BR112019025065B1 - COSMETIC COMPOSITION, FILM PREPARATION PROCESS, COSMETIC PROCESS AND USE OF COSMETIC COMPOSITION - Google Patents

Abstract

COMPOSITION, FILM PREPARATION PROCESS, FILM, COSMETIC PROCESS AND COMPOSITION USE. The present invention relates to a composition, preferably a cosmetic composition and more preferably a cosmetic composition for the skin, comprising: (a) at least one particle, comprising 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 one non-polymeric acid having two or more pKa values or its salt(s), or at least one non-polymeric base having two or more pKb values or their salt(s); and (b) at least one physiologically acceptable volatile medium. The composition according to the present invention is stable and can have a number of cosmetic functions.

Description

FIELD OF THE INVENTION

[001] The present invention relates to a composition that includes particles of polyion complexes and a film of particles of polyion complexes, as well as a film preparation process using particles of polyion complexes and use of polyion complex particles for film preparation.

BACKGROUND OF THE INVENTION

[002] The poly-ion complex that is formed with an anionic polymer and a cationic polymer is already known.

[003] The use of a film made with a poly-ion complex for cosmetic purposes is also proposed, for example, by WO 2013/153678 and JP-A-2014-227389. The film described in WO 2013/153678 and JP-A-2014-227389 can provide some cosmetic effects.

[004] The preparation of the film described in WO 2013/153678 and JP-A-2014-227389 requires, however, a spin coating process that requires substrate rotation at high speed and therefore it can be difficult to prepare the film in situ on a keratin substrate, such as skin.

[005]JP-A-2015-107939 describes the preparation of films made with polyion complexes for cosmetic purposes, by spraying the first solution of an anionic polymer and a cationic polymer and spraying the second solution of the other among the anionic polymer and the cationic polymer on a keratin substance in order to mix the anionic and cationic polymers to form a film that includes the polyion complex. This preparation can prepare the film in situ on a keratinous substance such as skin.

[006] It may, however, be difficult to prepare the above film through the spraying process described in JP-A-2015-107939 without careful control, as it may not be easy to control the amounts of the first and second solutions to be sprayed. Particularly, relatively thick film preparation using the sputtering process described in JP-A-2015-107939 can be difficult.

[007] An option to easily elaborate a film produced with a polyion complex can be the use of a polyion complex in the form of particles. JP-A-2005-36190, for example, describes a dispersion that includes particles of polyion complexes that have been formed by an anionic polymer and a cationic polymer.

SHORT DESCRIPTION OF THE INVENTION

[008] It has been found, however, that dispersions that include particles of polyion complexes are not always stable. If the dispersion is unstable, particles of polyion complexes tend to precipitate out.

[009] The first objective of the present invention is therefore to provide a stable composition, such as a stable dispersion, which includes particles of polyion complexes.

[0010] The object of the present invention can be achieved by a composition, preferably a cosmetic composition, and more preferably a cosmetic composition for the skin, comprising: a. at least one particle, comprising: - 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 one non-polymeric acid having two or more pKa values or its salt(s) or at least one non-polymeric base having two or more pKb values or its salt(s); and b. at least one physiologically acceptable volatile medium.

[0011] The cationic polymer may have at least one positively charged and/or positively charged portion selected from the group consisting of primary, secondary or tertiary amino group, quaternary ammonium group, guanidine group, biguanide group, group imidazole, imino group and pyridyl group.

[0012] The cationic polymer can be 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 and its salts.

[0013] The anionic polymer may have at least one negatively charged and/or negatively charged portion selected from the group consisting of sulfuric group, sulfate group, sulfonic group, sulfonate group, phosphoric group, phosphate group, group phosphonic group, phosphonate group, carboxylic group and carboxylate group.

[0014] The anionic polymer can be selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers, anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meta) acids acrylics, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl) sulphate, dextran sulphate, chondroitin sulphate, (co)polymaleic acids, (co)polyfumaric acids, (co)polymers of maleic acid and its salts.

[0015] The amphoteric polymer may contain: - at least one positively charged and/or positively charged moiety selected from the group consisting of primary, secondary or tertiary amino group, quaternary ammonium group, guanidine group, biguanide group , imidazole group, imino group and pyridyl group; and - at least one negatively charged and/or capable of being negatively charged moiety selected from the group consisting of sulfuric group, sulfate group, sulfonic group, sulfonate group, phosphoric group, phosphate group, phosphonic group, phosphonate group, group carboxylic and carboxylate group.

[0016] The amphoternium polymer can be selected from the group consisting of polyquaternium-22, polyquaternium-39, polyquaternium-53, polyquaternium-64, polyquaternium-51, polyquaternium-61 and mixtures thereof.

[0017] The amount of polymer(s) in the composition according to the present invention may be from 0.001 to 25% by weight, preferably 0.1 to 20% by weight and, more preferably, 0.3 to 15% by weight, based on the total weight of the composition.

[0018] The non-polymeric acid having two or more pKa values may contain at least two acid groups selected from the group consisting of carboxylic group, sulfuric group, sulfonic group, phosphoric group, phosphonic group, phenolic hydroxyl group and mixtures thereof .

[0019] The non-polymeric acid that has two or more pKa values or its salt(s) may be selected from the group consisting of terephthalilidene dicamphor sulfonic acid and its salts (Mexoryl SX), Yellow 6 (Yellow By do Sol FCF), ascorbic acid, phytic acid, their salts and mixtures thereof.

[0020] The non-polymeric base having two or more pKb values may contain at least two basic groups selected from the group consisting of amino group, guanidine group, biguanide group, imidazole group, imino group, pyridyl group and mixtures thereof.

[0021] The non-polymeric base having two or more pKb values or its salt(s) may be selected from the group consisting of arginine, lysine, histidine, cysteine, tyrosine, tryptophan, ornithine and mixtures thereof.

[0022] The amount of the non-polymeric acid that has two or more pKa values or its salt(s) or of the non-polymeric base that has two or more pKb values or its salt(s) in the composition accordingly with the present invention it may be from 0.0001 to 30% by weight, preferably from 0.01 to 20% by weight and, more preferably, from 0.1 to 15% by weight, with respect to the total weight of the composition.

[0023] The particle (a) may comprise (c) at least one hydrophobic amino acid other than the non-polymeric acid or base.

[0024] The pH of the composition according to the present invention can be from 3 to 9, preferably from 3.5 to 8.5 and more preferably from 4 to 8.

[0025] The amount of particle (a) in the composition according to the present invention may be from 0.001 to 60% by weight, preferably from 0.1 to 50% by weight, and more preferably from 1 to 40% by weight , with respect to the total weight of the composition.

[0026] Second objective of the present invention is to provide a process that can easily prepare a film made with particles of polyion complexes.

[0027] The above objective of the present invention can be achieved by means of a film preparation process, preferably cosmetic film, which comprises: - application to a substrate, preferably a keratin substrate and, more preferably, to the skin, of a composition according to the present invention; and - drying the composition.

[0028] A third objective of the present invention is to provide a film prepared with particles of poly-ion complexes.

[0029] The above objective of the present invention can be achieved by: 1. film, preferably cosmetic film, prepared by means of a process comprising: - application to a substrate, preferably a keratin substrate and, more preferably, to the skin , of the composition according to the present invention; and - drying the composition; or 2. film, preferably cosmetic film, comprising: - 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 one non-polymeric acid having two or more pKa values or its salt(s) or at least one non-polymeric base having two or more pKb values or its salt(s).

[0030] The present invention also relates to a cosmetic process for keratin substrates, such as the skin, which comprises: - applying the composition according to the present invention to the keratin substrate; and - drying the composition to form a cosmetic film on the keratin substrate.

[0031] The cosmetic film obtained in this way can be 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.

[0032] The present invention also relates to the use of the composition according to the present invention for preparing a cosmetic film on a keratin substrate such as skin, wherein the cosmetic film is resistant to water at pH 7 or less and is removable with water having a pH of greater than 7, preferably 8 or greater, and most preferably 9 or greater. DETAILED DESCRIPTION OF THE INVENTION

[0033] After diligent research, the inventors discovered that it is possible to provide a stable composition, such as a stable dispersion, which includes polyion complex particles, by combining the polyion complex particles with base(s) or non-polymeric acid(s) having two or more dissolution constants or salt(s) thereof. The composition according to the present invention therefore comprises: a. at least one particle, comprising: - 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 one non-polymeric acid having two or more pKa values or its salt(s) or at least one non-polymeric base having two or more pKb values or its salt(s); and b. at least one physiologically acceptable volatile medium.

[0034] Furthermore, the inventors have found that it is possible to provide a process that can easily prepare a film comprising particles of polyion complexes. The process according to the present invention is therefore a film preparation process, preferably cosmetic film, the process comprising: - applying to a substrate, preferably a keratin substrate, the composition according to the present invention; and - drying the composition.

[0035] Furthermore, the inventors have discovered that it is possible to provide a film comprising particles of polyion complexes. The film according to the present invention is therefore: 1. film, preferably cosmetic film, prepared by means of a process comprising: - application to a substrate, preferably a keratin substrate and, more preferably, to the skin, of a composition according to the present invention; and - drying the composition; or 2. film, preferably cosmetic film, comprising: - 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 one non-polymeric acid having two or more pKa values or its salt(s) or at least one non-polymeric base having two or more pKb values or its salt(s).

[0036] The composition according to the present invention is stable for a long period of time and can be used to easily prepare a film of a polyion complex by applying the composition to a substrate, preferably a keratin substrate, such as such as skin and hair, most preferably skin, and drying the composition.

[0037] The polyion complex film according to the present invention can have a number of cosmetic functions.

[0038] The film itself according to the present invention may, for example, have cosmetic effects such as wetting due to the oil(s), as well as absorption or adsorption of bad odor, changing the appearance of keratin substrates such as the skin, altering the feel of the keratin substrate and/or protecting the keratin substrate from, for example, dust or pollutants.

[0039] If the polyion complex film includes at least one cosmetic active ingredient, the film may have cosmetic effects provided by the cosmetic active ingredient(s). If the polyion complex film includes, for example, at least one cosmetic active ingredient selected from UV filters, antiaging agents, antisebum agents, deodorant agents, antiperspirant agents, whitening agents and mixtures thereof, the film can filter out rays UV, treating skin aging, absorbing sebum on the skin, controlling skin odor, controlling perspiration on the skin and/or lightening the skin.

[0040] The film according to the present invention may be transparent and therefore may not be easily perceived even when the film is relatively thick.

[0041] Furthermore, the film according to the present invention is water resistant and therefore can remain on a keratin substrate such as skin, even if the surface of the keratin substrate is wet due to, for example, sweat and rain.

[0042] Furthermore, the film according to the present invention can be easily removed from a keratin substrate such as skin under alkaline conditions. The film according to the present invention is therefore difficult to remove with water, although it can easily be removed with soap, which can provide alkaline conditions.

[0043] If the film according to the present invention includes a hydrophilic or water-soluble UV filter, therefore, the film according to the present invention can exhibit UV protection effects that are water resistant (waterproof) and can be long-lasting, but can be easily removed with soap that can provide alkaline conditions.

[0044] The composition, process, film and the like according to the present invention will be explained in more detail below.

[0045] Poly-ion complex particle:

[0046] The composition according to the present invention includes (a) at least one particle which is a polyion complex particle. Two or more different types of particles (a) can be used in combination. Therefore, a single type of particle (a) or a combination of different types of particles (a) can be used.

[0047] The size of the poly-ion complex particle can be from 5 nm to 100 μm, preferably from 100 nm to 50 μm, more preferably from 200 nm to 30 μm, and even more preferably from 500 nm at 20 µm. Particle size of less than 1 μm can be measured using a dynamic light scattering method and particle size of more than 1 μm can be measured by an optical microscope. This particle size can be based on the numerical average diameter.

[0048] The amount of the particle(s) (a) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.1% by weight or more, and more preferably 1 % by weight or more, based on the total weight of the composition.

[0049] The amount of the particle(s) (a) in the composition according to the present invention may be 60% by weight or less, preferably 50% by weight or less, and more preferably 40% by weight weight or less, relative to the total weight of the composition.

[0050] The amount of the particle(s) (a) in the composition according to the present invention can be from 0.001 to 60% by weight, preferably from 0.1 to 50% by weight and, more preferably, 1 to 40% by weight, based on the total weight of the composition.

[0051] It is preferable that the particle (a) is amphiphilic and insoluble in oil or water.

[0052] The particle (a) includes at least one polymer or combination of polymers. Specifically, particle (a) includes: 1. at least one cationic polymer and at least one amphoteric polymer; 2. at least one anionic polymer and at least one amphoteric polymer; or 3. at least one amphoteric polymer.

[0053] There is no limit to the type of cationic, anionic and amphoteric polymers. Two or more different types of cationic polymers can be used in combination. Therefore, a single type of cationic polymer or a combination of different types of cationic polymers can be used. Two or more different types of anionic polymers can be used in combination. Therefore, a single type of anionic polymer or a combination of different types of anionic polymers can be used. Two or more different types of amphoteric polymers can be used in combination. Therefore, a single type of amphoteric polymer or a combination of different types of amphoteric polymers can be used.

[0054] In (1) above, the ratio between the amount, such as the chemical equivalent, of the cationic polymer(s)/amphoteric polymer(s) may be 0.05-18 , preferably 0.1-10 and most preferably 0.5-5.0. In particular, it may be preferred that the amount of cationic groups of the cationic polymer(s)/the amount of anionic and cationic groups of the amphoteric polymer(s) is 0.05-18 , more preferably 0.1-10, and even more preferably 0.5-5.0.0.

[0055] In (2) above, the ratio between the amount, such as the chemical equivalent, of the anionic polymer(s)/amphoteric polymer(s) can be 0.05-18 , preferably 0.1-10 and most preferably 0.5-5.0. In particular, it may be preferred that the amount of anionic groups of the anionic polymer(s)/the amount of anionic and cationic groups of the amphoteric polymer(s) is 0.05-18 , more preferably 0.1-10, and even more preferably 0.5-5.0.

[0056] The total amount of the polymer(s) according to any one of the above (1) to (3) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.1 % by weight or more, and more preferably 1% by weight or more, based on the total weight of the composition.

[0057] The total amount of the polymer(s) according to any one of (1) to (3) above in the composition according to the present invention may be 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less, based on the total weight of the composition.

[0058] The total amount of polymer(s) according to any one of (1) to (3) above in the composition according to the present invention may be from 0.001 to 25% by weight, preferably from 0. 1 to 20% by weight, and more preferably 1 to 15% by weight, based on the total weight of the composition.

[0059] Cationic polymer:

[0060] The cationic polymer has a positive charge density. The charge density of the cationic polymer can be from 0.01 meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g and more preferably from 0.1 to 10 meq/g.

[0061] It may be preferred 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 5000 or more.

[0062] Unless otherwise defined in the descriptions, “molecular weight” indicates number average molecular weight.

[0063] The cationic polymer may have at least one positively charged and/or positively charged portion selected from the group consisting of primary, secondary or tertiary amino group, quaternary ammonium group, guanidine group, biguanide group, group imidazole, imino group and pyridyl group. The term "amino group" (primary) herein denotes an -NH 2 group.

