bisazetidiniums, bishaloacyidiamines, bisalkyl halides, epihalohydrins, diepoxides and bisunsaturated derivatives; the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mole per amine group of the polyaminoamide; these polyaminoamides being optionally alkylated or, if they comprise at least one tertiary amine function, they can be quaternized. Such polymers are described, for example, in French patents Nos. 2,252,840 and 2,368,508,
[0169] (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 from 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, and the alkylene group comprises from 1 to 4 carbon atoms, such as an ethylene group. Such polymers are described, for example, in French patent No. 1,583,363. In at least one embodiment, these derivatives may be chosen from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.
[0170] (8) Polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio of polyalkylene polyamine to dicarboxylic acid may range from 0.8:1 to 1.4:1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine group of the polyaminoamide ranging from 0.5:1 to 1.8:1.
[0171] (9) Alkyldiallylamine cyclopolymers and dialkyldiallyl- cyclopolymers ammonium, such as homopolymers and copolymers comprising, as the main constituent of the chain, at least one unit chosen from the units of formulas (Ia) and (Ib): --------------— CW XÇ(R - / \ Rio Rm JCfÿk (Ib) ..............«Wt ■■■■■■ XÇ(RU) —CHS—
[0172] where:
[0173] k and t, identical or different, are equal to 0 or 1, the sum k+t being equal to 1;
[0174] R12 is chosen from hydrogen and methyl groups;
[0175] Rio and Rn, which may be the same or different, are chosen from alkyl groups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group comprises, for example, from 1 to 5 carbon atoms, and lower (Ci-C4)amidoalkyl groups or R10 and Ru may form, with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl and morpholinyl;
[0176] Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate. These polymers are described, for example, in French patent No. 2,080,759 and in its Certificate of Addition 2,190,406.
[0177] In one embodiment, Rio and Rio, identical or different, are chosen from alkyl groups comprising from 1 to 4 carbon atoms.
[0178] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chloride such as the homopolymer of dimethyldiallylammonium chloride sold under the name "MERQUAT® 100" by the company CALGON (and its counterparts of low weight average molecular weight) and the copolymers of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".
[0179] Quaternary diammonium polymers comprising at least one recurring unit of formula (II): Rn Ris ® — hT— Ar~ | r | x Ri 4 Rî§
[0180] where:
[0181] Rn, Ru, Rb, and Ri6, which may be the same or different, are chosen from aliphatic, alicyclic and arylaliphatic groups comprising from 1 to 20 carbon atoms and aliphatic lower hydroxyalkyl groups, or Rn, Ru, Ri5 and Ri6 may form, together or separately, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second heteroatom other than nitrogen, or alternatively Rn, Ru, R[5, and R[6, which may be the same or different, are chosen from linear or branched C1-C6 alkyl groups substituted by at least one group chosen from nitrile groups, ester groups, acyl groups, amide groups, -CO-O-Rp-E groups and -CO-NH-Rp-E groups, where Rn is an alkylene group and E is a quaternary ammonium group ;
[0182] Ai and Bb which may be identical or different, are chosen from polymethylene groups comprising from 2 to 20 carbon atoms, linear or branched, saturated or unsaturated, and which may comprise, linked or intercalated in the main chain, at least one entity chosen from aromatic nuclei, 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
[0183] X is an anion derived from an inorganic or organic acid;
[0184] Ai, Rn, and R15 can form, with the two nitrogen atoms to which they are linked, a piperazine ring;
[0185] if Ai is chosen from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, Bi can be chosen from:
[0186] -(CH2)n-CO-E'-OC-(CH2)n-
[0187] where E' is chosen from:
[0188] a) glycol residues of formula -OZO-, in which Z is chosen from linear or branched hydrocarbon groups and groups of the following formulas:
[0189] -(CH2-CH2-O)X-CH2-CH2-
[0190] -[CH2-CH(CH3)-O]y-CH2-CH(CH3)-
[0191] in which x and y, identical or different, are chosen from whole numbers ranging from 1 to 4, which represent a defined and unique degree of polymerization, and numbers ranging from 1 to 4, which represent an average degree of polymerization;
[0192] b) a bis-secondary diamine residue such as piperazine derivatives;
[0193] c) bis-primary diamine residues of formula -NH-Y-NH-, in which Y is chosen from linear or branched hydrocarbon groups and the divalent group -CH2 -CH2-SS-CH2-CH2- and
[0194] d) ureylene groups of formula -NH-CO-NH-.
[0195] In at least one embodiment, X is an anion such as chloride or bromide.
[0196] Such polymers are described, for example, in French Patent Nos. 2,320,330; 2,270,846; 2,316,271; 2,336,434 and 2,413,907 and American Patent 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.
[0197] Non-limiting examples of such polymers include those comprising at least one repeating unit of formula (III): Rts Ris (in)
[0198] where
[0199] Rn, Ru, Rb, and R[6, which may be the same or different, are chosen from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbon atoms, n and p, which may be the same or different, are integers ranging from 2 to 20, and X is an anion derived from an inorganic or organic acid.
[0200] (11) Polyquaterary ammonium polymers comprising units of formula (IV): Rts™
[0201] where:
[0202] Ri8, R19, R20, and R2b, identical or different, are chosen from hydrogen, methyl groups, ethyl groups, propyl groups, [3-hydroxypropyl, [3-hydroxyethyl, â-hydroxypropyl groups, -CH2CH2 (OCH2CH2)POH groups, in which p is selected from integers from 0 to 6, provided that R[8, R19, R20, and R2[ are not simultaneously hydrogen,
[0203] r and s, identical or different, are chosen from integers ranging from 1 to 6,
[0204] q is chosen from integers ranging from 0 to 34,
[0205] X is an anion such as a halide and
[0206] A is chosen from dihalide radicals and -CH2-CH2-O-CH2-CH2-.
[0207] Such compounds are described, for example, in European patent application No. 0 122 324.
[0208] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0209] Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers comprising units selected from vinylpyridine and vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.
[0210] According to one embodiment of the present invention, the at least one cationic polymer is chosen from cellulose ether derivatives comprising quaternary ammonium groups, such as the products marketed under the name "JR 400" by the company UNION CARBIDE CORPORATION, cationic cyclopolymers such as, for example, homopolymers and copolymers of dimethyldiallylammonium chloride marketed under the names MERQUAT® 100, MERQUAT® 550 and MERQUAT® S by the company CALGON, guar gums modified with a 2,3-epoxypropyltrimethylammonium salt and quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0211] (13) Polyamines
[0212] As a cationic polymer, it is also possible to use (co)polyamines, which may be homopolymers or copolymers, with a plurality of amino groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in a polymer backbone or a pendant group, if present, of the (co)polyamines.
[0213] Examples of (co)polyamines include chitosan, (co)polyallylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polydimethylaminoethylenemethacrylates, (co)polyvinylpyridines such as (co)poly-1-methyl-2-vinylpyridines, (co)polyimines such as (co)polyethyleneimines, (co)polypyridines such as (co)poly(quaternary pyridines), (co)polybiguanides such as (co)polyaminopropyl biguanides, (co)polylysines, (co)polyornithines, (co)poly arginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinyl acetals and their salts.
[0214] As (co)polyamines, it is preferable to use (co)polylysines. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine which can be produced by bacterial fermentation. Polylysine can be an α-polylysine or an ε-polylysine. For example, polylysine can be an ε-polylysine such as ε-Poly-L-lysine, generally used as a natural preservative in food products. Polylysine is a polyelectrolyte soluble in polar solvents such as water, propylene glycol and glycerol. Polylysine is commercially available in various forms, such as poly D-lysine and poly L-lysine. Polylysine can be in salt and / or solution form.
[0215] (14) Cationic polyamino acids
[0216] As the cationic polymer, it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers, with a plurality of amino groups and carboxyl groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in a polymer backbone or a pendant group, if present, of the cationic polyamino acids. The carboxyl group may be present in a pendant group, if present, of the cationic polyamino acids.
[0217] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, steardimonium hydroxyprolyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimonium hydroxypropyl hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed soy protein, etc.
[0218] The following descriptions relate to preferable embodiments of the cationic polymer.
[0219] It may be preferable for the cationic polymer to be chosen from cationic starches.
[0220] Examples of cationic starches that may be mentioned are starches modified by a 2,3-epoxypropyltrimethylammonium salt (for example the chloride), such as the product called hydroxypropyltrimonium chloride starch according to the INC1 nomenclature and sold under the name SENSOMER Cl-50 at Ondeo or Pencare TM DP 1015 at Ingredion.
[0221] It may also be preferable for the cationic polymer to be chosen from cationic gums.
[0222] The gums may be, for example, chosen from the group consisting of cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum and gum arabic.
[0223] Examples of cationic gum include cationic polygalactomannan derivatives such as guar gum derivatives and cassia gum derivatives, e.g., CTFA: Guar Hydroxypropyltrimonium Chloride, Hydroxypropyl Guar Hydroxypropyltrimonium Chloride and Cassia Hydroxypro-pyltrimonium Chloride. Guar Hydroxypropyltrimonium Chloride is commercially available under the Jaguar™ series of trade names from Rhodia Inc. and the N-Hance series of trade names from Ashland Inc. Cassia Hydroxypropyltrimonium Chloride is commercially available under the trademarks Sensomer™ CT-250 and Sensomer™ CT-400 from Lubrizol Advanced Materials, Inc or ClearHance™ from Ashland Inc.
[0224] It may also be preferable for the cationic polymer to be chosen from chitosans.
[0225] It may be preferable that the cationic polymer is selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkylammonium chloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as cationized collagen, cationic cellulosic polymers and their salts.
[0226] It may be even more preferable that the cationic polymer is selected from the group consisting of polylysine, polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch, hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan, and a mixture thereof.
[0227] The amount of the cationic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.
[0228] The amount of the 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.
[0229] The amount of the cationic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, and better still from 0.05% to 5% by weight, relative to the total weight of the composition.
[0230] (Anionic polymer)
[0231] An anionic polymer has a positive charge density. The charge density of the anionic polymer may be from 0.1 meq / g to 20 meq / g, preferably from 1 to 15 meq / g, and more preferably 4 to 10 meq / g if the anionic polymer is a synthetic anionic polymer, and the average degree of substitution of the anionic polymer may be 0.1 to 3.0, preferably 0.2 to 2.7, and more preferably 0.3 to 2.5 if the anionic polymer is a natural anionic polymer.
[0232] It may be preferable that the molecular weight of the anionic polymer is 300 or more, preferably 1,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, more preferably 50,000 or more, more preferably 100,000 or more, and most preferably 1,000,000 or more.
[0233] Unless otherwise defined in the descriptions, "molecular weight" may mean number average molecular weight.
[0234] According to the present invention, the anionic polymer is chosen from hyaluronic acid and its derivatives.
[0235] Hyaluronic acid can be represented by the following chemical formula.
[0236] In the context of the present invention, the term “hyaluronic acid” covers in particular the basic unit of hyaluronic acid of formula:
[0237] It is the smallest fraction of hyaluronic acid comprising a disac-charidic dimer, namely D-glucuronic acid and N-acetylglucosamine.
[0238] The term "hyaluronic acid and its derivatives" also includes, within the scope of the present invention, the linear polymer comprising the polymeric unit described above, linked together in the chain via an alternation of (1,4) and (1,3) glycosidic bonds, having a molecular weight (MW) which can range from 380 to 13,000,000 daltons. This molecular weight depends largely on the source from which the hyaluronic acid is obtained and / or the methods of preparation.
[0239] The term “hyaluronic acid and its derivatives” also includes, within the scope of the present invention, hyaluronic acid salts. As salts, mention may be made of alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts and mixtures thereof.
[0240] 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.
[0241] Consequently, the term “hyaluronic acid and its derivatives” includes all fractions or subunits of hyaluronic acid having a molecular weight included in particular in the range of molecular weights recalled above.
[0242] In the context of the present invention, hyaluronic acid fractions having no inflammatory activity are preferably used.
[0243] As an illustration of the different fractions of hyaluronic acid, reference may be made to the document “Hyaluronan fragments: an information-rich System”, R. Stern et al., European Journal of Cell Biology 58 (2006) 699-715, which reviews the listed biological activities of hyaluronic acid as a function of its molecular weight.
