JP2024047990A - Composition containing hyaluronic acid-based polyion complex and highly absorbent polymer - Google Patents

Abstract

[Problem] To provide a stable composition containing a hyaluronic acid-based polyion complex having an enhanced sebum control effect. [Solution] The present invention relates to a composition comprising (a) at least one cationic polymer, (b) at least one anionic polymer, (c) at least one non-polymeric acid having two or more pKa values and its salt, (d) at least one superabsorbent polymer, and (e) water, wherein (b) the anionic polymer is selected from hyaluronic acid and its derivatives, and (d) the superabsorbent polymer is in the form of particles having an average particle size of 5 μm to 500 μm, preferably 10 μm to 400 μm, more preferably 15 μm to 300 μm. The composition according to the present invention is stable for a long period of time. The composition according to the present invention can provide an excellent sebum control effect. [Selected Figure] None

Description

The present invention relates to a composition containing a polyion complex and a superabsorbent polymer, and a cosmetic method using the composition.

Hyaluronic acid is the main glycosaminoglycan found in the skin. Therefore, fibroblasts mainly synthesize collagen, non-collagenous matrix glycoproteins (fibronectin, laminin), proteoglycans and elastin. Keratinocytes, for their part, mainly synthesize sulfated glycosaminoglycans and hyaluronic acid. Hyaluronic acid is also called hyaluronan (HA).

Hyaluronic acid is present in free form in the epidermis and dermis and is responsible for the turgor of the skin. This polysaccharide can in fact retain large volumes of water, up to 1000 times its mass. In this sense, hyaluronic acid plays an important role in increasing the amount of water bound in the tissue and also in the mechanical properties of the skin and in the formation of wrinkles.

Hyaluronic acid has been widely used as a cosmetic ingredient due to its high moisturizing effect.

WO2021/125069 discloses a polyion complex that may be composed of at least one cationic polymer and at least one anionic polymer, in which the anionic polymer is selected from hyaluronic acid and its derivatives.

WO2021/125069 European Patent Application No. 0080976 French Patent No. 2077143 French Patent No. 2393573 French Patent No. 1492597 U.S. Patent No. 4,131,576 U.S. Patent No. 3,589,578 U.S. Patent No. 4,031,307 French Patent No. 2162025 French Patent No. 2280361 French Patent No. 2252840 French Patent No. 2368508 French Patent No. 1583363 U.S. Patent No. 3,227,615 U.S. Patent No. 2,961,347 French Patent No. 2080759 Additional Patent No. 2190406 of French Patent No. 2080759 French Patent No. 2320330 French Patent No. 2270846 French Patent No. 2316271 French Patent No. 2336434 French Patent No. 2413907 U.S. Patent No. 2,273,780 U.S. Patent No. 2,375,853 U.S. Patent No. 2,388,614 U.S. Patent No. 2,454,547 U.S. Patent No. 3,206,462 U.S. Patent No. 2261002 U.S. Patent No. 2,271,378 U.S. Patent No. 3,874,870 U.S. Patent No. 4001432 U.S. Patent No. 3,929,990 U.S. Patent No. 3,966,904 U.S. Patent No. 4,005,193 U.S. Patent No. 4,025,617 U.S. Patent No. 4,025,627 U.S. Patent No. 4,025,653 U.S. Patent No. 4,026,945 U.S. Patent No. 4027020 European Patent Application No. 0122324

CTFA Dictionary Reference: "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699-715 D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification," Biomaterials 19 (1998) pp. 2101-2127 L. BRANNON-PAPPAS and R. HARLAND, "Absorbent polymer technology, Studies in polymer science 8", Elsevier, 1990 Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics ASTM Standard 445 Appendix C

It has been found that compositions containing hyaluronic acid-based polyion complexes can become unstable over time and that the compositions can exert a relatively limited sebum control effect.
Therefore, one object of the present invention is to provide a stable composition comprising a hyaluronic acid-based polyion complex, which has an enhanced sebum control effect.

The above object of the present invention is to
(a) at least one cationic polymer;
(b) at least one anionic polymer;
(c) at least one non-polymeric acid or salt thereof having two or more pKa values;
(d) at least one superabsorbent polymer;
(e) water,
(b) the anionic polymer is selected from hyaluronic acid and its derivatives;
(d) This can be achieved by a composition, wherein the superabsorbent polymer is in the form of particles having an average particle size of 5 μm to 500 μm, preferably 10 μm to 400 μm, more preferably 15 μm to 300 μm.

(a) The cationic polymer may have at least one positively charged and/or positively charged moiety selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups.

(a) The cationic polymer may be selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as chitosan and (co)polylysine, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, chitosan, and salts thereof.

The amount of (a) cationic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, based on the total mass of the composition.

The composition according to the present invention may contain, as an anionic polymer (b), at least two types of hyaluronic acid having different molecular weights, preferably a first hyaluronic acid having a molecular weight of 100 kDa or less and a second hyaluronic acid having a molecular weight of 500 kDa or more, more preferably a first hyaluronic acid having a molecular weight of 50 kDa or less and a second hyaluronic acid having a molecular weight of 1000 kDa or more.

The amount of (b) anionic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, based on the total mass of the composition.

(c) The non-polymeric acid or salt thereof having two or more pKa values may be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof, more preferably phytic acid or salt thereof.

The amount of (c) the non-polymeric acid or its salt having two or more pKa values in the composition according to the present invention may be 0.01% to 15% by weight, preferably 0.05% to 10% by weight, more preferably 0.1% to 5% by weight, based on the total weight of the composition.

(d) The superabsorbent polymer may be selected from crosslinked (meth)acrylic or (meth)acrylate polymers, starch grafted with acrylic or acrylate polymers, and mixtures thereof.

The amount of (d) superabsorbent polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, based on the total mass of the composition.

The amount of (e) water in the composition according to the present invention may be 50% by mass to 95% by mass, preferably 60% by mass to 90% by mass, and more preferably 70% by mass to 85% by mass, based on the total mass of the composition.

The pH of the composition according to the present invention may be from 3 to 9, preferably from 3.3 to 8.0, more preferably from 3.5 to 8.

The composition according to the present invention may further comprise (f) at least one oil.

The composition according to the present invention may be a cosmetic composition, preferably a skin cosmetic composition, more preferably a skin care cosmetic composition.

The present invention also provides a cosmetic method for keratinous materials, such as the skin, comprising the steps of:
applying a composition according to the invention to a keratinous material;
and drying the composition to form a cosmetic film on the keratinous material.

As a result of intensive research, the present inventors have discovered that it is possible to provide a stable composition containing a hyaluronic acid-based polyion complex that has an enhanced sebum control effect.

Therefore, the composition according to the invention
(a) at least one cationic polymer;
(b) at least one anionic polymer;
(c) at least one non-polymeric acid or salt thereof having two or more pKa values;
(d) at least one superabsorbent polymer;
(e) water,
(b) the anionic polymer is selected from hyaluronic acid and its derivatives;
(d) The superabsorbent polymer is in the form of particles having an average particle size of from 5 μm to 500 μm, preferably from 10 μm to 400 μm, and more preferably from 15 μm to 300 μm.

The composition according to the invention is stable for a long period of time. The composition is stable even when it contains oil.

The composition according to the present invention can provide an excellent sebum control effect. For example, the film formed by the composition according to the present invention can absorb sebum or oil and can maintain it in the film even for a long period of time. The sebum control effect can be attributed to an optical matte effect on keratinous materials such as skin.

Furthermore, the composition according to the invention can be applied without forming agglomerates, which may be in the form of noodles.

Furthermore, the composition according to the present invention is based on hyaluronic acid or its derivatives and can provide cosmetic effects such as a moisturizing effect.

In addition, the composition according to the present invention can be less sticky. For example, the stickiness of a composition according to the present invention that contains hyaluronic acid as a component that forms a polyion complex can be reduced compared to a composition that contains hyaluronic acid without forming a polyion complex.

The compositions, methods, etc. according to the present invention will now be described in more detail.

[Polyion complex]
The composition according to the present invention comprises (a) at least one cationic polymer, (b) at least one anionic polymer, and (c) at least one non-polymeric acid or salt thereof having two or more pKa values, as described below.

The above components (a), (b) and (c) can form a polyion complex. The polyion complex can be in the form of particles. Two or more different types of particles can be present in combination. Thus, a single type of particle or a combination of different types of particles can be present in the composition according to the present invention.

When the polyion complex particles are in the form of particles, the size of the particles may be 5 nm to 100 μm, preferably 100 nm to 50 μm, more preferably 200 nm to 40 μm, and even more preferably 500 nm to 30 μm. Particle sizes less than 1 μm can be measured by dynamic light scattering, and particle sizes greater than 1 μm can be measured by optical microscopy. The particle size can be based on the number average diameter.

