FR3161108A1 - Composition comprising Drometrizole Trisiloxane, a hydrophilic organic filter, with a mass ratio of hydrophilic organic filters / lipophilic organic filters greater than 0.3, alcohol-free - Google Patents

Abstract

Title: Composition comprising Drometrizole Trisiloxane, a hydrophilic organic filter, with a mass ratio of hydrophilic organic filters / lipophilic organic filters greater than 0.3, alcohol-free. The present invention therefore relates to a composition, and in particular a cosmetic or dermatological composition, comprising: a) Drometrizole Trisiloxane; and b) at least one hydrophilic organic UV filter; the mass ratio between the hydrophilic organic UV filters and the lipophilic organic UV filters being greater than 0.3; the quantity of ethanol being less than or equal to 3% by weight relative to the total weight of the composition.

Description

Composition comprising Drometrizole Trisiloxane, a hydrophilic organic filter, with a mass ratio of hydrophilic organic filters to lipophilic organic filters greater than 0.3, alcohol-free

The present invention relates to a composition, and in particular a cosmetic or dermatological composition, comprising Drometrizole Trisiloxane and at least one hydrophilic organic UV filter, the mass ratio between hydrophilic organic UV filters and lipophilic organic UV filters being greater than 0.3, and the amount of ethanol being less than or equal to 3% by weight relative to the total weight of the composition.

To date, a wide variety of photoprotective compositions are already known to protect keratinous materials, and more specifically the skin, against the harmful effects induced by UVA and/or UVB radiation. Essentially, they contain a combination of several organic or inorganic UV filters, delivered in an oily and/or aqueous phase, as an active anti-UV agent, and are generally offered in an emulsion or gel formulation.

It is also known that high filter ratios are needed to achieve high levels of filtering efficiency.

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

Thus, formulations with high filtering power can present uncomfortable or even unpleasant sensory aspects, masking the freshness and comfort of the formulas. In particular, the difficulty for high-SPF photoprotective formulations is often to limit, or even avoid, a significant feeling of greasiness and stickiness, resulting in a lack of lightness in the textures obtained, as well as a white cast upon application, making it invisible on the skin.

Furthermore, some cosmetic formulations sometimes cause sensory discomfort such as "pilling," which is the formation of lint during application and/or after drying and/or absorption into the skin. This phenomenon is particularly noticeable when the sunscreen formula contains a high concentration of hydrophilic filters.

This flaw is a major drawback for the user, as the application is neither smooth nor pleasant due to the fuzzy texture it creates during application or removal. Furthermore, it leaves the skin feeling dirty. This can significantly impair the photoprotective properties of sunscreens.

To mitigate the aforementioned undesirable effects, and in particular to achieve a cooling effect upon application and an invisible finish on the skin, aqueous formulations have already been considered. However, these aqueous compositions containing UV filters can have the disadvantage of being sticky and therefore uncomfortable, as well as being very runny.

It has also been proposed to structure an aqueous gel containing filters using polymers. However, this solution is not satisfactory because the structural polymers generally used are not always very resistant to electrolytes and can also degrade the sensory properties of the compositions in terms of stickiness.

To mitigate the aforementioned adverse effects, the implementation of aqueous compositions containing UV filters in combination with other specific compounds has already been considered.

Therefore, the combined use of clay-based mineral thickeners has been proposed to stabilize the compositions and potentially reduce the stickiness of photoprotective compositions. However, clays can bleach the compositions, causing them to lose their transparency properties.

Consequently, it remains difficult to reconcile, in the same photoprotective composition, opposing technical performances, such as a high level of UV protection which most often implies a greasy and sticky finish on the skin, and a pleasant sensory experience materialized in particular by a feeling of freshness, and an absence of the pilling phenomenon.

There is still a need for a photoprotective composition with a high level of UV protection and which is advantageously transparent on the skin.

In particular, there remains a need for a photoprotective composition with a high level of UV protection, with pleasant sensory properties, which does not pill during and after application, and which is advantageously refreshing, and preferably transparent on the skin.

This need for such a photoprotective composition is all the more pressing given the booming market for daily sun protection. More and more hybrid products offering both skincare and SPF 15-20 protection are being launched, but the challenge remains to achieve higher SPF values, for example, 30 or higher, or even 50 or higher, with a pleasant sensory experience for daily application.

We therefore seek to have a product with high SPF while retaining the sensory codes of skincare: Appearance, texture, consistency, sensory experience.

In particular, the aim of the invention is to develop a product allowing good homogeneity of the composition and good quality of deposition of the composition on the skin in order to obtain in particular an interesting sensory experience such as a reduction, or even an absence, of the appearance of pilling during and after application, while allowing high daily photoprotection.

There also remains a need for a photoprotective composition with a high level of UV protection and perfectly stable, i.e. not subject to demixing phenomena.

The present invention is specifically designed to meet these needs.

The present invention therefore relates to a composition, and in particular a cosmetic or dermatological composition, comprising:
a) Drometrizole Trisiloxane; And
b) at least one hydrophilic organic UV filter;
the mass ratio between hydrophilic organic UV filters and lipophilic organic UV filters being greater than 0.3;
the quantity of ethanol being less than or equal to 3% by weight relative to the total weight of the composition.

Against all expectations, the inventors found that the implementation, in a photoprotective composition of Drometrizole Trisiloxane in association with one or more hydrophilic organic UV filters, the mass ratio between the hydrophilic organic UV filters and the lipophilic organic UV filters being greater than 0.3, and the quantity of ethanol being less than or equal to 3% by weight relative to the total weight of the composition, makes it possible to obtain a galenic formulation with a strong photoprotective power, with good cosmetic properties, in particular that does not pill during and after application and with a non-greasy, non-sticky and non-shiny finish, and which is nevertheless stabilized over time.

Advantageously, the implementation of this composition allows access to a galenic formulation which is stabilized, presenting a pleasant sensory experience for daily use and a strong anti-UV protective power.

Thus, this photoprotective composition advantageously combines properties that are generally antagonistic to each other.

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

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

It also relates to a non-therapeutic cosmetic process to limit skin darkening and/or improve the color and/or homogeneity of the complexion, including the application to the surface of the keratinous material of at least one composition as defined above.

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

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

For the purposes of this invention, "pilling" consists of the appearance of solid, residual particles on the skin's surface during application. These particles are visible and can be felt under the fingers.

Within the framework of the invention, the filtering efficiency is evaluated from the evaluation of the SPF and the UVAPF.

For the purposes of this invention, " SPF " (Sun Protection Factor) refers to the sun protection factor, which measures the level of protection against UVB radiation. The SPF value corresponds to the ratio between the minimum time required to obtain a sunburn with a sunscreen composition and that without the 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 Sun Protection Factor (SPF) can be evaluated in vitro using the Labsphere® spectrophotometer. The plate is the material onto which the solar composition is applied. For this protocol, polymethyl methacrylate (PMMA) plates have proven ideal. A specific protocol, presented as an example, is currently undergoing ISO approval under the name ISO Committee Draft 23675.

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

For the purposes of this invention, UVAPF refers to the index characterizing protection against UVA radiation. Specifically, this index can be measured in vivo using the Persistent Pigment Darkening ( PPD ) method, ISO 24442:2022 protocol, which measures skin color observed 2 to 4 hours after UVA exposure. UVA protection can also be assessed in vitro using the Labsphere® spectrophotometer. The plate is the material onto which the sunscreen composition is applied. For this protocol, polymethyl methacrylate (PMMA) plates have proven ideal. ISO 24443:2021 protocol describes such an in vitro method.

Other features, aspects and advantages of the invention will become apparent from the detailed description that follows.

The composition according to the invention is intended for topical application and therefore contains a physiologically acceptable medium. Hereinafter, "physiologically acceptable medium" means a medium compatible with keratinous materials.

In the context of the present invention, "keratinous material" means in particular the skin, the scalp, keratinous fibers such as eyelashes, eyebrows, hair, and body hair, nails, mucous membranes such as lips, and more particularly the skin and mucous membranes (body, face, eye contour, eyelids, lips, preferably body, face and lips).

