WO2024262652A1

WO2024262652A1 - Composition comprising hydrophobicized cationic polymer and water-insoluble particle

Info

Publication number: WO2024262652A1
Application number: PCT/JP2024/080073
Authority: WO
Inventors: Tatsushi Isojima; Rohit Jain; Takehiko Kasai; Shinichi Matsufuji; Masashi Maeda
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2023-06-20
Filing date: 2024-05-14
Publication date: 2024-12-26
Anticipated expiration: 2025-12-20

Abstract

The present invention relates to a composition comprising: (a-1) at least one cationic polymer; (a-2) at least one monovalent non-polymeric acid or a salt thereof; (b-1) at least one fatty acid; and (c) at least one water-insoluble particle, wherein the (c) water-insoluble particle is negatively charged. The composition according to the present invention is useful for cosmetic applications, and can include at least one environmentally- friendly ingredient.

Description

DESCRIPTION

TITLE OF INVENTION

COMPOSITION COMPRISING

HYDROPHOBICIZED CATIONIC POLYMER AND WATER-INSOLUBLE PARTICLE

TECHNICAL FIELD

The present invention relates to a composition including at least one hydrophobicized cationic polymer and at least one water-insoluble particle, as well as a cosmetic process using the composition.

BACKGROUND ART

The formulation of environmentally- friendly cosmetic products, which are designed and developed considering environmental issues, is becoming a major goal in an effort to meet global challenges.

It is therefore essential to propose more sustainable compositions, preparation processes and ingredients to address these environmental concerns.

In this context, it is important to develop new cosmetic compositions with a better carbon footprint, particularly by promoting the use of renewable raw materials and/or materials with a good index of naturalness and/or materials of natural origin and, more particularly, materials of plant origin while reducing the use of compounds of petrochemical origin.

A polyion complex, which is formed with an anionic polymer and a cationic polymer, has already been known.

For example, WO 2021/125069 discloses a composition which is useful for cosmetic treatments and comprises at least one polyion complex particle comprising at least one cationic polymer, at least one anionic polymer and at least one non-polymeric acid having two or more pKa values. WO 2021/125069 also discloses that the composition disclosed therein may include oil and may be in the form of an emulsion.

DISCLOSURE OF INVENTION

A first objective of the present invention is to provide a composition which can comprise at least one particle based on at least one cationic polymer, at least one fatty acid, and at least one water-insoluble particle, and which is useful for cosmetic applications.

In addition, a second objective of the present invention is to provide a composition which can include at least one environmentally- friendly ingredient.

The above objectives of the present invention can be achieved by a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, comprising: (a-1) at least one cationic polymer;

(a-2) at least one monovalent non-polymeric acid or a salt thereof;

(b-1) at least one fatty acid; and (c) at least one water-insoluble particle, wherein the (c) water-insoluble particle is negatively charged. The (a-1) cationic polymer may have a molecular weight (Da) of more than 20,000.

The (a-1) cationic polymer maybe selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as (co)polylysines and chitosans, cationic (co)polyaminoacids such as collagen, cationic cellulose polymers, and salts thereof.

The amount of the (a-1) cationic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

The (a-2) monovalent non-polymeric acid may be a monovalent non-polymeric organic acid, preferably a monovalent non-polymeric carboxylic acid, and more preferably a monovalent hydroxy acid such as lactic acid and salicylic acid.

The amount of the (a-2) monovalent non-polymeric acid or a salt thereof in the composition according to the present invention may be from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, and more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.

The composition according to the present invention may further comprise (a-3) water.

The amount of the (a-3) water in the composition according to the present invention may be from 40% to 99% by weight, preferably from 45% to 97% by weight, and more preferably from 50% to 95% by weight, relative to the total weight of the composition.

The (b-1) fatty acid may be selected from C₄-C₂₂, preferably C₆-C₂₀, and more preferably C₈- C₁₈ saturated and unsaturated, linear or branched fatty acids.

The amount of the (b-1) fatty acid(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition. The composition according to the present invention may further comprise (b-2) at least one alcohol, preferably selected from the group consisting of ethanol, pentyl eneglycol, glycerin, and a mixture thereof, and more preferably selected from the group consisting of ethanol, pentyleneglycol, and a mixture thereof. The amount of the (b-2) alcohol(s) in the composition according to the present invention may be from 1% to 20% by weight, preferably from 3% to 15% by weight, and more preferably from 5% to 10% by weight, relative to the total weight of the composition.

The (c) water-insoluble particle may be selected from metal oxides, preferably titanium oxides, zinc oxides and iron oxides, and more preferably titanium oxides, which have been surface-treated with at least one acid or a salt thereof, preferably at least one polyvalent acid or a salt thereof, and more preferably phytic acid or a salt thereof.

The amount of the (c) water-insoluble particle(s) in the composition according to the present invention may be from 0.01% to 30% by weight, preferably from 0.05% to 20% by weight, and more preferably from 0.1% to 15% by weight, relative to the total weight of the composition.

The (a-1) cationic polymer, the (b-1) fatty acid, and the (c) water- insoluble particle can form at least one complex.

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 shows an optical microscope image of the composition according to Example 1.

Fig. 2 shows an optical microscope image of the composition according to Comparative Example 3.

BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have discovered that it is possible to provide a composition which comprises at least one particle based on, at least, at least one cationic polymer and at least one fatty acid, is useful for cosmetic applications, and can include at least one environmentally- friendly ingredient.

Thus, the composition according to the present invention comprises:

(a-1) at least one cationic polymer;

(a-2) at least one monovalent non-polymeric acid or a salt thereof;

(b-1) at least one fatty acid; and

(c) at least one water-insoluble particle, wherein the (c) water- insoluble particle is negatively charged.

The composition according to the present invention can form at least one particle comprising, at least, the (a-1) cationic polymer and the (b-1) fatty acid. The (a-1) cationic polymer and the (b-1) fatty acid can form at least one complex. This particle can be a gel particle, the size of which is typically micron-order such as 0.3 to 10 microns. The particle is not in the form of a line or fiber, but may be in the form of a globe or be spherical. Thus, the aspect ratio of the particle may be less than 5, preferably less than 3, and more preferably less than 2. The “size” of the particle may be the longest diameter of the particle.

The (a-1) cationic polymer, the (b-1) fatty acid and the (c) water-insoluble particle can also form at least one complex.

The composition according to the present invention may be in the form of a dispersion.

The composition according to the present invention may be in the form of a gel. Furthermore, the composition according to the present invention may show dilatancy effects.

The composition according to the present invention can provide good feeling to touch (good texture). For example, the composition according to the present invention can provide smooth feeling when applying the composition onto a substrate such as a keratin substance (e.g., skin).

The composition according to the present invention can form a film. When the composition according to the present invention is applied onto a substrate such as a keratin substance (e.g., skin) and dried, the particles in the composition according to the present invention can reduce their size and form a continuous film.

The composition according to the present invention can be stable such that it does not cause caking. Thus, the composition according to the present invention can be stored for a long period of time.

The composition according to the present invention can have good wettability. Therefore, when the composition according to the present invention is applied onto a substrate such as a keratin substance (e.g., skin), the composition according to the present invention can cover well the surface of the substrate due to the high affinity with the substrate.

The composition according to the present invention can also have good film-forming ability. Therefore, when the composition according to the present invention is applied onto a substrate such as a keratin substance (e.g., skin) and dried, the composition according to the present invention can form a uniform film without cracks.

The composition according to the present invention can form a water-insoluble film. Thus, the composition according to the present invention can provide a water-proof cosmetic film which is stable even under wet conditions due to sweat or rain. Therefore, the cosmetic effects of the cosmetic film can be maintained for a long period of time.

The composition according to the present invention can provide good feeling to touch (good texture). For example, the composition according to the present invention can provide a smooth feeling when applying the composition onto a substrate such as a keratin substance (e.g., skin).

The composition according to the present invention can provide a natural look without an unnatural white appearance. When the composition according to the present invention is applied onto a substrate such as a keratin substance (e.g., skin) and dried, the composition according to the present invention can form a transparent film which does not negatively affect the appearance of the substrate.

The composition according to the present invention can form a resilient film. Thus, the composition according to the present invention can provide a cosmetic film with good texture such as elasticity.

Accordingly, the composition according to the present invention is useful for cosmetic applications.

If the (a-1) at least one cationic polymer is obtained from natural resources, the (a-1) cationic polymer can be an environmentally- friendly ingredient. For example, the (a-1) cationic polymer may be selected from chitosans which are environmentally friendly. Therefore, the composition according to the present invention can include an environmentally- friendly ingredient.

In addition, the ingredients (a-2) and (b-1) can be originated from renewable materials such as plants and/or biodegradable materials. Therefore, the composition according to the present invention can be environmentally- friendly.

