JP2024090989A - Stable dispersion composition comprising a retinoid - Google Patents

Abstract

The present invention provides a composition in the form of a stable dispersion comprising at least one retinoid, wherein the retinoid is stable under exposure to light and under elevated temperature conditions.
[Solution] The present invention relates to a dispersion composition comprising a continuous phase and multiple dispersed phases, the composition comprising: (a) at least one retinoid; (b) at least one compound capable of providing a solution having a transmittance of 10% or less, preferably 5% or less, and more preferably 2% or less for light having a wavelength of 290 to 420 nm along an optical path length of 10 mm, wherein the concentration of the compound in the solution is 0.9% by weight based on the total weight of the solution; (c) at least one hydrophilic antioxidant other than component (b); and (d) at least one cationic polymer.
[Selection diagram] None

Description

The present invention relates to a stable dispersion composition containing at least one retinoid, preferably a stable cosmetic dispersion composition containing at least one retinoid.

Retinoids are known to be useful, for example, in cosmetics, as they can act as anti-aging actives that can be used, for example, to treat wrinkles. However, they tend to be unstable under some conditions. For example, although retinol is soluble in lipophilic solvents, solutions of retinol can rapidly discolour (yellowing/browning) and retinol in solution can degrade over time.

To date, several prior art documents have disclosed compositions containing retinoids. For example, WO2021/123337 discloses a composition containing at least retinol, di-t-butyl pentaerythrityl tetrahydroxycinnamate, and ethylenediamine disuccinate.

WO1996/018380 also discloses the use of a) one or more compounds from the group of flavonoids or b) a combination of an active substance containing one or more compounds selected from the group of flavonoids and one or more compounds selected from the group of cinnamic acid derivatives, c) optionally with the additional use of one or more compounds from the group of imidazole derivatives, and/or d) optionally with the additional use of one or more compounds from the group of antioxidants or metal chelators or equivalent substances, for stabilizing sensitive and unstable cosmetic or dermatologically active ingredients or components, which may include vitamins A, C or E, or their derivatives.

WO1996/007396 also discloses a skin care composition comprising an oil-in-water emulsion and a retinoid selected from the group consisting of vitamin A alcohol, vitamin A aldehyde, retinyl acetate, retinyl palmitate, and mixtures thereof.

Compositions containing retinoids also have a tendency to discolor and become odorous depending on light or temperature conditions, and have stability issues in that the retinoids in the compositions degrade over time under exposure to light or at elevated temperatures.

WO2021/123337 WO1996/018380 WO1996/007396 Patent application FR2370377 Patent application EP0199636 Patent application EP0325540 Patent application EP0402072 EP-A-307,626 FR-2,400,358 FR-2,400,359 EP-A-487404 EP-A-425066 Patent Publication No. 05-213736 European Patent Application No. 0080976 French Patent No. 2077143 French Patent No. 2393573 French Patent No. 2162025 French Patent No. 2280361 French Patent No. 2252840 French Patent No. 2368508 French Patent No. 1583363 U.S. Patent No. 3,227,615 U.S. Patent No. 2,961,347 French Patent No. 2080759 Additional Patent No. 2190406 French Patent No. 2320330 French Patent No. 2270846 French Patent No. 2316271 French Patent No. 2336434 French Patent No. 2413907 U.S. Patent No. 2,273,780 U.S. Patent No. 2,375,853 U.S. Patent No. 2,388,614 U.S. Patent No. 2,454,547 U.S. Patent No. 3,206,462 U.S. Patent No. 2,261,002 U.S. Patent No. 2,271,378 U.S. Patent No. 3,874,870 U.S. Patent No. 4,001,432 U.S. Patent No. 3,929,990 U.S. Patent No. 3,966,904 U.S. Patent No. 4,005,193 U.S. Patent No. 4,025,617 U.S. Patent No. 4,025,627 U.S. Patent No. 4,025,653 U.S. Patent No. 4,026,945 U.S. Patent No. 4,027,020 European Patent Application No. 0122324 French Patent No. 1492597 U.S. Patent No. 4,131,576 U.S. Patent No. 3,589,578 U.S. Patent No. 4,031,307 Patent application FR0853634 Patent application EP-A-0955039 Patent application US2004-175338 Patent application FR2908769 Patent application FR2704754 Patent application FR2877004 Patent application FR2854160 Patent application EP0511118 Patent application WO94/11338 Patent application FR2698095 Patent application FR2737205 Patent application EP0755925 Patent application FR2825920 EP-A-317542 EP-A-399133 EP-A-516102 EP-A-509382 US-A-5364633 US-A-5411744

"The Flavonoids", Harborne J. B., Mabry T. J., Helga Mabry, 1975, pp. 1-45 Chang et al., JOSC, Vol. 61, No. 6, June 1984 C.M. Hansen, "The three dimensional solubility parameters," J. Paint Technol, vol. 39, p. 105 (1967) Article by Meylan and Howard: Atom/Fragment contribution method for estimating octanol-water partition coefficients, J. Pharm. Sci., 84: 83-92, 1995. Exploring QSAR:hydrophobic, electronic and steric constants (ACS professional reference book, 1995) http://esc.syrres.com/interkow/kowdemo.htm

The object of the present invention is to provide a composition in the form of a stable dispersion containing at least one retinoid, wherein the retinoid is stable under exposure to light or under high temperature conditions.

The above object of the present invention is to provide a dispersion composition comprising a continuous phase and a plurality of dispersed phases,
(a) at least one retinoid;
(b) at least one compound capable of providing a solution having a transmittance of 10% or less, preferably 5% or less, and more preferably 2% or less for light having a wavelength of 290-420 nm along an optical path length of 10 mm, wherein the concentration of the compound in the solution is 0.9% by weight based on the total weight of the solution;
(c) at least one hydrophilic antioxidant other than component (b);
(d) at least one cationic polymer.

(a) The retinoid is present in the dispersed phase.

(b) the compound, (c) the hydrophilic antioxidant, and (d) the cationic polymer are present in the continuous phase.

(a) The retinoid may be retinol.

The amount of (a) retinoid in the composition according to the present invention may be within the range of 0.01% to 5% by weight, preferably 0.05% to 3% by weight, and more preferably 0.1% to 1% by weight, based on the total weight of the composition.

(b) The compound may be selected from polyphenols, preferably quercetin, isoquercetin, rutin, glucosylrutin, and mixtures thereof.

The amount of compound (b) in the composition according to the present invention may be in the range of 0.01% by mass to 5% by mass, preferably 0.05% by mass to 3% by mass, more preferably 0.1% by mass to 2% by mass, based on the total mass of the composition.

(c) The hydrophilic antioxidant may be selected from ascorbic acid, ascorbate salts, and combinations thereof.

The amount of (c) hydrophilic antioxidant in the composition may be in the range of 1% by weight to 30% by weight, preferably 5% by weight to 20% by weight, and more preferably 10% by weight to 15% by weight, based on the total weight of the composition.

(d) The cationic polymer may be selected from cationic polysaccharides, preferably non-cellulosic cationic polysaccharides, more preferably cationic gums, in particular cationic galactomannan gums.

The amount of (d) cationic polymer in the composition may be in the range of 0.01% by mass to 10% by mass, preferably 0.05% by mass to 5% by mass, and more preferably 0.1% by mass to 2% by mass, based on the total mass of the composition.

The continuous phase may be an aqueous continuous phase.

The dispersed phase includes capsules.

The amount of the dispersed phase in the composition is in the range of 0.1% to 30% by weight, preferably 1% to 20% by weight, more preferably 3% to 15% by weight, and even more preferably 5% to 10% by weight, based on the total weight of the composition.

The present invention also relates to a cosmetic method for treating keratinous materials, such as the skin, comprising the step of applying a composition according to the present invention to the keratinous materials.

As a result of intensive research, the present inventors have discovered that it is possible to provide a dispersion composition containing at least one type of retinoid, which has the form of a stable dispersion and is capable of maintaining the retinoid in the composition at a sufficient residual rate even when exposed to light or at high temperatures.

The composition according to the present invention is a dispersion composition comprising a continuous phase and a plurality of dispersed phases,
(a) at least one retinoid;
(b) at least one compound capable of providing a solution having a transmittance of 10% or less, preferably 5% or less, and more preferably 2% or less for light having a wavelength of 290-420 nm along an optical path length of 10 mm, wherein the concentration of the compound in the solution is 0.9% by weight based on the total weight of the solution;
(c) at least one hydrophilic antioxidant other than component (b);
(d) It may be characterized by a combination with at least one cationic polymer.

The compositions and methods according to the present invention are described in more detail below.

[Composition]
The composition according to the present invention has the form of a stable dispersion with multiple dispersed phases.The expression "stable dispersion" here means that the multiple dispersed phases are stable over time without settling or floating up.The composition according to the present invention can also maintain the retinoid in the composition with a sufficient residual ratio even under exposure to light and at high temperature.The dispersion here differs from the emulsion in that the dispersed phase of the present invention is not a droplet of oil, water, etc.

The composition according to the invention may preferably be used as a cosmetic composition, in particular as a leave-on cosmetic composition. The composition according to the invention may be intended for application to keratinous materials, such as the skin, for example the skin of the face, neck or body, the lips, the scalp and the hair. The composition according to the invention has a cosmetic effect on keratinous materials, in particular an anti-aging, whitening and/or anti-wrinkle effect.

The composition according to the present invention exhibits a stable morphology as a dispersion. In other words, each of the dispersed phases is well dispersed in the composition without settling or floating up. In particular, the composition according to the present invention exhibits a stable morphology as a dispersion over time, even at high temperatures, e.g., 55°C. In other words, each of the dispersed phases is well dispersed in the composition without settling or floating up over time, even at high temperatures, e.g., 55°C.

The composition according to the present invention can maintain the retinoid (a) in the composition at a sufficient residual rate (e.g., 75% or more) even under exposure to light (e.g., UV light) and at high temperatures (e.g., 55°C). In other words, the deterioration of the retinoid (a) in the composition according to the present invention caused by light and high temperatures can be reduced. Therefore, the composition according to the present invention can provide a cosmetic effect that is stable over time based on the retinoid (a) in the composition.

The compositions according to the invention may be transparent or translucent.

Clarity can be measured by measuring turbidity (for example, turbidity can be measured with a 2100Q (commercially available from HACH) equipped with a round cell (diameter 25 mm x height 60 mm) and a tungsten filament bulb capable of emitting visible light (between 400 nm and 800 nm, preferably 400-500 nm). Measurements can be performed on undiluted compositions. A blank can be determined using distilled water.

The compositions according to the invention may preferably have a turbidity of less than 200 NTU, preferably less than 150 NTU, more preferably less than 100 NTU, even more preferably less than 50 NTU.

The composition according to the present invention comprises: (a) at least one retinoid; (b) at least one compound capable of providing a solution having a transmittance of 10% or less for light having a wavelength of 290 to 420 nm along an optical path length of 10 mm, the concentration of the compound in the solution being 0.9% by weight based on the total weight of the solution; (c) at least one hydrophilic antioxidant other than component (b); and (d) at least one cationic polymer.

The components of the composition according to the present invention are described in more detail below.

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

(a) The retinoid may be retinol (vitamin A), retinal (vitamin A aldehyde), retinoic acid (vitamin A acid), or an ester of retinol with a _C2-20 acid, such as the propionate, acetate, linoleate, or palmitate ester of retinol (retinyl palmitate).

(a) Among the retinoids, mention may be made of retinol, retinal, retinoic acid, in particular all-trans retinoic acid and 13-cis retinoic acid, retinol derivatives such as retinyl acetate, retinyl propionate or retinyl palmitate, and the retinoids described in the following patent applications: FR2370377, EP0199636, EP0325540 and EP0402072.

According to a preferred embodiment of the present invention, (a) the retinoid is retinol or proretinol.

