EP4633597A1

EP4633597A1 - Composition comprising a uv-screening agent, a suitably selected lipophilic polymer and a carrageenan

Info

Publication number: EP4633597A1
Application number: EP23821247.6A
Authority: EP
Inventors: Manon DORCHIES; Salahddine SOUDANI; Stéphane DOUEZAN
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2022-12-16
Filing date: 2023-12-07
Publication date: 2025-10-22
Also published as: WO2024126253A1; CN121099983A; FR3143344A1

Abstract

The present invention relates to a composition, and in particular a cosmetic or dermatological composition, comprising at least one UV-screening agent, at least one suitably selected lipophilic polymer and at least one carrageenan, and to the use of said composition in the cosmetic and dermatological fields, in particular for caring for and treating keratin materials, and in particular for caring for, protecting and/or making up the skin of the body or the face, or for haircare.

Description

Composition comprising a UV-screening agent, a suitably selected lipophilic polymer and a carrageenan

The present invention relates to a composition, and in particular a cosmetic or dermatological composition, comprising at least one UV-screening agent, at least one suitably selected lipophilic polymer and at least one carrageenan, and to the use of said composition in the cosmetic and dermatological fields, in particular for caring for and treating keratin materials, and notably for caring for, protecting and/or making up the skin of the body or the face, or for haircare.

A wide variety of photoprotective compositions are already known to date for protecting keratin materials, and more particularly the skin, against the harmful effects induced by UVA and/or UVB radiation. They mostly contain a combination of several organic or inorganic UV-screening agents, conveyed in an oily phase and/or in an aqueous phase as anti-UV active agent and are generally proposed in a presentation form of emulsion or gel type.

It is known that radiation with wavelengths of between 280 nm and 400 nm permits tanning of the human epidermis and that radiation with wavelengths of between 280 and 320 nm, known as UV-B rays, harms the development of a natural tan. Such exposure is also liable to induce impairment in the biomechanical properties of the epidermis, which is reflected by the appearance of wrinkles, leading to premature ageing of the skin.

It is also known that UV-A rays with wavelengths of between 320 and 400 nm penetrate more deeply into the skin than UV-B rays. UV-A rays cause immediate and persistent browning of the skin. Daily exposure to UVA rays, even for a short period, under normal conditions can lead to degradation of the collagen and elastin fibres, which is reflected by a change in the skin’s microrelief, the appearance of wrinkles and non-uniform pigmentation (liver spots, or heterogeneity of the complexion).

Protection against UVA and UVB radiation is therefore necessary. An effective photoprotective product must protect against both UVA and UVB radiation.

Many photoprotective compositions have been proposed to date to overcome the effects induced by UVA and/or UVB radiation. They generally contain organic UV screening agents and/or inorganic UV screening agents, which function according to their intrinsic chemical nature and according to their intrinsic properties by absorption, reflection or scattering of the UV radiation. They generally contain mixtures of liposoluble organic screening agents and/or of water-soluble UV-screening agents combined with metal oxide pigments such as titanium dioxide or zinc oxide.

Many cosmetic compositions intended to limit darkening of the skin, and to improve the colour and uniformity of the complexion have been proposed to date. It is well known in the field of antisun products that such compositions can be obtained by using UV-screening agents, and in particular UVB-screening agents. Some compositions may also contain UVA-screening agents. This screening system must cover UVB protection for the purpose of limiting and controlling the neosynthesis of melanin promoting overall pigmentation, but must also cover UVA protection in order to limit and control the oxidation of the already existing melanin resulting in darkening of the skin.

The conditions under which an antisun composition is used are extremely varied and depend on the activities practised by the consumer. Use on the beach is very common, leading to applications on both dry and wet skin, notably after swimming.

However, on wet skin, the active substances, such as the UV-screening agents, tend to become diluted, impairing their skin protection properties.

Among the different textures of existing antisun compositions, the majority are difficult to apply to wet skin. Specifically, spreading the composition on wet skin may result in a significant whitening effect, which is not very pleasant for the consumer, and inhomogeneity of the protective film, which affects the level of skin protection. The production of a homogeneous, transparent appearance then requires the composition to be massaged into the skin for a very long time.

Thus, there is a real need to provide an antisun composition that does not have the drawbacks mentioned above, i.e. an antisun composition that is stable, compatible with application to both dry and wet skin, and with a high level of in vivo sun protection efficacy (SPF), whether the product is applied to dry or wet skin.

The Applicant has discovered, surprisingly, that a composition comprising one or more UV-screening agents, one or more suitably selected lipophilic polymers, and one or more polysaccharides chosen from carrageenans, allows the abovementioned objectives to be achieved; notably to obtain a screening composition which has excellent compatibility with wet skin, which allows it to be applied to both dry and wet skin, and which leads to a high SPF on both dry and wet skin.

Disclosure of the invention

One subject of the present invention is thus a composition, and in particular a cosmetic or dermatological composition, comprising:

a) at least one UV-screening agent;

b) at least one lipophilic polymer comprising monomer units of formulae (A) and (B):

in which:

R1, independently of each other, are chosen from alkyl or alkenyl radicals;

with at least 60% by weight of the groups R1 being radicals chosen from stearyl and behenyl radicals, the weight percentage being relative to the sum of all the groups R1 present in the polymer;

the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the group R1 ranges from 1:30 to 1:1; and

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

c) at least one carrageenan.

