FR3145281A1 - COMPOSITION COMPRISING A POLYIONIC COMPLEX BASED ON HYALURONIC ACID AND A HYDROPHILIC ANTIOXIDANT - Google Patents

Abstract

Composition comprising a polyionic complex based on hyaluronic acid and a hydrophilic antioxidant The present invention relates to a composition comprising: (a) at least one complex comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer, or at least one amphoteric polymer, and at least one non-polymeric acid having two or more pKa values or one or more salts thereof or at least one non-polymeric base having two or more pKb values or one or more salts thereof; (b) at least one lipophilic antioxidant; and (c) water, wherein the anionic polymer is selected from hyaluronic acid, salts thereof and derivatives thereof, and the amphoteric polymer is selected from cationic hyaluronic acid and salts thereof. The composition according to the present invention may be transparent or translucent and may provide long-lasting antioxidant effects. Figure for abstract: none

Description

COMPOSITION COMPRISING A POLYIONIC COMPLEX BASED ON HYALURONIC ACID AND A HYDROPHILIC ANTIOXIDANT

The present invention relates to a composition including a polyionic complex and a film of a polyionic complex, as well as a method of preparing a film using a polyionic complex and a cosmetic method using a polyionic complex.

PRIOR ART

Hyaluronic acid is a predominant glucosaminoglycan found in the skin. Thus, fibroblasts mainly synthesize collagens, non-collagen matrix glycoproteins (fibronectin, laminin), proteoglycans, and elastin. Keratinocytes, on the other hand, mainly synthesize sulfated glycosaminoglycans and hyaluronic acid. Hyaluronic acid is also called hyaluronan (HA).

Hyaluronic acid is present in the free state in the epidermis and dermis and is responsible for the turgor of the skin. This polysaccharide can in fact retain a large volume of water, corresponding to up to 1000 times its weight. In this sense, hyaluronic acid plays an important role in increasing the amounts of bound water in tissues, as well as in the mechanical properties of the skin and in the formation of wrinkles.

Hyaluronic acid is widely used as a cosmetic ingredient due to its high moisturizing effects.

However, an aqueous solution of hyaluronic acid is sticky, which can result in an uncomfortable texture. Additionally, a hyaluronic acid film, which forms when an aqueous solution of hyaluronic acid dries on the skin, is sticky, and this film can also result in an uncomfortable texture.

WO 2021/125069 discloses the reduction of stickiness due to hyaluronic acid by forming a polyionic complex particle with a cationic polymer and hyaluronic acid as an anionic polymer.

DISCLOSURE OF THE INVENTION

It is necessary to propose a composition including a polyionic complex based on hyaluronic acid, which can be transparent or translucent and can offer long-lasting antioxidant effects.

Thus, a first objective of the present invention is to provide a composition which can be transparent or translucent and can provide long-lasting antioxidant effects.

1. au moins un complexe polyionique, comprenant

The above objective of the present invention can be achieved by a composition, comprising:

1. at least one polyionic complex, comprising

at least one cationic polymer and at least one anionic polymer,

at least one cationic polymer and at least one amphoteric polymer,

at least one anionic polymer and at least one amphoteric polymer, or

at least one amphoteric polymer,

And
at least one non-polymeric acid having two or more pKa values or salt(s) thereof, or

1. au moins un antioxydant hydrophile ; et
2. de l'eau,

at least one non-polymeric base having two or more pKb values or salt(s) thereof;

1. at least one hydrophilic antioxidant; and
2. water,

in which

the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives, and

the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

The cationized hyaluronic acid may have at least one group containing a quaternary ammonium group and has a degree of cationization of 0.05 to 0.6, preferably 0.1 to 0.5 and more preferably 0.15 to 0.4.

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

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

The total amount of the cationic and/or anionic and/or amphoteric polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.

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

The amount of the non-polymeric acid having two or more pKa values or salt(s) thereof or non-polymeric base having two or more pKb values or salt(s) thereof in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.

The hydrophilic antioxidant (b) may be selected from ascorbic acid, derivatives thereof, salts thereof and mixtures thereof.

The amount of the hydrophilic antioxidant (b) in the composition according to the present invention may be from 0.01% to 30% by weight, preferably from 0.05% to 25% by weight and more preferably from 0.1% to 20% by weight, relative to the total weight of the composition.

The amount of water (c) in the composition according to the present invention may be from 10% to 99% by weight, preferably from 30% to 97% by weight and more preferably from 50% to 95% by weight, relative to the total weight of the composition.

The composition according to the present invention may further comprise (d) at least one surfactant, preferably chosen from nonionic surfactants and more preferably chosen from fatty acid polyglyceryl esters.

A second objective of the present invention is to provide a method for preparing a film capable of providing long-lasting antioxidant effects.

The above objective of the present invention can be achieved by a method of preparing a film, preferably a cosmetic film, comprising:

the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

drying the composition.

A third objective of the present invention is to provide a film capable of providing long-lasting antioxidant effects.

1. Un film, de préférence un film cosmétique, préparé par un procédé comprenant :

The above objective of the present invention can be achieved by:

1. A film, preferably a cosmetic film, prepared by a process comprising:

the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

drying the composition,

1. Un film, de préférence un film cosmétique, comprenant :

Or

1. A film, preferably a cosmetic film, comprising:

(a) at least one polyionic complex, comprising

at least one cationic polymer and at least one anionic polymer,

at least one cationic polymer and at least one amphoteric polymer,

at least one anionic polymer and at least one amphoteric polymer, or

at least one amphoteric polymer, and

at least one non-polymeric acid having two or more pKa values or salt(s) thereof, or

at least one non-polymeric base having two or more pKb values or salt(s) thereof;

(b) at least one hydrophilic antioxidant;

And

optionally (d) at least one surfactant, preferably chosen from nonionic surfactants and more preferably chosen from polyglyceryl esters of fatty acids,

in which

the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives; and

the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

The present invention also relates to a cosmetic process for a keratinous substance such as skin, comprising

the application to the keratinous substance of the composition according to the present invention; and

drying the composition to form a cosmetic film on the keratinous substance.

1. au moins un complexe polyionique, comprenant

After careful research, the inventors have discovered that it is possible to provide a composition which can be transparent or translucent and can provide long-lasting antioxidant effects. Thus, the composition according to the present invention comprises:

1. at least one polyionic complex, comprising

at least one cationic polymer and at least one anionic polymer,

at least one cationic polymer and at least one amphoteric polymer,

at least one anionic polymer and at least one amphoteric polymer, or

at least one amphoteric polymer,

And
at least one non-polymeric acid having two or more pKa values or salt(s) thereof, or

1. au moins un antioxydant hydrophile ; et
2. de l'eau,

at least one non-polymeric base having two or more pKb values or salt(s) thereof;

1. at least one hydrophilic antioxidant; and
2. water,

in which

the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives, and

the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

Furthermore, the inventors have discovered that it is possible to provide a method for preparing a film that can produce long-lasting antioxidant effects. Thus, the method according to the present invention is a method for preparing a film, preferably a cosmetic film, the method comprising:

the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

drying the composition.

1. Un film, de préférence un film cosmétique, préparé par un procédé comprenant :

Furthermore, the inventors have discovered that it is possible to provide a film which can provide long-lasting antioxidant effects. Thus, the film according to the present invention is

1. A film, preferably a cosmetic film, prepared by a process comprising:

the application to a substrate, preferably a keratinous substance, of the composition according to the present invention; and

drying the composition,

1. Un film, de préférence un film cosmétique, comprenant :

Or

1. A film, preferably a cosmetic film, comprising:

(a) at least one polyionic complex, comprising

at least one cationic polymer and at least one anionic polymer,

at least one cationic polymer and at least one amphoteric polymer,

at least one anionic polymer and at least one amphoteric polymer, or

at least one amphoteric polymer, and

at least one non-polymeric acid having two or more pKa values or salt(s) thereof, or

at least one non-polymeric base having two or more pKb values or salt(s) thereof;

(b) at least one hydrophilic antioxidant;

And

optionally (d) at least one surfactant, preferably chosen from nonionic surfactants and more preferably chosen from polyglyceryl esters of fatty acids,

in which

the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives; and

the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

The composition and film according to the present invention can be transparent and translucent.

The composition and film according to the present invention can provide long-lasting antioxidant effects.

Thus, the present invention may be useful for protecting skin from damage caused by peroxidation of, for example, unsaturated lipids such as sebum, where the damage may be impaired desquamation, decreased squalene, acne and blackheads, dull skin and aging, such as the formation of wrinkles and/or fine lines.

Furthermore, the composition and film according to the present invention can provide long-lasting cosmetic effects and/or an improved moisturizing texture based on hyaluronic acid or cationized hyaluronic acid.

Furthermore, the stickiness of the composition according to the present invention can be reduced compared to a composition including hyaluronic acid, which does not form a polyionic complex.

A film comprising a polyionic complex, wherein the film may include at least one surfactant, can be readily prepared by applying the composition to a substrate, preferably a keratinous substance such as skin and hair, and more preferably skin, and drying the composition.

The stickiness of the film according to the present invention can be reduced compared to a hyaluronic acid film which does not form a polyionic complex.

The film according to the present invention may be porous. The surface of the film according to the present invention may not be flat but may be rough.

The film according to the present invention can have various cosmetic functions. For example, the film can provide moisturizing effects based on hyaluronic acid or cationized hyaluronic acid in the polyionic complex.

The film according to the present invention is capable of capturing sebum, mattifying the appearance of a keratinous substance such as skin, absorbing or adsorbing bad odor and/or protecting the keratinous substance against dirt or pollutants, for example.

If the film includes at least one cosmetic active ingredient such as oil(s), the film may also have cosmetic effects provided by the cosmetic active ingredient(s). For example, if the polyionic complex film includes at least one cosmetic active ingredient selected from UV filters, anti-aging agents other than the hydrophilic antioxidant (b), anti-sebum agents, deodorant agents, antiperspirant agents, whitening agents, and a mixture thereof, the film may filter UV rays, treat skin aging, absorb sebum on the skin, control odor on the skin, control perspiration on the skin, and/or whiten the skin.

The film according to the present invention may be transparent or translucent and, therefore, may not be easily perceived even when the film is relatively thick.

Furthermore, the film according to the present invention is water-resistant and, therefore, it can remain on a keratinous substance such as skin even if the surface of the keratinous substance is wet due to, for example, sweat or rain.

Furthermore, the film according to the present invention can be easily removed from a keratinous substance such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can provide alkaline conditions.

Thus, if the film according to the present invention includes a hydrophilic or water-soluble UV filter, the film according to the present invention can exhibit UV protection effects that are water-resistant (waterproof) and can be durable, but can be easily removed with soap that can provide alkaline conditions.

The composition, process, film and the like according to the present invention will be described in more detail hereinafter.

[Polyionic complex]

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

The polyionic complex (a) can take the form of a particle.

The size of the polyionic complex particle may be from 5 nm to 100 μm, preferably from 100 nm to 50 μm, more preferably from 200 nm to 40 μm, and even more preferably from 500 nm to 30 μm. A particle size of less than 1 μm may be measured by a dynamic light scattering method, and a particle size of greater than 1 μm may be measured by an optical microscope. This particle size may be based on a number average diameter.

The amount of the polyionic complex(es) (a) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more and more preferably 0.1% by weight or more, relative to the total weight of the composition.

The amount of the polyionic complex(es) (a) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and more preferably 5% by weight or less, relative to the total weight of the composition.

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

1. au moins un polymère cationique et au moins un polymère anionique ;

1. au moins un polymère cationique et au moins un polymère amphotère ;
2. au moins un polymère anionique et au moins un polymère amphotère ; ou
3. au moins un polymère amphotère.

The polyionic complex (a) includes at least one polymer or a combination of polymers. More specifically, the polyionic complex (a) includes:

1. at least one cationic polymer and at least one anionic polymer;

1. at least one cationic polymer and at least one amphoteric polymer;
2. at least one anionic polymer and at least one amphoteric polymer; or
3. at least one amphoteric polymer.

There is no limit on the type of cationic polymers. Two or more different types of cationic polymers can be used in combination. Thus, a single type of cationic polymer or a combination of different types of cationic polymers can be used.