The term "retinol" is intended to mean all isomers of retinol, i.e., all-trans retinol, 13-cis retinol, 11-cis retinol, 9-cis retinol, and 3,4-didehydroretinol.

Retinyl palmitate is a representative example of pro-retinol.

(a) The retinoid is preferably retinol.

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

On the other hand, the amount of (a) retinoid in the composition according to the present invention may be 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less, based on the total mass of the composition.

The amount of (a) retinoid in the composition according to the present invention may be within the range of 0.01% to 5% by weight, preferably 0.05% to 3% by weight, and more preferably 0.1% to 1% by weight, based on the total weight of the composition.

In the context of this specification, any combination of upper and lower parameter values can be used to express a preferred range of a parameter, e.g., an amount.

(Light-shielding compound)
The composition according to the invention comprises (b) at least one compound capable of providing a solution having a transmittance of 10% or less, preferably 5% or less, more preferably 2% or less for light having a wavelength of 290-420 nm along an optical path length of 10 mm, wherein the concentration of the (b) compound in the solution is 0.9% by weight based on the total weight of the solution. Thus, a single type of such (b) compound or a combination of different types of such (b) compounds may be used.

(b) compounds can provide low light transmittance. Therefore, (b) compounds are sometimes called light-blocking compounds.

(b) The compound may be present in the continuous phase of the present invention.

More preferably, the (b) compound is capable of providing a solution having zero (0) transmittance for light having a wavelength of 290 to 420 nm along an optical path length of 10 mm, and the concentration of the (b) compound in the solution is 0.9% by weight based on the total weight of the solution.

Even more preferably, the (b) compound is capable of providing a solution having zero (0) transmittance for light having a wavelength of 290 to 420 nm along an optical path length of 10 mm, and the concentration of the (b) compound in the solution is greater than 0.1% by weight based on the total weight of the solution.

The solvent for the solution is not limited as long as the (b) compound is solubilized in the solvent, and the solvent has no absorbance for light having a wavelength of 290 to 420 nm. For example, hydrophilic solvents such as water and ethanol may be used as the solvent.

Transmittance can be measured by a spectrophotometer, for example, a UV-Visible/NIR Spectrophotometer V-750 by JASCO Corp.

The (b) compound can provide a solution having a transmittance of 10% or less, preferably 5% or less, more preferably 2% or less, and even more preferably zero (0)% for any light having a wavelength between 290 nm and 420 nm along a 10 mm optical path length. In other words, the (b) compound solution can reduce or block any light having a wavelength between 290 nm and 420 nm.

The (b) compound can reduce or block light having the above-mentioned specific wavelengths that can reach the (a) retinoid in the composition according to the present invention and decompose the (a) retinoid. Therefore, the (b) compound can contribute to enhancing the photostability of the (a) retinoid and can reduce the decomposition of the (a) retinoid in the composition according to the present invention.

(b) The compound may be selected from polyphenols.

- Polyphenols The expression "polyphenols" is understood to mean compounds containing several phenolic hydroxyl groups. Phenolic hydroxyl groups mean hydroxyl groups attached to aromatic rings such as benzene and naphthalene rings. The phenolic hydroxyl groups may optionally be etherified or esterified.

The polyphenols may be selected from those that have antioxidant properties.

The polyphenol may be selected, for example, from flavonoids.

Preferred flavonoids are represented by the general formula (I):

(Wherein,
A", B", C" and D" represent, independently of one another, H, OH, -R' or -OR', where R' represents a saccharide residue of formula R'OH,
E" represents H, -OH or -OX', X' is

represents
F", G" and J" are independently of each other H, -OH or _-OCH3 ;
_X1 represents _-CH2- , -CO- or -CHOH-;
Or general formula (II):

(Wherein,
A', C' and D' represent, independently of one another, H, -OH, _-OCH3 , -R' or -OR', where R' represents the residue of a sugar of formula R'OH,
E' represents H, -OH or -OR', R' represents a saccharide residue of formula R'OH,
B', F', G' and J' represent, independently of each other, H, -OH, _-OCH3 , _-OCH2 - _CH2- OH, or -OR', where R' represents the residue of a sugar of formula R'OH.
It can be equivalent to.

Among the sugars R'OH, mention may be made of rutinose, glucose, apiose, rhamnose, lobinose, neohesperidose, or combinations thereof.

Compounds of formulae (I) and (II) are known. They can be obtained, inter alia, by the methods described in "The Flavonoids", Harborne J. B., Mabry T. J., Helga Mabry, 1975, pp. 1-45.

The flavonoids may be selected from flavones, flavonols, isoflavones, flavanols, flavanones, anthocyanidins, and mixtures thereof.

Among the flavonoids that can be used for the present invention, mention may be made of apigenin, apiin, apigetrin, vitexin, chrysin, tringin, luteolin, orientin, galangin, quercetin, isoquercetin, rutin, glucosylrutin, quercitrin, isoquercitrin, kaempferol, astragalin, kaempferitrin, robinin, myricetin, daidzein, daidzin, genistein, genistein, glycitein, glycitin, catechin, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, theaflavin, naringenin, narirutin, naringin, hesperetin, hesperidin, glucosylhesperidin, anthocyanidin, anthocyanin, cyanidin, cyanin, delphinidin, delphinin, pelargonidin, and pelargonin.

Certain polyphenols that can be used are present in plants and can be extracted therefrom by known methods. Extracts from tea leaves (Camellia sinensis or Camellia japonica) can be used. Mention may in particular be made of the green tea extract sold under the name SUNPHENON® by the company Taiyo, which contains, inter alia, flavonoids.

As a polyphenol, a mixture of glucosylrutin and rutin sold under the name ALPHA GLUCOSYL RUTIN by QINGDAO TAITONG PHARMACEUTICAL CO., LTD. can be used.

Among the polyphenols that can be used, mention may also be made of polyphenols such as carnosic acid and carnosol, which can be extracted, for example, from rosemary, either by extraction followed by distillation (Chang et al., JOSC, Vol. 61, No. 6, June 1984) or by extraction with a non-polar solvent such as hexane to remove odorous substances, followed by extraction with a polar solvent such as ethanol, as described in EP-A-307,626.

Polyphenols are also known as (2,5-dihydroxyphenyl)alkylene carboxylic acids and their derivatives (especially esters and amides) of formula (III):

(Wherein,
R ₁ ″ represents —O-Alk, OH or —N(r′)(r”), where Alk represents a linear or branched C ₁ -C ₂₀ alkyl or C ₂ -C ₂₀ alkenyl, optionally substituted with one or more hydroxyl or alkoxy groups;
r' and r" independently represent H, _C1 - _C20 alkyl, _C2 - _C6 hydroxyalkyl, or _C3 - _C6 polyhydroxyalkyl, or alternatively r' and r" together with the nitrogen atom to which they are attached form a heterocyclic ring;
r is a number including zero such that the -( _CH2 ) _r - _COR1 chain contains up to 21 carbon atoms;
R ₂ ″ and R ₃ ″ independently represent H or C ₁ -C ₄ alkyl; in addition, R ₂ ″ can also represent C ₁ -C ₄ alkoxy.
may be selected from.

Compounds of formula (III) are known or can be prepared according to known methods, for example methods similar to those described in patents FR-2,400,358 and FR-2,400,359.

The polyphenol may also be selected from esters or amides of caffeic acid.

Among the esters of caffeic acid, in particular those of formula (IV):

(Wherein,
Z represents a C ₁ -C ₈ alkyl, such as methyl, or a residue of phytol.
Compounds of the formula:

Among the amides of caffeic acid, in particular those of formula (V):

(Wherein,
Z' represents C ₁ -C ₈ , in particular C ₆ -C ₈ alkyl.
Compounds of the formula:

Compounds of formula (IV) or (V) are known or can be prepared according to known methods.

(b) The compound is
It may be selected from the group consisting of quercetin, isoquercetin, rutin, glucosylrutin, and mixtures thereof.

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

On the other hand, the amount of compound (b) in the composition according to the present invention may be 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less, based on the total mass of the composition.

The amount of compound (b) in the composition according to the present invention may be in the range of 0.01% by mass to 5% by mass, preferably 0.05% by mass to 3% by mass, more preferably 0.1% by mass to 2% by mass, based on the total mass of the composition.

(hydrophilic antioxidant)
The composition of the present invention includes (c) at least one hydrophilic antioxidant other than component (b). A single type of hydrophilic antioxidant may be used, or two or more different types of hydrophilic antioxidants may be used in combination.

(c) the at least one hydrophilic antioxidant is different from (b) a compound capable of providing a solution having a transmittance of 10% or less, preferably 5% or less, more preferably 2% or less for light having a wavelength of 290 to 420 nm along an optical path length of 10 mm, and the concentration of the compound in the solution is 0.9% by weight based on the total weight of the solution.

(c) A hydrophilic antioxidant may be present in the continuous phase of the present invention.

The term "antioxidant" as used herein refers to a chemical compound, enzyme, or other organic molecule that prevents free radicals from causing oxidation of molecules such as those found in keratinous materials. Antioxidants can protect such molecules from damage by reacting with oxidizing agents.

(c) The antioxidant is hydrophilic. The term "hydrophilic" as used herein means a substance that is water-soluble. The term "water-soluble" as used herein means a substance that can dissolve in an amount of 0.1 g or more, 1 g or more, or 10 g or more in 100 mL of water at room temperature (25° C.) and atmospheric pressure (10 ⁵ Pa).

The hydrophilic antioxidant may be selected from natural and synthetic antioxidants, preferably natural antioxidants.

(c) Examples of hydrophilic antioxidants include, but are not limited to, ascorbic acid and its derivatives, hydroxyacetophenone, dihydrochalone, zinc PCA, baicalin, ferulic acid, pine bark extract, and polydatin. Preferably, (c) the hydrophilic antioxidant is selected from natural antioxidants, such as ascorbic acid, dihydrochalone, baicalin, ferulic acid, pine bark extract, and polydatin.

Ascorbic acid, also known as vitamin C, is a well-known cosmetic active ingredient. It is used as an anti-aging, whitening and/or anti-wrinkle ingredient in keratinous materials, especially in the skin, due to its ability to stimulate collagen synthesis and reduce melanin. Ascorbic acid generally refers to L-ascorbic acid.

The ascorbic acid is preferably L-ascorbic acid or vitamin C. Its structure is represented by the following formula:

The derivative of ascorbic acid may be a salt of ascorbic acid. The salt of ascorbic acid is preferably a medicamentously acceptable salt. Examples of the salt of ascorbic acid include, but are not limited to, salts with organic bases (e.g., salts with tertiary amines such as trimethylamine salts, triethylamine salts, monoethanolamine salts, triethanolamine salts, and pyridine salts, basic ammonium salts such as arginine, etc.), and salts with inorganic bases (e.g., alkali metal salts such as ammonium salts, sodium salts, and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, aluminum salts, etc.).

Due to their chemical structure (α-keto lactone) which makes them highly sensitive to certain environmental parameters such as light, heat and aqueous media, ascorbic acid derivatives may be advantageously used in the form of sugar esters of ascorbic acid or metal salts of phosphated ascorbic acid.

Sugar esters of ascorbic acid that can be used in the present invention are, inter alia, glycosyl, mannosyl, fructosyl, fucosyl, galactosyl, N-acetylglucosamine, N-acetylmuramic acid derivatives of ascorbic acid and mixtures thereof, more particularly ascorbyl-2 glucoside, or 2-O-α-D glucopyranosyl of L-ascorbic acid, or 6-O-D galactopyranosyl of L-ascorbic acid. The latter compounds and methods for their preparation are described, inter alia, in documents EP-A-487404, EP-A-425066 and JP-A-05-213736.