[0244] 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 of between 50 kDa and 5,000 kDa, in particular between 100 kDa and 5,000 kDa, in particular between 400 kDa and 5,000 kDa. In this case, the term used is high molecular weight hyaluronic acid.
[0245] Alternatively, the hyaluronic acid fractions that may also be suitable for the use covered by the present invention have a molecular weight of between 50 kDa and 400 kDa. In this case, the term used is intermediate molecular weight hyaluronic acid.
[0246] Alternatively, the hyaluronic acid fractions which may be suitable for the use covered by the present invention have a molecular weight of less than 50 kDa.
[0247] In this case, the term used is low molecular weight hyaluronic acid.
[0248] It may be preferable to use a combination of two hyaluronic acids or or salts thereof, including a combination of a high molecular weight hyaluronic acid or salt thereof, and an intermediate molecular weight hyaluronic acid or salt thereof; a combination of a high molecular weight hyaluronic acid or salt thereof and a low molecular weight hyaluronic acid or salt thereof; and a combination of a hyaluronic acid intermediate molecular weight luronic acid or a salt thereof and low molecular weight hyaluronic acid or a salt thereof.
[0249] Finally, the term “hyaluronic acid and its derivatives” also includes hyaluronic acid esters, in particular those in which all or part of the carboxylic groups of the acid functions are esterified by alkyls or oxyethylenated alcohols, containing from 1 to 20 carbon atoms, in particular with a degree of substitution at the level of the D-glucuronic acid of the hyaluronic acid ranging from 0.5 to 50%.
[0250] Mention may in particular be made of methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. Such esters have in particular been described in D. Campoccia et al. “Semisynthetic resorbable materials from hyaluronan esterification”, Biomaterials 19 (1998) 2101-2127.
[0251] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.
[0252] The molecular weights indicated above are also valid for hyaluronic acid esters.
[0253] The hyaluronic acid may in particular be the hyaluronic acid supplied by the company Hyactive under the trade name CPN (MW: 10 to 150 kDa), by the company Soliance under the trade name Cristalhyal (MW: 1,1x106), by the company Bioland under the name Nutra HA (MW: 820,000 Da), by the company Bioland under the name Nutra AF (MW: 69,000 Da), by the company Bioland under the name Oligo HA (MW: 6100 Da) or by the company Vam Farmacos Metica under the name D Factor (MW: 380 Da).
[0254] The amount of the anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and preferably 0.05% by weight or more, relative to the total weight of the composition.
[0255] The amount of the anionic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
[0256] The amount of the anionic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, and better still from 0.05% to 5% by weight, relative to the total weight of the composition.
[0257] (Amphoteric polymer)
[0258] An amphoteric polymer has both a positive charge density and a negative charge.
[0259] The positive charge density of the amphoteric polymer may be from 0.01 meq / g to 20 meq / g, preferably from 0.05 to 15 meq / g, and even more preferably from 0.1 to 10 meq / g.
[0260] The negative charge density of the amphoteric polymer may 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.
[0261] It may be preferable that the molecular weight of the amphoteric polymer is 500 or more, preferably 1,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more.
[0262] It may be preferable that the molecular weight of the amphoteric polymer is 1,000,000 or less, preferably 900,000 or less, and more preferably 800,000 or less.
[0263] Unless otherwise defined in the descriptions, “molecular weight” may mean number average molecular weight.
[0264] According to the present invention, the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.
[0265] Cationized hyaluronic acid comprises at least one cationic group, such as an ammonium group, in its molecule. The cationic group does not indicate a countercation of the salt, because the countercation is not in the hyaluronic acid molecule.
[0266] As salts, mention may be made of alkali metal salts such as sodium salt, alkaline earth metal salts such as magnesium salts, ammonium salts and mixtures thereof.
[0267] The cationized hyaluronic acid may have at least one group containing a quaternary ammonium group.
[0268] The cationized hyaluronic acid and / or a salt thereof may have a structure represented by the following general formula (1): (1)
[0269] where
[0270] R4 to R9 individually represent a hydrogen atom or a group containing a quaternary ammonium group (excluding the case where all R4 to R9 represent hydrogen atoms), and n represents an integer from 2 to 5000.
[0271] Examples of the group containing a quaternary ammonium group represented by R4 to R9 in the general formula (1) above include the groups represented by the following general formula (2): (2)
[0272] where
[0273] R1 to R3 individually represent hydrocarbon groups and X represents a monovalent anion.
[0274] Examples of the hydrocarbon groups represented by R1 to R3 above in general formula (2) include a linear or branched alkyl group, an unsaturated hydrocarbon group and an aromatic hydrocarbon group. Among these, the alkyl group is preferable. Examples of the alkyl group include alkyl groups having 1 to 30 (preferably 1 to 6) carbon atoms. It is preferable that the hydrocarbon groups represented by R1 to R3 are alkyl groups having 1 to 3 carbon atoms.
[0275] Examples of a monovalent pennant represented by X in the general formula (2) above include a halogen ion such as a fluorine ion, a bromine ion, a chlorine ion, and an iodine ion.
[0276] The quaternary ammonium group-containing group may be introduced by replacing the hydrogen atom of the carboxyl group included in the hyaluronic acid and / or a salt thereof used as a raw material (hereinafter referred to as "hyaluronic acid raw material and / or a salt thereof") with the quaternary ammonium group-containing group. In this case, the quaternary ammonium group-containing group is bonded to the oxygen atom of the (-C(=O)O—) group included in the cationized hyaluronic acid and / or a salt thereof according to this embodiment.The fact that the group containing a quaternary ammonium group is bonded to the oxygen atom of the (-C(=O)O-) group included in the cationized hyaluronic acid and / or a salt thereof according to this embodiment can be confirmed by the presence of a peak attributed to the carbon atom of the -C(=O)O- group to which the group containing the quaternary ammonium group is bonded via the oxygen atom, determined by analyzing the chemical shift of the nuclear magnetic resonance (13C NMR) spectrum.
[0277] Specifically, the group containing a quaternary ammonium group can be obtained by reacting the carboxyl group (and / or the hydroxyl group) of the raw material hyaluronic acid and / or a salt thereof with a cationizing agent which contains a quaternary ammonium group. It is preferable that the cationizing agent is at least one 2,3-epoxypropyltrialkylammonium halide represented by following general formula (3) and a 3-halo-2-hydroxypropyltrialkylammonium halide represented by the following general formula (4). The reaction of the raw material hyaluronic acid and / or a salt thereof with the cationizing agent is described in the production process below. (3)
[0278] where
[0279] R1 to R3 are the same as defined for general formula (2), and X represents a halogen atom. R 5 * X” Y OH R 2
[0280] where
[0281] R1 to R3 are the same as defined for general formula (2), and X represents a halogen atom.
[0282] Examples of halogen atoms represented by X and Y in the above general formulas (3) and (4) include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.
[0283] The cationized hyaluronic acid may have at least one group containing a quaternary ammonium group and has a degree of cationization of 0.05 to 0.6, preferably 0.1 to 0.5, and more preferably 0.15 to 0.4.
[0284] The degree of cationization (i.e., the degree of substitution with the group containing a quaternary ammonium group) of the cationized hyaluronic acid and / or a salt thereof according to this embodiment can be determined by calculating the nitrogen content of the raw material sodium hyaluronate and the nitrogen content of the cationized hyaluronic acid by the semi-micro Kjeldahl method, and determining the degree of cationization by the following expression based on the increase in the nitrogen content.
[0285] When the nitrogen content of the raw material sodium hyaluronate is called Nn(%) and the nitrogen content of the cationized hyaluronic acid having a cationization degree of (x) is called Ns(%), the relationship between the increase in nitrogen content (Ns-Nn) and the cationization degree (x) is represented by the following expression.
[0286] Ns-Nn(%)
[0287] =[14x / (molecular weight of the disaccharide unit of cationized hyaluronic acid)]xlOO
[0288] =[14x / (molecular weight of the disaccharide unit of the raw material sodium hyaluronate)+129.5x]xl00
[0289] =[14x / (4OL3+129.5x)]xlOO
[0290] Therefore, the degree of cationization (i.e., the degree of substitution with the group containing a quaternary ammonium group) can be calculated by the following expression.
[0291] Degree of cationization(x)=[(Ns-NN)x401.3] / [1400-129.5*(Ns-NN)]
[0292] The degree of cationization of a cationized hyaluronic acid when a raw material hyaluronic acid is unknown can be calculated by the above expression assuming that the raw material sodium hyaluronate is sodium hyaluronate having a purity of 99% or more.
[0293] It is possible that 1% or more, preferably 5% or more, and more preferably 10% or more and / or 50% or less, preferably 40% or less and more preferably 30% or less of the anionic groups in the hyaluronic acid are replaced by a cationic group, preferably a group containing a quaternary ammonium group, and more preferably the group containing a quaternary ammonium group represented by the general formula (2) above.
[0294] As cationized hyaluronic acid, mention may be made of hydroxypropyltrimonium hyaluronate marketed under the names Hyaloveil and Hyaloveul-MPF by Kewpie in Japan.
[0295] The amount of the amphoteric polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.
[0296] The amount of the amphoteric 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.
[0297] The amount of the amphoteric polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, and better still from 0.05% to 5% by weight, relative to the total weight of the composition.
[0298] (Non-polymeric acid having at least two acid dissociation constants)
[0299] The composition according to the present invention may comprise at least one non-polymeric acid having at least two pKa values or salt(s) thereof, i.e. at at least one non-polymeric acid having at least two acid dissociation constants or salt(s) thereof. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined at a constant temperature such as 25°C.
[0300] The non-polymeric acid having two or more pKa values or salt(s) thereof may be included in particle (a). The non-polymeric acid having two or more pKa values may function as a crosslinker, particularly an anionic crosslinker, for the cationic polymer and / or the amphoteric polymer.
[0301] It is preferable that the non-polymeric acid having two or more pKa values or salt(s) thereof is used with a cationic polymer and an anionic polymer.
[0302] The term "non-polymeric" herein means that the acid is not obtained by polymerizing two or more monomers. Therefore, non-polymeric acid does not correspond to an acid obtained by polymerizing two or more monomers such as polycarboxylic acid.
[0303] It is preferable that the molecular weight of the non-polymeric acid having two or more pKa values or salt(s) thereof is 1000 or less, preferably 800 or less, and more preferably 700 or less.
[0304] There is no limit to the type of non-polymeric acid having two or more pKa values or salt(s) thereof. Two or more different types of non-polymeric acids having two or more pKa values or their salts may be used in combination. Thus, a single type of non-polymeric acid having two or more pKa values or one of their salts or a combination of different types of non-polymeric acids having two or more pKa values or their salts may be used.
[0305] The term "salt" herein refers to a salt formed by addition of appropriate base(s) to the non-polymeric acid having two or more pKa values, which can be obtained from a reaction with the non-polymeric acid having two or more pKa values with the base(s) according to methods known to those skilled in the art. As a salt, mention may be made of metal salts, for example, alkali metal salts such as Na and K, and alkaline earth metal salts such as Mg and Ca, and ammonium salts.
[0306] The non-polymeric acid having two or more pKa values or salt(s) thereof may be an organic acid or salt(s) thereof, and preferably a hydrophilic or water-soluble organic acid or salt(s) thereof.
[0307] The non-polymeric acid having two or more pKa values may have at least two acid groups selected from the group consisting of a carboxylic group, a sulfuric group, a sulfonic group, a phosphoric group, a phosphonic group, a phenolic hydroxyl group, and a mixture thereof.
[0308] The non-polymeric acid having two or more pKa values may be a non-polymeric polyvalent acid.
[0309] The non-polymeric acid having two or more pKa values may be selected from the group consisting of dicarboxylic acids, disulfonic acids and diphosphoric acids, and a mixture thereof.