In what follows, and unless otherwise indicated, the boundaries of a range of values are included in that range, 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 to".

According to the invention, "preventing" or "prevention" means 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 keratinous material.

By "organic UVA filter" we mean any organic chemical molecule capable of absorbing at least UVA radiation in the wavelength range between 320 and 400 nm; said molecule also being able to 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.

The term "emulsion" refers to any macroscopically homogeneous, kinetically stable composition comprising at least two immiscible phases; one being the continuous dispersing phase and the other being dispersed within said continuous phase in the form of droplets. The two phases are generally kinetically stabilized by at least one emulsifying system, which generally includes at least one emulsifying surfactant.

Oil-in-water emulsions are classified into two main types: direct oil-in-water emulsions, consisting of a continuous aqueous dispersing phase and a discontinuous dispersed oil phase, and inverse water-in-oil emulsions, consisting of a continuous oily dispersing phase and a discontinuous dispersed aqueous phase. Multiple emulsions also exist, such as water-in-oil-in-water and oil-in-water-in-oil emulsions.

Detailed description of the invention UV filters

The composition according to the invention comprises Drometrizole Trisiloxane and at least one hydrophilic organic UV filter. It may also comprise at least one additional lipophilic organic UV filter other than Drometrizole Trisiloxane.

Lipophilic organic UV filters

By "lipophilic organic filter" we mean any cosmetic or dermatological organic compound that filters UV radiation and is capable of being completely dissolved in molecular form in a liquid oil phase or of being solubilized in colloidal form (for example in micellar form) in a liquid oil phase.

Lipophilic organic filters are notably selected from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; β,β-diphenyl acrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, particularly those cited in US patent 5624663; 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 US 5,237,071, 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; α-alkylstyrene derived dimers such as those described in patent application DE19855649; 4,4-diarylbutadiene 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, benzylidene camphor 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 notably 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 notably under the trade name PARSOL® 1789 by the company DSM Nutritional Products,

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

β,β-Diphenylacrylate compounds:
Octocrylene, sold notably under the trade name "UVINUL® N 539 T" by BASF,

Benzophenone compounds:
Benzophenone-3 or Oxybenzone, sold under the trade name "UVINUL® M 40" by BASF,
Diethylamino hydroxybenzoyl hexyl benzoate sold under the trade name "UVINUL® A Plus" or in a mixture with ethylhexyl methoxycinnamate under the trade name "UVINUL® A Plus B" by 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, particularly in solid form such 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 "TINOSORB® S" by BASF,
- Ethylhexyl Triazone, sold notably under the trade name "UVINUL® T 150" by BASF,
- Diethylhexyl Butamido Triazone sold under the trade name "UVASORB® HEB" by the company 3V SIGMA,
- Symmetrical triazine filters substituted with naphthalenyl groups or polyphenyl groups described in US patent 6,225,467, application WO2004/085412 (see compounds 6 and 9) or the document "Symetrical 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.

Hydrophilic organic UV filters

For the purposes of this invention, hydrophilic organic UV filter means a water-soluble organic UV filter or a water-dispersible organic UV filter.

By "water-soluble organic filter" we mean any organic filter capable of being totally 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.

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

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

These filters conform to the following general formula (I):
[Chem 1]

in which F denotes a hydrogen atom, an alkali metal, or an NH( _R1 ) ₃₊ ^radical , where the _R1 radicals, which may be identical or different, denote a hydrogen atom, an alkyl or hydroxyalkyl radical in _C1 to _C4 , or an Mn+ group, Mn+ denoting a versatile metal cation in which n is equal to 2, 3, or 4, Mn+ preferably denoting a metal cation selected from Ca2 ⁺ , Zn2 ⁺ , Mg2 ⁺ , Ba2 ⁺ , Al3 ^+, and Zr4 ⁺ . 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 isomers fall within the scope of the present invention.

Among the water-soluble organic UVA filters that can be used according to the present invention, we can also mention 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 and in patent application EP-A-0669323.

Compounds comprising at least two benzoazolyl groups according to the invention correspond to the following general formula (II):
[Chem 2]
(II)
in which,
- Z represents an organic valence (l + n) residue comprising one or more double bonds placed such that it completes the double bond system of at least two benzoazolyl groups as defined inside the brackets to form a totally conjugated set;
- X' designates S, O or NR ⁶ ;
- R ¹ designates a hydrogen atom, an alkyl in C ₁ to C ₁₈ , an alkoxy in C ₁ to C ₄ , an aryl in C ₅ to C ₁₅ , an acyloxy in C ₂ to C ₁₈ , a SO ₃ Y or COOY group;
- the radicals R ² , R ³ , R ⁴ and R ⁵ , identical or different, designate a nitro group or a radical R ¹ ;
- R ⁶ designates a hydrogen atom, a _C1 to _C4 alkyl or a _C1 to _C4 hydroxyalkyl;
- Y designates 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 nitrogenous 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 with the following structure, sold notably under the name "NEO HELIOPAN® AP" by the company Symrise, is particularly preferred:
[Chem 3]

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

Water-soluble organic UVB filters usable according to the present invention are in particular selected 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 notably under the trade name "EUSOLEX 232 ^® " by MERCK.

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

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

The term "alkanolamine" refers to a _C2 - _C10 compound comprising at least one amine group (primary, secondary, or tertiary) and at least one alcohol group (usually primary). Suitable examples of alkanolamines include 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, by the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular in aqueous dispersion form,

Methylene bis-(hydroxyphenyl benzotriazole) compounds:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol
in the form of an aqueous dispersion of micronized particles having a volume average particle size ranging 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 ranges 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 BASF, or
in the form of an aqueous dispersion of micronized particles having a volume 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-( _C8 - _C20 )alkyl-ester of polyglycerol having a degree of glycerol polymerization 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 BASF,

Triazine compounds:
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in its water-dispersible form, INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer, under the trade name TINOSORB® S LiteAqua by BASF,
- symmetric triazine filters substituted with naphthalenyl groups or polyphenyl groups used in micronized form (average particle size of 0.02 to 3 µm) which can be obtained for example by 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 BASF and which is covered in patent applications WO06/035000, WO06/034982, WO06/034991, WO06/035007, WO2006/034992, WO2006/034985,

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

According to a first particular embodiment of the invention, the composition comprises at least one water-dispersible filter.

According to a second particular embodiment of the invention, the composition comprises at least one water-soluble filter and at least one water-dispersible filter.

According to a third particular embodiment of the invention, the quantity of 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid) is less than or equal to 3% by weight relative to the total weight of the composition.

According to a preferred embodiment of the invention, the composition is free of 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid).

By "free from 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid)", for the purposes of the present invention, means an amount of 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid) of less than 2% by weight, preferably less than 1% by weight, and even more preferably less than 0.5% by weight relative to the total weight of the composition.

According to a fourth embodiment, the hydrophilic filter(s) present in the composition are hydrodispersible filters.

In the composition according to the invention, the mass ratio between hydrophilic organic UV filters and lipophilic organic UV filters (mass quantity of hydrophilic organic UV filters divided by mass quantity of lipophilic organic UV filters) is greater than 0.3.

According to a particular embodiment of the invention, the mass ratio between hydrophilic organic UV filters and lipophilic organic UV filters is between 0.35 and 1.

Inorganic UV filters

According to a particular embodiment of the invention, the compositions comprise at least one inorganic UV filter.

The inorganic UV filters that can be used according to the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having an average particle size of 0.5 µm or less, 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 described in particular in Annex VI, updated on 22/09/2021, of European Cosmetics Regulation No. 1223/2009, but are not limited to this list.