For this portion, the metal salt of phosphated ascorbic acid may be selected from alkali metal ascorbyl phosphates, alkaline earth metal ascorbyl phosphates, and transition metal ascorbyl phosphates.

The derivative of ascorbic acid may preferably be selected from salts of ascorbic acid or ascorbic acid phosphates, such as, inter alia, sodium ascorbate, sodium ascorbyl phosphate or magnesium ascorbyl phosphate, acetate esters of ascorbic acid, or sugar esters of ascorbic acid, including saccharide esters and, inter alia, glycosyl ascorbic acid.

In a preferred embodiment, (c) the antioxidant is selected from ascorbic acid, its salts, and combinations thereof.

The amount of (c) hydrophilic antioxidant in the composition according to the present invention may be 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total mass of the composition.

On the other hand, the amount of (c) hydrophilic antioxidant in the composition according to the present invention may be 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the composition.

The amount of (c) hydrophilic antioxidant in the composition according to the present invention may be in the range of 1% by weight to 30% by weight, preferably 5% by weight to 20% by weight, more preferably 10% by weight to 15% by weight, based on the total weight of the composition.

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

(d) A cationic polymer may be present in the continuous phase of the present invention.

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

The molecular weight of the cationic polymer can be 1000 or more, preferably 50000 or more, more preferably 100000 or more, and even more preferably 1000000 or more.

Unless otherwise defined in this specification, "molecular weight" means number average molecular weight.

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

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

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

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

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

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

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

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

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

(4) Polyaminoamide derivatives obtained by condensation of polyalkylenepolyamines with polycarboxylic acids followed by alkylation with bifunctional agents, such as adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers, in which the alkyl groups contain 1 to 4 carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene groups contain 1 to 4 carbon atoms, such as ethylene groups. Such 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.

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

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

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

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

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

Formula (II):

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

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

Polymers of this type are described, for example, in French Patents Nos. 2320330, 2270846, 2316271, 2336434 and 2413907, and in U.S. Patents Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,000, and 2,372,411,721. 2, 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.

A non-limiting example of such a polymer is represented by formula (III):

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

(7) Formula (IV):

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

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

(8) Quaternary polymer 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 containing units selected from vinylpyridine units and vinylpyridinium units, condensates of polyamines with epichlorohydrin, quaternary polyureylenes, and chitin derivatives.

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

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

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

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

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

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

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

(11) Cationic polysaccharides
(d) The cationic polymer of the present invention may preferably be selected from cationic polysaccharides.

The charge density of the cationic polysaccharide can be 0.01 meq/g to 20 meq/g, preferably 0.05 to 15 meq/g, and more preferably 0.1 to 10 meq/g.

The molecular weight of the cationic polysaccharide may be 1000 or more, preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 1,000,000 or more.

Unless otherwise defined in this specification, "molecular weight" means number average molecular weight.

The cationic polysaccharide may have at least one positively charged and/or positively charged moiety selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups. The term (primary) "amino group" here means _-NH2 group. (a) The cationic polysaccharide preferably has at least one quaternary ammonium group.

The cationic polysaccharides may be homopolymers or copolymers. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from three or more types of monomers, for example terpolymers obtained from three types of monomers.

The cationic polysaccharide may be selected from natural and synthetic cationic polysaccharides.

The cationic polysaccharide is preferably selected from cationic cellulose polymers.

According to the present invention, "cationic cellulose polymer" refers to any non-silicified (non-silicon) cellulose polymer that contains cationic groups and/or groups that can be ionized to cationic groups, and preferably does not contain anionic groups and/or groups that can be ionized to anionic groups.

The term "cellulose" polymer, according to the present invention, denotes any polysaccharide compound having at least 20 glucose residue chains in its structure linked by β-1,4 bonds. Cellulose polymers may be associative, i.e., have at least one _C8 - _C30 fatty chain in their structure.

Cationic cellulose polymers suitable for use preferably have a weight average molecular weight (Mw) between about 5000 and 5.10 ⁶ , preferably between about 10 ³ and 3.10 ⁶ .

Non-limiting examples of cationic cellulose polymers are as follows:

(10-1) Cationic cellulose derivatives, such as cellulose ether derivatives containing quaternary ammonium groups, such as those described in French Patent No. 1492597, for example the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammonium derivatives of hydroxyethylcellulose reacted with epoxides substituted with trimethylammonium groups.

(10-2) Cationic cellulose derivatives, such as cellulose copolymers and cellulose derivatives grafted with water-soluble monomers of quaternary ammonium, as well as those described in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, such as hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted with salts selected from methacryloylethyltrimethylammonium, methacrylamidepropyltrimethylammonium and dimethyldiallylammonium salts. Commercially available products corresponding to these polymers include, for example, the products sold under the names "Celquat® L 200" and "Celquat® H 100" by National Starch.

(10-3) A cationic cellulose polymer having at least one quaternary ammonium group containing at least one fatty chain.
The fatty chain of the quaternized cellulose modified by a group containing at least one linear fatty chain may be linear alkyl, linear or branched aryl alkyl, linear alkyl aryl, preferably linear alkyl (these groups contain at least 8 carbon atoms, preferably 8 to 30 carbon atoms, more preferably 10 to 24 or 10 to 14 carbon atoms), or a mixture thereof.

Preferably, quaternized hydroxyethyl cellulose modified with a group containing at least one linear fatty chain, such as linear alkyl, linear aryl alkyl, linear alkyl aryl, preferably linear alkyl (these groups contain 8 carbon atoms, in particular 8 to 30 carbon atoms, more preferably 10 to 24 or 10 to 14 carbon atoms), or a mixture thereof, can be mentioned. Preferably, the formula (Ib):

(Wherein,
- R represents an ammonium group RaRbRcN ⁺ -, Q-, where Ra, Rb, Rc are the same or different and represent a hydrogen atom or a linear, C1-C30, alkyl, preferably alkyl, and Q- represents an anionic counterion, for example a halide, for example a chloride or bromide ion,
- R' represents an ammonium group R'aR'bR'cN ⁺ -, Q'-, where R'a, R'b, R'c are the same or different and represent a hydrogen atom or a linear, C1-C30, alkyl, preferably alkyl, and Q'- represents an anionic counterion, for example a halide, for example a chloride ion or a bromide ion, preferably an alkyl,
It is understood that at least one of the groups Ra, Rb, Rc, R'a, R'b, and R'c represents a linear, C8-C30, alkyl;
- n, x and y are the same or different and represent integers between 1 and 10000.
Hydroxyethyl cellulose of the formula (I) can be mentioned.

Preferably, in formula (Ib), at least one of the groups Ra, Rb, Rc, R'a, R'b, and R'c represents a linear C8-C30 alkyl, preferably C10-C24 or C10-C14, and in particular a dodecyl group (C12). Preferably, the other groups represent a linear C1-C4 alkyl, in particular methyl.

Preferably, in formula (Ib), only one of the groups Ra, Rb, Rc, R'a, R'b, R'c represents a linear C8-C30 alkyl, preferably C10-C24 or C10-C14, in particular a dodecyl group (C12). Preferably, all the other groups represent a linear C1-C4 alkyl, in particular methyl.

More preferably, R may be a group selected from -N ⁺ (CH ₃ ) _3, ^Q'- and -N ⁺ (C ₁₂ H ₂₅ )(CH ₃ ) _2, ^Q- , preferably N ⁺ (CH ₃ ) _3, ^Q'- .

More preferably, R' can be a -N ⁺ (C ₁₂ H ₂₅ )(CH ₃ ) _2, Q' ^- group.

The percentage of nitrogen may vary from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, and more preferably from 0.5 to 3% by weight, based on the total polymer weight.

In particular, polymers having the following INCI names:
Polyquaternium-24, such as the product QUATRISOFT LM 200® sold by the company AMERCHOL/DOW CHEMICAL;
PG-hydroxyethylcellulose cocodimonium chloride, such as the product CRODACEL QM®,
PG-hydroxyethylcellulose lauryldimonium chloride (C12 alkyl), such as the product CRODACEL QL®, and
PG-hydroxyethylcellulose stearyldimonium chloride (C18 alkyl), such as the product CRODACEL QS® sold by the company CRODA
Examples include:

Mention may also be made of hydroxyethyl cellulose of formula (Ib), where R is a trimethylammonium halide salt and R' is a dimethyldodecylammonium halide salt, preferably R is trimethylammonium chloride Cl-, (CH3)3N+- and R' is dimethyldodecylammonium chloride Cl-, (CH3)2(C12H25)N+-. Polymers of this type are known under the INCI name Polyquaternium-67, and commercial products include SOFTCAT POLYMER SL® polymers from AMERCHOL/DOW CHEMICAL, such as SL-100, SL-60, SL-30, SL-5 and SX-1300X.

More particularly, the cationic cellulose polymer is chosen from hydroxyethyl cellulose reacted with trimethylammonium epoxide and lauryldimethylammonium epoxide (INCI name Polyquaternium-67), preferably sold under the name Softcat Polymer SL-100 or Softcat Polymer SX-1300X by the company Amerchol.

(10-4) The non-cellulosic cationic polysaccharide may be selected from cationic gums, in particular cationic galactomannan gum (cationic guar), cationic starch, cationic hyaluronic acid, chitosan and dextran hydroxypropyltrimonium chloride.

The term "cationic galactomannan gum" refers to any galactomannan gum that contains cationic groups and/or groups that can be ionized to cationic groups.

Galactomannans are polysaccharides essentially composed of galactose and mannose units, where the mannose units are linked by 1-4 glycosidic bonds and the galactose branches arise from 1-6 bridges to the mannose units. Each ring of galactose or mannose units (i.e. sugar units) has three free hydroxyl groups available for chemical reactions. Galactomannans are commonly found in the endosperm of legumes, such as guar or carob kernels.

Preferred cationic groups are selected from those containing primary, secondary, tertiary, and/or quaternary amine groups.

The cationic galactomannan gums used generally have a weight average molecular weight of between about 500 and 5×10 ⁶ , preferably between about 10 ³ and 3×10 ⁶ .

A group of cationic galactomannans suitable for use according to the invention are, for example, gums containing trialkyl(C ₁ -C ₄ )ammonium cationic groups. Preferably, between 2% and 30% of the number of hydroxyl functional groups of these gums bear trialkylammonium cationic groups.

Among these trialkylammonium groups, mention may be made in great detail of trimethylammonium and triethylammonium groups.

Even more preferably, these groups represent 5% to 20% by weight of the total weight of the modified galactomannan gum.

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

These galactomannan gums, in particular those derived from guar modified with cationic groups, are already known products per se and are described, for example, in U.S. Pat. Nos. 3,589,578 and 4,031,307.

According to the present invention, the cationic galactomannan gum is preferably a guar gum containing hydroxypropyltrialkylammonium groups, more preferably a guar gum containing hydroxypropyltrimethylammonium groups, i.e., a guar gum modified with, for example, 2,3-epoxypropyltrimethylammonium chloride.

These galactomannan gums, in particular those derived from guar modified with cationic groups, are already known products per se and are described, for example, in US Pat. Nos. 3,589,578 and 4,031,307. Other such products are sold, in particular, by Rhodia under the trade names Jaguar EXCEL, Jaguar C13 S, Jaguar C15, Jaguar C17 and Jaguar C162 (guar hydroxypropyltrimonium chloride), by Degussa under the name Amilan® Guar (guar hydroxypropyltrimonium chloride) and by Aqualon under the name N-Hance® 3000 (guar hydroxypropyltrimonium chloride). Hydroxypropyl guar hydroxypropyltrimonium chloride, the hydroxypropyl derivative of guar hydroxypropyltrimonium chloride, is commercially available from Rhodia Inc. under the trade name Jaguar® series. Cassia hydroxypropyltrimonium chloride is commercially available from Lubrizol Advanced Materials, Inc. under the trademarks Sensomer™ CT-250 and Sensomer™ CT-400, or from Ashland Inc. under the trademark ClearHance™.