The amount of particles in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of particles in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition.

The amount of particles 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, more preferably from 0.1% to 5% by weight, based on the total weight of the composition.

When the composition according to the invention includes at least one oil (f) as described below, a plurality of particles can be present at the interface between the (e) water and the (f) oil. The particles can thus stabilize the emulsion. For example, when the (e) water constitutes the continuous phase and the (f) oil constitutes the dispersed phase, the particles can form an O/W emulsion that can resemble a so-called Pickering emulsion.

Alternatively, the particles may form a capsule having a hollow portion. The (f) oil may be present within the hollow portion. In other words, the (f) oil may be incorporated into the capsule. The capsule wall may consist of a continuous layer or film formed from the particles. Without wishing to be bound by theory, it is believed that the particles may reorganize at the interface between the (e) water and the (f) oil to spontaneously form a capsule having a hollow portion for containing the (f) oil. For example, a continuous phase consisting of the (e) water and a dispersed phase consisting of the (f) oil in a capsule may form an O/W emulsion, which may also resemble a so-called Pickering emulsion.

The above means that the particles themselves are amphiphilic. They are insoluble in oil or water.

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

The (a) cationic polymer has a positive charge density. The charge density of the (a) cationic polymer may be 0.01 meq/g to 20 meq/g, preferably 0.05 to 15 meq/g, and more preferably 0.1 to 10 meq/g.

(a) It may be preferred that the molecular weight of the cationic polymer is 500 or more, preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more. Unless otherwise defined in the description, "molecular weight" means number average molecular weight.

(a) The cationic polymer may have at least one positive charge and/or may have a moiety that has a positive charge selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups. The term "(primary) amino group" as used herein means the _-NH2 group.

(a) The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and terpolymers obtained from more than two types of monomers, for example three types of monomers.

(a) The cationic polymer can be selected from natural and synthetic cationic polymers. Non-limiting examples of (a) cationic polymers are as follows:

(1) Derived from esters and amides of acrylic or methacrylic acid, having the formula:

(Wherein,
R ₁ and R ₂ may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups;
_R3 may be the same or different and is selected from hydrogen and _CH3 ;
the symbols A, which may be the same or different, are selected from linear or branched alkyl groups containing 1 to 6 carbon atoms, for example 2 to 3 carbon atoms, and hydroxyalkyl groups containing 1 to 4 carbon atoms;
R ₄ , R ₅ and R ₆ may be the same or different and are selected from alkyl groups containing 1 to 18 carbon atoms, and benzyl groups, and in at least one embodiment alkyl groups containing 1 to 6 carbon atoms;
X ⁻ is an anion derived from an inorganic or organic acid, such as methosulfate, and a halide ion, such as chloride and bromide.
Homopolymers and copolymers comprising at least one unit selected from the units:

The copolymers of family (1) above may also contain at least one unit derived from a comonomer, which may be selected from acrylamide, methacrylamide, diacetone acrylamide, acrylamides and methacrylamides whose nitrogen atoms are substituted with (C ₁ -C ₄ ) lower alkyl groups, groups derived from acrylic or methacrylic acid and their esters, vinyl lactams such as vinyl pyrrolidone and vinyl caprolactam, and vinyl esters.

Examples of family (1) copolymers include, but are not limited to, the following:
Copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halides;
Copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, such as those described in European Patent Application No. 0080976;
Copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate,
Quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as those described in French Patents Nos. 2 077 143 and 2 393 573;
Dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymer,
Vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, as well as crosslinked methacryloyloxy(C ₁ -C ₄ )alkyltri(C ₁ -C ₄ )alkylammonium salt polymers, such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride followed by homopolymerization or copolymerization with a compound containing olefinic unsaturation, such as methylenebisacrylamide.

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

It is preferred that the cationic cellulose polymer has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group, more preferably a quaternary trimethylammonium group.

Quaternary ammonium groups have the chemical formula (I):

(Wherein,
_R1 and _R2 each represent a _C1 - _C3 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group;
_R3 represents a _C1 - _C24 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group;
^X- represents an anion, preferably a halide ion, more preferably a chloride ion;
n represents an integer of 0 to 30, preferably 0 to 10, more preferably 0;
_R4 represents a _C1 - _C4 alkylene group, preferably an ethylene group or a propylene group.
The quaternary ammonium group-containing group may be represented by the formula:

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

The quaternary ammonium group-containing group is preferably -O- _CH2 -CH(OH) _-CH2 -N ⁺ ( _CH3 ) ₃ .

(3) Cationic cellulose polymers, such as cellulose copolymers, and cellulose derivatives grafted with water-soluble quaternary ammonium monomers, such as those described in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for example hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted with salts selected from methacryloylethyltrimethylammonium, methacrylamidepropyltrimethylammonium and dimethyldiallylammonium salts.

Commercially available products corresponding to these polymers include, for example, products sold under the names "Celquat® L 200" and "Celquat® H 100" by National Starch.

(4) Non-cellulosic cationic polysaccharides such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid and dextran hydroxypropyltrimonium chloride, as described in U.S. Pat. Nos. 3,589,578 and 4,031,307. Guar gum modified with salts such as the chloride of 2,3-epoxypropyltrimethylammonium (guar hydroxypropyltrimonium chloride) can also be used.

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

(5) Polymers containing piperazinyl units and divalent alkylene or hydroxyalkylene groups, optionally interrupted by at least one element selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, and also the oxidation and/or quaternization products of these polymers. Such polymers are described, for example, in French Patents Nos. 2 162 025 and 2 280 361.

(6) Water-soluble polyaminoamides, for example prepared by polycondensation of acidic compounds with polyamines; these polyaminoamides may be crosslinked with an element selected from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bisunsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacyldiamines; bisalkylhalides; oligomers obtained by reaction of bifunctional compounds reactive with elements selected from bishalohydrins, bisazetidiniums, bishaloacyldiamines, bisalkylhalides, epihalohydrins, diepoxides and bisunsaturated derivatives; the crosslinking agent is used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may be optionally alkylated or, if they contain at least one tertiary amine function, they may be quaternized. Such polymers are described, for example, in French Patents Nos. 2252840 and 2368508.

(7) Polyaminoamide derivatives obtained by condensation of polyalkylenepolyamines with polycarboxylic acids followed by alkylation with bifunctional agents, for example adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl groups contain from 1 to 4 carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene groups contain from 1 to 4 carbon atoms, such as ethylene groups. Such polymers are described, by way of example, in French Patent No. 1 583 363. In at least one embodiment, these derivatives can be chosen from adipic acid/dimethylaminohydroxypropyldiethylenetriamine polymers.

(8) Polymers obtained by reacting a polyalkylenepolyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of polyalkylenepolyamine to dicarboxylic acid may range from 0.8:1 to 1.4:1, and the polyaminoamide obtained therefrom is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups of polyaminoamide ranging from 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Pat. Nos. 3,227,615 and 2,961,347.

(9) Cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallyl-ammonium, for example, having as the main chain building blocks the formulae (Ia) and (Ib):

[Wherein,
k and t may be the same or different and are equal to 0 or 1, the sum k+t being equal to 1;
R ₁₂ is selected from hydrogen and a methyl group;
R ₁₀ and R ₁₁ may be the same or different and are selected from alkyl groups containing 1 to 6 carbon atoms, hydroxyalkyl groups, the alkyl group containing, for example, 1 to 5 carbon atoms, and lower (C ₁ -C ₄ ) amidoalkyl groups, or R ₁₀ and R ₁₁ together with the nitrogen atom to which they are attached may form a heterocyclic group, such as piperidinyl and morpholinyl;
Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate.
Homopolymers and copolymers containing at least one unit selected from the units.
These polymers are described, for example, in French patent no. 2 080 759 and its addition no. 2 190 406.

In one embodiment, R ₁₀ and R ₁₁ , which may be the same or different, are selected from alkyl groups containing 1 to 4 carbon atoms.

Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chlorides, such as the dimethyldiallylammonium chloride homopolymer sold under the name "MERQUAT® 100" by CALGON (and its analogs of lower weight average molecular weight), and the copolymer of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".