Unlike conventional antisun compositions, the composition of the invention allows satisfactory application to wet skin combined with a high level of sun protection.

Specifically, the composition of the invention has good working properties. It spreads easily on both wet and dry skin and allows uniform application without the appearance of a whitish film on the skin.

The composition also makes it possible to screen out UV rays to a high SPF, consequently resulting in better skin protection, whether the composition is applied to dry or wet skin.

The composition of the invention is also stable over time.

Moreover, the composition of the invention has good cosmetic properties, notably in terms of the tacky feel. Specifically, it is pleasant and sparingly tacky.

The present invention also relates to a non-therapeutic cosmetic process for caring for and/or making up a keratin material, comprising the application, to the surface of said keratin material, of at least one composition according to the invention as defined previously.

A subject of the present invention is notably a process for the non-therapeutic cosmetic treatment of the skin, in particular human skin, notably dry skin and/or wet skin, against UV radiation, which consists in applying to said skin the composition according to the invention as defined previously.

The invention also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the keratin material, of at least one composition according to the invention as defined previously.

The invention also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material, comprising the application, to the surface of the keratin material, of at least one composition according to the invention as defined previously.

Other subjects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

According to the present invention, the term “stable over time” refers to a composition which, after one month, preferably after two months, of storage at a temperature ranging from 4°C to 45°C, does not show any macroscopic change in colour, odour or viscosity, or any variation in pH, and also no variation in microscopic appearance.

For the purposes of the present invention, the term “good compatibility on wet skin” means that when the composition is applied at a rate of 2 mg.cm^-2 to the skin or a skin substitute substrate that has been previously wetted, a homogeneous film that is transparent to the naked eye is obtained.

For the purposes of the present invention, the term “SPF” means the sun protection factor, which measures the level of protection against UVB rays. The SPF value corresponds to the ratio between the minimum time it takes to obtain a sunburn with an antisun composition to the time it takes without a product. More specifically, the “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) may be evaluated in vitro using the Labsphere® spectrophotometer. The sheet is the material onto which the antisun composition is applied. Polymethyl methacrylate (PMMA) sheets have proven to be ideal for this protocol.

Evaluation of the Sun Protection Factor (SPF) of the compositions may also be performed in vivo according to the protocol ISO/EN 24444 “Cosmetics - Sun protection test methods - in-vivo determination of the sun protection factor (SPF) (2019)”.

For the purposes of the present invention, the term “PPD” (Persistent Pigment Darkening) means the index characterizing protection against UVA rays. In particular, the PPD measures the colour of the skin observed 2 to 4 hours after exposure to UVA rays. This method has been adopted since 1996 by the Japanese Cosmetic Industry Association (JCIA) as the official test procedure for the UVA labelling of products and is frequently used by test laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin. Measurement Standards for UVA protection efficacy. Issued November 21, 1995 and effective as of January 1, 1996).

Other characteristics, aspects and advantages of the invention will emerge on reading the detailed description that follows.

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

In the context of the present invention, the term “keratin material” notably means the skin, the scalp, keratin fibres such as the eyelashes, the eyebrows, head hair, bodily hair, the nails, and mucous membranes such as the lips, and more particularly the skin and mucous membranes (of the body, face, area around the eyes, eyelids or lips, preferably of the body, face and lips).

In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ...”.

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

According to the invention, the term “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 ageing of a keratin material.

The term “organic UVA-screening agent” refers to any organic chemical molecule that is capable of absorbing at least UVA radiation in the wavelength range between 320 and 400 nm; said molecule may also additionally absorb UVB radiation in the wavelength range between 280 and 320 nm.

The term “organic UVB-screening agent” refers to any organic chemical molecule that is 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” means any kinetically stable macroscopically homogeneous composition comprising at least two mutually immiscible phases, one being the continuous dispersing phase and the other being dispersed in said continuous phase in the form of droplets. The two phases are kinetically stabilized using at least one emulsifying system comprising, in general, at least one emulsifying surfactant.

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

Detailed description of the invention UV-screening agents

The composition in accordance with the invention comprises at least one UV-screening agent.

The UV-screening agent(s) may be chosen from lipophilic organic UV-screening agents, hydrophilic organic UV-screening agents and inorganic UV-screening agents.

Lipophilic organic UV-screening agents

The term “lipophilic organic screening agent” means any cosmetic or dermatological organic compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid fatty phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.

The lipophilic organic screening agents are notably chosen from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, in particular those cited in patent US 5 624 663; benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds, as described in patents EP 669 323 and US 2 463 264; methylenebis(hydroxyphenylbenzotriazole) compounds, as described in patent applications US 5 237 071, US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 119; benzoxazole compounds, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 101 62 844; screening polymers and screening silicones, such as those described notably in patent application WO 93/04665; α-alkylstyrene-based dimers, such as those described in patent application DE 198 55 649; 4,4-diarylbutadiene compounds, as described in patent applications EP 0 967 200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133 980 and EP 133 981, and mixtures thereof.