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

In a preferred embodiment of the present invention, (d) the cationic polymer is selected from cationic polysaccharides, preferably non-cellulosic cationic polysaccharides, more preferably cationic gums, in particular cationic galactomannan gums.

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

The amount of (d) cationic polymer in the composition according to the present invention may be 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less, based on the total mass of the composition.

The amount of (d) cationic polymer in the composition according to the present invention may be in the range of 0.01% by mass to 10% by mass, preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 2% by mass, based on the total mass of the composition.

Dispersed phase The composition according to the present invention comprises a plurality of dispersed phases. Each dispersed phase is well dispersed in the composition without settling or floating. In addition, the dispersed phase of the present invention is not a droplet of oil, water, etc., so the dispersed composition according to the present invention is not an emulsion.

The shape of the dispersed phase is not particularly limited. The dispersed phase may be of any shape, regardless of the crystal form (e.g., lamellar, cubic, hexagonal, orthorhombic, etc.), and may be platelet-shaped, spherical, or oblong.

The size of the dispersed phase is not particularly limited. For example, the number average primary diameter of the dispersed phase is in the range of 5 nm to 10 mm, preferably 10 nm to 5 mm.

For the purposes of this invention, the term "primary particle size" means the largest dimension that can be measured between two diametrically opposed points on an individual particle. The term "number average diameter" means the diameter given by the statistical particle size distribution to half the population, referred to as D50. The size of the dispersed phase can be measured by observation with a SEM (scanning electron microscope), TEM (transmission electron microscope), optical microscope or laser diffraction particle size distribution analyzer.

The dispersed phase of the present invention may comprise or consist of capsules or inorganic fillers. The term "filler" should be understood to mean any form of mineral or natural particle that is insoluble in the medium of the composition, regardless of the temperature at which the composition is prepared.

In a preferred embodiment, the continuous phase may be an aqueous continuous phase, so that in a preferred embodiment, the dispersed phase is water-insoluble or shape-retaining in water. For the purposes of the present invention, the term "water-insoluble" refers here to a material that is soluble in water at a concentration of less than 0.1% by weight, in particular less than ^0.01 % by weight, relative to the total weight of water, at room temperature (25°C) and atmospheric pressure (105 Pa).

Capsules The term "capsule" is intended herein to mean a particle or bead comprising a core, also called "inner core", surrounded by a coating based on one or more layers or films, also called "shell" or "outer layer". The shell may comprise one layer or two or more layers.

The shape of the capsule is not particularly limited. For example, the capsule may be in the shape of a sphere.

The capsule preferably comprises a core and at least one shell surrounding the core.

The number of layers or coatings in a shell is not limited, but it may be preferred that the shell includes one layer or coating.

In one embodiment of the present invention, the shell may include at least one polysaccharide other than (d) the cationic polymer. In other words, the layer or coating in the shell may be formed of at least one polysaccharide other than (d) the cationic polymer.

Capsules can be prepared by encapsulating the core, which can be done by any conventional method. For example, the core-forming composition and the shell-forming composition can be co-extruded. In this case, the extruded core-forming composition can form the core and the shell-forming composition can form the shell. The co-extruded core/shell structure can be converted into a core/shell particle that corresponds to a capsule.

The size of the capsules is not particularly limited. For example, the number average primary diameter of the capsules is in the range of 100 μm to 10 mm, preferably 250 μm to 7 mm, more preferentially 500 μm to 5 mm, even more preferably 750 μm to 3 mm, in particular 1 mm to 2 mm.

Inorganic Filler The inorganic filler may preferably be selected from inorganic UV filter powders and inorganic coloring fillers.

- Inorganic UV filter powder The inorganic UV filter powder used for the present invention can be effective in the UV-A and/or UV-B region, preferably in the UV-B region, or in the UV-A and UV-B regions. The powdery cosmetic composition according to the present invention can contain a further additional UV filter in addition to the inorganic UV filter powder. The active UV filter region of the inorganic UV filter powder and the active UV filter region of the additional UV filter are preferably complementary to each other to provide comprehensive UV protection. For example, it is preferred that the inorganic UV filter powder is active at least in the UV-B region, and the additional UV filter is active at least in the UV-A region. The inorganic UV filter powder can be hydrophilic and/or lipophilic.

The inorganic UV filter powder may be in the form of fine particles having an average primary particle size of less than 200 nm, preferably less than 180 nm, more preferably between 5 nm and 180 nm, even more preferably between 5 nm and 150 nm, and even more preferably between 10 nm and 100 nm. The average primary particle size here means the number-average diameter-mean diameter given by the statistical particle size distribution to half of the population, and is referred to as D50. For example, such a number-average diameter-mean diameter of the inorganic UV filter powder can be measured by SEM (scanning electron microscope) and/or TEM (transmission electron microscope).

The inorganic UV filter powder may be selected from metal oxides such as titanium oxide (amorphous or crystalline, in the rutile and/or anatase form), zinc oxide, zirconium oxide or cerium oxide, all of which are well-known UV photoprotectors. Preferably, the inorganic UV filter powder is selected from the group consisting of titanium dioxide, zinc oxide and cerium oxide.

The inorganic UV filter powder may be coated or uncoated. The coating is not particularly limited, and any conventional coating may be used. For example, the coating may include at least one compound selected from the group consisting of alumina, silica, aluminum hydroxide, silicone, silanes, fatty acids or salts thereof (e.g., sodium, potassium, zinc, iron or aluminum salts), fatty alcohols, lecithin, amino acids, polysaccharides, proteins, alkanolamines, waxes, such as beeswax, (meth)acrylic polymers, organic UV filters, and (per)fluoro compounds.

- Inorganic Colouring Fillers The term "inorganic colouring fillers" is here understood to include inorganic pigments, pearlescent agents and reflective particles, as well as mixtures thereof.

The term "pigment" should be understood to mean white or colored particles of any shape that are insoluble in physiological media and are intended to color the composition.

Among the pigments that may be mentioned are optionally surface-treated titanium dioxide, for example pigmented titanium dioxide of the rutile type, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and also metal powders, for example aluminum powder and copper powder.

The term "pearlescent agent" should be understood to mean any form of colored particles, which may or may not be iridescent, produced in particular by certain mollusks in their shells or otherwise synthesized, and which have a color effect through optical interference.

Examples of pearlescent agents that may be mentioned include pearlescent pigments, such as titanium mica coated with iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, and pearlescent pigments based on bismuth oxychloride. The pearlescent agents may also be particles of mica, the surface of which is overlain by at least two successive layers of metal oxides and/or organic dyes. The pearlescent agents may have a color or color glitter, more particularly, of yellow, pink, red, bronze, orange, brown, gold and/or copper.

The term "reflective particles" denotes particles that, due to their size, structure, especially the thickness of the layer they form, as well as their physical and chemical properties and surface condition, are able to reflect incident light. This reflection can, where appropriate, be of sufficient intensity to produce, when applied to a support to be made up, excessively bright spots, i.e. spots brighter in comparison with the environment, visible to the naked eye, on the surface of the composition or mixture, by appearing shiny.

The reflective particles can be selected so as not to significantly alter the coloring effect produced by the colorants with which they are combined, and more particularly to optimize this effect in terms of color yield.

Whatever its form, the reflective particles may or may not have a multi-layer structure, and if they do have a multi-layer structure, they may have at least one layer, particularly of reflective material, for example of uniform thickness.

If the reflective particles do not have a multilayer structure, they can consist, for example, of metal oxides, in particular synthetically obtained titanium oxide or iron oxide.

When the reflective particles have a multilayer structure, the particles may for example comprise a natural or synthetic substrate, in particular a synthetic substrate, at least partially coated with at least one layer of a reflective material, in particular with at least one layer of a metal or metallic material. The substrate may be made of one or more organic and/or inorganic materials.

More specifically, the substrate may be selected from glass, ceramic, graphite, metal oxides, alumina, silica, silicates, especially aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list being non-limiting.

The reflective material may include a layer of metal or metallic material.

Again, examples of reflective particles comprising a mineral substrate coated with a metal layer include particles comprising a borosilicate substrate coated with silver.

Metallic substrates, such as particles containing silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, manganese, steel, bronze or titanium, can also be used, said substrates being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide or silicon oxide, and mixtures thereof.

In some specific embodiments of the present invention, the dispersed phase comprises or consists of at least one capsule.

In a further particular embodiment, the (a) retinoid is present in a capsule. For example, the core of the capsule may comprise the (a) retinoid. Encapsulation of the (a) retinoid may prevent or reduce contact between the (a) retinoid and (c) at least one hydrophilic antioxidant, such as ascorbic acid, and may reduce changes in color (particularly brightness) of the composition according to the invention. Thus, the capsule may reduce color evolution of the composition according to the invention.

In some embodiments, essential components (b)-(d) are present in the continuous phase of the composition.

The amount of the dispersed phase in the composition according to the present invention may be 0.1% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, based on the total weight of the composition.

On the other hand, the amount of the dispersed phase in the composition according to the present invention may be 30% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less, based on the total weight of the composition.

The amount of dispersed phase in the composition according to the invention may be in the range of 0.1% to 30% by weight, preferably 1% to 20% by weight, more preferably 3% to 15% by weight, and even more preferably 5% to 10% by weight, based on the total weight of the composition.

The continuous phase may be a dispersion medium for the multiple dispersed phases of the present invention. The continuous phase may therefore be in the form of a liquid at 25° C. and atmospheric pressure (760 mmHg).

The form of the continuous phase is not particularly limited. In general, the continuous phase is liquid at room temperature (25° C.) and atmospheric pressure (10 ⁵ Pa). The continuous phase can take various forms, such as a solution, an aqueous solution, a lotion, an emulsion, a cream, a gel, a liquid gel, a paste, a serum, a suspension, a dispersion, a fluid, a milk, an emulsion (O/W or W/O form), etc.

The continuous phase of the present invention can preferably be an aqueous continuous phase. In another preferred embodiment, the continuous phase can be an aqueous solution.

In some particular embodiments of the present invention, the continuous phase of the present invention comprises a small amount of oil or is oil-free. For example, the continuous phase may comprise oil in an amount of 0% to 5% by weight, preferably 0% to 3% by weight, more preferably 0% to 1% by weight, especially 0% to 0.1% by weight, based on the total weight of the continuous phase. In another embodiment, the continuous phase is oil-free.

The viscosity of the continuous phase in the composition according to the invention is not particularly limited, but may generally be, for example, in the range of 4000 to 8000 Pa·s at 25°C. For the purposes of the present invention, the viscosity may be measured at 25°C using a viscometer or rheometer, preferably having a cone-plate or parallel-plate geometry.

(Optional Ingredients)
The dispersed and continuous phases in the composition may contain optional ingredients in addition to the essential ingredients (a)-(d) described above.

- Oil The composition according to the invention may comprise at least one oil. Two or more oils may be used in combination. Thus, a single type of oil may be used or a combination of different types of oils may be used.

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

The oil may be present in the dispersed phase. In one embodiment, the dispersed phase comprises at least one oil.

The oil may be selected from polar oils or non-polar oils.

The term "polar oil" means here any lipophilic compound which, at 25° C., has a solubility parameter characteristic of dispersive interactions, δ _d , greater than 16 and a solubility parameter characteristic of polar interactions, δ _p , strictly greater than 0. The solubility parameters δ _d and δ _p are defined according to the Hansen classification.

The definition and calculation of solubility parameters in the Hansen three-dimensional solubility space are described in the paper C.M. Hansen, "The three dimensional solubility parameters," J. Paint Technol, Vol. 39, p. 105 (1967).

