FR3146067A1 - COSMETIC COMPOSITION BASED ON ZINC OXIDE AND BISETHYHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE - Google Patents

Abstract

Cosmetic composition based on zinc oxide and Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine The present invention relates to a composition, preferably cosmetic, comprising, in a physiologically acceptable medium: from 4.5% to 10% by weight relative to the total weight of the composition of 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), and from 5% to 25% by weight relative to the total weight of the composition of zinc oxide, the composition comprising less than 3% by weight relative to the total weight of the composition of other UV filter(s). It also relates to a method for non-therapeutic cosmetic treatment of keratin materials, preferably of the skin, comprising the application to said keratin materials of a composition according to the invention. Figure for abstract: none

Description

Cosmetic composition based on zinc oxide and Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

The present invention relates to a composition, preferably cosmetic, comprising, in a physiologically acceptable medium, zinc oxide and 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), in specific amounts, said composition being substantially free of other UV filter(s).

It is known that radiation with wavelengths between 280 nm and 400 nm allows the tanning of human epidermis, while radiation with wavelengths between 280 and 320 nm, called UVB rays, impairs the development of a natural tan. Exposure is also likely to cause a detrimental change in the biomechanical properties of the epidermis, resulting in the appearance of wrinkles leading to premature aging of the skin (i.e. photoaging).

It is also known that UVA rays with a wavelength between 320 and 400 nm penetrate deeper into the skin than UVB rays. UVA rays cause immediate and persistent browning of the skin. Daily exposure to UVA rays, even for a short time, under normal conditions can damage collagen fibers and elastin, which results in a change in the microrelief of the skin, the appearance of wrinkles and uneven pigmentation (spots, uneven skin tone).

Numerous studies show the need for effective protection against UVA and/or UVB to prevent sunburn and/or photoaging.

However, many consumers question the safety of sunscreens, which limits their use. Zinc oxide in particular has a very good reputation and is increasingly used.

In order to obtain a product with high protection, it is also generally necessary to combine a significant number of sun filters and/or high filter rates to achieve high levels of filtering efficiency.

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

There is therefore a need to offer consumers highly effective sun protection products, containing a reduced number of sun filters at the lowest possible concentration, while maintaining good cosmetic appeal.

The invention meets this need.

In particular, surprisingly, the Applicant has discovered that a composition comprising the combination of zinc oxide and 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine; BEMT), without any other sunscreen, in specific quantities, exhibits a synergistic effect in terms of sunscreen filtration, and thus an unexpected efficacy.

The present invention thus relates to a composition, preferably cosmetic, comprising, in a physiologically acceptable medium:

from 4.5% to 10% by weight relative to the total weight of composition of 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), and

from 5% to 25% by weight relative to the total weight of zinc oxide composition,

the composition comprising less than 3% by weight relative to the total weight of the composition of other UV filter(s).

By "physiologically acceptable medium" is meant a medium compatible with keratin materials. By "keratin materials" is meant in particular the skin, the scalp, keratin fibres such as eyelashes, eyebrows, hair, and body hair, nails, mucous membranes such as the 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 limits of a domain of values are included in this domain, in particular in the expressions “between” and “ranging from … to …”.

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

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

For the purposes of the present invention, the term " SPF " (Sun Protection Factor) means the sun protection factor, which measures the level of protection against UVB. The SPF value corresponds to the ratio between the minimum time required to obtain sunburn with an antisun 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 SPF (Sun Protection Factor) assessment can be carried out in vitro using the Labsphere® spectrophotometer. The plate is the material on which the sunscreen composition is applied. For this protocol, polymethylmethacrylate (PMMA) plates have proven to be ideal. A particular 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 the compositions can also be carried out in-vivo according to the ISO 24444:2019 protocol “Cosmetics-Sun protection test methods-In-vivo determination of the sun protection factor (SPF)”.

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

The present invention also relates to a method for non-therapeutic cosmetic treatment of keratin materials, preferably the skin, comprising the application to said keratin materials of a composition according to the invention.

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

The composition according to the invention comprises from 4.5% to 10% by weight relative to the total weight of the composition of 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine).

For example, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine marketed under the name TINOSORB® S by BASF or under the name PARSOL® SHIELD by DSM can be used. It can also be found in its water-dispersible form with the INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer, under the trade name TINOSORB® S LiteAqua by BASF.

The composition according to the invention preferably comprises from 5% to 9% by weight relative to the total weight of the composition, preferably from 5.5% to 8% by weight, preferably from 5.7% to 7% by weight of 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine).

Zinc oxide

The composition according to the invention comprises from 5% to 25% by weight relative to the total weight of the composition of zinc oxide.

Zinc oxide is an inorganic UV filter.

According to a particular embodiment of the invention, it is in the form of particles having an average elementary particle size less than or equal to 0.5 µm, 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.

Zinc oxide particles are pigments that 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, hydrated silica, proteins (collagen, elastin), alkanolamines, silicon oxides, triethoxycaprylylsilane, metal oxides or sodium hexametaphosphate.

Examples of uncoated zinc oxide pigments include:

- those marketed under the name “Z-COTE®” by the company BASF;

- those marketed under the name “NanoArc® Zinc Oxide” by the company Nanophase Technologies;

- those marketed under the name "MZ-500", "MZ-300", "MZ-200" or "MZ-150" by the company TAYCA; or

- those marketed under the name Solaveil MZP3 by the company CRODA.