(10) Formula (II)

{wherein
R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and are selected from aliphatic, cycloaliphatic and arylaliphatic groups containing 1 to 20 carbon atoms, and lower hydroxyalkyl aliphatic groups, or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ together with the nitrogen atom to which they are attached or separately may form a heterocycle optionally containing a second heteroatom other than nitrogen, or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and are selected from linear or branched C 1 -C 6 alkyl groups substituted with at least one group selected from nitrile, ester, acyl, amide, -CO-OR ₁₇ -E and -CO-NH-R ₁₇ -E groups, where R ₁₇ is an _alkylene group and E is a _quaternary ammonium group;
A ₁ and B ₁ may be the same or different and are selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked or inserted in the main chain, at least one element selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups and ester groups;
X ⁻ is an anion derived from an inorganic or organic acid;
A ₁ , R ₁₃ and R ₁₅ together with the two nitrogen atoms to which they are attached may form a piperazine ring;
When A ₁ is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B ₁ is
-( _CH2 ) _n -CO-E'-OC-( _CH2 ) _n-
[In the formula, E' is
a) a compound of the formula -OZO-, where Z is a linear or branched hydrocarbon-based group and
-( _CH2 - _CH2 -O) _x - _CH2 - _CH2-
-[CH2 _- CH( _CH3 )-O] _y - _CH2 -CH( _CH3 )-
(wherein x and y may be the same or different and are selected from integers ranging from 1 to 4 representing a unique defined degree of polymerization, and numbers ranging from 1 to 4 representing an average degree of polymerization).
a glycol residue selected from the group consisting of
b) bis-secondary diamine residues, such as piperazine derivatives;
c) bis-primary diamine residues of the formula -NH-Y-NH-, where Y is selected from linear or branched hydrocarbon-based radicals and the divalent radical _-CH2 - _CH2 -SS- _CH2 - _CH2- , and
d) a ureylene group of the formula -NH-CO-NH-
A quaternary diammonium polymer comprising at least one repeat unit of:

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

Polymers of this type are described, for example, in French Patents Nos. 2320330, 2270846, 2316271, 2336434 and 2413907, and in U.S. Patents Nos. 2273780, 2375853, 2388614, 2454547, 3206462, 2413907, and 2413907. 261002, 2271378, 3874870, 4001432, 3929990, 3966904, 4005193, 4025617, 4025627, 4025653, 4026945 and 4027020.

Non-limiting examples of such polymers include those of formula (III):

(wherein R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and are selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms; n and p may be the same or different and are integers ranging from 2 to 20; and X ⁻ is an anion derived from an inorganic or organic acid.)
Examples of the repeating unit include those containing at least one of the following repeating units:

(11) Formula (IV):

[Wherein,
R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ may be the same or different and are selected from hydrogen, a methyl group, an ethyl group, a propyl group, a β-hydroxyethyl group, a β-hydroxypropyl group, and a -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p OH group (wherein p is an integer selected from the range of 0 to 6), with the proviso that R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are not simultaneously hydrogen;
r and s may be the same or different and are selected from integers ranging from 1 to 6;
q is selected from an integer ranging from 0 to 34;
X ⁻ is an anion, for example a halide ion;
A is selected from the group consisting of dihalides and _-CH2 - _CH2 -O- _CH2 - _CH2- .
A polyquaternary ammonium polymer comprising units of

Such compounds are described, for example, in European Patent Application No. 0122324.

(12) Quaternary Polymers of Vinylpyrrolidone and Vinylimidazole Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimine, polymers containing units selected from vinylpyridine units and vinylpyridinium units, condensates of polyamines with epichlorohydrin, quaternary polyureylenes, and chitin derivatives.

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

(13) Polyamines
It is also possible to use (co)polyamines as (a) cationic polymers, which may be homopolymers or copolymers, having several amino groups. The amino groups may be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone of the (co)polyamine or, if present, in pendant groups.

Examples of (co)polyamines include chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate, (co)polyvinylpyridine such as (co)poly-1-methyl-2-vinylpyridine, (co)polyimine such as (co)polyethyleneimine, (co)polypyridine such as (co)poly(quaternary pyridine), (co)polybiguanide such as (co)polyaminopropyl biguanide, (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinyl acetal, and salts thereof.

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

(14) Cationic polyamino acids
(a) As cationic polymer it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers having multiple amino and carboxyl groups. The amino groups may be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone of the cationic polyamino acid or in pendant groups, if present. The carboxyl groups may be present in pendant groups, if present, of the cationic polyamino acid.

Examples of cationic polyamino acids include cationic collagen, cationic gelatin, steardimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed soy protein, etc.

The following description relates to preferred embodiments of (a) cationic polymers.

(a) It may be preferred that the cationic polymer is selected from cationic starches.

As examples of cationic starches, mention may be made of starches modified with 2,3-epoxypropyltrimethylammonium salts (e.g. chloride), such as the product known by the INCI name Starch Hydroxypropyltrimonium Chloride, sold under the name SENSOMER Cl-50 by Ondeo or Pencare® DP 1015 by Ingredion.

It may also be preferred that the (a) cationic polymer is selected from cationic gums.

The gum may be selected, for example, from the group consisting of cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum and gum arabic.

Examples of cationic gums include cationic polygalactomannan derivatives such as guar gum derivatives and cassia gum derivatives such as CTFA: guar hydroxypropyltrimonium chloride, hydroxypropyl guar hydroxypropyltrimonium chloride and cassia hydroxypropyltrimonium chloride. Guar hydroxypropyltrimonium chloride is commercially available from Rhodia Inc. under the Jaguar™ trade name series and from Ashland Inc. under the N-Hance trade name series. Cassia hydroxypropyltrimonium chloride is commercially available from Lubrizol Advanced Materials, Inc. under the trade names Sensomer™ CT-250 and Sensomer™ CT-400, or from Ashland Inc. under ClearHance™.

(a) It may be preferred that the cationic polymer is selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as chitosan and (co)polylysine, cationic (co)polyamino acids, such as cationized collagen, cationic cellulose polymers, and salts thereof.

(a) It may be more preferred that the cationic polymer is selected from the group consisting of polylysine, such as poly-α-lysine and poly-ε-lysine, polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan, and mixtures thereof.

The amount of (a) cationic polymer in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of (a) cationic polymer in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the composition.

The amount of (a) cationic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, based on the total mass of the composition.

(anionic polymer)
The composition according to the present invention comprises (b) at least one anionic polymer. Two or more different types of anionic polymers may be used in combination. Thus, a single type of anionic polymer or a combination of different types of anionic polymers may be used.

The (b) anionic polymer has a positive charge density. The charge density of the (b) anionic polymer may be 0.1 meq/g to 20 meq/g, preferably 1 to 15 meq/g, more preferably 4 to 10 meq/g, when the (b) anionic polymer is a synthetic anionic polymer, and the average degree of substitution of the (b) anionic polymer may be 0.1 to 3.0, preferably 0.2 to 2.7, more preferably 0.3 to 2.5, when the (b) anionic polymer is a natural anionic polymer.

According to the present invention, (b) the anionic polymer is selected from hyaluronic acid and its derivatives.

Hyaluronic acid has the chemical formula:

It can be expressed as:

In the context of the present invention, the term "hyaluronic acid" refers specifically to the compound of the formula:

contains the basic unit of hyaluronic acid.

This is the smallest part of hyaluronic acid, containing a disaccharide dimer, i.e., D-glucuronic acid and N-acetylglucosamine.

The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, linear polymers comprising the above polymer units linked together in a chain via alternating β(1,4) and β(1,3) glycosidic bonds, with a molecular weight (MW) that can range between 380 and 13,000,000 daltons. This molecular weight depends mainly on the source from which the hyaluronic acid is obtained and/or on the method of preparation.

The term "hyaluronic acid and its derivatives" also includes, in the context of the present invention, hyaluronic acid salts. Examples of salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

In its natural state, hyaluronic acid is present in the percellular gel in the matrix of connective tissues of vertebrate organs, such as the dermis and epithelial tissues, specifically in the epidermis, synovial fluid of joints, vitreous humor, human umbilical cord, and crest process.

The term "hyaluronic acid and its derivatives" therefore includes all fractions or subunits of hyaluronic acid having molecular weights within the above molecular weight ranges in particular.

In the context of the present invention, hyaluronic acid fractions that do not have inflammatory activity are preferably used.

As an example of various hyaluronan fractions, reference can be made to the article "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699-715, which reviews the enumerated biological activities of hyaluronan according to its molecular weight.

According to a preferred embodiment of the invention, the hyaluronic acid fractions suitable for use encompassed by the present invention have a molecular weight between 2,000 Da and 5,000,000 Da.

Hyaluronic acid fractions that may also be suitable for uses encompassed by the present invention may have a molecular weight between 400,000 Da and 5,000,000 Da. In this case, the term used is high molecular weight hyaluronic acid.