According to this Hansen space,
δ _D characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular collisions,
δ _p characterizes the Debye interaction between permanent dipoles and the Keesom interaction between induced and permanent dipoles,
δh characterizes the specific interaction force (e.g., hydrogen bond, acid/base, donor/acceptor, etc.),
δ _a is determined by the equation δ _a =(δ _p ² +δ _h ¹ ) ^1/2 , where the parameters δ _p , δ _h , δ _d , and δ _a are expressed in (J/cm ³ ) ^1/2 .

The polar oil may be preferably selected from the group consisting of vegetable or animal oils, for example triglycerides, ester oils, ether oils and mixtures thereof, more preferably from the group consisting of ester oils, ether oils and mixtures thereof, even more preferably from ester oils.

The active oil may in particular be chosen from the following oils:
Hydrocarbon polar oils, such as phytostearyl esters, for example phytostearyl oleate, phytostearyl isostearate, and lauroyl/octyldodecyl/phytostearyl glutamate (Ajinomoto Co., Eldew PS203), triglycerides of fatty acid esters of glycerol, in particular those whose fatty acids are C ₄ -C ₃₆ , especially C ₁₈ -C ₃₆ , these oils being optionally linear or branched, saturated or unsaturated; these oils may be, inter alia, heptanoic or octanoic triglycerides), wheat germ oil, sunflower oil, grape seed oil, sesame seed oil (820.6 g/mol), corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy seed oil, pumpkin oil, cucurbit oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, kukui oil, passion flower oil, or musk rose oil; shea butter; or caprylic/capric triglycerides, such as Stearineries. those sold by the company Dubois or under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;
- synthetic ethers containing from 10 to 40 carbon atoms, such as dicaprylyl ether;
- hydrocarbon esters of the formula RCOOR', where RCOO represents a carboxylic acid residue containing 2 to 40 carbon atoms and R' represents a hydrocarbon chain containing 1 to 40 carbon atoms, such as cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, stearic acid or isostearate, isostearyl isostearate, octyl stearate, diisopropyl adipate, heptanoic acid esters, especially isostearyl heptanoate, octanoic acid esters, decanoic acid esters or ricinoleic acid esters of alcohols or polyalcohols, such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate and 2-ethylhexyl palmitate, alkyl benzoates, polyethylene glycol diheptanoate, propylene glycol 2-diethylhexanoate and mixtures thereof, C ₁₂ to C _15- alcohol benzoate, hexyl laurate, neopentanoate esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate and 2-octyldodecyl neopentanoate, isononanoate esters such as isononyl isononanoate, isotridecyl isononanoate and octyl isononanoate, oleyl erucate, isopropyl lauroyl sarcosine, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behenate and myristyl myristate,
polyesters obtained by condensation of unsaturated fatty acid dimers and/or trimers with diols, such as those described in patent application FR0853634, in particular polyesters obtained, for example, by condensation of dilinoleic acid with 1,4-butanediol. In this respect, mention may be made, inter alia, of the polymer sold under the name Viscoplast 14436H by the company Biosynthis (INCI name: Dilinoleic acid/butanediol copolymer), or else of copolymers of polyols with dimer diacids and their esters, such as Hailuscent ISDA;
Polyol esters and pentaerythritol esters, such as dipentaerythrityl tetrahydroxystearate/tetraisostearate,
aliphatic alcohols containing from 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol and oleyl alcohol;
- _C12 to _C22 higher fatty acids, such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof;
- fatty acids containing from 12 to 26 carbon atoms, such as oleic acid;
dialkyl carbonates, in which the two alkyl chains are optionally identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC® by the company Cognis,
- non-volatile oils of high molecular weight, for example between 400 g/mol and 10 000 g/mol, in particular between 650 g/mol and 10 000 g/mol, such as:
i) vinylpyrrolidone copolymers, for example the vinylpyrrolidone/1-hexadecene copolymer Antaron V-216 (MW = 7300 g/mol) sold or manufactured by the company ISP;
ii) Esters, such as:
a) linear fatty acid esters having a total carbon number in the range of 35 to 70, such as pentaerythrityl tetrapelargonate (MW = 697.05 g/mol);
b) Hydroxylated esters, such as polyglycerol-2 triisostearate (MW = 965.58 g/mol);
c) aromatic esters, such as tridecyl trimellitate (MW = 757.19 g/mol), _C12 - _C15 alcohol benzoate esters, 2-phenylethyl ester of benzoic acid and butyloctyl salicylate;
d) esters of C ₂₄ -C ₂₈ branched fatty acids or fatty alcohols, such as, for example, those described in patent application EP-A-0955039, especially triisoarachidyl citrate (MW = 1033.76 g/mol), pentaerythrityl tetraisononanoate (MW = 697.05 g/mol), glyceryl triisostearate (MW = 891.51 g/mol), glyceryl tris(2-decyl)tetradecanoate (MW = 1143.98 g/mol), pentaerythrityl tetraisostearate (MW = 1202.02 g/mol), polyglyceryl-2 tetraisostearate (MW = 1232.04 g/mol) or else pentaerythrityl tetrakis(2-decyl)tetradecanoate (MW = 1538.66 g/mol),
e) esters and polyesters of dimer diols with mono- or dicarboxylic acids, such as esters of dimer diols with fatty acids and esters of dimer diols with dimer dicarboxylic acids, such as Lusplan DD-DA5® and Lusplan DD-DA7® sold by Nippon Fine Chemicals Co., Ltd., and those described in patent application US 2004-175338, the contents of which are incorporated herein by reference;
- and mixtures thereof.

The term "polar hydrocarbon-based oil" as used herein means a polar oil essentially formed or even composed of carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, but containing no silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

It is preferred that the oil has a log P value of 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less. It may also be preferred that the oil has a log P value of 1.0 or more, more preferably 1.5 or more, even more preferably 2.0 or more. Thus, it may also be preferred that the oil has a log P value of 1.0 to 7.0, more preferably 1.5 to 6.5, even more preferably 2.0 to 6.0.

The log P value is the logarithm to the base 10 of the apparent partition coefficient of octan-1-ol/water. The log P value is known and is determined by standard tests for determining the concentration of oil in octan-1-ol and water. The log P can be calculated according to the method described in Meylan and Howard, Atom/Fragment contribution method for estimating octanol-water partition coefficients, J. Pharm. Sci., 84: 83-92, 1995. This value can also be calculated using a number of commercially available software packages that determine the log P as a function of molecular structure. An example is the Epiwin software from the United States Environmental Protection Agency.

This value can be calculated using, among others, Solaris software V4.67 from ACD (Advanced Chemistry Development), and can also be taken from Exploring QSAR: hydrophobic, electronic and steric constants (ACS professional reference book, 1995). There are also Internet sites that provide approximate values (address: http://esc.syrres.com/interkow/kowdemo.htm).

The oil may have at least two moieties selected from the group consisting of amide bonds, ester bonds and mixtures thereof. An amide bond is meant here to be -CONR- (R represents a hydrogen atom or a linear or branched C ₁ -C ₁₈ alkyl group, preferably a methyl group) and an ester bond is meant here to be -COO-. In other words, the oil may have two or more amide bonds, two or more ester bonds or a mixture of at least one amide bond and at least one ester bond.

The oil may have at least two moieties selected from the group consisting of ether bonds, ester bonds, and mixtures thereof. An ether bond herein means -O- and an ester bond herein means -COO-. In other words, the oil may have two or more ether bonds, two or more ester bonds, or a mixture of at least one ether bond and at least one ester bond.

The oil may preferably be selected from the group consisting of isopropyl lauroyl sarcosine, octyldodecanol, and mixtures thereof.

On the other hand, an example of a non-polar oil is squalane.

The oil may be selected from triglycerides, which are esters derived from glycerol and three fatty acids, sometimes called triacylglycerols.

The triglyceride for the oil preferably has at least one unsaturated fatty acid residue. In other words, the triglyceride for the oil is preferably an ester derived from glycerol and at least one unsaturated fatty acid. Thus, the triglyceride for the oil can be (i) an ester derived from glycerol and one unsaturated fatty acid and two saturated fatty acids, (ii) an ester derived from glycerol and two unsaturated fatty acids and one saturated fatty acid, or (iii) an ester derived from glycerol and three unsaturated fatty acids. When two or more unsaturated fatty acids are used, they may be the same or different. When two saturated fatty acids are used, they may be the same or different.

According to the present invention, "unsaturated fatty acids" means fatty acids containing at least one carbon-carbon double or triple bond. These are more particularly fatty acids with long chains, i.e. they can have from 8 to 32 carbon atoms, preferably from 12 to 26 carbon atoms, more preferably from 14 to 22 carbon atoms.

The fatty acids may be monounsaturated, such as petroselinic acid (C12), palmitoleic acid (C16) and oleic acid (C18), or polyunsaturated, i.e. presenting at least two carbon-carbon double bonds, such as linoleic acid (C18) and linolenic acid (C18).

More preferably, the triglyceride for the oil has at least one polyunsaturated fatty acid residue. In other words, more preferably, the triglyceride for the oil is an ester derived from glycerol and at least one polyunsaturated fatty acid.

The polyunsaturated fatty acids may be selected from omega-3, omega-6, and omega-9 fatty acids, characterized by the position of unsaturation closest to the terminal methyl group.

Polyunsaturated fatty acids containing between 18 and 22 carbon atoms, particularly those selected from omega-3 and omega-6 fatty acids, may be more preferred.

Among the polyunsaturated fatty acids of the omega-3 series, mention may be made of α-linolenic acid (18:3, omega-3), stearidonic acid (18:4, omega-3), 5,8,11,14,17-eicosapentaenoic acid, i.e. EPA (20:5, omega-3), and 4,7,10,13,16,19-docosahexaenoic acid, i.e. DHA (22:6, omega-3), docosapentaenoic acid (22:5, omega-3), and n-butyl-5,11,14-eicosatrienoic acid.

Among the polyunsaturated fatty acids of the omega-6 series, there can be mentioned linoleic acid (18:2, omega-6), which has 18 carbon atoms and two unsaturations, gamma-linolenic acid (18:3, omega-6), which has 18 carbon atoms and three unsaturations, dihomogamma (gama)linolenic acid (20:3, omega-6), which has 20 carbon atoms and three unsaturations, arachidonic acid, i.e. 5,8,11,14 eicosatetraenoic acid (20:4, omega-6), and docosatetraenoic acid (22:4, omega-6).

An example of an omega-9 fatty acid is mead acid (20:3, omega-9).

The polyunsaturated fatty acid may be selected from alpha-linolenic acid, gamma-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and mixtures thereof.

Among the fatty acids forming the fatty acid residues in the triglycerides for the oil, the amount of polyunsaturated fatty acids can be 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of fatty acids.

Among the fatty acids forming the fatty acid residues in the triglycerides for the oil, the mass ratio of the amount of polyunsaturated fatty acids/the amount of monounsaturated fatty acids may be greater than 1.0, preferably greater than 1.5, more preferably greater than 2.0.

The oil may be selected from vegetable oils.

For example, the oil may be selected from the group consisting of soybean oil, rapeseed oil, cottonseed oil, rice oil, corn oil, grapeseed oil, sesame oil, linseed oil, and mixtures thereof.

The oil is preferably selected from the group consisting of soybean oil, corn oil, cottonseed oil, grapeseed oil and mixtures thereof.

The amount of oil in the composition according to the present invention may be in the range of 0.1% to 20% by weight, preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight, based on the total weight of the composition.

- Polysaccharides The composition according to the present invention may contain at least one polysaccharide other than the (d) cationic polymer. A single type of polysaccharide may be used, or two or more different types of polysaccharides may be used in combination.

(d) The polysaccharide other than the cationic polymer may be present in the dispersed phase and/or the continuous phase. Preferably, the polysaccharide is present in both the dispersed phase and the continuous phase.

