FR3149779A1 - Composition comprising a UV filter, at least 1% by weight of ascorbic acid and a scleroglucan gum - Google Patents

Abstract

TITLE: Composition comprising a UV filter, at least 1% by weight of ascorbic acid and a scleroglucan gum The present invention relates to a composition, and in particular a cosmetic or dermatological composition, comprising at least one UV filter, at least 1% by weight relative to the total weight of the composition of ascorbic acid, and at least one scleroglucan gum, as well as the use of said composition in the cosmetic and dermatological fields, in particular for the care, treatment of keratin materials, and in particular for the care, protection and/or makeup of the skin of the body or face, or for hair care.

Description

Composition comprising a UV filter, at least 1% by weight of ascorbic acid and a scleroglucan gum

The present invention relates to a composition, and in particular a cosmetic or dermatological composition, comprising at least one UV filter, at least 1% by weight, preferably at least 5% by weight relative to the total weight of the composition of ascorbic acid, and at least one scleroglucan gum, as well as the use of said composition in the cosmetic and dermatological fields, in particular for the care, treatment of keratin materials, and in particular for the care, protection and/or makeup of the skin of the body or face, or for hair care.

It is known that light radiation with wavelengths between 280 nm and 400 nm causes the browning of human skin. Rays with wavelengths more particularly between 280 and 320 nm, known as UV-B, cause erythema and skin burns that can harm the development of a natural tan.

For these reasons, as well as for aesthetic reasons, there is a constant demand for means of controlling this natural tan in order to control the colour of the skin: it is therefore appropriate to filter UV-B radiation. It is also known that UV-A rays, with wavelengths between 320 and 400 nm, which cause the skin to brown, are likely to cause alterations in the skin, particularly in the case of sensitive skin or skin that is continuously exposed to solar radiation. In particular, UV-A rays cause a loss of elasticity in the skin and the appearance of wrinkles, leading to premature skin ageing.

Thus, for aesthetic and cosmetic reasons, such as preserving the natural elasticity of the skin, for example, more and more people want to control the effect of UV-A rays on their skin. It is therefore desirable to filter UV-A radiation as well.

In order to ensure protection of the skin and keratin materials against UV radiation, photoprotective compositions are generally used, comprising organic filters, active in UV-A and active in UV-B.

Many cosmetic compositions intended for photoprotection of the skin have been proposed to date. These compositions generally contain, in an emulsified liquid support (preferably oil-in-water emulsion), one or more organic molecules, capable of absorbing ultraviolet radiation, soluble in the oily and/or aqueous phase. The use of mineral pigments of metal oxide such as titanium dioxide in such sun compositions is increasingly frequent because these particles, invisible to the naked eye thanks to their small size, make it possible to increase the protection index of the compositions containing them.

It is also known that high filter rates are necessary to achieve high levels of filtering efficiency.

However, high levels of UV filters do not lend themselves to easy development of compositions with a stabilised and pleasant texture.

Thus, formulations with high filtering power generally have uncomfortable or even unpleasant sensory aspects that mask the freshness and comfort of the formulas. In particular, the weak point of photoprotective formulations with a high protection index is often a significant feeling of oiliness and stickiness, and therefore a lack of lightness of the textures obtained, but also a white appearance on application and therefore not invisible on the skin.

Furthermore, the introduction of high-content UV filters generally causes destabilization problems. This instability can sometimes even cause a phase shift of the emulsion and/or a loss of viscosity of the composition, making the formulation ineffective or even unusable.

One of the major drawbacks of these photo-protective emulsions containing organic filters and/or mineral filters lies in the difficulty of reconciling good product stability, ease of application of the product, effective sun protection, and a fresh, non-sticky feel.

In addition, the daily photoprotection market is booming. More and more hybrid products providing skin care and protection with SPF 15-20 are being launched, but there remains the challenge of having higher SPF values, for example greater than or equal to 30, or even greater than or equal to 50, with a pleasant sensoriality for daily application. The world of skincare remains very different from the field of photoprotection in terms of consumer experience, which increases the complexity of formula development.

We are therefore looking to have skincare products with high sun protection while maintaining the sensory codes of skincare: Appearance, texture, consistency, sensory.

In cosmetic applications, it is common to add ascorbic acid (vitamin C) as a skin regenerating active ingredient by stimulating the synthesis of collagen responsible for skin firmness, or as a depigmenting agent, because this vitamin reduces the production of melanin responsible for brown spots. Ascorbic acid is also known for its antioxidant properties.

However, when ascorbic acid is introduced into aqueous media (such as emulsions or serums) at high levels (i.e. greater than 1% by weight, preferably greater than 5% by weight), its formulation is difficult to achieve, because it destabilizes and changes color drastically.

This is why there are aqueous compositions on the market such as serums or solutions, which include ascorbic acid in powder form to be dissolved extemporaneously. The disadvantage of this type of product is that vitamin C ends up degrading in the aqueous medium. These products are thus losing their appeal because consumers prefer, for reasons of practicality, serums without prior manipulation, with the guarantee of color stability and without chemical degradation.

In addition, the introduction of high levels of vitamin C into a cosmetic composition can lead to destabilization of the formula, for example when it is in the form of an emulsion, a phase shift with release of the oily phase can be observed.

Thus, there is a need for a cosmetic composition comprising UV filters and ascorbic acid which is stable, i.e. which remains the same colour as originally (generally white) and the same texture, and which does not degrade the active ingredient, while exhibiting high photoprotective properties.

The Applicant surprisingly discovered that the presence of one or more scleroglucan gums in a filtering composition made it possible to introduce a high level of vitamin C into this composition while maintaining effective sun protection and great stability of the composition.

The present invention therefore relates to a composition, and in particular a cosmetic or dermatological composition, comprising:
a) at least one UV filter;
b) at least 1% by weight, preferably at least 5% by weight of ascorbic acid relative to the total weight of the composition; and
(c) at least one scleroglucan gum.

Against all expectations, the inventors have found that the implementation, in a cosmetic composition, of at least one UV filter, of at least 1% by weight, preferably at least 5% by weight of ascorbic acid and of at least one scleroglucan gum makes it possible to obtain a composition that is easy to spread, with high photoprotective power and which is nevertheless stabilized over time, also having good cosmetic properties such as a refreshing power and a non-greasy and non-sticky texture.

The invention also relates, according to another of its aspects, to the use of a composition as defined above, for the care of keratin materials, in particular the skin of the body and/or the face.

The invention also relates, according to yet another of its aspects, to a non-therapeutic cosmetic process for making up and/or caring for keratin materials, in particular the skin of the body and/or face, comprising at least the application to said keratin materials of a cosmetic composition as defined above.

It also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the color and/or uniformity of the complexion comprising the application to the surface of the keratin material of at least one cosmetic composition as defined above.

It also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of aging of a keratin material comprising the application to the surface of the keratin material of at least one cosmetic composition as defined above.

The composition according to the invention has good stability. This stability can be evaluated macroscopically and/or microscopically, after storage for 24 hours, one week, one month, or two months, at room temperature (25°C), at 4°C, at 45°C, or at 55°C. A stable composition generally retains its pleasantness and its sensory signature upon application over time. More precisely, the stability of a composition can be evaluated qualitatively, for example by the absence of phase shift phenomena or the appearance of crystals, or quantitatively by monitoring the evolution of parameters such as viscosity or pH.

By "stable over time" according to the present invention is meant a composition which after 1 month, preferably after 2 months, of storage at a temperature ranging from 4 to 45°C shows only few macroscopic changes such as changes in color, odor, viscosity, pH, as well as slight variations in microscopic appearance.