[0064] The cationic polymer can be homopolymer or copolymer. The term "copolymer" is understood to indicate both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.

[0065] The cationic polymer can be selected from natural and synthetic cationic polymers. Non-limiting examples of cationic polymers are as follows. 1. Homopolymers and copolymers derived from acrylic or methacrylic amides and esters, comprising at least one unit selected from units of the formulas below: wherein: - R1 and R2, which may be identical or different, are selected from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms, such as methyl and ethyl groups; - R3, which can be identical or different, is selected from hydrogen and CH3; - the symbols A, which may be identical or different, are selected from linear or branched alkyl groups comprising 1 to 6 carbon atoms, such as 2 to 3 carbon atoms, and hydroxyalkyl groups comprising 1 to 4 atoms of carbon; - R4, R5 and R6, which may be identical or different, are selected from alkyl groups comprising 1 to 18 carbon atoms and benzyl groups and, in at least one embodiment, alkyl groups comprising 1 to 6 atoms of carbon; and - X is an anion derived from organic or inorganic acid such as halides and methosulfate anions such as chloride and bromide.

[0066] The copolymers of family (1) may also comprise at least one unit derived from comonomers that may be selected from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen atom by lower alkyl groups (C1 -C4), groups derived from acrylic or methacrylic acids and their esters, vinyl lactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.

[0067] Examples of copolymers of the family (1) include, but are not limited to: - copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with dimethyl halide; - copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in European Patent Application No. 0,080,976; - copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate; - quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, described, for example, in French Patents Nos. 2,077,143 and 2,393,573; - dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers; - vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers; and - polymers of cross-linked methacryloxyalkyl(C1-C4)trialkyl(C1-C4)ammonium salts, such as polymers obtained by means of homopolymerization of quaternized dimethylaminoethyl methacrylate with methyl chloride, or by means of copolymerization of acrylamide with methacrylate dimethylaminoethyl quaternized with methyl chloride, wherein the homopolymerization or copolymerization is followed by crosslinking with a compound containing olefinic unsaturation, such as methylenebisacrylamide. 2. Cationic cellulose derivatives, such as cellulose ether derivatives comprising quaternary ammonium groups described, for example, in French Patent No. 1,492,597, as polymers sold under the names “JR” (JR 400, JR 125 and JR 30M) or “LR” (LR 400 and LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose which have reacted with an epoxide substituted by a trimethylammonium group. 3. Cationic cellulose derivatives such as cellulose copolymers and cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and described, for example, in US Patent No. 4,131,576, such as hydroxyalkylcelluloses, for example, hydroxymethyl, hydroxyethyl and grafted hydroxypropylcelluloses, for example, with a salt selected from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium salts.

[0068] Commercial products corresponding to these polymers include, for example, products sold under the name “Celquat® L 200” and “Celquat® H 100” by the company National Starch. 4. Non-cellulose-based cationic polysaccharides described in US Patent Nos. 3,589,578 and 4,031,307, such as guar gums comprising cationic trialkylammonium groups, cationic hyaluronic acid, and hydroxypropyl trimonium chloride dextran. Guar gums modified with a salt, such as 2,3-epoxypropyltrimethylammonium chloride (guar hydroxypropyltrimonium chloride) may also be used.

[0069] These products are sold, for example, under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162 by the company MEYHALL. 5. Polymers comprising piperazinyl units and bivalent alkylene or hydroxyalkylene groups comprising straight or branched chains, optionally interrupted with at least one entity selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, as well as oxidation products and /or quaternization of these polymers. Such polymers are described, for example, in French Patents Nos. 2,162,025 and 2,280,361. 6. Water-soluble polyamino amides prepared, for example, by polycondensation of acid compound with polyamine; wherein said polyamino amides are possibly cross-linked with an entity selected from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bi-unsaturated derivatives; bis-halohydrins; bisazetidiniums; bis-haloacyldiamines; bisalkyl halides; oligomers resulting from the reaction of a bifunctional compound that is reactive with an entity selected from bis-halohydrins, bisazetidiniums, bis-haloacyldiamines, bisalkyl halides, epihalohydrins, diepoxides and bi-unsaturated derivatives; wherein the crosslinking agent is used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; wherein these polyamino amides are optionally alkylated or, if they comprise at least one tertiary amine function, can be quaternized. Such polymers are described, for example, in French Patents Nos. 2,252,840 and 2,368,508. 7. Polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids, followed by alkylation with bifunctional agents, such as adipic acid polymers and dialkylaminohydroxyalkyldialkylenetriamine in which the alkyl group comprises from one to four carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene group comprises from one to four 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 can be selected from polymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine. 8. Polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids comprising from 3 to 8 carbon atoms. carbon. The molar ratio between polyalkylene polyamine and dicarboxylic acid can range from 0.8:1 to 1.4:1; wherein the resulting polyamino amide reacts with epichlorohydrin in a molar ratio between epichlorohydrin and the secondary amine group of the polyamino amide ranging from 0.5:1 to 1.8:1. Such polymers are described, for example, in US Patent Nos. 3,227,615 and 2,961,347. 9. Alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers, such as homopolymers and copolymers comprising, as the main component of the chain, at least one unit selected from units of formulas (Ia) and (Ib): where: - ket, which may be identical or different, are equal to 0 or 1, where the sum k+t is equal to 1; - R12 is selected from hydrogen and methyl groups; - R10 and R11, which may be identical or different, are selected from alkyl groups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group comprises, for example, 1 to 5 carbon atoms, and amidoalkyl groups lower (C1-C4), or R10 and R11 may form, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl and morpholinyl; and - Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate. These polymers are described, for example, in French Patent No. 2,080,759 and its Certificate of Addition 2,190,406.

[0070] In one embodiment, R10 and R11, which may be identical or different, are selected from alkyl groups comprising 1 to 4 carbon atoms.

[0071] Examples of such polymers include, but are not limited to, (co)polydiallyldialkyl ammonium chloride, such as the homopolymer dimethyldiallylammonium chloride sold under the name “MERQUAT® 100” by the company CALGON (and its low average molecular weight counterparts) and acrylamide diallyldimethylammonium chloride copolymers sold under the trade name “MERQUAT® 550”.

[0072] Quaternary diammonium polymers comprising at least one repeating unit of formula (II): wherein: - R13, R14, R15 and R16, which may be identical or different, are selected from aliphatic, alicyclic and arylaliphatic groups comprising from 1 to 20 carbon atoms and lower hydroxyalkyl aliphatic groups or, alternatively, R13, R14, R15 and R16 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, R13, R14, R15 and R16, which may be identical or different , are selected from linear or branched C1-C6 alkyl groups, substituted by at least one group selected from nitrile groups, ester groups, acyl groups, amide groups, -CO-O-R17-E groups and -CO groups -NH-R17-E, wherein R17 is an alkylene group and E is a quaternary ammonium group; - A1 and B1, which may be identical or different, are selected from polymethylene groups comprising from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and may comprise, linked or interspersed in the main chain , at least one entity selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups and ester groups; and - X- is an anion derived from organic or inorganic acid; - A1, R13 and R15 can form, together with the two nitrogen atoms to which they are attached, a piperazine ring; - if A1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B1 can be selected from: where E' is selected from: a. glycol residues of the formula -OZO-, where Z is selected from linear or branched hydrocarbon-based groups and groups of the formulas below: where x and y, which can be identical or different, are selected from integers ranging from 1 to 4, which indicate a definite and exclusive degree of polymerization, and numbers ranging from 1 to 4, which indicate an average degree of polymerization; B. bis-minor diamine residue such as piperazine derivatives; w. bis-primary diamine residues of the formula -NH-Y-NH-, wherein Y is selected from linear or branched hydrocarbon-based groups and the bivalent group -CH2-CH2-SS-CH2-CH2-; and d. ureylene groups of the formula -NH-CO-NH-.

[0073] In at least one embodiment, X- is an anion such as chloride or bromide.

[0074] Polymers of this type are described, for example, in French Patents No. 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907; and US Patents Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990,

[0075] Exam polymers include those comprising at least formula (III): wherein R13, R14, R15 and R16, which may be identical or different, are selected from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbon atoms, n and p , which may be identical or different, are integers ranging from 2 to 20 and X- is an anion derived from organic or inorganic acid. 11. Polyquaternary ammonium polymers comprising units of formula (IV): where: - R18, R19, R20 and R21, which may be identical or different, are selected from hydrogen, methyl groups, ethyl groups, propyl groups, β-hydroxyethyl groups, β-hydroxypropyl groups, groups - CH2CH2(OCH2CH2 )pOH, where p is selected from integers ranging from 0 to 6, with the proviso that R18, R19, R20 and R21 are not simultaneously hydrogen; - res, which can be identical or different, are selected from integers ranging from 1 to 6; - q is selected from integers ranging from 0 to 34; - X- is an anion such as halide; and - A is selected from dihalide radicals and -CH2-CH2-O-CH2-CH2-.

[0076] These compounds are described, for example, in European Patent Application No. 0,122,324. 12. Quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0077] 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.

[0078] According to one embodiment of the present invention, the at least one cationic polymer is selected from cellulose ether derivatives comprising quaternary ammonium groups, such as the products sold under the name "JR 400" by the company UNION CARBIDE CORPORATION, cationic cyclopolymers, such as dimethyldiallylammonium chloride homopolymers and copolymers sold under the names MERQUAT® 100, MERQUAT® 550 and MERQUAT® S by the CALGON company, guar gums modified with a 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole. 13. Polyamines.

[0079] As a cationic polymer, it is also possible to use (co)polyamines, which can be homopolymers or copolymers, with a series of amino groups. The amino group can be a primary, secondary, tertiary or quaternary amino group. The amino group can be present in a polymer main chain or pendant group, when present, of (co)polyamines.

[0080] As an example of (co)polyamines, we can mention chitosan, (co)polyallylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polydimethylaminoethylenemethacrylates, (co)polyvinylpyridines such as (co) )poly-1-methyl-2-vinylpyridines, (co)polyimines such as (co)polyethyleneimines, (co)polypyridines such as (co)poly(quaternary) pyridines, (co)polybiguanides such as (co)polyaminopropyl biguanides , (co)polylysines, (co)polyornithines, (co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinylacetals and their salts.

[0081]As (co)polyamines, it is preferable to use (co)polylysines. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine that can be produced through bacterial fermentation. Poly-lysine can be, for example, ε-poly-L-lysine, typically used as a natural preservative in food products. Polylysine is a polyelectrolyte that is soluble in polar solvents such as water, propylene glycol and glycerol. Poly-lysine is commercially available in various forms such as poly D-lysine and poly L-lysine. Polylysine can be presented in salt and/or solution form. 14. Cationic polyamino acids.

[0082] As a cationic polymer, it may be possible to use cationic polyamino acids, which may be cationic copolymers or homopolymers, with a series of amino groups and carboxyl groups. The amino group can be a primary, secondary, tertiary or quaternary amino group. The amino group can be present in the main chain of the polymer or pendant group, when present, of the cationic polyamino acids. The carboxyl group may be present on a pendant group, when present, of the cationic polyamino acids.

[0083] As examples of cationic polyamino acids, we can mention cationized collagen, cationized gelatin, hydrolyzed wheat protein hydroxypropyl steardimonium, hydrolyzed wheat protein hydroxypropyl cocodimonium, hydrolyzed conchiolin protein hydroxypropyltrimonium, hydrolyzed soy protein hydroxypropyl steardimonium, hydrolyzed soy protein hydroxypropyltrimonium, hydrolyzed soy protein hydroxypropyl cocodimonium and the like.

[0084] It may be preferable that 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, (co) ) cationic polyamino acids such as cationized collagen and their salts.

[0085] The amount of the cationic polymer(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.1% by weight or more and, more preferably, 1% by weight or more, based on the total weight of the composition.

[0086] The total amount of the cationic polymer(s) in the composition according to the present invention may be 25% by weight or less, preferably 20% by weight or less, and more preferably 15 % by weight or less, based on the total weight of the composition.

[0087] The amount of cationic polymer(s) in the composition according to the present invention can be from 0.001 to 25% by weight, preferably from 0.1 to 20% by weight and, more preferably , 1 to 15% by weight, based on the total weight of the composition.

[0088] Anionic polymer:

[0089] The anionic polymer has a positive charge density. The charge density of the anionic polymer can be from 0.1 meq/g to 20 meq/g, preferably from 1 to 15 meq/g and more preferably from 4 to 10 meq/g if the anionic polymer is a synthetic anionic polymer and the average degree of substitution of the anionic polymer can be from 0.1 to 3.0, preferably from 0.2 to 2.7, and more preferably from 0.3 to 2.5, if the anionic polymer is a natural anionic polymer.

[0090] It may be preferred that the molecular weight of the anionic polymer is 1,000 or more, preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 1,000,000 or more.

[0091] The anionic polymer may have at least one portion with a negative charge and/or that may receive a negative charge selected from the group consisting of sulfuric group, sulfate group, sulfonic group, sulfonate group, phosphoric group, phosphate group, group phosphonic group, phosphonate group, carboxylic group and carboxylate group.

[0092] The anionic polymer can be homopolymer or copolymer. The term "copolymer" is understood to indicate both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.

[0093] The anionic polymer can be selected from natural and synthetic anionic polymers.

[0094] The anionic polymer may comprise at least one hydrophobic chain.

[0095] The anionic polymer that can comprise at least one hydrophobic chain can be obtained by copolymerizing a monomer (a) selected from carboxylic acids comprising a,e-ethylenic unsaturation (a' monomer) and 2- acrylamido-2-methylpropanesulfonic (monomer a”) with a monomer that is not surface active (b) that comprises ethylenic unsaturation other than (a) and/or monomer (c) that comprises ethylenic unsaturation resulting from the reaction of an acrylic monomer that comprises a,e-monoethylenic unsaturation or of an isocyanate monomer comprising monoethylenic unsaturation with a monohydric nonionic amphiphilic component or with a primary or secondary fatty amine.

[0096] The anionic polymer with at least one hydrophobic chain can therefore be obtained by means of two synthetic routes: - copolymerization of monomers (a') and (c), (a'), (b) and (c) , (a”) and (c) or (a”), (b) and (c); or - modification (particularly esterification or amidation) of a copolymer formed from the monomers (a') or the monomers (a') and (b) or (a”) and (b), by a non-ionic amphiphilic mono- hydric or amine primary or secondary grease.

[0097] Specific mention can be made, such as 2-acrylamido-2-methylpropanesulfonic acid copolymers, of those described in the article Micelle formation of random copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescende and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10 - 3694-3704 and in patent applications EP-A-0,750,899 and EP-A-1,069,172.

[0098] The carboxylic acid comprising α,β-monoethylenic unsaturation that constitutes the monomer (a') can be selected from various acids, particularly acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. It is preferably acrylic or methacrylic acid.