[0310] The non-polymeric acid having at least two pKa values or salt(s) thereof may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid and their salts; aspartic acid, glutamic acid and their salts; terephthalylidene dicamphor sulfonic acid or its salts (Mexoryl SX), Benzophenone-9; phytic acid and its salts;Red 2 (Amaranth), Red 102 (New Coccine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brilliant Blue FCF), Blue 2 (Indigo Carmine), Red 201 (Lithol Rubine B), Red 202 (Lithol Rubine BCA), Red 204 (Red Lake CB A), Red 206 (Lithol Red CA), Red 207 (Lithol Red BA), Red 208 (Lithol Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 227 (Fast Acid Magenta), Yellow 203 (Quinoline Yellow WS), Green 201 (Alizanine Cyanine Green F), Green 204 (Pyranine Conc), Green 205 (Light Green SF Yellowish), Blue 203 (Patent Blue CA), Blue 205 (Alfazurine FG), Red 401 (Violamine R), Red 405 (Permanent Re F5R), Red 502 (Ponceau 3R), Red 503 (Ponceau R), Red 504 (Ponceau SX), Green 401 (Naphthol Green B), Green 402 (Guinea Green B) and Black 401 (Naphthol Blue Black);folic acid, ascorbic acid, erythorbic acid and their salts; cystine and its salts; EDTA and its salts; glycyrrhizin and its salts and a mixture thereof. ;
[0311] It may be preferable that the non-polymeric acid having at least two pKa values or salt(s) thereof is selected from the group consisting of terephthalylidene dicamphor sulfonic acid and its salts (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and their salts and a mixture thereof.
[0312] The amount of non-polymeric acid having two or more pKa values or salt(s) thereof 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.
[0313] The amount of non-polymeric acid having two or more pKa values or salt(s) thereof in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
[0314] The amount of non-polymeric acid having two or more pKa values or salt(s) thereof in the composition according to the present invention may be from 0.001% 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.
[0315] (Non-polymeric base having at least two base dissociation constants)
[0316] The composition according to the present invention may comprise at least one non-polymeric base having at least two pKb values or salt(s) thereof, i.e. at least one non-polymeric base having at least two base dissociation constants or salt(s) thereof. The pKb value (base dissociation constant) is well known to those skilled in the art and must be determined at a constant temperature such as 25°C.
[0317] The non-polymeric base having two or more pKb values or salt(s) thereof may be included in particle (a). The non-polymeric base having two or more pKb values may function as a crosslinker, particularly a cationic crosslinker, for the anionic polymer and / or amphoteric polymers.
[0318] It is preferable that the non-polymeric acid having two or more pKb values or salt(s) thereof is used with a cationic polymer and an anionic polymer.
[0319] The term "non-polymeric" herein means that the base is not obtained by polymerizing two or more monomers. Therefore, the non-polymeric base does not correspond to a base obtained by polymerizing two or more monomers such as polyallylamine.
[0320] It is preferable that the molecular weight of the non-polymeric base having two or more pKb values or salt(s) thereof is 1000 or less, preferably 800 or less, and more preferably 700 or less.
[0321] There is no limit to the type of non-polymeric base having two or more pKb values or salt(s) thereof. Two or more different types of non-polymeric bases having two or more pKb values or their salts may be used in combination. Thus, a single type of non-polymeric base having two or more pKb values or a salt thereof or a combination of different types of non-polymeric bases having two or more pKb values or their salts may be used.
[0322] As salt, mention may be made of ammonium salts, for example, inorganic acid salts such as HCl and HNO3, and organic acid salts such as carboxylic acids and sulfonic acids.
[0323] The non-polymeric base having at least two pKb values or salt(s) thereof may be an organic base or salt(s) thereof, and preferably a hydrophilic or water-soluble organic base or salt(s) thereof.
[0324] The non-polymeric base having at least two pKb values may have at least two basic groups selected from the group consisting of an amino group, a guanidine group, a biguanide group, an imidazole group, an imino group, a pyridyl group and a mixture thereof.
[0325] The non-polymeric base having two or more pKb values may be selected from the group consisting of non-polymeric diamines such as ethylenediamine, propylenediamine, pentanediamine, hexanediamine, urea and its derivatives and guanidine and its derivatives, non-polymeric polyamines such as spermine and spermidine, basic amino acids and a mixture thereof.
[0326] The non-polymeric base having at least two or more pKb values or salt(s) thereof may be selected from the group consisting of arginine, lysine, histidine and a mixture thereof.
[0327] The amount of non-polymeric base having two or more pKb values or salt(s) thereof in the composition according to the present invention may be 0.001 wt% or more, preferably 0.005 wt% or more, and more preferably 0.01 wt% or more, based on the total weight of the composition.
[0328] The amount of the non-polymeric base having two or more pKb values or salt(s) thereof in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
[0329] The amount of non-polymeric base having at least two pKb values or salt(s) thereof in the composition of the present invention may be selected from salt(s) thereof in the group consisting of arginine, lysine, histidine, cysteine, cystine, tyrosine, tryptophan, omithine and a mixture thereof.
[0330] It may be preferable that the non-polymeric base 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.
[0331] [Surfactant]
[0332] The composition according to the present invention comprises (b) at least one surfactant. Two or more surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used.
[0333] The surfactant used in the present invention may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants and non-ionic surfactants.
[0334] (Anionic surfactants)
[0335] The composition according to the present invention may comprise at least one anionic surfactant. Two or more anionic surfactants may be used in combination.
[0336] It is preferable that the anionic surfactant is selected from the group consisting of (C6-C30) alkyl sulfates, (C6-C30) alkyl ether sulfates, (C6-C30) alkylamido sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; (C6-C30) alkyl sulfonates, (C6-C30) alkylamide sulfonates, (C6-C30) alkylaryl sulfonates, â-olefin sulfonates, paraffin; (C6-C30) alkyl phosphates; (C6-C30) alkyl sulfosuccinates, (C6-C30) ether sulfosuccinates, (C6-C30) alkylamide sulfosuccinates; (C6-C30) alkyl sulfoacetates; (C6-C24) acyl sarcosinates; (C6-C24) acyl glutamates; (C6-C30) alkyl polyglycoside carboxylic ethers; (C6-C30) alkyl polyglycoside sulfosuccinates; (C6-C30) alkyl sulfosuccinamates; (C6-C24) acyl isethionates; N-(C6-C24) acyl taurates; C6-C30 fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (C8-C20) acyl lactylates; (C6-C30) alkyl-D-galactoside uronic acid salts; polyoxyalkylenated (C6-C30) alkyl ether carboxylic acid salts;salts of polyoxyalkylenated (C6-C30) alkylarylether carboxylic acids and salts of polyoxyalkylenated (C6-C30) alkylamidoether carboxylic acids and the corresponding acid forms.;
[0337] In at least one embodiment, the anionic surfactants are in the form of salts such as alkali metal salts such as sodium; alkaline earth metal salts such as magnesium; ammonium salts; amine salts and amino alcohol salts. Depending on the conditions, they may also be in acid form.
[0338] It is more preferable that the anionic surfactant is selected from (C6-C30) alkyl sulfate salts, (C6-C30) alkyl ether sulfates or (C6-C30) alkyl ether carboxylic acid, salified or not.
[0339] (Amphoteric surfactants)
[0340] The composition according to the present invention may comprise at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.
[0341] The amphoteric or zwitterionic surfactants may be, for example, (non-limiting list), amine derivatives such as aliphatic secondary or tertiary amines, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain comprising 8 to 22 carbon atoms and containing at least one water-solubilizing anionic group (for example, carboxylate, sulfonate, sulfate, phosphate or phosphonate).
[0342] The amphoteric surfactant may preferably be chosen from the group consisting of betaines and amidoaminecarboxylated derivatives.
[0343] It is preferable that the amphoteric surfactant is chosen from betaine type surfactants.
[0344] The betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phos-phobetaines and alkylamidoalkylsulfobetaines, in particular, (C8-C24)alkylbetaines, (C8-C24)alkylamido(Ci-C8)alkylbetaines, sulphobetaines and (C8-C24)alkylamido(Ci-C8 )alkylsulphobetaines. In one embodiment, the amphoteric surfactants of betaine type are selected from (C8-C24)alkylbetaines, (C8-C24)alkylamido(Ci-C8)alkylsulphobetaines, sulphobetaines and phosphobetaines.
[0345] By way of non-limiting examples, mention may be made of the compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th edition, 2014, under the names cocobetaine, laurylbetaine, cetylbetaine, coco / oleamidopropylbetaine, cocamido-propylbetaine, palmitamidopropylbetaine, stearamidopropylbetaine, cocamidoethylbetaine, cocamidoethylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine, stearamidopropylbetaine, cocamidoethylbetaine, cocamidoethylbetaine, cocamidoethylbetaine, cocamidoethylbetaine, cocamidoethylbetaine, oleamidopropylhydroxysultaine, cocohydroxy-sultaine, laurylhydroxysultaine and cocosultaine, alone or in mixtures.
[0346] The betaine-type amphoteric surfactant is preferably an alkylbetaine and an al-kylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine.
[0347] Among the amidoaminecarboxylated derivatives, mention may be made of the products marketed under the name Miranol, as described in US patents Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures:
[0348] Ri-CONHCH2CH2-N+(R2)(R3)(CH2COO) M+
[0349] Where: Ri denotes an alkyl radical of an acid Ri-COOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical,
[0350] R2 denotes a beta-hydroxyethyl group,
[0351] R3 denotes a carboxymethyl group,
[0352] M+ denotes a cationic ion derived from alkali metals such as the sodium ion; the ion ammonium or an ion derived from an organic amine;
[0353] X denotes an organic or inorganic anionic ion such as halides, acetates, phosphates, nitrates, (CrC4)alkyl sulfates, (CrC4)-alkyl or (CrC4)arylalkyl sulfonates, in particular methyl sulfate and ethyl sulfate, or M+ and X are not present;
[0354] Ri'-CONHCH2CH2-N(B)(C) (B2)
[0355] Where:
[0356] R / denotes an alkyl radical of an acid Ri'-COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, such as a C7, C9, C h or C13 alkyl radical, a Cp alkyl radical and its iso form, or an unsaturated Cp radical,
[0357] B represents -CH2CH2OX',
[0358] C represents -(CH2)Z-Y', with z=1 or 2,
[0359] X' denotes a group -CH2-COOH, -CH2-COOZ', -CH2CH2-COOH, -CH2CH2 -COOZ' or a hydrogen atom and
[0360] Y' denotes a radical -COOH, -COOZ', -CH2-CHOH-SO3Z', -CH2-CHOH-SO3H or a radical -CH2-CH(OH)-SO3-Z',
[0361] Z' represents an ion of an alkali or alkaline earth metal such as a sodium ion, an ion derived from an organic amine or an ammonium ion;
[0362] and
[0363] Ra-NH-CH(Y”)-(CH2)nC(O)-NH-(CH2)nN(Rd)(Re) (B'2)
[0364] Where:
[0365] Y" denotes -C(O)OH, -C(O)OZ", -CH2-CH(OH)-SO3H or -CH2-CH(OH)-SO3-Z' ', where Z" denotes a cationic ion derived from an alkali metal or alkaline earth metals such as a sodium ion, an ion derived from an organic amine or an ammonium ion;
[0366] Rd and Re denote a C1-C4 alkyl or C1-C4 hydroxyalkyl radical;
[0367] R, denotes a Cio-C3o alkyl or alkenyl group of an acid and
[0368] n and n' independently denote an integer from 1 to 3.
[0369] It is preferable that the amphoteric surfactant of formula B1 and B2 is chosen from (C8-C24)-alkyl amphomonoacetates, (C8-C24)-alkyl amphodiacetates, (C8-C24)-alkyl amphomonopropionates and (C8-C24)-alkyl amphodipropionates.
[0370] These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodi-propionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate acid and Disodium Caprylamphodipropionate acid,
[0371] For example, mention may be made of cocoamphodiacetate marketed under the trade name Miranol® C2M concentrate by the company Rhodia Chimie.
[0372] Among the compounds of formula (B'2), mention may be made of diethylaminopropyl cocoas-partamide (CTFA) marketed by the company CHIMEX under the name CHIMEXANE HB.
[0373] (Cationic surfactants)
[0374] The composition according to the present invention may comprise at least one cationic surfactant. Two or more cationic surfactants may be used in combination.