The polysaccharide is preferably selected from polysaccharides derived from plants. In other words, the polysaccharide is preferably of plant origin.

On the other hand, it is also preferred that the polysaccharide is not selected from cellulose and its derivatives.

According to the invention, the term "polysaccharides of plant origin" means, in particular, polysaccharides obtained from the plant kingdom (plants or algae), as opposed to polysaccharides obtained by biotechnology, in the latter case, for example, xanthan gum, produced in particular by fermentation with the bacterium Xanthomonas campestris.

As examples of polysaccharides of plant origin that can be used according to the invention, mention may be made, inter alia, of the following:
a) algae extracts, such as alginates, carrageenans and agar-agar, and mixtures thereof. Examples of carrageenans that may be mentioned include Satiaguum UTC30® and UTC10® from the company Degussa, and an alginate that may be mentioned is sodium alginate sold under the name Kelcosol® by the company ISP;
b) gums, such as guar gum and its non-ionic derivatives (hydroxypropyl guar), gum arabic, konjac gum or mannan gum, tragacanth gum, ghatti gum, karaya gum or locust bean gum; examples that may be mentioned include the guar gum sold under the name Jaguar HP105® by the company Rhodia; mannan and konjac gum® (1% gluconomannan) sold by the company GfN,
c) modified or unmodified starches, such as those obtained from cereals, such as wheat, corn or rice, from legumes, such as blonde pea, from tubers, such as potato or cassava, and tapioca starch; dextrins, such as corn dextrin; examples which may be mentioned in particular include rice starch Remy DR I® sold by the company Remy; corn starch B® from the company Roquette; potato starch modified with 2-chloroethylaminodipropionic acid and neutralized with sodium hydroxide, sold under the name Structure Solanace® by the company National Starch; native tapioca starch powder sold under the name Tapioca pure® by the company National Starch,
d) Dextrins, such as dextrin extracted from corn, available from National Starch under the trade name Index®, and mixtures thereof.

Preferably, the polysaccharide is selected from an algae extract.

The algae extract may be selected from alginates, carrageenans and agars, and mixtures thereof. Preferably, alginates or agars, or mixtures thereof, may be used.

The amount of polysaccharide in the composition according to the present invention may be in the range of 0.001% to 5% by weight, preferably 0.005% to 3% by weight, more preferably 0.01% to 1% by weight, based on the total weight of the composition.

Lipophilic Antioxidants The composition according to the invention may comprise at least one lipophilic antioxidant. A single type of lipophilic antioxidant may be used, but two or more different types of lipophilic antioxidants may also be used in combination.

Lipophilic antioxidants are (a) different from retinoids.

The lipophilic antioxidant may preferably be present in the dispersed phase.

Lipophilic antioxidant means that the partition coefficient of the antioxidant between n-butanol and water is greater than 1, more preferably greater than 10, and even more preferably greater than 100.

Lipophilic antioxidants include phenolic antioxidants having a hindered phenol structure or semi-hindered phenol structure in the molecule. Specific examples of such compounds include the following: 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid (having the INCI name pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono- or di- or tri-(α-methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,5-di- tert-Butylhydroquinone, 2,5-di-tert-amylhydroquinone, tris[N-(3,5-di-tert-butyl-4-hydroxybenzyl)]isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, butylidene-1,1 bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionato]methane, triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3, 5-triazine-2,4,6-trione, 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,6-bis[(octylthio)methyl]-o-cresol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

Lipophilic antioxidants may also include: BHA (butylated hydroxyl anisole) and BHT (butylated hydroxyl toluene), vitamin E (i.e. tocopherol and tocotrienol) and its derivatives, such as phosphate derivatives, e.g. TPNA® sold by Showa Denko K.K., coenzyme Q10 (i.e. ubiquinone), idebenone, certain carotenoids, such as lutein, astaxanthin, beta-carotene, phenolic acids and derivatives (e.g. chlorogenic acid).

Lipophilic antioxidants which may also be mentioned include dithiolanes, such as asparagusic acid or derivatives thereof, such as siliceous dithiolane derivatives, especially those described, for example, in patent application FR 2 908 769.

Lipophilic antioxidants that may also be mentioned include:
Glutathione and its derivatives (GSH and/or GSHOEt), such as glutathione alkyl esters (e.g. those described in patent applications FR2704754 and FR2908769);
Cysteine and its derivatives, such as N-acetylcysteine or L-2-oxothiazolidine-4-carboxylic acid. Reference may also be made to the following: the cysteine derivatives described in patent applications FR2877004 and FR2854160;
Certain enzymes, such as catalase, superoxide dismutase (SOD), lactoperoxidase, glutathione peroxidase and quinone reductase, to protect against oxidative stress;
benzylcyclanones; substituted naphthalenones; pidolates (among others those described in patent application EP 0511118); caffeic acid and its derivatives, gamma oryzanol; melatonin, sulforaphane and extracts containing it (except watercress),
diisopropyl esters of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, as described inter alia in patent applications WO 94/11338, FR 2 698 095, FR 2 737 205 or EP 0 755 925,
Deferoxamine (or Desferal), described in patent application FR2825920.

Lipophilic antioxidants which can also be used are chalcones, more particularly phloretin or neohesperidin, the diisopropyl ester of N,N'-bis(benzyl)ethylenediamine-N,N'-diacetic acid, or extracts of pinus maritime bark, such as PYCNOGENOL®.

Examples of lipophilic antioxidants include pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, tocopherol, resveratrol, propyl gallate, butylated hydroxyl toluene, butylated hydroxyl anisole, ascorbyl palmitate, tocopherol, and mixtures thereof.

It is preferable that the lipophilic antioxidant is biodegradable. In this sense, BHT, which is not biodegradable, is not preferable as a lipophilic antioxidant. Therefore, it is preferable not to use BHT as a lipophilic antioxidant. Furthermore, it is preferable that the composition according to the present invention does not contain BHT.

The term "free" here means that the composition according to the invention may contain a limited amount of BHT. However, it is preferred that the amount of BHT is limited to less than 1% by weight, more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, relative to the total weight of the composition. Most preferably, the composition according to the invention is free of BHT.

More preferably, the lipophilic antioxidant is selected from tocopherol, pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, and mixtures thereof.

The amount of lipophilic antioxidant in the composition according to the invention may be in the range of 0.01% to 5% by weight, preferably 0.05% to 3% by weight, more preferably 0.1% to 1% by weight, based on the total weight of the composition.

Chelating Agents The composition according to the invention may comprise at least one chelating agent. A single type of chelating agent may be used, but two or more different types of chelating agents may also be used in combination.

A chelating agent may be present in the continuous phase of the present invention.

Chelating agents may include:
(i) Aminocarboxylic acids, such as the compounds having the following INCI names: diethylenetriaminepentaacetic acid (DTPA), ethylenediaminedisuccinic acid (EDDS) and trisodium ethylenediaminedisuccinate, e.g. Octaquest from Octel. E30, ethylenediaminetetraacetic acid (EDTA), ethylenediamine-N,N'-diglutaric acid (EDDG), glycinamide-N,N'-disuccinic acid (GADS), 2-hydroxypropylenediamine-N,N'-disuccinic acid (HPDDS), ethylenediamine-N,N'-bis(ortho-hydroxyphenylacetic acid) (EDDHA), N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED), nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA), N-2-hydroxyethyl-N,N-diacetic acid and glyceryl iminodiacetic acid (references EP-A-317542 and EP-A-399 133), iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid (as described in EP-A-516102), beta-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid and aspartic acid-N-monoacetic acid (as described in EP-A-509382), chelating agents based on iminodisuccinic acid (IDSA) (as described in EP-A-509382), ethanoldiglycinic acid, phosphonobutanetricarboxylic acids, such as the compound sold under the reference Bayhibit AM by the company Bayer, tetrasodium glutamic acid diacetate (GLDA), such as Dissolvine GL 38 or 45S from Akzo Nobel,
(ii) Chelators based on mono- or polyphosphonic acids, such as the compounds having the following INCI names: diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), ethane-1-hydroxy-1,1,2-triphosphonic acid (E1HTP), ethane-2-hydroxy-1,1,2-triphosphonic acid (E2HTP), ethane-1-hydroxy-1,1-diphosphonic acid (EHDP), ethane-1,1,2-triphosphonic acid (ETP), ethylenediaminetetramethylenephosphonic acid (EDTMP), and hydroxyethane-1,1-diphosphonic acid (HEDP);
(iii) Chelating agents based on polyphosphate, such as compounds having the following INCI names: sodium tripolyphosphate (STP), tetrasodium diphosphate, hexametaphosphate, sodium metaphosphate, phytic acid, their salts and derivatives;
and mixtures thereof.

More preferably, the chelating agent is trisodium ethylenediamine disuccinate.

The amount of chelating agent in the composition according to the present invention may be in the range of 0.001% to 3% by weight, preferably 0.005% to 2% by weight, more preferably 0.01% to 1% by weight, based on the total weight of the composition.

- Water The composition according to the present invention may comprise water.

Water in the compositions according to the invention can form a continuous phase. Water may also be present in the dispersed phase.

The amount of water in the composition according to the present invention may be 50% by weight or more, preferably 55% by weight or more, more preferably 60% by weight or more, based on the total weight of the composition.

On the other hand, the amount of water in the composition according to the present invention may be 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less, based on the total weight of the composition.

The amount of water in the composition according to the present invention may be in the range of 50% to 90% by weight, preferably 55% to 85% by weight, more preferably 60% to 80% by weight, based on the total weight of the composition.

- Polyol The composition according to the invention may further comprise at least one polyol different from the polyphenol. A single type of polyol may be used, but also two or more different types of polyols may be used in combination.

The polyol may be present in the dispersed phase.

The term "polyol" as used herein means an alcohol having two or more hydroxyl groups, and does not include sugars or their derivatives. Derivatives of sugars include sugar alcohols obtained by reducing one or more carbonyl groups of a sugar, and sugars or sugar alcohols in which the hydrogen atom of one or more hydroxyl groups is replaced by at least one substituent, such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group or a carbonyl group.

The polyol can be a _C2 to _C12 polyol, preferably a _C2 to _C9 polyol, containing at least two hydroxy groups, preferably from 2 to 5 hydroxy groups.

The polyol may be a natural or synthetic polyol. The polyol may have a linear, branched or cyclic molecular structure.

The polyol may be selected from glycerin and its derivatives, and glycols and its derivatives. The polyol may be selected from the group consisting of glycerin, diglycerin, polyglycerin, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, caprylyl glycol, 1,3-propanediol, 1,5-pentanediol, polyethylene glycol (5 to 50 ethylene oxide groups), and mixtures thereof.

The amount of polyol in the composition according to the present invention may be 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the total mass of the composition.

On the other hand, the amount of polyol in the composition according to the present invention may be 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, based on the total weight of the composition.

Thus, the polyol may be present in the composition according to the invention in an amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, for example from 1% to 10% by weight, relative to the total weight of the composition.

- pH Adjusting Agent The pH of the composition according to the present invention can be adjusted to a desired value using at least one pH adjusting agent commonly used in cosmetics, such as an acidifying agent or a basifying agent.