The composition may comprise at least one oil which is different from the (b-1) fatty acid. However, the amount of the oil(s) may be limited such that the amount of the oil(s) is less than 1% by weight, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight, relative to the total weight of the composition. Thus, the composition according to the present invention in this embodiment can reduce stickiness derived from oil(s).

Hereinafter, the present invention will be explained in a more detailed manner.

[Composition]

Thus, the composition according to the present invention comprises:

(a-1) at least one cationic polymer;

(a-2) at least one monovalent non-polymeric acid or a salt thereof;

(b-1) at least one fatty acid; and

(c) at least one water-insoluble particle, wherein the (c) water-insoluble particle is negatively charged.

In the composition according to the present invention, the (a-1) cationic polymer, the (b-1) fatty acid, and the (c) water-insoluble particle can form at least one complex.

A positively chargeable and/or positively charged moiety such as an amino (-NH₂) or ammonium (-NH₃ ⁺) group of the (a-1) cationic polymer can ionically interact with the carboxylic acid (-COOH) or carboxylate (-COO-) group of the (b-1) fatty acid to form a complex. The complex includes at least one hydrophobic moiety derived from the fatty moiety of the (b-1) fatty acid. Therefore, the (a-1) cationic polymer can be hydrophobized by the (b-1) fatty acid by forming the complex.

The following diagram shows an example of hydrohobization of chitosan as the (a-1) cationic polymer by the (b-1) fatty acid which is represented by R-COOH wherein R denotes a fatty moiety of the (b-1) fatty acid, i.e., an example of forming a complex of chitosan as the (a-1) cationic polymer and the (b-1) fatty acid.

The complexes formed by the (a-1) cationic polymers and the (b-1) fatty acids can aggregate to form at least one particle, due to the hydrophobic interaction among the hydrophobic moieties of the complexes.

The following diagram shows an example of particles formed by the aggregation of the complexes formed by the (a-1) cationic polymers (represented by lines) and the (b-1) fatty acids (represented by small dots).

Thus, the composition according to the present invention form at least one particle comprising, at least, the (a-1) cationic polymer and the (b-1) fatty acid. In other words, at least, the (a-1) cationic polymer and the (b-1) fatty acid in the composition according to the present invention can form at least one particle. The above particle is very small, and therefore, it is not visually recognizable.

The (a-2) monovalent non-polymeric acid or a salt thereof may interact with the above particle. Thus, the above particle may also comprise the (a-2) monovalent non-polymeric acid or a salt thereof.

The above particle has a positive charge derived from the (a-1) cationic polymer.

Thus, the above particle can ionically interact with the (c) water-insoluble particles which have been negatively charged, for example, due to surface-treatment of the water-insoluble particles.

The following diagram shows an example of interaction of the above particle with the negatively charged (c) water-insoluble particles (represented by large dots). The positive charge of the particle is represented by “+”, while the negative charge of the (c) waterinsoluble particle is represented by "-".

The above ionic interaction can form a further complex in the form of particles in which each particle comprises the (a-1) cationic polymer, the (b-1) fatty acid, and the negatively charged (c) water-insoluble particle. These particles do not aggregate.

If the (a-1) cationic polymer and the negatively charged (c) water-insoluble particle are directly combined, strong ionic interaction between them causes aggregation which results in caking. However, by hydrophobizing the (a-1) cationic polymer with the (b-1) fatty acid, the aggregation can be prevented. Therefore, the composition according to the present invention does not cause caking but can be a fluid.

(Cationic Polymer)

The composition according to the present invention comprises (a-1) at least one cationic polymer. A single type of cationic polymer may be used, or two or more different types of cationic polymers may be used in combination.

A cationic polymer has a positive charge density. The charge density of the (a-1) cationic polymer may be from 0.01 meq/g to 20 meq/g, preferably from 0.05 meq/g tol5 meq/g, and more preferably from 0.1 meq/g to 10 meq/g.

It may be preferable that the molecular weight of the (a-1) cationic polymer be 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.

It may be in particular preferable that the (a-1) cationic polymer has a molecular weight of more than 20,000.

Unless otherwise defined in the descriptions, “molecular weight” means a weight average molecular weight.

The (a-1) cationic polymer may have at least one positively chargeable and/or positively charged moiety selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group, and a pyridyl group. The term (primary) “amino group” here means a group of-NH₂.

The (a-1) cationic polymer may be a homopolymer or a copolymer. The term “copolymer” is understood to mean both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers which are in turn obtained from three kinds of monomers.

The (a-1) cationic polymer may be selected from natural and synthetic cationic polymers, and preferably from natural cationic polymers. Non-limiting examples of the cationic polymers are as follows.

(1) Homopolymers and copolymers derived from acrylic or methacrylic esters and amides and comprising at least one unit chosen from units of the following formulas:

wherein: R₁ and R₂, which may be identical or different, are chosen from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms, for instance, methyl and ethyl groups;

R₃, which may be identical or different, is chosen from hydrogen and CH₃; the symbols A, which may be identical or different, are chosen from linear or branched alkyl groups comprising from 1 to 6 carbon atoms, for example, from 2 to 3 carbon atoms and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;

R₄, R₅, and R₆, which may be identical or different, are chosen from alkyl groups comprising from 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment, alkyl groups comprising from 1 to 6 carbon atoms; and

X is an anion derived from an inorganic or organic acid, such as methosulphate anions and halides, for instance, chloride and bromide. The copolymers of family (1) may also comprise at least one unit derived from comonomers which may be chosen from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen atom with (C₁-C₄) lower alkyl groups, groups derived from acrylic or methacrylic acids and esters thereof, vinyllactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.

Examples of copolymers of family (1) include, but are not limited to: copolymers of acrylamide and of dimethylaminoethyl methacrylate quatemized with dimethyl sulphate or with a dimethyl halide, copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in European Patent Application No. 0 080 976, copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium methosulphate, quatemized or nonquatemized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, described, for example, in French Patent Nos. 2 077 143 and 2 393 573, dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, quatemized vinylpyrrolidone/ dimethyl aminopropylmethacrylamide copolymers, and crosslinked methacryloyloxy(C₁-C₄)alkyltri(C₁-C₄)alkylammonium salt polymers such as the polymers obtained by homopolymerization of dimethylamino ethyl methacrylate quatemized with methyl chloride, or by copolymerization of acrylamide with dimethyl amino ethyl methacrylate quatemized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with a compound containing an olefinic unsaturation, for example, methylenebisacrylamide.

(2) Cationic cellulose polymers such as cellulose ether derivatives comprising one or more quaternary ammonium groups described, for example, in French Patent No. 1 492 597, such as the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the company Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.

It is preferable that the cationic cellulose polymer have at least one quaternary ammonium group, preferably a quaternary trialkyl ammonium group, and more preferably a quaternary trimethyl ammonium group.

The quaternary ammonium group may be present in a quaternary ammonium group- containing group which may be represented by the following chemical formula (I):

wherein each of R₁ and R₂ denotes a C_1-3 alkyl group, preferably a methyl or ethyl group, and more preferably a methyl group,

R₃ denotes a C_1-24 alkyl group, preferably a methyl or ethyl group, and more preferably methyl group, X- denotes an anion, preferably a halide, and more preferably a chloride, n denotes an integer from 0-30, preferably 0-10, and more preferably 0, and

R₄ denotes a C_1-4 alkylene group, preferably an ethylene or propylene group.

The leftmost ether bond (-O-) in the above chemical formula (I) can attach to the sugar ring of the polysaccharide.

It is preferable that the quaternary ammonium group-containing group be -O-CH₂-CH(OH)- CH₂-N⁺(CH₃)₃.

(3) Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with a water-soluble monomer of quaternary ammonium, and described, for example, in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for instance, hydroxymethyl-, hydroxyethyl-, and hydroxypropylcelluloses grafted, for example, with a salt chosen from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, and dimethyldiallylammonium salts.

Commercial products corresponding to these polymers include, for example, the 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 U.S. Pat. Nos. 3,589,578 and 4,031,307, such as guar gums comprising cationic trialkylammonium groups, cationic hyaluronic acid, and dextran hydroxypropyl trimonium chloride. Guar gums modified with a salt, for example the chloride, of 2,3-epoxypropyltrimethylammonium (guar hydroxypropyltrimonium chloride) may also be used.

Such products are sold, for instance, under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17, and JAGUAR® C162 by the company MEYHALL.

(5) Polymers comprising piperazinyl units and divalent alkylene or hydroxyalkylene groups comprising straight or branched chains, optionally interrupted with at least one entity chosen from oxygen, sulphur, nitrogen, aromatic rings, and heterocyclic rings, and also the oxidation and/or quatemization products of these polymers. Such polymers are described, for example, in French Patent Nos. 2 162 025 and 2 280 361.