In the context of the invention, the filtering efficiency is evaluated from the evaluation of the SPF and the UVAPF.

For the purposes of the present invention, the term " SPF " (Sun Protection Factor) means: the sun protection factor, which measures the level of protection against UVB. The SPF value corresponds to the ratio between the minimum time required to obtain sunburn with a photoprotective composition and that without product. More specifically, the term " SPF " is defined in the article A new substrate to measure sunscreen protection factors throughout the ultraviolet spectrum , J. Soc. Cosmet. Chem., 40, 127-133 (May/June 1989).

The SPF (Sun Protection Factor) assessment can be carried out in vitro using the Labsphere® spectrophotometer. The plate is the material on which the photoprotective composition is applied. For this protocol, polymethylmethacrylate (PMMA) plates have proven to be ideal. A specific protocol is currently being approved by ISO under the name ISO Committee Draft 23675.

The evaluation of the Sun Protection Factor (SPF) of the compositions can also be carried out in-vivo according to the ISO 24444: 2019 protocol “Cosmetics-Sun protection test methods-In-vivo determination of the sun protection factor (SPF)”.

For the purposes of the present invention, UVAPF means the index characterizing protection against UVA. In particular, this index can be measured in vivo according to the “PPD” (Persistent Pigment Darkening) method, ISO-24442: 2022 protocol, by the color of the skin observed 2 to 4 hours after exposure to UVA. The evaluation of protection against UVA can also be measured in vitro using a Labsphere® spectrophotometer. The plate is the material on which the sunscreen composition is applied. For this protocol, polymethylmethacrylate (PMMA) plates have proven to be ideal. The ISO 24443: 2021 protocol describes such an in vitro method.

Other features, aspects and advantages of the invention will become apparent upon reading the detailed description which follows.

The composition according to the invention is intended for topical application and therefore contains a physiologically acceptable medium. Here, the term “physiologically acceptable medium” means a medium compatible with keratin materials.

In the context of the present invention, the term “keratin material” is understood to mean in particular the skin, the scalp, the keratin fibers such as the eyelashes, the eyebrows, the hair, and the body hairs, the nails, the mucous membranes such as the lips, and more particularly the skin and the mucous membranes (body, face, eye contour, eyelids, lips, preferably body, face and lips).

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “between” and “ranging from … to …”.

Furthermore, the expressions “at least one” and “at least” used in this description are respectively equivalent to the expressions “one or more” and “greater than or equal”.

By “prevent” or “prevention”, according to the invention, is meant the fact of reducing the risk of occurrence or slowing down the occurrence of a given phenomenon, namely, according to the present invention, the signs of aging of a keratin material.

By “organic UVA filter” is meant any organic chemical molecule capable of absorbing at least UVA radiation in the wavelength range between 320 and 400 nm; said molecule can also additionally absorb UVB radiation in the wavelength range between 280 and 320 nm.

By “organic UVB filter” we mean any organic chemical molecule capable of exclusively absorbing UVB radiation in the wavelength range between 280 and 320 nm.

According to a particular embodiment of the invention, the composition is in the form of an emulsion.

By "emulsion" is meant any macroscopically homogeneous composition that is kinetically stable comprising at least two phases that are immiscible with each other; one being the continuous dispersing phase and the other being dispersed in said continuous phase in the form of droplets. The two phases may be kinetically stabilized by at least one emulsifying system generally comprising at least one emulsifying surfactant.

A distinction is made between oil-in-water emulsions called "direct" consisting of a continuous aqueous dispersing phase and a discontinuous oily dispersed phase and water-in-oil emulsions called inverse consisting of a continuous oily dispersing phase and a discontinuous aqueous dispersed phase. There are also multiple emulsions such as water-in-oil-in-water or oil-in-water-in-oil emulsions.

Detailed description of the invention UV filters

The composition in accordance with the invention comprises at least one UV filter.

The UV filter(s) may be chosen from lipophilic organic UV filters, hydrophilic organic UV filters and inorganic UV filters.

Lipophilic organic UV filters

By "lipophilic organic filter" we mean any organic cosmetic or dermatological compound filtering UV radiation capable of being completely dissolved in the molecular state in a liquid fatty phase or of being solubilized in colloidal form (for example in micellar form) in a liquid fatty phase.

The lipophilic organic filters are in particular chosen from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds in particular those cited in patent US5624663; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds as described in patents EP669323 and US 2,463,264; methylene bis-(hydroxyphenyl benzotriazole) compounds as described in applications US5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP893119; benzoxazole compounds as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and filter silicones such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes compounds as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981; and mixtures thereof.

Preferably, the lipophilic organic filter(s) are chosen from salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof.

Examples of lipophilic organic photoprotective agents include those designated below by their INCI name and/or chemical name.

Cinnamic compounds:
Ethylhexyl Methoxycinnamate sold in particular under the trade name PARSOL® MCX by the company DSM Nutritional Products;
Isoamyl p-Methoxycinnamate sold under the trade name NEO HELIOPAN E 1000 ® by the company Symrise,

Dibenzoylmethane compounds:
Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL® 1789 by the company DSM Nutritional Products,

Salicylic compounds:
Homosalate sold under the name “Parsol® HMS” by the company DSM Nutritional Products,
Ethylhexyl Salicylate sold under the name “NEO HELIOPAN® OS” by the company Symrise,

β,β-diphenylacrylate compounds:
Octocrylene sold in particular under the trade name “UVINUL® N 539 T” by the company BASF,

Benzophenone compounds:
Benzophenone-3 or Oxybenzone, sold under the trade name “UVINUL® M 40” by the company BASF,
Diethylamino hydroxybenzoyl hexyl benzoate sold under the trade name “UVINUL® A Plus” or in mixture with ethylhexyl methoxycinnamate under the trade name “UVINUL® A Plus B” by the company BASF,

Benzylidene camphor compounds:
4-Methylbenzylidene camphor sold under the name “EUSOLEX® 6300” by the company MERCK,

Phenyl benzotriazole compounds:
Drometrizole Trisiloxane manufactured under the name “MEXORYL® XL” by the company NOVEAL,

Methylene bis-(hydroxyphenyl benzotriazole) compounds:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol, in particular in solid form as the product sold under the trade name “MIXXIM BB/100 ®” by the company FAIRMOUNT CHEMICAL,

Triazine compounds:
- 3,3'-(1,4-Phenylene)bis(5,6-diphenyl-1,2,4-triazine), INCI name Phenylene Bis-Diphenyl triazine,
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name “Parsol Shield ®” by the company DSM and under the trade name “TINOSORB® S” by the company BASF,
- Ethylhexyl Triazone sold in particular under the trade name “UVINUL® T 150” by the company BASF,
- Diethylhexyl Butamido Triazone sold under the trade name “UVASORB® HEB” by the company 3V SIGMA,
- symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups described in patent US6,225,467, application WO2004/085412 (see compounds 6 and 9) or the document “Symmetrical Triazine Derivatives” IP.COM IPCOM000031257 Journal, INC WEST HENRIETTA, NY, US (September 20, 2004),

Anthranilic compounds:
Menthyl anthranilate sold under the trade name “NEO HELIOPAN® MA” by the company Symrise,

Benzalmalonate compounds:
Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name “PARSOL SLX ®” by the company HOFFMANN LA ROCHE.

According to a particular embodiment, the composition in accordance with the invention comprises Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine.

Hydrophilic organic UV filters

For the purposes of the present invention, the term “hydrophilic organic UV filter” means a water-soluble organic UV filter or a water-dispersible organic UV filter.