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

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

Metallic 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 aluminum salts of fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

Coated pigments are more specifically 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,
- of 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 "TTO-55 (A)®" products from the ISHIHARA company,
- of 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,
- of silica, alumina and alginic acid such as the product "MT-100AQ®" from the company TAYCA,
- of alumina and aluminum laurate,
- iron oxide and iron stearate,
- zinc oxide and zinc stearate,
- of silica and alumina and treated with silicone such as the products "MTY-500SAS®" or "MICROTITANIUM DIOXIDE MT-100SAS®" from the company TAYCA,
- of silica, alumina, aluminum stearate and treated with silicone,
- made of silica and treated with silicone,
- of alumina and treated with silicone such as the "TTO-55(S)®" products from the ISHIHARA company,
- of triethanolamine,
- stearic acid such as the product "TTO-55 (C)®" from the ISHIHARA company,
- sodium hexametaphosphate,
- TiO2 treated with octyl trimethyl silane,
- TiO2 treated with polydimethylsiloxane,
- TiO2 anatase/rutile treated with polydimethylhydrogenosiloxane
- TiO2 coated with triethylhexanoin, aluminum stearate, alumina, sold under the trade name "Solaveil™ CT-200" by CRODA,
- TiO2 coated with aluminum stearate, alumina and silicone, sold under the trade name "Solaveil™ CT-12W" by CRODA,
- TiO2 coated with lauroyl lysine,
- TiO2 coated with C9-C15 fluoroalcohol phosphate and aluminium hydroxide.

Other examples include TiO2 pigments doped with at least one transition metal such as iron, zinc, manganese, and particularly manganese. Preferably, these doped pigments are in the form of an oil dispersion. The oil in the dispersion is preferably selected from triglycerides, including caprylic/capric acid triglycerides. The oil dispersion of titanium dioxide particles may also include one or more dispersing agents, such as a sorbitan ester like sorbitan isostearate, or a polyoxyalkylated fatty acid and glycerol ester like TRI-PPG3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3 POLYRICINOLEATE. Preferably, the oil dispersion of titanium dioxide particles includes at least one dispersing agent selected from polyoxyalkylated fatty acid and glycerol esters. One can cite more particularly 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 ISOSTEARATE with 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, for example, sold 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 include, 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 polymethylhydrogenesiloxane;
- 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 by silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane).

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

We can also mention 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 includes inorganic UV filters, titanium oxide pigments, coated or uncoated, are particularly preferred.

According to the invention, the composition is free of inorganic filters.

For the purposes of this invention, "free from inorganic UV filters" means an amount of inorganic UV filters less than 2% by weight, preferably less than 1% by weight, and even more preferably less than 0.5% by weight relative to the total weight of the composition.

According to a particular embodiment of the invention, the total quantity of hydrophilic organic UV filters in the composition is greater than or equal to 5% by weight of the total weight of the composition.

According to a preferred embodiment, the total quantity of hydrophilic organic UV filters is between 5% and 15% by weight of the total weight of the composition.

In one particular embodiment, the total quantity of UV filters present in the composition is greater than or equal to 15% by weight of the total weight of the composition. In a preferred embodiment, the total quantity of UV filters present in the composition is between 15% and 35% by weight, preferably between 18% and 25% by weight of the total weight of the composition.

For the purposes of this invention, "total quantity of UV filters" means the sum of the concentrations of each of the UV filters present in the composition, in particular lipophilic organic UV filters, hydrophilic organic UV filters, and inorganic UV filters.

Hydrophilic copolymers of AMPS

According to another particular embodiment, the composition according to the invention comprises at least one hydrophilic copolymer comprising at least one acrylamido 2-methylpropane sulfonic acid monomer (AMPS®).

For the purposes of this invention, "copolymer" means a polymer comprising at least two distinct monomer units.

For the purposes of this invention, "hydrophilic polymer" means a water-soluble or water-dispersible polymer. "Water-soluble or water-dispersible" means polymers which, when introduced into an aqueous phase at 25°C at a mass concentration of 1%, allow the formation of a macroscopically homogeneous and transparent solution, i.e., having a maximum light transmittance value at a wavelength of 500 nm through a 1 cm thick sample of at least 60%, preferably at least 70%.

According to a preferred embodiment, the composition according to the invention comprises at least one copolymer, crosslinked or non-crosslinked, comprising at least the monomer acrylamido 2-methylpropanesulfonic acid (AMPS®), in free form or in form partially or totally neutralized by a mineral base (sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di-, or tri-ethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine, as well as mixtures of these compounds.

They are preferably totally or almost totally neutralized, that is to say neutralized to at least 90%.

The copolymers of AMPS® according to the invention can be crosslinked or non-crosslinked.

By cross-linked polymer, we mean a non-linear polymer that exists in the form of a three-dimensional network insoluble in water but inflatable in water and leading to the formation of a chemical gel.

When polymers are crosslinked, the crosslinking agents can be chosen from among the olefinic polyunsaturated compounds commonly used for crosslinking polymers obtained by radical polymerization.

Examples of crosslinking agents include divinylbenzene, diallyl ether, dipropylene glycol diallylether, polyglycol diallylethers, triethylene glycol divinylether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di(meth)acrylate, diallyl urea, trimethylol propane triacrylate, methylene bis-acrylamide, methylene bis-methacrylamide, triallyl amine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallylether, allyl (meth)acrylate, allylic ethers of sugar alcohols, or other allyl- or vinyl ethers of polyfunctional alcohols, as well as allylic esters of acid derivatives. phosphoric and/or vinylphosphonic, or mixtures of these compounds.

According to a preferred embodiment of the invention, the crosslinking agent is selected from methylene-bis-acrylamide, allyl methacrylate, or trimethylol propane triacrylate (TMPTA). The degree of crosslinking generally ranges from 0.01% to 10% by mole, and more particularly from 0.2% to 2% by mole relative to the polymer.

According to the invention, monomers derived from 2-acrylamido-2-methylpropane sulfonic acid (AMPS®) preferably conform to the following general formula:
[Chem 4]

in which X+ denotes a cationic counterion, in particular an alkali or alkaline earth metal, or an ammonium, preferably ammonium, or a mixture of cations; R1 denotes a hydrogen atom or an alkyl radical, linear or branched in _C1 - _C6 such as methyl, preferably _R1 denotes a hydrogen atom.

Preferably, the monomer(s) of 2-acrylamido-2-methylpropane sulfonic acid according to the invention are partially or totally salified in the form of an ammonium salt.

Preferably, the monomer(s) of 2-acrylamido-2-methylpropane sulfonic acid according to the invention are totally salified, preferably in the form of an ammonium salt.

The AMPS® polymers suitable for the invention are water-soluble or water-dispersible. In this case, they are copolymers obtained from AMPS® and one or more hydrophilic or hydrophobic ethylenic unsaturates and, if they are crosslinked, one or more crosslinking agents such as those defined above. When said copolymers comprise hydrophobic ethylenic unsaturates, these may or may not contain fatty chains.

According to a first particular embodiment, in the copolymer(s) obtained from AMPS® and one or more hydrophobic ethylenic unsaturated monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above, the hydrophobic ethylenic unsaturated monomers do not have a fat chain and are preferably present in small quantities.

According to a second particular embodiment, in the copolymer(s) obtained from AMPS® and one or more hydrophobic ethylenic unsaturated monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above, the hydrophobic ethylenic unsaturated monomers comprise at least one fatty chain.

For the purposes of this invention, "fatty chain" means any hydrocarbon chain comprising at least 8 carbon atoms.

The water-soluble or water-dispersible copolymers of AMPS® according to the invention contain water-soluble ethylenic unsaturation monomers or hydrophobic monomers or mixtures thereof.

Water-soluble comonomers can be ionic or non-ionic. According to a particular embodiment of the invention, the water-soluble comonomers are non-ionic.

Examples of ionic water-soluble comonomers include the following compounds and their salts:
- styrene sulfonic acid,
- vinylsulfonic acid and (meth)allylsulfonic acid,
- vinyl phosphonic acid,
- maleic acid,
- itaconic acid,
- crotonic acid,
- water-soluble vinyl monomers with the following formula:
[Chem 5]


in which:
- R ₁ is chosen from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇ ;
- X ₁ is chosen from:
- alkyl oxides of the type -OR ₂ where R ₂ is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms, substituted by at least one sulfonate (-SO ₃ ^- ) and/or sulfate (-SO ₄ ^- ) and/or phosphate (-PO ₄ ^2- ) group.