(6) Water-soluble polyamino amides prepared, for example, by polycondensation of an acidic compound with a polyamine; these polyamino amides possibly being crosslinked with an entity chosen from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bisunsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacyidiamines; bisalkyl halides; oligomers resulting from the reaction of a difunctional compound which is reactive with an entity chosen from bishalohydrins, bisazetidiniums, bishaloacyidiamines, bisalkyl halides, epihalohydrins, diepoxides, and bisunsaturated derivatives; the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polyamino amides optionally being alkylated or, if they comprise at least one tertiary amine function, they may be quatemized. Such polymers are described, for example, in French Patent 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 difunctional agents, for example, adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises from 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, and the alkylene group comprises from 1 to 4 carbon atoms, such as an ethylene group. Such polymers are described, for instance, in French Patent No. 1 583 363. In at least one embodiment, these derivatives may be chosen from adipic acid/dimethylaminohydroxypropyldi ethylenetri amine polymers .

(8) Polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids comprising from 3 to 8 carbon atoms. The molar ratio of the polyalkylene polyamine to the dicarboxylic acid may range from 0.8:1 to 1.4:1; the polyamino amide resulting therefrom being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyamino amide ranging from 0.5:1 to 1.8: 1. Such polymers are described, for example, in U.S. Pat. Nos. 3,227,615 and 2,961,347.

(9) Cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallyl-ammonium, such as homopolymers and copolymers comprising, as the main constituent of the chain, at least one unit chosen from units of formulas (la) and (lb):

wherein: k and t, which may be identical or different, are equal to 0 or 1 , the sum k+t being equal to 1 ;

R₁₂ is chosen from hydrogen and methyl groups; R₁₀ and R₁₁, which may be identical or different, are chosen from alkyl groups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group comprises, for example, from 1 to 5 carbon atoms, and lower (C₁-C₄)amidoalkyl groups, 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, bisulphate, bisulphite, sulphate, and phosphate. These polymers are described, for example, in French Patent No. 2 080 759 and in its Certificate of Addition 2 190 406. In one embodiment, R₁₀ and R_{1 1}, which may be identical or different, are chosen from alkyl groups comprising from 1 to 4 carbon atoms.

Examples of such polymers include, but are not limited to, (co)polydiallyldialkyl ammonium chloride such as the dimethyidiallylammonium chloride homopolymer sold under the name "MERQUAT® 100" by the company CALGON (and its homologues of low weight-average molecular mass) and the copolymers of diallyldimethylammonium chloride and of acrylamide sold under the name "MERQUAT® 550".

(10) 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 chosen 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 chosen from linear or branched C₁-C₆ alkyl groups substituted with at least one group chosen from nitrile groups, ester groups, acyl groups, amide groups, -CO-O-R₁₇-E groups, and -CO-NH-R₁₇-E groups, wherein R₁₇ is an alkylene group and E is a quaternary ammonium group;

A₁ and B₁, which may be identical or different, are chosen from polymethylene groups comprising from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may comprise, linked or intercalated in the main chain, at least one entity chosen from aromatic rings, oxygen, sulphur, sulphoxide groups, sulphone groups, disulphide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups, and ester groups, and X- is an anion derived from an inorganic or organic acid;

A₁, R₁₃, and R₁₅ may form, together with the two nitrogen atoms to which they are attached, a piperazine ring; if A₁ is chosen from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B₁ may be chosen from:

-(CH₂)_n-CO-E'-OC-(CH₂)_n- wherein E' is chosen from: a) glycol residues of formula -O-Z-O-, wherein Z is chosen from linear or branched hydrocarbon-based groups and groups of the following formulas: -(CH₂-CH₂-O)_x-CH₂-CH₂-

-[CH₂-CH(CH₃)-O]_y-CH₂-CH(CH₃)- wherein x and y, which may be identical or different, are chosen from integers ranging from 1 to 4, which represent a defined and unique degree of polymerization, and numbers ranging from 1 to 4, which represent an average degree of polymerization; b) bis-secondary diamine residue such as piperazine derivatives; c) bis-primary diamine residues of formula -NH-Y-NH-, wherein Y is chosen from linear or branched hydrocarbon-based groups and the divalent group -CH₂-CH₂-S-S-CH₂-CH_2-; and d) ureylene groups of formula -NH-CO-NH-.

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

Polymers of this type are described, for example, in French Patent Nos. 2 320 330; 2 270 846; 2 316 271; 2 336 434; and 2 413 907 and U.S. Pat. Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261,002; 2,271,378; 3,874,870; 4,001,432; 3,929,990; 3,966,904; 4,005,193; 4,025,617; 4,025,627; 4,025,653; 4,026,945; and 4,027,020.

Non-limiting examples of such polymers include those comprising at least one repeating unit of formula (III):

wherein

R₁₃, R₁₄, R₁₅, and R₁₆, which may be identical or different, are chosen 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 an inorganic or organic acid.

(11) Poly quaternary ammonium polymers comprising units of formula (IV):

wherein: R₁₈, R₁₉, R₂₀, and R₂₁ , which may be identical or different, are chosen from hydrogen, methyl groups, ethyl groups, propyl groups, β-hydroxyethyl groups, β-hydroxypropyl groups, - CH₂CH₂(OCH₂CH₂)_POH groups, wherein p is chosen from integers ranging from 0 to 6, with the proviso that R₁₈, R₁₉, R₂₀, and R₂₁ are not simultaneously hydrogen, r and s, which may be identical or different, are chosen from integers ranging from 1 to 6, q is chosen from integers ranging from 0 to 34, X- is an anion such as a halide, and A is chosen from radicals of dihalides and -CH₂-CH₂-O-CH₂-CH₂-.

Such compounds are described, for instance, in European Patent Application No. 0 122 324.

(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole.

Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers comprising units chosen from vinylpyridine and vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes, and chitin derivatives.

According to one embodiment of the present invention, the (a-1) cationic polymer is chosen from cellulose ether derivatives comprising quaternary ammonium groups, such as the products sold under the name "JR 400" by the company UNION CARBIDE CORPORATION, cationic cyclopolymers, for instance, the homo-polymers and copolymers of dimethyldiallylammonium chloride sold under the names MERQUAT® 100, MERQUAT® 550, and MERQUAT® S by the company CALGON, guar gums modified with a 2,3 -epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and of vinylimidazole.

(13) Polyamines

As the (a-1) cationic polymer, it is also possible to use (co)polyamines, which may be homopolymers or copolymers, with a plurality of amino groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in a polymer backbone or a pendent group, if present, of the (co)polyamines.

As an example of the (co)polyamines, mention may be made of chitosans, (co)polyallylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polydimethylaminoethylenemethacrylates, (co)polyvinylpyridines such as (co)poly-l- methyl-2-vinylpyridines, (co)polyimines such as (co) polyethyleneimines, (co)polypyridines such as (co)poly(quatemary pyridines), (co)polybiguanides such as (co)polyaminopropyl biguanides, (co)polylysines, (co)polyomithines, (co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinylacetals, and salts thereof.

As the (co)polyamines, it may be preferable to use (co)polylysines. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine can be ε-Poly-L-lysine, typically used as a natural preservative in food products. Polylysine is a polyelectrolyte which is soluble in polar solvents such as water, propylene glycol and glycerol. Polylysine is commercially available in various forms, such as poly D-lysine and poly L-lysine. Poly-L- Lysine is preferable. Polylysine can be in salt and/or solution form.

(14) Cationic Polyamino acids

As the (a-1) cationic polymer, it may be possible use cationic polyaminoacids, which may be cationic homopolymers or copolymers, with a plurality of amino groups and carboxyl groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in a polymer backbone or a pendent group, if present, of the cationic polyaminoacids. The carboxyl group may be present in a pendent group, if present, of the cationic polyaminoacids.

As examples of the cationic polyaminoacids, mention may be made of cationized collagen, cationized gelatin, steardimoium hydroxyprolyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimomum hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed soy protein, and the like.

The following descriptions relate to preferable embodiments of the cationic polymer.

It is preferable that the (a-1) cationic polymer be selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as (co)polylysines and chitosans, cationic (co)polyaminoacids such as collagen, cationic cellulose polymers, and salts thereof.

It is more preferable that the (a-1) cationic polymer be selected from chitosans.

It is preferable that the chitosan have a molecular weight (Da) of more than 20,000, preferably more than 50,000, and more preferably more than 80,000. In other words, the (a-1) cationic polymer is a high molecular weight chitosan.

The molecular weight (Da) of the chitosan maybe less than 1,000,000, preferably less than 500,000, and more preferably less than 300,000.

Thus, the molecular weight (Da) of the chitosan may be more than 20,000 and less than 1,000,000, preferably more than 50,000 and less than 500,000, and more preferably more than 80,000 and less than 300,000.

Unless otherwise defined in the descriptions, “molecular weight” means a weight average molecular weight. The molecular weight can be measured or determined by a gel permeation chromatography, for example, in accordance with ASTM D5296-19.

Chitosan is very uncommon in nature. It is only reported in the exoskeletons of certain insects such as termite queens and in the cell walls of a particular class of fungi, zygomycetes.