By "water-soluble organic filter" is meant any organic filter capable of being completely dissolved in molecular form in a liquid aqueous phase, or of being dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

The term "water-dispersible organic filter" means any organic filter capable of forming in a liquid aqueous phase a homogeneous suspension of particles with a volume average size of less than 100 microns. The volume average size is determined by laser diffraction granulometry.

Among the water-soluble organic UVA filters that can be used according to the present invention, mention may be made of benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) and its various salts, described in particular in patent applications FR-A-2528420 and FR-A-2639347. Mention may in particular be made of benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) such as that manufactured under the name “MEXORYL® SX” by the company NOVEAL.

These filters correspond to the following general formula (I):

in which, F denotes a hydrogen atom, an alkali metal or a radical NH(R ₁ ) ₃ ⁺ in which the radicals R ₁ , which may be identical or different, denote a hydrogen atom, a C ₁ to C ₄ alkyl or hydroxyalkyl radical, or a group Mn+, Mn+ denoting a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn+ preferably denoting a metal cation chosen from Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ and Zr ⁴⁺ . It is understood that the compounds of formula (I) above can give rise to the "cis-trans" isomer around one or more double bond(s) and that all the isomers fall within the scope of the present invention.

Among the water-soluble organic UVA filters which can be used according to the present invention, mention may also be made of compounds comprising at least two benzoazolyl groups with sulfonic groups such as those described in patent application EP-A-0669323.

They are described and prepared according to the syntheses indicated in US patent 2,463,264 as well as in patent application EP-A-0669323.

The compounds comprising at least two benzoazolyl groups in accordance with the invention correspond to the following general formula (II):

in which:
- Z represents an organic residue of valence (l + n) comprising one or more double bonds placed in such a way that it completes the double bond system of at least two benzoazolyl groups as defined inside the brackets to form a fully conjugated set;
- X' denotes S, O or NR ⁶ ;
- R ¹ denotes a hydrogen atom, a C ₁ to C ₁₈ alkyl, a C ₁ to C ₄ alkoxy, a C ₅ to C ₁₅ aryl, a C ₂ to C ₁₈ acyloxy, an SO ₃ Y or COOY group;
- the radicals R ² , R ³ , R ⁴ and R ⁵ , identical or different, denote a nitro group or a radical R ¹ ;
- R ⁶ denotes a hydrogen atom, a C ₁ to C ₄ alkyl or a C ₁ to C ₄ hydroxyalkyl;
- Y denotes a hydrogen atom, Li, Na, K, NH ₄ , 1/2Ca, 1/2Mg, 1/3Al or a cation resulting from the neutralization of a free acid group by an organic nitrogen base;
- m is 0 or 1;
- n is a number from 2 to 6;
- l is a number from 1 to 4;
- provided that l + n does not exceed the value 6.

Among these compounds, 1,4-bis-benzimidazolyl-phenylen-3,3',5,5'-tetrasulfonic acid (INCI name: Disodium Phenyl Dibenzimidazole Tetra-sulfonate) or one of its salts of the following structure (III) sold in particular under the name "NEO HELIOPAN® AP" by the company Symrise will be particularly preferred:

Preferably, the water-soluble filter capable of absorbing UVA is benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) such as that manufactured under the name "MEXORYL SX" by NOVEAL.

The water-soluble organic UVB filters that can be used according to the present invention are notably chosen from water-soluble cinnamic derivatives such as ferulic acid or 3-methoxy-4-hydroxycinnamic acid; water-soluble benzylidene camphor compounds; water-soluble phenylbenzimidazole compounds; water-soluble p-aminobenzoic compounds (PABA); water-soluble salicylic compounds, and mixtures thereof.

Examples of water-soluble organic UVB filters include phenyl benzimidazole compounds, such as 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid) sold in particular under the trade name “EUSOLEX 232 ^® ” by MERCK.

The composition according to the invention may also comprise at least one mixed water-soluble filter capable of absorbing UVA and UVB rays.

When the water-soluble UV filter is of the sulfonic acid type, it is preferably associated with an organic base, such as an alkanolamine.

By "alkanolamine" is meant a _C2 - _C10 compound comprising at least one primary, secondary or tertiary amine function and at least one alcohol function, generally primary. As suitable alkanolamine, mention may be made of 2-amino-2-(hydroxymethyl)-1,3-propanediol (INCI name: TROMETHAMINE) and triethanolamine.

Among the water-dispersible organic filters, the following filters can be mentioned.

Benzophenone compounds:
1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (CAS 919803-06-8) as described in application WO2007/071584; this compound being advantageously used in micronized form (volume average size of 0.02 to 2 µm) which can be obtained for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular in the form of an aqueous dispersion,

Methylene bis-(hydroxyphenyl benzotriazole) compounds:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol
in the form of an aqueous dispersion of micronized particles having a mean particle size by volume which varies from 0.01 to 5 μm, and more preferably from 0.01 to 2 μm, and more particularly from 0.020 to 2 μm, with at least one alkylpolyglycoside surfactant of structure C _n H _2n+1 O(C ₆ H ₁₀ O ₅ ) _x H in which n is an integer from 8 to 16 and x is the mean degree of polymerization of the unit (C ₆ H ₁₀ O ₅ ) and varies from 1.4 to 1.6 such as the aqueous dispersions described in patent GB-A-2 303 549, in particular the product sold under the trade name "TINOSORB® M" by the company BASF, or
in the form of an aqueous dispersion of micronized particles having a volume average particle size which varies from 0.02 to 2 μm, and more preferably from 0.01 to 1.5 μm, and more particularly from 0.02 to 1 μm, in the presence of at least one mono-(C ₈ -C ₂₀ )alkyl-ester of polyglycerol having a degree of polymerization of glycerol of at least 5 such as the aqueous dispersions described in application WO2009/063392, in particular the product marketed under the name Tinosorb WPGL by the company BASF,

Triazine compounds:
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in its water-dispersible form with the INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer, under the trade name TINOSORB® S LiteAqua by the company BASF,
- symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups used in micronized form (average particle size of 0.02 to 3 µm) obtainable for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119, and in particular in aqueous dispersion form, in particular 2,4,6-tris(bi-phenyl)-triazine and 2,4,6-tris(ter-phenyl)-triazine marketed under the name TINOSORB® A2B by the company BASF and which is included in patent applications WO06/035000, WO06/034982, WO06/034991, WO06/035007, WO2006/034992, WO2006/034985,

Benzoxazole compounds:
2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole, CAS number 904-39-2.

Inorganic UV filters

The inorganic UV filters that can be used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having an average elementary particle size of less than or equal to 0.5 µm, more preferably between 0.005 and 0.5 µm, and even more preferably between 0.01 and 0.2 µm, even better between 0.01 and 0.1 µm, and more particularly between 0.015 and 0.05 µm. They are notably described in Annex VI updated on 09/22/2021 of the European Cosmetic Products Regulation number 1223/2009, but are not limited to this list.

They can be chosen in particular from titanium, zinc, iron, zirconium, cerium oxides or their mixtures.

Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0 518 773. As commercial pigments, mention may be made of the products sold by the companies CRODA, TAYCA, and MERCK.

Metal oxide pigments can be coated or uncoated.