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

As examples of lipophilic organic photoprotective agents, mention may be made of those denoted hereinbelow under their INCI name and/or their chemical name:

Cinnamic compounds:

Ethylhexyl methoxycinnamate notably sold 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:

Butylmethoxydibenzoylmethane notably sold under the trade name Parsol® 1789 by the company DSM Nutritional Products,

Salicylic compounds:

Homosalate sold under the name Parsol® HMS by the company DSM Nutritional Products,

Ethylhexyl salicylate sold under the name Neo Heliopan® OS by the company Symrise,

β,β-Diphenylacrylate compounds:

Octocrylene, notably sold under the trade name Uvinul® N 539 T by the company BASF,

Benzophenone compounds:

Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul® M 40 by BASF,

Hexyl (diethylamino-hydroxybenzoyl)benzoate, sold under the trade name Uvinul® A Plus or, as a mixture with ethylhexyl methoxycinnamate, under the trade name Uvinul® A Plus B by the company BASF,

Benzylidenecamphor compounds:

4-Methylbenzylidenecamphor, sold under the name Eusolex® 6300 by the company Merck,

Phenylbenzotriazole compounds:

Drometrizole trisiloxane manufactured under the name Mexoryl® XL by the company Noveal,

Methylenebis(hydroxyphenylbenzotriazole) compounds:

Methylenebis(benzotriazolyl)tetramethylbutylphenol notably 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), having the INCI name Phenylene Bis-Diphenyl Triazine,

- bis-Ethylhexyloxyphenol methoxyphenyl triazine sold under the trade name Tinosorb® S by the company BASF,

- Ethylhexyl triazone, notably sold under the trade name Uvinul® T150 by the company BASF,

- Diethylhexylbutamidotriazone sold under the trade name Uvasorb® HEB by the company 3V Sigma,

- the symmetrical triazine screening agents substituted with naphthalenyl groups or polyphenyl groups, described in patent US 6 225 467, patent application WO 2004/085 412 (see compounds 6 and 9) or the document “Symmetrical Triazine Derivatives” IP.COM IPCOM000031257 Journal, INC West Henrietta, NY, US (20 September 2004),

Anthranilic compounds:

Menthyl anthranilate sold under the trade name Neo Heliopan® MA by the company Symrise,

Benzalmalonate compounds:

Polyorganosiloxane bearing benzalmalonate functions, such as Polysilicone-15, sold under the trade name Parsol SLX® by the company Hoffmann-LaRoche.

Hydrophilic organic UV-screening agents

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

The term “water-soluble organic screening agent” means any organic screening agent that can be fully dissolved in molecular form in a liquid aqueous phase or that can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

The term “water-dispersible organic screening agent” means any organic screening agent that is capable of forming, in a liquid aqueous phase, a homogeneous suspension of particles with a volume-mean size of less than 100 microns. The volume-mean size is determined by laser diffraction granulometry.

Among the water-soluble organic UVA-screening agents that may be used according to the present invention, mention may be made of benzene-1,4-bis(3-methylidene-10-camphorsulfonic) acid (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) and the various salts thereof, notably described in patent applications FR-A-2528420 and FR-A-2639347. Mention may notably be made of benzene-1,4-bis(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) such as the product which is manufactured under the name Mexoryl® SX by the company Noveal.

These screening agents correspond to the general formula (I) below:

in which F denotes a hydrogen atom, an alkali metal or a radical NH(R₁)₃ ⁺ in which the radicals R₁, which may be identical or different, denote a hydrogen atom, a C₁ to C₄ alkyl or hydroxyalkyl radical or a group Mn⁺, Mn⁺ denoting a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn⁺ preferably denoting a metal cation chosen from Ca²⁺, Zn²⁺, Mg²⁺, Ba²⁺, Al³⁺ and Zr⁴⁺. It is clearly understood that the compounds of formula (I) above can give rise to the “cis-trans” isomer around one or more double bonds and that all the isomers fall within the context of the present invention.

Among the water-soluble organic UVA-screening agents that may be used according to the present invention, mention may also be made of compounds including at least two benzazolyl groups bearing sulfonic groups, such as those described in patent application EP-A-0669323.

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

The compounds including at least two benzazolyl groups in accordance with the invention correspond to the general formula (II) below:

(II)

in which:

- Z represents an organic residue of valency (l + n) including one or more double bonds placed such that it completes the system of double bonds of at least two benzazolyl groups as defined inside the square brackets so as to form a fully conjugated assembly;

- X’ denotes S, O or NR⁶;

- R¹denotes a hydrogen atom, a C₁ to C₁₈ alkyl, a C₁ to C₄ alkoxy, a C₅ to C₁₅ aryl, a C₂ to C₁₈ acyloxy, or a group SO₃Y or COOY;

- the radicals R², R³, R⁴ and R⁵, which may be identical or different, denote a nitro group or a radical R¹;

- R⁶ denotes a hydrogen atom, a C₁ to C₄ alkyl or a C₁ to C₄ hydroxyalkyl;

- Y denotes a hydrogen atom, Li, Na, K, NH₄, 1/2Ca, 1/2Mg, 1/3Al or a cation resulting from the neutralization of a free acid group with an organonitrogen base;

- m is 0 or 1;

- n is a number from 2 to 6;

- l is a number from 1 to 4;

- with the proviso that 1 + n does not exceed the value 6.

Among these compounds, preference will most particularly be given to 1,4-bis(benzimidazolyl)phenylene-3,3’,5,5’-tetrasulfonic acid (INCI name: Disodium Phenyl Dibenzimidazole Tetrasulfonate) or a salt thereof, having the following structure, notably sold under the name Neo Heliopan® AP by the company Symrise:

Preferably, the water-soluble screening agent that is capable of absorbing UVA rays is benzene-1,4-bis(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) such as the product which is manufactured under the name Mexoryl SX by Noveal.