The pH of the composition according to the present invention may be 9.0 or less, preferably 8.5 or less, more preferably 8.0 or less, even more preferably 7.5 or less, particularly 7.0 or less, at 25°C, and may be 2.5 or more, preferably 3.0 or more, more preferably 3.5 or more.

pH regulators may be present in the continuous phase of the present invention. Among the acidifying agents, examples include inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

Among the basifying agents, examples include hydroxide salts of alkali metals or alkaline earth metals, such as sodium hydroxide or potassium hydroxide; quaternary ammonium hydroxide salts and guanidinium hydroxide; alkali metal silicates, such as sodium metasilicate; carbonates and bicarbonates, in particular carbonates and bicarbonates of primary amines, secondary amines or tertiary amines, carbonates and bicarbonates of alkali metals or alkaline earth metals or carbonates and bicarbonates of ammonium; and compounds of the formula:

(Wherein,
W is a C ₁ -C ₆ alkylene residue optionally substituted with a hydroxyl group or a C ₁ -C ₆ alkyl group;
Rx, Ry, Rz and Rt may be the same or different and represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or a C ₁ -C ₆ aminoalkyl group.
Mention may be made, inter alia, of 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The pH adjuster may be used in an amount ranging from 0.001% to 15% by weight, preferably from 0.01% to 10% by weight, more preferably from 0.1% to 5% by weight, and particularly preferably from 1% to 5% by weight, based on the total weight of the composition.

- Non-ionic surfactant The composition according to the invention may comprise at least one non-ionic surfactant. If two or more non-ionic surfactants are used, they may be the same or different.

Nonionic surfactants may be present in the continuous phase of the present invention.

The nonionic surfactant may have an HLB (hydrophilic lipophilic balance) value of 3.0 to 7.0, preferably 3.5 to 6.0, more preferably 4.0 to 5.0. Alternatively, the nonionic surfactant may have an HLB value of 11 to 17, preferably 12 to 16, more preferably 13 to 15. When two or more nonionic surfactants are used, the HLB value is determined by a weighted average of the HLB values of all the nonionic surfactants.

The non-ionic surfactant may be selected from:
(1) a surfactant selected from polyglyceryl fatty acid esters, polyoxyalkylenated alkyl glycerides, and polyoxyalkylenated fatty ethers;
(2) Mixed esters of fatty acids or fatty alcohols, carboxylic acids, and glycerol;
(3) fatty acid esters of sugars, and fatty alcohol ethers of sugars;
(4) A surfactant selected from fatty esters of sorbitan, oxyalkylenated fatty esters of sorbitan, and oxyalkylenated fatty esters;
(5) Block copolymers of ethylene oxide (A) and propylene oxide (B);
(6) Polyoxyethylenated (1-40EO) and polyoxypropylenated (1-30PO) alkyl ( _C16 - _C30 ) ethers;
(7) Silicone surfactants, and
(8) Mixtures of these.

The surfactant (1) may be fluid at a temperature of 45°C or less.

The surfactant (1) may in particular be:
- polyglyceryl fatty acid esters of at least one, preferably one, fatty acid containing at least one saturated or unsaturated, linear or branched _C8 - _C22 hydrocarbon group, for example a _C8 - _C22 alkyl or alkenyl group, preferably a _C8 - _C18 alkyl or alkenyl group, more preferably a _C8 - _C12 alkyl or alkenyl group, and of 2 to 12 glycerols, preferably of 2 to 10 glycerols, more preferably of 2 to 8 glycerols,
- polyoxyethylenated (PEGylated) alkyl glycerides, such as polyethylene glycol derivatives of mixtures of mono-, di- and triglycerides of caprylic and capric acid (preferably having from 2 to 30 ethylene oxide units, more preferably having from 2 to 20 ethylene oxide units, even more preferably having from 2 to 10 ethylene oxide units), such as PEG-6 (caprylic/capric) glyceride, PEG-7 (caprylic/capric) glyceride, and PEG-7 glyceryl cocoate,
- polyoxyethylenated fatty ethers of at least one, preferably one, aliphatic alcohol containing at least one saturated or unsaturated, linear or branched _C8 - _C22 hydrocarbon group, for example a _C8 - _C22 alkyl or alkenyl group, preferably a _C8 - _C18 alkyl or alkenyl group, more preferably a _C8 - _C12 alkyl or alkenyl group, and from 2 to 60 ethylene oxide units, preferably from 2 to 30 ethylene oxide units, more preferably from 2 to 10 ethylene oxide units, and
- A mixture of these.

The polyglyceryl fatty acid ester preferably has a polyglycerol moiety derived from 2 to 30 glycerols, more preferably from 2 to 20 glycerols, and even more preferably from 4 to 12 glycerols.

The polyglyceryl fatty acid esters may be selected from mono-, di- and triesters of saturated or unsaturated acids, preferably saturated acids, containing from 8 to 22 carbon atoms, preferably from 8 to 18 carbon atoms, more preferably from 8 to 12 carbon atoms, such as caprylic acid, capric acid, lauric acid, oleic acid, stearic acid, isostearic acid and myristic acid. An example of a polyglyceryl fatty acid ester may be polyglyceryl-10 isostearate.

The polyoxyalkylenated fatty ethers, preferably polyoxyethylenated fatty ethers, may contain from 2 to 60 ethylene oxide units, preferably from 2 to 30 ethylene oxide units, more preferably from 2 to 10 ethylene oxide units. The fatty chain of the ether may be chosen in particular from lauryl, behenyl, arachidyl, stearyl and cetyl units, and mixtures thereof, such as cetearyl. Examples of ethoxylated fatty ethers that may be mentioned are lauryl alcohol ethers containing 2, 3, 4 and 5 ethylene oxide units (CTFA names: laureth-2, laureth-3, laureth-4 and laureth-5), such as the products sold under the names Nikkol BL-2 by Nikko Chemicals Co., Ltd., Emalex 703 by Nippon Emulsion Co., Ltd., Nikkol BL-4 by Nikko Chemicals Co., Ltd. and EMALEX 705 by Nippon Emulsion Co., Ltd. Mention may also be made, for example, of stearyl alcohol ethers containing 2, 3, 4, 5 and 20 ethylene oxide units (CTFA names: steareth-2, steareth-3, steareth-4, steareth-5 and steareth-20), such as the products sold under the names Emalex 602 by Nippon Emulsion Co., Ltd., Emalex 603 by Nippon Emulsion Co., Ltd., Nikkol BS-4 by Nikko Chemicals Co., Ltd. and Emalex 605 by Nippon Emulsion Co., Ltd.

Also preferred are polyoxyalkylenated fatty ethers which are polyethylene glycol ethers of C ₈ to C ₂₄ fatty alcohols and their polyoxyalkylenated derivatives, and polypropylene glycol ethers of C ₄ to C ₂₄ fatty alcohols, such as PPG-14 butyl ether and PPG-15 stearyl ether.

(2) Mixed esters of fatty acids or fatty alcohols, carboxylic acids and glycerol can be used as the nonionic surfactants described above and can be selected in particular from the group comprising mixed esters of fatty acids or fatty alcohols having an alkyl or alkenyl chain containing 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, alpha-hydroxy acids and/or succinic acid and glycerol. The alpha-hydroxy acids can be, for example, citric acid, lactic acid, glycolic acid or malic acid, and mixtures thereof.

The alkyl chains of the fatty acids or alcohols from which the mixed esters that can be used in the nanoemulsions of the invention are derived may be linear or branched, saturated or unsaturated. They may be, inter alia, stearate, isostearate, linoleate, oleate, behenate, arachidonate, palmitate, myristate, laurate, caprate, isostearyl, stearyl, linoleyl, oleyl, behenyl, myristyl, lauryl or capryl chains, and mixtures thereof.

Examples of mixed esters that can be used in the nanoemulsions of the invention include the mixed ester of glycerol with a mixture of citric acid, lactic acid, linoleic acid and oleic acid (CTFA name: glyceryl citric acid/lactic acid/linoleic acid/oleate) sold by Huls under the name Imwitor 375, the mixed ester of succinic acid and isostearyl alcohol with glycerol (CTFA name: isostearyl diglyceryl succinate) sold by Huls under the name Imwitor 780 K, the mixed ester of citric acid and stearic acid with glycerol (CTFA name: glyceryl citrate stearate) sold by Huls under the name Imwitor 370, and the mixed ester of lactic acid and stearic acid with glycerol (CTFA name: glyceryl lactate stearate) sold by Danisco under the name Lactodan B30 or Rylo LA30.

The (3) sugar fatty acid ester usable as the nonionic surfactant can be particularly selected from the group including esters or ester mixtures of _C8 - _C22 fatty acids with sucrose, maltose, glucose or fructose, and esters or ester mixtures of _C14 - _C22 fatty acids with methylglucose.

The _C8 - _C22 or _C14 - _C22 fatty acids forming the fatty units of the esters that may be used in the present invention comprise saturated or unsaturated, linear alkyl or alkenyl chains containing from 8 to 22 or from 14 to 22 carbon atoms, respectively. The fatty units of the esters may in particular be chosen from stearates, behenates, arachidonates, palmitates, myristates, laurates and caprates, and mixtures thereof. Stearates are preferably used.

The (3) sugar fatty alcohol ethers that can be used as the nonionic surfactants may be solid at a temperature of 45° C. or less and may be particularly selected from the group including ethers or ether mixtures of C ₈ -C ₂₂ fatty alcohols with glucose, maltose, sucrose or fructose, and ethers or ether mixtures of C ₁₄ -C ₂₂ fatty alcohols with methyl glucose. These are in particular alkyl polyglucosides.

The _C8 - _C22 or _C14 - _C22 fatty alcohols forming the fatty units of the ethers that may be used in the nanoemulsions of the invention comprise saturated or unsaturated, linear alkyl or alkenyl chains containing from 8 to 22 or from 14 to 22 carbon atoms, respectively. The fatty units of the ethers may in particular be chosen from the decyl, cetyl, behenyl, arachidyl, stearyl, palmityl, myristyl, lauryl, capryl and hexadecanoyl units, and mixtures thereof, such as cetearyl. As an example of fatty alcohol ethers of sugars, mention may be made of caprylyl/capryl glucoside.

(4) Fatty esters of sorbitan and oxyalkylenated fatty esters of sorbitan that can be used as the nonionic surfactants can be selected from the group consisting of _C16 - _C22 fatty acid esters of sorbitan and oxyethylenated _C16 - _C22 fatty acid esters of sorbitan. These can be formed from at least one fatty acid containing at least one saturated linear alkyl chain, each containing 16 to 22 carbon atoms, and sorbitol or ethoxylated sorbitol. The oxyethylenated esters can generally contain 1 to 100 ethylene glycol units, preferably 2 to 40 ethylene oxide (EO) units.

These esters may be chosen in particular from stearates, behenates, arachidates, palmitates and mixtures thereof. Stearates and palmitates are preferably used.

The (4) oxyalkylenated fatty ester, preferably ethoxylated fatty ester, which may be used as the nonionic surfactant, may be an ester formed from 1 to 100 ethylene oxide units, preferably 2 to 60 ethylene oxide units, more preferably 2 to 30 ethylene oxide units, and at least one fatty acid chain containing 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 8 to 12 carbon atoms. The fatty chain of the ester may be selected in particular from stearate, behenate, arachidate and palmitate units, and mixtures thereof. Examples of ethoxylated fatty esters that may be mentioned are stearic acid esters containing 40 ethylene oxide units, such as the product sold under the name Myrj 52 (CTFA name: PEG-40 stearate) by the company ICI, and behenic acid esters containing 8 ethylene oxide units (CTFA name: PEG-8 behenate), such as the product sold under the name Compritol HD5 ATO by the company Gattefosse.

The block copolymer of ethylene oxide (A) and propylene oxide (B) that can be used as the nonionic surfactant is represented by the formula (I):
HO( _C2H4O ) _{x ( C3H6O} ) _{y ( C2H4O ) z} H (I)
(wherein x, y, and z are integers such that x+z is within the range of 2 to 100, and y is within the range of 14 to 60).
and mixtures thereof, and more particularly from block copolymers of formula (I) having an HLB value in the range of from 8.0 to 14.0.