Coated pigments are pigments that have undergone one or more surface treatments of a chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

Coated pigments are more particularly coated titanium oxides:
- hydrated silica such as the product “MT-100WP” from the company TAYCA,
- silica and iron oxide such as the product "SUNVEIL F®" from the company IKEDA,
- silica and alumina such as the products "MT-500SA®" and "MT-100SA®" from the company TAYCA, "TIOVEIL™ AQ-N" from the company CRODA,
- alumina such as the products "TTO-55 (A)®" from the company ISHIHARA,
- alumina and aluminum stearate such as the products "MT-100TV®, MT-100Z®, MT-01®" from the company TAYCA, the product "Solaveil™ CT100" from the company CRODA and the product "Eusolex T-AVO®" from the company MERCK,
- silica, alumina and alginic acid such as the product "MT-100AQ®" from the company TAYCA,
- alumina and aluminum laurate,
- iron oxide and iron stearate,
- zinc oxide and zinc stearate,
- silica and alumina and treated with a silicone such as the products "MTY-500SAS®" or "MICROTITANIUM DIOXIDE MT-100SAS®" from the company TAYCA,
- silica, alumina, aluminum stearate and treated with silicone,
- silica and treated with silicone,
- alumina and treated with silicone such as the products "TTO-55(S)®" from the company ISHIHARA,
- triethanolamine,
- stearic acid such as the product "TTO-55 (C)®" from the company ISHIHARA,
- sodium hexametaphosphate,
- TiO2 treated with octyl trimethyl silane,
- TiO2 treated with polydimethylsiloxane,
- anatase/rutile TiO2 treated with polydimethylhydrogensiloxane,
- TiO2 coated with triethylhexanoin, aluminum stearate, alumina sold under the trade name “Solaveil™ CT-200” from CRODA,
- TiO2 coated with aluminum stearate, alumina and silicone sold under the trade name “Solaveil™ CT-12W” from CRODA,
- TiO2 coated with lauroyl lysine,
- TiO2 coated with C9-C15 fluoroalcohol phosphate and aluminum hydroxide.

Mention may also be made of TiO2 pigments doped with at least one transition metal such as iron, zinc, manganese and more particularly manganese. Preferably, said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric/caprylic acids. The oily dispersion of titanium oxide particles may additionally comprise one or more dispersing agents such as, for example, a sorbitan ester such as sorbitan isostearate, a polyoxyalkylenated fatty acid and glycerol ester such as TRI-PPG3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3 POLYRICINOLEATE. Preferably, the oily dispersion of titanium oxide particles comprises at least one dispersing agent chosen from polyoxyalkylenated fatty acid and glycerol esters. More particularly, mention may be made of the oily dispersion of manganese-doped TiO2 particles in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3-POLYRICINOLEATE and SORBITAN ISOSTERATE with the INCI name: TITANIUM DIOXIDE (and) TRI-PPG-3 MYRISTYLETHER CITRATE (and) POLYGLYCERYL-3 RICINOLEATE (and) SORBITAN ISOSTEARATE or the product sold under the trade name “OPTISOL™ OTP-1” by the company CRODA.

Uncoated titanium oxide pigments are sold, for example, by the company TAYCA under the trade names "MT-500B" or "MT-600B®", by the company Evonik under the name "DEGUSSA P 25".

Uncoated zinc oxide pigments are, for example:
- those marketed under the name “Z-COTE®” by the company BASF;
- those marketed under the name “NanoArc® Zinc Oxide” by the company Nanophase Technologies.

Examples of coated zinc oxide pigments include:
- ZnO coated with polymethylhydrogensiloxane;
- CRODA’s “Solaveil™ CZ-100” dispersed in C12-15 alkyl benzonate (INCI: Zinc Oxide (and) C12-15 Alkyl Benzoate (and) Polyhydroxystearic Acid (and) Isostearic Acid);
- those marketed under the name and "DAITOPERSION Zn-60VA®" by the company Daito Kasei (dispersions in C9-12 alkane with a dispersing agent);
- those marketed under the name "SPD-Z5®" by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane).

Uncoated cerium oxide pigments may be, for example, those sold under the name RHODIGARD® W185 by the company Solvay.

Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the equal-weight mixture of titanium dioxide and cerium dioxide coated with silica, as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone or coated with alumina, silica and glycerin.

When the composition according to the invention comprises inorganic UV filters, titanium oxide pigments, coated or uncoated, are particularly preferred.

According to a particular embodiment, the total amount of UV filters present in the composition is greater than or equal to 15% by weight of the total weight of the composition. According to a preferred embodiment, the total amount of UV filters present in the composition is between 15% and 35% by weight, preferably between 16% and 25% by weight of the total weight of the composition.

For the purposes of the present invention, the term “total quantity of UV filters” means the sum of the concentrations of active material in each of the UV filters present in the composition, in particular the lipophilic organic UV filters, the hydrophilic organic UV filters, and the inorganic UV filters.

Ascorbic acid

Ascorbic acid for the purposes of the invention preferably corresponds to L-ascorbic acid, or vitamin C. Its structure is the formula (IV):

The composition according to the invention comprises at least 1% by weight of ascorbic acid relative to the total weight of the composition, preferably at least 5% by weight, more preferably at least 7% by weight.

Preferably, the composition comprises from 1% to 30% by weight of ascorbic acid, preferably from 5% to 25% by weight, more preferably from 7% to 20% by weight, and even more preferably from 8% to 15% by weight relative to the total weight of the composition.

Scleroglucan gums

The composition according to the invention comprises one or more scleroglucan gums.

Scleroglucan gums are polysaccharides of microbial origin produced by a Sclerotium fungus, particularly Sclerotium rolfsii. They are polysaccharides consisting solely of glucose units.

The scleroglucan gums may be modified or unmodified. Preferably, the scleroglucan gums used in the present invention are unmodified.

Examples of scleroglucan gums that can be used in the present invention are, without limitation, the products sold under the name ACTIGUM CS, in particular ACTIGUM CS 11, by the company SANOFI BIO INDUSTRIES and under the name AMIGUM or AMIGEL by the company ALBAN MULLER INTERNATIONAL.

Other scleroglucan gums, such as the glyoxal-treated one described in French patent application No. 2,633,940, may also be used.

The scleroglucan gum(s) which can be used according to the invention preferably represent a total content ranging from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, and even more preferably from 0.1 to 3% by weight relative to the total weight of the composition.

Lipophilic polymers

According to a particular embodiment of the invention, the composition comprises at least one lipophilic polymer comprising monomeric units of formula (A) and (B):

in which:
R1, independently of each other, are chosen from alkyl or alkenyl radicals;
with at least 60% by weight of the R1 groups being radicals selected from stearyl and behenyl radicals, the weight percentage relating to the sum of all the R1 groups present in the polymer;
the weight ratio of the sum of all hydroxyethyl acrylate units to the sum of all acrylate units bearing the R1 group is from 1:30 to 1:1; and
the sum of the total of units A and B is at least 95% by weight of the total weight of the polymer.

Preferably, R1 consists of alkyl radicals, preferably C16-C22 alkyl radicals, and more preferably stearyl radicals (C18) or behenyl radicals (C22).

Preferably, at least 70% by weight of the R1 groups are stearyl or behenyl radicals, preferably at least 80% by weight, and more preferably at least 90% by weight.

According to a preferred embodiment, all R1 groups are behenyl radicals.

According to another preferred embodiment, all R1 groups are stearyl radicals.

Preferably, said weight ratio ranges from 1:15 to 1:1, preferably from 1:10 to 1:4.

Advantageously, the polymer units present in the polymer consist of the units (A) and (B) described above.

According to a particular embodiment of the invention, the polymer has a number-average molecular weight Mn ranging from 2,000 to 9,000 g/mol, preferably ranging from 5,000 to 9,000 g/mol. The number-average molecular weight can be measured with the gel permeation chromatography method, for example according to the method described in the example below.

Preferably, the polymer has a melting temperature ranging from 40°C to 70°C, and preferably ranging from 45°C to 67°C. The melting temperature is measured by differential scanning calorimetry (or DSC), for example according to the method described in the example below.