In point (1) above, the ratio of the amount, for example the chemical equivalent, of the cationic polymer(s)/the anionic polymer(s) may be 0.05-18, preferably 0.1-10 and, more preferably, 0.5-5.0. In particular, it may be preferable that the number of cationic groups of the cationic polymer(s)/the number of anionic groups of the anionic polymer(s) is 0.05-18, more preferably, 0.1-10 and even more preferably, 0.5-5.0.

In item (2) above, the ratio of the amount, for example the chemical equivalent, of the cationic polymer(s)/the amphoteric polymer(s) may be 0.05-18, preferably 0.1-10 and more preferably 0.5-5.0. In particular, it may be preferable that the number of cationic groups of the cationic polymer(s)/the number of cationic and anionic groups of the amphoteric polymer(s) is 0.05-18, more preferably 0.1-10 and even more preferably 0.5-5.0.

In item (3) above, the ratio of the amount, for example the chemical equivalent, of the anionic polymer(s)/the amphoteric polymer(s) may be 0.05-18, preferably 0.1-10 and more preferably 0.5-5.0. In particular, it may be preferable that the number of anionic groups of the anionic polymer(s)/the number of cationic and anionic groups of the amphoteric polymer(s) is 0.05-18, more preferably 0.1-10 and even more preferably 0.5-5.0.

The total amount of the polymer(s) according to any one of points (1) to (4) above in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.

The total amount of the polymer(s) according to any one of points (1) to (4) above in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and more preferably 5% by weight or less, relative to the total weight of the composition.

The total amount of the polymer(s) according to any one of points (1) to (4) above in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.

(Cationic polymer)

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

It may be preferable that the molecular weight of the cationic polymer is 500 or more, preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more.

Unless otherwise specified in the descriptions, “molecular weight” means number average molecular weight.

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

The cationic polymer may be a homopolymer or a copolymer. By "copolymer" is meant both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.

1. Homopolymères et copolymères dérivés d’esters et d’amides acryliques ou méthacryliques et comprenant au moins un motif choisi parmi les motifs des formules suivantes :

The cationic polymer may be selected from natural and synthetic cationic polymers. Non-limiting examples of the cationic polymers are as follows.

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

in which:

R ₁ and R ₂ , which may be the same or different, are selected from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms, for example, methyl and ethyl groups;

R ₃ , which may be the same or different, is selected from hydrogen and CH ₃ ;

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

R ₄ , R ₅ and R ₆ , which may be the same or different, are selected from alkyl groups comprising from 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment, alkyl groups comprising from 1 to 6 carbon atoms and

X is an anion derived from an inorganic or organic acid, such as methosulfate anions and halides, e.g. chloride and bromide.

The copolymers of family (1) may also comprise at least one unit derived from comonomers which may be selected from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen atom with C ₁ -C ₄ lower alkyl groups, groups derived from acrylic or methacrylic acids and esters thereof, vinyllactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.

Examples of copolymers of family (1) include, but are not limited to:

copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide,

copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in European patent application No. 0 080 976,

copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate,

quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl methacrylate or acrylate copolymers, described, for example, in French patents Nos. 2,077,143 and 2,393,573,

dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers,

vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers and

1. Polymères de cellulose cationiques tels que les dérivés d’éther de cellulose comprenant un ou plusieurs groupes ammonium quaternaire décrits, par exemple, dans le brevet français n° 1 492 597, tels que les polymères commercialisés sous les noms « JR » (JR 400, JR 125, JR 30M) ou « LR » (LR 400, LR 30M) par la société Union Carbide Corporation. Ces polymères sont également définis dans le dictionnaire CTFA comme des ammoniums quaternaires d'hydroxyéthylcellulose ayant réagi avec un époxyde substitué par un groupe triméthylammonium.

crosslinked polymers of methacryloyloxy(C ₁ -C ₄ )alkyltri(C ₁ -C ₄ )alkylammonium salts such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with a compound containing olefinic unsaturation, in particular methylenebisacrylamide.

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

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

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

in which

each of the groups R ₁ and R ₂ denotes a C _1-3 alkyl group, preferably a methyl or ethyl group and more preferably a methyl group,

R ₃ denotes a C _1-24 alkyl group, preferably a methyl or ethyl group and more preferably a methyl group,

X- denotes an anion, preferably a halide and more preferably a chloride,

n denotes an integer from 0 to 30, preferably from 0 to 10 and more preferably equal to 0, and

R ₄ denotes a C _1-4 alkylene group, preferably an ethylene or propylene group.

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

1. Polymères de cellulose cationiques tels que les copolymères de cellulose et les dérivés de cellulose greffés avec un monomère soluble dans l'eau d’ammonium quaternaire et décrits, par exemple, dans le brevet U.S. n° 4 131 576, tels que les hydroxyalkylcelluloses, par exemple, les hydroxyméthyl-, hydroxyéthyl- et hydroxypropylcelluloses greffées, par exemple, avec un sel choisi parmi les sels de méthacryloyléthyltriméthylammonium, de méthacrylamidopropyltriméthylammonium et de diméthyldiallylammonium.

It is preferred that the group containing the quaternary ammonium group is -O-CH ₂ -CH(OH)-CH ₂ -N ⁺ (CH ₃ ) ₃ .

1. Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and described, for example, in U.S. Patent No. 4,131,576, such as hydroxyalkylcelluloses, for example, hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted, for example, with a salt selected from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium salts.

1. Polysaccharides cationiques non cellulosiques décrits dans les brevets U.S. n° 3 589 578 et 4 031 307, tels que les gommes de guar comprenant des groupes trialkylammonium cationiques, de l’acide hyaluronique cationique et du chlorure de dextrane hydroxypropyl trimonium. Des gommes de guar modifiées avec un sel, par exemple le chlorure, de 2,3-époxypropyltriméthylammonium (chlorure de guar hydroxypropyltrimonium) peuvent également être utilisées.

Commercial products corresponding to these polymers include, for example, the products marketed under the names “Celquat® L 200” and “Celquat® H 100” by the company National Starch.

1. Non-cellulosic cationic polysaccharides described in U.S. Patent Nos. 3,589,578 and 4,031,307, such as guar gums comprising cationic trialkylammonium groups, cationic hyaluronic acid, and dextran hydroxypropyl trimonium chloride. Guar gums modified with a salt, e.g., chloride, of 2,3-epoxypropyltrimethylammonium (guar hydroxypropyltrimonium chloride) may also be used.

1. Des polymères comprenant des motifs pipérazinyle et des groupes alkylène ou hydroxyalkylène divalents comprenant des chaînes droites ou ramifiées, facultativement interrompues avec au moins une entité choisie parmi l’oxygène, le soufre, l’azote, les cycles aromatiques et les cycles hétérocycliques, ainsi que les produits d’oxydation et/ou de quaternisation de ces polymères. Ces polymères sont décrits, par exemple, dans les brevets français n° 2 162 025 et 2 280 361.
2. Polyamino-amides solubles dans l’eau préparés, par exemple, par polycondensation d’un composé acide avec une polyamine ; ces polyamino-amides étant facultativement réticulés avec une entité choisie parmi les épihalohydrines ; les diépoxydes ; les dianhydrides ; les dianhydrides insaturés ; les dérivés biinsaturés ; les bishalohydrines ; les bisazetidiniums ; les bishaloacyidiamines ; les halogénures de bisalkyle ; les oligomères résultant de la réaction d’un composé difonctionnel qui est réactif avec une entité choisie parmi les bishalohydrines ; les bisazétidiniums, les bishaloacyldiamines, les halogénures de bisalkyle ; les épihalohydrines ; les dihydroxydes et les dérivés bisinsaturés ; l’agent de réticulation étant utilisé dans une quantité allant de 0,025 à 0,35 mole par groupe amine du polyaminoamide ; ces polyaminoamides étant facultativement alkylés ou, s’ils comprennent au moins une fonction de amine tertiaire, il peuvent être quaternisés. Ces polymères sont décrits, par exemple, dans les brevets français n° 2 252 840 et 2 368 508.
3. Dérivés polyamino-amides résultant de la condensation de polyamines de polyalkylène avec des acides polycarboxyliques, suivie de l’alkylation avec des agents difonctionnels, par exemple, des polymères d’acide adipique/dialkylaminohydroxyalkyldialkylènetriamine dans lesquels le groupe alkyle comprend de 1 à 4 atomes de carbone, tels que des groupes méthyle, éthyle et propyle, et le groupe alkylène comprend de 1 à 4 atomes de carbone, tels qu’un groupe éthylène. Ces polymères sont décrits, par exemple, dans le brevet français n° 1 583 363. Dans au moins un mode de réalisation, ces dérivés peuvent être choisis parmi des polymères d’acide adipique/diméthylaminohydroxypropyldiéthylènetriamine.
4. Polymères obtenus par réaction d’une polyamine de polyalkylène comprenant deux groupes amine primaires et au moins un groupe amine secondaire, avec un acide dicarboxylique choisi parmi l’acide diglycolique et des acides aliphatiques dicarboxyliques saturés comprenant de 3 à 8 atomes de carbone. Le rapport molaire de la polyamine de polyalkylène sur l’acide dicarboxylique peut aller de 0,8:1 à 1,4:1 ; le polyamino amide résultant de cette réaction avec l’épichlorhydrine dans un rapport molaire de l’épichlorhydrine sur le groupe amine secondaire de la polyamino amide allant de 0,5:1 à 1,8:1. Ces polymères sont décrits, par exemple, dans les brevet U.S. n° 3 227 615 et 2 961 347.
5. Cyclopolymères d’alkyldiallylamine et cyclopolymères de dialkyldiallyl-ammonium, tels que les homopolymères et copolymères comprenant, en tant que constituant principal de la chaîne, au moins un motif parmi les motifs de formules (Ia) et (Ib) :

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

1. Polymers comprising piperazinyl units and divalent alkylene or hydroxyalkylene groups comprising straight or branched chains, optionally interrupted with at least one entity selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, as well as the oxidation and/or quaternization products of these polymers. These polymers are described, for example, in French patents Nos. 2,162,025 and 2,280,361.
2. Water-soluble polyamino amides prepared, for example, by polycondensation of an acidic compound with a polyamine; said polyamino amides being optionally crosslinked with a moiety selected from epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; biunsaturated derivatives; bishalohydrins; bisazetidiniums; bishaloacydiamines; bisalkyl halides; oligomers resulting from the reaction of a difunctional compound which is reactive with a moiety selected from bishalohydrins; bisazetidiniums, bishaloacyldiamines, bisalkyl halides; epihalohydrins; dihydroxides and bisunsaturated derivatives; the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mole per amine group of the polyamino amide; these polyaminoamides being optionally alkylated or, if they comprise at least one tertiary amine function, they can be quaternized. These polymers are described, for example, in French patents Nos. 2,252,840 and 2,368,508.
3. Polyamino-amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids, followed by alkylation with difunctional agents, for example, adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises from 1 to 4 carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene group comprises from 1 to 4 carbon atoms, such as an ethylene group. These polymers are described, for example, in French patent No. 1,583,363. In at least one embodiment, these derivatives may be selected from adipic acid/dimethylaminohydroxypropyldiethylenetriamine polymers.
4. Polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids comprising from 3 to 8 carbon atoms. The molar ratio of the polyalkylene polyamine to the dicarboxylic acid can range from 0.8:1 to 1.4:1; the polyamino amide resulting from this reaction with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine group of the polyamino amide ranging from 0.5:1 to 1.8:1. These polymers are described, for example, in U.S. Patent Nos. 3,227,615 and 2,961,347.
5. Alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers, such as homopolymers and copolymers comprising, as the main constituent of the chain, at least one unit among the units of formulae (Ia) and (Ib):

in which:

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

R ₁₂ is selected from hydrogen and methyl groups;

R ₁₀ and R ₁₁ , which may be the same or different, are selected from alkyl groups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group comprises, for example, from 1 to 5 carbon atoms and C ₁ -C ₄ lower amidoalkyl groups, or R ₁₀ and R ₁₁ may form, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl and morpholinyl; and

Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate. These polymers are described, for example, in French patent No. 2,080,759 and in its certificate of addition 2,190,406.