[0099] The copolymer may comprise a monomer (b) comprising monoethylenic unsaturation which has no surfactant property. Preferred monomers are those that provide water-insoluble polymers when homopolymerized. They can be selected, for example, from C1-C4 alkyl acrylates and methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. The most specifically preferred monomers are methyl acrylate and ethyl acrylate. The other monomers that can be used are, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile and vinylidene chloride. Non-reactive monomers are preferred, wherein such monomers are those in which the isolated ethylene group is the only group that is reactive under the conditions of polymerization. Optionally, however, monomers comprising groups that react under the effect of heat, such as hydroxyethyl acrylate, can optionally be used.

[00100] The monomer (c) is obtained by reacting an acrylic monomer comprising α,β monoethylenic unsaturation, such as (a) or an isocyanate monomer comprising monoethylenic unsaturation with a monohydric nonionic amphiphilic compound or primary or secondary grease amine.

[00101] The non-ionic monohydric amphiphilic compounds or the primary or secondary fatty amines used to produce the non-ionic monomer (c) are well known. Monohydric nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds comprising an alkylene oxide which forms the hydrophilic part of the molecule. Hydrophobic compounds are generally composed of an aliphatic alcohol or alkylphenol and, in such compounds, a carbonaceous chain comprising at least six carbon atoms constitutes the hydrophobic part of the amphiphilic compound.

[00102] Preferred monohydric nonionic amphiphilic compounds are compounds having the formula (V) below: R-(OCH2CHR')m-(OCH2CH2)n-OH (V) in which R is selected from groups alkyl or alkylene comprising 6 to 30 carbon atoms and alkylaryl groups containing alkyl radicals comprising 8 to 30 carbon atoms, R' is selected from alkyl groups comprising 1 to 4 carbon atoms, n is an average number ranging from about 1 to 150 and m is an average number ranging from about 0 to 50, provided that n is at least equal to m.

[00103] Preferably, in the compounds of formula (V), the R group is selected from alkyl groups comprising from 12 to 26 carbon atoms and alkylphenyl groups in which the alkyl group is C8-C13; the R' group is the methyl group; m = 0 and n = 1 to 25.

[00104] Preferred primary and secondary fatty amines are composed of one or two alkyl chains comprising from 6 to 30 carbon atoms.

[00105] The monomer used to form the non-ionic urethane monomer (c) can be selected from compounds with high variation. Use can be made of any compound comprising copolymerizable unsaturation, such as acrylic, methacrylic or allylic unsaturation. Monomer (c) can be particularly obtained from isocyanate comprising monoethylenic unsaturation, such as particularly α,α-dimethyl-m-isopropenylbenzyl isocyanate.

[00106] The monomer (c) can be particularly selected from acrylates, methacrylates or itaconates of oxyethylenated C6-C30 fatty acids (1 to 50 EO), such as steareth-20 methacrylate, oxyethylenated behenyl methacrylate (25 EO) , oxyethylene monoacetyl itaconate (20 EO), oxyethylene monostearyl itaconate (20 EO) or the acrylate modified by polyoxyethylene C12-C24 alcohols (25 EO) and oxyethylenated C6-C30 fatty alcohol dimethyl-m-isopropenylbenzyl isocyanates (1 to 50 EO), such as, particularly, oxyethylenated behenyl alcohol dimethyl-m-isopropenylbenzyl isocyanate.

[00107] According to a specific embodiment of the present invention, the anionic polymer is selected from acrylic terpolymers obtained from (a) carboxylic acid comprising a,e-ethylenic unsaturation; (b) a monomer which is not surface active, which comprises ethylenic unsaturation other than (a); and (c) a nonionic urethane monomer which is the reaction product of a monohydric nonionic amphiphilic compound with an isocyanate comprising monoethylenic unsaturation.

[00108] Specific mention may be made, as anionic polymers comprising at least one hydrophobic chain, of the acrylic acid/ethyl acrylate/alkyl acrylate terpolymer, such as the product in the form of a 30% aqueous dispersion sold with the name Acusol 823 by Rohm & Haas, the steareth-20 acrylates/methacrylate copolymer, such as the product sold under the name Aculyn 22 by Rohm & Haas, the (meth)acrylic acid/ethyl acrylate/behenyl methacrylate terpolymer oxyethylenated (25 EO), such as the aqueous emulsion product sold under the name Aculyn 28 by Rohm &Haas; acrylic acid/oxyethylenated monoacetyl itaconate (20 EO) copolymer, such as the 30% aqueous dispersion product sold under the name Structure 3001 by National Starch; acrylic acid/oxyethylenated monostearyl itaconate (20 EO) copolymer, such as the 30% aqueous dispersion product sold under the name Structure 2001 by National Starch; acrylates/acrylate modified by C12-C24 alcohol polyoxyethylene (25 EO) copolymer, such as the 30-32% copolymer latex sold under the name Synthalen W2000 by 3V SA; or ethoxylated behenyl alcohol terpolymer dimethylmethisopropenylbenzyl isocyanate/methyl acrylate/methyl acrylate/methacrylic acid, such as the product in the form of a 24% aqueous dispersion comprising 40 ethylene oxide groups described in EP-A-0,173,109.

[00109] Anionic polymers can also be Polyester-5, such as the product sold under the name Eastman AQ® 55S Polymer by Eastman Chemical, which has the chemical formula below: A: dicarboxylic acid moiety. G: glycol moiety. SO3-Na+: sodium sulfo group. OH: hydroxyl group.

[00110] It may be preferable that the anionic polymer is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (for example, carboxymethylcellulose), anionic (co)polyamino acids such as (co)polyglutamic acids , (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl) sulfate, dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polymaleic acids, ( co)polyfumarics, (co)polymers of maleic acid and their salts.

[00111] The maleic acid copolymer may comprise one or more comonomers of maleic acid and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms and styrene.

[00112] Therefore, "maleic acid copolymer" is understood as indicating any polymer obtained through the copolymerization of one or more comonomers of maleic acid and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or iso-octylene and styrene, in which, optionally, the maleic acid comonomers are wholly or partially hydrolysed. Hydrophilic polymers will preferably be used, that is, polymers that have solubility in water greater than or equal to 2 g/l.

[00113] In an advantageous aspect of the present invention, the maleic acid copolymer may have a mole fraction of maleic acid units from 0.1 to 1, more preferably from 0.4 to 0.9.

[00114] The weight average molar mass of the maleic acid copolymer can be from 1000 to 500,000, preferably from 1000 to 50,000.

[00115] It is preferred that the maleic acid copolymer is a styrene/maleic acid copolymer, and more preferably sodium styrene/maleic acid copolymer.

[00116] Preferably, a copolymer of styrene and maleic acid in a 50/50 ratio will be used.

[00117] For example, the styrene/maleic acid copolymer (50/50), in the form of a 30% ammonium salt in water, sold under the reference SMA1000H® by Cray Valley, or the copolymer of styrene/maleic acid (50/50), as a 40% sodium salt in water, sold under part number SMA1000HNa® by Cray Valley.

[00118] The use of styrene/maleic acid copolymer such as sodium styrene/maleic acid copolymer can increase the wetting capacity of a film prepared by means of the composition according to the present invention.

[00119] The amount of anionic polymer(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.1% by weight or more and, more preferably, 1% by weight or more, based on the total weight of the composition.

[00120] The amount of cationic polymer(s) in the composition according to the present invention may be 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less relative to the total weight of the composition.

[00121] The total amount of anionic polymer(s) in the composition according to the present invention can be from 0.001 to 25% by weight, preferably from 0.1 to 20% by weight and, more preferably, 1 to 15% by weight, based on the total weight of the composition.

[00122] Amphoteric polymer:

[00123] Amphoteric polymers have positive charge density and negative charge density.

[00124] The positive charge density of the amphoteric polymer can be from 0.01 meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g and more preferably from 0.1 to 10 meq/g.

[00125] The negative charge density of the amphoteric polymer can be from 0.01 meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g and more preferably from 0.1 to 10 meq/g.

[00126] It may be preferred that the molecular weight of the amphoteric polymer is 500 or more, preferably 1000 or more, more preferably 2000 or more, and even more preferably 5000 or more.

[00127] Unless otherwise defined in the descriptions, “molecular weight” indicates numerical average molecular weight.

[00128] The amphoteric polymer may contain: - at least one portion with a positive charge and/or that can receive a positive charge selected from the group consisting of primary, secondary or tertiary amino group, quaternary ammonium group, guanidine group, biguanide group , imidazole group, imino group and pyridyl group; and - at least one negatively charged and/or capable of being negatively charged moiety selected from the group consisting of sulfuric group, sulfate group, sulfonic group, sulfonate group, phosphoric group, phosphate group, phosphonic group, phosphonate group, group carboxylic and carboxylate group.

[00129] The amphoteric polymer can be homopolymer or copolymer. The term "copolymer" is understood to indicate both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.

[00130] The amphoteric polymers that can be used according to the present invention can be selected from polymers that contain K and M units randomly distributed in the polymer chain, where K indicates a unit that is derived from a monomer that contains at least one basic nitrogen atom and M indicates a unit that is derived from an acidic monomer that contains one or more carboxylic or sulfonic groups or, alternatively, K and M may indicate groups that are derived from zwitterionic monomers of carboxybetines or sulfobetaines. K and M may also indicate a chain of cationic polymers containing primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulfonic group linked via a hydrocarbon radical or, alternatively, K and M. M are part of a polymer chain with an α,β-dicarboxylic ethylene unit in which one of the carboxylic groups has been reacted with a polyamine containing one or more primary or secondary amine groups.

[00131] The amphoteric polymers corresponding to the definition provided above that are preferably more specific are selected from the following polymers: 1. Polymers resulting from the copolymerization of monomers derived from vinyl compounds that carry carboxylic groups, such as, more specifically acrylic acid , methacrylic acid, maleic acid and alphachloroacrylic acid, and basic monomers derived from substituted vinyl compounds containing at least one basic atom, such as, more specifically, dialkylaminoalkyl acrylate and methacrylate, dialkylaminoalkylmethacrylamide and acrylamide. These compounds are described in US Patent No. 3,836,537. Mention may also be made of sodium acrylate/acrylamidopropyltrimethylammonium chloride copolymer sold under the name POLYQUART KE 3033 by the company HENKEL. The vinyl compound can also be a dialkyldiallylammonium salt, such as dimethyldiallylammonium chloride. Copolymers of acrylic acid and the latter monomer are supplied under the names MERQUAT 280, MERQUAT 295, MERQUAT 2003 PR, MERQUAT 3330 PR and MERQUAT PLUS 3330 by the company Lubrizol. 2. Polymers containing units that are derived from: a. at least one monomer selected from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical; B. at least one acidic comonomer containing one or more reactive carboxylic groups; and c. at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

[00132] The more specifically preferred N-substituted acrylamides or methacrylamides according to the present invention are groups whose alkyl radicals contain from 2 to 12 carbon atoms, more specifically N-ethylacrylamide, N-tert-butylacrylamide, N-tert- octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

[00133] The acid comonomers are selected, more specifically, from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids, as well as alkyl monoesters containing from one to four carbon atoms of maleic or fumaric acids or anhydrides.

[00134] The preferred basic comonomers are aminoethyl, butylaminoethyl, N,N'-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.

[00135] Copolymers whose name CTFA (4th ed., 1991) is copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate are particularly used, such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH. 3. Wholly or partially alkylated and cross-linked polyamino amides derived from polyamino amides of the following general formula: -[-CO-R4-CO-Z-]- in which R4 denotes a bivalent radical derived from saturated dicarboxylic acid, mono or aliphatic acid dicarboxylic acid with ethylenic double bond, lower alkanol ester containing from 1 to 6 carbon atoms of these acids or radical which is derived from the addition of any of the mentioned acids with a bis-primary or bis-secondary amine and Z denotes a polyalkylene radical - bis-primary, mono- or bis-secondary polyamine and preferably indicates: a. in proportions from 60 to 100 mol%, the radical -NH-[(CH2)x-NH-]p- where x=2 and p=2 or 3 or, alternatively, x=3 and p=2, where this radical it is derived from diethylenetriamine, triethylenetetraamine or dipropylenetriamine; B. in proportions from 0 to 40 mol%, the radical (IV) above, where x=2 and p=1, which is derived from ethylenediamine or the radical which is derived from piperazine: w. in proportions from 0 to 20 mol%, the radical -NH-(CH2)6-NH- which is derived from hexamethylenedamine, in which these polyamino amines are cross-linked by means of the addition of a bifunctional cross-linking agent selected from epi-halo- hydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mol of cross-linking agent per amine group of the polyamino amide and alkylated by means of the action of acrylic acid, chloroacetic acid or alkane sultone or their salts.

[00136] Saturated carboxylic acids are preferably selected from acids containing 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic and 2,4,4-trimethyladipic, terephthalic acid and acids with ethylene double bond, such as acrylic, methacrylic and itaconic acids.

[00137] The alkanesultones used in the alkylation are preferably propane or butanesultone and the salts of the alkylating agents are preferably the sodium or potassium salts. 4. Polymers containing zwitterionic units of the formula: wherein R5 indicates a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z indicate an integer from 1 to 3, R6 and R7 indicate a hydrogen, methyl, ethyl or propyl atom, R8 and R9 indicate an atom hydrogen or alkyl radical such that the sum of the carbon atoms in R8 and R9 does not exceed 10.

[00138] The polymers comprising these units may also comprise units derived from non-zwitterionic monomers, such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides, methacrylamides or vinyl acetate.