Alternatively, hyaluronic acid fractions that may also be suitable for uses encompassed by the present invention may have a molecular weight between 200,000 Da and 400,000 Da. In this case, the term used is intermediate molecular weight hyaluronic acid.

Additionally or alternatively, hyaluronic acid fractions that may also be suitable for uses encompassed by the present invention may have a molecular weight of less than 200,000 Da. In this case, the term used is low molecular weight hyaluronic acid.

Finally, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid esters containing 1 to 20 carbon atoms, in particular those in which the degree of substitution of the D-glucuronic acid level of hyaluronic acid ranges from 0.5 to 50%, in particular those in which all or part of the carboxylic acid groups of the acid functions are esterified with oxyethylated alkyls or alcohols.

In particular, mention may be made of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. Such esters are described in detail in D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) pp. 2101-2127.

The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.

The molecular weights shown above are also valid for hyaluronic acid esters.

The hyaluronic acid may be, in particular, the hyaluronic acid supplied by Hyactive under the trade name CPN (MW: 10-150 kDa), by Soliance under the trade name Cristalhyal (MW: 1.1 times, 10 ⁶ ), by Bioland under the name Nutra HA (MW: 820,000 Da), by Bioland under the name Nutra AF (MW: 69,000 Da), by Bioland under the name Oligo HA (MW: 6100 Da), or by Vam Farmacos Metica under the name D Factor (MW: 380 Da).

It is preferred that the composition according to the present invention contains at least two types of hyaluronic acid having different molecular weights, such as (b) anionic polymer.

It may be preferred that the two types of hyaluronic acid are a combination of high molecular weight hyaluronic acid and medium molecular weight hyaluronic acid, a combination of high molecular weight hyaluronic acid and low molecular weight hyaluronic acid, or a combination of medium molecular weight hyaluronic acid and low molecular weight hyaluronic acid.

It may be preferred that the composition according to the present invention comprises a first hyaluronic acid having a molecular weight of 100 kDa or less and a second hyaluronic acid having a molecular weight of 500 kDa or more, and more preferably comprises a first hyaluronic acid having a molecular weight of 50 kDa or less and a second hyaluronic acid having a molecular weight of 1000 kDa or more.

The ratio of the amount of the first hyaluronic acid to the amount of the second hyaluronic acid may be 90:10 to 10:90, preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.

By using a combination of at least two hyaluronic acids with different molecular weights, the texture of the composition according to the invention can be improved and the risk of noodle formation can be further reduced.

The amount of (b) anionic polymer in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of (b) anionic polymer in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the composition.

The amount of (b) anionic polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, based on the total mass of the composition.

(Non-polymeric acids with two or more acid dissociation constants)
The composition according to the present invention comprises (c) at least one non-polymeric acid or salt thereof having two or more pKa values, i.e., at least one non-polymeric acid or salt thereof having two or more acid dissociation constants. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined at a certain temperature, e.g., 25°C.

(c) A non-polymeric acid or salt thereof having two or more pKa values can be included in a polyion complex, which can be in the form of a particle. The non-polymeric acid having two or more pKa values can function as a crosslinker for (a) the cationic polymer, or for (a) the cationic polymer and (b) the anionic polymer.

The term "non-polymeric" is used herein to mean that the acid is not obtained by polymerizing two or more monomers. Thus, non-polymeric acids do not correspond to acids obtained by polymerizing two or more monomers, such as polycarboxylic acids.

(c) The molecular weight of the non-polymeric acid or its salt having two or more pKa values is preferably 1000 or less, more preferably 800 or less, and even more preferably 700 or less.

(c) There is no limitation on the type of non-polymeric acid or salt thereof having two or more pKa values. Two or more different types of non-polymeric acids or salts thereof having two or more pKa values may be used in combination. Thus, a single type of non-polymeric acid or salt thereof having two or more pKa values, or a combination of different types of non-polymeric acids or salts thereof having two or more pKa values, may be used.

The term "salt" as used herein means a salt formed by adding a suitable base to a non-polymeric acid having two or more pKa values, which can be obtained from the reaction of a non-polymeric acid having two or more pKa values with a base according to methods known to those skilled in the art. Salts can include metal salts, such as salts with alkali metals such as Na and K, and salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

(c) The non-polymeric acid or salt thereof having two or more pKa values may be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof.

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

A non-polymeric acid having two or more pKa values may be a non-polymeric polyacid.

The non-polymeric acid having two or more pKa values may be selected from the group consisting of dicarboxylic acids, disulfonic acids, and diphosphoric acids, and mixtures thereof.

(c) Non-polymeric acids or their salts having two or more pKa values are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid, and their salts; aspartic acid, glutamic acid, and their salts; terephthalylidene dicamphorsulfonic acid or its salts (Mexoryl SX), benzophenone-9; phytic acid and its salts; Red No. 2 (Amaranth), Red No. 102 (New Coccine), Yellow No. 5 (Tartrazine), Yellow No. 6 (Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Red No. 201 (Lisol Rubin B), Red No. 202 (Lisol Rubin BCA), Red No. 204 (Lake Red CBA), Red No. 206 (Lisol Red CA), Red No. 207 (Lisol Red BA), Red No. 208 (Lisol Red SR), Red No. 219 (Brilliant Lake Red R), Red No. 220 (Deep Maroon), Red No. 227 ( Fast Acid Magenta), Yellow No. 203 (Quinoline Yellow WS), Green No. 201 (Alizanin Cyanine Green F), Green No. 204 (Pyranine Conc), Green No. 205 (Light Green SF Yellow), Blue No. 203 (Patent Blue CA), Blue No. 205 (Alphazurine FG), Red No. 401 (Violamin R), Red No. 405 (Permanent Red F5R), Red No. 502 (Ponceau 3R), Red No. 503 (Ponceau R), Red No. 504 (Ponceau SX), Green No. 401 (Naphthol Green B), Green No. 402 (Guinea Green B) and Black No. 401 (Naphthol Blue Black); folic acid, ascorbic acid, erythorbic acid, and salts thereof; cystine and salts thereof; EDTA and salts thereof; glycyrrhizin and salts thereof; and mixtures thereof.

(c) It may be preferred that the non-polymeric acid or salt thereof having two or more pKa values is selected from the group consisting of terephthalylidene dicamphorsulfonic acid and its salts (Megizolyl SX), Yellow No. 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and their salts, and mixtures thereof.

The amount of (c) the non-polymeric acid or its salt having two or more pKa values in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of (c) the non-polymeric acid or its salt having two or more pKa values in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition.

The amount of (c) the non-polymeric acid or its salt having two or more pKa values in the composition according to the present invention may be 0.01% to 15% by weight, preferably 0.05% to 10% by weight, more preferably 0.1% to 5% by weight, based on the total weight of the composition.

[Super absorbent polymer]
The composition according to the present invention comprises (d) at least one superabsorbent polymer. Two or more different types of superabsorbent polymers may be used in combination. Thus, a single type of superabsorbent polymer or a combination of different types of superabsorbent polymers may be used.

The term "superabsorbent polymer" is understood to mean a polymer which, in its dry state, is capable of spontaneously absorbing at least 20 times its own mass of aqueous fluids, in particular water, in particular distilled water. Such superabsorbent polymers are described in the book "Absorbent Polymer Technology, Studies in Polymer Science 8" by L. BRANNON-PAPPAS and R. HARLAND, Elsevier, 1990.

These polymers have a high capacity for absorbing and retaining water and aqueous fluids. After absorbing the aqueous fluid, the particles of the polymer thus impregnated with the aqueous fluid remain insoluble in the aqueous fluid and therefore retain their separate particulate state.

(d) A superabsorbent polymer may have a water absorption capacity ranging from 20 to 2000 times its own weight (i.e., 20 g to 2000 g of water are absorbed per gram of absorbent polymer), preferably from 30 to 1500 times, and even better from 50 to 1000 times. These water absorption properties are defined for distilled water under standard conditions of temperature (25°C) and pressure (760 mmHg, i.e., 100,000 Pa).

The water absorption value of a polymer can be determined by dispersing 0.5 g of polymer in 150 g of aqueous solution, waiting 20 minutes, filtering the non-absorbed solution through a 150 μm filter for 20 minutes, and weighing the non-absorbed water.

The (d) superabsorbent polymer used in the composition of the present invention is in the form of particles, which, once hydrated, swell with the form of soft beads.

(d) The average particle size of the superabsorbent polymer particles is 5 μm or more, preferably 10 μm or more, and more preferably 15 μm or more.

(d) The average particle size of the superabsorbent polymer particles is 500 μm or less, preferably 400 μm or less, and more preferably 300 μm or less.