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

As examples of water-soluble organic UVB-screening agents, mention may be made of phenylbenzimidazole compounds, such as 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid) notably sold under the trade name Eusolex 232^® by Merck.

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

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

The term “alkanolamine” means a C₂-C₁₀ compound comprising at least one primary, secondary or tertiary amine function and at least one alcohol, generally primary alcohol, function. As suitable alkanolamines, mention may be made of 2-amino-2-(hydroxymethyl)-1,3-propanediol (INCI name: Tromethamine) and triethanolamine.

Among the water-dispersible organic screening agents, mention may be made of the following screening agents.

Benzophenone compounds:

1,1’-(1,4-Piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]methanone] (CAS 919803-06-8), such as described in patent application WO 2007/071 584; this compound advantageously being used in micronized form (volume-mean size of 0.02 to 2 µm), which may be obtained, for example, according to the micronization process described in patent applications GB-A-2 303 549 and EP-A-893 119, and notably in the form of an aqueous dispersion.

Methylenebis(hydroxyphenylbenzotriazole) compounds:

Methylenebis(benzotriazolyl)tetramethylbutylphenol,

in the form of an aqueous dispersion of micronized particles having a volume-mean particle size ranging from 0.01 to 5 μm, and more preferentially from 0.01 to 2 μm, and more particularly from 0.020 to 2 μm, with at least one alkylpolyglycoside surfactant having the structure C_nH_2n+1O(C₆H₁₀O₅)_xH in which n is an integer from 8 to 16 and x is the average degree of polymerization of the (C₆H₁₀O₅) unit and ranges from 1.4 to 1.6, such as the aqueous dispersions described in patent GB-A-2 303 549, notably the product sold under the trade name Tinosorb® M by the company BASF, or

in the form of an aqueous dispersion of micronized particles having a volume-mean particle size ranging from 0.02 to 2 μm, more preferentially 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 polyglycerol ester having a degree of polymerization of glycerol of at least 5, such as the aqueous dispersions described in patent application WO 2009/063392, notably the product sold under the name Tinosorb WPGL by the company BASF,

Triazine compounds:

- Bis(ethylhexyloxyphenol)methoxyphenyl triazine in its water-dispersible form, having the INCI name Bis(ethylhexyloxyphenol)methoxyphenyl triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer, under the trade name Tinosorb® S LiteAqua by the company BASF,

- symmetrical triazine screening agents substituted with naphthalenyl groups or polyphenyl groups used in micronized form (mean particle size of 0.02 to 3 µm) which may be obtained, for example, via the micronization process described in patent applications GB-A-2 303 549 and EP-A-893119, and notably in aqueous dispersion form, notably 2,4,6-tris(biphenyl)triazine and 2,4,6-tris(terphenyl)triazine sold under the name Tinosorb® A2B by the company BASF and included in patent applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992 and WO 2006/034985,

Benzoxazole compounds:

2-[4-(1,3-Benzoxazol-2-yl)phenyl]-1,3-benzoxazole, having the CAS No. 904-39-2.

Inorganic UV-screening agents

The inorganic UV screening agents that may be used in accordance with the present invention are metal oxide pigments. More preferentially, the inorganic UV-screening agents of the invention are metal oxide particles with a mean elementary particle size of less than or equal to 0.5 µm, more preferentially between 0.005 and 0.5 µm, even more preferentially between 0.01 and 0.2 µm, better still between 0.01 and 0.1 µm and more particularly between 0.015 and 0.05 µm. They are notably described in appendix VI, updated on 22/09/2021, of the European regulation on cosmetic products number 1223/2009, but are not limited to that list.

They may notably be chosen from titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, or mixtures thereof.

Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0 518 773. Commercial pigments that may be mentioned include the products sold by the companies Croda, Tayca and Merck.

The metal oxide pigments may be coated or uncoated.

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

The coated pigments are more particularly titanium oxides that have been coated:

- with hydrated silica, such as the product MT-100WP from the company Tayca,

- with silica and iron oxide, such as the product Sunveil F® from the company Ikeda,

- with silica and alumina, such as the products MT 500 SA® and MT 100 SA® from the company Tayca, and Tioveil™ AQ-N from the company Croda,

- with alumina, such as the product TTO-55 (A)® from the company Ishihara,

- with alumina and aluminium stearate, such as the products MT 100 TV®, MT 100 Z® and MT-01® from the company Tayca, the product Solaveil CT100 from the company Croda and the product Eusolex T-AVO® from the company Merck,

- with silica, alumina and alginic acid, such as the product MT-100 AQ® from the company Tayca,

- with alumina and aluminium laurate,

- with iron oxide and iron stearate,

- with zinc oxide and zinc stearate,

- with silica and alumina and treated with a silicone, such as the products MTY-500SAS® or Microtitanium Dioxide MT-100 SAS® from the company Tayca,

- with silica, alumina, aluminium stearate and treated with a silicone,

- with silica and treated with a silicone,

- with alumina and treated with a silicone, such as the product TTO-55(S)® from the company Ishihara,

- with triethanolamine,

- with stearic acid, such as the product TTO-55 (C)® from the company Ishihara,

- with sodium hexametaphosphate,

- TiO₂ treated with octyl trimethyl silane,

- TiO₂ treated with a polydimethylsiloxane,

- anatase/rutile TiO₂ treated with a polydimethylhydrogenosiloxane,

- TiO₂ coated with triethylhexanoin, aluminium stearate and alumina sold under the trade name Solaveil™ CT-200 by Croda,

- TiO₂ coated with aluminium stearate, alumina and silicone sold under the trade name Solaveil™ CT-12W by Croda,

- TiO₂ coated with lauroyl lysine,

- TiO₂ coated with C9-C15 fluoro alcohol phosphate and aluminium hydroxide.