[0375] The cationic surfactant may be chosen from the group consisting of optionally polyoxyalkylenated, primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
[0376] Examples of quaternary ammonium salts that may be mentioned include, but are not limited to:
[0377] those of general formula (B3) below:
[0378] where
[0379] Rb R2, R3, and R4, which may be the same or different, are selected from linear and branched aliphatic radicals, comprising from 1 to 30 carbon atoms and, optionally, comprising heteroatoms such as oxygen, nitrogen, sulfur and halogens. The aliphatic radicals may be selected, for example, from alkyl, alkoxy, C2-C6 polyoxyalkylene, alkylamide, (C12-C22)alkylamido (C2-C6)alkyl, (C12-C22)alkylacetate and hydroxyalkyl radicals and aromatic radicals such as aryl and alkylaryl; and X is selected from (C2-C6) alkyl halides, phosphates, acetates, lactates, sulfates and alkyl- or alkylaryl- sulfonates;
[0380] imidazoline quaternary ammonium salts, for example, those of formula (B4) below: (B4) î > ! I TO .CH>—CH.—NfW— CQ — R« I C ~ y" I \ K-» | A
[0381] where:
[0382] R5 is selected from alkenyl and alkyl radicals comprising from 8 to 30 carbon atoms, for example, derivatives of tallow or coconut fatty acids;
[0383] R6 is selected from hydrogen, C1-C4 alkyl radicals, and alkenyl and alkyl radicals comprising from 8 to 30 carbon atoms;
[0384] R7 is selected from C1-C4 alkyl radicals;
[0385] R8 is selected from hydrogen and C1-C4 alkyl radicals;
[0386] X is selected from halides, phosphates, acetates, lactates, sulfates alkyl, alkyl sulfonates and alkylaryl sulfonates. In one embodiment, R5 and R6 are, for example, a mixture of radicals selected from alkenyl and alkyl radicals, comprising from 12 to 21 carbon atoms, such as tallow fatty acid derivatives, R7 is methyl and R8 is hydrogen. Examples of such products include, in particular, Quatemium-27 (CTFA 1997) and Quatemium-83 (CTFA 1997), which are marketed under the names “Rewoquat®” W75, W90, W75PG and W75HPG by the company Witco;
[0387] di or tri quaternary ammonium salts of formula (B5): (B5) | R^ | | n--(CHà — N — I l Ws J
[0388] where:
[0389] R9 is chosen from aliphatic radicals comprising from 16 to 30 carbon atoms;
[0390] Rio is selected from hydrogen or alkyl radicals, comprising from 1 to 4 carbon atoms or a group -(CH2)3 (Ri6a)(Ri7a)(Ri8a)N+X-_;
[0391] Ru, Rn, Rb, Ru, Riôa, Rna, and Ri8a which may be identical or different, are chosen from hydrogen and alkyl radicals comprising from 1 to 4 carbon atoms and
[0392] X is selected from halides, acetates, phosphates, nitrates, ethyl sulfates and methyl sulfates.
[0393] An example of such a diquatemary ammonium salt is FINQUAT CT-P from FINETEX (Quatemium-89) or FINQUAT CT (Quatemium-75)
[0394] and
[0395] quaternary ammonium salts comprising at least one ester function, such as those of formula (B6) below: o (ÇsH2sO)z—R25 (B6) h L R24---C---(O-CrHr2(OH)ri)y---N — (CtHf2(OH)t1-O)x—R23 R22
[0396] where:
[0397] R22 is selected from C1-C6 alkyl radicals and hydroxyalkyl and di- radicals C1-C6 hydroxyalkyl;
[0398] R23 is chosen from:
[0399] of the radical below: —G----------
[0400] of linear and branched, saturated and unsaturated C1-C22 hydrocarbon radicals, R27, and hydrogen,
[0401] R25 is chosen from:
[0402] of the radical below: O ' R—c—
[0403] of linear and branched C1-C6 hydrocarbon radicals, saturated and unsaturated in R 29 and hydrogen,
[0404] R24, R26, and R28, which may be the same or different, are selected from linear and branched, saturated and unsaturated C7-C2i hydrocarbon radicals;
[0405] r, s and t, identical or different, are chosen from the integers ranging from 2 to 6;
[0406] rl and tl, which may each be the same or different, are 0 or 1, and r2+rl=2r and t l+2t=2t;
[0407] y is chosen from the integers ranging from 1 to 10;
[0408] x and z, identical or different, are chosen from whole numbers ranging from 0 to 10;
[0409] X is selected from simple and complex, organic and inorganic anions, provided that the sum of x+y+z is between 1 and 15, that when x is 0, R23 indicates R27, and that when z is 0, R25 indicates R27. R22 may be selected from linear and branched alkyl radicals. In one embodiment, R22 is selected from linear alkyl radicals. In another embodiment, R22 is selected from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example, methyl and ethyl radicals. In one embodiment, the sum of x+y+z is from 1 to 10. When R23 is the hydrocarbon radical R27, it may be long and have from 12 to 22 carbon atoms or short and have from 1 to 3 carbon atoms.
[0410] When R25 is a hydrocarbon-based radical R29, it may include, for example, from 1 to 3 carbon atoms. When R25 is the hydrocarbon radical R29, it may include, for example, from 1 to 3 carbon atoms. By way of non-exhaustive example, in one embodiment, R24, R26 and R28, which may be the same or different, are selected from linear and branched, saturated and unsaturated Cn-C2i hydrocarbon radicals, for example, from linear and branched, saturated and unsaturated Cn-C2i alkyl and alkenyl radicals. In another embodiment, x and z, which may be the same or different, are 0 or 1. In one embodiment, y is 1. In another embodiment, r, s, and t, which may be the same or different, are 2 or 3, e.g., 2.The anion X may be selected from, for example, halides, such as chloride, bromide and iodide and C1-C4 alkyl sulfates, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other ammonium-compatible anion having an ester function, are other non-limiting examples of anions that may be used according to the . present invention. In one embodiment, the anion X is selected from chloride and methyl sulfate.
[0411] In another embodiment, the ammonium salts of formula (B6) may be used, wherein:
[0412] R22 is selected from methyl and ethyl radicals,
[0413] x and y are equal to 1;
[0414] z is equal to 0 or 1;
[0415] r, s and t are equal to 2;
[0416] R23 is chosen from:
[0417] of the radical below: c---
[0418] methyl, ethyl, and C14-C22 hydrocarbon radicals and hydrogen;
[0419] R25 is chosen from:
[0420] of the radical below: j '
[0421] and hydrogen;
[0422] R24, R26 and R28, which may be the same or different, are chosen from linear and branched, saturated and unsaturated C13-C17 hydrocarbon radicals, for example, from linear and branched, saturated and unsaturated C13-C17 alkyl and alkenyl radicals.
[0423] In one embodiment, the hydrocarbon radicals are linear.
[0424] Non-limiting examples of compounds of formula (B6) that may be mentioned include salts of, for example, methyl chloride and sulfate, dia-cyloxyethyl-dimethylammonium, diacyloxyethyl-hydroxyethyl-methylammonium, monoacyloxyethyl-dihydroxyethyl-methylammonium, triacyloxyethyl-methyl-lammonium, monoacyloxyethyl-hydroxyethyl-dimethyl-ammonium and mixtures thereof. In one embodiment, the acyl radicals may comprise from 14 to 18 carbon atoms, and may be derived, for example, from a vegetable oil such as, for example, palm oil and sunflower oil. When the compound comprises several acyl radicals, these radicals may be the same or different.
[0425] These products can be obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine, optionally oxyalkylenated, on fatty acids or on mixtures of fatty acids of vegetable or animal origin, or by transesterification of their methyl esters. This esterification can be followed by quaternization using an alkylating agent chosen from among alkyl halides, for example, methyl and ethyl halides; dialkyl sulfates, for example, dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrin and glycerol chlorohydrin.
[0426] Such compounds are, for example, marketed under the names Dehyquart® by the company Cognis, Stepanquat® by the company Stepan, Noxamium® by the company Ceca, and “Rewoquat® WE 18” by the company Rewo-Goldschmidt.
[0427] Among other non-limiting examples of ammonium salts which can be used in the compositions according to the present invention, mention may be made of ammonium salts comprising at least one ester function described in US Patent Nos. 4,874,554 and 4,137,180.
[0428] The quaternary ammonium salts mentioned above which can be used in the composition according to the present invention include, in particular, those corresponding to formula (I), for example, tetraalkylammonium chlorides such as dialkyldimethylammonium and alkyltrimethylammonium chlorides in which the alkyl radical comprises approximately 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium and benzyldimethylstearylammonium chloride; palmitylamidopropyltrimethylammonium chloride and stearamidopropyldimethyl(myristylacetate)ammonium chloride, marketed under the name "Ceraphyl® 70" by the company Van Dyk.
[0429] According to one embodiment, the cationic surfactant usable in the composition according to the present invention is chosen from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, Quatemium-83, Quaternium-87, Quatemium-22, behenylamidopropyl-2,3-dihydroxypropyldimethylammonium chloride, palmitylamidopropyltrimethylammonium chloride and stearamidopropyldimethylamine.
[0430] (Non-ionic surfactants)
[0431] The composition according to the present invention may comprise at least one non-ionic surfactant. Two or more non-ionic surfactants may be used in combination.
[0432] Non-ionic surfactants are well-known compounds in themselves (see, for example, “Handbook of Surfactants” by M.R. Porter, Blackie & Son (Glasgow and London), 1991, pp. 116-178). 116-178). Thus, they may be chosen from alcohols, alpha-diols, alkylphenols and fatty acid esters, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, it is possible for the number of ethylene oxide or propylene oxide groups to vary from 2 to 50, and for the number of glycerol from 1 to 30. Maltose derivatives may also be mentioned. also mention, without limitation, copolymers of ethylene oxide and / or propylene oxide; condensates of ethylene oxide and / or propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 moles of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1.5 to 5 glycerol groups, such as from 1.5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 moles of ethylene oxide; ethoxylated oils of vegetable origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; mono or diesters of polyethoxylated fatty acids of glycerol (C6-C24) alkylpolyglycosides; N-(C6-C24)alkylglucamine derivatives; amine oxides such as C10-C14alkylamine oxides or N-(C10-C14)acylaminopro-pylmorpholine oxides; silicone surfactants and mixtures thereof.
[0433] The non-ionic surfactants may preferably be chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or polyglycerolated non-ionic surfactants. The oxyalkylenated units are more particularly oxyethylenated or oxypropylenated units, or a combination thereof, and are preferably oxyethylenated units.
[0434] Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants include:
[0435] monooxyalkylenated or polyoxyalkylenated alkylphenols in (C8-C24),
[0436] saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C8-C30 alcohols,
[0437] saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C8-C3o amides,
[0438] esters of saturated or unsaturated, linear or branched C8-C30 acids and monoalkylene glycols or polyalkylene glycols,
[0439] monooxyalkylated or polyoxyalkylated esters of saturated or unsaturated, linear or branched C8-C30 acids and of sorbitol,
[0440] saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated vegetable oils,
[0441] condensates of ethylene oxide and / or propylene oxide, among others, alone or in mixtures.
[0442] The surfactants preferably contain a number of moles of ethylene oxide and / or propylene oxide of between 1 and 100 and better still between 2 and 50. According to one of the embodiments of the present invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylenated fatty ester (polyethylene glycol ester of fatty acid).