Coated zinc oxide pigments include for example:

- ZnO coated with polymethylhydrogensiloxane;

- CRODA’s “Solaveil™ CZ-100” dispersed in C12-15 alkyl benzonate (INCI: Zinc Oxide (and) C12-15 Alkyl Benzoate (and) Polyhydroxystearic Acid (and) Isostearic Acid);

- those marketed under the name and "DAITOPERSION Zn-60VA®" by the company Daito Kasei (dispersions in C9-12 alkane with a dispersing agent);

- those marketed under the name "SPD-Z5®" by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);

- ZnO coated with hydrated silica, such as that marketed by TAYCA under the name “MZ-500HP”;

-ZnO coated with hydrated silica, triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone and hydrogen dimethicone (H-Me-Si), such as that marketed by TAYCA under the name MZ-510 HPSX;

- ZnO coated with stearic acid or isostearic acid, such as those marketed by TAYCA under the name “MZ-505T”, “MZY-505EX” or “MZY-304EX”;

- ZnO coated with silicone oil, such as those marketed by TAYCA under the name “MZX-510HPS”, “MZY-505S”, “MZY-510M3S”, “MZ-505M”, “MZY-303S”, “MZY-303M”, “MZY-203S”, “MZY-210M3S” or “MZY-153S”; or

- ZnO coated with triethoxycaprylylsilane, such as those marketed by BASF under the name Z-COTE HP1, or by TAYCA under the name “MZX-508OTS”, “MZY-203OTS” or “MZX-304OTS” or by DSM under the name PARSOL ZX, or by CRODA under the name Solaveil MZP7.

According to a preferred embodiment of the invention, the ZnO coating comprises at least hydrated silica.

The composition according to the invention preferably comprises from 5% to 20% by weight relative to the total weight of the composition, preferably from 5% to 15% by weight of zinc oxide, preferably from 5% to 10% by weight.

Other UV filter(s)

The composition according to the invention comprises less than 3% by weight relative to the total weight of the composition of other UV filter(s).

Preferably, the composition according to the invention comprises less than 2% by weight, preferably less than 1% by weight relative to the total weight of the composition of other UV filter(s).

Preferably, the composition according to the invention is completely free of other UV filter(s).

By “other UV filter(s)” we mean UV filters other than zinc oxide and Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine.

These other UV filters can be chosen from lipophilic organic UV filters, hydrophilic organic UV filters and inorganic UV filters.

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

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

Preferably, the lipophilic organic filter(s) are chosen from salicylic compounds, dibenzoylmethane compounds, benzylidenecamphor compounds; benzophenone compounds; triazine compounds other than Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine; benzotriazole compounds; and mixtures thereof.

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

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

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

The inorganic UV filters that can be used are metal oxide pigments, distinct from zinc oxide. More preferably, the inorganic UV filters can be chosen in particular from titanium, iron, zirconium, cerium oxides or their mixtures.

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

Aqueous phase

The composition according to the invention may comprise at least one aqueous phase.

Preferably, the composition according to the invention comprises at least water.

The aqueous phase may comprise at least one other organic solvent soluble in water, at 25°C, chosen for example from:

- C1-C4 monoalkanols. The term “ _C1 - _C4 monoalkanol” means any saturated, linear or branched alkane compound having from 1 to 4 carbon atoms and a single hydroxyl function (OH). The _C1 -C4 monoalkanol( _s) present in the compositions of the invention may be chosen from methanol, ethanol, propanol, isopropanol, butanol or mixtures thereof. Ethanol will be chosen more particularly;

- polyols having in particular from 2 to 20 carbon atoms, preferably from 2 to 6 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, hexylene glycol, 1,3-propanediol, pentylene glycol, simple sugars, water-soluble polyalkylene glycols; and

- their mixtures.

Preferably, the composition according to the invention comprises at least one polyol, preferably chosen from glycerol, 1,3-propanediol and their mixtures.

They are generally present at concentrations ranging from 0.5 to 40% by weight, more preferably from 3 to 30%, and preferably from 5% to 10% by weight relative to the total weight of the composition.

The composition preferably comprises from 20 to 90% by weight of water relative to the total weight of the composition, preferably from 30 to 90% by weight, preferably from 40 to 70% by weight.

Thickening polymer

The composition according to the invention may comprise at least one thickening polymer.

According to a particular embodiment, these polymers are water-soluble, water-dispersible or water-swellable.

Among the thickening polymers that can be used, mention may be made of natural polymers, crosslinked homopolymers or copolymers of acrylic or methacrylic acid, homopolymers of 2-acrylamido-2-methylpropanesulfonic acid, crosslinked or not, or their salts, and copolymers of acrylamido-2-methylpropanesulfonic acid or its salts and one or more nonionic monomers, crosslinked or not, alone or in mixtures.

Natural polymers include xanthan gum, sclerotium gum, carob bean gum, and cellulose and its derivatives such as hydroxyethylcellulose.

Among the crosslinked homopolymers of acrylic acid, mention may be made of those crosslinked by an allyl ether of alcohol of the sugar series, such as for example the products sold under the names CARBOPOL 980, 981, 954, 2984 and 5984 by the company NOVEON or the products sold under the names SYNTHALEN M and SYNTHALEN K by the company 3 VSA. These polymers are also called carbomers.

Preferably, an at least partially neutralized acrylic acid homopolymer is used. The homopolymer used according to the invention is in particular chosen from sodium polyacrylates and potassium polyacrylates. Sodium polyacrylate is preferably used.