Examples of non-ionic water-soluble comonomers include:
- N-vinylacetamide and N-methyl N-vinylacetamide,
- N-vinylformamide and N-methyl N-vinylformamide,
- maleic anhydride,
- vinylamine,
- N-vinyllactams containing a cyclic alkyl group with 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,
- vinyl alcohol with the formula _CH2 =CHOH,
- water-soluble vinyl monomers with the following formula:
[Chem 6]

in which:
- R ₃ is chosen from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇ ;
- X ₂ is chosen from alkyl oxides of type -OR ₄ where R ₄ is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons, possibly substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether.

Examples include glycidyl (meth)acrylate, hydroxyethyl methacrylate, and ethylene glycol, diethylene glycol, or polyalkylene glycol (meth)acrylates.

Examples of hydrophobic comonomers without a fat chain include:
- styrene and its derivatives such as 4-butylstyrene, alpha methylstyrene and vinyltoluene;
- vinyl acetate with the formula _CH2 =CH- _OCOCH3 ;
- vinyl ethers of formula CH ₂ =CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms;
- acrylonitrile;
- caprolactone;
- vinyl chloride and vinylidene chloride;
- silicone derivatives, leading after polymerization to silicone polymers such as methacryloxypropyltris(trimethylsiloxy)silane and silicone methacrylamides;
- hydrophobic vinyl monomers with the following formula:
[Chem 7]

in which:
- R ₄ is chosen from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇ ;
- X ₃ is chosen from:
- alkyl oxides of type -OR ₅ where R ₅ is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms.

Examples include methyl methacrylate, ethyl methacrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl acrylate, isobornyl acrylate, and 2-hexyl ethyl acrylate.

The water-soluble or water-dispersible AMPS® copolymers of the invention preferably have a molar mass ranging from 50,000 g/mol to 100,000,000 g/mol, preferably from 80,000 g/mol to 100,000,000 g/mol, and even more preferably from 100,000 g/mol to 70,000,000 g/mol.

Examples of water-soluble or water-dispersible copolymers of AMPS according to the invention include:
- copolymers of AMPS® and vinylpyrrolidone or vinylformamide such as that used in the commercial product sold under the name Aristoflex AVC® by the company Clariant (name CTFA: Ammonium Acryloyldimethyltaurate/ VP Copolymer) but neutralized by sodium hydroxide or potassium hydroxide;
- copolymers of AMPS® and hydroxyethyl acrylate, such as the AMPS®/hydroxyethyl acrylate copolymer as used in the commercial product sold under the name Simulgel NS® by the company Seppic (CTFA name: Hydroxyethyl Acrylate/Sodium Acryloyldimethyltaurate copolymer (And) Squalane (And) Polysorbate 60) or as the product marketed under the name Copolymer Acrylamido-2-Methyl propane Sulfonate de Sodium/Hydroxyethyl acrylate as the commercial product Sepinov EMT 10 from the company Seppic (INCI name: Hydroxyethyl Acrylate/Sodium Acryloyldimethyl taurate copolymer).

Preferred water-soluble or water-dispersible copolymers of AMPS according to the invention include copolymers of AMPS® and hydroxyethyl acrylate.

Among the water-soluble or water-dispersible copolymers of AMPS that can be used in the context of the invention, we can also mention copolymers comprising at least one monomer of 2-acrylamido-2-methylpropane sulfonic acid (AMPS®), at least one monomer with a hydrophobic group and at least one monomer with ethylenic unsaturation not comprising a hydrophobic group.

Preferably, when the water-soluble or water-dispersible copolymer of AMPS comprises at least one 2-acrylamido-2-methylpropane sulfonic acid (AMPS®) monomer, at least one hydrophobic monomer and at least one ethylenic unsaturation monomer not comprising a hydrophobic group, the hydrophobic group is a hydrocarbon fatty chain comprising 6 to 50 carbon atoms, branched or unbranched, saturated or unsaturated.

The copolymer(s) can be crosslinked in the presence of a crosslinking agent.

According to a particular embodiment of the invention, the AMPS copolymer(s) are crosslinked.

Preferably, the copolymer(s) of AMPS® are crosslinked by a crosslinking agent, and even more preferably they are crosslinked by trimethylol propane triacrylate.

The copolymer(s) of AMPS® may also include at least one hydrophobic monomer, which is preferably an ethylenically unsaturated monomer comprising at least one hydrocarbon fatty chain comprising 6 to 50 carbon atoms, preferably 6 to 22 and more particularly 12 to 18 carbon atoms.

The monomer with a hydrophobic group is preferably chosen from acrylates or acrylamides of the following formula:
[Chem 8]

in which R ₁ designates a hydrogen atom or an alkyl radical, linear or branched in C ₁ -C ₆ , preferably methyl; Y designates O or NH; R ₂ designates a hydrocarbon radical comprising from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms and even more preferably from 12 to 18 carbon atoms; x designates a number from 0 to 100.

According to a particular embodiment of the invention, in formula 8, Y designates an oxygen atom.

According to a particular embodiment of the invention, in formula 8, group R1 represents a methyl.

According to a particular embodiment of the invention, x represents an integer between 3 and 25, preferably x is equal to 4.

According to a particular embodiment of the invention, in formula 8, the group R2 represents an alkyl radical comprising 12 to 18 carbon atoms.

According to an even more preferred embodiment of the invention, in formula 8, Y denotes an oxygen atom, group R1 represents a methyl, group R2 represents an alkyl radical comprising 12 to 18 carbon atoms, and x represents an integer between 3 and 25, preferably x is equal to 4.

According to a particular embodiment of the invention, the hydrophobic monomer of formula 8 is tetraethoxylated lauryl methacrylate (4OE), corresponding to the compound of formula 8 in which the group Y designates O, the group R2 represents an alkyl radical comprising 12 carbon atoms and x is equal to 4.

Preferably, the monomer with a hydrophobic group is tetraethoxylated lauryl methacrylate.

According to a particular embodiment of the invention, the AMPS® copolymer may comprise at least one monomer of formula 8 in which x is equal to 0, with Y representing an oxygen atom, group R ₁ representing a methyl, group R ₂ representing an alkyl radical comprising 12 to 18 carbon atoms.

In this embodiment, the monomer with a hydrophobic group is preferably lauryl methacrylate.

According to a particular embodiment, the AMPS® copolymer comprises at least one monomer of formula 8 in which x is equal to 0, preferably with Y denoting an oxygen atom, the group R ₁ representing a methyl, the group R ₂ representing an alkyl radical comprising 12 to 18 carbon atoms and at least one monomer of formula 8 in which Y denotes an oxygen atom, the group R ₁ representing a methyl, the group R ₂ representing an alkyl radical comprising 12 to 18 carbon atoms, and x represents an integer between 3 and 25, preferably x is equal to 4.

Preferably, the AMPS® copolymer comprises lauryl methacrylate and tetraethoxylated lauryl methacrylate as hydrophobic group monomers.

The copolymer(s) of AMPS® also include at least one ethylenically unsaturated monomer without a hydrophobic group, preferably conforming to the following general formula:
[Chem 9]

in which R ₁ designates a hydrogen atom or an alkyl radical, linear or branched in C ₁ -C ₄ , preferably R ₁ designates a hydrogen atom, R ₂ designates a linear or branched alkyl radical in C ₁ -C ₄ and R ₃ designates a linear or branched alkyl radical in C ₁ -C ₄ , preferably R ₂ and R ₃ designate a methyl.

The monomer with ethylenic unsaturation not comprising a hydrophobic group is chosen from (meth)acrylamides such as acrylamide, (meth)acrylic acids and their esters ((meth)acrylates) such as (2-hydroxyethyl) acrylate, vinylpyrrolidone, N-( _C1 - _C4 )alkylacrylamides, N,N-di( _C1 - _C4 )alkylacrylamide such as N,N-dimethylacrylamide.

Preferably, the monomer with ethylenic unsaturation not comprising a hydrophobic group is N,N-dimethyl acrylamide.