[0443] Among the examples of polyoxyethylenated saturated fatty alcohol (or C8-C30 alcohols) which may be mentioned include adducts of ethylene oxide with lauryl alcohol, in particular those containing from 5 to 50 oxyethylene units and more particularly those containing from 7 to 12 oxyethylene units (CTFA designations Laureth-7 to Laureth-50); adducts of ethylene oxide with behenyl alcohol, in particular those containing from 9 to 50 oxyethylene units (CTFA designations Beheneth-9 to Beheneth-50); adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), in particular those containing from 10 to 50 oxyethylene units (CTFA designations Ceteareth-10 to Ceteareth-50); adducts of ethylene oxide with cetyl alcohol, in particular those containing from 10 to 50 oxyethylene units (CTFA designations Ceteth-10 to Ceteth-50); adducts of ethylene oxide with stearyl alcohol, in particular those containing from 10 to 50 oxyethylene units (CTFA designations Steareth-10 to Steareth-20);adducts of ethylene oxide with isostearyl alcohol, in particular those containing from 10 to 50 oxyethylene units (CTFA designations Isosteareth-10 to Isosteareth-50) and mixtures thereof.;
[0444] Examples of polyoxyethylenated unsaturated fatty alcohols (or C8-C30 alcohols) that may be mentioned include adducts of ethylene oxide with oleyl alcohol, particularly those containing from 2 to 50 oxyethylene units and more particularly those containing from 10 to 40 oxyethylene units (CTFA designations Oleth-10 to Oleth-40) and mixtures thereof.
[0445] As examples of monoglycerolated or polyglycerolated surfactants, C8-C40 monoglycerolated or polyglycerolated alcohols will preferably be used.
[0446] In particular, C8-C40 monoglycerolated or polyglycerolated alcohols corresponding to the following formula:
[0447] RO-[CH2-CH(CH2OH)-O]mH or RO-[CH(CH2OH)-CH2O]mH
[0448] in which R represents a linear or branched C8-C40 and preferably C8-C30 alkyl or alkenyl radical and m represents a number between 1 and 30 and preferably between 1.5 and 10.
[0449] Examples of compounds suitable in the context of the present invention include lauryl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 moles of glycerol, oleyl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 moles of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 moles of glycerol, cetearyl alcohol containing 6 moles of glycerol, oleocetyl alcohol containing 6 moles of glycerol and octadecanol containing 6 moles of glycerol.
[0450] Alcohol can represent a mixture of alcohols in the same way that the value of m represents a statistical value, meaning that, in a commercial product, several species of polyglycerolated fatty alcohols can coexist in the form of a mixture.
[0451] Among the monoglycerolated or polyglycerolated alcohols, it is preferable to use a C8 / Cio alcohol containing 1 mole of glycerol, a C10 / C12 alcohol containing 1 mole of glycerol and a C12 alcohol containing 1.5 moles of glycerol.
[0452] The C8-C40 monoglycerolated or polyglycerolated fatty esters can correspond to the following formula:
[0453] R'O-[CH2-CH(CH2OR'”)-O]mR” or R'O-[CH(CH2OR”')-CH2O]mR”
[0454] in which each of R', R" and R" independently represents a hydrogen atom, or a linear or branched C8-C40 and better still C8-C30 alkenyl or alkenyl-CO radical, provided that at least one of the radicals R', R" and R"' is not a hydrogen atom, and that m is a number between 1 and 30 and preferably between 1.5 and 10.
[0455] Examples of polyoxyethylenated fatty esters include adducts of ethylene oxide with esters of lauric, palmitic, stearic or behenic acid, and mixtures thereof, in particular those containing from 9 to 100 oxyethylenated units, such as PEG-9 to PEG-50 Laurate (CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 Palmitate (CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA names:
[0456] PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (CTFA names
[0457] PEG-9 behenate to PEG-50 behenate); polyethylene glycol monostearate 100 EO (CTFA name: PEG-100 stearate) and mixtures thereof.
[0458] According to one of the embodiments of the present invention, the non-ionic surfactant may be chosen from esters of polyols with saturated or unsaturated chain fatty acids containing, for example, from 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units, such as glyceryl esters of a C8-C24, preferably C12-C22, fatty acid or fatty acids, and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sorbitol esters of one or more C8-C24, preferably C12-C22, fatty acids and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units;sugar esters (sucrose, maltose, glucose, fructose and / or alkylglycose) of a C8-C24 fatty acid or fatty acids, preferably C12-C22 and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, more preferably from 10 to 100 oxyalkylene units; fatty alcohol ethers of a C8-C24 fatty alcohol or alcohols, preferably C12-C22 and their mixtures.;
[0459] As glyceryl esters of fatty acids, glyceryl stearate (glyceryl mono-, di- and / or tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate and mixtures thereof may be mentioned, and as polyoxyalkylated derivatives thereof, mono-, di- or triester of fatty acids with a polyoxyalkylenated glycerol (mono-, di- or triester of fatty acids with a polyalkylenated glycol ether of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di- and tristearate, such as PEG-20 glyceryl stearate (mono-, di- and / or tristearate) such as PEG-7 glyceryl cocoate.
[0460] Mixtures of these surfactants, such as, for example, the product containing glyceryl stearate and PEG-100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEGIN by Goldschmidt (CTFA name: glyceryl stearate SE), may also be used.
[0461] The sorbitol esters of C8-C24 fatty acids and their polyoxyalkylenated derivatives may be chosen from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate, sorbitan sesquioleate and alkoxylated sorbitan fatty acid esters containing, for example, from 20 to 100 EO, such as sorbitan monostearate (CTFA name: sorbitan stearate), marketed by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA designation: sorbitan palmitate), marketed by the company ICI under the name Span 40, sorbitan tristearate 20 EO (CTFA designation: polysorbate 65), marketed by the company ICI under the name Tween 65, polyethylene sorbitan trioleate (polysorbate 85), or products marketed under the trade names Tween 20 (polysorbate 20) or Tween 60 by Uniqema.
[0462] As esters of fatty acids and glucose or alkylglucose, glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters, methylglucoside diester of oleic acid (CTFA name: Methyl glucose dioleate), methylglucoside mixed ester and oleic acid / hydroxystearic acid mixture (CTFA name: Methyl glucose dioleate / hydroxystearate), methylglucoside ester of isostearic acid (CTFA name: Methyl glucose isostearate), methylglucoside ester of lauric acid (CTFA name: Methyl glucose laurate), the mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesquiisostearate),the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by the company AMERCHOL and their mixtures.
[0463] As ethoxylated ethers of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and methylglucose, and in particular the polyethylene glycol ether of the diester of methylglucose and stearic acid with approximately 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by the company AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methylglucose and stearic acid with approximately 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by the company AMERCHOL and that marketed under the name Grillocose PSE-20 by the company GOLDSCHMIDT and their mixtures can be cited as examples.
[0464] Examples of sucrose esters that may be mentioned are sucrose palmitostearate, sucrose stearate and sucrose monolaurate.
[0465] As sugar ethers, alkylpolyglucosides may be used, and, for example, decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel, and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl / capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818 / UP by Henkel, cetostearyl glucoside optionally mixed with cetostearyl alcohol, marketed, for example, under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example,in the form of a mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, co-coylethylglucoside, for example, in the form of a mixture (35 / 65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and their mixtures may in particular be cited.
[0466] Mention may also be made of mixtures of glycerides of alkoxylated vegetable oils such as mixtures of ethoxylated glycerides (200 EO) of palm and copra (7 EO).
[0467] The non-ionic surfactant according to the present invention preferably contains a C12-C22 branched alkenyl or acyl chain, in particular an oleyl or isostearyl group. More preferably, the non-ionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.
[0468] According to one of the embodiments of the present invention, the non-ionic surfactant may be chosen from copolymers of ethylene oxide and of propylene, in particular copolymers of the following formula:
[0469] HO(C2H4O)a(C3H6O)b(C2H4O)cH
[0470] in which a, b and c are integers such that a+c ranges from 2 to 100 and b ranges from 14 to 60, and mixtures thereof.
[0471] According to one of the embodiments of the present invention, the non-ionic surfactant may be chosen from silicone surfactants. Mention may be made, without limitation, of those disclosed in documents US-A-5364633 and US-A-5411744.
[0472] The silicone surfactant may preferably be a compound of formula (I):
[0473] Where:
[0474] Rb R2, and R3, independently of each other, represent a C1-C6 alkyl radical or a -(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4 radical, at least one Rb R2, or R3 radical not being an alkyl radical; R4 being a hydrogen, an alkyl radical or an acyl radical;
[0475] A is an integer between 0 and 200;
[0476] B is an integer between 0 and 50; provided that A and B are not simultaneously equal to zero;
[0477] x is an integer between 1 and 6;
[0478] y is an integer between 1 and 30 and
[0479] z is an integer between 0 and 5.
[0480] According to a preferred embodiment of the present invention, in the compound of formula (I), the alkyl radical is a methyl radical, x is an integer between 2 and 6 and y is an integer between 4 and 30.
[0481] As examples of silicone surfactants of formula (I), mention may be made of the compounds of formula (II): (CH3)3SiO - [(CH3)2SiO]A - (CH3SiO)B - Si(CH3)3 I (H) (CH2)2-(OCH2CH2)y-OH
[0482] in which A is an integer between 20 and 105, B is an integer between 2 and 10 and y is an integer between 10 and 20.
[0483] As examples of silicone surfactants of formula (I), mention may also be made of the compounds of formula (III):
[0484] H-(OCH2CH2)y-(CH2)3-[(CH3)2SiO]A -(CH2)3-(OCH2CH2)y-OH (III)
[0485] in which A' and y are integers between 10 and 20.
[0486] The compounds of the present invention which can be used are those marketed by the company Dow Corning under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667. Compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II) in which, respectively, A equals 22, B equals 2 and y equals 12; A equals 103, B equals 10 and y equals 12; A equals 27, B equals 3 and y equals 12.
[0487] Compound Q4-3667 is a compound of formula (III) in which A equals 15 and y equals 13.
[0488] It is preferable that the surfactant (b) is chosen from non-ionic surfactants.
[0489] It is even better that the surfactant (b) is chosen from poly- fatty acid esters glyceryl.
[0490] The polyglyceryl fatty acid ester may have a polyglycerol moiety derived from 2 to 10 glycerols, preferably 2 to 8 glycerols, and more preferably 2 to 6 glycerols. In other words, the polyglyceryl fatty acid ester may comprise 2 to 10 polyglyceryl units, preferably 2 to 8 polyglyceryl units, and more preferably 2 to 6 polyglyceryl units. If all of the polyglyceryl fatty acid ester has a shorter polyglyceryl chain (e.g., less than 10 polyglyceryl units, preferably less than 8 polyglyceryl units, and more preferably less than 6 polyglyceryl units), the stability of the composition according to the present invention may be improved.
[0491] The polyglyceryl fatty acid ester may be chosen from mono, di and tri esters of linear or branched, saturated or unsaturated, preferably saturated, fatty acids comprising from 4 to 32 carbon atoms, preferably from 8 to 26 carbon atoms, and better still from 10 to 20 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid and myristic acid.
[0492] It is preferable that the surfactant (b) is chosen from monoesters of saturated or unsaturated polyglyceryl fatty acids.
[0493] The polyglyceryl fatty acid ester may have an HLB (Hydrophilic / Lipophilic Balance) value of 4.0 to 16.0, preferably 4.5 to 15.5, and more preferably 5.0 to 15.0. The term HLB ("Hydrophilic-Lipophilic Balance") is well known to those skilled in the art and reflects the ratio of the hydrophilic portion to the lipophilic portion in the molecule. If two or more polyglyceryl fatty acid esters are used, the HLB value is determined by the weighted average of the HLB values of all the polyglyceryl fatty acid esters.
[0494] The polyglyceryl fatty acid ester may be selected from the group consisting of PG-2 stearate (HLB: 5.0), PG-2 isostearate (HLB: 5.5), PG-2 oleate (HLB: 6.5), PG-2 caprate (HLB: 9.5), PG-2 laurate (HLB: 8.5), PG-4 oleate (HLB: 8.8), PG-4 laurate (HLB: 10.4), PG-4 isostearate (HLB: 8.2), PG-5 laurate (HLB: 15.8), PG-6 isostearate (HLB: 10.8), PG-3 cocoate (HLB: 12.0), PG-3 caprate (HLB: 10.0), PG-4 caprylate (HLB: 14), PG-4 caprate (HLB: 14.0), PG-5 myristate (HLB: 15.4), PG-5 stearate (HLB: 15.0), PG-5 oleate (HLB: 14.9), PG-6 caprylate (HLB: 14.6), PG-6 caprate (HLB: 13.1), PG-6 laurate (HLB: 14.5), and mixtures thereof.