Therefore, the average particle size of the particles of the (d) superabsorbent polymer is 5 μm to 500 μm, preferably 10 μm to 400 μm, and more preferably 15 μm to 300 μm.

The average particle size according to the present invention may be a number average particle size. The number average particle size may be determined by microscopy. The average particle size may be expressed by the Heywood diameter.

(d) When the particles of the superabsorbent polymer are aggregates of primary particles, particle size, as used herein, refers to the size of the aggregate. Thus, in this case, particle size refers to the size of the secondary particles.

Preferably, the (d) superabsorbent polymer used in the present invention can be provided in the form of spherical particles.

The (d) superabsorbent polymer used in the present invention may preferably be a crosslinked acrylic homopolymer or copolymer, which is preferably neutralized, and which is provided in particulate form.

(d) Superabsorbent polymers include the following:
Crosslinked (meth)acrylic acid or (meth)acrylate polymers, preferably crosslinked homopolymers or copolymers of (meth)acrylic acid and/or (meth)acrylate, more preferably crosslinked sodium polyacrylate, such as those sold under the names Octacare X100, X110 and RM100 by the company Avecia, those sold under the names Flocare GB300 and Flosorb 500 by the company SNF, those sold under the names Luquasorb 1003, Luquasorb 1010, Luquasorb 1280 and Luquasorb 1100 by the company BASF, those sold under the names Water Lock G400 and G430 (INCI name: acrylamide/sodium acrylate copolymer) by the company Grain Processing, or Aqua Keep 10 SH NF by Sumitomo Seika Chemicals, or Aqupec MG N40R (INCI name: sodium carbomer) by Sumitomo Seika Chemicals, under the name Aqupec by Sumitomo Seika Chemicals HV-501E, Aqupec 505E, Aqupec 505ED, Aqupec 801EG, Aqupec 801EG-300, Aqupec 805EG, Aqupec 805EG-300 and Aqupec SW-705E, and the names Carbopol 934 Polymer, Carbopol 940 Polymer, Carbopol 941 Polymer, Carbopol 980 Polymer and Carbopol 981 Polymer given by the company Lubrizol, acrylic or acrylate polymers, in particular starch grafted with sodium polyacrylate (homopolymers and copolymers), such as those sold under the names Sanfresh ST-100C, ST100MC and IM-300MC by Sanyo Chemical Industries Co., Ltd. or Makimousse 25 and Makimousse 12 (INCI name: sodium starch polyacrylate) sold by Daito Chemical Industry Co., Ltd.;
acrylic polymers (homopolymers or copolymers), in particular hydrolyzed starch grafted with acryloacrylamide/sodium acrylate copolymers, such as those sold under the names Water Lock A-240, A-180, B-204, D-223, A-100, C-200 and D-223 by the company Grain Processing (INCI name: Starch/acrylamide/sodium acrylate copolymer);
Starch-, gum- and cellulose-based polymers, such as those sold under the name Lysorb 220 by the company Lysac, which contain starch, guar gum and sodium carboxymethylcellulose;
As well as blends of these.

(d) The superabsorbent polymer may be selected from crosslinked (meth)acrylic or (meth)acrylate polymers, starch grafted with acrylic or acrylate polymers, and mixtures thereof.

Preferably, (d) the superabsorbent polymer can be chosen from crosslinked sodium polyacrylates in the form of particles, more preferably in the form of spherical particles, having a number average size (or mean diameter) of less than 100 microns. These polymers preferably have a water absorption capacity of 10 to 100 g/g, preferably 20 to 80 g/g, and even better still 50 to 70 g/g.

The amount of (d) superabsorbent polymer in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of (d) superabsorbent polymer in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the composition.

The amount of (d) superabsorbent polymer in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, based on the total mass of the composition.

[water]
The composition according to the present invention comprises (e) water.

The amount of (e) water in the composition according to the present invention may be 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total mass of the composition.

The amount of (e) water in the composition according to the present invention may be 95% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less, based on the total mass of the composition.

The amount of (e) water in the composition according to the present invention may be 50% by mass to 95% by mass, preferably 60% by mass to 90% by mass, and more preferably 70% by mass to 85% by mass, based on the total mass of the composition.

[pH]
The pH of the composition according to the invention may be from 3 to 9, preferably from 3.3 to 8.5, more preferably from 3.5 to 8.

At a pH of 3 to 9, the polyion complex formed by components (a) to (c) can be very stable.

The pH of the composition according to the present invention can be adjusted by adding at least one alkaline agent and/or at least one acid other than (c) a non-polymeric acid or a salt thereof having two or more pKa values. The pH of the composition according to the present invention can also be adjusted by adding at least one buffering agent.

(Alkaline agent)
The composition according to the present invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

The alkaline agent may be an inorganic alkaline agent. It is preferred that the inorganic alkaline agent is selected from the group consisting of ammonia; alkali metal hydroxides; alkaline earth metal hydroxides; alkali metal phosphates and monohydrogen phosphates, such as sodium phosphate or sodium monohydrogen phosphate.

Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. As an inorganic alkaline agent, sodium hydroxide is preferred.

The alkaline agent may be an organic alkaline agent. It is preferable that the organic alkaline agent is selected from the group consisting of monoamines and derivatives thereof, diamines and derivatives thereof, polyamines and derivatives thereof, basic amino acids and derivatives thereof, oligomers of basic amino acids and derivatives thereof, polymers of basic amino acids and derivatives thereof, urea and derivatives thereof, and guanidine and derivatives thereof.

Examples of organic alkaline agents include alkanolamines, such as mono-, di- and tri-ethanolamine, and isopropanolamine; urea, guanidine and their derivatives; basic amino acids, such as lysine, ornithine or arginine; and diamines, such as those having the structure:

(wherein R represents an alkylene, such as propylene, optionally substituted with a hydroxyl group or a _C1 -C4 alkyl group; _R1 , _R2 , _R3 and _R4 independently represent a hydrogen atom, an alkyl group or a _C1 - _{C4 hydroxyalkyl} group, which can be exemplified by 1,3-propanediamine and its derivatives).
Preferred are arginine, urea and monoethanolamine.

Depending on their solubility, the alkaline agents can be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, more preferably 0.03% to 5% by weight, based on the total weight of the composition.

(acid)
The composition according to the invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.

The acid may be any inorganic or organic acid commonly used in cosmetics, preferably an inorganic acid. Monobasic and/or polybasic acids may be used. Monobasic acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) may be used. HCl is preferred.

Depending on their solubility, the acids may be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, more preferably 0.03% to 5% by weight, based on the total weight of the composition.

(Buffer)
The composition according to the invention may comprise at least one buffering agent. Two or more buffering agents may be used in combination. Thus, a single type of buffering agent or a combination of different types of buffering agents may be used.

Buffers include acetate buffers (e.g., acetic acid + sodium acetate), phosphate buffers (e.g., sodium dihydrogen phosphate + disodium hydrogen phosphate), citrate buffers (e.g., citric acid + sodium citrate), borate buffers (e.g., boric acid + sodium borate), tartrate buffers (e.g., tartaric acid + sodium tartrate dihydrate), Tris buffers (e.g., tris(hydroxymethyl)aminomethane), and Hepes buffers (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[oil]
The composition according to the invention may comprise (f) at least one oil. When two or more oils are used, they may be the same or different.

In this specification, "oil" means a fatty compound or substance that is in the form of a liquid or paste (non-solid) at atmospheric pressure (760 mmHg) and at room temperature (25°C). As oils, those commonly used in cosmetics can be used, alone or in combination. These oils can be volatile or non-volatile.

(f) The oil may be a non-polar oil, such as a hydrocarbon oil, a silicone oil, or the like; a vegetable oil or an animal oil, and a polar oil, such as an ester oil or an ether oil, or a mixture thereof.

(f) The oil may be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

Examples of vegetable oils include, for example, apricot oil, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.

Examples of animal oils include squalene and squalane.

Examples of synthetic oils include alkane oils, such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

The ester oil is preferably a liquid ester of a saturated or unsaturated, linear or branched, _C1 - _C26 aliphatic mono- or polyacid and a saturated or unsaturated, linear or branched, _C1 - _C26 aliphatic mono- or polyalcohol, the total number of carbon atoms in the ester being 10 or more.

Preferably, in the case of esters of monohydric alcohols, at least one of the alcohols and acids from which the esters of the invention are derived is branched.

Among the monoesters of monoacids and monohydric alcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates, such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C ₄ -C ₂₂ di- or tricarboxylic acids with C ₁ -C ₂₂ alcohols, as well as esters of mono-, di- or tricarboxylic acids with non-sugar C ₄ -C ₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.