Examples of these acrylic polymers which are already neutralized before their implementation include:

- sodium polyacrylates such as those marketed under the name Cosmedia SP® containing 90% dry matter and 10% water, or Cosmedia SPL® in reverse emulsion containing approximately 60% dry active matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company Cognis;

- partially neutralized sodium polyacrylates, in particular in the form of an inverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel® EM by the company BASF; and

- their mixtures.

It is also possible to use a polymer of acrylic acid that has not been previously neutralized, which is then partially or completely neutralized before implementation by any appropriate means and in particular by adding any base such as sodium hydroxide, potash, an alkanolamine such as triethanolamine. In this way, sodium polyacrylates are obtained in particular. Potassium polyacrylates are also suitable for the present invention.

Among the crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylate, mention may be made of the product sold under the name VISCOATEX 538C by the company COATEX which is a crosslinked copolymer of (meth)acrylic acid and C1-C4 ethyl acrylate in aqueous dispersion at 38% active material, or the product sold under the name ACULYN 33 by the company ROHM & HAAS which is a crosslinked copolymer of acrylic acid and ethyl acrylate in aqueous dispersion at 28% active material. More particularly, mention may be made of the crosslinked methacrylic acid/ethyl acrylate copolymer in the form of a 30% aqueous dispersion manufactured and sold under the name CARBOPOL AQUA SF-1 by the company NOVEON.

Homopolymers of 2-acrylamido-2-methyl-propanesulfonic acid (AMPS®, Lubrizol monomer) or their salts may be crosslinked or not. Such a homopolymer may have a number average molecular weight ranging from 1000 to 20,000,000 g/mol, preferably ranging from 20,000 to 5,000,000 and more preferably still from 100,000 to 1,500,000 g/mol.

In particular, 2-acrylamido-2-methylpropanesulfonic acid and its partially or completely neutralized forms are used.

When the polymers are crosslinked, the crosslinking agents can be chosen from the polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by radical polymerization. Examples of crosslinking agents which may be mentioned are divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di(meth)acrylate, trimethylol propane triacrylate, methylene bis acrylamide, methylene bis methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallyl ethylenediamine, tetraallyloxy ethane, trimethylol propane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, as well as allyl esters of phosphoric acid derivatives and/or vinylphosphonic, or mixtures of these compounds.

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

The homopolymer only contains monomers with a sulfonic group and, if it is crosslinked, one or more crosslinking agents.

Preferred 2-acrylamido-2-methylpropanesulfonic acid homopolymers are generally characterized by comprising, randomly distributed:

(a) from 90 to 99.9% by weight of units of the following general formula:

in which X ⁺ denotes a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, at most 10 mol% of the X ⁺ cations being able to be H ⁺ protons;

and crosslinking units originating from at least one monomer having at least two olefinic double bonds, the weight proportions being defined relative to the total weight of the polymer.

The more particularly preferred homopolymers according to the invention comprise from 98 to 99.5% by weight of units of formula (I) above and from 0.2 to 2% by weight of crosslinking units.

Polymers of this type include, in particular, the crosslinked and neutralized homopolymer of 2-acrylamido 2-methylpropane sulfonic acid, marketed by the company Clariant under the trade name “Hostacerin AMPS®” (INCI name: Ammonium Polyacryldimethyltauramide).

The polymer may also be an amphiphilic homopolymer (or hydrophobically modified homopolymer) chosen from random amphiphilic polymers of 2-acrylamido-2-methylpropanesulfonic acid modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, such as those described in document WO-A-00/31154, which are grafted homopolymers.

Copolymers of acrylamido-2-methyl propane sulfonic acid or its salts and one or more nonionic monomers may be crosslinked or non-crosslinked.

When the polymers are crosslinked, the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by radical polymerization. Such agents are described above.

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

The copolymers according to the invention are obtained from AMPS® (Lubrizol monomer) and one or more hydrophilic or hydrophobic ethylenically unsaturated nonionic monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above.

The 2-acrylamido-2-methylpropanesulfonic acid monomer of the copolymer contained in the composition according to the invention is in free form or is partially or totally neutralized by a mineral base (soda, potash, ammonia) or an organic base such as mono-, di-, or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine as well as the mixture of these compounds.

Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer is partially or completely salified in the form of an ammonium or sodium salt.

Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer is fully salified, preferably in the form of ammonium or sodium salt.

AMPS® (Lubrizol monomer) copolymers contain one or more nonionic monomers selected from water-soluble ethylenically unsaturated monomers, hydrophobic monomers, or mixtures thereof.

Among the non-ionic water-soluble monomers, we can cite for example:

- (meth)acrylamide,

- N-vinylacetamide and N-methyl N-vinylacetamide,

- N-vinylformamide and N-methyl N-vinylformamide,

- maleic anhydride,

- vinylamine,

- N-vinyllactams comprising a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,

- vinyl alcohol of formula CH ₂ =CHOH,

- water-soluble vinyl monomers of the following formula (2):

in which:

- R ₁₅ is selected from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇

- X ₂ is chosen from alkyl oxides of the type –OR ₁₆ where R ₁₆ is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 6 carbons, optionally substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether.

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

Preferably, the water-soluble monomer is chosen from acrylamide, vinylpyrrolidone, hydroxyalkyl(meth)acrylates, more particularly vinylpyrrolidone.