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

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

Quaternary diammonium polymers comprising at least one repeating unit of formula (II):
(II)

in which:

R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , which may be the same or different, are selected from aliphatic, alicyclic and arylaliphatic groups comprising from 1 to 20 carbon atoms and lower aliphatic hydroxyalkyl groups, or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , together or separately, with the nitrogen atoms to which they are attached, heterocycles alternatively comprising a second heteroatom other than nitrogen, or R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ which may be the same or different, are selected from linear or branched C ₁ -C ₆ alkyl groups substituted by at least one group selected from alkyl groups, ester groups, acyl groups, amide groups, -CO-OR ₁₇ -E groups and groups -CO-NH-R ₁₇ -E, where R ₁₇ is an alkylene group and E is a quaternary ammonium group;

A ₁ and B ₁ , which may be identical or different, are chosen from polymethylene groups comprising from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may comprise, linked or intercalated in the main chain, at least one entity chosen from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups and ester groups, and

X ^- denotes an anion derived from an inorganic or organic acid;

At ₁ , R ₁₃ and R ₁₅ can form, in conjugation with the two nitrogen atoms to which they are attached, a piperazine ring;

if A ₁ is chosen from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B ₁ may be chosen from:

-(CH ₂ ) _n --CO-E'-OC-(CH ₂ ) _n -

1. des résidus glycoliques de formule -O-Z-O-, où Z est choisi parmi des groupes hydrocarbonés linéaires ou ramifiés et des groupes des formules suivantes :

where E' is chosen from:

1. glycolic residues of formula -OZO-, where Z is selected from linear or branched hydrocarbon groups and groups of the following formulas:

-(CH ₂ -CH ₂ -O) _x -CH ₂ -CH ₂ -

-[CH ₂ -CH(CH ₃ )-O] _y -CH ₂ -CH(CH ₃ )-

1. un résidu de diamine bis-secondaire tel que des dérivés de pipérazine ;
2. des résidus de diamine bis-primaire de formule -NH-Y-NH-, dans lesquels Y est choisi parmi des groupes hydrocarbonés linéaires ou ramifiés et le groupe divalent -CH₂-CH₂-S-S-CH₂-CH₂-_;et
3. des groupes uréylène de formule -NH-CO-NH-.

where x and y, which may be the same or different, are chosen from integers ranging from 1 to 4, which represent a defined and unique degree of polymerization, and numbers ranging from 1 to 4, which represent an average degree of polymerization;

1. a bis-secondary diamine residue such as piperazine derivatives;
2. bis-primary diamine residues of formula -NH-Y-NH-, in which Y is selected from linear or branched hydrocarbon groups and the divalent group -CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ - _; and
3. ureylene groups of formula -NH-CO-NH-.

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

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

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

in which

1. Polymères d'ammonium polyquaternaire comprenant des motifs de formule (IV) :

R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , which may be the same or different, are selected from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbon atoms, n and p, which may be the same or different, are integers ranging from 2 to 20, and X ^- is an anion derived from an inorganic or organic acid.

1. Polyquaternary ammonium polymers comprising units of formula (IV):

in which:

R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , which may be the same or different, are selected from hydrogen, methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl, -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p OH groups, in which p is selected from integers between 0 and 6, provided that R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are not simultaneously hydrogen,

r and s, which may be the same or different, are chosen from integers ranging from 1 to 6,

q is chosen from integers ranging from 0 to 34,

- X ^- is an anion, such as a halide and

A is selected from dihalide radicals and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

1. Polymères quaternaires de vinylpyrrolidone et de vinylimidazole.

These compounds are described, for example, in European patent application No. 0 122 324.

1. 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 polyethyleneimines, polymers comprising units selected from vinylpyridine and vinylpyridinium, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives.

1. Polyamines

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

1. Polyamines

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

Examples of (co)polyamines include chitosan, (co)polylamines, (co)polyvinylamines, (co)polyanilines, (co)polyvinylimidazoles, (co)polydimethylaminoethylenemethacrylates, (co)polyvinylpyridines such as (co)poly-1-methyl-2-vinylpyridines, (co)polyimines such as (co)polyimines, (co)polypyridines such as (co)poly(quaternary pyridines), (co)polybiguanides such as (co)polyaminopropyl biguanides, (co)polylysines, (co)polyornithines, (co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses, amino(co)polyvinyl acetals and salts thereof.

1. Polyacides aminés cationiques

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

1. Cationic polyamino acids

As a cationic polymer, it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers, with a plurality of amino groups and carboxyl groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in a polymer backbone or a pendant group, if any, of the cationic polyamino acids. The carboxyl group may be present in a pendant group, if any, of the cationic polyamino acids.

Examples of cationic polyamino acids include cationized collagen, cationized gelatin, hydroxypropyl steardimonium hydrolyzed wheat protein, hydroxypropyl cocodimonium hydrolyzed wheat protein, hydroxypropyl trimonium hydrolyzed conchiolin protein, hydroxypropyl steardimonium hydrolyzed soy protein, hydroxypropyl trimonium hydrolyzed soy protein, hydroxypropyl cocodimonium hydrolyzed soy protein, and the like.

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

It may be preferable to choose the cationic polymer from cationic starches.

Examples of cationic starches include starches modified with a 2,3-epoxypropyltrimethylammonium salt (e.g., chloride), such as the product known as Starch Hydroxypropyltrimonium Chloride according to the INCl nomenclature and sold under the name SENSOMER Cl-50 from Ondeo or Pencare ^TM DP 1015 from Ingredion.

It may also be preferable to choose the cationic polymer from cationic gums.

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

Examples of cationic gum include cationic polygalactomannan derivatives such as guar gum derivatives and cassia gum derivatives, for example CTFA: Guar Hydroxypropyltrimonium Chloride, Hydroxypropyl Guar Hydroxypropyltrimonium Chloride and Cassia Hydroxypropyltrimonium Chloride. Guar hydroxypropyltrimonium chloride is commercially available under the Jaguar™ family of trade names from Rhodia Inc. and the N-Hance family of trade names from Ashland Inc. Cassia hydroxypropyltrimonium chloride is commercially available under the brand names Sensomer™ CT-250 and Sensomer™ CT-400 from Lubrizol Advanced Materials, Inc. or ClearHance ^TM from Ashland Inc.

It may also be preferable to choose the cationic polymer from chitosans.

It may be more preferable to select the cationic polymer from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as (co)polylysines, cationic (co)polyamino acids such as cationized collagen, cationic cellulose polymers and salts thereof.

It may be even more preferable to select the cationic polymer from the group consisting of polylysine, polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan and a mixture thereof.

The amount of the cationic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.

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

The amount of the cationic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, and more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.

(Anionic polymer)

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

It may be preferable that the molecular weight of the anionic polymer is 300 or more, preferably 1,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, more preferably 50,000 or more, more preferably 100,000 or more, and more preferably 1,000,000 or more.

Unless otherwise specified in the descriptions, “molecular weight” means number average molecular weight.

According to the present invention, the anionic polymer is chosen from hyaluronic acids, their salts and their derivatives.

Hyaluronic acid can be represented by the following chemical formula.

In the context of the present invention, the term "hyaluronic acid" covers in particular the basic unit of hyaluronic acid of formula:

It is the smallest fraction of hyaluronic acid comprising a disaccharide dimer, namely D-glucuronic acid and N-acetylglucosamine.

The term “derivatives” of hyaluronic acid also includes, in the context of the present invention, the linear polymer comprising the polymeric unit described above, linked together in the chain via alternating β(1,4) and β(1,3) glycosidic bonds, having a molecular weight (MW) which can vary between 380 and 13,000,000 daltons. This molecular weight depends largely on the source from which the hyaluronic acid is obtained and/or the preparation methods.

The term "salts" of hyaluronic acid includes, in the context of the present invention, any salts of hyaluronic acid. As salts, mention may be made of alkali metal salts such as sodium 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 pericellular gels, in the basic substance of connective tissues of vertebrate organs such as the dermis and epithelial tissues and, in particular, in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord and in the crista galli apophysis.

Thus, the term “hyaluronic acid” includes all fractions or subunits of hyaluronic acid having a molecular weight in particular in the molecular weight range recalled above.

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

As an illustration of the various hyaluronic acid fractions, reference may be made to the paper “Hyaluronan fragments: an information-rich system”, R. Stern et al., European Journal of Cell Biology 58 (2006) 699-715, which reviews the listed biological activities of hyaluronic acid as a function of its molecular weight.

According to a preferred embodiment of the present invention, the hyaluronic acid fractions suitable for the use covered by the present invention have a molecular weight of between 50 kDa and 5,000 kDa, in particular, between 100 kDa and 5,000 kDa, most particularly, between 400 kDa and 5,000 kDa. In this case, it is referred to as high molecular weight hyaluronic acid.

Alternatively, hyaluronic acid fractions which may also be suitable for the use covered by the present invention have a molecular weight between 50 kDa and 400 kDa. In this case, it is referred to as intermediate molecular weight hyaluronic acid.

Alternatively again, the hyaluronic acid fractions which may be suitable for the use covered by the present invention have a molecular weight of less than 50 kDa. In this case, it is referred to as low molecular weight hyaluronic acid.

It may be preferable to use a combination of two or more hyaluronic acids or salts thereof, such as a combination of high molecular weight hyaluronic acid or salt thereof and intermediate molecular weight hyaluronic acid or salt thereof; a combination of high molecular weight hyaluronic acid or salt thereof and low molecular weight hyaluronic acid or salt thereof; and a combination of intermediate molecular weight hyaluronic acid or salt thereof and low molecular weight hyaluronic acid or salt thereof.

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

Examples include methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. These esters have been described in particular in D. Campoccia et al. “Semisynthetic resorbable materials from hyaluronan esterification”, Biomaterials 19 (1998) 2101-2127.

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

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

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

The amount of the anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.

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

The amount of the anionic polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight, and more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.

(Amphoteric polymer)

An amphoteric polymer has both a positive charge density and a negative charge density.

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

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

It may be preferable that the molecular weight of the amphoteric polymer is 500 or more, preferably 1,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more.

It may be preferable that the molecular weight of the amphoteric polymer is less than or equal to 1,000,000, preferably less than or equal to 900,000, and more preferably less than or equal to 800,000.

Unless otherwise specified in the descriptions, “molecular weight” means number average molecular weight.

According to the present invention, the amphoteric polymer is chosen from cationized hyaluronic acid and salts thereof.

Cationized hyaluronic acid includes at least one cationic group, such as an ammonium group, in its molecule. The cationic group does not indicate a countercation of the salt, because the countercation is not in the hyaluronic acid molecule.

As salts, mention may be made of alkali metal salts such as sodium salt, alkaline earth metal salts such as magnesium salts, ammonium salts and mixtures thereof.

Cationized hyaluronic acid may have at least one group containing a quaternary ammonium group.

Cationized hyaluronic acid and/or a salt thereof may have a structure represented by the following general formula (1):
(1)

in which

R ⁴ to R ⁹ individually represent a hydrogen atom or a group containing a quaternary ammonium group (excluding a case where all R ⁴ to R ⁹ represent hydrogen atoms), and n represents an integer from 2 to 5,000.

Examples of the group containing a quaternary ammonium group represented by R ⁴ to R ⁹ in the general formula (1) above include the groups represented by the following general formula (2):
(2)

in which

R ¹ to R ³ individually represent hydrocarbon groups and X ^- represents a monovalent anion.

Examples of hydrocarbon groups represented by R ¹ to R ³ in the above general formula (2) include a linear or branched alkyl group, an unsaturated hydrocarbon group and an aromatic hydrocarbon group. Among these, the alkyl group is preferable. Examples of the alkyl group include alkyl groups having 1 to 30 (preferably 1 to 6) carbon atoms. It is preferable that the hydrocarbon groups represented by R ¹ to R ³ are alkyl groups having 1 to 3 carbon atoms.

Examples of the monovalent anion represented by X ^- in the general formula (2) above include a halogen ion such as a fluorine ion, a bromine ion, a chlorine ion, and an iodine ion.

The quaternary ammonium group-containing group can be introduced by replacing the hydrogen atom of the carboxyl group included in the hyaluronic acid and/or a salt thereof used as a raw material (hereinafter referred to as "raw material hyaluronic acid and/or a salt thereof") with the quaternary ammonium group-containing group. In this case, the quaternary ammonium group-containing group is bonded to the oxygen atom of the (-C(═O)O--) group included in the cationized hyaluronic acid and/or a salt thereof according to this embodiment. That the quaternary ammonium group-containing group is bonded to the oxygen atom of the (-C(═O)O-) group included in the cationized hyaluronic acid and/or a salt thereof according to this embodiment can be confirmed by the presence of a peak assigned to the carbon atom of the -C(═O)O- group to which the quaternary ammonium group-containing group is bonded via the oxygen atom, determined by analyzing the chemical shift of the nuclear magnetic resonance ( ¹³ C NMR) spectrum.