In particular, mention may be made of diethyl sebacate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, bis(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl glycol diheptanoate, and diethylene glycol diisononanoate.

As ester oils, sugar esters and diesters of _C6 - _C30 , preferably _C12 - _C22, fatty acids can be used. It is recalled that the term "sugar" means an oxygen-bearing hydrocarbon-based compound containing at least 4 carbon atoms, with or without aldehyde or ketone functions, and containing several alcohol functions. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned are sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, as well as their derivatives, in particular alkyl derivatives, such as methyl derivatives, for example methylglucose.

The sugar esters of fatty acids may in particular be chosen from the group comprising esters or mixtures of esters of the aforementioned sugars with linear or branched, saturated or unsaturated _C6 - _C30 , preferably _C12 - _C22 fatty acids. These compounds, when unsaturated, may have from 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

The esters according to this variant can also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleic acid esters, lauric acid esters, palmitic acid esters, myristic acid esters, behenic acid esters, coconut oil fatty acid esters, stearic acid esters, linoleic acid esters, linolenic acid esters, capric acid esters and arachidonic acid esters, or mixtures thereof, such as, in particular, the mixed esters of oleopalmitic acid, oleostearic acid and palmitostearic acid, and pentaerythrityl tetraethylhexanoate.

More particularly, mono- and diesters are used, in particular the mono- or dioleate, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates of sucrose, glucose or methylglucose.

An example that may be mentioned is methylglucose dioleate, the product sold under the name Glucate® DO by the company Amerchol.

Examples of preferred ester oils include, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/2-ethylhexyl caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, Examples of the glyceryl stearate include isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, cetearyl isononanoate, and mixtures thereof.

Examples of artificial triglycerides include capryl caprylyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, tri(capric/caprylic)glyceryl, and tri(capric/caprylic/linolenic)glyceryl.

Examples of silicone oils include linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, etc.; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc., and mixtures thereof.

Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS), and liquid polyorganosiloxanes containing at least one aryl group.

These silicone oils may also be organically modified. The organically modified silicones that may be used in the present invention are silicone oils as defined above and which contain in their structure one or more organic functional groups that are linked via a hydrocarbon-based group.

Organopolysiloxanes are defined in more detail in Chemistry and Technology of Silicones by Walter Noll (1968), Academic Press. They may be volatile or nonvolatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point between 60° C. and 260° C., and even more particularly chosen from:
(i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5, silicon atoms. These are, for example, octamethylcyclotetrasiloxane, sold in particular under the name Volatile Silicone® 7207 by Union Carbide or under the name Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane, sold in particular under the name Volatile Silicone® 7158 by Union Carbide and under the name Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane, sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, for example of the formula:

Mention may also be made of Silicone Volatile® FZ 3109 sold by the company Union Carbide.
Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as a mixture (50/50) of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol, and a mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis(2,2,2',2',3,3'-hexatrimethylsilyloxy)neopentane;
(ii) Linear, volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5 x ^{10-6 m2} /s at 25°C. An example is decamethyltetrasiloxane, sold in particular under the name SH 200 by Toray Silicone. Silicones belonging to this category are also described in an article published in Cosmetics and Toiletries, Vol. 91, January 1976, pages 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM Standard 445, Annex C.

Non-volatile polydialkylsiloxanes can also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, but is not limited to, the following commercial products:
Silbione® oils of the 47 and 70047 series or Mirasil® oils sold by the company Rhodia, such as, for example, 70047 V 500000 oil;
the Mirasil® series of oils sold by the company Rhodia;
- Dow Corning 200 series oils, for example DC200, with a viscosity of 60,000 ^mm2 /s, as well as
- Viscasil® oils manufactured by General Electric and certain oils of the SF series manufactured by General Electric (SF 96, SF 18).

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the 48 series oils from Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes, such as phenylsilicone oils.

Phenyl silicone oil has the formula:

(Wherein,
R ₁ to R ₁₀ are each independently a saturated or unsaturated, linear, cyclic or branched C ₁ to C ₃₀ hydrocarbon-based group, preferably a C ₁ to C ₁₂ hydrocarbon-based group, more preferably a C ₁ to C ₆ hydrocarbon-based group, in particular a methyl, ethyl, propyl or butyl group;
m, n, p and q are each independently an integer from 0 to 900, inclusive, preferably from 0 to 500, inclusive, more preferably from 0 to 100, inclusive;
However, the sum n+m+q is not 0.
The phenyl silicone may be selected from the group consisting of phenyl silicones.

Examples that may be mentioned are products sold under the following names:
- Rhodia Silbione® oils, 70641 series;
Rhodorsil® 70633 and 763 series oils from Rhodia,
- Dow Corning oil Dow Corning 556 Cosmetic Grade Fluid,
- PK series silicones from Bayer, e.g. product PK20,
- Certain oils of the SF series manufactured by General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (in the above formula, R ₁ to R ₁₀ are methyl, p, q and n=0, and m=1) is preferred.

Organo-modified liquid silicones may contain in particular polyethyleneoxy and/or polypropyleneoxy groups. Thus, silicone KF-6017 proposed by Shin-Etsu Chemical Co., Ltd. and Silwet® L722 and L77 oils manufactured by Union Carbide can be mentioned.

The hydrocarbon oil may be chosen from:
- linear or branched, optionally cyclic, C ₆ -C ₁₆ lower alkanes, examples which may be mentioned include hexane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isododecane and isodecane;
- Linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes, such as Parleam®, and squalane.

Preferred examples of hydrocarbon oils include, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (e.g., liquid paraffin), paraffin, petrolatum or petrolatum, naphthalene, etc.; hydrogenated polyisobutene, isoeicosane, and decene/butene copolymers; and mixtures thereof.

The term "fatty" in fatty alcohols refers to the inclusion of a relatively large number of carbon atoms. Thus, alcohols having 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are included within the scope of fatty alcohols. Fatty alcohols may be saturated or unsaturated. Fatty alcohols may be linear or branched.

The fatty alcohols can have the structure R-OH, where R is selected from saturated and unsaturated, linear and branched groups containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to ₂₀ carbon atoms. In at least one embodiment, R can be selected from _C12 - _C20 alkyl groups and _C12 -C20 alkenyl groups. R can be unsubstituted or substituted with at least one hydroxyl group.

Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

The fatty alcohol is preferably a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from linear or branched, saturated or unsaturated _C6 - _C30 alcohols, preferably linear or branched, saturated _C6 - _C30 alcohols, more preferably linear or branched, saturated _C12 - _C20 alcohols.

The term "saturated fatty alcohol" means herein an alcohol with a long aliphatic saturated carbon chain. The saturated fatty alcohol is preferably selected from any linear or branched, saturated C6- _C30 fatty alcohol. Among the linear or branched, saturated _C6 - _C30 fatty alcohols, linear or branched, saturated _C12 - _C20 fatty alcohols may be preferably used. _Any linear or branched, saturated _C16 - _C20 fatty alcohol may be more preferably used. Branched _C16 - _C20 fatty alcohols may be even more preferably used.

Examples of saturated fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (e.g., cetearyl alcohol), and behenyl alcohol may be used as the saturated fatty alcohol.

According to at least one embodiment, the fatty alcohols used in the compositions according to the invention are preferably selected from octyldodecanol, hexyldecanol, and mixtures thereof.

According to the present invention, the (f) oil may be surrounded by a plurality of polyion complex particles, or the (f) oil may be present within a hollow portion of a capsule formed by the polyion complex particles. In other words, the (f) oil may be coated by the polyion complex particles, or the capsule formed by the polyion complex particles contains the (f) oil within the hollow portion of the capsule.

(f) Oil surrounded by the polyion complex particles or present in the hollow portion of the capsule formed by the polyion complex particles cannot directly come into contact with keratinous materials such as skin. Therefore, even if (b) Oil has a sticky or oily feel when used, the composition according to the present invention does not cause a sticky or oily feel when used.

The amount of oil (f) in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of (f) oil in the composition according to the present invention may be 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total mass of the composition.

The amount of oil (f) in the composition according to the present invention may be from 0.01% to 50% by mass, preferably from 0.05% to 40% by mass, and more preferably from 0.1% to 30% by mass, based on the total mass of the composition.

[Optional ingredients]
In addition to the above-mentioned essential components, the composition according to the present invention may contain at least one optional component typically used in cosmetics, which may specifically include surfactants or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents, such as polyols, particularly (f) glycols other than oils, silicones and silicone derivatives, natural extracts derived from animals or plants, waxes, fillers, UV screening agents, etc., within the range that does not impair the effects of the present invention.