[00139] As an example, one can mention the copolymer of butyl methacrylate/dimethylcarboxymethylammonioethyl methacrylate, such as the product sold under the name DIAFORMER Z301 by the company SANDOZ. 5. Polymers derived from chitosan containing monomeric units corresponding to formulas (VI), (VII) and (VIII) below: in which the unit (VI) is present in proportions from 0 to 30%, the unit (VII) in proportions from 5 to 50% and the unit (VIII) in proportions from 30 to 90%, it being understood that, in this unit (VIII), R10 represents a radical of the formula: where: - if q=0, R11, R12 and R13, which are identical or different, independently indicate a hydrogen atom, methyl, hydroxyl, acetoxy or amino residue, monoalkylamine residue or dialkylamine residue optionally interrupted by one or more atoms of nitrogen and/or optionally substituted by one or more amino, hydroxyl, carboxyl, alkylthio or sulfonic groups, or an alkylthio residue whose alkyl group leads to an amino residue, where at least one of the radicals R11, R12 and R13 is, in this case, a hydrogen atom; or - if q=1, R11, R12 and R13 independently indicate a hydrogen atom, as well as the salts formed by these compounds with bases or acids. 6. Polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the trade name “EVALSAN” by the company JAN DEKKER. 7. Polymers corresponding to the general formula (IX), such as those described, for example, in French Patent 1,400,366: where R14 indicates a hydrogen atom, CH3O, CH3CH2O or phenyl radical, R15 indicates hydrogen or lower alkyl radical such as methyl or ethyl, R16 indicates hydrogen or lower alkyl radical such as methyl or ethyl, R17 indicates a lower alkyl radical , such as methyl or ethyl, or a radical corresponding to the formula: -R18-N(R16)2, where R18 denotes a group -CH2-CH2-, -CH2-CH2-CH2- or -CH2-CH(CH3) - and R16 has the meanings indicated above; as well as the higher homologs of these radicals, which contain up to 6 carbon atoms. 8. -DXDX- type amphoteric polymers selected from: a. polymers obtained through the action of chloroacetic acid, sodium chloroacetate or compounds containing at least one unit of the formula: -DXDXD- (X) in which D indicates a radical: and X denotes the symbol E or E', E or E', which are the same or different, indicate a bivalent radical which is an alkylene radical with a straight or branched chain containing up to seven carbon atoms in the main chain which is unsubstituted or substituted by hydroxyl groups and may also contain oxygen, nitrogen or sulfur atoms and one to three aromatic and/or heterocyclic rings; in which the oxygen, nitrogen and sulfur atoms are present in the form of ether, thioether, sulfoxide, sulfone, sulphonium, alkylamine or alkenylamine groups or hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and /or urethane. B. Polymers of the formula: -DXDX- (XI) where D denotes a radical: and X denotes the symbol E or E' and, at least once, E'; wherein E has the meaning given above and E' is a bivalent radical which is a straight or branched chain alkylene radical containing up to seven carbon atoms in the main chain, which is unsubstituted or substituted by one or more hydroxyl radicals and contains one or more nitrogen atoms, where the nitrogen atom is replaced by an alkyl chain optionally interrupted by an oxygen atom and which necessarily contains one or more carboxyl-functional groups or one or more hydroxyl-functional groups and is betainized by means of reaction with chloroacetic acid or sodium chloroacetate. 9. (C1-C5) alkyl vinyl ether/maleic anhydride copolymers partially modified by semi-amidation with N,N-dialkylaminoalkylamine, such as N,N-dimethylaminopropylamine, or by semi-esterification with N,N-dialkanolamine. These copolymers may also contain other vinyl comonomers, such as vinylcaprolactam.

[00140] Particularly preferred amphoteric polymers according to the present invention are those of the family (1), particularly those containing a dialkyldiallyl ammonium salt as a cationic monomer.

[00141] The amphoternium polymers can be selected from polyquaternium-22, polyquaternium-39, polyquaternium-53, polyquaternium-64, polyquaternium-51, polyquaternium-61 and mixtures thereof. Polyquaternium-39 and polyquaternium-53, such as Merquat 3330 PR and Merquat 2003 PR, sold by Lubrizol, are most preferred.

[00142] The amount of the amphoteric polymer(s) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.1% by weight or more and, more preferably, 1% by weight or more, based on the total weight of the composition.

[00143] The amount of the amphoteric polymer(s) in the composition according to the present invention may be 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less relative to the total weight of the composition.

[00144] The amount of the amphoteric polymer(s) in the composition according to the present invention can be from 0.001 to 25% by weight, preferably from 0.1 to 20% by weight and, more preferably , 1 to 15% by weight, based on the total weight of the composition.

[00145] Non-polymeric acid that contains two or more dissociation constants:

[00146] The composition according to the present invention may include at least one non-polymeric acid that has two or more pKa values or its salt(s), that is, at least one non-polymeric acid that contains two or more acidic dissociation constants or their salt(s). The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined under constant temperature, such as 25°C.

[00147] Non-polymeric acid having two or more pKa values or its salt(s) can be included in particle (a). Non-polymeric acid having two or more pKa values can function as a crosslinker for cationic polymer, anionic polymer and amphoteric polymers.

[00148] The expression “non-polymeric” indicates that the acid is not obtained through the polymerization of two or more monomers. Non-polymeric acid does not therefore correspond to an acid obtained by polymerizing two or more monomers, such as polycarboxylic acid.

[00149] It is preferable that the molecular weight of the non-polymeric acid having two or more pKa values or its salt(s) is 1000 or less, preferably 800 or less, and most preferably 700 or less.

[00150] There is no limit to the type of non-polymeric acid that has two or more pKa values or its salt(s). Two or more different types of non-polymeric acids having two or more pKa values or their salts can be used in combination. One can therefore use a single type of non-polymeric acid having two or more pKa values or one of its salts, or a combination of different types of non-polymeric acids having two or more pKa values or its salts.

[00151] The term "salt" in this descriptive report indicates a salt formed by adding appropriate base(s) to non-polymeric acid that has two or more pKa values, which can be obtained by reacting 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 the salt, there can be mentioned metal salts such as salts with alkali metals such as Na and K, salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

[00152] The non-polymeric acid having two or more pKa values or its salt(s) may be an organic acid or its salt(s), preferably a hydrophilic or water-soluble organic acid or its(s) salt(s).

[00153] The non-polymeric acid having two or more pKa values may contain at least two acid groups selected from the group consisting of carboxylic group, sulfuric group, sulfonic group, phosphoric group, phosphonic group, phenolic hydroxyl group and mixtures thereof .

[00154]The non-polymeric acid that has two or more pKa values may be a non-polymeric polyvalent acid.

[00155] The non-polymeric acid that has two or more pKa values can be selected from the group consisting of dicarboxylic acids, disulfonic acids, diphosphoric acids and mixtures thereof.

[00156] The non-polymeric acid that has two or more pKa values or its salt(s) 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 its salts; aspartic acid, glutamic acid and their salts; terephthalilidene 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 (Portuguese Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brilliant Blue FCF), Blue 2 (Indigo Carmine ), Red 201 (Lithol Ruby B), Red 202 (Lithol Ruby BCA), Red 204 (Lithol Red CBA), Red 206 (Lithol Red CA), Red 207 (Lithol Red BA), Red 208 (Lithol Red SR), Red 219 (Bright Lacquer Red R), Red 220 (Deep Brown), Red 227 (Acid Fast Magenta), Yellow 203 (Quinoline Yellow WS), Green 201 (Cyanine Green Alizanine F), Green 204 (Piranine Conc.), Green 205 (Light Green SF Yellowish), Blue 203 (CA Patent Blue), Blue 205 (Alfazurine FG), Red 401 (Violamine R), Red 405 (Permanent Red F5R), Red 502 (Ponceau 3R), Red 503 (Ponceau R ), Red 504 (Ponceau SX), Green 401 (Naphtol Green B), Green 402 (Guinea Green B) and Black 401 (Naphtol Blue Black); folic acid, ascorbic acid, erythorbic acid and their salts; cystine and its salts; EDTA and its salts; glycyrrhizin and its salts; and their mixtures.

[00157] It may be preferable that the non-polymeric acid having two or more pKa values or its salt(s) is selected from the group consisting of terephthalilidene dicamphor sulfonic acid and its salts (Mexoryl SX), Yellow 6 (Por do Sol Yellow FCF), ascorbic acid, phytic acid, their salts and mixtures.

[00158] The amount of non-polymeric acid having two or more pKa values or its salt(s) in the composition according to the present invention may be 0.0001% by weight or more, preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, based on the total weight of the composition.

[00159] The amount of the non-polymeric acid having two or more pKa values or its salt(s) in the composition according to the present invention may be 30% by weight or less, preferably 20% by weight or less and, more preferably, 15% by weight or less, based on the total weight of the composition.

[00160] The amount of non-polymeric acid that has two or more pKa values or its salt(s) in the composition according to the present invention can be from 0.0001 to 30% by weight, preferably from 0.01 to 20% by weight and, more preferably, from 0.1 to 15% by weight, based on the total weight of the composition.

[00161] Non-polymeric base that contains two or more basic dissociation constants:

[00162] The composition according to the present invention may include at least one non-polymeric base that has two or more pKb values or its salt(s), that is, at least one non-polymeric base that contains two or more basic dissociation constants or their salt(s). The pKb value (basic dissociation constant) is well known to those skilled in the art and should be determined under constant temperature, such as 25°C.

[00163] The non-polymeric base having two or more pKb values or its salt(s) can be included in the particle (a). The non-polymeric base having two or more pKb values can function as a crosslinker for cationic polymer, anionic polymer and amphoteric polymers.

[00164] The expression “non-polymeric” indicates that the base is not obtained through the polymerization of two or more monomers. The non-polymer base therefore does not correspond to a base obtained through the polymerization of two or more monomers, such as polyallylamine.

[00165] 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 most preferably 700 or less.

[00166] There is no limit for the type of non-polymeric base that has two or more pKb values or its salt(s). Two or more different types of non-polymeric bases having two or more pKb values or their salts can be used in combination. One can therefore use a single type of non-polymeric base having two or more pKb values or one of their salts, or a combination of different types of non-polymeric bases having two or more pKb values or their salts.

[00167] The term "salt" in this descriptive report indicates a salt formed by adding appropriate acid(s) to the non-polymeric base that has two or more pKb values, which can be obtained from reaction with the non-polymeric base having two or more pKb values with the acid(s) according to methods known to those skilled in the art. As the salt, there can be mentioned ammonium salts such as salts with inorganic acid such as HCl and HNO3, and salts with organic acid such as carboxylic acids and sulfonic acids.

[00168] The non-polymeric base having two or more pKb values or its salt(s) may be an organic base or its salt(s), preferably a hydrophilic or water-soluble organic base or its(s) salt(s).

[00169] The non-polymeric base having two or more pKb values may contain at least two basic groups selected from the group consisting of amino group, guanidine group, biguanide group, imidazole group, imino group, pyridyl group and mixtures thereof.

[00170] The non-polymeric base having two or more pKb values can be selected from the group consisting of non-polymeric diamines, such as ethylenediamine, propylenediamine, pentanediamine, hexanediamine, urea and its derivatives, guanidine and its derivatives, non-polyamines polymeric such as spermine and spermidine, basic amino acids and mixtures thereof.

[00171] The non-polymeric base having two or more pKb values or its salt(s) may be selected from the group consisting of arginine, lysine, histidine, cysteine, cystine, tyrosine, tryptophan, ornithine and their mixtures.

[00172] It may be preferable that the non-polymeric base having two or more pKb values or its salt(s) is selected from the group consisting of arginine, lysine, histidine and mixtures thereof.

[00173] The amount of the non-polymeric base having two or more pKb values or its salt(s) in the composition according to the present invention may be 0.0001% by weight or more, preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, based on the total weight of the composition.

[00174] The amount of the non-polymeric base having two or more pKb values or its salt(s) in the composition according to the present invention may be 30% by weight or less, preferably 20% by weight or less and, more preferably, 15% by weight or less, based on the total weight of the composition.

[00175] The amount of the non-polymeric base having two or more pKb values or its salt(s) in the composition according to the present invention may be from 0.0001 to 30% by weight, preferably from 0.01 to 20% by weight and, more preferably, from 0.1 to 15% by weight, based on the total weight of the composition.

[00176] Hydrophobic amino acid:

[00177] The particle (a) in the composition according to the present invention may include (c) at least one hydrophobic amino acid other than the above non-polymeric acid that has two or more pKb values or its salt(s) or the above non-polymeric base having two or more pKb values or salt(s) thereof. Two or more hydrophobic amino acids can be used in combination.

[00178] The term “hydrophobic amino acid” may be selected from the group consisting of isoleucine, leucine, valine, methionine, phenylalanine, threonine, glycine, cysteine, alanine and mixtures thereof. It is preferred that the hydrophobic amino acid (c) is selected from leucine, phenylalanine and mixtures thereof.

[00179] The hydrophobic amino acid (c) can be useful to control the hydrophobicity of the particle (a).

[00180] The amount of hydrophobic amino acid(s) (c) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.01% by weight or more, and most preferably 0.1% by weight or more, based on the total weight of the composition.

[00181] The amount of hydrophobic amino acid(s) (c) in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and most preferably , 1% by weight or less, based on the total weight of the composition.

[00182] The amount of hydrophobic amino acid(s) (c) in the composition according to the present invention may be from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight and, more preferably, 0.1 to 1% by weight, based on the total weight of the composition.

[00183] Physiologically acceptable volatile medium:

[00184] The composition according to the present invention comprises at least one physiologically acceptable volatile medium (b).

[00185] The expression "physiologically acceptable" volatile medium is intended to indicate a volatile medium that is particularly suitable for applying the composition according to the present invention to the keratin substance(s).

[00186] The term “volatile” indicates that the physiologically acceptable medium (b) can evaporate under normal atmospheric pressure, such as 1 atm, and at ambient temperature, such as 25 °C.

[00187] The physiologically acceptable medium is generally adapted to the nature of the support to which the composition according to the present invention must be applied, as well as the form in which the composition according to the present invention must be packaged.

[00188] The physiologically acceptable volatile medium (b) may comprise at least one hydrophilic organic solvent, water or one of their mixtures.

[00189] As a hydrophilic organic solvent, mention may be made, for example, of monoalcohols containing from 2 to 6 carbon atoms, such as ethanol or isopropanol; polyols, especially containing from 2 to 20 carbon atoms, preferably containing from 2 to 10 carbon atoms, and more preferably containing from 2 to 8 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, caprylyl glycol, dipropylene glycol or diethylene glycol; glycol ethers (especially containing from 3 to 16 carbon atoms) such as (C1-C4) alkyl ethers of mono, di or tripropylene glycol; (C1-C4)alkyl ethers of mono, di or triethylene glycol and mixtures thereof.

[00190] The amount of (b) at least one physiologically acceptable volatile medium, preferably water, in the composition according to the present invention can be from 50 to 99% by weight, preferably from 60 to 97% by weight and, more preferably, 70 to 95% by weight, with respect to the total weight of the composition.

[00191] Cosmetic active ingredient:

[00192] The composition according to the present invention may comprise at least one cosmetic active ingredient. There is no limitation for the cosmetic active ingredient. Two or more cosmetic active ingredients can be used in combination. Therefore, a single type of cosmetic active ingredient or a combination of different types of cosmetic active ingredients can be used.

[00193] Among the cosmetic active ingredients to be used, one can mention UV filters, antioxidants, hygiene agents, free radical extractors, humectants, whitening agents, liporegulators, anti-acne agents, anti-dandruff agents, anti-aging agents, softeners, anti-wrinkle agents , keratolytic agents, coolants, antibacterial agents, antifungal agents, antiperspirants, deodorants, skin conditioners, anesthetics, nourishing agents, fat absorbers or moisture absorbers.

[00194] It is preferable that the non-polymeric acid that has two or more pKa values can function as a cosmetic active agent. If non-polymeric acid having two or more pKa values can function as a cosmetic active agent, it may not be necessary for the composition according to the present invention to include cosmetic active agent(s).

[00195] The composition according to the present invention may comprise the cosmetic active ingredient(s) in an amount of 0.01 to 50% by weight, preferably from 0.1 to 40% by weight weight, more preferably from 1 to 30% by weight and even more preferably from 2 to 20% by weight, based on the total weight of the composition.

[00196] UV filter:

[00197] Second preferred embodiment of the present invention, the cosmetic active ingredient can be selected from UV filters.

[00198]There is no limit for the type of UV filter. Two or more types of UV filters can be used in combination. You can therefore use a single type of UV filter or a combination of different types of UV filters. The UV filter can be selected from the group consisting of inorganic UV filter, organic UV filter and mixtures thereof.

[00199] Inorganic UV filter:

[00200] The composition according to the present invention may comprise at least one inorganic UV filter. If two or more inorganic UV filters are used, they can be identical or different, preferably identical.