Specifically, the quaternary ammonium group-containing group can be obtained by reacting the carboxyl group (and/or hydroxyl group) of the raw material hyaluronic acid and/or a salt thereof with a cationizing agent that contains a quaternary ammonium group. It is preferable that the cationizing agent is at least one of a 2,3-epoxypropyltrialkylammonium halide represented by the following general formula (3) and a 3-halo-2-hydroxypropyltrialkylammonium halide represented by the following general formula (4). The reaction of the raw material hyaluronic acid and/or a salt thereof with the cationizing agent is described in the following production method.
( 3 )

in which

R ¹ to R ³ are the same as those defined for general formula (2), and X represents a halogen atom.
(4)

in which

R ¹ to R ³ are the same as those defined for general formula (2), and X and Y individually represent halogen atoms.

Examples of halogen atoms represented by X and Y in the general formulas (3) and (4) above include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.

The cationized hyaluronic acid may have at least one group containing a quaternary ammonium group and has a degree of cationization of 0.05 to 0.6, preferably 0.1 to 0.5 and more preferably 0.15 to 0.4.

The degree of cationization (i.e., the degree of substitution by the group containing a quaternary ammonium group) of the cationized hyaluronic acid and/or a salt thereof according to this embodiment can be determined by calculating the nitrogen content of the raw material sodium hyaluronate and the nitrogen content of the cationized hyaluronic acid by the semi-micro Kjeldahl method, and calculating the degree of cationization by the following expression on the basis of the increase in the nitrogen content.

When the nitrogen content of the raw material sodium hyaluronate is denoted by N _N (%) and the nitrogen content of the cationized hyaluronic acid having a cationization degree of (x) is denoted by N _S (%), the relationship between the increase in nitrogen content (N _S -N _N ) and the cationization degree (x) is represented by the following expression.

N _S -N _N (%)

=[14x/(molecular weight of the disaccharide unit of cationized hyaluronic acid)]×100

=[14x/(molecular weight of disaccharide unit of raw material sodium hyaluronate)+129.5x]×100

=[14x/(401.3+129.5x)]×100

Therefore, the degree of cationization (i.e., the degree of substitution by the group containing the quaternary ammonium group) can be calculated by the following expression.

Degree of cationization(x)=[(N _S -N _N )×401.3]/[1400-129.5*(N _S -N _N )]

The degree of cationization of a cationized hyaluronic acid when a raw material hyaluronic acid is unknown can be calculated by the above expression assuming that the raw material sodium hyaluronate is sodium hyaluronate having a purity of 99% or more.

It is possible that 1% or more, preferably 5% or more, and more preferably 10% or more and/or 50% or less, preferably 40% or less and more preferably 30% or less of the anionic groups in the hyaluronic acid are replaced by a cationic group, preferably a quaternary ammonium group-containing group and more preferably the quaternary ammonium group-containing group represented by the general formula (2) above.

As a cationized hyaluronic acid, we can cite hydroxypropyltrimonium hyaluronate marketed under the names Hyaloveil and Hyaloveul-MPF by Kewpie in Japan.

The amount of amphoteric polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more and more preferably 0.05% by weight or more, relative to the total weight of the composition.

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

The amount of the amphoteric polymer(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.03% to 10% by weight and more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.

(Non-polymeric acid having two or more acid dissociation constants)

The composition according to the present invention may include at least one non-polymeric acid having two or more pKa values or one or more salts thereof, i.e. at least one non-polymeric acid having two or more acid dissociation constants or one or more salts thereof. The pKa value (acid dissociation constant) is well known to those skilled in the art and must be determined at a constant temperature such as 25°C.

The non-polymeric acid having two or more pKa values or a salt(s) thereof may be included in the polyionic complex (a). The non-polymeric acid having two or more pKa values may serve as a crosslinking agent, in particular an anionic crosslinking agent, for the cationic polymer and/or the amphoteric polymer.

It is preferable that the non-polymeric acid having two or more pKa values or the salt(s) thereof be used with a cationic polymer and an anionic polymer.

The term "non-polymeric" here means that the acid is not obtained by polymerization of two or more monomers. Therefore, non-polymeric acid does not correspond to an acid obtained by polymerization of two or more monomers such as a polycarboxylic acid.

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

There is no limit to the type of the nonpolymeric acid having two or more pKa values or the salt(s) thereof. Two or more different types of nonpolymeric acids having two or more pKa values or salts thereof may be used in combination. Thus, a single type of nonpolymeric acid having two or more pKa values or a salt thereof or a combination of different types of nonpolymeric acids having two or more pKa values or salts thereof may be used.

Herein, the term "salt" means a salt formed by the addition of suitable base(s) to the non-polymeric acid having two or more pKa values, which can be obtained from a reaction with the non-polymeric acid having two or more pKa values with the base(s) according to methods known to those skilled in the art. As a salt, mention may be made of metal salts, for example alkali metal salts such as Na and K and alkaline earth metal salts such as Mg and Ca, and ammonium salts.

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

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

Non-polymeric acid having two or more pKa values may be non-polymeric polyvalent acid.

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

The non-polymeric acid having two or more pKa values or the salt(s) thereof may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid and their salts; aspartic acid, glutamic acid and their salts; terephthalylidene dicamphor sulfonic acid or its salts (Mexoryl SX), Benzophenone-9; phytic acid and its salts;Red 2 (Amaranth), Red 102 (New Coccine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brillant blue FCF), Blue 2 (Indigo Carmine), Red 201 (Lithol Rubine B), Red 202 (Lithol Rubine BCA), Red 204 (Lake Red CBA), Red 20 6 (Lithol Red CA), Red 207 (Lithol Red BA), Red 208 (Lithol Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 227 (Fast Acid Magenta), Yellow 203 (Quinoline Yellow WS), Green 201 (Alizanine Cyanine Green F), Green 204 (Pyranine Conc), Green 205 (Light Green SF Yellowish), Blue 203 (Patent Blue CA), Blue 205 (Alfazurine FG), Red 401 (Violamine R), Red 405 (Permanent Re F5R), Red 502 (Ponceau 3R), Red 503 (Ponceau R), Red 504 (Ponceau SX), Green 401 (Naphthol Green B), Green 402 (Guinea Green B) and Black 401 (Naphthol Blue Black); folic acid, ascorbic acid, erythorbic acid and their salts; cystine and its salts; EDTA and its salts; glycyrrhizin and its salts; and a mixture thereof.

It may be preferable that the non-polymeric acid having two or more pKa values or the salt(s) thereof is selected from the group consisting of terephthalylidene dicamphor sulfonic acid and its salts (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salts, and a mixture thereof.

The amount of the non-polymeric acid having two or more pKa values or the salt(s) thereof in the composition according to the present invention may be 0.001 wt% or more, preferably 0.005 wt% or more and more preferably 0.01 wt% or more, relative to the total weight of the composition.

The amount of the non-polymeric acid having two or more pKa values or the salt(s) thereof in the composition according to the present invention may be 15 wt% or less, preferably 10 wt% or less and more preferably 5 wt% or less, relative to the total weight of the composition.

The amount of the non-polymeric acid having two or more pKa values or the salt(s) thereof in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.

(Non-polymeric base having two or more base dissociation constants)

The composition according to the present invention may include at least one non-polymeric base having two or more pKa values or salt(s) thereof, i.e. at least one non-polymeric base having two or more base dissociation constants or salt(s) thereof. The pKa value (acid dissociation constant) is well known to those skilled in the art and must be determined at a constant temperature such as 25°C.

The non-polymeric base having two or more pKb values or the salt(s) thereof may be included in the polyionic complex (a). The non-polymeric base having two or more pKb values may serve as a crosslinking agent, in particular a cationic crosslinking agent, for the anionic polymer and/or amphoteric polymers.

It is preferable that the non-polymeric acid having two or more pKb values or the salt(s) thereof be used with a cationic polymer and an anionic polymer.

The term "non-polymeric" here means that the base is not obtained by polymerization of two or more monomers. Therefore, non-polymeric base does not correspond to a base obtained by polymerization of two or more monomers, such as polyallylamine.

It is preferable that the molecular weight of the non-polymeric base having two or more pKb values or salt(s) thereof is 1000 or less, preferably 800 or less and more preferably 700 or less.

There is no limit to the type of the non-polymeric base having two or more pKb values or salt(s) thereof. Two or more different types of non-polymeric bases having two or more pKb values or salts thereof may be used in combination. Thus, a single type of non-polymeric base having two or more pKb values or salt thereof or a combination of different types of non-polymeric bases having two or more pKb values or salts thereof may be used.

Herein, the term "salt" means a salt formed by the addition of suitable acid(s) to the non-polymeric acid having two or more pKb values, which can be obtained from a reaction of the non-polymeric base having two or more pKb values with the acid(s) according to methods known to those skilled in the art. As a salt, mention may be made of ammonium salts, for example salts with inorganic acids such as HCl and HNO ₃ , and salts with organic acids such as carboxylic acids and sulfonic acids.

The non-polymeric base having two or more pKb values or the salt(s) thereof may be an organic base or salt(s) thereof, and preferably a hydrophilic or water-soluble organic base or salt(s) thereof.

The non-polymeric base having two or more pKb values may have at least two basic groups selected from the group consisting of an amino group, a guanidine group, a biguanide group, an imidazole group, an imino group, a pyridyl group and a mixture thereof.

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

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

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

The amount of the non-polymeric base having two or more pKb values or the salt(s) thereof in the composition according to the present invention may be 0.001 wt% or more, preferably 0.005 wt% or more and more preferably 0.01 wt% or more, relative to the total weight of the composition.

The amount of the non-polymeric base having two or more pKb values or the salt(s) thereof in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and more preferably 5% by weight or less, relative to the total weight of the composition.

The amount of the non-polymeric base having two or more pKb values or the salt(s) thereof in the composition according to the present invention may be from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight and more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.

[Hydrophilic antioxidants]

The composition according to the present invention includes (b) at least one hydrophilic antioxidant. Two or more hydrophilic antioxidants may be used in combination. Thus, a single type of hydrophilic antioxidant or a combination of different types of hydrophilic antioxidants may be used.

According to the present invention, the antioxidant agents are compounds or substances which can scavenge the different forms of radicals which may be present in the skin; preferably, they simultaneously scavenge all the different forms of radicals present.

Hydrophilic antioxidant agent (b) means that the partition coefficient of the antioxidant agent between n-butanol and water is < 1, more preferably, < 0.5 and even more preferably, < 0.1.

It is preferable that the hydrophilic antioxidant (b) is selected from ascorbic acid, derivatives thereof, salts thereof and mixtures thereof.

Ascorbic acid derivatives, for example, ascorbyl glucoside may be mentioned. By "ascorbyl glucoside" is meant the condensation product of glucose, in the D form, i.e. in the α- or β-glucopyranose or α- or β-furanose form, or in the L form, with ascorbic acid, preferably in the L form. L-ascorbic acid 2-O-α-D-glucopyranoside may be preferred for use in the present invention. It is available in particular from Hayashibara.

Examples of ascorbic acid derivatives also include ascorbic acid ethers. Ascorbic acid ethers may be alkyl ethers of ascorbic acid, such as ethyl ascorbic acid, particularly 3-O-ethyl ascorbic acid.

As salts of ascorbic acid, there may be mentioned metal salts of ascorbic acid, for example, sodium ascorbate, magnesium ascorbylphosphate and sodium ascorbylphosphate.

It may be preferable that the hydrophilic antioxidant (b) is selected from the group consisting of ascorbic acid, ascorbyl glycoside, ethyl ascorbic acid, sodium ascorbate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate and a mixture thereof.

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

The amount of the hydrophilic antioxidant(s) (b) in the composition according to the present invention may be 30% by weight or less, preferably 25% by weight or less and more preferably 20% by weight or less, relative to the total weight of the composition.

The amount of the hydrophilic antioxidant(s) (b) in the composition according to the present invention may be from 0.01% to 30% by weight, preferably from 0.05% to 25% by weight and more preferably from 0.1% to 20% by weight, relative to the total weight of the composition.

[Water]

The composition according to the present invention comprises (c) water.

The amount of water (c) may be 10% by weight or more, preferably 30% by weight or more and more preferably 50% by weight or more, relative to the total weight of the composition.