The composition according to the present invention may contain the above optional components in an amount of 0.01% to 50% by weight, preferably 0.05% to 30% by weight, more preferably 0.1% to 10% by weight, based on the total weight of the composition.

However, it is preferred that the compositions according to the invention contain a very limited amount of surfactant or emulsifier. The amount of surfactant or emulsifier in the compositions according to the invention may be 1% by weight or less, preferably 0.1% by weight or less, more preferably 0.01% by weight or less, relative to the total weight of the composition. It is particularly preferred that the compositions according to the invention do not contain surfactants or emulsifiers.

[Composition]
The composition according to the present invention may be intended to be used as a cosmetic composition. Therefore, the cosmetic composition according to the present invention may be intended to be applied to keratinous materials. Keratinous materials herein mean materials that contain keratin as a main component, examples of which include skin, scalp, nails, lips, hair, etc. Therefore, it is preferred that the cosmetic composition according to the present invention is used for a cosmetic method for keratinous materials, particularly skin.

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

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

The compositions according to the present invention can be prepared by simple or easy mixing using conventional mixing means such as a stirrer. Therefore, strong shear, for example with a homogenizer, is not required. Also, heating is not required.

When the composition according to the present invention contains (f) oil, the oil can be in the form of an emulsion, an O/W emulsion, or a W/O emulsion. It is preferable that the composition according to the present invention is in the form of an O/W emulsion, because the O/W emulsion form can impart a refreshing sensation due to (e) water forming the external phase.

It is more preferred that the amount of surfactant or emulsifier in the emulsion, specifically the O/W emulsion, is 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, based on the total weight of the composition, since surfactants can adversely affect water resistance. It is particularly preferred that the emulsion, specifically the O/W emulsion, is free of surfactants or emulsifiers.

[Coating]
The composition according to the present invention can be used to easily prepare a film, referred to as a film according to the present invention. (a) a cationic polymer and (b) an anionic polymer capable of forming a polyion complex, and (c) a non-polymeric acid or its salt having two or more pKa values, can be combined to form a continuous film.

The present invention therefore also relates to a method for preparing a film, preferably a decorative film, optionally having a thickness of more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more, comprising:
applying a composition according to the invention onto a substrate, preferably a keratinous material, more preferably the skin;
and drying said composition.

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

Because the above-mentioned method for preparing a film according to the present invention includes a step of applying a composition according to the present invention onto a substrate, preferably a keratinous material, more preferably onto the skin, and a step of drying the composition, the method according to the present invention does not require any spin coating or spraying, and therefore even a relatively thick film can be easily prepared. Therefore, the method for preparing a film according to the present invention can prepare a relatively thick film without using any special equipment such as a spin coater or a sprayer.

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

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

If the substrate is not a keratinous material, it is preferred that the substrate is water-soluble, since it is possible to leave behind a coating according to the invention by washing the substrate with water. Examples of water-soluble materials include poly(meth)acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate, etc. PVA is preferred.

When the non-keratin substrate is in the form of a sheet, the substrate may have a thickness that exceeds the thickness of the coating according to the present invention in order to facilitate handling of the coating attached to the substrate sheet. The thickness of the non-keratin substrate sheet is not limited, but may be from 1 μm to 5 mm, preferably from 10 μm to 1 mm, more preferably from 50 to 500 μm.

It is more preferred that the coating according to the present invention is removable from the non-keratin substrate. The method of removal is not limited. Thus, the coating according to the present invention may be peeled off from the non-keratin substrate, or may be removed by dissolving the substrate sheet in a solvent such as water.

The present invention also provides
(1) A coating, preferably a decorative coating, optionally having a thickness of preferably more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more,
applying a composition according to the invention onto a substrate, preferably a keratinous material, more preferably the skin;
and drying said composition.
as well as
(2) A film, preferably a cosmetic film, optionally having a thickness of preferably more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more, comprising: (a) at least one cationic polymer; (b) at least one anionic polymer; (c) at least one non-polymeric acid or salt thereof having two or more pKa values; and optionally (f) at least one oil,
(b) It may concern a film, preferably a cosmetic film, in which the anionic polymer is selected from hyaluronic acid and its derivatives.

The above explanations regarding (a) cationic polymers and (b) anionic polymers, (c) non-polymeric acids or salts thereof having two or more pKa values, and (f) oils can be applied to the above coatings (1) and (2).

The coating according to the present invention thus obtained above can be self-supporting. The term "self-supporting" means in this specification that the coating according to the present invention can be in the form of a sheet and can be handled as an independent sheet without the aid of a substrate or support. Therefore, the term "self-supporting" can have the same meaning as "self-supporting".

It is preferred that the coating according to the present invention is hydrophobic.

The term "hydrophobic" as used herein means that the solubility of the polymer in water (preferably in a volume of 1 liter) at 20-40°C, preferably 25-40°C, more preferably 30-40°C, is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, based on the total weight of the polymer. Most preferably, the polymer is not soluble in water.

When the film according to the present invention is hydrophobic, the film can have water-resistant properties and can therefore remain on the keratinous material, such as the skin, even when the surface of the keratinous material is wet, for example, from sweat and rain. Therefore, when the film according to the present invention provides any cosmetic effect, the cosmetic effect can last for a long time.

On the other hand, the film according to the present invention can be easily removed from keratinous materials such as skin under alkaline conditions, such as a pH of 8 to 12, preferably 9 to 11. Thus, the film is difficult to remove with water, but can be easily removed with soap that can provide such alkaline conditions.

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

As used herein, the term "biocompatible" polymer means that the polymer does not have excessive interactions between the polymer and cells in the body, including the skin, and that the polymer is not recognized as foreign by the body.

As used herein, the term "biodegradable" polymer means that the polymer can be broken down or broken down in the body, for example by the metabolism of the body itself or by the metabolism of microorganisms that may be present in the body. Biodegradable polymers can also be broken down by hydrolysis.

When the coating according to the present invention comprises a biocompatible and/or biodegradable polymer, the coating causes little or no irritation to the skin and does not cause any rashes. In addition, due to the use of biocompatible and/or biodegradable polymers, the coating according to the present invention can adhere well to the skin.

The film according to the invention can be used for the cosmetic treatment of keratinous materials, preferably the skin, in particular the face. The film according to the invention can be in any shape or form. For example, the film can be used as a full face mask sheet or a patch for parts of the face, such as the cheeks, nose, and around the eyes.

When the film according to the present invention contains at least one hydrophilic or water-soluble UV blocking agent, the film can provide a UV blocking effect derived from the hydrophilic or water-soluble UV blocking agent. Normally, hydrophilic or water-soluble UV blocking agents can be removed from the surface of a keratin substrate such as skin by water such as sweat and rain. However, since the hydrophilic or water-soluble UV blocking agent is contained in the film, it is difficult to remove the hydrophilic or water-soluble UV blocking agent by water, and thus a long-lasting UV blocking effect can be obtained.

[Cosmetic methods and uses]
The present invention also provides
a cosmetic method for keratinous materials such as skin, comprising the steps of applying to the keratinous materials a composition according to the present invention and drying the composition to form a cosmetic film on the keratinous materials;
It also relates to the use of the composition according to the invention for preparing a cosmetic film on keratinous materials such as the skin.

Cosmetic method means in this specification a non-therapeutic cosmetic method for caring for and/or making up the surface of a keratinous material such as the skin.

In both the above method and use, the decorative film is resistant to water having a pH of 7 or less and is removable with water having a pH of greater than 7, preferably 8 or more, more preferably 9 or more.

In other words, the decorative coating can be water-resistant under neutral or acidic conditions, such as a pH of 7 or less, preferably in the range of 6 to 7, more preferably in the range of 5 to 7, while the decorative coating can be removed under alkaline conditions, such as a pH of more than 7, preferably 8 or more, more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, even more preferably 11.

Accordingly, the cosmetic film can be water-resistant and therefore can remain on the keratinous material, such as the skin, even when the surface of the keratinous material is wet, for example, due to sweat and rain. On the other hand, the cosmetic film can be easily removed from the keratinous material, such as the skin, under alkaline conditions. Thus, the film according to the present invention is difficult to remove with water, but can be easily removed with soap that can provide alkaline conditions.

When the cosmetic film comprises a UV filter, which may be present in the composition according to the invention, the cosmetic film can protect keratinous materials, such as skin, from UV radiation, thereby reducing skin darkening, improving skin tone and evenness, and/or treating skin aging.

Furthermore, the cosmetic film described above may have cosmetic effects such as capturing sebum, imparting a matte appearance to keratinous substrates such as skin, absorbing or adsorbing odors, and/or protecting keratinous materials from, for example, dirt or pollutants, due to the properties of the polyion complex particles in the cosmetic film, even if the cosmetic film does not contain any cosmetic active ingredients.