Preferably, the AMPS® copolymer is chosen from copolymers of 2-acrylamido-2-methylpropane sulfonic acid, preferably fully salified, N,N-dimethylacrylamide, tetraethoxylated lauryl methacrylate and lauryl methacrylate, preferably crosslinked, such as the copolymer marketed under the name Sepimax zen by the company Seppic, and with the INCI name Polyacrylate crosspolymer-6.

According to a particular embodiment of the invention, the composition comprises at least one copolymer of AMPS® and hydroxyethyl acrylate, such as for example the AMPS®/hydroxyethyl acrylate copolymer such as that used in the commercial product sold under the name Simulgel NS® by the company Seppic (CTFA name: Hydroxyethyl Acrylate/Sodium Acryloyldimethyltaurate copolymer (And) Squalane (And) Polysorbate 60) or such as the product marketed under the name Copolymer Acrylamido-2-Methyl propane Sulfonate de Sodium/Hydroxyethyl acrylate such as the commercial product Sepinov EMT 10 of the company Seppic (INCI name: Hydroxyethyl Acrylate/Sodium Acryloyldimethyl taurate copolymer).

The copolymer(s) of AMPS® described above may be present in concentrations ranging from 0.1 to 10% by weight, more preferably from 0.2 to 5% by weight and even more preferably from 0.5 to 3% by weight relative to the total weight of the composition.

Charges

According to a particular embodiment of the invention, the composition comprises at least one filler selected from porous silica spherical particles, cellulose spherical particles, and N-acylated amino acid powders.

By filler, we must understand particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured.

The charges used in the present invention can be characterized by their specific surface area per unit mass or per unit volume, their size expressed in volume mean diameter D(4.3), their uncompacted density, and/or their oil absorption capacity.

The specific surface area per unit mass can be determined by the nitrogen absorption method known as the BET (Brunauer-Emmett-Teller) method, described in "The Journal of the American Chemical Society," vol. 60, page 309, February 1938, and corresponding to the international standard ISO 5794/1 (Annex D). The BET specific surface area corresponds to the total specific surface area of the particles considered.

The specific surface area per unit volume is given by the relation: S _V = S _M x ρ where ρ is the packed density expressed in g/cm ³ and S _M is the specific surface area per unit mass expressed in m ² /g, as defined above.

Within the framework of the present invention, this density can be assessed according to the following protocol, known as the packed density protocol:
Forty grams of powder are poured into a graduated cylinder; the cylinder is then placed on the STAMPF VOLUMETER STAV 2003 apparatus; the cylinder is then subjected to a series of 2500 compactions (this operation is repeated until the volume difference between two consecutive tests is less than 2%); the final volume Vf of compacted powder is then measured directly on the cylinder. The compacted density is determined by the ratio m/Vf, in this case 40/Vf (Vf being expressed in ^cm³ and m in g).

The oil absorption capacity measured at the Wet Point, and noted Wp, corresponds to the amount of oil that must be added to 100 g of particles to obtain a homogeneous paste.

It is measured according to the so-called Wet Point method or method for determining oil uptake of powder described in standard NF T 30-022. It corresponds to the quantity of oil adsorbed on the available surface of the powder and/or absorbed by the powder by Wet Point measurement, described below.

A quantity m = 2 g of powder is placed on a glass plate, and oil (isononyl isononanoate) is added drop by drop. After adding 4 to 5 drops of oil to the powder, the mixture is stirred with a spatula, and oil is continued to be added until clumps of oil and powder form. From this point on, the oil is added one drop at a time, and the mixture is then triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste should spread easily on the glass plate without cracking or lumps. The volume Vs (expressed in ml) of oil used is then recorded.

The oil intake corresponds to the Vs / m ratio.

The particle sizes can be measured by static light scattering using a commercial particle size analyzer such as the Malvern MasterSizer 2000. The data are processed based on Mie scattering theory. This theory, accurate for isotropic particles, allows for the determination of an "effective" particle diameter in the case of non-spherical particles. This theory is notably described in Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

According to a particular embodiment, the fillers that can be used in the present invention have an oil absorption capacity of 0.25 g/g to 3.5 g/g, preferably from 0.93 g/g to 2.5 g/g, or even from 1.25 g/g to 2.5 g/g.

According to a particular embodiment, the charges that can be used in the present invention have a size expressed in average volume diameter D(4,3) ranging from 0.1 µm to 40 µm, preferably from 0.5 µm to 20 µm, and even more preferably from 1 µm to 16 µm.

According to a particular embodiment, the charges used in the present invention have an unpacked density ranging from 0.2 g/ ^cm³ to 2.2 g/ ^cm³ .

According to a particular embodiment, they have a specific surface area ranging from 30 to 1000 ^m² /g, and more particularly from 150 to 800 ^m² /g.

In this application, "spherical particles" means particles having the shape or substantially the shape of a sphere, insoluble in the medium of the composition according to the invention, even at the melting temperature of the medium (approximately 100 °C).

According to a particular embodiment of the invention, the spherical porous silica particles are microparticles. Preferably, they have a size expressed as volume average diameter D(4,3) ranging from 0.5 to 30 µm, more particularly from 1 to 20 µm, and preferably from 1 to 16 µm.

Examples of porous silica microbeads include the following commercial products: Silica Beads SB-150, SB-300 or SB 700, preferably SB 300 from MYOSHI KASEI; the SUNSPHERE range from Asahi Glass AGC SI-TECH, notably Sunsphere H-51 or Sunsphere 12L, Sunsphere H-201, H-52 and H-53; Sunsil 130 from Sunjin; Spherica P-1500 from Ikeda Corporation; Sylosphere from Fuji Silysia; the Silica Pearl and Satinier ranges from JGC Catalysts and Chemicals, particularly Satinier M13 and M16, the MSS-500 silicas from KOBO, particularly MSS-500-20N, and the Silica Shells from KOBO.

According to a particular embodiment, the spherical cellulose particles usable within the framework of the invention are microparticles. Preferably, they have a size expressed in volume mean diameter D(4,3) ranging from 0.1 to 35 µm, preferably from 1 to 20 µm, and more particularly from 4 to 15 µm.

Examples of spherical cellulose microparticles include solid cellulose beads marketed under the names CELLULOBEADS D-10, CELLULOBEADS D-5 and CELLULOBEADS USF by the company DAITO KASEI KOGYO.

N-acylated amino acids can include an acyl group with 8 to 22 carbon atoms, such as 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, or cocoyl. The amino acid can be, for example, lysine, glutamic acid, or alanine, preferably lysine.

In a particular embodiment, the N-acylated amino acid(s) comprise an acyl group having 10 to 14 carbon atoms. Preferably, this is the lauroyl group. Advantageously, the N-acylated amino acid powder can be a lauroyl lysine powder such as that marketed under the name AMIHOPE LL by AJINOMOTO or that marketed under the name CORUM 5105 S by CORUM.

According to a particular embodiment of the invention, the fillers chosen from among spherical porous silica particles, spherical cellulose particles, and N-acylated amino acid powders have a heterogeneous particle size distribution, that is to say a large size distribution for a size expressed in average diameter in volume given.

According to a particular embodiment, the composition according to the invention comprises at least three fillers selected from spherical porous silica particles, spherical cellulose particles, and N-acylated amino acid powders.

According to another particular embodiment, the composition according to the invention comprises at least three distinct fillers, the first of which is chosen from spherical porous silica particles, in particular spherical porous silica microparticles, the second is chosen from spherical cellulose particles, and the third is chosen from N-acylated amino acid powders.

According to a preferred embodiment, the total quantity of fillers selected from porous silica spherical particles, cellulose spherical particles, and N-acylated amino acid powders is between 1% and 4% by weight, preferably between 2% and 4% by weight of the total weight of the composition. According to another preferred embodiment, the mass ratio (cellulose spherical particles + N-acylated amino acid powders) / (porous silica spherical particles) is between 0.25 and 1.

The composition according to the invention may further comprise at least one additional filler other than spherical porous silica particles, spherical cellulose particles, and N-acylated amino acid powders.

Fatty phase

According to a particular embodiment, the composition according to the invention comprises at least one fatty phase.