[00201] The inorganic UV filter used for the present invention can be active in the UV-A and/or UV-B region. The inorganic UV filter can be hydrophilic and/or lipophilic. The inorganic UV filter is preferably insoluble in solvents such as water and ethanol commonly used in cosmetics.

[00202] It is preferable for the inorganic UV filter to be in the form of fine particles, so that its average (primary) particle diameter ranges from 1 nm to 50 nm, preferably 5 nm to 40 nm and, more preferably , 10 nm to 30 nm. The mean (primary) particle size or mean (primary) particle diameter at present is the arithmetic mean of the diameter.

[00203] The inorganic UV filter can be selected from the group consisting of silicon carbide, metal oxides that may or may not be coated and mixtures thereof.

[00204] Preferably, inorganic UV filters can be selected from pigments (average primary particle size: generally from 5 nm to 50 nm, preferably from 10 nm to 50 nm) formed with metal oxides, such as pigments formed with oxide of titanium (amorphous or crystalline in the form of rutile and/or anatase), iron oxide, zinc oxide, zirconium oxide or cerium oxide, all of which are UV photoprotective agents that are intrinsically known. Preferably, the inorganic UV filters can be selected from titanium oxide, zinc oxide and most preferably titanium oxide.

[00205] The inorganic UV filter may or may not be coated. The inorganic UV filter can have at least one coating. The coating may comprise at least one compound selected from the group consisting of alumina, silica, aluminum hydroxide, silicones, silanes, fatty acids or their salts (such as sodium, potassium, zinc, iron or aluminum salts), alcohols fatty acids, lecithin, amino acids, polysaccharides, proteins, alkanolamines, waxes such as beeswax, (meth)acrylic polymers, organic UV filters and (per)fluoro compounds.

[00206] It is preferable that the coating includes at least one organic UV filter. As the organic UV filter in the coating, a dibenzoylmethane derivative such as butyl methoxydibenzoylmethane (Avobenzone) and 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1, 3,3-tetramethylbutyl)phenol] (methylene bisbenzotriazolyl tetramethylbutylphenol) marketed as “TINOSORB M” by BASF.

[00207] As is known, the silicones in the coating(s) may be organosilicon polymers or oligomers comprising a linear or cyclic and branched or cross-linked structure, with variable molecular weight, obtained through polymerization and /or polycondensation of suitable functional silanes and essentially composed of repeating main units in which silicon atoms are connected to each other via oxygen atoms (siloxane bonding), in which optionally substituted hydrocarbon radicals are connected directly to said silicon atoms through a carbon atom.

[00208] The term “silicones” also encompasses silanes necessary for their preparation, particularly alkylsilanes.

[00209] The silicones used for the coating(s) may preferably be selected from the group consisting of alkylsilanes, polydialkylsiloxanes and polyalkylhydrosilanes. Even more preferably, the silicones are selected from the group consisting of octyltrimethylsilanes, polydimethylsiloxanes and polymethylhydrosiloxanes.

[00210] Naturally, organic UV filters made with metallic oxides may, before being treated with silicones, have been treated with other surface-forming agents, particularly with cerium oxide, alumina, silica, aluminum compounds, silicon compounds or your mixtures.

[00211] The coated inorganic UV filter may have been prepared by subjecting the inorganic UV filter to one or more surface treatments of a chemical, electronic, mechanical-chemical and/or mechanical nature with any of the compounds described above, as well as polyethylenes , metal alkoxides (titanium or aluminum alkoxides), metal oxides, sodium hexametaphosphate and those shown, for example, in Cosmetics & Toiletries, February 1990, vol. 105, pgs. 53-64.

[00212] Coated inorganic UV filters can be titanium oxides coated with: - silica, such as the product “Sunveil” by Ikeda; - silica and iron oxide, such as Ikeda's “Sunveil F” product; - silica and alumina, such as the products “Microtitanium Dioxide MT 500 SA” by Tayca, “Tioveil” by Tioxide and “Mirasun TiW 60” by Rhodia; - alumina, such as the products “Tipaque TTO-55 (B)” and “Tipaque TTO-55 (A)” from Ishihara and “UVT 14/4” from Kemira; - alumina and aluminum stearate, such as the product “Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z or MT-01” by Tayca, the products “Solaveil CT-10 W” and “Solaveil CT 100” by Uniqema and Merck's “Eusolex T-AVO” product; - alumina and aluminum laurate, such as the product “Microtitanium Dioxide MT 100 S” by Tayca; - iron oxide and iron stearate, such as the product “Microtitanium Dioxide MT 100 F” by Tayca; - zinc oxide and zinc stearate, such as Tayca's “BR351” product; - silica and alumina, treated with silicone, such as the products “Microtitanium Dioxide MT 600 SAS”, “Microtitanium Dioxide MT 500 SAS” and “Microtitanium Dioxide MT 100 SAS” by Tayca; - silicone-treated silica, alumina and aluminum stearate, such as Titan Kogyo's “STT-30-DS” product; - silica, treated with silicone, such as Kemira's “UV-Titan X 195” product; - alumina, treated with silicone, such as the products “Tipaque TTO-55 (S)” by Ishihara or “UV Titan M 262” by Kemira; - triethanolamine, such as Titan Kogyo's product “STT-65-S”; - stearic acid, such as the product “Tipaque TTO-55 (C)” from Ishihara; or - sodium hexametaphosphate, such as Tayca's “Microtitanium Dioxide MT 150 W”.

[00213] Other silicone-treated titanium oxide pigments are preferably TiO2 treated with octyltrimethylsilane, whose average individual particle size is 25 to 40 nm, such as that sold under the brand name “T 805” by Degussa Silices, TiO2 treated with polydimethylsiloxane, which has an average individual particle size of 21 nm, such as that marketed under the trade name “70250 Cardre UF TiO2Si3” by Cardre and polydimethylhydroxysiloxane-treated anatase/rutile TiO2, which has an average individual particle size of 25 nm , such as that sold under the brand name “Microtitanium Dioxide USP Hydrophobic Grade” by Color Techniques.

[00214] Preferably, the coated TiO2 below can be used as a coated inorganic UV filter: - stearic acid (and) aluminum hydroxide (and) TiO2, such as Tayca's “MT-100 TV” product, with particle diameter 15 nm medium primer; - dimethicone (and) stearic acid (and) aluminum hydroxide (and) TiO2, such as the product “SA-TTO-S4” by Miyoshi Kasei, with an average primary particle diameter of 15 nm; - silica (and) TiO2, such as Tayca's “MT-100 WP” product, with an average primary particle diameter of 15 nm; - dimethicone (and) silica (and) aluminum hydroxide (and) TiO2, such as Tayca's “MT-Y02” and “MT-Y-110 M3S” products, with an average primary particle diameter of 10 nm; - dimethicone (and) aluminum hydroxide (and) TiO2, such as the product “SA-TTO-S3” by Miyoshi Kasei, with an average primary particle diameter of 15 nm; - dimethicone (and) alumina (and) TiO2, such as the product “UV TITAN M170” by Sachtleben, with an average primary particle diameter of 15 nm; and - silica (e) aluminum hydroxide (e) alginic acid (e) TiO2, such as Tayca's “MT-100 AQ” product, with an average primary particle diameter of 15 nm.

[00215] In terms of filtering and UV capacity, TiO2 coated with at least one organic UV filter is most preferred. One can use, for example, Avobenzone (and) Stearic Acid (and) Aluminum Hydroxide (and) TiO2, such as Tayca's “HXMT-100ZA” product, with average primary particle diameter of 15 nm.

[00216] Uncoated titanium oxide pigments are, for example, marketed by Tayca under the brand names “Microtitanium Dioxide MT500B” or “Microtitanium Dioxide MT600B”, by Degussa under the brand name “P 25”, by Wacker under the brand name “Oxido de Titanio Transparente PW”, by Miyoshi Kasei with the brand name “UFTR”, by Tomen with the brand name “ITS” and by Tioxide with the brand name “Tioveil AQ”.

[00217] Uncoated zinc oxide pigments are, for example: - those sold under the brand name “Z-cote” by Sunsmart; - those marketed under the “Nanox” brand by Elementis; and - those marketed under the brand name “Nanogard WCD 2025” by Nanophase Technologies.

[00218] Coated zinc oxide pigments are, for example: - those sold under the brand name “Zinc Oxide CS-5” by Toshiba (ZnO coated with polymethylhydrosiloxane); - those marketed under the brand name “Zinc Oxide Nanogard FN” by Nanophase Technologies (in the form of a 40% dispersion in Finsolv TN, C12-C15 alkyl benzoate); - those sold under the brand names “Daitopersion Zn-30” and “Daitopersion Zn-50” by Daito (dispersions in oxyethylenated polydimethylsiloxane/cyclopolymethylsiloxane comprising 30% or 50% zinc nanooxides coated with silica and polymethylhydrosiloxane); - those marketed under the brand name “NFD Ultrafine ZnO” by Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl in the form of a dispersion in cyclopentasiloxane); - those marketed under the brand name "SPD-Z1" by Shin-Etsu (ZnO coated with an acrylic polymer grafted with silicone dispersed in cyclodimethylsiloxane); - those marketed under the brand name "Escalol Z100" by ISP (ZnO treated with alumina dispersed in a mixture of ethylhexyl methoxycinnamate/PVP-hexadecene/methicone copolymer); - those marketed under the brand name “Fuji ZnO-SMS-10” by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); and those marketed under the brand name “ Nanox Gel TN” by Elementis (55% dispersed ZnO in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate).

[00219] Uncoated cerium oxide pigments are marketed, for example, under the brand name “Colloidal Cerium Oxide” by Rhone-Poulenc.

[00220] Uncoated iron oxide pigments are marketed, for example, by Arnaud under the brands “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45 BL AQ”, “Nanogard FE 45R AQ” and "Nanogard WCD 2006 (FE 45R)", or by Mitsubishi branded "TY-220".

[00221] Coated iron oxide pigments are marketed, for example, by Arnaud under the brands “Nanogard WCD 2008 (FE 45B FN)”, “Nanogard WCD 2009 (FE 45B 556)”, “Nanogard FE 45 BL 345” and “Nanogard FE 45 BL”, or by BASF under the brand “Transparent Iron Oxide”.

[00222] Mention may also be made of mixtures of metallic oxides, particularly titanium dioxide and cerium dioxide, including a mixture of equal weights of silica-coated titanium dioxide and silica-coated cerium dioxide sold by Ikeda with the brand “Sunveil A”, as well as a mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, such as the product “M 261” marketed by Kemira, or coated with alumina, silica and glycerol, such as the product “M 211”, marketed by Kemira.

[00223]Coated inorganic UV filters are preferred as the UV filtering effects of inorganic UV filters can be enhanced. Furthermore, the coating(s) can help disperse, evenly or uniformly, the UV filters in the compositions according to the present invention.

[00224] If inorganic UV filter(s) in the form of fine particles are used, films according to the present invention that can be prepared from the composition according to the present invention can also have the effect of not providing a white appearance, but a clear or transparent appearance, as the fine particles of the inorganic UV filters do not aggregate, but can be spread evenly or homogeneously on the film. It should be noted that fine particles free of inorganic UV filter(s) easily aggregate to impart a white appearance to the skin.

[00225] Organic UV filter:

[00226] The composition according to the present invention may comprise at least one organic UV filter. If two or more organic UV filters are used, they can be identical or different, preferably identical.

[00227] The organic UV filter used for the present invention can be active in the UV-A and/or UV-B region. The organic UV filter can be hydrophilic and/or lipophilic.

[00228]The organic UV filter can be solid or liquid. The terms "solid" and "liquid" indicate solid and liquid, respectively, at 25 °C under 1 atm.

[00229] The organic UV filter can be selected from the group consisting of anthranilic compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic compounds; camphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole compounds; imidazoline compounds; bis-benzoazolyl compounds; p-aminobenzoic acid (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; screening polymers and screening silicones; dimers derived from α-alkylstyrene; 4,4-diarylbutadiene compounds; guaiazulene and its derivatives; rutin and its derivatives; and their mixtures.

[00230] As examples of the organic UV filter(s), those listed below with their INCI names and their mixtures may be mentioned: - anthranilic compounds: methyl anthranilate, marketed under the brand name “Neo Heliopan MA” by Haarmann and Reimer; - dibenzoylmethane compounds: butyl methoxydibenzoylmethane, marketed specifically under the brand name "Parsol 1789" by Hoffmann-La Roche; and isopropyl dibenzoylmethane; - cinnamic compounds: ethylhexyl methoxycinnamate, marketed specifically under the brand name "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, marketed under the brand name “Neo Heliopan E 1000” by Haarmann and Reimer; cinoxate (2-ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl dimethoxycinnamate ethylhexanoate; - salicylic compounds: homosalate (homomethyl salicylate), marketed under the brand name “Eusolex HMS” by Rona/EM Industries; ethylhexyl salicylate, marketed under the brand name “Neo Heliopan OS” by Haarmann &Reimer; glycol salicylate; butyl octyl salicylate; phenyl salicylate; dipropylene glycol salicylate, marketed under the brand name “Dipsal” by Scher; and TEA salicylate, marketed under the brand name “Neo Heliopan TS” by Haarmann and Reimer; - camphor compounds, particularly benzylidene camphor derivatives: 3-benzylidene camphor, manufactured under the trade name “Mexoryl SD” by Chimex; 4-methylbenzylidene camphor, marketed under the brand name “Eusolex 6300” by Merck; benzylidene camphor sulfonic acid, manufactured under the trademark “Mexoryl SL” by Chimex; camphor benzalkonium methosulfate, manufactured under the trade name “Mexoryl SO” by Chimex; terephthalilidene dicamphor sulfonic acid, manufactured under the trade name “Mexoryl SX” by Chimex; and polyacrylamidomethyl benzylidene camphor, manufactured under the trademark “Mexoryl SW” by Chimex; - benzophenone compounds: benzophenone-1 (2,4-dihydroxybenzophenone), marketed under the brand name “Uvinul 400” by BASF; benzophenone-2 (tetrahydroxybenzophenone), marketed under the brand name “Uvinul D50” by BASF; benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or oxybenzone, marketed under the brand name “Uvinul M40” by BASF; benzophenone-4 (hydroxymethoxy benzophenone sulfonic acid), marketed under the brand name “Uvinul MS40” by BASF; benzophenone-5 (sodium hydroxymethoxy benzophenone sulfonate); benzophenone-6 (dihydroxy dimethoxy benzophenone), marketed under the brand name “Helisorb 11” by Norquay; benzophenone-8, marketed under the brand name “Spectra-Sorb UV-24” by American Cyanamid; benzophenone-9 (disodium dihydroxy dimethoxy benzophenone disulfonate), marketed under the brand name “Uvinul DS-49” by BASF; benzophenone-12 and n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate (UVINUL A+ from BASF); - β,β-diphenylacrylate compounds: octocrylene, specifically marketed under the brand name “Uvinul N539” by BASF; and ectocrylene, marketed specifically under the brand name “Uvinul N35” by BASF; - triazine compounds: diethylhexyl butamido triazone, marketed under the brand name “Uvasorb HEB” by Sigma 3V; 2,4,6-tris(4'-aminobenzalmalonate dineopentyl)-s-triazine, bis-ethylhexyloxyphenol methoxyphenyl triazine, marketed under the trade name “TINOSORB S” by CIBA GEIGY and ethylhexyl triazone, marketed under the trade mark “ UVINUL T150” by BASF; - benzotriazole compounds, particularly phenylbenzotriazole derivatives: 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, linear and branched; and those described in USP 5,240,975; - benzalmalonate compounds: dineopentyl 4'-methoxybenzalmalonate and polyorganosiloxanes comprising groups with benzalmalonate functionality, such as polysilicone-15, marketed under the trade name “Parsol SLX” by Hoffmann-LaRoche; - benzimidazole compounds, particularly phenylbenzimidazole derivatives: phenylbenzimidazole sulfonic acid, particularly marketed under the brand name “Eusolex 232” by Merck, and phenyl dibenzimidazole tetrasulfonate disodium, marketed under the brand name “Neo Heliopan AP” by Haarmann &Reimer; - imidazoline compounds: dimethoxybenzylidene dioxoimidazoline ethylhexyl propionate; - bisbenzoazolyl compounds: derivatives are described in EP 669,323 and in US Patent No. 2,463,264; - para-aminobenzoic acid compounds: PABA (p-aminobenzoic acid), ethyl PABA, ethyl dihydroxypropyl PABA, pentyl dimethyl PABA, ethylhexyl dimethyl PABA, particularly marketed under the brand name “Escalol 507” by ISP, glyceryl PABA and PEG-25 PABA, marketed under the brand name “Uvinul P25” by BASF; - methylene bis-(hydroxyphenylbenzotriazole) compounds, such as 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol] marketed in solid form under the brand name “Mixxim BB/200” by Fairmount Chemical, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] marketed in micronized form in aqueous dispersion under the trade mark “Tinosorb M” by BASF or branded “Mixxim BB/100” by Fairmount Chemical and its derivatives as described in US Patent Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE-197 26 184 and EP- 893,119; - drometrizol trisiloxane, marketed under the brand name “Silatrizol” by Rhodia Chimie or “Mexoryl XL” by L'Oreal, as indicated below: - benzoxazole compounds: 2,4-bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine, marketed under the brand name Uvasorb K2A by Sigma 3V; - selection polymers and selection silicones: the silicones described in WO 93/04665; - dimers derived from α-alkylstyrene: the dimers described in DE-19855649; and - 4,4-diarylbutadiene compounds: 1,1-dicarboxy(2,2'-dimethylproyl)-4,4-diphenylbutadiene.