Mention may also be made of TiO₂ pigments doped with at least one transition metal such as iron, zinc or manganese and more particularly manganese. Preferably, said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric/caprylic acids. The oily dispersion of titanium oxide particles may also include one or more dispersants, for instance a sorbitan ester, for instance sorbitan isostearate, or a polyoxyalkylenated fatty acid ester of glycerol, for instance TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium oxide particles includes at least one dispersant chosen from polyoxyalkylenated fatty acid esters of glycerol. Mention may be made more particularly of the oily dispersion of TiO₂ particles doped with manganese in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate and sorbitan isostearate having the INCI name: titanium dioxide (and) TRI-PPG-3 myristyl ether citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate, or the product sold under the trade name Optisol™ OTP-1 by the company Croda.

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

The uncoated zinc oxide pigments are, for example:

- those sold under the name Z-Cote® by the company BASF;

- those sold under the name NanoArc® Zinc Oxide by the company Nanophase Technologies.

The coated zinc oxide pigments are, for example:

- ZnO coated with polymethylhydrogenosiloxane;

- Solaveil™ CZ-100 from Croda, dispersed in C12-15 alkyl benzoate (INCI: Zinc Oxide (and) C12-15 Alkyl Benzoate (and) Polyhydroxystearic Acid (and) Isostearic Acid);

- those sold under the name Daitopersion Zn-60VA® by the company Daito Kasei (dispersions in C9-12 alkane with a dispersant);

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

The uncoated cerium oxide pigments may be, for example, those sold under the name Rhodigard® W185 by the company Solvay.

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

When the composition in accordance with the invention comprises inorganic UV-screening agents, coated or uncoated titanium oxide pigments are particularly preferred.

According to a particular embodiment, the total amount of UV-screening agents present in the composition is greater than or equal to 15% by weight relative to the total weight of the composition. According to a preferred embodiment, the total amount of UV-screening agents present in the composition is between 15% and 35% by weight and preferably between 18% and 25% by weight relative to the total weight of the composition.

For the purposes of the present invention, the term “total amount of UV screening agent” means the sum of the active material concentrations of each of the UV-screening agents present in the composition, in particular lipophilic organic UV-screening agents, hydrophilic organic UV-screening agents and inorganic UV-screening agents.

Lipophilic polymers

The composition in accordance with the invention comprises at least one lipophilic polymer comprising monomer units of formulae (A) and (B):

in which:

R₁, independently of each other, are chosen from alkyl or alkenyl radicals;

with at least 60% by weight of the groups R₁ being radicals chosen from stearyl and behenyl radicals, the weight percentage being relative to the sum of all the groups R₁ present in the polymer;

the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the group R₁ ranges from 1:30 to 1:1; and

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

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

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

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

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

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

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

The polymer has a number-average molecular weight Mn ranging from 2000 to 9000 g/mol, preferably ranging from 5000 to 9000 g/mol. The number-average molecular weight may be measured via the gel permeation chromatography method, for example according to the method described in the example hereinbelow.

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

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

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

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

The polymerization may be performed according to known methods, such as solution polymerization or emulsion polymerization.

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

The lipophilic polymer(s) used in the context of the invention and as described previously may be present in the composition in an active material amount 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.

Carrageenans

The composition according to the invention comprises at least one carrageenan.

Carrageenans are polysaccharides extracted from algae, and are used in the food industry as gelling agents. In particular, they are sulfated polysaccharides which constitute the cell walls of various red algae, from which they may be obtained.

Among these red algae, mention may be made, in a non-limiting manner, of Kappaphycus alvarezii, Eucheuma denticulatum, Eucheuma spinosum, Chondrus crispus, Betaphycus gelatinum, Gigartina skottsbergii, Gigartina canaliculata, Sarcothalia crispata, Mazzaella laminaroides, Hypnea musciformis, Mastocarpus stellatus and Iridaea cordata.

Carrageenans include long galactan chains formed by disaccharide units.

They are composed of alternating (1→3) β-D-galactopyranose (G unit) and (1→4) α-galactopyranose (D unit) or 3,6-anhydro-a-galactopyranose (AnGal unit). Each sugar unit may be sulfated one or more times in position 2, 3, 4 or 6.

Methyl groups, pyruvic acids and also other sugar units may also be grafted onto the basic structures described previously.

Carrageenans were initially subdivided into subfamilies according to their solubility in KCl, and then according to the number and position of the sulfate groups and the presence of 3’,6’-anhydro bridges on the galactopyranosyl residues.

There are at least fifteen listed carrageenans, the structure of which depends on the algae of origin and the extraction method.

Among the most common are the carrageenans mentioned below:

These carrageenans are thus often obtained in the form of mixtures of different structures such as, but not limited to, mixtures of κΘ, κι, κμ forms.

The carrageenans that can be used may notably be chosen from carrageenans of the μ, κ, v, ι, λ, Θ type and mixtures thereof, in any proportions. Carrageenans of λ form, κ form or ι form, or mixtures thereof, will notably be used.