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

The amount of water (c) may be from 10% to 99% by weight, preferably from 30% to 97% by weight and more preferably from 50% to 95% by weight, relative to the total weight of the composition.

[Surfactant]

The composition according to the present invention may further include (d) at least one surfactant. Two or more surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used.

The surfactant used in the present invention may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants and nonionic surfactants.

(Anionic surfactants)

The composition according to the present invention may comprise at least one anionic surfactant. Two or more anionic surfactants may be used in combination.

It is preferable that the anionic surfactant is selected from the group consisting of (C ₆ -C ₃₀ )alkyl sulfates, (C ₆ -C ₃₀ )alkyl ether sulfates, (C ₆ -C ₃₀ )alkylamido ether sulfates, alkylaryl polyether sulfates, and monoglyceride sulfates; (C ₆ -C ₃₀ )alkylsulfonates, (C ₆ -C ₃₀ )alkylamide sulfonates, (C ₆ -C ₃₀ )alkylaryl sulfonates, α-olefin sulfonates, and paraffin sulfonates; (C ₆ -C ₃₀ )alkyl phosphates; (C ₆ -C ₃₀ )alkyl sulfosuccinates, (C ₆ -C ₃₀ )alkyl ether sulfosuccinates, and (C ₆ -C ₃₀ )alkylamide sulfosuccinates; (C ₆ -C ₃₀ )alkyl sulfoacetates; (C ₆ -C ₂₄ )acyl sarcosinates; (C ₆ -C ₂₄ )acyl glutamates; (C ₆ -C ₃₀ )alkylpolyglycoside carboxylic ethers; (C ₆ -C ₃₀ )alkylpolyglycoside sulfosuccinates; (C ₆ -C ₃₀ )alkyl sulfosuccinamates; (C ₆ -C ₂₄ )acyl isethionates; N-(C ₆ -C ₂₄ )acyl taurates; C ₆ -C ₃₀ fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (C ₈ -C ₂₀ )acyl lactylates; (C ₆ -C ₃₀ )alkyl-D-galactoside uronic acid salts; salts of polyoxyalkylenated (C ₆ -C ₃₀ )alkyl ether carboxylic acids; salts of polyoxyalkylenated (C ₆ -C ₃₀ )alkylaryl ether carboxylic acids and salts of polyoxyalkylenated (C ₆ -C ₃₀ )alkylamido ether carboxylic acids; and their corresponding acid forms.

In at least one embodiment, the anionic surfactants are in the form of salts such as alkali metal salts, for example sodium; alkaline earth metal salts, for example magnesium; ammonium salts; amine salts; amino alcohol salts. Depending on the conditions, they can also be in acid form.

It is preferable that the anionic surfactant be chosen from salts of
( _C6 - _C30 )alkyl sulfate, ( _C6 - _C30 )alkyl ether sulfates or polyoxyalkylenated ( _C6 - _C30 )alkyl ether carboxylic acid, salified or not.

(Amphoteric surfactants)

The composition according to the present invention may comprise at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.

The amphoteric or zwitterionic surfactants may be, for example (non-limiting list), amine derivatives such as secondary or tertiary aliphatic amines, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain comprising 8 to 22 carbon atoms and containing at least one water-soluble anionic group (e.g. carboxylate, sulfate, phosphate or phosphonate).

The amphoteric surfactant may preferably be selected from the group consisting of betaines and amidoaminecarboxylated derivatives.

It is preferable that the amphoteric surfactant be chosen from betaine-type surfactants.

The betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines and alkylamidoalkylsulfobetaines, in particular, (C ₈ -C ₂₄ )alkylbetaines, (C ₈ -C ₂₄ )alkylamido(C ₁ -C ₈ )alkylbetaines, sulfobetaines and (C ₈ -C ₂₄ )alkylamido(C ₁ -C ₈ )alkylsulfobetaines. In one embodiment, the betaine-type amphoteric surfactants are selected from (C ₈ -C ₂₄ )alkylbetaines, (C ₈ -C ₂₄ )alkylamido(C ₁ -C ₈ )alkylsulfobetaines, sulfobetaines and phosphobetaines.

Non-limiting examples include compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th Edition, 2014, as cocobetaine, laurylbetaine, cetylbetaine, coco/oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine, stearamidopropylbetaine, cocamidoethylbetaine, cocamidopropylhydroxysultaine, oleamidopropylhydroxysultaine, cocohydroxysultaine, laurylhydroxysultaine, and cocosultaine, alone or in mixtures.

The betaine-type amphoteric surfactant is preferably an alkylbetaine and an alkylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine.

Among the carboxylated amidoamine derivatives, there may be mentioned the products sold under the name Miranol, as described in U.S. Patent Nos. 2,528,378 and 2,781,354 and classified in the CTFA Dictionary, 3rd Edition, 1982 (the disclosures of which are incorporated herein by reference), under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures:

R ₁ -CONCH ₂ CH ₂ -N ⁺ (R ₂ )(R ₃ )(CH ₂ COO ^- ) M ⁺ X ^- (B1)

in which:

R ₁ denotes an alkyl radical of an acid R ₁ -COOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical,

R ₂ denotes a beta-hydroxyethyl group,

R ₃ denotes a carboxymethyl group,

M ⁺ denotes a cationic ion derived from alkali metals such as sodium; an ammonium ion; or an ion derived from an organic amine;

X ^- denotes an organic or inorganic anionic ion such as halides, acetates, phosphates, nitrates, alkyl(C ₁ -C ₄ )sulfates, alkyl(C ₁ -C ₄ )- or alkyl(C ₁ -C ₄ )aryl-sulfonates, in particular methylsulfate and ethylsulfate; or M ⁺ and X ^- are not present;

R ₁ '-CONCH ₂ CH ₂ -N(B)(C) (B2)

in which:

R ₁ ' denotes an alkyl radical of an acid R ₁ '-COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, such as a C ₇ , C ₉ , C ₁₁ or C ₁₃ alkyl radical, a C ₁₇ alkyl radical and its isoform, or an unsaturated C ₁₇ radical,

B represents -CH ₂ CH ₂ OX',

C represents -(CH ₂ ) _z -Y', with z=1 or 2,

X' denotes a group -CH ₂ -COOH, -CH ₂ -COOZ', -CH ₂ CH ₂ -COOH, -CH ₂ CH ₂ -COOZ' or a hydrogen atom, and

Y' denotes a radical -COOH, -COOZ', -CH ₂ -CHOH-SO ₃ Z', -CH ₂ -CHOH-SO ₃ H or a radical -CH ₂ -CH(OH)-SO ₃ -Z',

in which Z' represents an ion of an alkali or alkaline earth metal such as sodium, an ion derived from an organic amine or an ammonium ion;

And

R _a'' -NH-CH(Y'')-(CH ₂ ) _n -C(O)-NH-(CH ₂ ) _n' -N(Rd)(Re) (B'2)

in which:

Y'' denotes -C(O)OH, -C(O)OZ'', -CH ₂ -CH(OH)-SO ₃ H or -CH ₂ -CH(OH)-SO ₃ -Z'', where Z'' denotes a cationic ion derived from an alkali or alkaline earth metal such as sodium, an ion derived from an organic amine or an ammonium ion;

Rd and Re denote a _C1 - _C4 alkyl or _C1 - _C4 hydroxyalkyl radical;

R _a'' denotes a C ₁₀ -C ₃₀ alkyl or alkenyl group of an acid, and

n and n' independently denote an integer from 1 to 3.

It is preferable that the amphoteric surfactant of formula B1 and B2 is selected from (C ₈ -C ₂₄ )-alkyl amphomonoacetates, (C ₈ -C ₂₄ )alkyl amphodiacetates, (C ₈ -C ₂₄ )alkyl amphomonopropionates and (C ₈ -C ₂₄ )alkyl amphodipropionates.

These compounds are classified in the CTFA Dictionary, 5th Edition, 1993, as Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium Caprylamphodipropionate, Lauroamphodipropionic acid, and Cocoamphodipropionic acid.

An example is cocoamphodiacetate sold by the company Rhodia Chimie under the trade name Miranol® C2M concentrate.

Among the compounds of formula (B'2) we can cite sodium diethylaminopropyl cocoaspartamide (CTFA) marketed by CHIMEX under the name CHIMEXANE HB.

(Cationic surfactants)

The composition according to the present invention may comprise at least one cationic surfactant. Two or more cationic surfactants may be used in combination.

The cationic surfactant may be selected from the group consisting of optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts and mixtures thereof.

Examples of quaternary ammonium salts that may be cited include, but are not limited to:

those of general formula (B3) below:
(B3)

in which

R ₁ , R ₂ , R ₃ , and R ₄ , which may be the same or different, are selected from linear and branched aliphatic radicals comprising from 1 to 30 carbon atoms and optionally including heteroatoms such as oxygen, nitrogen, sulfur and halogens. The aliphatic radicals may be selected, for example, from alkyl, alkoxy, polyoxyalkylene C ₂ -C ₆ alkylamide, (C ₁₂ -C ₂₂ )alkylamido(C ₂ -C ₆ )alkyl, ( C ₁₂ -C ₂₂ )alkylacetate and hydroxyalkyl radicals; and aromatic radicals such as aryl and alkylaryl; and X ^- is selected from halides, phosphates, acetates, lactates, (C ₂ -C ₆ ) alkyl sulfates and alkyl- or alkylaryl-sulfonates;

imidazoline quaternary ammonium salts, for example those of formula (B4) below:
(B4)

in which:

R ₅ is chosen from alkenyl and alkyl radicals, containing from 8 to 30 carbon atoms, for example derivatives of tallow or coconut fatty acids;

R ₆ is selected from hydrogen, C ₁ - C _{4 alkyl radicals,} and alkenyl and alkyl radicals including from 8 to 30 carbon atoms;

R ₇ is chosen from C ₁ - C ₄ alkyl radicals;

R ₈ is selected from hydrogen and C ₁ - C ₄ alkyl radicals; and

X ^- is selected from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates and alkylaryl sulfonates. In one embodiment, R ₅ and R ₆ are, for example, a mixture of radicals selected from alkenyl and alkyl radicals including from 12 to 21 carbon atoms, such as tallow fatty acid derivatives, R ₇ is methyl and R ₈ is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W/75PG and W75HPG by Witco;

Di- or tri-quaternary ammonium salts of formula (B5):
(B5)

in which:

R ₉ is chosen from aliphatic radicals comprising from 16 to 30 carbon atoms;

R ₁₀ is selected from hydrogen or alkyl radicals including from 1 to 4 carbon atoms or a group -(CH ₂ ) ₃ (R _16a )(R _17a )(R _18a )N ⁺ X- _- ;

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R _16a , R _17a , and R _18a , which may be the same or different, are selected from hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; and

X ^- is selected from halides, acetates, phosphates, nitrates, ethyl sulfates and methyl sulfates.