As copolymers of AMPS® (Lubrizol monomer) in accordance with the invention with hydrophilic monomers, we can cite for example:

- copolymers of acrylamido-2-methyl propane sulfonic acid and vinylpyrrolidone such as in particular the commercial product ARISTOFLEX AVC sold by CLARIANT;

- cross-linked acrylamide/sodium acrylamido-2-methyl propane sulfonate copolymers, such as that used in the commercial product SEPIGEL 305® (INCI name: Polyacrylamide/C ₁₃ -C ₁₄ Isoparaffin/ Laureth-7) or that used in the commercial product sold under the name SIMULGEL 600® (INCI name: Acrylamide / Sodium Acryloyldimethyltaurate / Isohexadecane / Polysorbate-80) by the company SEPPIC;

- copolymers of AMPS® (Lubrizol monomer) and hydroxyethyl acrylate, such as for example the AMPS® sodium/hydroxyethyl acrylate copolymer such as that used in the commercial product sold under the name SIMULGEL NS® by the company SEPPIC or under the name SEPINOV EMT10 by the company SEPPIC;

- hydrophobically modified AMPS® copolymers such as the copolymer known under the INCI name: AMMONIUM ACRYLOYLDIMETHYLTAURATE / STEARETH-25 METHACRYLATE CROSSPOLYMER sold under the trade name ARISTOFLEX HMS by the company CLARIANT.

Preferably, the thickening polymer is AMPS® sodium/hydroxyethyl acrylate copolymer.

The concentration of thickening polymer (i.e. active material) generally ranges from 0.05 to 10% by weight relative to the total weight of the composition, and preferably from 0.1 to 5% by weight, preferably from 0.2 to 1% by weight.

The compositions according to the invention may be in the form of a gel, or in the form of an emulsion, in particular an oil-in-water emulsion.

When the composition according to the invention is in the form of an oil-in-water emulsion, it comprises an oily phase dispersed in an aqueous phase.

Oily phase

The term "oily phase" designates, according to the invention, a liquid phase at 20-25°C and at a pressure of 1.01325 10 ⁵ Pa. Such an "oily phase" generally comprises at least one oil. The term "oil" designates any fatty substance in liquid form at room temperature (20 to 25°C) and at atmospheric pressure (760 mm Hg).

Preferably, the composition according to the invention comprises an oily phase. Preferably, the composition according to the invention is an oil-in-water emulsion.

The amount of oily phase can range for example from 1 to 50% by weight, preferably from 3 to 45% by weight, preferably from 5% to 40% by weight relative to the total weight of the composition.

The oily phase may comprise at least one oil, in particular a cosmetic oil. It may also contain other fatty substances.

As oils which can be used in the composition of the invention, we can cite for example:

- hydrocarbon oils of animal origin, such as perhydrosqualene;

- hydrocarbon oils of plant origin, such as liquid triglycerides of fatty acids containing 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn, soybean, pumpkin, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado oils, triglycerides of caprylic/capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, coco-caprylate/caprate (esterified oil from coconut oil), jojoba oil, shea butter oil;

- synthetic esters and ethers, in particular of fatty acids, such as oils of formulas R1COOR2 and R1OR2 in which R1 represents the residue of a fatty acid containing from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or not, containing from 3 to 30 carbon atoms, such as for example Purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearylmalate, triisocetyl citrate, fatty alcohol heptanoates, octanoates, decanoates; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetraisostearate or dipentaerythrityl pentaisononanoate;

- linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, branched-chain hydrocarbon oils containing 10 to 20 carbon atoms such as isohexadecane, isododecane, isoparaffins and their mixtures, petroleum jelly, polydecenes, polyisobutenes, hydrogenated polyisobutenes such as, for example, Parléam® marketed by NIPPON OIL FATS, PANALANE H-300 E marketed by AMOCO, VISEAL 20000 marketed by SYNTEAL, REWOPAL PIB 1000 marketed by WITCO, or PARLEAM LITE marketed by NOF Corporation;

- partially hydrocarbon and/or silicone fluorinated oils such as those described in document JP-A-2-295912;

- silicone oils such as volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, pendant or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes; or

- their mixtures.

As indicated above, the composition according to the invention may comprise, in the oily phase, other ingredient(s). These additional ingredients may be chosen from other fatty substances such as waxes, lipophilic polymers such as semi-crystalline polymers and their mixtures.

According to a particular embodiment, the composition in accordance with the invention comprises at least one semi-crystalline polymer.

Among the semi-crystalline polymers, mention may be made of polymers having a functionalized crystalline side chain (in English "functionalized side chain crystalline polymers" or FSCC) and polymers having a crystalline side chain (in English "side chain crystalline polymers" or SCC). As examples of such polymers, mention may be made of poly C10-30 alkyl acrylate (TEGO SP 13-1 or TEGO SP 13-6), Behenyl Acrylate/Hydroxyethylacrylate copolymers and Stearyl Acrylate/Hydroxyethylacrylate copolymers.

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

in which:

R ₁ , independently of each other, are chosen from alkyl or alkenyl radicals;

with at least 60% by weight of the R ₁ groups being radicals selected from stearyl and behenyl radicals, the weight percentage relating to the sum of all the R ₁ groups present in the polymer;

the weight ratio of the sum of all hydroxyethyl acrylate units to the sum of all acrylate units bearing the R ₁ group is from 1:30 to 1:1; and

the sum of the total of units A and B is at least 95% by weight of the total weight of the polymer.