According to a first embodiment, when the polymer is such that at least 60% by weight of the R1 groups are stearyl radicals, then the polymer generally has a melting point ranging from 40 to 60°C, and preferably ranging from 45 to 55°C.

According to a second embodiment, when the polymer is such that at least 60% by weight of the R1 groups are behenyl radicals, then the polymer generally has a melting point ranging from 60 to 70°C, and preferably ranging from 63 to 67°C.

The polymer used according to the invention can be prepared by polymerization of monomer of formula CH2=CH-COO-R1, R1 having the meaning described above, and 2-hydroxyethyl acrylate.

The polymerization can be carried out according to known methods, such as solution or emulsion polymerization.

The polymerization is for example described in document US 2007/0264204.

The lipophilic polymer(s) used in the context of the invention and as described above may be present in the composition in an amount of active material ranging from 0.05 to 10% by weight, preferably from 0.1% to 5% by weight, and better still from 0.2 to 3% by weight relative to the total weight of the composition.

Aqueous phase

The composition in accordance with the invention comprises at least one aqueous phase.

The aqueous phase contains water, and possibly other organic solvents soluble or miscible in water at 25°C.

The water used may contain sterile demineralized water and/or floral water such as rose water, cornflower water, chamomile water or lime blossom water, and/or natural thermal or mineral water.

An aqueous phase suitable for the invention may comprise, for example, water chosen from a natural spring water, such as La Roche-Posay water, Vittel water, Saint Gervais Mont Blanc water, or Vichy water, or a floral water.

Water-soluble or miscible solvents suitable for the invention include short-chain monoalcohols, for example C ₁ -C _{4 ,} such as ethanol and isopropanol, diols or polyols, such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol, and sorbitol, and mixtures thereof.

According to a particular form of the invention, the overall aqueous phase, including all the hydrophilic substances of the composition capable of being solubilized in this same phase, including the hydrophilic filters, represents from 40% to 80% by weight, and preferably from 55% to 75% by weight relative to the total weight of the composition.

Fat phase

The composition in accordance with the invention may comprise at least one fatty phase.

The fatty phase may consist of all fatty substances conventionally used in the cosmetic or dermatological fields; it may in particular comprise at least one oil. The fatty phase further comprises the lipophilic filter(s) present in the composition according to the invention.

Oil is any fatty substance in liquid form at room temperature (20 – 25 °C) and atmospheric pressure (760 mm Hg). These oils can be volatile or non-volatile.

For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with the skin or keratin fiber in less than one hour, at room temperature and atmospheric pressure. The volatile oil(s) of the invention are volatile cosmetic oils, liquid at room temperature, having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40,000 Pa (10 ^-3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg).

By "non-volatile oil" is meant an oil remaining on the skin or keratin fiber at room temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 10 ^-3 mm Hg (0.13 Pa).

For the purposes of the present invention, the term “hydrocarbon oil” means any oil containing mainly carbon and hydrogen atoms, and possibly one or more heteroatoms, in particular nitrogen and oxygen. Thus, these oils may in particular contain one or more ester, ether, fluorine, carboxylic acid and/or alcohol groups.

The term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

As non-volatile hydrocarbon oils which can be used according to the invention, we may notably cite:
(i) hydrocarbon oils of vegetable origin such as glyceride triesters which are generally triesters of fatty acids and glycerol whose fatty acids may have chain lengths varying from _C4 to _C24 , the latter being able to be linear or branched, saturated or unsaturated; These oils include wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose; or caprylic/capric acid triglycerides such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;
(ii) synthetic ethers having from 10 to 40 carbon atoms;
(iii) linear or branched hydrocarbons, of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof;
(iv) synthetic esters such as oils of formula RCOOR' in which R represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R' represents a hydrocarbon chain, in particular a branched chain, containing from 1 to 40 carbon atoms provided that R + R' is ≥ 10, such as for example Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoate such as the product sold under the trade name "Finsolv TN®" or "Witconol TN®" by the company WITCO or "TEGOSOFT TN ®" by the company EVONIK GOLDSCHMIDT, 2-ethylphenyl benzoate such as the commercial product sold under the name "X-TEND 226®" by the company ISP, lanolate isopropyl, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate such as the product sold under the name "Dub Dis" by the company Stearinerie Dubois, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and pentaerythritol esters; citrates or tartrates such as linear C12-C13 dialkyl tartrates such as those sold under the name COSMACOL ETI® by the company ENICHEM AUGUSTA INDUSTRIALE as well as linear C14-C15 dialkyl tartrates such as those sold under the name COSMACOL ETL® by the same company; acetates;
(v) fatty alcohols which are liquid at room temperature with a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecylpentadecanol;
(vi) carbonates such as dicaprylyl carbonate such as the product sold under the name “Cetiol CC®” by the company Cognis;
and their mixtures.

Among the non-volatile hydrocarbon oils that can be used according to the invention, the following will be particularly preferred: glyceride triesters and in particular caprylic/capric acid triglycerides, synthetic esters and in particular diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, dicaprylyl carbonate, isononyl isononanoate, oleyl erucate, C12-C15 alcohol benzoate, 2-ethylphenyl benzoate and fatty alcohols, in particular octyldodecanol. Preferably, the non-volatile hydrocarbon oils are chosen from diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate and dicaprylyl carbonate.

As volatile hydrocarbon oils that can be used according to the invention, mention may in particular be made of hydrocarbon oils having from 8 to 16 carbon atoms, and in particular branched C8-C16 alkanes such as C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, oils sold under the trade names Isopars or Permetyls, branched C8-C16 esters, isohexyl neopentanoate, and mixtures thereof.

Mention may also be made of the alkanes described in the patent applications of the company Cognis WO 2007/068371, or WO2008/155059 (mixtures of distinct alkanes and different by at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil. Mention may be made of the mixtures of n-undecane (C11) and n-tridecane (C13) obtained in examples 1 and 2 of the application WO2008/155059 of the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97®, as well as their mixtures.

Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Solt® by the company SHELL, may also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof.

The non-volatile silicone oils may be chosen in particular from non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, pendant and/or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.

As volatile silicone oils, mention may be made, for example, of volatile linear or cyclic silicone oils, in particular those having a viscosity ≤ 8 centistokes (8 10 ^-6 m ² /s), and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, mention may be made in particular of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.

We can also cite volatile linear alkyltrisiloxane oils such as:
3-butyl 1,1,1,3,5,5,5-heptamethyl trisiloxane,
3-propyl 1,1,1,3,5,5,5-heptamethyl trisiloxane, and
3-ethyl 1,1,1,3,5,5,5-heptamethyl trisiloxane.

Fluorinated volatile oils, such as nonafluoromethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane and mixtures thereof, may also be used.

The fatty phase according to the invention may also comprise, mixed with or dissolved in the oil, other fatty substances.

Another fatty substance that may be present in the oily phase can be, for example:
- a fatty acid such as fatty acids containing 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid; preferably higher fatty acids in C12-C22, such as oleic acid, linoleic acid, linolenic acid;
- a wax chosen from waxes such as lanolin, beeswax, carnauba or candelilla wax, paraffin wax, lignite wax or microcrystalline wax, ceresin or ozokerite, synthetic waxes such as polyethylene waxes, Fischer-Tropsch waxes;
- a gum chosen from silicone gums (dimethiconol),
- a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, fatty acid triglycerides and their derivatives,
- and their mixtures.

When present, the overall fatty phase, including all the lipophilic substances of the composition capable of being solubilized in this same phase, including the lipophilic filters, represents from 20% to 60% by weight, and preferably from 25% to 45% by weight relative to the total weight of the composition.