According to a particular embodiment, the composition in accordance with the invention comprises at least one carrageenan predominantly comprising ι forms, or exclusively in ι form.

According to another particular embodiment, the composition in accordance with the invention comprises at least one carrageenan predominantly comprising λ forms, or exclusively in λ form.

Preferably, the composition in accordance with the invention comprises at least one carrageenan predominantly comprising ι forms, or exclusively in ι form and at least one carrageenan predominantly comprising λ forms, or exclusively in λ form. In this case, the ratio between the carrageenans predominantly comprising ι forms or exclusively in ι form and the carrageenans predominantly comprising λ forms or exclusively in λ form is between 0.2 and 5, preferentially between 0.75 and 1.25.

The term “predominantly” means that the percentage of this type of chain in the composition of the product is greater than or equal to 50%, and this proportion may be greater than or equal to 80% in certain embodiments.

According to a particular embodiment, the carrageenans according to the invention are carrageenans derived from Chondrus crispus or Kappaphycus alvarezii. Preferably, the carrageenans are derived from Chondrus crispus.

The molecular weight of the carrageenans that are useful for the present invention may be between 300 and 100×10⁶ daltons. Their molecular weight may preferentially be between 10×10³ daltons and 10×10⁶ daltons.

Carrageenans that are particularly suitable for use according to the invention may notably be extracted from Chondrus crispus, such as those sold by the company Cargill. In particular, a carrageenan according to the invention may be the product Satiagum UPC 410 sold by the company Cargill.

Other carrageenans that are suitable for use according to the invention are the products AEC Carrageenan Gel and AEC Carrageenan Powder sold by the company A&E Connock (Perfumery & Cosmetics), the products Gelcarin GP379 and Gelcarin GP812, Gelcarin GP911, SeaSpen PF, Viscarin GP109, Viscarin GP209 and Viscarin GP328 sold by the company FMC Corporation, and the products Genugel Carrageenan and Genuvisco Carrageenan sold by the company CP Kelco.

The carrageenan(s) are generally present in the composition in accordance with the invention in a content of between 0.2% and 10.0% by weight, better still between 0.5% and 7.0% by weight, relative to the total weight of the composition.

Waxes

According to a particular embodiment, the composition in accordance with the invention comprises at least one wax.

The wax(es) are generally a lipophilic compound that is solid at room temperature (25°C), with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30°C, which may be up to 200°C and usually up to 120°C.

For the purposes of the invention, the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in the standard ISO 11357-3; 1999. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments.

Preferably, the waxes that may be used in the composition of the present invention have a heat of fusion ∆Hf of greater than or equal to 70 J/g.

Preferably, the waxes include at least one crystallizable part, which is visible by X-ray observation.

The measuring protocol is as follows:

A sample of 5 mg of wax placed in a crucible is subjected to a first temperature ramp passing from -20°C to 120°C, at a heating rate of 10°C per minute, it is then cooled from 120°C to -20°C at a cooling rate of 10°C per minute and is finally subjected to a second temperature ramp passing from -20°C to 120°C at a heating rate of 5°C per minute. During the second temperature rise, the following parameters are measured:

- the melting temperature or melting point (m.p.) of the wax, as mentioned previously, corresponding to the temperature of the most endothermic peak observed in the melting curve, representing the variation of the difference in power absorbed as a function of the temperature,

- ∆Hf: the heat of fusion of the wax, corresponding to the integral of the entire melting curve obtained. This enthalpy of fusion of the wax is the amount of energy required to cause the compound to change from the solid state to the liquid state. It is expressed in J/g.

When they are present in the composition in accordance with the invention, the wax(es) may be present in a total content ranging from 1% to 10% by weight relative to the total weight of the fatty phase, better still from 2% to 7% by weight relative to the total weight of the fatty phase.

When they are present in the composition in accordance with the invention, the wax(es) may be present in a total content ranging from 0.1% to 7% by weight relative to the total weight of the composition, better still from 1% to 5% by weight relative to the total weight of the composition.

According to a preferred embodiment, the composition in accordance with the invention more precisely comprises at least one hard wax.

For the purposes of the present invention, the term “hard wax” means a wax having a melting point of greater than or equal to 50°C, in particular ranging from 50 to 100°C, more preferentially between 50 and 90°C.

Advantageously, for the purposes of the present invention, the term “hard wax” means a wax having, at 20°C, a hardness of greater than 5 MPa, notably ranging from 5 to 30 MPa, preferably greater than 6 MPa, better still ranging from 6 to 25 MPa.

To perform these hardness measurements, the wax is melted at a temperature equal to the melting point of the wax + 20°C. To do this, 30 g of wax are placed in a 100 ml beaker with a diameter equal to 50 mm, which is itself placed on a magnetic stirring hotplate.

About 15 g of melted wax are poured into a stainless steel container 80 mm in diameter and 15 mm deep, preheated to 45°C in an oven. The wax is then left to recrystallize in a temperature-controlled room at 20°C for 24 hours before being measured.

The mechanical properties of the wax or wax mixture are determined in a temperature-controlled room at 20°C, using the texturometer sold under the name TA-XT2i by the company Swantech, equipped with a stainless steel cylinder 2 mm in diameter.