[0495] It may be preferable that the surfactant (b) is selected from the group consisting of PG-4 caprate (HLB: 14.0), PG-2 isostearate (HLB: 5.5), and a mixture thereof.
[0496] It is preferable that the composition according to the present invention comprises at least two polyglyceryl fatty acid esters.
[0497] It is preferable that the (b) surfactant is chosen from
[0498] at least one first polyglyceryl fatty acid ester having an HLB value of 4.0 to 8.0, preferably 4.5 to 8.0, and more preferably 5.0 to 8.0;
[0499] at least one second polyglyceryl fatty acid ester having an HLB value of 12.0 to 16.0, preferably 12.0 to 15.5, and more preferably 12.0 to 15.0 and
[0500] a mixture thereof.
[0501] The amount of the (b) surfactant(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition.
[0502] The amount of the (b) surfactant(s) in the composition according to the present invention may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the composition.
[0503] The amount of the (b) surfactant(s) in the composition according to the present invention may be from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, and better still from 0.1% to 10% by weight, relative to the total weight of the composition.
[0504] [Water]
[0505] The composition according to the present invention comprises (c) water.
[0506] The amount of water (c) may be 10% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight or more, relative to the total weight of the composition.
[0507] The amount of water (c) may be 99% by weight or less, preferably 97% by weight or less, and more preferably 95% by weight or less, relative to the total weight of the composition.
[0508] The amount of water (c) may be from 10 to 99% by weight, preferably from 30 to 97% by weight, and better still from 50 to 95% by weight, relative to the total weight of the composition.
[0509] [pH]
[0510] The pH of the composition according to the present invention may be from 2.0 to 9.0, preferably from 2.5 to 8.5, and more preferably from 3.0 to 8.0.
[0511] At pH 2.0 to 9.0, particle (a) may be very stable.
[0512] The pH of the composition according to the present invention may be adjusted by adding at least one alkaline agent and / or at least one acid, other than non-polymeric acid having two or more pKa values or salt(s) thereof or non-polymeric base having two or more pKb values or salt(s) thereof to be incorporated into the particle (a). The pH of the composition according to the present invention may also be adjusted by adding at least one buffering agent.
[0513] (Alkaline agent)
[0514] The composition according to the present invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Therefore, a single type of alkaline agent or a combination of different types of alkaline agents may be used.
[0515] The alkaline agent may be an inorganic alkaline agent. It is preferable that the inorganic alkaline agent is selected from the group consisting of ammonia; alkali metal hydroxides; alkaline earth metal hydroxides; alkali metal phosphates and monohydrogen phosphates such as sodium phosphate or sodium monohydrogen phosphate.
[0516] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. As an inorganic alkaline agent, sodium hydroxide is preferable.
[0517] The alkaline agent may be an organic alkaline agent. It is preferable that the organic alkaline agent is selected from the group consisting of monoamines and their derivatives; diamines and their derivatives; polyamines and their derivatives; basic amino acids and their derivatives; oligomers of basic amino acids and their derivatives; polymers of basic amino acids and their derivatives; urea and its derivatives and guanidine and its derivatives.
[0518] Examples of organic alkaline agents include alkanolamines such as mono-, di- and triethanolamine, and isopropanolamine; urea, guanidine and their derivatives; basic amino acids such as lysine, ornithine or arginine and diamines such as those described in the structure below:
[0519] where R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a C1-C4 alkyl radical and Rh R2, R3 and R4 independently denote a hydrogen atom, an alkyl radical or a C1-C4 hydroxyalkyl radical, which can be exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferable.
[0520] The alkaline agent(s) may be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, better still 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.
[0521] (Acid)
[0522] 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.
[0523] As the acid, mention may be made of all mineral or organic acids, preferably mineral acids, commonly used in cosmetic products. A monovalent acid and / or a polyvalent acid may be used. A monovalent acid such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) may be used. HCl is preferable.
[0524] The acid(s) may be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, more preferably 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.
[0525] (Buffering agent)
[0526] The composition according to the present invention may comprise at least one buffering agent. Two or more buffering agents may be used in combination. Therefore, a single type of buffering agent or a combination of different types of buffering agents may be used.
[0527] As buffering agent, mention may be made of an acetate buffer (e.g., acetic acid + sodium acetate), a phosphate buffer (e.g., sodium dihydrogen phosphate + disodium hydrogen phosphate), a citrate buffer (e.g., citric acid + sodium citrate), a borate buffer (e.g., boric acid + sodium borate), a tartrate buffer (e.g., tartaric acid + sodium tartrate dihydrate), a Tris buffer (e.g., tris(hydroxymethyl)aminomethane) and a Hepes buffer (4-(2-hydroxyethyl)-l-piperazineethanesulfonic acid).
[0528] [Oil]
[0529] The composition according to the present invention may comprise (d) at least one oil. If two or more oils (d) are used, they may be the same or different.
[0530] Here, by "oil" is meant a fatty compound or substance which is in the form of a liquid or a paste (not solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As oils, those generally used in cosmetics can be used alone or in combination. These oils can be volatile or non-volatile.
[0531] The oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a vegetable or animal oil and an ester oil or an ether oil or a mixture thereof.
[0532] The oil may be chosen from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.
[0533] Examples of vegetable oils include, for example, apricot oil, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil and mixtures thereof.
[0534] Examples of animal oils include, for example, squalene and squalane.
[0535] Examples of synthetic oils include alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.
[0536] The ester oils are preferably liquid esters of linear or branched C1-C26 saturated or unsaturated aliphatic monoacids or polyacids and linear or branched C1-C26 saturated or unsaturated aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
[0537] Preferably, for the monoalcohol esters, at least one of the alcohol and the acid from which the esters of the present invention are derived is branched.
[0538] Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl or ethyl myristate, isocetyl stearate, 2-ethylhexyl neononanoate, isonate, and isostearyl neopentanoate.
[0539] Esters of C4-C22 di or tricarboxylic acids and C1-C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and non-sugar C4-C26 dihydroxy, trihydroxy, tetra or pentahydroxy alcohols may also be used.
[0540] Mention may in particular be made of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.
[0541] As ester oils, esters and diesters of C6-C30 sugars and preferably C12-C22 fatty acids can be used. It is recalled that the term "sugar" means oxygenated hydrocarbon compounds comprising several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.
[0542] Examples of suitable sugars include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and their derivatives, including alkylated derivatives such as methylated derivatives, for example, methylglucose.
[0543] The fatty acid sugar esters may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched, saturated or unsaturated C6-C30 and preferably C[2-C22] fatty acids. If they are unsaturated, these compounds may have one to three conjugated or unconjugated carbon-carbon double bonds.
[0544] The esters according to this variant can also be chosen from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.
[0545] These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as in particular mixed esters of oleopalmitate, oleostearate and palmitostearate, as well as tetraethyl pentaerythrityl hexanoate.
[0546] More particularly, monoesters and diesters are used, and in particular monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates of sucrose, glucose or methylglucose.
[0547] As an example, we can cite the product marketed under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
[0548] Examples of preferable ester oils include, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate / caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearopropyl, isocetyl stearate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate and mixtures thereof.
[0549] Examples of artificial triglycerides include, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate / caprylate) and glyceryl tri(caprate / caprylate) caprylate / linolenate.
[0550] Examples of silicone oils that may be mentioned include, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, etc. cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like and mixtures thereof.
[0551] Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
[0552] These silicone oils can also be organomodified. The organomodified silicones that can be used according to the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached by a hydrocarbon group.
[0553] Organopolysiloxanes are further defined in Chemistry and Technology of Silicones (1968) by Walter Noll, Academie Press. They may be volatile or non-volatile.
[0554] When they are volatile, the silicones are more particularly chosen from those having a boiling point between 60°C and 260°C, and even more particularly from:
[0555] (i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably from 4 to 5 silicon atoms. These include, for example, octamethylcyclotetrasiloxane marketed in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane marketed under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane marketed under the name Silsoft 1217 by the company Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type such as Silicone Volatile® FZ 3109 marketed by the company Union Carbide, of formula: D D ----HQ — CH, j CH, with D" ' """ ® ~ ® with D' : "" Ss ™ Q CH3 CgH1?
[0556] Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis(2,2,2',2 le ',3,3'-hexatrimethylsilyloxy)neopentane and
[0557] (ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity less than or equal to 5x106 m2 / s at 25°C. An example is deca-methyltetrasiloxane marketed in particular under the name SH 200 by the Toray Silicone Company. Silicones in this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pages 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of silicones is measured at 25°C according to ASTM 445 Appendix C.
[0558] Non-volatile polydialkylsiloxanes can also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may mainly be made of polydimethylsiloxanes with trimethylsilyl end groups.
[0559] Among these polydialkylsiloxanes, the following commercial products may be mentioned, without limitation:
[0560] - Silbione ® oils of the 47 and 70 047 series or Mirasil ® oils commer marketed by Rhodia, such as, for example, oil 70 047 V 500 000;
[0561] - oils from the Mirasil ® series marketed by the company Rhodia;
[0562] - Dow Corning's 200 series oils, such as DC200 having a viscosity of 60,000 mm2 / s and
[0563] - General Electric Viscasil ® oils and certain SF series oils (SF 96, SF 18) from General Electric.
[0564] Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known as dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.
[0565] Among the silicones with aryl groups, mention may be made of polydiarylsiloxanes, in particular polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenylated silicone oil.
[0566] The phenylated silicone oil can be chosen from phenylated silicones of the following formula:
[0567] Where
[0568] Ri to Rio, independently of each other, are saturated or unsaturated, linear, cyclic or branched hydrocarbon radicals in C1-C30, preferably hydrocarbon radicals in CrCi2 and better still, hydrocarbon radicals in C1 - C6, in particular methyl, ethyl, propyl or butyl radicals and
[0569] m, n, p and q are, independently of one another, integers from 0 to 900 inclusive, preferably from 0 to 500 inclusive, and better still from 0 to 100 inclusive,
[0570] Provided that the sum n+m+q is not 0.
[0571] Examples include products marketed under the following names:
[0572] - Silbione® oils of the 70 641 series from Rhodia;
[0573] - oils of the Rhodorsil® 70 633 and 763 series from Rhodia;
[0574] - Dow Corning 556 Cosmetic Grade Fluid oil from Dow Corning;
[0575] - Bayer PK series silicones, such as product PK20;
[0576] - certain General Electric SF series oils, such as SF 1023, SF 1154, SF 1250 and SF 1265.
[0577] As the phenyl silicone oil, phenyl trimethicone (R10 to R10 represent methyl groups, p, q, and n = 0; m = 1 in the above formula) is preferable.
[0578] Organomodified liquid silicones may in particular contain polyethyleneoxy and / or polypropyleneoxy groups. Examples include KF-6017 silicone offered by Shin-Etsu, and Silwet® L722 and L77 oils from Union Carbide.
[0579] The hydrocarbon oils can be chosen from:
[0580] - linear or branched lower C6-Ci6 alkanes, possibly cyclic. A Examples include hexane, undecane, dodecane, tridecane, isoparaffins such as, for example, isohexadecane, isododecane and isodecane and
[0581] - linear or branched hydrocarbons containing more than 16 carbon atoms, such as such as paraffin oils, liquid petrolatum, polydecenes and hydrogenated polyisobutenes such as Parleam and squalane.
[0582] As preferred examples of hydrocarbon oils, mention may be made, for example, of linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g. liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, etc., hydrogenated polyisobutene, isoeicosane and decene / butene copolymer and mixtures thereof.
[0583] The term "fatty" in fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols that have 4 or more, preferably 6 or more, and most preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols. Fatty alcohol may be saturated or unsaturated. Fatty alcohol may be linear or branched.
[0584] The fatty alcohol may have the structure R-OH in which R is selected from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R is selected from C12-C20 alkyl and C12-C20 alkenyl groups. R may be substituted or not by at least minus one hydroxyl group.
[0585] Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenic alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleic alcohol, palmitoleyl alcohol, arachidonyl alcohol, alcohol and mixtures thereof.
[0586] It is preferable that the fatty alcohol is a saturated fatty alcohol.