Preferably, R ₁ consists of alkyl radicals, preferably C16-C22 alkyl radicals, and more preferably stearyl radicals (C18) or behenyl radicals (C22).

Preferably, at least 70% by weight of the R ₁ groups are stearyl or behenyl radicals, preferably at least 80% by weight, and more preferably at least 90% by weight.

According to a preferred embodiment, all R ₁ groups are behenyl radicals.

According to another preferred embodiment, all R ₁ groups are stearyl radicals.

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

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

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

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

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

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

The polymer used according to the invention can be prepared by polymerization of monomer of formula CH2=CH-COO-R ₁ , R ₁ having the meaning described above, and 2-hydroxyethyl acrylate.

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

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

The lipophilic polymer(s) used in the context of the invention and as described above may be present in the composition in an amount of active material ranging from 0.05 to 10% by weight, preferably from 0.1% to 5% by weight, and better still from 0.2 to 2% by weight relative to the total weight of the composition.

Surfactants

The composition according to the invention may comprise at least one surfactant, preferably chosen from nonionic surfactants.

Preferably, the surfactant is chosen from polyethoxylated fatty alcohols. The fatty alcohol is preferably a C ₁₆ -C ₂₂ fatty alcohol comprising from 2 to 100 ethylene oxide units. The fatty chain of the alcohol may be chosen from stearyl, behenyl, arachidyl, palmityl, cetyl units and mixtures thereof, such as cetearyl, and preferably a stearyl chain.

The number of ethylene oxide units may range from 2 to 50, preferably from 2 to 30, and more preferably from 2 to 25.

Preferably, the surfactant is chosen from stearyl alcohol comprising 2 ethylene oxide units (steareth-2), stearyl alcohol comprising 20 ethylene oxide units (steareth-20) and mixtures thereof.

Preferably, the composition comprises a mixture of steareth-2 and steareth-20.

The surfactant(s) may be present in the composition according to the invention in a total content ranging from 0.1% to 7% by weight, relative to the total weight of the composition, and preferably ranging from 0.5% to 5% by weight, and preferentially ranging from 1% to 4% by weight.

Photostabilizer

The composition according to the invention may comprise at least one photostabilizer.

The term "light stabilizer" means an organic compound that prevents UV filters from undergoing degradation processes upon UV radiation or by destabilization due to the presence of other compounds, which may be for example other UV filters. The light stabilizer protects the UV filter either by structural or geometric means or by dissipating the energy of the UV filter in order to reduce the possibility of destabilization.

Preferably, the light stabilizer is selected from butyloctyl salicylate, benzotriazolyl dodecyl p-cresol, ethylhexyl methoxycrylene, polyester-8, diethylhexyl syringylidenemalonate, trimethoxybenzylidene pentanedione, diethylhexyl 2,6-naphthalate, polyester-25 and mixtures thereof.

Butyloctyl salicylate is a synthetic ester of salicylic acid and 2-butyloctanol. It is marketed under the name HallBrite BHB® by Hallstar.

Benzotriazolyl dodecyl p-cresol is marketed by BASF under the name Tinogard® TL.

Ethylhexyl methoxycrylene is marketed by Hallstar under the name SolaStay® S1.

Polyester-8 is a copolymer of adipic acid and neopentyl glycol terminated with cyanodiphenyl propenoic acid with a molecular weight of approximately 1900 daltons. It is notably marketed under the name Polycrylene® by Hallstar.

Diethylhexyl syringylidenemalonate is a stabilizer for light-sensitive ingredients. It has the formula:

It is notably marketed by Merck KGaA under the name Oxynex® ST Liquid.

Trimethoxybenzylidene pentanedione is marketed as Synoxyl HSS by Sytheon.

Diethylhexyl 2,6-naphthalate is a light stabilizer and emollient. It is marketed by Symrise under the name Corapan TQ.

Polyester-25 is a bis-methoxycrylene/octyldodecyl adipic acid/methylpropanediol copolymer. It is marketed by Hallstar under the name SolaStay® P1.

Preferably, the composition according to the invention comprises a mixture of photostabilizers, preferably a mixture of ethylhexyl methoxycrylene and diethylhexyl syringylidenemalonate, optionally with butyloctyl salicylate.

The amount of photostabilizer(s) may range for example from 0.5 to 15% by weight, preferably from 1 to 10% by weight, preferably from 1.3% to 6% by weight relative to the total weight of the composition.

According to a particular embodiment, the composition according to the invention further comprises cosmetically acceptable active ingredients and/or excipients, such as preservatives, sequestrants, acids and/or bases.

By "cosmetically acceptable" we mean compatible with the skin and/or its appendages, which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness, redness), likely to discourage the consumer from using this composition.

Among the preferred sequestrants, mention may be made of salts of ethylenediaminedisuccinic acid.

Ethylenediaminedisuccinic acid is a compound with the following formula:

Preferably, the salt of ethylenediaminedisuccinic acid is selected from alkali metal salts, such as potassium salts and sodium salts, ammonium salts, and amine salts. The alkali metal salts of ethylenediaminedisuccinic acid are more particularly preferred.

Preferably, the salt of ethylenediaminedisuccinic acid used according to the invention is trisodium ethylenediaminedisuccinate.

Such a compound is, for example, that marketed under the name Natrlquest® E30 by the company Innospec Active Chemicals, or that marketed under the name Octaquest E30® by the company Octel Performance Chemicals.