Chitosan may be obtained by deacetylation of chitin. Chitin is a polysaccharide composed of several N-acetyl-D-glucosamine units linked together by a type β bond (1,4).

The ideal chemical structure of chitosan is a sequence of β-D-glucosamine monomers connected by a glycosidic bond (1→4).

"Chitosan" according to the present invention means any copolymer formed of constituent units N-acetyl-D-glucosamine and D-glucosamine, whose degree of acetylation is less than 90%, preferably less than 80%, preferably less than 70%, preferably less than 60%, preferably less than 50%. Chitosan consists of glucosamine sugar units (deacetylated units) and N- acetyl-D-glucosamine units (acetylated units) linked together by β type bonds (1,4) and is a polymer of the Poly (N-acetyl-D-glucosamine)-poly (D-glucosamine) type.

More preferably, the degree of acetylation of chitosan is less than or equal to 40%, preferably less than or equal to 35%, preferably less than or equal to 25%, preferably less than or equal to 15%, and preferably less than or equal to 10%.

The degree of acetylation is the percentage of acetylated units relative to the number of total units, it can be determined by Fourier transform infrared spectroscopy (FT-IR) or by titration by a strong base.

The chitosan of the present invention is preferably a polysaccharide prepared from a fungal origin. In particular, it is extracted and purified from safe and abundant food or biotechnological fungal sources such as Agaricus bisporus or Aspergillus niger.

The chitosan of the present invention is preferably derived from the mycelium of a fungus of the Ascomycete type, and in particular Aspergillus niger and/or a Basidiomycete fungus, and in particular Lentinula edodes (shiitake) and/or Agaricus bisporus. Preferably the fungus is Aspergillus niger.

Chitosan may be of GMO (Genetically Modified Organisms) origin, but preferably is of nonGMO origin.

The chitosan according to the present invention is native, that is to say that it is not modified. In particular, it does not contain any chemical modification.

One method of preparing chitosan is that described in WO03/068824.

Preferably, the chitosan used in the present invention is in a powder form. It is marketed by Kitozyme under the name Kiosmetine or Kionutrime, for example, Kiosmetine-CSH and Kiosmetine P.

It is preferable that the (a-1) be selected from chitosans, and more preferably chitosans with a molecular weight (Da) of more than 20,000.

The amount of the (a-1) cationic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition.

The amount of the (a-1) cationic polymer(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.

(Monovalent Non-Polymeric Acid or Salt Thereof)

The composition according to the present invention comprises (a-2) at least one monovalent non-polymeric acid or a salt thereof. A single type of monovalent non-polymeric acid or a salt thereof or a combination of different types of monovalent non-polymeric acids or salts thereof may be used. The term “non-polymeric” here means that the acid is not obtained by polymerizing two or more monomers. Therefore, the non-polymeric acid does not correspond to an acid obtained by polymerizing two or more monomers such as polyacrylic acids.

The term “salt” here means a salt formed by addition of suitable base(s) to the monovalent non-polymeric acid, which may be obtained from a reaction with the monovalent non- polymeric acid with the base(s) according to methods known to those skilled in the art. As the salt, mention may be made of metal salts, for example salts with alkaline metal such as Na and K, and salts with alkaline earth metal such as Mg and Ca, and ammonium salts.

It is preferable that the molecular weight of the (a-2) monovalent non-polymeric acid or salt thereof be less than 1,000, preferably 500 or less, and more preferably 200 or less.

The (a-2) monovalent non-polymeric acid or a salt thereof can be included in the aqueous phase formed by the (a-3) water. The (a-2) monovalent non-polymeric acid or a salt thereof may promote the dissolution of the (a-1) cationic polymer in the (a-3) water.

The (a-2) monovalent non-polymeric acid has a single acid group which may be selected from the group consisting of a carboxylic group, a sulfuric group, a sulfonic group, a phosphoric group, a phosphonic group, and a mixture thereof.

The (a-2) monovalent non-polymeric acid or a salt thereof may be selected from monovalent organic or inorganic acids and salts thereof.

It is preferable that the (a-2) monovalent non-polymeric acid be a monovalent organic acid, and more preferably a monovalent non-polymeric carboxylic acid.

The monovalent non-polymeric carboxylic acid may be selected from hydroxy acids, and preferably alpha-hydroxy acids and beta-hydroxy acids. As the alpha-hydroxy acids, mention may be made of, for example, lactic acid and glycolic acid. As the beta-hydroxy acids, mention may be made of, for example, salicylic acid.

Thus, the monovalent non-polymeric acid may be a monovalent non-polymeric organic acid, preferably a monovalent non-polymeric carboxylic acid, and more preferably a monovalent hydroxy acid such as lactic acid and salicylic acid. If the (a-1) cationic polymer is selected from chitosans, lactic acid and salicylic acid are in particular preferable, because they can dissolve chitosans effectively and have little smell.

The amount of the (a-2) monovalent non-polymeric acid(s) or salt(s) thereof in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition.

The amount of the (a-2) monovalent non-polymeric acid(s) or salt(s) thereof in the composition according to the present invention may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the composition.

The amount of the (a-2) monovalent non-polymeric acid(s) or salt(s) thereof in the composition according to the present invention may be from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, and more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.

(Water)

The composition according to the present invention may comprise (a-3) water.

The (a-3) water can form an aqueous phase which is a continuous phase of the composition according to the present invention.

The amount of the (a-3) water may be 40% by weight or more, preferably 45% by weight or more, and more preferably 50% by weight or more, relative to the total weight of the composition.

The amount of the (a-3) water may be 99% by weight or less, preferably 97% by weight or less, and more preferably 95% by weight or less, relative to the total weight of the composition.

The amount of the (a-3) water may be from 40% to 99% by weight, preferably from 45% to 97% by weight, and more preferably from 50% to 95% by weight, relative to the total weight of the composition.

(Fatty Acid)

The composition according to the present invention comprises (b-1) at least one fatty acid. A single type of fatty acid may be used, or two or more different types of fatty acids may be used in combination.

The (b-1) fatty acid can hydrophobize the (a-1) cationic polymer.

The term “fatty acid” here means a carboxylic acid with a long aliphatic carbon chain.

The (b-1) fatty acid has at least 4 carbon atoms, preferably at least 6 carbon atoms, and more preferably at least 8 carbon atoms. The (b-1) fatty acid may comprise up to 26 carbon atoms, preferably up to 24 carbon atoms, and more preferably up to 22 carbon atoms. It is preferable that the (b-1) fatty acid be selected from C₄-C₂₆ fatty acid, more preferably C₆-C₂₄ fatty acid, and even more preferably C₈-C₂₂ fatty acid.

The (b-1) fatty acid may be selected from saturated or unsaturated, linear or branched fatty acids. Thus, the (b-1) fatty acid may be selected from C₄-C₂₆, preferably C₆-C₂₄, and more preferably C₈-C₂₂ saturated and unsaturated, linear or branched fatty acids.

As the unsaturated, linear or branched fatty acids, mono-unsaturated, linear or branched fatty acids or polyunsaturated, linear or branched fatty acids may be used. As the unsaturated moiety of the unsaturated, linear or branched fatty acids, a carbon-carbon double bond or a carbon-carbon triple bond may be mentioned.

As the saturated fatty acid, mention may be made of, for example, caprylic acid (C₈), pelargonic acid (C₉), capric acid (C₁₀), lauric acid (C₁₂), myristic acid (C₁₄), pentadecanoic acid (C₁₅), palmitic acid (C₁₆), heptadecanoic acid (C₁₇), stearic acid (C₁₈), isostearic acid (C₁₈), nonadecanoic acid (C19), arachidic acid (C₂₀), behenic acid (C₂₂), and lignoceric acid (C₂₄).

As the unsaturated fatty acid, mention maybe made of, for example, myristoleic acid (C₁₄), palmitoleic acid (C₁₆), oleic acid (C₁₈), linoleic acid (C₁₈), linolenic acid (C₁₈), elaidic acid (C₁₈), arachidonic acid (C₂₀), eicosenoic acid (C₂₀), erucic acid (C₂₂), and nervonic acid (C₂₄).

It is preferable that the (b-1) fatty acid be selected from C₈-C₁₈ saturated or unsaturated, linear or branched fatty acids, and more preferably from the group consisting of caprylic acid, capric acid, oleic acid, linoleic acid, stearic acid, isostearic acid and mixtures thereof.

The (b-1) fatty acid may be in the form of a free acid or in the form of a salt thereof. As a salt of the fatty acid, mention may be made of an inorganic salt such as an alkali metal salt (a sodium salt, a potassium salt, or the like) and an alkaline earth metal salt (a magnesium salt, a calcium salt, or the like); and an organic salt such as an ammonium salt (a quaternary ammonium salt or the like) and an amine salt (a triethanolamine salt, a triethylamine salt, or the like). A single type of fatty acid salt or a combination of different type of fatty acid salts may be used. Further, a combination of one or more fatty acid in the form of a free acid and one or more fatty acid in the form of a salt may be used, in which one or more type of salts may also be used.