[00231] It is preferred that the organic UV filter(s) be selected from the group consisting of: - butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethyl salicylate n-hexyl-hexyl, octocrylene, phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, 1,1'-(1,4-piperazinodi- yl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone 4-methylbenzylidene camphor, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, 2,4,6-tris(4'-aminobenzalmalonate dineopentyl)-s-triazine, 2,4,6-tris(4'-aminobenzalmalonate diisobutyl)-s-triazine, n-Butyl 2,4-bis-(4'-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyloxy)disiloxanyl]propyl}amino)-s-triazine , 2,4,6-tris-(diphenyl)-triazine, 2,4,6-tris(tert-phenyl)triazine, methylene bisbenzotriazolyl tetramethylbutylphenol, drometrizol trisiloxane, polysilicone-15, dineopentyl 4'-methoxybenzalmalonate, 1,1 -dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethyl- hexyl)imino-1,3,5-triazine, camphor benzylkonium methosulfate and mixtures thereof.

[00232] It is possible that the UV filter is water-soluble or dispersible in water, particularly water-soluble. As an example of the water-soluble UV filter, Mexoryl SX can be mentioned. Typically, the water-soluble or water-dispersible UV filter can be washed off the surface of a keratin substrate, such as skin, by water, such as sweat and rain. As the water-soluble or water-dispersible UV filter is included in the film according to the present invention, which can be prepared from the composition according to the present invention, however, it is difficult for the water-soluble or water-dispersible UV filter to be removed of the film by water, which results in long-lasting UV blocking effects.

[00233] Bleaching agent:

[00234] According to the preferred embodiment of the present invention, the cosmetic active ingredient can be selected from whitening agents.

[00235] There is no limit for the type of bleaching agent. Two or more types of bleaching agents can be used in combination. Therefore, a single type of bleaching agent or a combination of different types of bleaching agents can be used.

[00236] As examples of the bleaching agent, there may be mentioned ascorbic acid or its derivatives, kojic acid or its derivatives, tranexamic acid or its derivatives, resorcinol or its derivatives, alkoxysalicylic acid or its salts, adenosine phosphate or its salts, hydroquinone or their glycosides or derivatives, glutathione, 4-(4-hydroxyphenyl)-2-butanol, magnolignan (5,5'-dipropylbiphenyl-2,2'-diol), chamomilla recutita and the like.

[00237] Ascorbic acid has D configuration or L configuration and the L configuration is preferably employed. Ascorbic acid is also called vitamin C and has melanin production inhibition effects due to the strong effects of ascorbic acid reduction. The ascorbic acid derivatives may be ascorbic acid salts and the ascorbic acid salts are preferably selected from sodium ascorbate, magnesium ascorbyl phosphate and sodium ascorbyl phosphate. Derivatives of ascorbic acids can be ascorbic acid glycosides or ascorbic acid esters. As an example of ascorbic acid glycosides, for example, ascorbyl glycoside can be mentioned. As examples of ascorbic acid esters, mention may be made, for example, of silyl ascorbate, tocopheryl ascorbate and alkyl ascorbate. As the alkyl ascorbate, methyl ascorbate or ethyl ascorbate is preferably used. Particularly, ascorbyl glucoside is preferable. Ascorbic acid or its derivatives can be used alone or in combination with two or more of its types.

[00238] As detailed examples of ascorbic acid derivatives, one can mention, for example, 5,6-di-O-dimethylsilyl ascorbate, which is commercially available as PRO-AA from Exsymol SAM; dl-alpha-tocopheryl-2-1-ascorbyl phosphate, which is commercially available as SEPIVITAL EPC from Senju Pharmaceutical Co., Ltd.; sodium ascorbyl phosphate, which is commercially available as Stay-C 50 from Roche; ascorbyl glucoside, which is commercially available from Hayashibara Biochemical Labs., Inc.; 3-O-ethyl ascorbic acid; and the like.

[00239] Ascorbic acid or its derivative is preferably used in combination with a copolymer of styrene and maleic anhydride. Particularly, at least a part of the maleic anhydride unit of the above-mentioned copolymer is preferably hydrolyzed. The aforementioned hydrolyzed maleic anhydride unit may be in the form of an alkaline salt, such as sodium salt, potassium salt, lithium salt or the like. The maleic anhydride unit mentioned above preferably occupies 0.4 to 0.9 mol per mol of the entire copolymer, and the ratio of the maleic anhydride unit to the styrene unit is preferably 50:50. Particularly, it is preferable that the ratio between maleic anhydride unit and styrene unit is preferably 50:50 and that ammonium salt or sodium salt is used. By employing ascorbic acid or its derivative in combination with the above-mentioned copolymer, the stability of ascorbic acid or its derivative is increased. As the copolymer mentioned above, for example, a copolymer of styrene and maleic anhydride (50/50) in the form of ammonium salt in a concentration of 30% in water, which is commercially available as product No. SMA 1000, can be used. H (trademark) of Atofina Chemicals, Inc.; or a copolymer of styrene and maleic anhydride (50/50) in the form of sodium salt in a 40% concentration in water, which is commercially available as product no. SMA 1000 H Na (trademark) from Atofina Chemicals, Inc. The copolymer mentioned above is used in a concentration ranging from 0.1 to 20% by weight and, preferably, ranging from 0.1 to 10% by weight, with respect to the total weight of the bleaching agent for topical application.

[00240] As an example of kojic acid derivatives, one can mention, for example, kojic acid glycoside.

[00241] As examples of tranexamic acid derivatives, tranexamic acid dimers (such as trans-4-(transaminomethylcyclohexanecarbonyl)aminomethylcyclohexane carboxylic acid hydrochloric acid), esters of tranexamic acid and hydroquinone (such as trans 4'-hydroxyphenyl-4-aminomethylcyclohexane carboxylate), esters of tranexamic acid and gentisic acid (such as (trans-4-aminomethylcyclohexanecarbonyloxy)-5-hydroxybenzoic acid and its salts), tranexamic amides (such as methylamide of trans-4-aminomethylcyclohexanecarboxylic acid and its salts, trans-4-(p-methoxybenzoyl)aminomethylcyclohexanecarboxylic acid and its salts and trans-4-guanidinomethylcyclohexanecarboxylic acid and its salts) and the like.

[00242] As examples of resorcinol derivatives, there can be mentioned, for example, 4-n-butylresorcinol (Rucinol) and the like.

[00243] Alkoxysalicylic acid is a compound in which any of the hydrogen atoms in position 3, position 4 or position 5 of salicylic acid is replaced by an alkoxy group. The alkoxy group mentioned above is preferably any one of methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group and isobutoxy group, more preferably methoxy group or ethoxy group. As examples of the compound, there can be mentioned, for example, 3-methoxysalicylic acid, 3-ethoxysalicylic acid, 4-methoxysalicylic acid, 4-ethoxysalicylic acid, 4-propoxysalicylic acid, 4-isopropoxysalicylic acid, 4-butoxysalicylic acid, 5 -methoxysalicylic acid, 5-ethoxysalicylic acid, 5-propoxysalicylic acid and the like. Salts of alkoxysalicylic acids are not particularly limited. As its examples, there can be mentioned, for example, alkali metal salts or alkaline earth metal salts such as sodium salts, potassium salts, calcium salts and the like, ammonium salts, amino acid salts and the like. 4-Methoxysalicylic acid potassium salt is preferred.

[00244] As examples of adenosine phosphate or its salts, there can be mentioned, for example, adenosine phosphate disodium and the like.

[00245] As examples of hydroquinone glycosides, mention may be made, for example, of hexose glycosides, such as hydroquinone alpha-D-glucose, hydroquinone beta-D-glucose, hydroquinone alpha-L-glucose, hydroquinone beta-L-glucose hydroquinone alpha-D-galactose, hydroquinone beta-D-galactose, hydroquinone alpha-L-galactose, hydroquinone beta-L-galactose and the like; pentose glycosides, such as hydroquinone alpha-D-ribose, hydroquinone beta-D-ribose, hydroquinone alpha-L-ribose, hydroquinone beta-L-ribose, hydroquinone alpha-D-arabinose, hydroquinone beta-D-arabinose, hydroquinone alpha- L-arabinose, hydroquinone beta-L-arabinose and the like; aminosugar glycosides such as hydroquinone alpha-D-glucosamine, hydroquinone beta-D-glucosamine, hydroquinone alpha-L-glucosamine, hydroquinone beta-L-glucosamine, hydroquinone alpha-D-galactosamine, hydroquinone beta-D-galactosamine, hydroquinone alpha -L-galactosamine, hydroquinone beta-L-galactosamine and the like; urocanic acid glycosides, such as hydroquinone alpha-D-glucuronic acid, hydroquinone beta-D-glucuronic acid, hydroquinone alpha-L-glucuronic acid, hydroquinone beta-L-glucuronic acid, hydroquinone alpha-D-galacturonic acid, hydroquinone beta acid -D-galacturonic acid, hydroquinone alpha-L-galacturonic acid, hydroquinone beta-L-galacturonic acid and the like; and the like. Of these compounds, beta-D-glucose hydroquinone (hereinafter referred to as “arbutin”) is preferable. As examples of hydroquinone derivatives or their glycosides, mention may be made, for example, of hydroquinone salts or their glycosides. Particularly, as examples of arbutin derivatives, for example, 6-O-caffeoylarbutin and the like can be mentioned.

[00246] As whitening active ingredients, L-ascorbic acid or its derivatives, kojic acid or its derivatives, tranexamic acid or its derivatives, arbutin or its derivatives and Rucinol are particularly preferred, more preferably ascorbic acid derivatives such as 3- O-ethyl-L-ascorbic acid and L-ascorbic acid glycoside.

[00247] pH:

[00248] The pH of the composition according to the present invention can be from 3 to 9, preferably from 3.5 to 8.5 and more preferably from 4 to 8.

[00249] Under pH 3 to 9, the particle (a) can be very stable.

[00250] The pH of the composition according to the present invention can be adjusted by adding at least one alkaline agent and/or at least one acid other than the non-polymeric acid having two or more pKa values or the non-polymeric base that has two or more pKb values, as explained below. The pH of the composition according to the present invention can also be adjusted by adding at least one buffering agent.

[00251] Alkaline agent:

[00252] The composition according to the present invention may comprise at least one alkaline agent. Two or more alkaline agents can be used in combination. Therefore, a single type of alkaline agent or a combination of different types of alkaline agents can be used.

[00253] It is preferable that the alkaline agent has only one pKb.

[00254] The alkaline agent may be an inorganic alkaline agent. It is preferred that the inorganic alkaline agent is selected from the group consisting of ammonia; alkali metal hydroxides; alkaline earth metal hydroxides; and their mixtures.

[00255] As examples of inorganic alkali metal hydroxides, we can mention sodium hydroxide and potassium hydroxide. As examples of the alkaline earth metal hydroxides, mention may be made of calcium hydroxide and magnesium hydroxide. As the inorganic alkaline agent, sodium hydroxide is preferable.

[00256] The alkaline agent may be an inorganic alkaline agent. It is preferred that the organic alkaline agent is selected from the group consisting of monoamines and their derivatives.

[00257] The alkaline agent(s) may be used in a total amount of 0.1 to 20% by weight, preferably from 0.2 to 10% by weight and, more preferably, 0.3 to 5% by weight, based on the total weight of the composition, depending on its solubility.

[00258] Acid:

[00259] The composition according to the present invention may comprise at least one acid. Two or more acids can be used in combination. Therefore, a single type of acid or a combination of different types of acids can be used.

[00260] It is preferable that the acid has only one pKa.

[00261] As the acid, one can mention any organic or inorganic acids, preferably inorganic acids, which are commonly used in cosmetic products. A monovalent acid can be used. A monovalent acid such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) can be used. HCl is preferable.

[00262] The acid(s) may be used in a total amount of 0.1 to 15% by weight, preferably 0.2 to 10% by weight and, more preferably, 0 .3 to 5% by weight, based on the total weight of the composition, depending on its solubility.

[00263] Buffer agent:

[00264] The composition according to the present invention may comprise at least one buffering agent. Two or more buffering agents can be used in combination. Therefore, a single type of buffering agent or a combination of different types of buffering agents can be used.