The oil phase can consist of any fats commonly used in cosmetics or dermatology. It may include at least one oil. The oil phase also includes any lipophilic filter(s) present in the formulation.

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

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

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

The term "siliconized oil" refers to an oil containing at least one silicon atom, and in particular at least one Si-O group.

Examples of non-volatile hydrocarbon oils that can be used according to the invention include:
(i) vegetable hydrocarbon oils such as glyceride triesters, which are generally fatty acid and glycerol triesters, the fatty acids of which may have varying chain lengths from _C4 to _C24 , the latter being linear or branched, saturated or unsaturated; These oils include wheat germ oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea butter, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, squash oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, rosehip oil; or caprylic/capric acid triglycerides such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by Dynamit Nobel;
(ii) synthetic ethers having 10 to 40 carbon atoms;
(iii) linear or branched hydrocarbons, of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as paream, squalane, and mixtures thereof;
(iv) synthetic esters such as oils of the formula RCOOR' in which R represents the remainder of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R' represents a hydrocarbon chain, particularly a branched one, 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 benzoates such as the product sold under the trade name "Finsolv TN®" or "Witconol TN®" by WITCO or "TEGOSOFT TN®" by EVONIK GOLDSCHMIDT, 2-ethylphenyl benzoate such as the commercial product sold under the name "X-TEND 226®" by 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 like those sold under the name COSMACOL ETI® by ENICHEM AUGUSTA INDUSTRIALE and linear C14-C15 dialkyl tartrates like those sold under the name COSMACOL ETL® by the same company; acetates;
(v) fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecylpentadecanol;
(vi) higher C12-C22 fatty acids, such as oleic acid, linoleic acid, linolenic acid;
(vii) 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 usable according to the invention, glyceride triesters, particularly caprylic/capric acid triglycerides, synthetic esters, particularly diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, dicaprylyl carbonate, isononyl isononanoate, oleyl erucate, C12-C15 alcohol benzoate, 2-ethylphenyl benzoate, and fatty alcohols, particularly octyldodecanol, are preferred. Preferably, the non-volatile hydrocarbon oils are selected from diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, and dicaprylyl carbonate.

Examples of usable volatile hydrocarbon oils according to the invention include hydrocarbon oils having 8 to 16 carbon atoms, and in particular C8-C16 branched alkanes such as petroleum-derived C8-C16 isoalkanes (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, C8-C16 branched esters, isohexyl neopentanoate, and mixtures thereof.

We can also mention the alkanes described in Cognis patent applications WO 2007/068371 and WO 2008/155059 (mixtures of distinct alkanes differing by at least one carbon atom). These alkanes are obtained from fatty alcohols, themselves derived from coconut or palm oil. Examples include the mixtures of n-undecane (C11) and n-tridecane (C13) obtained in Examples 1 and 2 of Cognis application WO 2008/155059. Also noteworthy are n-dodecane (C12) and n-tetradecane (C14), sold by Sasol under the brand names PARAFOL 12-97 and PARAFOL 14-97®, respectively, as well as mixtures thereof.

Other volatile hydrocarbon oils, such as petroleum distillates, particularly those sold under the name Shell Solt® by Shell, can also be used. In one embodiment, the volatile solvent is selected from volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof.

Non-volatile silicone oils can be chosen in particular from among non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes containing alkyl or alkoxy groups, during 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.

Examples of volatile silicone oils include linear or cyclic volatile silicone oils, particularly those with a viscosity ≤ 8 centistokes (8 x ^{10⁻⁶ m²} /s), and having, in particular, 2 to 7 silicon atoms. These silicones may optionally contain alkyl or alkoxy groups having 1 to 10 carbon atoms. Examples of volatile silicone oils usable in the invention include octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.

We can also mention 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 can also be used, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane and mixtures thereof.

The oily phase according to the invention may further comprise, mixed with or solubilized in the oil, other fatty substances.

Another type of fat that may be present in the oily phase could be, for example:
- a fatty acid chosen from among fatty acids having 8 to 30 carbon atoms different from fatty chain amino acids as defined above, such as stearic acid, lauric acid, palmitic acid and oleic acid;
- a gum chosen from among the silicone gums (dimethiconol),
- a pasty compound, such as polymeric or non-polymer silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, fatty acid triglycerides and their derivatives,
- and their mixtures.

According to a particular embodiment of the invention, the overall oily 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 70% by weight, and preferably from 30% to 50% by weight relative to the total weight of the composition.

Aqueous phase

According to a particular embodiment, the composition according to the invention comprises at least one aqueous phase.

The aqueous phase contains water, and possibly other organic solvents that are soluble or miscible in water.

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

Water-soluble or miscible solvents suitable for the invention include short-chain alcohols, and in particular monoalcohols having 1 to 4 carbon atoms such as ethanol, propanol, butanol, isopropanol, and isobutanol, 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.

The composition according to the invention comprises an amount of ethanol less than or equal to 3% by weight of the total weight of the composition.

According to a preferred embodiment of the invention, the composition is free of ethanol.

For the purposes of this invention, "ethanol-free" means an amount of ethanol less than 2% by weight, preferably less than 1% by weight, and even more preferably less than 0.5% by weight relative to the total weight of the composition.

According to a particular embodiment of the invention, the overall aqueous phase, including all hydrophilic substances of the composition capable of being solubilized in this same phase, represents from 30 to 80% by weight relative to the total weight of the composition.

Active cosmetic ingredients

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

Examples of cosmetic actives include moisturizing agents; natural extracts; vitamins and their derivatives; alpha-hydroxy acids; retinoids; extracts of algae, fungi, plants, yeasts and bacteria; enzymes; tightening agents; agents acting on microcirculation, and mixtures thereof.

It is easy for a person skilled in the art to adjust the quantity of cosmetic active ingredient according to the final use of the composition according to the present invention.

Additional adjuvants or additives

The composition of the present invention may also include conventional cosmetic adjuvants or additives, for example perfumes, chelating agents, preservatives and bactericides, additional thickeners, pH regulators, additional fillers, and mixtures thereof.

A person skilled in the art can select the quantity of additional adjuvants or additives so as not to impair the final use of the composition according to the present invention.

Pharmaceutical forms

According to a particular embodiment, the viscosity of the composition according to the invention, at 25 °C and under atmospheric pressure, is less than or equal to 500 mPa.s, preferably less than or equal to 300 mPa.s.

According to a preferred embodiment of the invention, the viscosity is greater than or equal to 20 mPa.s, preferably greater than or equal to 100 mPa.s.

Viscosity can be measured at 25 °C using a Rheomat RM180 ® rheometer from Maple Instruments, at a rotation speed of 200 rpm with a TV No. 2 mobile after 10 minutes. The viscosity value is obtained in Pa.s.

The compositions according to the invention can be prepared according to techniques well known to those skilled in the art. They can in particular be in the form of an emulsion, simple or complex (O/W, W/W, W/W/W or W/O/W) such as a cream, a lotion or a cream-gel.

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 (inverse 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 type, rotor-stator and HHP.

To obtain stable emulsions with a low polymer content (oil/polymer ratio >25), it is possible to perform the dispersion in concentrated phase and 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 droplet sizes down to 100 nm.

Emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic, or nonionic emulsifiers, used alone or in mixtures. Emulsifiers are selected appropriately depending on the emulsion to be obtained (oil-in-water or water-in-water).

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

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

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

Examples of glycerol and/or sorbitan esters include polyglycerol isostearate, such as the product marketed under the name Isolan GI 34® by Goldschmidt; sorbitan isostearate, such as the product marketed under the name Arlacel 987® by ICI; sorbitan isostearate and glycerol, such as the product marketed under the name Arlacel 986® by ICI, and mixtures thereof.