The measurement includes three steps: a first step after automatic detection of the surface of the sample, where the spindle moves at a measuring speed of 0.1 mm/s, and penetrates into the wax to a penetration depth of 0.3 mm, the software notes the maximum force value reached; a second “relaxation” step where the spindle remains in this position for one second and the force is noted after 1 second of relaxation; finally, a third “withdrawal” step in which the spindle returns to its initial position at a speed of 1 mm/s, and the probe withdrawal energy (negative force) is noted.

The hardness value corresponds to the maximum compression force measured in newtons divided by the area of the texturometer cylinder expressed in mm² in contact with the wax. The hardness value obtained is expressed in megapascals or MPa.

As examples of hard waxes, mention may notably be made of carnauba wax, candelilla wax, hydrogenated jojoba oil, hydrogenated palm oil, rice bran wax, sumac wax, sunflower wax, macadamia wax and hydrogenated olive oil such as Waxolive from the company Soliance, waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols such as those sold by the company Sophim under the trade names Phytowax Olive 16L55 and 18L57, waxes obtained by hydrogenation of castor oil esterified with cetyl or behenyl alcohol, for instance those sold under the trade names Phytowax Ricin 16 L 64 and Phytowax Ricin 22 L 73 by the company Sophim.

Use is preferably made of waxes of plant origin such as carnauba wax, candelilla wax, hydrogenated jojoba wax, sumac wax, the waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols, or rice bran wax.

The hard wax(es) are preferably polar.

The term “polar wax” means a wax whose solubility parameter calculated above its melting point δa is other than 0 (J/cm³)½.

In particular, the term “polar wax” means a wax whose chemical structure is formed essentially from, or even constituted of, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.

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

According to this Hansen space:

- δD characterizes the London dispersion forces derived from the formation of dipoles induced during molecular impacts;

- δp characterizes the Debye interaction forces between permanent dipoles and also the Keesom interaction forces between induced dipoles and permanent dipoles;

- δh characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.);

- δa is determined by the equation: δa = (δp² + δh²)½.

The parameters δp, δh, δD and δa are expressed in (J/cm³)½.

In addition, a composition according to the invention may comprise at least one soft wax, i.e. a wax whose melting point is strictly less than 50°C, and optionally a wax whose hardness is strictly less than 5 MPa.

However, a composition according to the invention preferably includes less than 5% by weight of soft waxes, preferably less than 2% by weight of soft waxes, and even more preferentially is free of soft waxes.

Silicone copolymers

According to a particular embodiment, the composition according to the present invention also comprises one or more silicone copolymers resulting from the copolymerization of at least one monomer of carboxylic acid and alcohol ester type with a C6 to C30, preferably C8 to C24, fatty chain, with at least one monomer containing a polyalkylsiloxane chain.

Among the carboxylic acid and fatty-chain alcohol ester type monomers that may be used according to the present invention, mention may notably be made of C6 to C30, preferably C8 to C24, fatty-chain alkyl acrylates, methacrylates, maleates, fumarates, itaconates and crotonates, and mixtures thereof.

Preferably, the monomer(s) of the C6 to C30 fatty-chain alcohol carboxylic acid ester type are chosen from C6 to C30, preferably C8 to C24, fatty-chain alcohol (meth)acrylic acid esters.

In other words, the monomer(s) of the carboxylic acid and C6 to C30 fatty-chain alkyl ester type are preferentially chosen from the compounds of structure (IV) and mixtures thereof:
(IV)

in which:

R1 represents a hydrogen atom or a methyl radical, and

R2 represents a linear or branched, saturated or unsaturated C6 to C30 and preferably C8 to C24 alkyl chain.

R2 advantageously represents a branched, saturated or unsaturated C8 to C24 alkyl chain.

According to a first particularly preferred embodiment, R1 represents a hydrogen atom and R2 represents a branched, saturated or unsaturated C8 to C12 alkyl chain, more preferentially a 2-ethylhexyl group.

According to a second, particularly preferred embodiment, R1 represents a hydrogen atom and R2 represents a linear, saturated or unsaturated C14 to C20 alkyl chain, more preferentially a stearyl group.

Preferably, the monomer(s) containing a polyalkylsiloxane chain are chosen from monomers of (meth)acrylic acid type esterified with a silicone group of structure (V):
(V)

in which:

R3 represents a hydrogen atom or a methyl radical, and

R4, R5, R6, R7 and R8 independently of each other, which may be identical or different, represent a linear or branched, saturated or unsaturated C1 to C30 alkyl chain,

n and m represent, independently of each other, an integer greater than or equal to 1.

Preferably, R3 represents a methyl.

Preferably, R4, R5, R6, R7 and R8, independently of each other, which may be identical or different, represent a linear or branched, saturated or unsaturated C1 to C24 and more preferentially C1 to C12 alkyl chain.

According to a particularly preferred embodiment, R3, R4, R5, R6, R7 and R8 represent a methyl.

The silicone copolymer(s) according to the present invention may optionally also comprise one or more additional monomers, and notably one or more carboxylic acid and C1 to C5 alcohol ester monomers. Preferably, the additional monomer(s) are chosen from esters of (meth)acrylic acid and of C1 to C4 alcohol and mixtures thereof, more preferentially from methyl esters of (meth)acrylic acid, butyl esters of (meth)acrylic acid, ethyl esters of (meth)acrylic acid, and mixtures thereof.