Finally, the present invention also relates to a method for non-therapeutic cosmetic treatment of keratin materials, preferably the skin, comprising the application to said keratin materials of a composition according to the invention. Such a method aims in particular to protect keratin materials, and in particular the skin, against UV radiation.

Concrete, but in no way limiting, examples illustrating the invention will now be given.

In the examples, the temperature is ambient (20°C) and expressed in degrees Celsius unless otherwise indicated, and the pressure is atmospheric pressure unless otherwise indicated.

In the examples, the quantities of the ingredients of the compositions are given in % by weight relative to the total weight of the composition (% w/w).

Examples:

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

Determination of molecular weight by gel permeation chromatography (GPC):

The sample is prepared by making a solution of the polymer at 10 mg/ml in tetrahydrofuran. The sample is placed in an oven at 54 °C for 10 minutes and then in an oscillating shaker for 60 minutes to aid dissolution. Upon visual inspection, the sample appears completely dissolved in the solvent.

The prepared sample was analyzed using two 300 x 7.5 mm polypore columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, a tetrahydrofuran mobile phase and refractive index detection. The sample was filtered through a 0.45 µm nylon filter before being injected into the liquid chromatograph. The standards used for calibration are the Easi Vial narrow polystyrene (PS) standards from Agilent Technologies.

Polystyrene standards ranging from 2,520,000 to 162 Daltons were used for calibration.

The system is equipped with a PSS SECcurity 1260 RI detector. The polystyrene calibration curve was used to determine the average molecular weight. The recording of the diagrams and the determination of the different molecular weights was done by the Win GPC Unichrom 81 program.

Determination of the melting point by differential scanning calorimetry (or DSC):

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

Behenyl acrylate / 2-hydroxyethyl acrylate copolymer (Polymer 1):

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

Molecular weight: Mn = 7300 g/mol, Mw = 21000, Mw/Mn = 2.8.

Melting point: 65°C.

Stearyl acrylate / 2-hydroxyethyl acrylate copolymer (Polymer 2):

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

Molecular weight: Mn = 7500 g/mol, Mw = 19000, Mw/Mn = 2.6.

Melting point: 49°C.

B/ Examples of formulations

Example 1: Measurement of SPF and UVAPF of comparative compositions and according to the invention

Comparative compositions C1 and C2, and according to the invention F1, were prepared by the protocol below:

Heat the fatty phase B1 to 80°C. Add phase B2 (ZnO) and leave to homogenize for 20 min under rotor stator, then maintain at 65°C; we obtain phase B.

Place the aqueous phase A1 in the manufacturing tank while stirring, heat to 65°C. Add phase A2, the mixture should have gained viscosity; we obtain phase A.

Emulsify with stirring at 65°C for 10 minutes, with addition of phase B to phase A. Cool to 35°C/40°C with stirring.

Ingredients C1
(% w/w) C2
(% w/w) F1
(%p/p) Phase Water Qsp 100 Qsp 100 Qsp 100 A1 TRISODIUM ETHYLENEDIAMINE DISUCCINATE (in 30% aqueous solution)
(NatrIquest E30 from Innospec Performance Chemicals) 0.15 0.15 0.15 A1 PROPANEDIOL 3 3 3 A1 GLYCERIN 7 7 7 A1 Xanthan gum 0.2 0.2 0.2 A2 HYDROXYETHYL ACRYLATE/SODIUM ACRYLOYLDIMETHYL TAURATE COPOLYMER 0.3
(0.26% in my) 0.3
(0.26% in my) 0.3
(0.26% in my) A2 BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(BEMT, Tinosorb S from BASF) 6 - 6 B1 DIETHYLHEXYL SYRINGYLIDENEMALONATE 0.5 0.5 0.5 B1 ETHYLHEXYL METHOXYCRYLENE
(SolaStay S1 by Hallstar) 1 1 1 B1 BUTYLOCTYL SALICYLATE 3 3 3 B1 COCO-CAPRYLATE/CAPRATE 21.62 23 17 B1 Dispersing agent(s) 0.5 0.5 0.5 B1 Wax 1 1 1 B1 C12-22 ALKYL ACRYLATE/HYDROXYETHYLACRYLATE COPOLYMER
Polymer 1 of the synthesis examples A/ above 1.5 1.5 1.5 B1 (co-)Curators Qs Qs Qs STEARETH-2 0.5 0.5 0.5 B1 STEARETH-20 1.5 1.5 1.5 B1 Zinc oxide (ZnO) coated with hydrated silica and silicones (MZ-510 HPSX from Tayca) - 9.23
(7% in my) 9.23
(7% in my) B2

m.a.: active ingredient

Filtering efficiency evaluation protocol

In-vitro: The sun protection factor (SPF) is determined according to the “in vitro” method described by M. Pissavini et al in International Journal of Cosmetic Science, 40, 263–268 (2018), based on the initial absorbance.

The in vitro UVA protection factor (UVAPF) of a sunscreen product against UVA radiation is calculated mathematically by in vitro spectral modeling according to the ISO 24443:2012 (Fr) protocol.

Each composition is applied to six rough PMMA plates, in the form of a homogeneous and regular deposit at a rate of 1 mg/cm2. Each composition is spread using an automated robot that makes regular and uniform movements on three plates called HD6 (molded granular plates) and three plates called SB6 (sandblasted granular plates). The plate is weighed before and after spreading. Once the six plates are spread, they are placed in Thermo-Masters in the dark at 25 °C for 30 minutes. The measurements are carried out using the UV-1000S spectrophotometer from Labsphère. Nine measurements per plate are carried out, then analyzed using an Excel spreadsheet providing the SPF and UVAPF values of the measured composition.