[0587] Therefore, the fatty alcohol may be chosen from linear or branched, saturated or unsaturated C6-C30 alcohols, preferably linear or branched, saturated C6-C30 straight or branched alcohols and better still linear or branched, saturated C12-C20 alcohols.
[0588] By "saturated fatty alcohol" is meant here an alcohol with a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol is chosen from all linear or branched fatty alcohols, saturated in C6-C30. Among the linear or branched fatty alcohols, saturated in C6-C30, linear or branched fatty alcohols, saturated in C12-C20 can preferably be used. All linear or branched fatty alcohols, saturated in C16-C20 can be used even better. Branched fatty alcohols in C16-C20 can be used even better.
[0589] Examples of saturated fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenic alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol), as well as behenyl alcohol, may be used as the saturated fatty alcohol.
[0590] According to at least one embodiment, the fatty alcohol used in the composition according to the present invention is preferably chosen from octyldodecanol, hexyldecanol and their mixtures.
[0591] According to the present invention, the oil (d) may be surrounded by a plurality of particles (a) or the oil (d) may be present in the hollow of a capsule formed by the particles (a). In other words, the oil (d) may be covered by the particles (a), or a capsule formed by the particles (a) includes the oil (d) in the hollow of the capsule.
[0592] The oil (d) which is surrounded by the particles (a) or present in the hollow of the capsule formed by the particles (a) cannot come into direct contact with a keratin substance such as the skin. Thus, even if the oil (d) has a sticky or greasy feeling in use, the composition according to the present invention will not provide a sticky or greasy feeling during use.
[0593] The amount (d) of oil(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, based on the total weight of the composition.
[0594] The amount (d) of oil(s) in the composition according to the present invention may be 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less, relative to the total weight of the composition.
[0595] The amount (d) of oil(s) in the composition according to the present invention may be from 0.01% to 50% by weight, preferably from 0.05% to 40% by weight, and better still from 0.1% to 30% by weight, relative to the total weight of the composition.
[0596] [Polyol]
[0597] The composition according to the present invention may comprise at least one polyol. If two or more polyols are used, they may be the same or different.
[0598] The term "polyol" herein means an alcohol having two or more hydroxy groups, and does not include a saccharide or a derivative thereof. The derivative of a saccharide includes a sugar alcohol which is obtained by reducing one or more carbonyl groups of a saccharide, as well as a saccharide or a sugar alcohol in which the hydrogen atom(s) in one or more hydroxy groups thereof has or has been replaced by at least one substituent such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group or a carbonyl group.
[0599] The polyols used in the present invention are liquid at room temperature such as 25°C under atmospheric pressure (760 mm Hg or 105 Pa).
[0600] The polyol may be a C2-24 polyol, preferably a C2-9 polyol, comprising at least 2 hydroxy groups, and preferably from 2 to 5 hydroxy groups.
[0601] The polyol may be a natural or synthetic polyol. The polyol may have a linear, branched or cyclic molecular structure.
[0602] The polyol may be selected from glycerins and their derivatives, and glycols and their derivatives. The polyol may be selected from the group consisting of glycerin, di-glycerin, polyglycerin, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, C6-C24 polyethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol.
[0603] The amount of the polyol(s) in the composition used in the present invention may be 1% by weight or more, preferably 3% by weight or more, and more preferably 5% by weight or more, relative to the total weight of the composition.
[0604] On the other hand, the amount of the polyol(s) in the composition used in the present invention may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the composition.
[0605] The amount of polyol(s) in the composition used in the present invention may range from 1 to 20% by weight, preferably from 3 to 15% by weight, and better still from 5 to 10% by weight, relative to the total weight of the composition.
[0606] [Optional additives]
[0607] The composition according to the present invention may comprise, in addition to the aforementioned components, components typically used in cosmetics, in particular hydrophilic or lipophilic thickeners, volatile or non-volatile organic solvents such as ethanol, silicones and silicone derivatives other than (d) oil, natural extracts derived from animals or plants, waxes and the like, in a range which does not alter the effects of the present invention.
[0608] The composition according to the present invention may comprise the above optional additive(s) in an amount of 0.01 to 50% by weight, preferably 0.05 to 30% by weight, and better still 0.1 to 10% by weight, relative to the total weight of the composition.
[0609] [Composition]
[0610] The composition according to the present invention may be intended to be used as a cosmetic composition. Thus, the cosmetic composition according to the present invention may be intended to be applied to a keratin substance. By keratin substance is meant here a material containing keratin as a main constituent element, and examples thereof include skin, scalp, nails, lips, hair, etc. Thus, it is preferable that the cosmetic composition according to the present invention is used for a cosmetic process of keratin material, in particular of the skin.
[0611] Thus, the cosmetic composition according to the present invention may be a cosmetic composition for the skin, preferably a skin care composition or a skin makeup composition, and even better a skin care composition.
[0612] The composition according to the present invention can be prepared by mixing the above essential and optional ingredients according to any of the methods which are well known to those skilled in the art.
[0613] The composition according to the present invention can be prepared by simple or easy mixing with a conventional mixing means such as an agitator. Thus, high shear by, for example, a homogenizer is not necessary. In addition, heating is not necessary.
[0614] If the composition according to the present invention comprises the oil(s) (d), it may be in the form of an emulsion, an O / W emulsion or a W / O emulsion. It is preferable that the composition according to the present invention is in the form of an O / W emulsion, because it can provide a sensation of freshness thanks to the water (c) which constitutes its external phase.
[0615] The composition according to the present invention can be used to easily prepare a film. The particles (a) can aggregate and integrate into a continuous film.
[0616] Thus, the present invention also relates to a process for preparing a film, preferably a cosmetic film, optionally with a thickness preferably greater than 0.1 μm, better still 0.5 μm or more, and even better still 1 μm or more comprising:
[0617] the application to a substrate, preferably a keratinous substance, better still the skin, of the composition according to the present invention and
[0618] drying the composition.
[0619] The upper limit of the thickness of the film according to the present invention is not limited. Thus, for example, the thickness of the film according to the present invention may be 1 mm or less, preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less.
[0620] The method for preparing a film according to the present invention comprising the steps of applying the composition according to the present invention to a substrate, preferably a keratin material, and more preferably the skin, and drying the composition, the method according to the present invention does not require any spin or spray coating, and therefore, it is possible to easily prepare even a relatively thick film. Thus, the method for preparing a film according to the present invention can prepare a relatively thick film without any special equipment such as centrifuges and spray machines.
[0621] Even though the film according to the present invention is relatively thick, it is still thin and may be transparent, and therefore, may not be easy to perceive. Thus, the film according to the present invention can be preferably used as a cosmetic film.
[0622] If the substrate is not a keratin material such as skin, the composition according to the present invention may be applied to a substrate made of any material other than keratin. The materials of the non-keratin substrate are not limited. Two or more materials may be used in combination. Thus, a single type of material or a combination of different types of materials may be used. In any case, it is preferable that the substrate be flexible or elastic.
[0623] If the substrate is not a keratin material, it is preferable that the substrate is water-soluble, since it is possible to remove the film according to the present invention by washing the substrate with water. Examples of water-soluble materials include poly(meth)acrylic acids, polyethylene glycols, polyacrylamides, polyvinyl alcohol (PVA), starch, cellulose acetates, etc. PVA is preferable.
[0624] 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 fixed on 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 pm to 1 mm, and better still 50 to 500 pm.
[0625] It is preferable that the film according to the present invention is detachable from the non-keratinous substrate. The detachment method is not limited. Therefore, the film according to the present invention can be peeled off from the non-keratinous substrate, or released by dissolving the substrate sheet in a solvent such as water.
[0626] The present invention also relates to:
[0627] (1) a film, preferably a cosmetic film, optionally with a thickness of preferably greater than 0.1 pm, more preferably 0.5 pm or more, and even more preferably 1 pm or more, prepared according to a process comprising:
[0628] the application to a substrate, preferably a keratin material, and better still the skin, of the composition according to the present invention and
[0629] drying the composition,
[0630] and
[0631] (2) A film, preferably a cosmetic film, optionally with a thickness of preferably greater than 0.1 pm, more preferably 0.5 pm or more, and even more preferably 1 pm or more, comprising:
[0632] at least one cationic polymer and at least one anionic polymer,
[0633] at least one cationic polymer and at least one amphoteric polymer,
[0634] at least one anionic polymer and at least one amphoteric polymer or
[0635] at least one amphoteric polymer;
[0636] at least one non-polymeric acid having two or more pKa values or salt(s) thereof or at least one non-polymeric base having two or more pKb values or salt(s) thereof;
[0637] at least one surfactant, preferably a non-ionic surfactant, and better still a polyglyceryl fatty acid ester;
[0638] and
[0639] optionally at least one oil,
[0640] where
[0641] the anionic polymer is chosen from hyaluronic acid and its derivatives and
[0642] the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.
[0643] The above explanations concerning cationic, anionic and amphoteric polymers as well as the above oil can be applied to those of the above films (1) and (2).
[0644] The film thus obtained above may be independent. The term "independent" herein means that the film may be in the form of a sheet and may be handled as an independent sheet without the aid of a substrate or support. Thus, the term "independent" may have the same meaning as "self-sufficient".
[0645] It is preferable that the film according to the present invention is hydrophobic.
[0646] The term "hydrophobic" in the present description means that the solubility of the polymer in water (preferably with a volume of 1 liter) at 20 to 40°C, preferably 25 to 40°C, and more preferably 30 to 40°C is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, relative to the total weight of the polymer. Most preferably, the polymer is not soluble in water.
[0647] If the film according to the present invention is hydrophobic, the film can have water-resistant properties, and thus, it can remain on a keratin substance such as skin even if the surface of the keratin substance is wet due to, for example, sweat and rain. Thus, when the film according to the present invention provides any cosmetic effect, the cosmetic effect can last for a long time.
[0648] On the other hand, the film according to the present invention can be easily removed from a keratin material such as skin under alkaline conditions such as a pH of 8 to 12, preferably 9 to 11. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can provide such alkaline conditions.
[0649] The film according to the present invention may comprise at least one biocompatible and / or biodegradable polymer layer. Two or more biocompatible and / or biodegradable polymers may be used in combination. Thus, a single type of biocompatible and / or biodegradable polymer or a combination of different types of biocompatible and / or biodegradable polymers may be used.
[0650] The term "biocompatible" polymer in the present description means that the polymer does not have excessive interaction between the polymer and the cells of the living body, including the skin, and the polymer is not recognized by the living body as a foreign material.
[0651] The term "biodegradable" polymer in the present description means that the polymer can be degraded or broken down in a living body due to, for example, the metabolism of the living body itself or the metabolism of microorganisms that may be present in the living body. In addition, the biodegradable polymer can be degraded by hydrolysis.
[0652] If the film according to the present invention comprises a biocompatible and / or biodegradable polymer, it is less irritating or non-irritating to the skin, and does not cause a skin rash. In addition, by using a biocompatible and / or biodegradable polymer, the cosmetic sheet according to the present invention can adhere well to the skin.
[0653] The film according to the present invention can be used for cosmetic treatments of keratin materials, preferably of the skin, in particular of the face. The film according to the present invention can be in any form. For example, It can be used as a full face mask sheet or as a patch for a part of the face like cheek, nose and eye area.
[0654] If the film according to the present invention comprises at least one hydrophilic or water-soluble UV filter, it can provide UV protection effects derived from the hydrophilic or water-soluble UV filter. Normally, a hydrophilic or water-soluble UV filter can be removed from the surface of a keratin substrate such as skin by water such as sweat and rain. However, since the hydrophilic or water-soluble UV filter is included in the film according to the present invention, it is difficult for the hydrophilic or water-soluble UV filter to be removed by water, thus resulting in long-lasting UV protection effects.
[0655] [Cosmetic process and use]
[0656] The present invention also relates to:
[0657] A cosmetic process for a keratin material such as skin, comprising applying to the keratin material the composition according to the present invention and drying the composition to form a cosmetic film on the keratin material and
[0658] a use of the composition according to the present invention for the preparation of a cosmetic film on a keratin material such as the skin.