Cosmetic active ingredients

The composition of the present invention may comprise at least one cosmetic active ingredient.

Examples of cosmetic active ingredients include moisturizing agents; natural extracts; vitamins other than vitamin C, and their derivatives (in particular esters); vitamin C derivatives (in particular esters); urea; caffeine; salicylic acid and its derivatives; alpha-hydroxy acids such as lactic acid or glycolic acid and their derivatives; retinoids; extracts of algae, fungi, plants, yeasts and bacteria; enzymes; tightening agents; agents acting on microcirculation, and mixtures thereof.

Additional adjuvants or additives

The composition of the present invention may also contain conventional cosmetic adjuvants or additives, for example, fragrances, chelating agents (e.g., tetrasodium glutamate diacetate and disodium EDTA), preservatives (e.g., chlorphenesin and phenoxy ethanol) and bactericides, additional thickeners (such as acrylamide/sodium acryloyldimethyltaurate copolymer, polysaccharides other than scleroglucans, including xanthan gum), pH adjusters (e.g., triethanolamine, citric acid, and sodium hydroxide), fillers (e.g., aluminum starch octenylsuccinate and polymethylsisesquioxane), and mixtures thereof.

A person skilled in the art will select the amount of cosmetic active ingredients, adjuvants or additional additives so as not to harm the final use of the composition according to the present invention.

Dosage forms

The compositions according to the invention can be prepared according to techniques well known to those skilled in the art.

The compositions in accordance with the invention may be presented in particular in the form of an emulsion, simple or complex (O/W, W/O, O/W/O or W/O/W), such as a cream or a milk, a cream gel, a serum or a fluid.

According to a particular embodiment of the invention, the composition is in the form of an emulsion. It may in particular be in the form of an oil-in-water emulsion (direct emulsion) or in the form of a water-in-oil emulsion (reverse emulsion). Preferably, the composition is in the form of an oil-in-water emulsion.

In the case of compositions in the form of oil-in-water or water-in-oil emulsions, the emulsification processes that can be used are of the blade or propeller, rotor-stator and HHP type.

To obtain stable emulsions with a low polymer content (oil/polymer ratio >25), it is possible to make the dispersion in concentrated phase then dilute the dispersion with the rest of the aqueous phase.

It is also possible, by HHP (between 50 and 800 bars), to obtain stable dispersions with drop sizes down to 100 nm.

The emulsions may contain at least one emulsifier selected from amphoteric, anionic, cationic or non-ionic emulsifiers, used alone or as a mixture. The emulsifiers are chosen appropriately depending on the emulsion to be obtained (W/O or O/W).

Examples of W/O emulsifying surfactants include alkyl esters or ethers of sorbitan, glycerol, polyol, glycerol or sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C®" by the company Dow Corning, and alkyl-dimethicone copolyols such as Laurylmethicone copolyol sold under the name "Dow Corning 5200 Formulation Aid" by the company Dow Corning; Cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R® by the company Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE O9® by the company Goldschmidt. One or more co-emulsifiers may also be added, which, advantageously, may be chosen from the group comprising polyol alkyl esters.

We can also cite non-silicone emulsifying surfactants, in particular alkyl esters or ethers of sorbitan, glycerol, polyol or sugars.

Examples of polyol alkyl esters include polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate such as the product marketed under the name Arlacel P135® by the company ICI.

As glycerol and/or sorbitan esters, mention may be made, for example, of polyglycerol isostearate, such as the product marketed under the name Isolan GI 34® by the company Goldschmidt; sorbitan isostearate, such as the product marketed under the name Arlacel 987® by the company ICI; sorbitan isostearate and glycerol, such as the product marketed under the name Arlacel 986® by the company ICI, and mixtures thereof.

For H/W emulsions, examples of nonionic emulsifying surfactants that may be mentioned include polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylenated) fatty acid and glycerol esters, such as the ester of polyethylene glycol and stearic acid with the INCI name PEG-100 STEARATE marketed under the name Myrj S100-PA-(SG) by the company CRODA; oxyalkylenated fatty acid and sorbitan esters; polyoxyalkylenated (in particular polyoxyethylenated and/or polyoxypropylenated) fatty acid esters, optionally in combination with a fatty acid and glycerol ester, such as the PEG-100 Stearate/Glyceryl Stearate mixture marketed, for example, by the company ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, in particular alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside marketed for example by Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearylglucoside optionally mixed with cetostearyl alcohol, marketed for example under the name Montanov 68® by Seppic, under the name Tegocare CG90® by Goldschmidt and under the name Emulgade KE3302® by Henkel, as well as arachidyl glucoside, for example in the form of a mixture of arachidic and behenic alcohols and arachidylglucoside marketed under the name Montanov 202® by Seppic. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described for example in document WO-A-92/06778.

As anionic surfactants for producing H/W emulsions, mention may be made of surfactants chosen from amino acids modified by at least one _C8 - _C30 hydrocarbon chain, preferably _C8 - _C24 , and their salts, in particular acyl glutamic acids (INCI name: acyl glutamic acid) or one of their salts (acyl glutamates), such as stearoyl glutamic acid or one of its salts, in particular sodium stearoyl glutamate (INCI name).

Such compounds are marketed under the name AMISOFT by the company AJINOMOTO and in particular under the references Amisoft CA, Amisoft LA, Amisoft HS 11 PF, Amisoft MK-11, Amisoft LK-11, Amisoft CK-11, or under the name EUMULGIN SG by the company COGNIS.

As anionic surfactants for producing H/W emulsions, mention may also be made of hydrophobic modified polysaccharides, in particular inulins modified by hydrophobic chains such as alkylcarbamate groups, in particular C8-C18 alkyl carbamate, and more particularly laurylcarbamate.

As an example of these compounds, we can notably cite the product sold under the name INUTEC SL1 by the company CREACHEM.

The compositions according to the invention may also be aqueous solutions, more preferably aqueous solutions with a slightly gelled appearance.

According to another particular embodiment, the composition according to the invention is a single-phase aqueous composition. This composition can be called a “serum”. By “serum”, we mean a composition with a fluid texture, a slightly gelled, runny appearance.

According to this embodiment, the composition is preferably substantially free of surfactants. By "substantially free of surfactants" is meant that the composition according to the invention has a surfactant content of less than or equal to 2% by weight, relative to the total weight of the composition, preferably less than or equal to 1% by weight. The surfactants may preferably be peptizers, the concentration of which is between 0.1 and 2% by weight; they allow the solubilization of a small quantity of oil(s) or lipophilic compounds or perfume(s) (i.e. concentration of perfume(s) or oil(s) or lipophilic compound(s) of between 0.05% and 2%).

EXAMPLES

The present invention will now be described more specifically by way of examples, which are in no way limiting of the scope of the invention. However, the examples serve to support specific features, variations, and preferred embodiments of the invention.

A/ Examples of synthesis of lipophilic polymers comprising monomeric units of formula (A) and (B) in accordance with the invention

Determination of molecular weight by gel permeation chromatography (GPC):
The sample is prepared by making a solution of the polymer at 10 mg/ml in tetrahydrofuran. The sample is placed in an oven at 54 °C for 10 minutes and then in an oscillating shaker for 60 minutes to aid dissolution. Upon visual inspection, the sample appears completely dissolved in the solvent.
The prepared sample was analyzed using two 300 x 7.5 mm polypore columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, a tetrahydrofuran mobile phase and refractive index detection. The sample was filtered through a 0.45 µm nylon filter before being injected into the liquid chromatograph. The standards used for calibration are the Easi Vial narrow polystyrene (PS) standards from Agilent Technologies.
Polystyrene standards ranging from 2,520,000 to 162 Daltons were used for calibration.
The system is equipped with a PSS SECcurity 1260 RI detector. The polystyrene calibration curve was used to determine the average molecular weight. The recording of the diagrams and the determination of the different molecular weights was done by the Win GPC Unichrom 81 program.