The results are as follows:

Formula C1 C2 F1 S PF s theoretical man of C1+C2 Filter system 6% BEMT 7% ZnO 6% BEMT
7% ZnO SPF in glass 43 8.7 69.8 51.7 UVAPF 18.9 4.2 27.4 23.1 Critical wavelength (nm) 371 369 372

The combination of ZnO and BEMT produces a synergistic effect allowing to obtain an unexpected efficiency and higher than that predicted by the sum of the efficiency of each filter taken individually: the SPF and the UVAPF are higher than the value expected in view of the intrinsic efficiency of each filter.

Example 2: Measurement of the dose effect of comparative compositions and those according to the invention

Comparative compositions A1* to A5* below were prepared as described in Example 1.

Ingredients A1* A2* A3* A4* A5* Phase Water Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100 A1 TRISODIUM ETHYLENEDIAMINE DISUCCINATE (in 30% aqueous solution)
(NatrIquest E30 from Innospec Performance Chemicals) 0.15 0.15 0.15 0.15 0.15 A1 PROPANEDIOL 3 3 3 3 3 A1 GLYCERIN 3 3 3 3 3 A1 Xanthan gum 0.2 0.2 0.2 0.2 0.2 A2 HYDROXYETHYL ACRYLATE/SODIUM ACRYLOYLDIMETHYL TAURATE COPOLYMER 0.3
(0.26% in my) 0.3
(0.26% in my) 0.3
(0.26% in my) 0.3
(0.26% in my) 0.3
(0.26% in my) A2 BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(BEMT, Tinosorb S from BASF) 6 - - - - B1 DIETHYLHEXYL SYRINGYLIDENEMALONATE 0.5 0.5 0.5 0.5 0.5 B1 ETHYLHEXYL METHOXYCRYLENE
(SolaStay S1 by Hallstar) 1 1 1 1 1 B1 COCO-CAPRYLATE/CAPRATE 23.59 27 26 24.25 23.04 B1 Polyhydroxystearic acid 0.5 0.5 0.5 0.75 0.9 B1 Wax 1 1 1 1 1 B1 C12-22 ALKYL ACRYLATE/HYDROXYETHYLACRYLATE COPOLYMER
Polymer 1 of the synthesis examples A/ above 1.5 1.5 1.5 1.5 1.5 B1 Conservatives Qs Qs Qs Qs Qs STEARETH-2 0.5 0.5 0.5 0.5 0.5 B1 STEARETH-20 1.5 1.5 1.5 1.5 1.5 B1 Zinc oxide coated with triethoxycaprylylsilane
Z-COTE HP1 (BASF) - 5.13
(5% in my) 7.18
(7% in my) 10.25
(10% in my) 12.31
(12% in my) B2 Citric acid Qs Qs Qs Qs Qs

The dose effect of these compositions is measured; the results are as follows:

Formula A1* A2* A3* A4* A5* SPF in vitro 31.9 6.2 9 12.6 15.7 Critical wavelength (nm) 371 375 376 376 376 UVAPF 15.8 5.3 7.6 10.4 12.5

Compositions B1 to B4 according to the invention below were prepared as described in Example 1.

Ingredients B1 B2 B3 B4 Phase Water Qsp 100 Qsp 100 Qsp 100 Qsp 100 A1 TRISODIUM ETHYLENEDIAMINE DISUCCINATE (in 30% aqueous solution)
(NatrIquest E30 from Innospec Performance Chemicals) 0.15 0.15 0.15 0.15 A1 PROPANEDIOL 3 3 3 3 A1 GLYCERIN 3 3 3 3 A1 Xanthan gum 0.2 0.2 0.2 0.2 A2 HYDROXYETHYL ACRYLATE/SODIUM ACRYLOYLDIMETHYL TAURATE COPOLYMER 0.3
(0.26% in my) 0.3
(0.26% in my) 0.3
(0.26% in my) 0.3
(0.26% in my) A2 BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(BEMT, Tinosorb S from BASF) 6 6 6 6 B1 DIETHYLHEXYL SYRINGYLIDENEMALONATE 0.5 0.5 0.5 0.5 B1 ETHYLHEXYL METHOXYCRYLENE
(SolaStay S1 by Hallstar) 1 1 1 1 B1 COCO-CAPRYLATE/CAPRATE 21 20 18.25 17.04 B1 Polyhydroxystearic acid 0.5 0.5 0.75 0.9 B1 Wax 1 1 1 1 B1 C12-22 ALKYL ACRYLATE/HYDROXYETHYLACRYLATE COPOLYMER
Polymer 1 of the synthesis examples A/ above 1.5 1.5 1.5 1.5 B1 Conservatives Qs Qs Qs Qs STEARETH-2 0.5 0.5 0.5 0.5 B1 STEARETH-20 1.5 1.5 1.5 1.5 B1 Zinc oxide coated with triethoxycaprylylsilane
Z-COTE HP1 (BASF) 5.13
(5% in my) 7.18
(7% in my) 10.25
(10% in my) 12.31
(12% in my) B2 Citric acid Qs Qs Qs Qs

The dose effect of these compositions is measured; the results are as follows:

Formula B1 B2 B3 B4 SPF in vitro 65.5 71.5 72.6 81.2 SPF theoretical sum 38.1
(A1*+A2*) 40.9
(A1*+A3*) 44.5
(A1*+A4*) 47.6
(A1*+A5*) Critical wavelength (nm) 373 374 375 375 UVAPF 31.3 35.3 37.3 42.1

The results show that the synergy is verified for the different levels of zinc oxides tested.