In addition, the cosmetic film can instantly change or modify the appearance of the skin, such as by changing the light reflection on the skin, even if the cosmetic film does not contain any cosmetic active ingredients. Thus, the cosmetic film can be capable of hiding skin imperfections such as pores or wrinkles. Furthermore, the cosmetic film can instantly change or modify the feel of the skin, such as by changing the surface roughness on the skin. Furthermore, the cosmetic film can instantly protect the skin from environmental stresses, such as pollutants, impurities, etc., by covering the surface of the skin and shielding the skin as a barrier.

The above cosmetic effects can be adjusted or controlled by varying the chemical composition, thickness and/or surface roughness of the above cosmetic coating.

When the cosmetic film includes at least one additional cosmetic active ingredient other than (f) oil, the cosmetic film can have a cosmetic effect brought about by the additional cosmetic active ingredient. For example, when the cosmetic film includes at least one cosmetic active ingredient selected from an anti-aging agent, a sebum suppressant, a deodorant agent, an antiperspirant, a whitening agent, and mixtures thereof, the cosmetic film can treat skin aging, absorb sebum on the skin, control odor on the skin, control sweat on the skin, and/or whiten the skin.

After application onto the skin, it is also possible to apply a makeup cosmetic composition onto the cosmetic film or cosmetic sheet according to the present invention.

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

(Examples 1 to 3 and Comparative Examples 1 to 4)
[Preparation]
Each of the compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 was prepared by mixing the ingredients shown in Table 1 according to the following steps 1 to 8.
1. Mix ingredients for Phase A and homogenize at 75°C +/- 5°C to obtain Phase A mixture.
2. The ingredients for Phase B were added to the Phase A mixture obtained in step 1 and homogenized at 75°C +/- 5°C to obtain a mixture of Phase A and Phase B.
3. Add ingredients for Phase C to the above mixture of Phase A and Phase B obtained through step 2 and homogenize at 75°C +/- 5°C to obtain a mixture of Phases A, B and C.
4. The ingredients for Phase D are added to the above mixture of Phases A, B and C obtained by step 3 and homogenized at 75°C +/- 5°C to obtain a mixture of Phases A, B, C and D.
5. Add ingredients for Phase E to the above mixture of Phases A, B, C and D obtained through step 4 and homogenize at 75°C +/- 5°C to obtain a mixture of Phases A, B, C, D and E.
6. Add ingredients for Phase F to the above mixture of Phases A, B, C, D and E obtained through step 5 and homogenize at 75°C +/- 5°C to obtain a mixture of Phases A, B, C, D, E and F.
7. Add ingredients for Phase G to the above mixture of Phases A, B, C, D, E and F obtained through step 6 and homogenize at room temperature to obtain a mixture of Phases A, B, C, D, E, F and G.
8. The ingredients for Phase H are added to the above mixture of Phases A, B, C, D, E, F and G obtained from step 7 and homogenized at room temperature to obtain a homogenous composition.

All values for ingredient amounts in Table 1 are based on "wt%" of active material.

(a) to (f) in Table 1 correspond to what is in the claims.

Particle size: Number average particle size determined by microscope

[evaluation]
(Sebum control)
Each of the compositions according to Examples 1-3 and Comparative Examples 1-4 was spread over the entire contrast sheet by an automatic film applicator to form a layer of 100 μm, and left to dry at 37° C. for 24 hours. Then, an artificial sebum/sweat composition having the formulation shown in Table 2 below was sprayed onto the above layer on the contrast card at room temperature. The amount of the artificial sebum/sweat composition sprayed onto each of the above layers was the same as each other.

After 24 hours, the surface roughness of the layer was observed by confocal microscopy and was evaluated according to the following criteria:
Good: High surface roughness Bad: Low surface roughness

A high surface roughness means that the layer absorbed the artificial sebum/sweat composition and kept it therein for a long time. A high surface roughness is also good for showing a matte effect. Therefore, a high surface roughness reflects a good sebum control effect.

The compositions according to Examples 1 to 3 were able to form a sufficiently rough surface. On the other hand, the compositions according to Comparative Examples 1 to 4 were unable to form a sufficiently rough surface. These results reflect that the combination of a polyion complex and a highly absorbent polymer can provide an enhanced anti-sebum effect, which can contribute to a matte appearance.

(noodle)
The artificial sebum/sweat composition shown in Table 2 above was applied onto Bioskin. Next, each of the compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto Bioskin, spread with a finger, and then dried at 40°C. Next, foundation was applied thereon and rubbed. The formation of noodles of the foundation was evaluated according to the following criteria.
Good: No or only slight noodle observed. Bad: Significant noodle observed.

Noodles: Agglomerates that appear as eraser residues produced during application.

The compositions according to Examples 1-3 caused little or no noodle formation. On the other hand, the compositions according to Comparative Examples 1-3 caused a significant amount of noodle formation. These results reflect that the polyion complex can inhibit the formation of noodle formation.

(Stability)
Each of the compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 was stored in a transparent container for two months at 45° C. The stability of the compositions was visually observed and evaluated according to the following criteria.
Good: The composition homogeneity was maintained.
Poor: The homogeneity of the composition was not maintained (water release or phase separation was noticeable).

The results are shown in Table 1.

The compositions according to Examples 1 to 3 were stable. On the other hand, the composition according to Comparative Example 4 was unstable. These results reflect that the superabsorbent polymer can enhance the stability of compositions containing polyion complexes.

Claims (15)

(a) at least one cationic polymer;
(b) at least one anionic polymer;
(c) at least one non-polymeric acid or salt thereof having two or more pKa values;
(d) at least one superabsorbent polymer;
(e) water,
(b) the anionic polymer is selected from hyaluronic acid and its derivatives;
(d) the superabsorbent polymer is in the form of particles having an average particle size of 5 μm to 500 μm, preferably 10 μm to 400 μm, more preferably 15 μm to 300 μm;
Composition. The composition according to claim 1, wherein (a) the cationic polymer has a portion that can have and/or has at least one positive charge 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 composition according to claim 1 or 2, wherein the (a) cationic polymer is selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as chitosan and (co)polylysine, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof. The composition according to any one of claims 1 to 3, wherein the amount of (a) cationic polymer is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, based on the total mass of the composition. (b) The composition according to any one of claims 1 to 4, comprising as an anionic polymer at least two types of hyaluronic acid having different molecular weights, preferably a first hyaluronic acid having a molecular weight of 100 kDa or less and a second hyaluronic acid having a molecular weight of 500 kDa or more, more preferably a first hyaluronic acid having a molecular weight of 50 kDa or less and a second hyaluronic acid having a molecular weight of 1000 kDa or more. (b) The composition according to any one of claims 1 to 5, wherein the amount of the anionic polymer is from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, based on the total weight of the composition. (c) The composition according to any one of claims 1 to 6, wherein the non-polymeric acid or its salt having two or more pKa values is an organic acid or its salt, preferably a hydrophilic or water-soluble organic acid or its salt, more preferably phytic acid or its salt. (c) The composition according to any one of claims 1 to 7, wherein the amount of the non-polymeric acid or salt thereof having two or more pKa values is 0.01% to 15% by weight, preferably 0.05% to 10% by weight, more preferably 0.1% to 5% by weight, based on the total weight of the composition. (d) The composition according to any one of claims 1 to 8, wherein the superabsorbent polymer is selected from crosslinked (meth)acrylic or (meth)acrylate polymers, starch grafted with acrylic or (meth)acrylate polymers, and mixtures thereof. (d) The composition according to any one of claims 1 to 9, wherein the amount of superabsorbent polymer is 0.01% to 15% by weight, preferably 0.05% to 10% by weight, more preferably 0.1% to 5% by weight, based on the total weight of the composition. (e) The composition according to any one of claims 1 to 10, wherein the amount of water is 50% by weight to 95% by weight, preferably 60% by weight to 90% by weight, more preferably 70% by weight to 85% by weight, based on the total weight of the composition. The composition according to any one of claims 1 to 11, having a pH of 3 to 9, preferably 3.3 to 8.0, more preferably 3.5 to 8. (f) The composition according to any one of claims 1 to 12, further comprising at least one oil. The composition according to any one of claims 1 to 13, which is a cosmetic composition, preferably a skin cosmetic composition, more preferably a skin care cosmetic composition. A cosmetic method for keratinous materials such as skin, comprising:
applying to a keratinous substance a composition according to any one of claims 1 to 14;
and drying the composition to form a cosmetic film on the keratinous material.