[00265] As a buffering agent, acetate buffer (for example, acetic acid + sodium acetate), phosphate buffer (for example, sodium dihydrogen phosphate + disodium hydrogen phosphate), citrate buffer (for e.g. citric acid + sodium citrate), borate buffer (e.g. boric acid + sodium borate), tartrate buffer (e.g. tartaric acid + sodium tartrate dihydrate), tris buffer (e.g. tris (hydroxymethyl)aminomethane) and Hepes buffer (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[00266] Optional additives:

[00267] The composition according to the present invention may comprise, in addition to the components mentioned above, components typically used in cosmetics, specifically such as dyes, powders, surfactants or emulsifiers, oils, thickeners, non-volatile organic solvents, silicones and derivatives of silicone, natural extracts derived from animals or vegetables, waxes and the like, within a range that does not harm the effects of the present invention.

[00268] 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, more preferably, 0.1 to 10% by weight, based on the total weight of the composition.

[00269] In one embodiment, the composition according to the present invention may include at least one oil. Two or more oils can be used in combination. Therefore, a single type of oil or a combination of different types of oils can be used. At this point, the term "oil" is understood to indicate a fatty substance that is liquid at room temperature (25 °C).

[00270] The oil(s) may be volatile or non-volatile.

[00271] The oil(s) may be of animal, vegetable, mineral or synthetic origin.

[00272] The expression “non-volatile oil” indicates oil that remains on a keratin substance at room temperature (25 °C) and atmospheric pressure. More specifically, non-volatile oil has an evaporation rate strictly below 0.01 mg/cm2/min.

[00273] To measure this evaporation speed, 15 g of oil or mixture of oils to be tested are placed in a crystallization dish with a diameter of 7 cm, which is placed on a scale in a large chamber of about 0.3 m3 with regulated temperature, under a temperature of 25 °C, and with regulated hygrometry, under a relative humidity of 50%. The liquid is maintained in free evaporation, without agitation, providing ventilation by means of a fan (Papst-Motoren, reference 8550 N, rotating at 2700 rpm) placed in a vertical position above the crystallization dish containing the mentioned oil or the mentioned mixture, in which the paddles are directed towards the crystallization dish, 20 cm away from the bottom of the crystallization dish. The mass of oil remaining in the crystallization dish is measured at regular intervals. Evaporation rates are expressed in mg of oil evaporated per unit area (cm2) and per unit time (minutes).

[00274] The expression “volatile oil” indicates any non-aqueous medium capable of evaporating in contact with the skin or lips in less than one hour at room temperature (25 °C) and atmospheric pressure. The volatile oil is a cosmetic volatile oil that is liquid at room temperature (25 °C). More specifically, volatile oil has an evaporation rate of 0.01 to 200 mg/cm2/min inclusive.

[00275] Volatile oils:

[00276]Volatile oils can be selected from oils based on hydrocarbons containing 8 to 16 carbon atoms, especially C8-C16 branched alkanes (also known as isoparaffins), such as isododecane (also known as 2,2 ,4,4,6-pentamethylheptane), isodecane and isohexadecane, such as the oils sold under the trade names Isopar® or Permethyl®.

[00277] Volatile oils that can also be used include volatile silicones, such as volatile linear or cyclic silicone oils, especially those with a viscosity less than or equal to 8 centistokes (cSt) (8 x 10-6 m2/s), especially containing from 2 to 10 silicon atoms, particularly 2 to 7 silicon atoms, said silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that can be used in the present invention, mention may be made especially of dimethicones with viscosities of 5 and 6 St, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane xane, dodecamethylpentasiloxane and their mixtures.

[00278] According to one embodiment, the cosmetic composition according to the present invention can comprise from 1 to 80% by weight or up to 5 to 70% by weight, up to 10 to 60% by weight and especially 15 to 50 % by weight of volatile oil, with respect to the total weight of the composition.

[00279] Non-volatile oils:

[00280] Non-volatile oils can be specially selected from silicone and/or fluoro oils based on non-volatile hydrocarbons.

[00281] Oils based on non-volatile hydrocarbons that may be specially mentioned include: - oils based on hydrocarbons of animal origin, such as perhydrosqualene; - oils based on hydrocarbons of vegetable origin, such as phytostearyl esters such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate (Ajinomoto, Eldew PS203), triglycerides formed from glycerol fatty acid esters, particularly where the fatty acids can have chain lengths ranging from C4 to C36, especially from C18 to C36, where such oils are possibly straight or branched, saturated or unsaturated; these oils can be especially heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy oil, winter squash oil, millet oil, barley oil, quinoa oil, rye oil, iguape nut oil, passion flower oil, shea butter, aloe vera oil, sweet almond oil, peach kernel oil, peanut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, canola oil, carrot oil, safflower oil, flax oil, rapeseed oil, cottonseed oil, coconut oil, pumpkin seed oil, wheat germ oil, jojoba oil, azucena oil, macadamia nut oil, corn oil, meadowfoam oil, St. John's wort oil, Monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, spring night oil, palm oil, blackcurrant seed oil, kiwi seed oil, grape seed oil, pistachio oil, winter squash oil, squash oil, musk oil, sesame oil, soybean oil, sunflower oil, castor oil, watermelon seed oil and mixtures thereof, or alternatively capric/caprylic acid triglycerides such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by Dynamit Nobel company; - linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and their derivatives, petroleum jelly, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam and squalane; - synthetic ethers containing from 10 to 40 carbon atoms; - synthetic esters, such as oils of the formula R1COOR2, in which R1 represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon-based chain, which is especially branched, containing from 1 to 40 carbon atoms, provided that the sum of the number of carbon atoms in the R1 and R2 chains is greater than or equal to 10; esters can be specially selected from fatty acid esters of alcohols such as cetostearyl octanoate, isopropyl alcohol esters such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, stearate isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, especially isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols , such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl benzoates, polyethylene glycol diheptanoate, 2-diethyl -propylene glycol hexanoate and mixtures thereof, C12-C15 alcohol benzoates, hexyl laurate, neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isotridecyl isononanoate and octyl isononanoate, and hydroxylated esters such as isostearyl lactate and diisostearyl malate; - polyol esters and pentaerythritol esters, such as dipentaerythrityl tetrahydroxystearate/tetraisostearate; - esters of diol dimers and diacid dimers, such as Lusplan DD-DA5® and Lusplan DD-DA7®, sold by the Nippon Fine Chemical company and described in US patent application 2004-175338; - copolymers of polyols and diacid dimers and their esters, such as Hailuscent ISDA or dilinoleic acid/butanediol copolymer; - fatty alcohols that are liquid at room temperature (25 °C), with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, such as 2-octyldodecanol, stearyl alcohol, isostearyl alcohol, alcohol cetyl, oleyl alcohol, 2-hexyldecanol, 2-butylethanol and 2-undecylpentadecanol; - C12-C22 higher fatty acids, such as oleic acid, linoleic acid or linolenic acid and mixtures thereof; - dialkyl carbonates, in which the two alkyl chains are possibly identical or different, such as dicaprylyl carbonate, sold under the name Cetiol CC® by Cognis; - oils with a high molar mass, particularly having a molar mass ranging from about 400 to about 10,000 g/mol, particularly about 650 to about 10,000 g/mol, particularly about 750 to about 7500 g/mol, and , more specifically, ranging from about 1000 to about 5000 g/mol. As oils with high molar mass that can be used in the present invention, special mention can be made of oils selected from: - lipophilic polymers; - esters of linear fatty acids with a total number of carbons ranging from 35 to 70; - hydroxylated esters; - aromatic esters; - C24-C28 branched fatty acid or fatty alcohol esters; - silicone oils; - oils of vegetable origin; and mixtures thereof; - fluoro and/or optionally partially hydrocarbon-based silicone oils, such as fluorosilicone oils, fluoropolyethers and fluorosilicones, as described in EP-A-847,752; - silicone oils, such as non-volatile linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendant or found at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxy silicates; and their mixtures.

[00282] Emulsifier:

[00283] In another embodiment, the composition according to the present invention may include at least one emulsifier. Two or more emulsifiers can be used in combination. Therefore, a single type of emulsifier or a combination of different types of emulsifiers can be used.

[00284] The emulsifier can be selected from non-ionic, anionic, amphoteric, zwitterionic, cationic emulsifiers and their mixtures. Examples of emulsifiers also include natural or synthetic polymeric emulsifiers.

[00285] Anionic emulsifiers include alkyl and alkyl ether sulfates, alkyl sulfonates, alkyl and alkyl ether phosphates, alkyl or alkyl ether sulfosuccinates, alkyl and alkyl ether carboxylates, in which the alkyl radical comprises from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, as well as anionic derivatives of alkyl polyglycosides, such as the citric, tartaric or sulfosuccinic ester of alkyl polyglycosides.

[00286]Nonionic emulsifiers can be broadly defined as compounds that contain a hydrophobic portion and a non-ionic hydrophilic portion. Examples of the hydrophobic moiety may be alkyl, alkyl aromatic and aryl aromatic moieties. Examples of hydrophilic moieties are polyoxyalkylenes, amine oxides and alkanol amides. Examples of nonionic emulsifiers are alkoxylated fatty alcohols or fatty acids, di- and tristyryl alkoxylated phenols, polyhydroxy fatty acid amides, sugar esters and polyesters, alkoxylated sugar esters, sorbitan and alkoxylated sorbitan fatty acid esters. Other examples of non-ionic emulsifiers include alkyl polyglycosides, such as coco polyglycosides.

[00287] Cationic emulsifiers useful in the present invention may contain hydrophilic amino or quaternary ammonium moieties that have a positive charge when dissolved in water. Examples of ammonium compounds are long chain alkyl trimethyl ammonium chloride, long chain alkyl benzyl dimethyl ammonium chloride, alkylamine hydrochlorides, alkylamine acetates and di(long chain alkyl) dimethyl ammonium bromide.

[00288] The amphoteric emulsifiers that can be used in the present invention can be those that can be broadly described as derivatives of aliphatic quaternary ammonium compounds, in which one of the aliphatic substituents contains an anionic water-solubilizing group, such as carboxylate, sulfonate and sulfate. Examples of amphoteric surfactants include cocoamphocarboxypropionate, cocoamphoacetate, cocoamphodiacetate and sodium lauroamphoacetate.

[00289] Examples of zwitterionic emulsifiers include alkyl betaines, starch betaines, alkyl sultaines, alkyl glycinates and alkyl carboxyglycinates.

[00290] Polymeric emulsifiers include, but are not limited to, carboxylic acid polymers that are cross-linked compounds that contain one or more monomers derived from acrylic acid, substituted acrylic acids, salts and derivatives of these acrylic acids and substituted acrylic acids. These carboxylic acid polymers also act as thickening agents. They can be cross-linked homopolymers of acrylic acid or one of its derivatives, such as acrylamidopropylsulfonic acid. They may also be crosslinked copolymers containing (i) first monomer selected from the group consisting of (meth)acrylic acid, derivatives thereof, short chain (ie C1-C4) acrylate ester monomers and mixtures thereof; and (ii) second monomer which is a long chain (ie, C8-C40) substituted polyethylene glycol acrylate ester monomer.

[00291]Examples of commercially available carboxylic acid polymers useful herein are Carbopol 1342, Pemulen TR-1 or TR-2 (INCI: cross-linked polymer of acrylates/C10-30 alkyl acrylate, from Lubrizol Corp.); Sepigel 305, Simulgel EG, Simulgel NS, Simulgel 600 (by Seppic S.A.); Viscolam AT100P and Viscofam AT64/P (from Lamberti S.p.A.).

[00292] Other materials that may be suitable as polymeric emulsifiers include ethylene oxide/propylene oxide block copolymers, such as those sold under the trade name Pluronic (BASF).

[00293] Other suitable polymeric emulsifiers include derivatives of natural polymers, such as polysaccharides, which may be derived from hydrophobic moieties. Additional examples of suitable emulsifiers that can be used in the composition according to the present invention are described in McCutcheon's Detergents and Emulsifiers, North American Edition (2003), Allured Publishing Corporation.

[00294] It is preferable that the emulsifier (d) is selected from polymeric emulsifiers, more preferably from associative polymers and, even more preferably, from acrylates/C10-30 alkyl acrylate crosslinked polymers, such like Pemulen TR2.

[00295] The amount of emulsifier(s) (d) in the composition according to the present invention may be from 0.01 to 15% by weight, preferably from 0.05 to 10% by weight and, more preferably 0.1 to 5% by weight, based on the total weight of the composition.

[00296] Composition:

[00297] The composition according to the present invention may be intended for use as a cosmetic composition. The cosmetic composition according to the present invention can therefore be intended for application on a keratinous substance. Keratin substance in the present tense denotes a material which contains keratin as the main constituent element, and its examples include the skin, scalp, nails, lips, hair and the like. It is preferable, therefore, that the cosmetic composition according to the present invention is used for a cosmetic process for the keratinous substance, particularly the skin.

[00298] The cosmetic composition according to the present invention can therefore be a skin cosmetic composition, preferably a skin care composition or a skin makeup composition, particularly a composition for protecting the skin against UV and /or air pollutants.

[00299] The composition according to the present invention can be in any form, such as solution, dispersion, emulsion, gel and paste. If the composition according to the present invention includes (c) at least one oil, the composition according to the present invention may be in the form of an emulsion, such as a W/O, O/W, W/O/ A and O/W/O, preferably O/W emulsion.

[00300] The composition according to the present invention can be prepared by mixing the above essential and optional ingredients according to any of the processes known to those skilled in the art.

[00301] Film:

[00302] The composition according to the present invention can be used for easy preparation of film that can be relatively thick. Particles (a) can aggregate and integrate into a continuous film.

[00303] The present invention also relates, therefore, to a film preparation process, preferably cosmetic film, with a thickness of preferably more than 0.1 μm, more preferably 1.5 μm or more and preferably even greater , 2 µm or more, comprising: - applying to a substrate, preferably to a keratin substrate and more preferably to the skin, the composition according to the present invention; and - drying the composition.

[00304] The upper limit of film thickness according to the present invention is not limited. The thickness of the film according to the present invention, therefore, may be, for example, 1 mm or less, preferably 500 µm or less, more preferably 300 µm or less, and even more preferably 100 µm or less.

[00305] As the process of preparing films according to the present invention includes the steps of applying the composition according to the present invention to a substrate, preferably a keratin substrate, more preferably to the skin, and drying the composition, the process according to the present invention does not require spin coating or spray coating and therefore it is possible to prepare even a relatively thick film easily. The film preparation process according to the present invention can therefore prepare relatively thick films without any special equipment, such as spraying and spin coating machines.

[00306] Even if the film according to the present invention is relatively thick, it is still thin and may be transparent, and therefore may not be easily perceived. The film according to the present invention can therefore preferably be used as a cosmetic film.

[00307] 8 If the substrate is not a keratin substrate, such as skin, the composition according to the present invention can be applied on a substrate prepared with any material other than keratin. Non-keratin substrate materials are not limited. Two or more materials can be used in combination. You can therefore use a single material type or a combination of different material types. In either case, it is preferred that the substrate be flexible or elastic.

[00308] If the substrate is not a keratin substance, it is preferable that the substrate is water soluble, as it is possible to leave the film according to the present invention by washing the substrate with water. As examples of the water-soluble materials, mention may be made of poly(meth)acrylic acids, polyethylene glycols, polyacrylamides, polyvinyl alcohol (PVA), starch, cellulose acetates and the like. PVA is preferable.