The amount of the (b-1) fatty acid(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition.

On the other hand, the amount of the (b-1) fatty acid(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.

Accordingly, the amount of the (b-1) fatty acid(s) in the composition according to the present invention may range from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

(Alcohol)

The composition according to the present invention may comprise (b-2) at least one alcohol. A single type of alcohol may be used, or two or more different types of alcohols may be used in combination.

The (b-2) alcohol may be in the form of a liquid at ambient temperature such as 25 °C under atmospheric pressure (760 mmHg or 10⁵ Pa).

The (b-2) alcohol may be volatile or non-volatile.

The term “volatile” means that the alcohol can evaporate under a normal atmospheric pressure such as 1 atm and at room temperature such as 25°C.

The (b-2) monovalent or divalent alcohol can function to facilitate complexing the (b-1) fatty acid with the (a-1) cationic polymer.

The (b-2) alcohol may be monovalent alcohol, preferably selected from monovalent aliphatic alcohols, monovalent aromatic alcohol, and mixtures thereof, and more preferably from monovalent aliphatic alcohols.

The monovalent aliphatic alcohol (mono-ol) may have 2 to 6 carbon atoms, preferably 2 or 3 carbon atoms, and one hydroxyl group. The examples of the monovalent aliphatic alcohol include ethanol, n-propanol, isopropanol, and a mixture thereof.

The monovalent aromatic alcohol may have 8 to 12 carbon atoms, preferably 8 to 10 carbon atoms, and more preferably 8 carbon atoms. The examples of the monovalent aromatic alcohol include benzyl alcohol, phenylethylalcohol, phenoxyethanol, and a mixture thereof.

The (b-2) alcohol may be divalent or polyvalent alcohol, preferably selected from divalent or polyvalent aliphatic alcohols, divalent or polyvalent aromatic alcohols, and mixtures thereof, and more preferably from divalent or polyvalent aliphatic alcohols.

The divalent aliphatic alcohol (di-ol) may have 2 to 8 carbon atoms, preferably 3 to 7 carbon atoms, and more preferably 4 to 6 carbon atoms, and two hydroxyl groups. The examples of the divalent aliphatic alcohol include ethyleneglycol, propyleneglycol, butyleneglycol, pentyleneglycol, hexyleneglycol, and a mixture thereof.

The polyvalent aliphatic alcohol does not encompass a saccharide or a derivative thereof. The derivative of a saccharide includes a sugar alcohol which is obtained by reducing one or more carbonyl groups of a saccharide, as well as a saccharide or a sugar alcohol in which the hydrogen atom or atoms in one or more hydroxy groups thereof has or have been replaced with at least one substituent such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group or a carbonyl group.

The polyvalent aliphatic alcohol (poly-ol) may have 3 to 10 carbon atoms, preferably 4 to 9 carbon atoms, and more preferably 5 to 8 carbon atoms, and three or more hydroxyl groups. The examples of the polyvalent aliphatic alcohol include glycerin and diglycerin.

It is preferable that the (b-2) alcohol be selected from the group consisting of ethanol, penyleneglycol and a mixture thereof.

The amount of the (b-2) alcohol(s) in the composition according to the present invention may be 1% by weight or more, preferably 3% by weight or more, and more preferably 5% by weight or more, relative to the total weight of the composition.

The amount of the (b-2) alcohol(s) in the composition according to the present invention may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the composition.

The amount of the (b-2) alcohol(s) in the composition according to the present invention may be from 1% to 20% by weight, preferably from 3% to 15% by weight, and more preferably from 5% to 10% by weight, relative to the total weight of the composition.

(Water-Insoluble Particle) The composition according to the present invention comprises (c) at least one water-insoluble particle. A single type of water-insoluble particle may be used, or two or more different types of water-insoluble particles may be used in combination.

According to the present invention, the (c) water-insoluble particle is negatively charged. In other words, the (c) water-insoluble particle has a negative charge.

For the purposes of the present invention, the term “water-insoluble” particle means a particle with a solubility in water at 25°C of less than 1 wt%, preferably less than 0.1 wt% and more preferably less than 0.01 wt%, relative to the total weight of the particle, and most preferably with no solubility.

The size of the (c) water-insoluble particle as a raw material is not limited. The (c) waterinsoluble particle may have an average (primary) particle size of 10 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 40 nm or more, and/or 2 μm or less, preferably 1 μm or less, and more preferably 500 nm or less. The average (primary) particle size can be determined as a numb er- average particle diameter and may be measured by an electron microscope.

The (c) water-insoluble particle is preferably in the form of a solid. More preferably, the (c) water-insoluble particle may form a powder. The (c) water-insoluble particle may be selected from pigments and/or fillers and/or inorganic UV filters.

Pigment:

The term "pigments" should be understood as meaning white or colored and inorganic or organic particles which are insoluble in the physiologically acceptable volatile medium and which are intended to color and/or opacify the resulting film.

The pigments preferably have an absorption ranging from 380 to 780 nm, and in at least one embodiment, an absorption with a maximum in this absorption range.

The pigments may be organic pigments. As used herein, the term "organic pigment" means any pigment that satisfies the definition in Ullmann's encyclopedia in the chapter on organic pigments. The organic pigment may be chosen, for example, from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalo cyanin, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, and quinophthalone compounds.

The at least one organic pigment may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanin blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370, and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, and 75470, and the pigments obtained by oxidative polymerization of indole or phenolic derivatives as described, for example, in French Patent No. 2 679 771.

These pigments may also be in the fonn of composite pigments as described, for example, in European Patent No. 1 184 426. These composite pigments may be composed, for instance, of particles comprising an inorganic nucleus at least partially coated with an organic pigment and at least one binder to fix the organic pigments to the nucleus.

Other examples may include pigmentary pastes of organic pigments such as the products sold by the company Hoechst under the names: Jaune Cosmenyl IOG: Pigment Yellow 3 (CI 11710); Jaune Cosmenyl G: Pigment Yellow 1 (CI 11680); Orange Cosmenyl GR: Pigment Orange 43 (CI 71105); Rouge Cosmenyl R": Pigment Red 4 (CI 12085); Carmine Cosmenyl FB: Pigment Red 5 (CI 12490); Violet Cosmenyl RL: Pigment Violet 23 (CI 51319); Bleu Cosmenyl A2R: Pigment Blue 15.1 (CI 74160); Vert Cosmenyl GG: Pigment Green 7 (CI 74260); and Noir Cosmenyl R: Pigment Black 7 (CI 77266).

The at least one pigment may also be chosen from lakes. As used herein, the term "lake" means insolublized dyes adsorbed onto insoluble particles, the complex or the compound thus obtained remaining insoluble during use.

The inorganic substrates onto which the dyes are adsorbed may include, for example, alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate, and aluminum.

Non-limiting examples of organic dyes include cochineal carmine and the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), and D&C Blue 1 (CI 42 090).

An additional non-limiting example of a lake is the product known under the following name: D&C Red 7 (CI 15 850: 1).

The at least one pigment may also be a pigment with special effects. As used herein, the term "pigments with special effects" means pigments that generally create a non-uniform colored appearance (characterized by a certain shade, a certain vivacity, and/or a certain lightness) that changes as a function of the conditions of observation (light, temperature, observation angles, etc.). They thus contrast with white or colored pigments that afford a standard uniform opaque, semi-transparent, or transparent shade.

Two types of pigment with special effects exist: those with a low refractive index, such as fluorescent, photochromic, and thermochromic pigments, and those with a high refractive index, such as nacres and flakes.

The at least one pigment may also be chosen from pigments with an interference effect that are not fixed onto a substrate, for instance, liquid crystals (Helicones HC from Wacker), and holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek).

The pigments with special effects may also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, and thermochromic pigments.

The pigment may also be an inorganic pigment, in a preferred embodiment. As used herein, the term "inorganic pigment" means any pigment that satisfies the definition in Ullmann's encyclopedia in the chapter on inorganic pigments. Preferably, the inorganic pigments comprise at least one inorganic material. Non-limiting examples of inorganic pigments that are useful in the present invention include metal oxides, in particular, transition metal oxides, such as zirconium oxides, cerium oxides, iron oxides, zinc oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium dioxide. The following inorganic pigments may also be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, and ZrO₂ as a mixture with TiO₂, ZrO₂, Nb₂O₅, CcO₂, and ZnS.

The pigment may also be a nacreous pigment such as a white nacreous pigment, for example, mica coated with titanium or with bismuth oxychloride, a colored nacreous pigment such as mica coated with titanium and with iron oxides, mica coated with titanium and, for example, with ferric blue or chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also a nacreous pigment based on bismuth oxychloride. Examples of such pigments may include the Cellini pigments sold by Engelhard (Mica-TiO₂-lake), Prestige sold by Eckart (Mica-TiO₂), and Colorona sold by Merck (Mica-TiO₂-Fe₂O₃).