Determination of the melting point by differential scanning calorimetry (or DSC):
This method describes the general procedure for determining the melting point of polymers by differential scanning calorimetry. This method is based on ASTM E791 and ASTM D 34182 and the DSC calibration is performed according to ASTM E 9672.

Behenyl acrylate / 2-hydroxyethyl acrylate copolymer (Polymer 1):
In a 4-necked flask equipped with a side-blade stirrer, an internal thermometer, two funnels, a reflux condenser, and an extension for two more necks, 175 g of behenyl acrylate, 25 g of 2-hydroxyethyl acrylate, and 0.4 g of 2,2'-azobis(2-methylbutyronitrile (Akzo Nobel) were added for 60 minutes at 80 °C in 40 g of isopropanol with stirring after removing oxygen from the system using a nitrogen purge for 20 minutes. The mixture was stirred at 80 °C for 3 hours. Then the solvent was removed by vacuum distillation, then 1 g of dilauryl peroxide was added and the reaction was continued for 60 minutes at 110 °C. The step was repeated. The mixture was then cooled to 90 °C and a jet demineralized water was added and stirred. The water was removed by vacuum distillation.
Molecular weight: Mn = 7300 g/mol, Mw = 21000, Mw/Mn = 2.8
Melting point: 65°C

Stearyl acrylate / 2-hydroxyethyl acrylate copolymer (Polymer 2):
In a 4-necked flask equipped with a side-blade stirrer, an internal thermometer, two funnels, a reflux condenser, and an extension for two more necks, 155 g of behenyl acrylate, 45 g of 2-hydroxyethyl acrylate, and 0.4 g of 2,2'-azobis(2-methylbutyronitrile (Akzo Nobel) were added for 90 minutes at 80 °C in 50 g of isopropanol with stirring after removing oxygen from the system using a nitrogen purge for 20 minutes. The mixture was stirred at 80 °C for 3 hours. Then the solvent was removed by vacuum distillation, then 1 g of dilauryl peroxide was added and the reaction was continued for 60 minutes at 125 °C. The step was repeated. The mixture was then cooled to 90 °C and a jet demineralized water was added and stirred. The water was removed by vacuum distillation.
Molecular weight: Mn = 7500 g/mol, Mw = 19000, Mw/Mn = 2.6
Melting point: 49°C

B/ Examples of formulations

The following examples serve to illustrate the invention without, however, being limiting in nature. In these examples, the quantities of the ingredients present in the compositions are given in % by weight of raw materials (RM) or active materials (AM) relative to the total weight of the composition.

Protocol for evaluating the stability of the compositions of the invention
The stability of the compositions is evaluated macroscopically (Appearance, Color, Odor, pH and viscosity) and microscopically, at 24 hours, 1 month and 2 months, at 4 °C, 25 °C and 45 °C.
Macroscopic stability is assessed by eye and microscopic stability is assessed using a white light optical microscope.

Method of preparation of the compositions
The manufacturing process of the exemplified compositions is classical.

Manufacturing in the main tank:

Introduce the raw materials of phase A1 into the tank. Place the tank under vacuum, stir with a paddle and turbine to homogenize phase A1 and heat until a temperature of 47 °C is obtained. Once the temperature is reached, stop heating and aspirate the raw materials of phase A2. Apply a turbine efficiency between 2000 rpm and 2500 rpm, still under vacuum at a temperature of 47 °C. Be careful to disperse well until a homogeneous medium is obtained without gel grains.

Once phases A1 and A2 are homogeneous, introduce phase B as prepared according to the manufacturing process defined below, stir the mixture well until a compliant emulsion is obtained, for a minimum of 10-15 minutes with a turbine efficiency of between 2500 rpm and 3000 rpm, still under vacuum and with a temperature of between 50 °C and 55 °C. Once a compliant emulsion is obtained, cool the preparation under scraper blades and under vacuum until a temperature of less than 35 °C is obtained. At this stage, introduce the raw materials of phases C1 and C2 with stirring of between 2500 rpm and 3000 rpm. Disperse until a compliant emulsion is obtained and good dispersion of the fillers with stirring of between 2500 rpm and 3000 rpm. Continue cooling under scraper blades and under vacuum if necessary. At 33°C, inert the manufacturing tank until the end of manufacturing, then at a temperature below 33°C, introduce the raw materials of phase D while stirring with a turbine efficiency of between 2500 rpm and 3000 rpm. Continue stirring until an emulsion conforms to the microscope. Once this stage is reached, introduce the raw materials of phases E1, E2 and E3 in this order and stir with a turbine efficiency of between 2500 rpm and 3000 rpm for 15 minutes.

Manufacturing process for phase B:

In a second tank, introduce the raw materials of phase B, heat to a temperature of 65-70 °C with a deflocculator. Homogenize until the medium has melted and is completely solubilized.

Transfer phase B to the main tank for emulsification.

Comparative example - Compositions 1 to 4
The following compositions 1 to 4 are prepared.
[Table 1]
Phase Composition 1
(invention) 2
(invention) 3
(comparative) 4
(comparative) A1 WATER / AQUA QSP 100 QSP 100 QSP 100 QSP 100 A1 GLYCERIN 3 3 3 3 A1 PROPANEDIOL 2.5 2.5 2.5 2.5 A1 CAPRYLYL GLYCOL 0.3 0.3 0.3 0.3 A1 ASSETS) 0.413 0.413 0.413 0.413 A1
SODIUM STEAROYL GLUTAMATE - - - 0.5 A2 POLYQUATERNIUM-67 0.11 0.11 0.11 0.11 A2 SCLEROTIUM GUM 0.1 0.1 - - B ASSETS) 0.3 0.3 0.3 0.3 B ISOPROPYL MYRISTATE 4 4 4 4 B ISOPROPYL PALMITATE 3.5 3.5 3.5 3.5 B DIISOPROPYL SEBACATE 4 4 4 4 B C12-15 ALKYL BENZOATE 4.8 4.8 4.8 4.8 B BUTYL METHOXYDIBENZOYLMETHANE
(PARSOL 1789 from DSM NUTRITIONAL PRODUCTS) 3.5 3.5 3.5 3.5 B ETHYLHEXYL TRIAZONE
(UVINUL T150 from BASF) 4.5 4.5 4.5 4.5 B DROMETRIZOLE TRISILOXANE
(MEXORYL XL from NOVEAL) 5 5 5 5 B BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(TINOSORB S from BASF) 3 3 3 3 B C12-22 ALKYL ACRYLATE/HYDROXYETHYLACRYLATE COPOLYMER
(Polymer 1) 2 - - - B STEARIC ACID - - - 1.5 C1 CHARGE(S) 1 1 1 1 C1 ASSETS) 2 2 2 2 C2 SCENT 0.2 0.2 0.2 0.2 C2 WATER / AQUA 0.896 0.896 0.896 0.896 C2 PENTYLENE GLYCOL 0.1 0.1 0.1 0.1 C2 TOCOPHEROL 1 1 1 1 D ALCOHOL DENAT. 8 8 8 8 E1 ASCORBIC ACID 12 12 12 12 E2 pH ADJUSTER QSP pH = 6 QSP pH = 6 QSP pH = 6 QSP pH = 6 E3 PHENYLBENZIMIDAZOLE SULFONIC ACID
(EUSOLEX 232 from MERCK) 0.75 0.75 0.75 0.75

Results obtained
The stability results obtained are as follows.
[Table 2]
Composition 1
(invention) 2
(invention) 3
(comparative) 4
(comparative) Macroscopic aspect After 24 hours at 25°C
Smooth, homogeneous, shiny fluid of ivory color.
No phase shift, no release.