An example of such a quaternary diammonium salt is FINQUAT CT-P from FINETEX (Quaternium-89) or FINQUAT CT (Quaternium-75);

And

quaternary ammonium salts including at least one ester function, such as those of formula (B6) below:
(B6)

in which:

R ₂₂ is chosen from C ₁ -C ₆ alkyl radicals and C ₁ -C ₆ hydroxyalkyl and dihydroxyalkyl radicals;

R ₂₃ is chosen from:

the radical below:
,

the linear and branched _C1 - _C22 saturated and unsaturated hydrocarbon radicals _R27 , and hydrogen,

R ₂₅ is chosen from:

the radical below:
,

the hydrocarbon radicals R ₂₉ , linear and branched, saturated and unsaturated in C ₁ - C ₆ , and hydrogen,

-R ₂₄ , R ₂₆ and R ₂₈ , which may be identical or different, are chosen from linear or branched, saturated and unsaturated C ₇ to C ₂₁ hydrocarbon groups;

r, s and t, which may be the same or different, are chosen from integers ranging from 2 to 6;

each of r1 and t1, which may be the same or different, is equal to 0 or 1, and r2+r1=2r and t1+2t=2t;

y is chosen from integers ranging from 1 to 10;

x and z, which may be the same or different, are chosen from integers ranging from 0 to 10;

X ^- is selected from simple and complex anions, organic and inorganic; provided that the sum x+y+z is from 1 to 15, that when x is equal to 0, R ₂₃ denotes R ₂₇ and that when z is equal to 0, R ₂₅ denotes R ₂₉ . R ₂₂ may be selected from linear and branched alkyl radicals. In one embodiment, R ₂₂ is selected from linear alkyl radicals. In another embodiment, R ₂₂ is selected from methyl, ethyl, hydroxyethyl and dihydroxypropyl radicals, for example methyl and ethyl radicals. In one embodiment, the sum x+y+z is from 1 to 10. When R ₂₃ is a hydrocarbon group R ₂₇ , it may be long and include from 12 to 22 carbon atoms, or short and include from 1 to 3 carbon atoms. When R ₂₅ is a hydrocarbon radical R ₂₉ , it may include, for example, from 1 to 3 carbon atoms. As a non-limiting example, in one embodiment, R ₂₄ , R ₂₆ and R ₂₈ , which may be the same or different, are selected from linear and branched, saturated and unsaturated C ₁₁ -C ₂₁ hydrocarbon radicals, for example from linear and branched, saturated and unsaturated C ₁₁ -C ₂₁ alkyl and alkenyl radicals. In another embodiment, x and z, which may be the same or different, are 0 or 1. In one embodiment, y is 1. In another embodiment, r, s and t, which may be the same or different, are 2 or 3, for example, 2. The anion X ^- may be selected, for example, from halides, such as chloride, bromide and iodide; and C ₁ -C _{4 alkyl sulfates,} such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other anion compatible with ammonium, including an ester function, are other non-limiting examples of anions that may be used according to the present invention. In one embodiment, the anion X ^- is selected from chloride and methyl sulfate.

In another embodiment, ammonium salts of formula (B6) may be used, wherein:

R ₂₂ is chosen from methyl and ethyl radicals,

x and y are equal to 1;

z is equal to 0 or 1;

r, s and t are equal to 2;

R ₂₃ is chosen from:

the radical below:
,

methyl, ethyl and _C14 - _C22 hydrocarbon radicals, and hydrogen;

R ₂₅ is chosen from:

the radical below:
,

and hydrogen;

R ₂₄ , R ₂₆ and R ₂₈ , which may be identical or different, are chosen from linear and branched, saturated and unsaturated C ₁₃ -C ₁₇ hydrocarbon radicals, for example from linear and branched, saturated and unsaturated C ₁₃ -C ₁₇ alkyl and alkenyl radicals.

In one embodiment, the hydrocarbon radicals are linear.

Non-limiting examples of compounds of formula (B6) that may be cited include salts, for example the chloride and methyl sulfate, of diiacyloxyethyl-dimethylammonium, diiacyloxyethyl-hydroxyethyl-methylammonium, monoacyloxyethyl-dihydroxyethyl-methylammonium, triacyloxyethyl-methylammonium, monoacyloxyethyl-hydroxyethyl-dimethylammonium, and mixtures thereof. In one embodiment, the acyl radicals may include from 14 to 18 carbon atoms, and may be derived from, for example, a vegetable oil, for example palm oil and sunflower oil. When the compound comprises several acyl radicals, these radicals may be the same or different.

These products can be obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or optionally oxyalkylenated alkyldiisopropanolamine on fatty acids or on mixtures of fatty acids of vegetable or animal origin, or by transesterification of their methyl esters. This esterification can be followed by a quaternization using an alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrin and glycerol chlorohydrin.

These compounds are sold, for example, under the names Dehyquart® by the company Cognis, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or "Rewoquat® WE 18" by the company Rewo-Goldschmidt.

Other non-limiting examples of ammonium salts that can be used in the composition according to the present invention include ammonium salts including at least one ester function described in U.S. Patent Nos. 4,874,554 and 4,137,180.

The above-mentioned quaternary ammonium salts which can be used in the composition according to the present invention include, but are not limited to, those corresponding to formula (I), for example, tetraalkylammonium chlorides, for example, dialkyldimethylammonium and alkyltrimethylammonium chlorides in which the alkyl radical includes from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium and benzyldimethylstearylammonium chloride; palmitylamidopropyltrimethylammonium chloride; and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk.

According to one embodiment, the cationic surfactant which can be used in the composition according to the present invention is selected from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, quaternium-83, quaternium-87, quaternium-22, behenylamidopropyl-2,3-dihydroxypropyldimethylammonium chloride, palmitylamidopropyltrimethylammonium chloride and stearamidopropyldimethylamine.

(Non-ionic surfactants)

The composition according to the present invention may comprise at least one nonionic surfactant. Two or more nonionic surfactants may be used in combination.

Nonionic surfactants are compounds well known in themselves (see, for example, in this regard, "Handbook of Surfactants" by MR Porter, Blackie & Son publishers (Glasgow and London), 1991, pages 116-178). Thus, they may, for example, be chosen from alcohols, alpha-diols, alkylphenols and fatty acid esters, these compounds being ethoxylated, propoxylated or glycerolated and comprising at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, knowing that the number of ethylene oxide or propylene oxide groups may range from 2 to 50, and the number of glycerol groups may range from 1 to 30. Maltose derivatives may also be mentioned. Mention may also be made, in a non-limiting manner, of copolymers of ethylene oxide and/or propylene oxide; condensates of ethylene oxide and/or propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1.5 to 5 glycerol groups, such as from 1.5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; ethoxylated oils of plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; mono or diesters of polyethoxylated fatty acids of alkylpolyglycosides (C ₆ -C ₂₄ ) of glycerol; N-alkylglucamine (C ₆ -C ₂₄ ) derivatives, amine oxides such as alkylamine (C ₁₀ -C ₁₄ ) oxides or N-acylaminopropylmorpholine (C ₁₀ -C ₁₄ ) oxides; silicone surfactants; and mixtures thereof.

The nonionic surfactants may preferably be chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, and are preferably oxyethylene units.

Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants which may be cited:

Monooxyalkylenated or polyoxyalkylenated alkylphenols ( _C8 - _C24 ),

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C ₈ - C ₃₀ alcohols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C ₈ - C ₃₀ amides,

esters of saturated or unsaturated, linear or branched, _C8 - _C30 acids and of polyalkylene glycols,

monooxyalkylenated or polyoxyalkylenated esters of saturated or unsaturated, linear or branched, _C8 - _C30 acids and of sorbitol,

saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated vegetable oils,

ethylene oxide and/or propylene oxide condensates, among others, alone or in mixture.

The surfactants preferably contain a number of moles of ethylene oxide and/or propylene oxide of between 1 and 100 and more preferably between 2 and 50. According to one of the embodiments of the present invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylenated fatty ester (polyethylene glycol ester of fatty acid).

Examples of polyoxyethylene fatty alcohols (or C ₈ -C ₃₀ alcohols) that may be cited include adducts of ethylene oxide with lauryl alcohol, in particular those containing from 5 to 50 oxyethylene units and more particularly those containing from 7 to 12 oxyethylene units (Laureth-7 to Laureth-12, as CTFA names); adducts of ethylene oxide with behenyl alcohol, in particular those containing from 9 to 50 oxyethylene units (Beheneth-9 to Beheneth-50, as CTFA names); adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing from 10 to 50 oxyethylene units (Ceteareth-10 to Ceteareth-50, for example, Ceteareth-33, as CTFA names); adducts of ethylene oxide with cetyl alcohol, especially those containing from 10 to 50 oxyethylene units (Ceteth-10 to Ceteth-50 as CTFA names); adducts of ethylene oxide with stearyl alcohol, especially those containing from 10 to 50 oxyethylene units (Steareth-10 to Steareth-50, for example, Steareth-20, as CTFA names); adducts of ethylene oxide with isostearyl alcohol, especially those containing from 10 to 50 oxyethylene units (Isosteareth-10 to Isosteareth-50, as CTFA names); and mixtures thereof.

Examples of unsaturated polyoxyethylenated fatty alcohols (or C ₈ - C ₃₀ alcohols) that may be cited include adducts of ethylene oxide with oleyl alcohol, particularly those containing from 2 to 50 oxyethylene units and more particularly those containing from 10 to 40 oxyethylene units (Oleth-10 to Oleth-40, as CTFA names); and mixtures thereof.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, _C8 to _C40 monoglycerolated or polyglycerolated alcohols are preferably used.

In particular, _C8 - _C40 monoglycerolated or polyglycerolated alcohols correspond to the following formula:

RO-[CH ₂ -CH(CH ₂ OH)-O] _m -H or RO-[CH(CH ₂ OH)-CH ₂ O] _m -H

in which R represents a linear or branched _C8 - _C40 and preferably _C8 - _C30 alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

Examples of compounds suitable in the context of the invention include lauryl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 moles of glycerol, oleyl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 moles of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 moles of glycerol, cetearyl alcohol containing 6 moles of glycerol, oleocetyl alcohol containing 6 moles of glycerol, and octadecanol containing 6 moles of glycerol.

Alcohol can represent a mixture of alcohols in the same way that the value of m represents a statistical value, meaning that in a commercial product several species of polyglycerolated fatty alcohol can coexist as a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is preferable to use the _C8 / _C10 alcohol containing 1 mole of glycerol, the _C10 / _C12 alcohol containing 1 mole of glycerol and the _C12 alcohol containing 1.5 mole of glycerol.

Monoglycerolated or polyglycerolated _C8 - _C40 fatty esters can correspond to the following formula:

R'O-[CH ₂ -CH(CH ₂ OR''')-O] _m -R'' or R'O-[CH(CH ₂ OR''')-CH ₂ O] _m -R''

where each of R', R'' and R'' independently represents a hydrogen atom, or a linear or branched C ₈ -C ₄₀ and preferably C ₈ -C ₃₀ alkyl-CO- or alkenyl-CO- radical provided that at least one of R', R'' and R''' is not a hydrogen atom and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

Examples of polyoxyethylene fatty esters that may be cited include adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (INCI names: behenate PEG-9 to behenate PEG-50); polyethylene glycol monostearate 100 EO (INCI name: PEG-100 stearate) and mixtures thereof.

According to one of the embodiments of the present invention, the surfactant may be chosen from polyol esters with fatty acids with a saturated or unsaturated chain containing for example from 8 to 24 carbon atoms, preferably from 12 to 22 carbon atoms, or their polyoxyalkylenated derivatives, preferably containing from 10 to 200, or more preferably, from 10 to 100 oxyalkylene units, such as glyceryl esters of a C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ , fatty acid, and their polyoxyalkylenated derivatives, preferably from 10 to 200, or more preferably, from 10 to 100 oxyalkylene units; sorbitol esters of a C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ , fatty acid, and their polyoxyalkylenated derivatives, preferably from 10 to 200, or more preferably from 10 to 100 oxyalkylene units; sugar esters (sucrose, maltose, glucose, fructose and/or alkylglycose) of a C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ , fatty acid, and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, or more preferably from 10 to 100 oxyalkylene units; fatty alcohol ethers; sugar ethers of one or more C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ , fatty alcohol(s); and mixtures thereof.

As glyceryl esters of fatty acids, mention may be made of glyceryl stearate (glyceryl mono-, di- and/or tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate and mixtures thereof, or as their polyoxyalkylenated derivatives, the mono-, di- or triester of fatty acids with a polyoxyalkylenated glycerol (fatty acid mono-, di- or triester with a polyalkylene glycol ether of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), such as PEG-20 glyceryl stearate (mono-, di-, tristearate and/or triisostearate).

Mixtures of these surfactants may also be used, for example, the product containing glyceryl stearate and PEG-100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEGIN by Goldschmidt (CTFA name: glyceryl stearate SE).

The sorbitol esters of C ₈ -C ₂₄ fatty acids and their polyoxyalkylenated derivatives may be chosen from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate and the esters of fatty acids and alkoxylated sorbitan containing, for example, from 20 to 100 EO, such as sorbitan monostearate (CTFA name: sorbitan stearate), marketed by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate), marketed by the company ICI under the name Span 40 or sorbitan tristearate 20 EO (CTFA name: polysorbate 65) marketed by the company ICI under the name Tween 65, sorbitan polyoxyethylene trioleate (polysorbate 85) or the compounds marketed under the trade names Tween 20 or Tween 60 by Uniqema.