Claims (13)

Composition, preferably cosmetic, comprising, in a physiologically acceptable medium:
from 4.5% to 10% by weight relative to the total weight of composition of 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), and
from 5% to 25% by weight relative to the total weight of zinc oxide composition,
the composition comprising less than 3% by weight relative to the total weight of the composition of other UV filter(s). Composition according to claim 1, characterized in that it comprises less than 2% by weight, preferably less than 1% by weight relative to the total weight of the composition of other UV filter(s). Composition according to claim 1 or 2, characterized in that it is completely free of other UV filter(s). Composition according to one of the preceding claims, characterized in that it comprises from 5% to 9% by weight relative to the total weight of the composition, preferably from 5.5% to 8% by weight, preferably from 5.7% to 7% by weight of 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine). Composition according to one of the preceding claims, characterized in that the zinc oxide is in the form of particles which may be coated or uncoated; preferably the coated pigments are pigments which 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, polyethylene, silicones, hydrated silica, proteins, alkanolamines, silicon oxides, triethoxycaprylylsilane, metal oxides or sodium hexametaphosphate. Composition according to one of the preceding claims, characterized in that the zinc oxide is chosen from uncoated zinc oxide pigments, ZnO coated with polymethylhydrogensiloxane, ZnO dispersed in C12-15 alkyl benzonate, ZnO coated with a silicone-grafted acrylic polymer and dispersed in cyclodimethylsiloxane, ZnO coated with hydrated silica, ZnO coated with hydrated silica, triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone and hydrogen dimethicone (H-Me-Si), ZnO coated with stearic acid or isostearic acid, ZnO coated with a silicone oil and ZnO coated with triethoxycaprylylsilane. Composition according to one of the preceding claims, characterized in that it comprises from 5% to 20% by weight relative to the total weight of the composition, preferably from 5% to 15% by weight, preferably from 5% to 10% by weight of zinc oxide. Composition according to one of the preceding claims, characterized in that it comprises an aqueous medium comprising at least water and optionally at least one other organic solvent soluble in water, at 25°C, chosen from C1-C4 monoalkanols and polyols having in particular from 2 to 20 carbon atoms, preferably from 2 to 6 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, hexylene glycol, 1,3-propanediol, pentylene glycol, simple sugars, water-soluble polyalkylene glycols and mixtures thereof; preferably, the composition comprises at least one polyol, preferably chosen from glycerol, 1,3-propanediol and mixtures thereof. Composition according to one of the preceding claims, characterized in that it is in the form of a gel, or in the form of an emulsion, in particular an oil-in-water emulsion, and comprises an oily phase dispersed in an aqueous phase. Composition according to claim 9, characterized in that the oily phase comprises at least one oil chosen from:
- hydrocarbon oils of animal origin, such as perhydrosqualene;
- hydrocarbon oils of plant origin, such as liquid triglycerides of fatty acids containing 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn, soya, pumpkin, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado oils, triglycerides of caprylic/capric acids, coco-caprylate/caprate, jojoba oil, shea butter oil;
- synthetic esters and ethers, in particular of fatty acids, such as oils of formulas R1COOR2 and R1OR2 in which R1 represents the residue of a fatty acid containing from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or not, containing from 3 to 30 carbon atoms, such as for example Purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearylmalate, triisocetyl citrate, fatty alcohol heptanoates, octanoates, decanoates; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetraisostearate or dipentaerythrityl pentaisononanoate;
- linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, branched-chain hydrocarbon oils containing 10 to 20 carbon atoms such as isohexadecane, isododecane, isoparaffins and their mixtures, petroleum jelly, polydecenes, polyisobutenes or hydrogenated polyisobutenes;
- partially hydrocarbon and/or silicone fluorinated oils;
- silicone oils such as volatile or non-volatile polymethylsiloxanes with a linear or cyclic silicone chain, liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, pendant or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes; and
- their mixtures. Composition according to claim 9 or 10, characterized in that the oily phase comprises at least one other fatty substance, preferably chosen from waxes, semi-crystalline polymers and their mixtures; preferably the semi-crystalline polymer is chosen from poly C10-30 alkyl acrylate, Behenyl Acrylate/Hydroxyethylacrylate copolymers and Stearyl Acrylate/Hydroxyethylacrylate copolymers. Composition according to one of the preceding claims, characterized in that it comprises at least one photostabilizer, preferably chosen from butyloctyl salicylate, benzotriazolyl dodecyl p-cresol, ethylhexyl methoxycrylene, polyester-8, diethylhexyl syringylidenemalonate, trimethoxybenzylidene pentanedione, diethylhexyl 2,6-naphthalate, polyester-25 and mixtures thereof; preferably it comprises a mixture of photostabilizers, preferably a mixture of ethylhexyl methoxycrylene and diethylhexyl syringylidenemalonate, optionally with butyloctyl salicylate. Process for non-therapeutic cosmetic treatment of keratin materials, preferably the skin, comprising the application to said keratin materials of a composition according to one of the preceding claims.