For O/W emulsions, examples of non-ionic emulsifying surfactants include polyoxyalkylated fatty acid and glycerol esters (particularly polyoxyethylated and/or polyoxypropylated) such as the polyethylene glycol and stearic acid ester with INCI name PEG-100 STEARATE, marketed under the name Myrj S100-PA-(SG) by the company CRODA; oxyalkylated fatty acid and sorbitan esters; polyoxyalkylated fatty acid esters (particularly polyoxyethylated and/or polyoxypropylated), possibly 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; oxyalkylated fatty alcohol ethers (oxyethylenated and/or oxypropylenated); sugar esters such as sucrose stearate; Fatty alcohol and sugar ethers, in particular alkyl polyglucosides (APGs) such as decyl glucoside and lauryl glucoside marketed for example by Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearyl glucoside possibly in mixture 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 the mixture of arachidic and behenic alcohols and arachidyl glucoside 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 can be in the form of a self-emulsifying composition, as described for example in document WO-A-92/06778.

Anionic surfactants used to make O/W emulsions include 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, notably 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 making H/W emulsions, we can also mention hydrophobic modified polysaccharides, in particular inulins modified by hydrophobic chains such as alkylcarbamate groups, in particular alkyl C8-C18 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.

When it is an emulsion, the aqueous phase of it may include a non-ionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins. J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).

The compositions according to the invention find their application in a large number of treatments, in particular cosmetic, of the skin, lips and hair, including the scalp, in particular for the protection and/or care of the skin, lips and/or hair, and/or for the makeup of the skin and/or lips.

Another object of the present invention is the use of the compositions according to the invention as defined above for the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and/or scalp, in particular skincare products, sun protection products and makeup products.

EXAMPLES

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

In these examples, the quantities of ingredients present in the compositions are given as a percentage by weight of raw materials relative to the total weight of the composition.

Method of preparing the exemplary compositions

Phase A is prepared as follows:
The raw materials of phases A1 and A2 are placed in a beaker and heated to 65 °C under magnetic stirring. Dispersion is achieved until a clear mixture is obtained.
Introduction of the raw materials of phase A3. Dispersion until a clear mixture is obtained while maintaining the temperature at 65 °C.
Phase B is prepared as follows:
The raw materials of phase B1 are introduced into a beaker and heated to 75 °C under stirring with scraper blades. Dispersion is achieved until a clear mixture is obtained.
Stop heating and add raw materials from phase B2 and then phase B3 while stirring. Dispersion until a homogeneous mixture is obtained and the temperature is maintained at 65 °C.
At 65 °C, phase A is slowly poured into phase B under rotor-stator agitation and scraper blades.
Dispersion until a suitable emulsion is obtained.
Dilution by introducing phase C under stirring.
Dispersion under rotor-stator agitation and scraper blades until a homogeneous mixture is obtained while starting the cooling process.
Cooling continues under scraper blades alone.
At a temperature < 30 °C, add phase D and the raw materials of phase E.
Dispersion under rotor-stator agitation and scraper blades until a homogeneous mixture is obtained while continuing to cool.
Continued cooling under scraper blades only if necessary.
Introduction of the F and G phases.
Dispersion under scraper blades only until a homogeneous mixture is obtained while maintaining the temperature.

Confocal Microscopy Studies

The microscopic study of the compositions is carried out using a Leica SP8 confocal microscope.

The advantage of confocal mode is a very fine definition of the observed focal plane, thanks to the presence of a diaphragm at the detector. Only photons originating from the focal plane are thus observed.
Displacements can be made in the three dimensions of space X, Y and Z. X and Y represent the lateral displacements of the sample, and Z represents the thickness of the sample.
The sample is observed using a 63x objective lens with oil to allow optical contact.

Two studies were conducted using confocal fluorescence microscopy.
The first study consists of observing the homogeneity of the emulsion (in bulk) while the second study allows us to observe the homogeneity of the deposit (spreading and drying of the composition on a glass slide).

To label the samples, 5 µL of a ^{10⁻² mol·L⁻¹} fluorophore solution is added to approximately 2 g of each of the compositions being studied. The labeling step is performed 24 hours before observation to allow for good diffusion of the fluorophores.
Two markers (fluorophores) are used for this study, fluorescein for the aqueous phase, and Nile Red for the oily phase.

Confocal fluorescence microscopy allows the selective observation of each phase of an emulsion by stimulating the fluorophores at their respective excitation wavelengths.
For the aqueous phase, the laser excites the Fluorescein molecule in the blue (458 nm), which re-emits in the green (500-550 nm).
For the oily phase, the laser excites the Nile Red molecule in the yellow (561 nm), which re-emits in the red (600-680 nm).

For observation of the bulk emulsion, a drop of the sample is placed on a glass slide.
For observation of the deposition, the sample is spread on a glass slide with a bar coater (automatic spreader) set to 25 µm. It is then placed under a fume hood to allow it to dry for 1 hour at room temperature.

Sensory evaluation protocol for plush toy making

The compositions were sensorially tested blind and monadic on a panel of 64 Chinese women per cell, aged 18 to 35, with all skin types (oily, normal and dry), regular consumers of cosmetic skin care compositions with a high SPF index, 50% being regular consumers of pharmaceutical products, including one of the top sellers UV Daily with SPF present on the Chinese market, and 50% being regular consumers of various photoprotection products (not necessarily pharmaceutical).
For this sensory evaluation, each volunteer applied the composition to be tested to the skin of their face at least once a day over a test period of 3 days.
The test was carried out in China, under temperature conditions between 21°C and 35°C, with an air humidity level between 80% and 90%.

Comparative Example 1 – Compositions 1 to 4

The following compositions are prepared.
[Table 1]
Phase Composition 1
(invention) 2
(comparative)
3
(comparative) 4
(invention) A1 WATER / AQUA 30 30 30 30 A1 PROPANEDIOL 3 3 3 3 A1 PENTYLENE GLYCOL 0.1 0.1 0.1 0.1 A1 COMPLEXING AGENT(S) 0.3 0.3 0.3 0.3 A1 CONSERVATORY AGENT(S) 0.65 0.5 0.65 A2 SODIUM STEAROYL GLUTAMATE
(AMISOFT HS 11 from AJINOMOTO) 0.3 0.3 0.3 0.3 A2 INULIN LAURYL CARBAMATE
(INUTEC SL1 from CREACHEM) 0.3 0.3 0.3 0.3 A3 PHENYLBENZIMIDAZOLE SULFONIC ACID
(EUSOLEX 232 from MERCK) 3 7 3 3 A3 SODIUM HYDROXIDE 0.44 1.02 0.44 0.44 B1 CETEARYL ALCOHOL (and) CETEARYL GLUCOSIDE
(MONTANOV 68 from SEPPIC) 1.4 1.4 1.4 1.4 B1 BUTYL METHOXYDIBENZOYLMETHANE
(PARSOL 1789 from DSM NUTRITIONAL PRODUCTS) 3 3 3 3 B1 BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(TINOSORB S from BASF) 3 3 3 3 B1 DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE
(UVINUL A PLUS GRANULAR from BASF) 2 2 2 2 B1 DROMETRIZOLE TRISILOXANE
(NOVEAL's MEXORYL XL) 1 - 1 1 B1 ETHYLHEXYL TRIAZONE
(UVINUL T150 from BASF) 3 2.5 3 3 B1 DICAPRYLYL CARBONATE 15 15 15 15 B2 DIMETHICONE 3.4 3.4 3.4 3.4 B3 HYDROXYETHYL ACRYLATE / SODIUM ACRYLOYLDIMETHYL TAURATE COPOLYMER
(SEPINOV EMT 10 from SEPPIC) 1.2 1.2 1.2 1.2 B3 XANTHAN GUM 0.1 0.1 0.1 0.1 C WATER / AQUA 18.18 15.1 12.68 17.83 D ASSETS) 4.28 4.28 4.28 4.28 E SILICA
(SUNSPHERE H51 from AGC Si-TECH) 2 2 2 2 E CELLULOSE
(CELLULOBEADS USF by DAITO KASEI KOGYO) 0.25 0.25 0.25 0.25 E LAUROYL LYSINE
(AMIHOPE LL from AJINOMOTO) 0.75 0.75 0.75 0.75 F METHYLENE BIS-BENZOTRIAZOLYL TETRAMETHYLBUTYLPHENOL (and) POLYGLYCERYL-10 LAURATE
(TINOSORB WPGL from BASF) 4 4 4 4 G ALCOHOL DENAT. - - 5 -

Confocal microscopy observations

The results obtained are as follows.
[Table 2]
Composition 1
(invention) 2
(comparative) 3
(comparative) 4
(invention) Microscopic appearance in bulk
(study 1) Tight, fine, well-defined emulsion Coarse, irregular emulsion Loose, irregular, poorly defined medium emulsion Tight, fine, well-defined emulsion Microscopic appearance after deposition on substrate
(study 2) Good distribution of phases between the bottom and top of the deposit Inhomogeneity of distribution between oily phase, aqueous phase and particles. Good distribution of phases between the bottom and top of the deposit Good distribution of phases between the bottom and top of the deposit

Compositions 1 and 4 according to the invention exhibit a fine, tightly packed emulsion with a homogeneous deposit on the substrate. They demonstrate excellent long-term stability and high-performance deposition to minimize the risk of pilling. Comparative composition 2, which does not contain Drometrizole Trisiloxane, exhibits poor emulsion quality with an inhomogeneous deposit on the substrate. Comparative composition 3, which contains alcohol, also exhibits poor emulsion quality.