The (6) polyoxyethylenated (1-40EO) and polyoxypropylenated (1-30PO) alkyl (C ₁₆ -C ₃₀ ) ethers that may be used as the nonionic surfactant may be selected from the group consisting of:
PPG-6 decyltetradeceth-30; polyoxyethylene (30) polyoxypropylene (6) tetradecyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PEN-4630;
PPG-6 decyltetradeceth-12; polyoxyethylene (12) polyoxypropylene (6) tetradecyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PEN-4612;
PPG-13 decyltetradeceth-24; polyoxyethylene (24) polyoxypropylene (13) decyltetradecyl ether, such as that sold by NOF Corporation as UNILUBE 50MT-2200B;
PPG-6 decyltetradeceth-20; polyoxyethylene (20) polyoxypropylene (6) decyltetradecyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PEN-4620;
PPG-4 ceteth-1; polyoxyethylene (1) polyoxypropylene (4) cetyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PBC-31;
PPG-8 ceteth-1; polyoxyethylene (1) polyoxypropylene (8) cetyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PBC-41;
PPG-4 ceteth-10; polyoxyethylene (10) polyoxypropylene (4) cetyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PBC-33;
PPG-4 ceteth-20; polyoxyethylene (20) polyoxypropylene (4) cetyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PBC-34;
PPG-5 ceteth-20; polyoxyethylene (20) polyoxypropylene (5) cetyl ether, such as that sold by Croda Inc. as Procetyl AWS;
PPG-8 ceteth-20; polyoxyethylene (20) polyoxypropylene (8) cetyl ether, such as that sold by Nikko Chemicals Co., Ltd. as Nikkol PBC-44; and
PPG-23 Steareth-34; Polyoxyethylene polyoxypropylene stearyl ether (34 EO) (23 PO), such as that sold as Unisafe 34S-23 by POLA Chemical Industries, Ltd. These can provide compositions that have long-term stability even when the temperature of the composition rises and falls within a relatively short period of time.

(7) Examples of silicone surfactants that can be used as the above nonionic surfactant include those disclosed in US-A-5364633 and US-A-5411744.

The silicone surfactant (7) as the nonionic surfactant is preferably represented by formula (I):

(Wherein,
R ₁ , R ₂ and R ₃ independently of one another represent a C ₁ -C ₆ alkyl group or a -(CH ₂ ) _x -(OCH ₂ CH ₂ ) _y -(OCH ₂ CH ₂ CH ₂ ) _z -OR ₄ group, in which at least one R ₁ , R ₂ or R ₃ group is not an alkyl group and R ₄ is hydrogen, an alkyl group or an acyl group,
A is an integer in the range of 0 to 200,
B is an integer ranging from 0 to 50, with the proviso that A and B are not both equal to 0;
x is an integer ranging from 1 to 6;
y is an integer ranging from 1 to 30;
z is an integer ranging from 0 to 5.
The compound may be:

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

An example of a silicone surfactant of formula (I) is a compound of formula (II):

(wherein A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10, and y is an integer ranging from 10 to 20).
Compounds of the formula:

Examples of silicone surfactants of formula (I) include those of formula (III):
H-( _OCH2CH2 ) _y- ( _CH2 ) ₃ -[( _{CH3 ) 2SiO} ] _A' -( _CH2 ) _{3- ( OCH2CH2} ) _y -OH (III)
(wherein A' and y are integers ranging from 10 to 20).
Compounds of the formula:

The nonionic surfactant may be present in the composition according to the invention in an amount of 0.01% to 5% by weight, preferably 0.05% to 3% by weight, more preferably 0.1% to 1% by weight, relative to the total weight of the composition.

- Additives The compositions according to the invention, and in particular the continuous phase of the invention, may also comprise, besides the components explained above, various adjuvants conventionally used in cosmetic and dermatological compositions, such as anionic, nonionic, cationic and amphoteric or zwitterionic polymers, anionic, cationic, amphoteric and nonionic surfactants, hydrophilic antioxidants, hydrophilic active ingredients, colorants, thickeners, sequestering agents, fragrances, dispersants, conditioning agents, film-forming agents, preservatives, co-preservatives, light stabilizers, such as tris(tetramethylhydroxypiperidinol) citrate, and mixtures thereof.

Hydrophilic active ingredients include vitamin B3 and derivatives, ascorbic acid and its derivatives, resorcinol derivatives, C-glycoside derivatives, salicylic acid and its derivatives, alpha-hydroxy acids, niacinamide, and mixtures thereof.

Hydrophilic active ingredients may be present in the continuous phase of the present invention.

The amount of additives contained in the composition according to the present invention is not limited, but may be 0.01 to 30% by mass based on the total mass of the composition according to the present invention.

The composition according to the present invention can be prepared by mixing the essential components described above and, if necessary, the optional components described above.

The method and means of mixing the above essential and optional components are not limited. Any conventional method and means can be used to mix the above essential and optional components to prepare the composition according to the present invention. The dispersion composition according to the present invention can be prepared by mixing the dispersed phase and the continuous phase.

[Method and Use]
The composition according to the invention is preferably a cosmetic or dermatological composition, preferably a cosmetic composition, more preferably a cosmetic composition for keratinous materials such as the skin.

The compositions according to the invention can be used for non-therapeutic methods, such as cosmetic methods for treating keratinous materials, e.g. skin, hair, mucous membranes, nails, eyelashes, eyebrows and/or scalp, by application to the keratinous materials.

The present invention therefore also relates to a cosmetic method for treating keratinous materials, such as the skin, comprising the step of applying a composition according to the present invention to the keratinous materials.

The composition according to the present invention can be used as an anti-aging, anti-wrinkle or turnover-promoting product for keratinous materials such as skin. In particular, the composition according to the present invention can be used as an anti-wrinkle skin cosmetic.

The above descriptions of components (a)-(d) and optional components of the composition according to the present invention are applicable to the components of the uses and methods according to the present invention.

The present invention will now be described in more detail with reference to examples, which should not be construed as limiting the scope of the present invention.

(Example 1 and Comparative Examples 1 to 3)
The following compositions according to Example 1 and Comparative Examples 1-3 were prepared according to the following protocol: All numerical values for the amounts of ingredients shown in Table 1 are based on "wt %" as active ingredients.

The preparation of the dispersion composition was carried out as follows.
(1) Isopropyl lauroyl sarcosine, octyldodecanol, Glycine soya (soybean) oil, butylparaben and tocopherol are mixed and heated at 75-80° C. to form a homogenous mixture, then cooled to room temperature and retinol is introduced to obtain a homogenous core-forming composition.
(2) Water, agar and alginate are mixed and heated to 75-80° C. to form a homogeneous shell-forming composition.
(3) The homogeneous core-forming composition and the homogeneous shell-forming composition are co-extruded to form capsules as multiple dispersed phases.
(4) Prepare the continuous phase by mixing the ingredients listed in Table 1.
(5) The dispersed phase is mixed with the continuous phase to prepare a dispersion.

[evaluation]
(Thermal and photostability)
Each of the compositions according to Example 1 and Comparative Examples 1 to 3 was filled into a transparent container and kept at 55° C. for 2 weeks or at room temperature for 24 hours under UV irradiation using Suntest CPS (Toyo Seiki Seisakusho Co., Ltd., 765 W/m ² ). After storage, each of the compositions was homogenized at 15,000 rpm for 10 minutes using a homogenizer to break capsules in the composition and prepare samples for HPLC analysis. The remaining percentages (%) of retinol and ascorbic acid after storage were measured by HPLC and calculated as a function of the control percentages (stored at 4° C. for 2 weeks) measured by HPLC. The remaining percentages (%) of retinol and ascorbic acid calculated in this way for each composition were evaluated according to the following evaluation criteria.
- Heat stability (2 weeks at 55℃)
Good (OK): 90 or more Bad (NG): less than 90
- Light stability (store in sunlight for 24 hours)
Good: 75 or more Bad: less than 75

(Dispersion and color stability)
Each of the compositions according to Example 1 and Comparative Examples 1 to 3 was filled into a glass bottle, and each of the glass bottles was kept at a temperature of 55° C. for two months.

Each vial was then inspected by visual observation for dispersion and color stability. For dispersion stability, the samples were inspected for whether the dispersion (capsules) were evenly dispersed in the composition. For color stability, the samples were inspected for color development. These characteristics were then evaluated according to the following evaluation criteria:
- Good dispersion stability: the capsules were uniformly dispersed in the composition.
Poor: Capsules were floating or settling in the composition.
- Good color development: No color change or slight color change to light brown.
Poor: The color had changed to brown.

The results are shown in Table 1.

The composition of Example 1, which contains the above-described components (a) to (d), maintained a stable dispersion form even under light exposure and at high temperatures, without the dispersed phase floating up or precipitating, and was able to maintain a sufficient residual amount of the retinoid therein.

On the other hand, the composition of Comparative Example 1, which did not contain component (c), was unable to maintain a sufficient residual rate of component (a) at high temperatures.

The composition of Comparative Example 2, which did not contain component (b), was unable to maintain a sufficient residual rate of component (a) when exposed to UV light.

The composition of Comparative Example 3, which did not contain component (d), was unable to maintain a dispersed form, and the capsules floated up in the composition.

Claims (15)

1. A dispersion composition comprising a continuous phase and a plurality of dispersed phases,
(a) at least one retinoid;
(b) at least one compound capable of providing a solution having a transmittance of 10% or less, preferably 5% or less, and more preferably 2% or less for light having a wavelength of 290 to 420 nm along an optical path length of 10 mm, wherein the concentration of the compound in the solution is 0.9% by weight based on the total weight of the solution;
(c) at least one hydrophilic antioxidant other than component (b);
(d) at least one cationic polymer. (a) The composition of claim 1, wherein the retinoid is present in a dispersed phase. The composition of claim 1 or 2, wherein (b) the compound, (c) the hydrophilic antioxidant, and (d) the cationic polymer are present in a continuous phase. (a) The composition according to any one of claims 1 to 3, wherein the retinoid is retinol. The composition according to any one of claims 1 to 4, wherein the amount of (a) retinoid in the composition is within the range of 0.01% to 5% by weight, preferably 0.05% to 3% by weight, more preferably 0.1% to 1% by weight, based on the total weight of the composition. The composition according to any one of claims 1 to 5, wherein the compound (b) is selected from polyphenols, preferably quercetin, isoquercetin, rutin, glucosylrutin, and mixtures thereof. The composition according to any one of claims 1 to 6, wherein the amount of the compound (b) in the composition is within the range of 0.01% by mass to 5% by mass, preferably 0.05% by mass to 3% by mass, more preferably 0.1% by mass to 2% by mass, based on the total mass of the composition. (c) The composition according to any one of claims 1 to 7, wherein the hydrophilic antioxidant is selected from ascorbic acid, an ascorbate salt, and a combination thereof. The composition according to any one of claims 1 to 8, wherein the amount of the hydrophilic antioxidant (c) in the composition is within the range of 1% by mass to 30% by mass, preferably 5% by mass to 20% by mass, more preferably 10% by mass to 15% by mass, based on the total mass of the composition. (d) A composition according to any one of claims 1 to 9, wherein the cationic polymer is selected from cationic polysaccharides, preferably non-cellulosic cationic polysaccharides, more preferably cationic gums, in particular cationic galactomannan gums. The composition according to any one of claims 1 to 10, wherein the amount of the cationic polymer (d) in the composition is within the range of 0.01% by mass to 10% by mass, preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 2% by mass, based on the total mass of the composition. The composition according to any one of claims 3 to 11, wherein the continuous phase is an aqueous continuous phase. The composition of any one of claims 1 to 12, wherein the dispersed phase comprises a capsule. The composition according to any one of claims 1 to 13, wherein the amount of the dispersed phase in the composition is 0.1% to 30% by weight, preferably 1% to 20% by weight, more preferably 3% to 15% by weight, and even more preferably 5% to 10% by weight, based on the total weight of the composition. A cosmetic method for treating keratinous materials such as the skin, comprising the step of applying to the keratinous materials a composition according to any one of claims 1 to 14.