Fatty acid esters of glucose or alkylglucose include glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters, methylglucoside diester of oleic acid (CTFA name: methylglucose dioleate), methylglucoside mixed ester and oleic acid/hydroxystearic acid mixture (CTFA name: Methyl glucose dioleate/hydroxystearate), methylglucoside ester of isostearic acid (CTFA name: methylglucose isostearate), methylglucoside ester of lauric acid (CTFA name: Methyl glucose laurate), the mixture of monoester and of methylglucoside diester and isostearic acid (CTFA name: Methyl glucose sesquiisostearate), the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate), and in particular the product marketed under the name Glucate SS by AMERCHOL and their mixtures.

As ethoxylated ethers of fatty acids and glucose or alkylglucose, mention may be made, for example, of ethoxylated ethers of fatty acids and methylglucose and, in particular, the polyethylene glycol ether of the diester of methylglucose and stearic acid with approximately 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methylglucose and stearic acid with approximately 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof.

Examples of sucrose esters include sucrose palmitostearate, sucrose stearate and sucrose monolaurate.

As sugar ethers, alkylpolyglucosides may be used, for example decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl/capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818/UP by Henkel, cetostearyl glucoside optionally mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example in the form of the mixture (35/65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof may in particular be mentioned.

Mixtures of glycerides of alkoxylated vegetable oils such as mixtures of ethoxylated palm (200 EO) and copra (7 EO) glycerides may also be mentioned.

The nonionic surfactant according to the present invention preferably contains a branched C ₁₂ - C ₂₂ alkenyl or acyl chain such as an oleyl or isostearyl group. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

According to one of the embodiments of the present invention, the nonionic surfactant may be chosen from copolymers of ethylene oxide and propylene oxide, in particular copolymers of the following formula:

HO(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H

in which a, b and c are integers such that a+c ranges from 2 to 100, and b ranges from 14 to 60, and mixtures thereof.

According to one of the embodiments of the present invention, the nonionic surfactant may be chosen from silicone surfactants. Mention may be made, without limitation, of those disclosed in documents US-A-5364633 and US-A-5411744.

The silicone surfactant may preferably be a compound of formula (I):

in which:

R ₁ , R ₂ and R ₃ , independently of one another, represent a C ₁ -C ₆ alkyl radical or a -(CH ₂ ) _x -(OCH ₂ CH ₂ ) _y -(OCH ₂ CH ₂ CH ₂ ) _z -OR ₄ radical, at least one radical R ₁ , R ₂ or R ₃ not being an alkyl radical; R ₄ being a hydrogen, an alkyl radical or an acyl radical;

A is an integer ranging from 0 to 200;

B is an integer from 0 to 50; provided that A and B are not simultaneously equal to zero;

x is an integer from 1 to 6;

y is an integer between 1 and 30; and

z is an integer ranging from 0 to 5.

According to a preferred embodiment of the present invention, in the compound of formula (I), the alkyl radical is a methyl radical, x is an integer ranging from 2 to 6 and y is an integer ranging from 4 to 30.

Examples of silicone surfactants of formula (I) include compounds of formula (II):

where A is an integer from 20 to 105, B is an integer from 2 to 10, and y is an integer from 10 to 20.

Examples of silicone surfactants of formula (I) include compounds of formula (III):

H-(OCH ₂ CH ₂ ) _y -(CH ₂ ) ₃ -[(CH ₃ ) ₂ SiO] _A' -(CH ₂ ) ₃ -(OCH ₂ CH ₂ ) _y -OH (III)

in which A’ and y are integers ranging from 10 to 20.

Compounds of the present invention that can be used are those sold by Dow Corning Company under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667. Compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II) in which, respectively, A is 22, B is 2 and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12.

Compound Q4-3667 is a compound of formula (III) where A is 15 and y is 13.

It is preferable that the surfactant (b) is chosen from nonionic surfactants.

It is more preferable that the surfactant (b) is selected from polyglyceryl esters of fatty acids.

It is preferable that the fatty acid polyglyceryl ester has a polyglycerol moiety derived from 2 to 10 glycerols, preferably 2 to 8 glycerols, and more preferably 2 to 6 glycerols. In other words, the fatty acid polyglyceryl ester may comprise 2 to 10 polyglyceryl units, preferably 2 to 8 polyglyceryl units, and more preferably 2 to 6 polyglyceryl units. If the entire fatty acid polyglyceryl ester has a shorter polyglyceryl chain (e.g., less than 10 polyglyceryl units, preferably less than 8 polyglyceryl units, and more preferably less than 6 polyglyceryl units), the stability of the composition according to the present invention can be enhanced.

The polyglyceryl ester of fatty acid may be selected from mono, di and triesters of linear or branched, saturated or unsaturated fatty acid, preferably of saturated fatty acid, including from 4 to 32 carbon atoms, preferably from 8 to 26 carbon atoms and more preferably from 10 to 20 carbon atoms, such as lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, caprylic acid and myristic acid.

It is preferable that the surfactant (b) is chosen in the form of polyglyceryl monoesters of saturated or unsaturated fatty acids.

The fatty acid polyglyceryl ester may have an HLB (Hydrophilic Lipophilic Balance) value of from 4.0 to 16.0, preferably from 4.5 to 15.5 and more preferably from 5.0 to 15.0. The term HLB (hydrophilic-lipophilic balance) is well known to those skilled in the art and reflects the ratio of the hydrophilic to the lipophilic portion in the molecule. If two or more fatty acid polyglyceryl esters are used, the HLB value is determined by the weighted average of the HLB values of all the fatty acid polyglyceryl esters.

The fatty acid polyglyceryl ester may be selected from the group consisting of PG-2 stearate (HLB: 5.0), PG-2 isostearate (HLB: 5.5), PG-2 oleate (HLB: 6.5), PG-2 caprate (HLB: 9.5), PG-2 laurate (HLB: 8.5), PG-4 oleate (HLB: 8.8), PG-4 laurate (HLB: 10.4), PG-4 isostearate (HLB: 8.2), PG-5 laurate (HLB: 15.8), PG-6 isostearate (HLB: 10.8), PG-3 cocoate (HLB: 12.0), PG-3 caprate (HLB: 10.0), PG-4 caprylate (HLB: 14), PG-4 caprate (HLB: 14.0), PG-5 myristate (HLB: 15.4), PG-5 stearate (HLB: 15.0), PG-5 oleate (HLB: 14.9), PG-6 caprylate (HLB: 14.6), PG-6 caprate (HLB: 13.1), PG-6 laurate (HLB: 14.5), and mixtures thereof.

It may be preferable that the surfactant (d) is selected from the group consisting of PG-4 caprate (HLB: 14.0), PG-2 isostearate (HLB: 5.5) and a mixture thereof.

It is preferable that the composition according to the present invention comprises at least two polyglyceryl fatty acid esters.

It is best to choose the surfactant (d) from

at least one first fatty acid polyglyceryl ester having an HLB value of from 4.0 to 8.0, preferably from 4.5 to 8.0 and more preferably from 5.0 to 8.0;

at least one second fatty acid polyglyceryl ester having an HLB value of from 12.0 to 16.0, preferably from 12.0 to 15.5 and more preferably from 12.0 to 15.0; and

and a mixture of these.

The amount of the surfactant(s) (d) in the composition according to the present invention may be 0.001% by weight or more, preferably 0.01% by weight or more and more preferably 0.1% by weight or more, relative to the total weight of the composition.

Furthermore, the amount of the surfactant(s) (d) in the composition according to the present invention may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the composition.

The amount of the surfactant(s) (d) in the composition according to the present invention may be from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight and more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.

[pH]

The pH of the composition according to the present invention may be from 2.0 to 9.0, preferably from 2.5 to 8.5 and more preferably from 3.0 to 8.0.

At pH 2.0 to 9.0, the (a) polyionic complex can be very stable.

The pH of the composition according to the present invention may be corrected by adding at least one alkaline agent and/or at least one acid, other than non-polymeric acid having two or more pKa values or salt(s) thereof or non-polymeric base having two or more pKb values or salt(s) thereof, for incorporation into the polyionic complex (a). The pH of the composition according to the present invention may also be corrected 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. The inorganic alkaline agent may be selected from the group consisting of the following elements: 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 preferable.

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

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

wherein R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a C ₁ -C ₄ alkyl radical, and R ₁ , R ₂ , R ₃ and R ₄ independently denote a hydrogen atom, an alkyl radical or a C ₁ -C ₄ hydroxyalkyl radical, as exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferred.

The alkaline agent(s) may be used in an amount ranging from 0.01% to 15% by weight, preferably from 0.02% to 10% by weight and more preferably from 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.

(Acid)

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

As an acid, all inorganic or organic acids, preferably inorganic, which are commonly used in cosmetic products can be mentioned. A monovalent acid and/or a polyvalent acid can be used. A monovalent acid such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) can be used. HCl is preferred.

The acid(s) may be used in an amount ranging from 0.01% to 15% by weight, preferably from 0.02% to 10% by weight and more preferably from 0.03% to 5% by weight, relative to the total weight of the composition, depending on their solubility.

(Buffering agent)

The composition according to the present 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.

As a buffering agent, there may be mentioned an acetate buffer (e.g., acetic acid + sodium acetate), a phosphate buffer (e.g., sodium dihydrogen phosphate + disodium hydrogen phosphate), a citrate buffer (e.g., citric acid + sodium citrate), a borate buffer (e.g., boric acid + sodium borate), a tartrate buffer (e.g., tartaric acid + sodium tartrate dihydrate), a Tris buffer (e.g., tris(hydroxymethyl)aminomethane) and a Hepes buffer (4-(2-hydroxyethyl)-1-pipeineethanesulfonic acid).

[Optional additives]

The composition according to the present invention may comprise, in addition to the above-mentioned components, components generally used in cosmetics, specifically, oils such as ester oils and hydrocarbon oils, hydrophilic or lipophilic UV filters, hydrophilic or lipophilic thickeners, volatile or non-volatile organic solvents such as glycerin, glycols and ethanol, silicones and silicone derivatives, natural extracts derived from animals or plants, waxes and the like, within a range that does not compromise the effects of the present invention.

The composition according to the present invention may comprise the above optional additive(s) in an amount of 0.01% to 50% by weight, preferably 0.05% to 30% by weight and more preferably 0.1% to 10% by weight, relative to the total weight of the composition.

[Composition]

The composition according to the present invention can be used as a cosmetic composition. Thus, the cosmetic composition according to the present invention can be intended to be applied to a keratinous substance. By keratinous substance is meant here a material containing keratin as a main constituent element and, by way of example, the skin, the scalp, the lips, the hair or body hair and the like. It is preferable that the cosmetic composition according to the present invention is used for a cosmetic process for the keratinous fiber, in particular the skin.

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

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

The composition according to the present invention can be prepared by simple or easy mixing with a conventional mixing means such as a stirrer. Therefore, there is no need for strong shearing, for example using a homogenizer. In addition, heating is not necessary.

The composition according to the present invention can be used to easily prepare a film.

Thus, the present invention also relates to a process for preparing a film, preferably a cosmetic film, optionally having a thickness of 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, comprising:

applying to a substrate, preferably a keratinous substance, more preferably the skin, the composition according to the present invention; and

drying the composition.

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

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

The film according to the present claims may be transparent or translucent and may provide antioxidant effects that may be long lasting.

Even though the film according to the present invention is relatively thick, it is still thin and may be transparent, and thus may not be easy to perceive. Thus, the film according to the present invention can be preferably used as a cosmetic film.

The film according to the present claims may be less sticky although it comprises a hyaluronic acid-based polymer.

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

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

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

It is more preferable that the film according to the present invention can be released from the non-keratinous substrate. The release mode is not limited. Therefore, the film according to the present invention can be peeled off from the non-keratinous substrate, or released by dissolving the substrate sheet in a solvent such as water.