[0659] By cosmetic process is meant here a non-therapeutic cosmetic method of caring for and / or making up the surface of a keratinous material such as the skin.
[0660] In the above method and use, the above cosmetic film is resistant to water with a pH of 7 or less, and can be removed with water with a pH of more than 7, preferably 8 or more, and more preferably 9 or more.
[0661] In other words, the above cosmetic film can be water-resistant under neutral or acidic conditions such as a pH of 7 or less, preferably in a range of 6 or more and 7 or less, and more preferably in a range of 5 or more and 7 or less, while the above cosmetic film can be removed under alkaline conditions such as a pH of more than 7, preferably 8 or more, and more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11.
[0662] Accordingly, the above cosmetic film can be water-resistant, and thus, it can remain on a keratin substance such as skin even if the surface of the keratin substance is wet due to, for example, sweat and rain. On the other hand, the above cosmetic film can be easily removed from a keratin material such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can provide alkaline conditions.
[0663] If the above cosmetic film includes a UV filter that may be present in the composition according to the present invention, the above cosmetic film can protect a keratin material such as the skin from UV rays, thereby limiting the darkening of the skin, improving the color and uniformity of the complexion, and / or treating skin aging.
[0664] Furthermore, the above cosmetic film may have cosmetic effects such as capturing sebum, mattifying the appearance of a keratin substrate such as the skin, absorbing or adsorbing unpleasant odors, and / or protecting the keratin material, for example, from dirt or pollutants, due to the properties of the polyionic complex particles present in the cosmetic film, even if the cosmetic film does not comprise any cosmetic active ingredient.
[0665] In addition, the above cosmetic film can immediately change or modify the appearance of the skin by changing the reflection of light on the skin and the like, even if the cosmetic film does not include any cosmetic active 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 modify the touch feeling of the skin by changing the surface roughness on the skin and the like. In addition, the above cosmetic film can immediately protect the skin by covering the surface of the skin and protecting the skin, as a barrier, from environmental stresses such as pollutants, contaminants and the like.
[0666] The above cosmetic effects can be adjusted or controlled by changing the chemical composition, thickness and / or surface roughness of the above cosmetic film.
[0667] If the above cosmetic film comprises at least one additional cosmetic active ingredient other than the oil (c), the cosmetic film may have cosmetic effects provided by the additional cosmetic active ingredient(s). For example, if the cosmetic film comprises at least one cosmetic active ingredient selected from anti-aging agents, anti-sebum agents, deodorant agents, antiperspirant agents, whitening agents, and a mixture thereof, the cosmetic film may treat skin aging, absorb sebum on the skin, control odor on the skin, control perspiration on the skin, and / or whiten the skin.
[0668] 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. EXAMPLES
[0669] The present invention will be described in more detail with the aid of examples. However, they should not be construed as limiting the scope of the present invention. [Example 1 and Comparative Example 1]
[0670] [Preparation]
[0671] Each of the compositions according to Example and Comparative Example 1 was prepared by mixing the ingredients shown in Table 1. The numerical values for the amounts of the ingredients are all based on the "weight percentage" of the active ingredients.
[0672] [Tables 1] Ex. 1 Ex. Comp. 1 Water qsp 100 qsp 100 Sodium Hyaluronate (1100 kDa) 0.50 0.50 Sodium Hyaluronate (50 kDa) 1.00 1.00 Polyepsilon-Lysine 0.80 0.80 Phytic Acid 0.28 0.28 Polyglyceryl-4 Caprate 1.80 - Polyglyceryl-2 Isostearate 1.70 - Ammonium Polyacryloyldimethyl Taurate 0.75 0.75 Hydroxypropyl Methylcellulose 0.10 0.10 Trisodium Ethylenediamine Disuccinate 0.25 0.25 Chlorphenesin 0.20 0.20 Phenoxyethanol 0.70 0.70 Moisturizing Texture Good Very Poor Adhesion Good Good Durability Very Good Very Poor
[0673] [Evaluations]
[0674] (Moisturizing texture)
[0675] Three panelists evaluated the texture, in terms of moisturizing sensation, of each of the compositions according to Example 1 and Comparative Example 1 during and after application of the composition. Specifically, each panelist applied each composition to their hand and spread it to evaluate the moisturizing sensation and rated it from 1 (low) to 5 (high). It was then classified into the following three categories based on the average score:
[0676] Very good: from 4 to 5
[0677] Good: from 3 to less than 4
[0678] Bad: more than 2 and less than 3
[0679] Very bad: from 1 to 2
[0680] The results are presented in Table 1.
[0681] (Adhesiveness)
[0682] Three panelists evaluated the texture, in terms of stickiness, of each of the compositions according to Example 1 and Comparative Example 1 during and after application of the composition. Specifically, each panelist applied each composition to their hand and spread it to evaluate the moisturizing sensation, and rated it from 1 (low) to 5 (high). It was then classified into the following three categories based on the average rating:
[0683] Very good: from 4 to 5
[0684] Good: from 3 to less than 4
[0685] Bad: more than 2 and less than 3
[0686] Very bad: from 1 to 2
[0687] The results are presented in Table 1.
[0688] (Durability)
[0689] A panelist's forearm was washed with hand soap. An area of forearm skin for this test was marked. The marked area measured 4 cm * 4 cm.
[0690] 32 ql of each composition was applied to the marked area and spread with a single finger with a finger cot. The marked area was completely dried and left for more than 10 minutes at room temperature. The contact angle [T=0] on the marked area was measured with a mobile surface analyzer (MSA-flex by KRUSS Corp.)
[0691] Rinse the marked area with tap water (300 ml for each area). The marked area was again completely dried and left for more than 10 minutes at room temperature. The contact angle [T=10] on the marked area was measured again with a mobile surface analyzer (MSA-flex by KRUSS Corp.)
[0692] The variation between the contact angle [T=10] and the contact angle [T=0] was evaluated according to the following criteria:
[0693] Very good: Below 30°
[0694] Good: from 30° to less than 50°
[0695] Bad: from 50° to less than 70°
[0696] Very bad: 70° or more
[0697] The results are presented in Table 1.
[0698] It is clear from the comparison between Example 1 and Comparative Example 1 that the use of a surfactant in combination with polyionic complex particles formed from sodium hyaluronate, polylysine and phytic acid can improve the moisturizing texture and long-lasting effects. [Examples 2-3 and comparative example 2]
[0699] [Preparation]
[0700] Each of the compositions according to Examples 2-3 and Comparative Example 2 was prepared by mixing the ingredients shown in Table 2. The numerical values for the amounts of the ingredients in Table 2 are all based on the "weight percentage" of the active ingredients.
[0701] [Tables2] Ex. 2 Ex. 3 Ex. Comp. 2 Water qsp 100 qsp 100 qsp 100 Sodium Hyaluronate (1100 kDa) 0.50 0.50 0.50 Sodium Hyaluronate (50 kDa) 1.00 1.00 1.00 Polyepsilon-Lysine 0.40 0.40 0.40 Phytic Acid 0.14 0.14 0.14 Polyglyceryl-4 Caprate 3.50 3.12 - Polyglyceryl-2 Isostearate 0.24 0.05 - Isopropyl Myristate 1.00 0.32 1.00 Betaine 1.00 1.00 1.00 Glycerin - 3.00 - Propylene Glycol - 3.00 - Polyacryloyldimethyl Taurate Ammonium Chloride 0.75 0.75 0.75 Hydroxypropyl Methylcellulose 0.10 0.10 0.10 Trisodium Ethylenediamine Disuccinate 0.25 0.25 0.25 Chlorphenesin 0.27 0.27 0.27 Caprylyl Glycol 0.30 0.30 0.30 Ethanol - 3.00 - Ethane Hydroxyethylpiperazine Sulfonic Acid 2.00 2.00 2.00 Diaminobutyroylbenzylamide Dipeptide Diacetate 0.50 0.50 0.50 Ascorbyl Glucoside 0.20 0.20 0.20 Cereal Seed Extract Secale (Rye) 0.10 0.10 0.10 Moisturizing texture Good Very Good Very bad Adhesion Very good Very good Very good Durability Very good Very good Very bad.
[0702] [Evaluations]
[0703] (Moisturizing texture)
[0704] Three panelists evaluated the texture, in terms of moisturizing sensation, of each of the compositions according to Examples 2-3 and Comparative Example 2 during and after application of the composition. Specifically, each panelist applied each composition to their hand and spread it to evaluate the moisturizing sensation and rated it from 1 (low) to 5 (high). It was then classified into the following three categories based on the average of the rating:
[0705] Very good: from 4 to 5
[0706] Good: from 3 to less than 4
[0707] Bad: more than 2 and less than 3
[0708] Very bad: from 1 to 2
[0709] The results are presented in Table 2.
[0710] (Adhesiveness)
[0711] Three panelists evaluated the texture, in terms of adhesiveness, of each of the compositions according to Examples 2-3 and Comparative Example 2 during and after application of the composition. Specifically, each panelist applied each composition to their hand and spread it to evaluate the feeling of hydration and rated it from 1 (low) to 5 (high). It was then classified into the following three categories based on the average of the rating:
[0712] Very good: from 4 to 5
[0713] Good: from 3 to less than 4
[0714] Bad: more than 2 and less than 3
[0715] Very bad: from 1 to 2
[0716] The results are presented in Table 1.
[0717] (Sustainability)
[0718] A panelist's forearm was washed with hand soap. An area of forearm skin for this test was marked. The marked area measured 4 cm * 4 cm.
[0719] 32 pl of each composition was applied to the marked area and spread with a single finger with a finger cot. The marked area was completely dried and left for more than 10 minutes at room temperature. The contact angle [T=0] on the marked area was measured with a mobile surface analyzer (MSA-flex by KRUSS Corp.)
[0720] Rinse the marked area with tap water (300 ml for each area). The marked area was again completely dried and left for more than 10 minutes at room temperature. The contact angle [T=10] on the marked area was measured again with a mobile surface analyzer (MSA-flex by KRUSS Corp.)
[0721] The variation between the contact angle [T=10] and the contact angle [T=0] was evaluated according to the following criteria:
[0722] Very good: Below 30°
[0723] Good: from 30° to less than 50°
[0724] Bad: from 50° to less than 70°
[0725] Very bad: 70° or more
[0726] The results are presented in Table 2.
[0727] It is clear from the comparison between Example 2 and Comparative Example 2 that the use of a surfactant in combination with polyionic complex particles formed from sodium hyaluronate, polylysine and phytic acid can improve the moisturizing texture and long-lasting effects.
[0728] Example 3 demonstrates that the use of polyol in the composition according to Example 2 can further improve the moisturizing texture.
Claims
Claims
1. A composition, comprising: (a) at least one particle, comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer or at least one amphoteric polymer, and at least phytic acid or salt(s) thereof; (b) at least one non-ionic surfactant selected from poly-glyceryl esters of fatty acids and (c) water wherein the anionic polymer is hyaluronic acid and the amphoteric polymer is selected from cationized hyaluronic acid and its salts.
2. A composition according to Claim 1, wherein the cationic polymer has at least one positively chargeable and / or positively charged moiety selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group.
3. A composition according to any one of claims 1 to 2, wherein the cationic polymer is selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as collagen, cationic cellulosic polymers and their salts.
4. A composition according to any one of Claims 1 to 3, wherein the amount of phytic acid or salt(s) thereof in the composition is from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, and more preferably from 0.01% to 5% by weight, based on the total weight of the composition.
5. A composition according to any one of Claims 1 to 4, wherein the composition further comprises (d) at least one oil.
6. A method of preparing a film, preferably a cosmetic film, comprising: applying to a substrate, preferably a keratin material, the composition according to any one of Claims 1 to 5 and drying the composition.
7. A film, preferably a cosmetic film, prepared by a process comprising: applying to a substrate, preferably a keratin material, the composition according to any one of Claims 1 to 5 and drying the composition.
8. A film, preferably a cosmetic film, comprising: at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer or at least one amphoteric polymer; at least phytic acid or salt(s) thereof; at least one polyglyceryl ester of fatty acids; and optionally at least one oil, wherein the anionic polymer is hyaluronic acid and the amphoteric polymer is selected from cationized hyaluronic acid and its salts.