[00309] If the non-keratin substrate is in the form of a sheet, it may have a thickness greater than that of the film according to the present invention, in order to facilitate the handling of the film attached to the substrate sheet. The thickness of the non-keratin substrate sheet is not limited, but can be from 1 µm to 5 mm, preferably from 10 µm to 1 mm, and more preferably from 50 to 500 µm.

[00310] It is more preferred that the film according to the present invention is releasable from the non-keratin substrate. Release mode is not limited. The film according to the present invention can therefore be peeled off the non-keratin substrate or released by dissolving the substrate sheet in a solvent such as water.

[00311] The present invention also relates to: 1. film, preferably cosmetic film, with a thickness of preferably more than 0.1 μm, more preferably 1.5 μm or more and, preferably even greater, 2 μm or more , prepared by means of a process comprising: - applying to a substrate, preferably to a keratin substrate and, more preferably, to the skin, a composition according to the present invention; and - drying the composition; and 2. a film, preferably a cosmetic film, with a thickness of preferably more than 0.1 µm, more preferably 1.5 µm or more, and even more preferably 2 µm or more, comprising: - 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 one non-polymeric acid having two or more pKa values or its salt(s) or at least one non-polymeric base having two or more pKb values or its salt(s).

[00312] The above explanations referring to cationic, anionic and amphoteric polymers, as well as the above non-polymeric acid that has two or more pKa values or its salt(s) and the non-polymeric base that has two or more pKb values or its salt(s) may apply to those in film (1) and (2) above.

[00313]The film obtained as above can be independent. The term "stand-alone" herein implies that the film can be presented in sheet form and handled as a stand-alone sheet without substrate or support assistance. The term “independent” can therefore have the same meaning as “self-sustaining”.

[00314] It is preferable that the film according to the present invention is hydrophobic.

[00315] The term "hydrophobic" in the present invention indicates that the solubility of the polymer in water (preferably with a volume of one liter) at 20 to 40 °C, preferably from 25 to 40 °C and, more preferably, from 30 to 40°C is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight and even more preferably less than 0.1% by weight, based on the total weight of the polymer. It is preferably higher that the polymer is not soluble in water.

[00316] If the film according to the present invention is hydrophobic, the film can have water resistance properties and therefore can remain on a keratin substrate such as the skin, even if the surface of the keratin substrate is wet due, for example, to sweat and rain. When the film according to the present invention provides cosmetic effects, therefore, the cosmetic effect can be long lasting.

[00317] On the other hand, the film according to the present invention can be easily removed from a keratin substrate such as skin under alkaline conditions, such as pH 8 to 12, preferably 9 to 11. with the present invention it is therefore difficult to remove with water, although it can be easily removed with soap, which can provide such alkaline conditions.

[00318] The film according to the present invention may comprise at least one layer of biocompatible and/or biodegradable polymer. Two or more biocompatible and/or biodegradable polymers can be used in combination. Therefore, a single type of biocompatible and/or biodegradable polymer or a combination of different types of biocompatible and/or biodegradable polymers can be used.

[00319] The term “biocompatible” polymer in the present invention indicates that the polymer has no excess interaction between the polymer and cells in the living body, including the skin, and the polymer is not recognized by the living body as external material.

[00320] The term “biodegradable” polymer in the present invention indicates that the polymer can be degraded or decomposed in a living body, due, for example, to the metabolism of the living body itself or to the metabolism of microorganisms that may be present in the body alive. Furthermore, the biodegradable polymer can be degraded through hydrolysis.

[00321] If the film according to the present invention includes a biocompatible and/or biodegradable polymer, it is less irritable or not irritating to the skin and does not cause rash. Furthermore, due to the use of biocompatible and/or biodegradable polymer, the cosmetic sheet according to the present invention can adhere well to the skin.

[00322] The film according to the present invention can be used for cosmetic treatments of keratin substances, preferably the skin, particularly the face. The film according to the present invention can be presented in any shape or format. It can be used, for example, as a full face mask sheet or plaster for a part of the face, such as the cheek, nose and around the eyes.

[00323] If the film according to the present invention includes at least one hydrophilic or water-soluble UV filter, it can provide UV blocking effects derived from the hydrophilic or water-soluble UV filter. Typically, the water-soluble or hydrophilic UV filter can be washed off the surface of a keratin substrate, such as skin, by water, such as sweat and rain. As the water-soluble or hydrophilic UV filter is included in the film according to the present invention, however, it is difficult for the water-soluble or hydrophilic UV filter to be removed from the film by water, which results in long-lasting UV blocking effects.

[00324] Process and cosmetic use:

[00325] The present invention also relates to: - cosmetic process for keratin substrates, such as the skin, which comprises: applying the composition according to the present invention to the keratin substrate; and drying the composition to form a cosmetic film on the keratin substrate; and - use of the composition according to the present invention for the preparation of a cosmetic film on a keratin substrate, such as the skin.

[00326] The cosmetic process herein indicates a non-therapeutic cosmetic method for makeup and/or care for the surface of keratin substrates, such as skin.

[00327] In the above use and process, 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.

[00328] In other words, the above cosmetic film can be water resistant under neutral or acidic conditions, such as pH 7 or less, preferably in the range of 6 or more and 7 or less, and most preferably in the range of 5 or more to 7 or less, while the above cosmetic film can be removed under alkaline conditions, such as pH of more than 7, preferably 8 or more, and most preferably 9 or more. The upper pH limit is preferably 13, more preferably 12, and even higher preferably 11.

[00329] Consequently, the above cosmetic film can be water resistant and therefore can remain on a keratin substrate such as skin, even if the surface of the keratin substrate is wet due to, for example, sweat and rain. On the other hand, the above cosmetic film can be easily removed from keratin substrates such as skin under alkaline conditions. The film according to the present invention is therefore difficult to remove with water, although it can easily be removed with soap, which can provide alkaline conditions.

[00330] 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 substrate such as skin from UV rays, in order to limit the darkening of the skin, improving skin color and evenness and/or treating skin aging.

[00331] In addition, the above cosmetic film may have cosmetic effects such as the absorption or adsorption of bad odor, changing the appearance of keratin substrates such as the skin, changing the touch sensation of the keratin substrate and/or protecting the keratin substrate, for example, against dust or pollutants, due to the properties of the poly-ion complex particles in the cosmetic film, even if the cosmetic film does not include cosmetic active ingredients.

[00332] 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. It may be possible, therefore, that the above cosmetic film hides skin defects such as pores or wrinkles. In addition, the above cosmetic film can immediately change or modify the feel of the skin, changing the hardness of the surface on the skin, and the like. Additionally, the above cosmetic film can immediately protect the skin by covering the surface of the skin and blocking the skin, as a barrier, against environmental stresses such as pollutants, contaminants and the like.

[00333]The above cosmetic effects can be adjusted or controlled by changing the chemical composition, thickness and/or surface hardness of the above cosmetic film.

[00334] If the above cosmetic film includes at least one cosmetic active ingredient, the cosmetic film may have cosmetic effects provided by the cosmetic active ingredient(s). If the cosmetic film includes, for example, at least one cosmetic active ingredient selected from anti-aging agents, anti-sebum agents, deodorant agents, antiperspirant agents, whitening agents and mixtures thereof, the cosmetic film can address skin aging, absorb sebum on the skin, control skin odors, control perspiration on the skin and/or lighten the skin.

[00335] It is also possible to apply a cosmetic make-up composition to the cosmetic sheet according to the present invention after application to the skin.

EXAMPLES

[00336] The present invention will be described in more detail in the form of examples. They should not, however, be construed as limiting the scope of the present invention.

[00337] Preparation of reticulated polyampholyte particles 1:

[00338] As a polyanion, an aqueous solution of 10% by weight of carboxymethylcellulose (CMC) was used. As a polycation, a 25% by weight aqueous solution of polylysine (PLYS) was used. As polyampholyte, a 20.54% by weight aqueous solution of polyquaternium-53 was used.

[00339] For Examples 1 to 6, according to the composition shown in Table 1 shown below, the ingredients shown in Table 1, except terephthalilidene dicamphor sulfonic acid (Mexoryl SX: MSX) were added to a beaker, heated to 70 ° C and mixed with a stirrer, such that the amount of each of the ingredients was as shown in Table 1. Next, an aqueous solution containing 33% by weight of MSX was added to the above mixture, so that the amount of MSX was as shown in Table 1. With the reduction of the pH of the mixture thus obtained, particles of cross-linked polyampholytes (CARP) were formed. A stable CARP dispersion was therefore successfully prepared. The medical numerical particle size of the obtained particle was 1 µm. All numerical values shown in Table 1 are based on “% by weight” of active material in each ingredient.

[00340] Mexoryl SX:

[00341] Preparation of reticulated polyampholyte particles 2:

[00342] As a polyanion, an aqueous solution of 10% by weight of carboxymethylcellulose (CMC) and sodium styrene/maleic acid copolymer (SMA) was used. As a polyampholyte, a 9.25% by weight aqueous solution of polyquaternium-39 was used.

[00343] For Examples 7 to 11, according to the composition shown in Table 2 shown below, the ingredients shown in Table 2, except terephthalilidene dicamphor sulfonic acid (Mexoryl SX: MSX) and/or phytic acid, were added to a beaker, heated to 70 °C and mixed with a stirrer, so that the amount of each of the ingredients was as shown in Table 2. Then, an aqueous solution containing 33% by weight of MSX and/or acid was added. phytic acid to the above mixture, so that the amount of MSX and/or phytic acid was as shown in Table 2. With the reduction of the pH of the mixture thus obtained, particles of cross-linked polyampholyte (CARP) were formed. A stable CARP dispersion was therefore successfully prepared. All numerical values shown in Table 2 are based on “% by weight” of active material in each ingredient.

[00344] Evaluation 1:

[00345] The appearance of the compositions according to Examples 1-11 was observed with microscopy and evaluated according to the following criteria: - Good: particles were formed. - Bad: no particles were formed.

[00346]The results are displayed in the “CARP Formation” row in Tables 1 and 2.

[00347] Evaluation 2:

[00348] The compositions according to Examples 1 to 11 were stored at room temperature for one month. The appearance of each of the compositions was observed visually and evaluated according to the following criteria: - Stable: no phase separation was observed or a slight phase separation was observed, but the general appearance was almost homogeneous. - Unstable: complete phase separation was observed.

[00349]The results are displayed in the “Stability” row in Tables 1 and 2.

[00350] Evaluation 3:

[00351] 50 mg of the CARP dispersion according to each of Examples 1 to 11 were applied to a surface of a polymethylmethacrylate (PMMA) plate (HELIOPLATE HD6) and dried at room temperature for one hour.

[00352] After drying, the PMMA plate was immersed in a calcium chloride solution (0.14 g/l) at room temperature for 15 minutes.

[00353] After dipping, the PMMA plate was pulled up and dried for one hour. The surface of the PMMA plate was visually observed and evaluated according to the following criteria: - Good: a film was present on the PMMA plate. - Bad: there was no film on the PMMA plate.

[00354]The results are displayed in the line “Resistivity to Water” in Tables 1 and 2. The thickness of the film obtained was 1 μm.

Claims (11)

1. COSMETIC COMPOSITION, and preferably a cosmetic composition for the skin, characterized in that it comprises: - a) at least one polyion complex particle, comprising: - 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 one non-polymeric acid having two or more pKa values or its salt(s); and (b) at least one physiologically acceptable volatile medium, wherein the non-polymeric acid having two or more pKa values or its salt(s) is selected from the group consisting of terephthalilidene dicamphor sulfonic acid, phytic acid , their salts and mixtures thereof; and the non-polymeric acid having two or more pKa values or its salt(s) is crosslinking for the cationic polymer, the anionic polymer and the amphoteric polymer. 2. COMPOSITION, according to claim 1, characterized in that the cationic polymer has at least one portion with a positive charge and/or that can receive a positive charge selected from the group consisting of primary, secondary or tertiary amino group, quaternary ammonium group , guanidine group, biguanide group, imidazole group, imino group and pyridyl group, particularly said 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 and their salts. 3. COMPOSITION according to any one of claims 1 to 2, characterized in that the anionic polymer has at least one portion with a negative charge and/or which can receive a negative charge selected from the group consisting of sulfuric group, sulfate group, group sulfonic group, sulfonate group, phosphoric group, phosphate group, phosphonic group, phosphonate group, carboxylic group and carboxylate group; particularly, said anionic polymer is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers, anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids , (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinyl) sulfate, dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polyfumaric acids, acid (co)polymers maleic acid and its salts. 4. COMPOSITION according to any one of claims 1 to 3, characterized in that the amphoteric polymer contains: - at least one portion with a positive charge and/or which can receive a positive charge selected from the group consisting of a primary, secondary amino group or tertiary, quaternary ammonium group, guanidine group, biguanide group, imidazole group, imino group and pyridyl group; and - at least one negatively charged and/or capable of being negatively charged moiety selected from the group consisting of sulfuric group, sulfate group, sulfonic group, sulfonate group, phosphoric group, phosphate group, phosphonic group, phosphonate group, group carboxylic and carboxylate group; particularly, said amphoternium polymer is selected from the group consisting of polyquaternium-22, polyquaternium-39, polyquaternium-53, polyquaternium-64, polyquaternium-51, polyquaternium-61 and mixtures thereof. 5. COMPOSITION according to any one of claims 1 to 4, characterized in that the amount of polymer(s) in the composition is from 0.001 to 25% by weight, preferably from 0.1 to 20% by weight and, more preferably from 1 to 15% by weight, with respect to the total weight of the composition. 6. COMPOSITION according to any one of claims 1 to 5, characterized in that the amount of non-polymeric acid having two or more pKa values or its salt(s) in the composition is from 0.0001 to 30% by weight , preferably from 0.01 to 20% by weight, and more preferably from 0.1 to 15% by weight, based on the total weight of the composition. 7. COMPOSITION according to any one of claims 1 to 6, characterized in that the pH of the composition is from 3 to 9, preferably from 3.5 to 8.5, and more preferably from 4 to 8. 8. COMPOSITION according to any one of claims 1 to 7, characterized in that the amount of the polyion complex particle (a) in the composition is from 0.001 to 60% by weight, preferably from 0.1 to 50% by weight , and more preferably from 1 to 40% by weight, based on the total weight of the composition. 9. FILM PREPARATION PROCESS, preferably a cosmetic film, characterized in that it comprises: - applying the cosmetic composition, as defined in any one of claims 1 to 8, to a substrate, preferably a keratin substrate, and more preferably to the skin; and - drying the cosmetic composition. 10. COSMETIC PROCESS for keratin substrates, such as the skin, characterized in that it comprises: - applying the cosmetic composition, as defined in any one of claims 1 to 8, to the keratin substrate; and - drying the cosmetic composition to form a cosmetic film on the keratin substrate. 11. USE OF THE COSMETIC COMPOSITION, as defined in any one of claims 1 to 8, characterized in that it is to prepare a cosmetic film on a keratin substrate such as the skin, in which the cosmetic film is resistant to water with pH 7 or less , and is removable with water having a pH of more than 7, preferably 8 or more, and most preferably 9 or more.