After 2 months at 4°C and 25°C
Smooth, homogeneous, shiny fluid of ivory color.
No phase shift, no release.

After 2 months at 45°C
Smooth, homogeneous, shiny fluid of light brown color.
No phase shift, no release.
After 24 hours at 25°C
Smooth, homogeneous, shiny fluid of ivory color.
No phase shift, no release.

After 2 months at 4°C and 25°C
Smooth, homogeneous, shiny fluid of ivory color.
No phase shift, no release.

After 2 months at 45°C
Smooth, homogeneous, shiny fluid of light brown color.
No phase shift, no release.
After 24 hours at 25°C
Smooth, homogeneous, shiny fluid of ivory color.
No phase shift, no release.

After 1 month at 4°C, 25°C, 45°C
Significant release of the fatty phase in the lower part of the composition. After 24 hours at 25°C
Smooth, homogeneous, shiny fluid of ivory color.
No phase shift, no release.

After 5 days at 4°C, 25°C, 45°C
Color change to yellow and release of the fatty phase in the upper part of the composition. Microscopic appearance After 24 hours at 25°C
Fine, regular emulsion with clean edges.





After 2 months at 4°C, 25°C, 45°C
Fine, regular emulsion, with sharp, receding edges. After 24 hours at 25°C
Medium emulsion, irregular, with sharp edges.


After 2 months at 4°C, 25°C, 45°C
Medium emulsion, irregular, with sharp edges. After 24 hours at 25°C
Average emulsion, uneven, loose edges.




After 1 month at 4°C, 25°C, 45°C
Medium uneven emulsion, loose edges. After 24 hours at 25°C
Coarse, uneven emulsion, holes in the emulsion, loose edges.

After 5 days at 25°C
Coarse, uneven emulsion, holes in the emulsion, loose edges.

Compositions 1 and 2 in accordance with the invention exhibit better stability over time and temperature than comparative compositions 3 and 4 which do not contain scleroglucan gum.

Claims (22)

Composition, in particular cosmetic or dermatological, comprising:
a) at least one UV filter;
(b) at least 1% by weight of ascorbic acid relative to the total weight of the composition; and
(c) at least one scleroglucan gum. Composition according to claim 1 in which the UV filter(s) are chosen from lipophilic organic UV filters, hydrophilic organic UV filters, and inorganic UV filters. Composition according to any one of claims 1 and 2, in which the lipophilic organic UV filter(s) are chosen from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds; methylene bis-(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; filter polymers and filter silicones; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes and mixtures thereof; preferably salicylic compounds, dibenzoylmethane compounds, benzylidenecamphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof. Composition according to any one of claims 1 to 3 comprising Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine. Composition according to any one of claims 1 to 4 in which the hydrophilic organic UV filter(s) are chosen from water-soluble organic UV filters and water-dispersible organic UV filters. Composition according to any one of claims 1 to 5 in which the water-soluble organic UV filter(s) are chosen from benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid); benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid); and their salts. Composition according to any one of claims 1 to 6, in which the water-dispersible organic UV filter(s) are chosen from Methylene bis-Benzotriazolyl Tetramethylbutylphenol in the form of an aqueous dispersion of micronized particles having an average particle size which varies from 0.01 to 5 μm, and more preferably from 0.01 to 2 μm, and more particularly from 0.020 to 2 μm, with at least one alkylpolyglycoside surfactant of structure C _n H _2n+1 O(C ₆ H ₁₀ O ₅ ) _x H in which n is an integer from 8 to 16 and x is the average degree of polymerization of the unit (C ₆ H ₁₀ O ₅ ) and varies from 1.4 to 1.6; Methylene bis-Benzotriazolyl Tetramethylbutylphenol in the form of an aqueous dispersion of micronized particles having an average particle size ranging from 0.02 to 2 μm, and more preferably from 0.01 to 1.5 μm, and more particularly from 0.02 to 1 μm, in the presence of at least one mono-(C ₈ -C ₂₀ )alkyl ester of polyglycerol having a degree of polymerization of glycerol of at least 5; Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in its water-dispersible form with the INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer; symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups used in micronized form (average particle size of 0.02 to 3 µm), and in particular in aqueous dispersion form, in particular 2,4,6-tris(bi-phenyl)-triazine and 2,4,6-tris(ter-phenyl)-triazine. Composition according to any one of claims 1 to 7 in which the ascorbic acid is L-ascorbic acid. Composition according to any one of claims 1 to 8 at least 5% by weight, preferably at least 7% by weight of ascorbic acid relative to the total weight of the composition. Composition according to any one of claims 1 to 9 comprising from 1% to 30% by weight of ascorbic acid, preferably from 5% to 25% by weight, more preferably from 7% to 20% by weight, and even more preferably from 8% to 15% by weight relative to the total weight of the composition. Composition according to any one of claims 1 to 10 in which the scleroglucan gum(s) represent from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, and even more preferably from 0.1% to 3% by weight relative to the total weight of the composition. Composition according to any one of claims 1 to 11 comprising at least one lipophilic polymer comprising monomeric units of formula (A) and (B):

in which:
R1, independently of each other, are chosen from alkyl or alkenyl radicals;
with at least 60% by weight of the R1 groups being radicals selected from stearyl and behenyl radicals, the weight percentage relating to the sum of all the R1 groups present in the polymer;
the weight ratio of the sum of all hydroxyethyl acrylate units to the sum of all acrylate units bearing the R1 group is from 1:30 to 1:1; and
the sum of the total of units A and B is at least 95% by weight of the total weight of the polymer. Composition according to claim 12 in which in the lipophilic acrylic polymer R1 consists of an alkyl radical, preferably a C ₁₆ -C ₂₂ alkyl radical, and more preferably a behenyl or stearyl radical. Composition according to any one of claims 12 and 13 in which in the lipophilic acrylic polymer at least 70% by weight of the R1 groups are behenyl or stearyl radicals, preferably at least 80% by weight, more preferably at least 90% by weight. Composition according to any one of claims 12 to 14 in which in the lipophilic acrylic polymer all the R1 groups are stearyl or behenyl radicals. Composition according to any one of claims 12 to 15 in which in the lipophilic acrylic polymer the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units carrying the group R1 ranges from 1:15 to 1:1, preferably ranges from 1:10 to 1:4. Composition according to any one of claims 12 to 16 in which the lipophilic acrylic polymer has a number average molecular weight Mn ranging from 5,000 to 9,000 g/mol. Composition according to any one of claims 12 to 17 in which the lipophilic acrylic polymer has a melting temperature ranging from 40°C to 70°C, and preferably ranging from 45°C to 67°C. Composition according to any one of claims 12 to 18 in which in the lipophilic acrylic polymer at least 60% by weight of the R1 groups are stearyl radicals, and said polymer has a melting point ranging from 40 to 60°C, and preferably ranging from 45 to 55°C. Composition according to any one of claims 12 to 19 in which in the lipophilic acrylic polymer at least 60% by weight of the R1 groups are behenyl radicals, and said polymer has a melting point ranging from 60°C to 70°C, and preferably ranging from 63°C to 67°C. Composition according to any one of claims 12 to 20 in which the lipophilic acrylic polymer(s) are present in an active material content ranging from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight, preferably ranging from 0.2% to 3% by weight relative to the total weight of the composition. Composition according to any one of claims 1 to 21 in the form of an emulsion, preferably in the form of an oil-in-water emulsion.