1. Un film, de préférence cosmétique, de préférence d’une épaisseur de préférence supérieure à 0,1 μm, plus préférablement, supérieure à 0,5 μm, et encore plus préférablement, supérieure à 1 μm, préparé par un procédé comprenant :

The present invention also relates to:

1. A film, preferably cosmetic, preferably having a thickness preferably greater than 0.1 μm, more preferably greater than 0.5 μm, and even more preferably greater than 1 μm, prepared by a process comprising:

the application to a substrate, preferably to a keratinous substance and more preferably to the skin, of the composition according to the present invention; and

drying the composition,

1. Un film, de préférence un film cosmétique, facultativement d’une épaisseur supérieure de préférence à 0,1 μm, plus préférablement, supérieure à 0,5 μm, encore plus préférablement, supérieure à 1 μm, comprenant :

1. au moins un complexe polyionique, comprenant

And

1. A film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.1 μm, more preferably greater than 0.5 μm, even more preferably greater than 1 μm, comprising:

1. at least one polyionic complex, comprising

at least one cationic polymer and at least one anionic polymer,

at least one cationic polymer and at least one amphoteric polymer,

at least one anionic polymer and at least one amphoteric polymer, or

at least one amphoteric polymer,

1. au moins un antioxydant hydrophile ;

at least one non-polymeric acid having two or more pKa values or one or more salts thereof, or at least one non-polymeric base having two or more pKb values or one or more salts thereof;

1. at least one hydrophilic antioxidant;

And

optionally (c) at least one surfactant, preferably chosen from nonionic surfactants, and more preferably chosen from polyglyceryl esters of fatty acids,

in which

the anionic polymer is chosen from hyaluronic acid and its salts; and

the amphoteric polymer is chosen from cationized hyaluronic acid and its salts.

The above explanations regarding cationic, anionic and amphoteric polymers as well as the above hydrophilic antioxidant and surfactant can be applied to those in films (1) and (2) above.

The film thus obtained may be self-supporting. The term “self-supporting” herein means that the film may be in the form of a sheet and may be handled as an independent sheet without the assistance of a substrate or support. Thus, the term “self-supporting” may have the same meaning as “self-supporting”.

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

In this specification, the term "hydrophobic" means that the solubility of the polymer in water (preferably with a volume of 1 liter) at 20-40 °C, preferably 25-40 °C, and more preferably 30-40 °C is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, based on the total weight of the polymer. It is most preferable that the polymer is not soluble in water.

If the film according to the present invention is hydrophobic, the film can have water-resistant properties and, therefore, it can remain on a keratinous substance such as skin even if the surface of the keratinous substance is wet due to, for example, sweat or rain. Thus, when the film according to the present invention provides a 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 a keratinous substance such as skin under alkaline conditions such as pH 8 to 12, preferably 9 to 11. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can provide such alkaline conditions.

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

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

The term "biodegradable" polymer in this specification means that the polymer can be degraded or broken down in a living body due to, for example, the metabolism of the living body itself, or the metabolism of microorganisms that may be present in the living body. In addition, the biodegradable polymer can be degraded by hydrolysis.

If the film according to the present invention comprises a biocompatible and/or biodegradable polymer, it is less irritable or non-irritable to the skin, and does not cause any rash. In addition, due to the use of a biocompatible and/or biodegradable polymer, the cosmetic sheet according to the present invention can adhere well to the skin.

The film according to the present invention can be used for cosmetic treatments of keratinous substances, preferably the skin, in particular the face. The film according to the present invention can take any form. For example, it can be used as a full mask sheet or as a patch for a part of the face such as the cheek, nose and eye contour.

If the film according to the present invention comprises at least one hydrophilic or water-soluble UV filter, it can provide UV-screening effects derived from the hydrophilic or water-soluble UV filter. Normally, a hydrophilic or water-soluble UV filter can be removed from the surface of a keratinous substrate such as skin by water such as sweat and rain. However, since the hydrophilic or water-soluble UV filter is included in the film according to the present invention, it is difficult to remove the hydrophilic or water-soluble UV filter with water, resulting in long-lasting UV-screening effects.

[Cosmetic process and use]

The present invention also relates to:

a cosmetic process for a keratinous substance such as skin, comprising: applying to the keratinous substance the composition according to the present invention; and drying the composition to form a cosmetic film on the keratinous substance; and

a use of the composition according to the present invention for the preparation of a cosmetic film on a keratinous substance such as the skin.

The cosmetic process here refers to a non-therapeutic cosmetic process for the care and/or makeup of the surface of a keratinous substance such as the skin.

In both the above process and use, the above cosmetic film is resistant to water of a pH of less than or equal to 7, and can be removed with water of a pH of greater than 7, preferably 8 or more, and most preferably 9 or more.

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

Therefore, the above cosmetic film can be water-resistant and thus can remain on a keratinous substance such as skin even if the surface of the keratinous substance is wet due to, for example, sweat or rain. On the other hand, the above cosmetic film can be easily removed from a keratinous substance such as skin under alkaline conditions. Therefore, the film according to the present invention is difficult to remove with water, while it can be easily removed with a soap which can provide alkaline conditions.

If the above cosmetic film comprises a UV filter which may be present in the composition according to the present invention, the above cosmetic film can protect a keratinous substance such as skin from UV rays, thereby limiting the darkening of the skin, improving the color and uniformity of the complexion, and/or treating skin aging.

Furthermore, the above cosmetic film may have cosmetic effects such as capturing sebum, mattifying the appearance of a keratin substrate such as skin, absorbing or absorbing a bad odor, and/or protecting the keratinous substance from, for example, dirt or pollutants, due to the properties of the polyionic complex in the cosmetic film, even if the cosmetic film does not contain any cosmetic active ingredients.

In addition, the above cosmetic film can immediately change or modify the appearance of the skin by changing the reflection of light on the skin and the like, even if the cosmetic film does not contain any cosmetic active ingredients. Therefore, it is possible that the above cosmetic film conceals skin defects such as pores or wrinkles. In addition, the above cosmetic film can immediately change or modify the touch feeling of the skin by changing the surface roughness of the skin and the like. In addition, the above cosmetic film can immediately protect the skin by covering the surface of the skin and shielding the skin, as a barrier, against environmental stresses such as pollutants, contaminants and the like.

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

If the above cosmetic film contains at least one additional cosmetic active ingredient such as an oil, the cosmetic film can have cosmetic effects provided by the at least one additional cosmetic active ingredient. For example, if the cosmetic film contains at least one cosmetic active ingredient selected from anti-aging agents other than the hydrophilic antioxidant (b), anti-sebum agents, deodorant agents, antiperspirant agents, whitening agents and a mixture 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 whitening of the skin.

It is also possible to apply a cosmetic makeup composition to the cosmetic film or sheet according to the present invention after its application to the skin.

EXAMPLES

The present invention will be described in more detail with the aid of examples. However, these examples should not be construed as limiting the scope of the present invention.

[Examples 1-2 and comparative example 1]

[Preparation]

Each of the compositions according to Examples 1 to 2 and Comparative Example 1 was prepared by mixing the ingredients listed in Table 1. The numerical values of the quantities of ingredients in Table 1 are all based on a “% by weight” of raw materials.

　 Ex. 1 Ex. 2 Ex.
comp. 1 Water qsp 100 qsp 100 qsp 100 Ascorbic acid 3,000 3,000 3,000 Polyglyceryl-4 caprate - 3,120 - Polyglyceryl-2 isostearate - 0.050 - Phytic acid 0.138 0.138 - Polyepsilon-Lysine 0.100 0.100 - Sodium hydroxide 0.032 0.032 - Sodium hyaluronate (M.W. 20-50 kDa) 1,000 1,000 1,000 Sodium hyaluronate
(MW 1,000-1,400 kDa) 0.500 0.500 0.500 Conservative quantum satisfaction quantum satisfaction quantum satisfaction Transparency Very good Very good Very good Durability of the antioxidant effect Good Very good Bad

[Evaluations]

(Transparency)

The appearance of each of the compositions was evaluated according to Examples 1-2 and Comparative Example 1. Specifically, each composition was poured into a transparent cylindrical glass container and evaluated for ease of seeing a background through the container, and each composition was placed on a hand and evaluated for ease of seeing the skin of the hand, in accordance with the following criteria:

Very good: The background is easily visible through the container (transparent)

Good: The background is visible through the container, although it is slightly blurred (translucent)

Correct: The background is not visible through the container, while the skin is easily visible (translucent)

Bad: Skin is not visible (opaque)

The results are shown in Table 1.

(Durability of the antioxidant effect)

0.6 g of a β-carotene solution (solvent: caprylic/capric triglyceride) with a concentration of 0.05% by weight and 0.2 g of each of the compositions according to Examples 1-2 and Comparative Example 1 were mixed to obtain a mixture.

0.4 g of the above mixture was applied to a filter (glass microfiber filter).

The filter was rinsed with tap water (300 mL, 23–27 °C).

The above filter was exposed to UV rays with a wavelength of 365 nm for 30 minutes to oxidize β-carotene.

If β-carotene is oxidized, the original yellow color derived from β-carotene fades.

The b* values in the L*a*b* space (CIE1976) before and after UV exposure (b* (T=0) and b* (T=30 min), respectively) of the filter were measured using a spectrocolorimeter (CM-700d manufactured by KONICA MINOLTA), and the difference between the b* value (T=0) and the b* value (T=30 min) was determined as Δb*. It should be noted that the b* value (T=0) of the filter before rinsing was in the range of 45 to 65.

The Δb* and b* values (T=30 min) were evaluated according to the following criteria.

Very good: Δb* <10 and b* (T=30 min) >30

Good: Δb* <10 and 30 > b* (T=30 min) >20

Bad: Δb* <10 and 20 > b* (T=30 min)

Very bad: Δb* >10

The results are shown in Table 1.

(Summary)

The compositions according to examples 1 and 2 may have transparent or translucent aspects.

It is clear from the comparison between Examples 1-2 and Comparative Example 1 that the use of a polyionic complex can prolong the antioxidant effects.

It is clear from the comparison between Example 1 and Example 2 that the use of a surfactant such as a polyglyceryl ester of fatty acid can further prolong the antioxidant effects, even under rinse conditions.

Claims (10)

Composition, comprising:
(a) at least one polyionic complex, comprising
at least one cationic polymer and at least one anionic polymer,
at least one cationic polymer and at least one amphoteric polymer,
at least one anionic polymer and at least one amphoteric polymer, or
at least one amphoteric polymer,
And
at least one non-polymeric acid having two or more pKa values or salt(s) thereof, or
at least one non-polymeric base having two or more pKb values or salt(s) thereof;
(b) at least one hydrophilic antioxidant; and
(c) water,
in which
the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives, and
the amphoteric polymer is chosen from cationized hyaluronic acid and its salts. The composition of claim 1, wherein the cationic polymer has at least one positively chargeable and/or positively charged moiety selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group. A composition according to any one of claims 1 to 2, wherein the cationic polymer is selected from the group consisting of alkyldiallylamine cyclopolymers and dialkyldiallylammonium cyclopolymers such as (co)polydiallyldialkyl ammonium chloride, (co)polyamines such as chitosans and (co)polylysines, cationic (co)polyamino acids such as collagen, cationic cellulose polymers and salts thereof. A composition according to any one of claims 1 to 3, wherein the non-polymeric acid having two or more pKa values or salt(s) thereof is(are) an organic acid or salt(s) thereof, preferably a hydrophilic or water-soluble organic acid or salt(s) thereof and more preferably a phytic acid or salts thereof. Composition according to any one of claims 1 to 4, in which the hydrophilic antioxidant (b) is selected from ascorbic acid, derivatives thereof, salts thereof and mixtures thereof. Composition according to any one of claims 1 to 5, in which the composition further comprises (d) at least one surfactant, preferably chosen from nonionic surfactants and more preferably chosen from polyglyceryl esters of fatty acids. A process for preparing a film, preferably a cosmetic film, comprising:
the application to a substrate, preferably to a keratinous substance, of the composition according to any one of claims 1 to 6; and
drying the composition. Film, preferably cosmetic film, prepared by a process comprising:
the application to a substrate, preferably to a keratinous substance, of the composition according to any one of claims 1 to 6; and
drying the composition. Film, preferably cosmetic film, comprising:
(a) at least one polyionic complex comprising
at least one cationic polymer and at least one anionic polymer,
at least one cationic polymer and at least one amphoteric polymer,
at least one anionic polymer and at least one amphoteric polymer, or
at least one amphoteric polymer, and
at least one non-polymeric acid having two or more pKa values or salt(s) thereof, or
at least one non-polymeric base having two or more pKb values or salt(s) thereof;
(b) at least one hydrophilic antioxidant;
And
optionally (c) at least one surfactant, preferably chosen from nonionic surfactants, and more preferably chosen from polyglyceryl esters of fatty acids,
in which
the anionic polymer is chosen from hyaluronic acid, its salts and its derivatives; and
the amphoteric polymer is chosen from cationized hyaluronic acid and its salts. Cosmetic process for a keratinous substance such as skin, comprising
the application to the keratinous substance of the composition according to any one of claims 1 to 6; and
drying the composition to form a cosmetic film on the keratinous substance.