In addition to nacres on a mica support, multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate, and aluminum, may be useful in accordance with the present disclosure.

Filler:

The term "filler" should be understood as meaning an uncolored particle that is solid at room temperature and atmospheric pressure, and insoluble in the physiologically acceptable volatile medium, even when these ingredients are brought to a temperature above room temperature. Of inorganic or organic nature thereof, fillers make it possible to confer firmness on the composition according to the present invention and/or softness and uniformity on the make-up which may be formed by the composition.

The filler may be chosen from mineral and organic fillers. When the fillers are organic fillers, they are polymeric organic fillers. The filler may be particles of any form, for example, platelet-shaped, spherical, and oblong, irrespective of their crystallographic form (for example lamellar, cubic, hexagonal, and orthorhombic).

The fillers that may be used in the composition according to the present invention can be made from various inorganic and/or organic materials, and may include, but are not limited to, titanium dioxide; talc; natural or synthetic mica; alumina; aluminosilicate; silica (or silicon dioxides); kaolin or other insoluble silicates such as clays; polyamides (Nylon®), poly-β- alanine and polyethylene powders; tetrafluoro ethylene polymer (Teflon®) powders, powder starch; boron nitride; acrylic acid polymer powders; silicone resin microbeads, for instance "Tospearls®" from the company Toshiba; bismuth oxychlorides; precipitated calcium carbonate; magnesium carbonate and magnesium hydrogen carbonate; hydroxyapatite; hollow silica microspheres such as "Silica Beads SB 700®" and "Silica Beads SB 700®" from the company Maprecos, "Sunspheres H-33®"and "Sunspheres H-51®" from the company Asahi Glass; acrylic polymer microspheres such as those made from crosslinked acrylate copolymer "Polytrap 6603®" from the company R.P. Scherrer and those made from polymethyl methacrylate "Micropearl M100®" from the company SEPPIC; polyurea powders; polyurethane powders such as the hexamethylene diisocyanate and trimethylol hexyl lactone copolymer powder sold under the name "Plastic Powder D-400®" by the company Toshiki; glass or ceramic microcapsules; microcapsules of methyl acrylate or methacrylate polymers or copolymers, or alternatively, vinylidene chloride and acrylonitrile copolymers, for instance, "Expancel®" from the company Expancel; elastomeric crosslinked organopolysiloxane powders such as those sold under the name "KSP100®" by the company Shinetsu Chemical; porous cellulose beads such as those sold under the name of Cellulose Beads USF® by the company Daito Kasei; and mixtures thereof.

Among the silicas that are useful in the composition of the present invention, mention may be made of crystalline, microcrystalline and non- crystalline silicas.

By way of example, crystalline silicas that may be mentioned include quartz, tridymite, cristobalite, keatite, coesite and stishovite. The microcrystalline silicas are, for example, diatomite.

Among the non-crystalline forms that may be used are vitreous silica and other types of amorphous silicas such as colloidal silicas, silica gels, precipitated silicas and fumed silicas, for instance aerosils, and pyrogenic silicas. Porous silica such as an aerogel (silica silylate) is preferable.

In one embodiment of the present invention, the (c) powder may comprise at least one inorganic material selected from the group consisting of talc, mica, silica, kaolin, sericite, calcinated talc, calcinated mica, calcinated sericite, synthetic mica, bismuth oxychloride, barium sulfate, boron nitride, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, and hydroxyapatite. The (c) powder may comprise selenium disulfide.

In another embodiment of the present invention, the (c) powder may comprise at least one organic material selected from the group consisting of polyurea, melamine-formaldehyde condensate, urea-formaldehyde condensate, aminoplast, polyurethane, polyacrylate, polyphosphate, polystyrene, polyester, polyamide, polyolefin, polysaccharide, silicone, silicone resin, protein, modified cellulose, and gum.

Inorganic UV Filter:

The inorganic UV filter used for the present invention may be active in the UV-A and/or UV- B region. The inorganic UV filter may be hydrophilic and/or lipophilic.

It is preferable that the inorganic UV filter be in the form of a fine particle such that the mean (primary) particle diameter thereof 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 here is an arithmetic mean diameter.

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

Preferably, the inorganic UV filters may be selected from inorganic particles (mean size of the primary particles: generally from 5 nm to 50 nm, preferably from 10 nm to 50 nm) formed of metal oxides, such as, titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide, which are all UV photoprotective agents that are well known per se. Preferably, the inorganic UV filters may be selected from titanium oxide, zinc oxide, and more preferably titanium oxide.

Surface Treatment:

The (c) water-insoluble particle may have been surface-treated to have negative charge. The surface-treatment can be performed by any conventional process.

For the purposes of the present invention, the surface-treatment is such that, for instance, a surface-treated powder conserves its intrinsic pretreatment pigmenting properties and a surface-treated filler conserves its intrinsic pretreatment filling properties.

The (c) water-insoluble particle may be surface-treated with at least one acid or a salt thereof.

The above acid may have one or more acid groups which may be selected from the group consisting of a carboxylic group, a sulfuric group, a sulfonic group, a phosphoric group, a phosphonic group, and a mixture thereof.

It is preferable that the above acid is non-polymeric. The term “non-polymeric” here means that the acid is not obtained by polymerizing two or more monomers. Therefore, the non- polymeric acid does not correspond to an acid obtained by polymerizing two or more monomers such as polyacrylic acids.

It is preferable that the molecular weight of the non-polymeric acid or salt thereof be less than 1,000, preferably less than 900, and more preferably less than 800.

It is preferable that the acid be selected from polyvalent acids and salts thereof.

The above polyvalent acid may be inorganic or organic.

As examples of inorganic polyvalent acid, mention may be made of sulphuric acid, phosphoric acid, sulfonic acid, phosphonic acid, and a mixture thereof.

As examples of organic polyvalent acid, mention may be made of dicarboxylic acids such as oxalic acid and malonic acid, tricarboxylic acids such as citric acid, and mixtures thereof.

It is more preferable that the polyvalent acid be phytic acid or a salt thereof.

Thus, it is preferable that the (c) water-insoluble particle be selected from metal oxides, more preferably titanium oxides, zinc oxides and iron oxides, and even more preferably titanium oxides, which have been surface-treated with at least one acid or a salt thereof, preferably at least one polyvalent acid or a salt thereof, and more preferably phytic acid or a salt thereof. The amount of the (c) water-insoluble particle(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition.

On the other hand, the amount of the (c) water-insoluble particle(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, relative to the total weight of the composition.

Accordingly, the amount of the (c) water-insoluble particle(s) in the composition according to the present invention may range from 0.01% to 30% by weight, preferably from 0.05% to 20% by weight, and more preferably from 0.1% to 15% by weight, relative to the total weight of the composition.

(Optional Ingredient)

The composition according to the present invention may comprise, in addition to the aforementioned ingredients, optional ingredient(s) typically employed in cosmetics, specifically, surfactants/emulsifiers, hydrophilic or lipophilic thickeners, derived from, for example, synthetic polymers other than the (a-1) cationic polymer; volatile or non-volatile organic solvents other than the (b-2) alcohol; anionic polymers; amphoteric polymers; nonionic polymers such as beta-glucan; silicones and silicone derivatives; natural extracts derived from animals or vegetables other than the (a-1) cationic polymer; waxes; and the like, within a range which does not impair the effects of the present invention.

The composition according to the present invention may comprise the above optional ingredient(s) in an amount of from 0.01% to 30% by weight, preferably from 0.05% to 20% by weight, and more preferably from 0.1 % to 10% by weight, relative to the total weight of the composition.

The composition according to the present invention may comprise at least one oil. Here, “oil” means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile.

However, it is preferable that the amount of the oil(s) in the composition according to the present invention be limited. Thus, the amount of oil(s) in the composition according to the present invention may be less than 1% by weight, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight, relative to the total weight of the composition. It may be particularly preferable that the composition according to the present invention includes no oil.

The amount of the surfactant(s)/emulsifier(s) and/or synthetic thickener(s) in the composition according to the present invention may be less than 1% by weight, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight, relative to the total weight of the composition. It is particularly preferable that the composition according to the present invention includes no surfactant/emulsifier or synthetic thickener.

The amount of the anionic polymer(s) or the amphoteric polymer(s) in the composition according to the present invention may be less than 1% by weight, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight, relative to the total weight of the composition. It is particularly preferable that the composition according to the present invention includes no anionic or amphoteric polymer.

[Preparation]

The composition according to the present invention can be prepared by mixing the essential ingredient(s) as explained above, and optional ingredient(s), if necessary, as explained above.

The method and means to mix the above essential and optional ingredients are not limited. Any conventional method and means can be used to mix the above essential and optional ingredients to prepare the composition according to the present invention.