Comparative Example 2 – Compositions 5 to 7

The following compositions are prepared.
[Table 3]
Phase Composition 5
(invention) 6
(comparative) 7
(comparative) A1 WATER / AQUA 30 30 30 A1 PROPANEDIOL 3 3 3 A1 PENTYLENE GLYCOL 0.1 0.1 0.1 A1 COMPLEXING AGENT(S) 0.3 0.3 0.3 A2 PEG-20 - 0.2 - A2 SODIUM STEAROYL GLUTAMATE
(AMISOFT HS 11 from AJINOMOTO) 0.3 0.3 0.3 A2 INULIN LAURYL CARBAMATE
(INUTEC SL1 from CREACHEM) 0.3 0.3 0.3 A3 PHENYLBENZIMIDAZOLE SULFONIC ACID
(EUSOLEX 232 from MERCK) 3 7 7 A3 SODIUM HYDROXIDE 0.44 1.02 1.02 B1 CETEARYL ALCOHOL (and) CETEARYL GLUCOSIDE
(MONTANOV 68 from SEPPIC) 1.4 1.4 1.4 B1 BUTYL METHOXYDIBENZOYLMETHANE
(PARSOL 1789 from DSM NUTRITIONAL PRODUCTS) 3 3 3 B1 BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(TINOSORB S from BASF) 3 3 3 B1 DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE
(UVINUL A PLUS GRANULAR from BASF) 2 2 2 B1 DROMETRIZOLE TRISILOXANE
(NOVEAL's MEXORYL XL) 1 - - B1 ETHYLHEXYL TRIAZONE
(UVINUL T150 from BASF) 3 2.5 2.5 B1 ETHYLHEXYL SALICYLATE - 5 5 B1 DICAPRYLYL CARBONATE 15 10 10 B2 DIMETHICONE 3.4 3.4 3.4 B2 ASSETS) 3.88 0.4 0.4 B3 HYDROXYETHYL ACRYLATE / SODIUM ACRYLOYLDIMETHYL TAURATE COPOLYMER
(SEPINOV EMT 10 from SEPPIC) 1.2 1.2 1.2 B3 XANTHAN GUM 0.1 0.1 0.1 C WATER / AQUA 22.56 23 26 E SILICA
(SUNSPHERE H51 from AGC Si-TECH) 2 2 2 E CELLULOSE
(CELLULOBEADS USF by DAITO KASEI KOGYO) 0.25 0.25 0.25 E LAUROYL LYSINE
(AMIHOPE LL from AJINOMOTO) 0.75 0.75 0.75 F METHYLENE BIS-BENZOTRIAZOLYL TETRAMETHYLBUTYLPHENOL (and) POLYGLYCERYL-10 LAURATE
(TINOSORB WPGL from BASF) 4 4 4 G ALCOHOL DENAT. - - 5

Sensory results obtained

The results obtained are as follows.
[Table 4]
Composition 5
(invention) 6
(comparative) 7
(comparative) % of consumers who received lint during and after application 3% 12% 12%

These results show that the composition according to the invention which includes Drometrizole Trisiloxane (MEXORYL XL from NOVEAL) exhibits reduced lint formation compared to comparative compositions not including Drometrizole Trisiloxane (MEXORYL XL from NOVEAL).

Claims (18)

Composition, particularly cosmetic or dermatological, comprising:
a) Drometrizole Trisiloxane; And
b) at least one hydrophilic organic UV filter;
the mass ratio between hydrophilic organic UV filters and lipophilic organic UV filters being greater than 0.3;
the quantity of ethanol being less than or equal to 3% by weight relative to the total weight of the composition. Composition according to claim 1 comprising at least one additional lipophilic organic UV filter, preferably selected from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; β,β-diphenyl acrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds; methylene bis-(hydroxyphenyl benzotriazole) compounds; benzoxazole compounds; filter polymers and silicone filters; α-alkylstyrene derivative dimers; 4,4-diarylbutadiene compounds and mixtures thereof; preferably salicylic compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; triazine compounds; Benzotriazole compounds; and mixtures thereof. Composition according to any one of claims 1 and 2 wherein the hydrophilic organic UV filter(s) are selected from water-soluble organic UV filters and water-dispersible organic UV filters, preferably water-dispersible organic UV filters. Composition according to claim 3 wherein the water-soluble organic UV filter(s) are selected from 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid); benzene 1,4-di(3-methylidene-10-camphosulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid); and their salts. Composition according to any one of claims 3 and 4 wherein the hydrodispersible organic UV filter(s) are selected from Methylene bis-Benzotriazolyl Tetramethylbutylphenol in the form of an aqueous dispersion of micronized particles having an average particle size ranging 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 ranges 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-( _C8 - _C20 )alkyl-ester of polyglycerol having a degree of glycerol polymerization of at least 5; Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in its hydrodispersible form with the INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer; symmetric triazine filters substituted with 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, notably 2,4,6-tris(bi-phenyl)-triazine and 2,4,6-tris(ter-phenyl)-triazine. Composition according to any one of claims 4 and 5 wherein the amount of 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid) is less than or equal to 3% by weight of the total weight of the composition. Composition according to any one of claims 1 to 6 wherein the total quantity of UV filters is greater than or equal to 15% by weight of the total weight of the composition. Composition according to any one of claims 1 to 7 wherein the mass ratio between hydrophilic organic UV filters and lipophilic organic UV filters is between 0.35 and 1. Composition according to any one of claims 1 to 8 comprising at least one hydrophilic copolymer comprising at least one acrylamido 2-methylpropane sulfonic acid monomer (AMPS®). Composition according to claim 9 wherein the AMPS copolymer(s) are selected from copolymers obtained from AMPS® and one or more hydrophilic or hydrophobic ethylenic unsaturation monomers and, if crosslinked, one or more crosslinking agents. Composition according to claim 10 wherein the hydrophilic ethylenic unsaturation monomer(s) are non-ionic. Composition according to any one of claims 10 and 11 wherein the hydrophobic ethylenic unsaturation monomer(s) comprise a fatty chain. Composition according to any one of claims 1 to 12 in the form of an emulsion, preferably in the form of an oil-in-water emulsion. Composition according to any one of claims 1 to 13 wherein the quantity in the fat phase is between 20% and 70% by weight of the total weight of the composition. Composition according to any one of claims 1 to 14 having a viscosity of composition less than or equal to 500 mPa.s. Composition according to any one of claims 1 to 15 comprising at least three distinct fillers, the first of which is selected from spherical porous silica particles, in particular spherical porous silica microparticles, the second is selected from spherical cellulose particles, and the third is selected from N-acylated amino acid powders. Composition according to claim 16 wherein the total quantity of fillers selected from porous silica spherical particles, cellulose spherical particles, and N-acylated amino acid powders is between 1% and 4% by weight, preferably between 2% and 4% by weight of the total weight of the composition. Composition according to any one of claims 16 and 17 wherein the mass ratio (spherical cellulose particles + N-acylated amino acid powders) / (spherical porous silica particles) is between 0.25 and 1.