The composition according to the present invention can be prepared by simple or easy mixing with a conventional mixing means such as a stirrer and a homogenizer. Also, heating may not be necessary. Therefore, the process for preparing the composition according to the present invention may be environmentally friendly.

It is preferable that the composition according to the present invention be prepared by a process comprising the following steps:

(1) mixing

(a-1) at least one cationic polymer,

(a-2) at least one monovalent non-polymeric acid or a salt thereof, and optionally (a-3) water to form a first mixture (a);

(2) mixing

(b-1) at least one fatty acid, and optionally (b-2) at least one alcohol to form a second mixture (b); and

(3) mixing the first mixture (a) and the second mixture (b) with a negatively charged (c) waterinsoluble particle to prepare the composition according to the present invention.

The negatively charged (c) water-insoluble particle may be prepared by mixing a water insoluble particle with at least one polyvalent acid or a salt thereof, preferably at least one polyvalent non-polymeric acid or a salt thereof, and more preferably phytic acid or a salt thereof.

The process for preparing the composition according to the present invention may further comprise an optional step of mixing at least one oil, provided that the amount of the oil(s) may be less than 1% by weight, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight, relative to the total weight of the composition.

[Cosmetic Application]

The composition according to the present invention may be intended to be used as a cosmetic composition. Thus, the cosmetic composition according to the present invention may be intended for application onto a keratin substance. Keratin substance here means a material containing keratin as a main constituent element, and examples thereof include the skin, scalp, nails, lips, hair, and the like. Thus, it is preferable that the cosmetic composition according to the present invention be used for a cosmetic process for the keratin substance, in particular skin.

Thus, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin makeup composition, and more preferably a skin care composition.

[Form]

The composition according to the present invention may be present in any form.

For example, the composition according to the present invention can be in the form of a dispersion. Also, the composition according to the present invention can be in the form of a gel-

In addition, the composition according to the present invention can be in the form of a powder.

[pH]

The pH of the composition according to the present invention may be from 3 to 9, preferably from 3.5 to 8, and more preferably from 4 to 7.

The pH of the composition according to the present invention may be adjusted by adding at least one alkaline agent and/or at least one acid other than the (a-2) monovalent non- polymeric acid or a salt thereof. The pH of the composition according to the present invention may also be adjusted by adding at least one buffering agent.

[Film]

The composition according to the present invention can be used for easily preparing a film. In other words, the composition according to the present invention can form a film.

Thus, the present invention may also relate to a process for preparing a film, preferably a cosmetic film, optionally with a thickness of preferably more than 0.5 μm, more preferably 1.0 μm or more, and even more preferably 1.5 μm or more, comprising: applying onto a substrate, preferably a keratin substance, more preferably skin, the composition according to the present invention; and drying the composition.

The upper limit of the thickness of the film according to the present invention is not limited. Thus, for example, the thickness of the film according to the present invention may be 300 μm or less, preferably 200 μm or less, and more preferably 100 μm or less.

Since the process for preparing a film according to the present invention includes the steps of applying the composition according to the present invention onto a substrate, preferably a keratin substance, and more preferably skin, and of drying the composition, the process according to the present invention does not require any spin coating or spraying, and therefore, it is possible to easily prepare even a relatively thick film. Thus, the process for preparing a film according to present invention can prepare a relatively thick film without any special equipment such as spin coaters and spraying machines.

When the composition according to the present invention is applied onto a substrate such as a keratin substance (e.g., skin) and dried, the particles in the composition according to the present invention can reduce their size and form a continuous film.

The film according to the present invention can be water-insoluble, and therefore, can be water-resistant. Thus, the film according to the present invention can remain on a keratin substance such as skin even if the surface of the keratin substance is wet due to, for example, sweat and rain. Thus, when the film according to the present invention provides any cosmetic effect, the cosmetic effect can last a long time.

The film according to the present invention can be transparent film which does not negatively affect the appearance of the substrate. Therefore, the composition according to the present invention can provide a natural look without an unnatural white appearance.

Also, the composition according to the present invention can form a resilient film. Thus, composition according to the present invention can provide a cosmetic film with good texture such as elasticity.

Accordingly, the composition and film according to the present invention are useful for cosmetic applications.

The particle in the film according to the present invention may include a core-shell particle in which the core may comprise mainly the (a-1) cationic polymer such as chitosan, while the shell may comprise mainly the (b-1) fatty acid. The core-shell particle may be combined with the (c) water-insoluble particle.

If the substrate is not a keratin substance such as skin, the composition according to the present invention may be applied onto a substrate made from any material other than keratin. The materials of the non-keratinous substrate are not limited. Two or more materials may be used in combination. Thus, a single type of material or a combination of different types of materials may be used. In any event, it is preferable that the substrate be flexible or elastic.

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

It is more preferable that the film according to the present invention be releasable from the non-keratinous substrate. The mode of release is not limited. For example, the film according to the present invention may be peeled from the non-keratinous substrate.

The present invention may also relate to:

(1) A film, preferably a cosmetic film, optionally with a thickness of preferably more than 0.5 μm, more preferably 1.0 μm or more, and even more preferably 1.5 μm or more, prepared by a process comprising: applying onto a substrate, preferably a keratin substance, and more preferably skin, the composition according to the present invention; and drying the composition, and

(2) A film, preferably a cosmetic film, optionally with a thickness of preferably more than 0.5 μm, more preferably 1.0 μm or more, and even more preferably 1.5 μm or more, comprising:

(a-1) at least one cationic polymer,

(a-2) at least one monovalent non-polymeric acid or a salt thereof,

(b-1) at least one fatty acid, and

The above explanations regarding the (a-1) cationic polymer, the (a-2) monovalent non- polymeric acid or a salt thereof, and (b-1) at least one fatty acid, as well as the (c) waterinsoluble particle, for the composition according to the present invention, can apply to those in the above film (2).

The film according to the present invention may also comprise (b-2) at least one alcohol, if the (b-2) alcohol is not volatile.

The film according to the present invention may be biocompatible and/or biodegradable.

The term “biocompatible” in the present specification means that the film does not have excess interaction between the film and cells in the living body including the skin, and the film is not recognized by the living body as a foreign material.

The term “biodegradable” in the present specification means that the film can be degraded or decomposed in a living body due to, for example, the metabolism of the living body itself or the metabolism of the microorganisms which may be present in the living body. Also, the biodegradable film can be degraded by hydrolysis. If the film according to the present invention is biocompatible and/or biodegradable, for example, it may be less irritable or not irritable to the skin and/or it may not contaminate environments.

In fact, the film according to the present invention can include (a-1) at least one cationic polymer selected from chitosans which are biodegradable polymers.

The film according to the present invention can be used for cosmetic treatments of keratin substances, preferably skin, in particular the face. The film according to the present invention can be in any shape or form.

[Cosmetic Process and Use]

The present invention also relates to: a cosmetic process for a keratin substance such as skin, comprising: applying to the keratin substance the composition according to the present invention; and drying the composition to form a cosmetic film on the keratin substance; or a use of the composition according to the present invention for the preparation of a cosmetic film on a keratin substance such as skin.

The cosmetic process here means a non-therapeutic cosmetic method for caring for and/or making up the surface of a keratin substance such as skin.

It is also possible to apply a makeup cosmetic composition onto the cosmetic film according to the present invention after it has been applied onto the skin.

The present invention may also relate to a use of (b-1) at least one fatty acid and (c) at least one water-insoluble particle, in a composition, comprising:

(a-1) at least one cationic polymer, wherein the (c) water-insoluble particle is negatively charged, in order to prepare at least one complex comprising the (a-1) cationic polymer and the (b-1) fatty acid, and the (c) water-insoluble particle.

The above explanations regarding the (a-1) cationic polymer, the (b-1) fatty acid, and the (c) water-insoluble particle, for the composition according to the present invention, can apply to those in the above use.

EXAMPLES

The present invention will be described in a more detailed manner by way of examples. However, they should not be construed as limiting the scope of the present invention.

Example 1 and Comparative Examples 1-3

[Preparations]

Each of the compositions according to Example 1 and Comparative Examples 1-3 was prepared by mixing the ingredients shown in Table 1. The numerical values for the amounts of the ingredients in Table 1 are all based on “% by weight” as raw materials.

The details of the preparation are as follows.

(Example 1)

First, 0.63 g of chitosan raw material in the form of an 80 wt% aqueous solution, 0.32 g of lactic acid, and 99.05 g of water were mixed to obtain a first mixture in an amount of 100 g.

Second, separately, 0.17 g of oleic acid and 9.83 g of ethanol were mixed to obtain a second mixture, in an amount of 10 g.

Third, separately, phytic acid and titanium dioxide were mixed and dispersed in water to obtain a third mixture as an aqueous dispersion including 40 wt% of TiO₂.

Then, 10 g of the first mixture and 1 g of the second mixture were mixed to obtain a liquid including hydrophobicized chitosan gel particles. This liquid was mixed with the third mixture in a weight ratio of 3: 1 (7.5 g of the liquid: 2.5 g of the third mixture) to obtain the composition according to Example 1. The pH of the composition according to Example 1 was adjusted by NaOH to be 5.

(Comparative Example 1)

First, 0.57 g of chitosan raw material in the form of an 80 wt% aqueous solution, 0.29 g of lactic acid, 1.60 g of oleic acid, 9.60 g of com oil, and 87.94 g of water were mixed to obtain a first mixture.

Second, separately, phytic acid and titanium dioxide were mixed, and dispersed in water, to obtain a second mixture as an aqueous dispersion including 40 wt% of TiO₂.

Then, the first mixture and the second mixture were mixed in a weight ratio of 3 : 1 (7.5 g of the first mixture: 2.5 g of the second mixture) to obtain a composition according to Comparative Example 1. The pH of the composition according to Example 1 was adjusted by NaOH to be 5.

(Comparative Example 2)

First, 100.18g of water and 9.82 g of ethanol were mixed to obtain a first mixture.

Second, separately, phytic acid and titanium dioxide were mixed, and dispersed in water, to obtain a second mixture as an aqueous dispersion including 40 wt% of TiO2.

Then, the first mixture and the second mixture were mixed in a weight ratio of 3 : 1 (7.5 g of the first mixture: 2.5 g of the second mixture) to obtain a composition according to Comparative Example 2. The pH of the composition according to Example 1 was adjusted by NaOH to be 5.

(Comparative Example 3) First, 0.63 g of chitosan raw material in the form of an 80 wt% aqueous solution, 0.32 g of lactic acid, and 99.05 g of water were mixed to obtain a first mixture in an amount of 100 g.

Second, separately, 9.83 g of ethanol and 0.17 g of water were mixed to obtain a second mixture.

Then, 10 g of the first mixture and 1 g of the second mixture were mixed to obtain a liquid including chitosan. This liquid was mixed with the third mixture in a weight ratio of 3: 1 (7.5 g of the liquid: 2.5 g of the third mixture) to obtain the composition according to Comparative Example 3. The pH of the composition according to Example 1 was adjusted by NaOH to be 5.

Table 1

[Evaluations]

The photographs of the composition according to Example 1 and the composition according to Comparative Example 3 were obtained by using an optical microscope, Keyence EZX70, as shown in Figs. 1 and 2, respectively.

It was found that the composition according to Example 1 includes particles, while the composition according to Comparative Example 3 did not include any particles.

It is clear that the particles in the composition according to Example 1 comprise, at least, chitosan, oleic acid, as well as titanium oxide treated with phytic acid.

(Caking) Each of the compositions according to Example 1 and Comparative Examples 1 -3 was stored in a transparent vessel at room temperature (25°C) for one day. The appearance of the compositions was visually observed and evaluated in accordance with the following criteria.

Good: Caking was observed

Poor: Caking was not observed

The results are shown in Table 1.

The composition according to Example 1 did not cause caking (fluid), while the compositions according to Comparative Examples 1-3 did.

(Wettability)

100 pl each of the composition according to Example 1 and Comparative Examples 1-3 was applied onto a transparent polymethylmethacrylate (PMMA) plate at room temperature (25 °C) to coat the plate.

The appearance of the wet coating before being dried on the plate was visually observed and evaluated in accordance with the following criteria.

Good: more than 70% of the surface of the plate was covered

Poor: 70% or less of the surface of the plate was covered

The results are shown in Table 1.

The composition according to Example 1 was able to coat almost all of the surface of the plate, while the compositions according to Comparative Examples 1-3 could not. It is clear that the composition according to Example 1 has good wettability.

(Film-Forming Ability)

100 pl each of the composition according to Example 1 and Comparative Examples 1-3 was applied onto a transparent polymethylmethacrylate (PMMA) plate at room temperature (25°C) to coat the plate, and the coating was dried at room temperature.

The appearance of the coating after being dried on the plate was visually observed and evaluated in accordance with the following criteria.

Good: no crack was found on the coating

Poor: crack was found on the coating

The results are shown in Table 1.

The composition according to Example 1 was able to provide a dry coating with no crack, while the compositions according to Comparative Examples 1-3 could not provide such a dry coating. It is clear that the composition according to Example 1 has good film- forming ability.

(Water Resistance) 100 pl each of the composition according to Example 1 and Comparative Examples 1-3 was applied onto a transparent polymethylmethacrylate (PMMA) plate at room temperature (25°C) to coat the plate, and the coating was dried at room temperature.

The plate was immersed into water at room temperature (25 °C) for 15 minutes.

The appearance of the coating on the plate was visually observed and evaluated in accordance with the following criteria.

Good: more than 50% of the coating remained

Poor: 50% or less of the coating remained

The results are shown in Table 1.

The composition according to Example 1 was able to provide a water-resistant film, while the compositions according to Comparative Examples 1-3 could not provide such a water- resistant film.

(Texture)

50 mg of each of the compositions according to Example 1 and Comparative Examples 1-3 was applied onto the hand of a panelist with a finger. The texture during the application was evaluated in accordance with the following criteria.

Good: Smooth

Poor: Squeaky

The results are shown in Table 1.

The composition according to Example 1 provided smooth feeling to touch, while the compositions according to Comparative Examples 1-3 provided squeaky feeling to touch. In addition, the composition according to Comparative Example 1 was also oily.

(Whiteness)

50 mg of each of the compositions according to Example 1 and Comparative Examples 1-3 was applied onto the hand of a panelist with a finger, and dried. The appearance of the applied hand was evaluated in accordance with the following criteria.

Good: Natural (not white)

Poor: White

The results are shown in Table 1.

The composition according to Example 1 provided a natural look without causing unnatural whiteness, while the compositions according to Comparative Examples 1-3 provided an unnatural look while causing whiteness.

Claims

1. A composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, comprising:

(a-1) at least one cationic polymer;

(a-2) at least one monovalent non-polymeric acid or a salt thereof;

(b-1) at least one fatty acid; and

2. The composition according to Claim 1, wherein the (a-1) cationic polymer has a molecular weight (Da) of more than 20,000.

3. The composition according to Claim 1 or 2, wherein the (a-1) cationic polymer is selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as (co)polylysines and chitosans, cationic (co)polyaminoacids such as collagen, cationic cellulose polymers, and salts thereof.

4. The composition according to any one of Claims 1 to 3, wherein the amount of the (a-1) cationic polymer(s) in the composition is from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

5. The composition according to any one of Claims 1 to 4, wherein the (a-2) monovalent non-polymeric acid is a monovalent non-polymeric organic acid, preferably a monovalent non-polymeric carboxylic acid, and more preferably a monovalent hydroxy acid such as lactic acid and salicylic acid.

6. The composition according to any one of Claims 1 to 5, wherein the amount of the (a-2) monovalent non-polymeric acid or a salt thereof in the composition is from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, and more preferably from 0.1 % to 10% by weight, relative to the total weight of the composition.

7. The composition according to any one of Claims 1 to 6, wherein the composition further comprises (a-3) water.

8. The composition according to Claim 7, wherein the amount of the (a-3) water in the composition is from 40% to 99% by weight, preferably from 45% to 97% by weight, and more preferably from 50% to 95% by weight, relative to the total weight of the composition.

9. The composition according to any one of Claims 1 to 8, wherein the (b-1) fatty acid is selected from C₄-C₂₂, preferably C₆-C₂₀, and more preferably C₈-C₁₈ saturated and unsaturated, linear or branched fatty acids.

10. The composition according to any one of Claims 1 to 9, wherein the amount of the (b-1) fatty acid(s) in the composition is from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

11. The composition according to any one of Claims 1 to 10, wherein the composition further comprises (b-2) at least one alcohol, preferably selected from the group consisting of ethanol, pentyleneglycol, glycerin, and a mixture thereof, and more preferably selected from the group consisting of ethanol, pentyleneglycol, and a mixture thereof.

12. The composition according to Claim 11, wherein the amount of the (b-2) alcohol(s) in the composition is from 1% to 20% by weight, preferably from 3% to 15% by weight, and more preferably from 5% to 10% by weight, relative to the total weight of the composition.

13. The composition according to any one of Claims 1 to 12, wherein the (c) waterinsoluble particle is selected from metal oxides, preferably titanium oxides, zinc oxides and iron oxides, and more preferably titanium oxides, which have been surface-treated with at least one acid or a salt thereof, preferably at least one polyvalent acid or a salt thereof, and more preferably phytic acid or a salt thereof.

14. The composition according to any one of Claims 1 to 13, wherein the amount of the (c) water-insoluble particle(s) in the composition is from 0.01% to 30% by weight, preferably from 0.05% to 20% by weight, and more preferably from 0.1% to 15% by weight, relative to the total weight of the composition.

15. The composition according to any one of Claims 1 to 14, wherein, at least, the (a-1) cationic polymer, the (b-1) fatty acid, and the (c) water-insoluble particle form at least one complex.