Preferably, the silicone copolymer(s) present in the composition(s) according to the present invention are chosen from copolymers resulting from the copolymerization of at least one monomer of structure (IV) in which R1 represents a hydrogen atom and R2 represents a saturated or unsaturated, branched C7 to C24 alkyl chain, with at least one monomer of structure (V) in which R3, R4, R5, R6, R7 and R8 all represent a methyl group, n is an integer between 1 and 6, and m represents an integer greater than or equal to 1; and mixtures thereof.

The silicone copolymer(s) are generally obtained according to the usual methods of polymerization and grafting, for example by radical polymerization of at least one monomer of polydimethylsiloxane type comprising at least one polymerizable radical group (for example on one of the ends of the chain or at both ends), as described previously, and at least one carboxylic acid alkyl ester monomer with a C7 to C30 fatty chain, as described, for example, in US-A-5 061 481 and US-A-5 219 560.

The silicone copolymer(s) obtained generally have a molecular weight ranging from about 3000 to 200 000, and preferably from about 5000 to 100 000.

The silicone copolymer(s) used in the composition according to the present invention may be in their native form or in a form dispersed in a solvent such as lower alcohols including from 2 to 8 carbon atoms, such as isopropyl alcohol, or oils, such as preferably volatile silicone oils, such as cyclopentasiloxane or a dimethicone, or even hydrocarbon-based oils, such as liquid paraffins, or isoparaffins, such as isododecane.

Preferably, the solvent is chosen from oils, and more preferentially from cyclopentasiloxane, linear pentadimethylsiloxane and mixtures thereof.

The silicone copolymer(s) that may be used in the composition according to the present invention are preferentially chosen from stearyl methacrylate, methyl methacrylate and propyl methacrylate copolymers containing a polydimethylsiloxane chain; methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and propyl methacrylate copolymers containing a polydimethylsiloxane chain; and mixtures thereof.

In particular, mention may be made of the acrylate/dimethicone copolymers (INCI name) sold by the company Shin-Etsu under the trade names KP-561 (copolymer of stearyl methacrylate, methyl methacrylate and propyl methacrylate containing a polydimethylsiloxane group); KP-541 in which the copolymer is dispersed in isopropyl alcohol; KP-545 in which the copolymer of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and propyl methacrylate bearing a polydimethylsiloxane group is dispersed in decamethyl cyclopentasiloxane; KP-545L in which the copolymer of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and propyl methacrylate bearing a polydimethylsiloxane group is dispersed in linear pentadimethylsiloxane; and KP-550 in which the copolymer of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and propyl methacrylate bearing a polydimethylsiloxane group is dispersed in isododecane.

Preferably, the silicone copolymer(s) present in the composition according to the invention are chosen from the products sold under the trade names KP-545 and KP-545L by the company Shin-Etsu.

The amount of the silicone copolymer(s), when they are present in the composition of the invention, preferably ranges from 0.1% to 10% by weight, more preferentially from 0.5% to 5% relative to the total weight of the composition.

Fatty phase

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

The fatty phase may consist of any fatty substance conventionally used in the cosmetic or dermatological fields: it notably comprises the wax(es) defined previously and may comprise at least one oil. The fatty phase also comprises the lipophilic screening agent(s), and also the fatty alcohol(s) present in the composition according to the invention.

The term “oil” means any fatty substance that is in liquid form at room temperature (20-25°C) and atmospheric pressure (760 mmHg). These oils may be volatile or non-volatile.

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

The term “non-volatile oil” means an oil that remains on the skin or the keratin fibre at room temperature and atmospheric pressure for at least several hours, and that notably has a vapour pressure of less than 10^-3 mmHg (0.13 Pa).

For the purposes of the present invention, the term “hydrocarbon-based oil” means any oil predominantly including 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, fluoro, carboxylic acid and/or alcohol groups.

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

As non-volatile hydrocarbon-based oils that may be used according to the invention, mention may notably be made of:

(i) hydrocarbon-based oils of plant origin, such as glyceride triesters, which are generally fatty acid triesters of glycerol, the fatty acids of which may have varied chain lengths from C₄ to C₂₄, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil and musk rose oil; or alternatively caprylic/capric acid triglycerides such as those sold by the company Stéarinerie Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;

(ii) synthetic ethers containing from 10 to 40 carbon atoms;

(iii) linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene, such as Parleam, squalane and mixtures thereof;

(iv) synthetic esters, such as the oils of formula RCOOR’ in which R represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R’ represents a hydrocarbon-based chain that is notably branched, containing from 1 to 40 carbon atoms, with the proviso that R + R’ ≥ 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, such as the product sold under the trade name Finsolv TN® or Witconol TN® by the company Witco or Tegosoft TN® by the company Evonik Goldschmidt, 2-ethylphenyl benzoate, such as the commercial product sold under the name X-Tend 226® by the company ISP, isopropyl lanolate, 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, alcohol or polyalcohol octanoates, decanoates or ricinoleates, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters; citrates or tartrates, such as linear C12-C13 dialkyl tartrates, such as those sold under the name Cosmacol ETI® by the company Enichem Augusta Industriale, and also linear C14-C15 dialkyl tartrates such as those sold under the name Cosmacol ETL® by the same company; acetates;

(v) fatty alcohols that are liquid at room temperature, bearing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or 2-undecylpentadecanol;

(vi) higher C12-C22 fatty acids such as oleic acid, linoleic acid or linolenic acid;

(vii) carbonates, such as dicaprylyl carbonate, such as the product sold under the name Cetiol CC® by the company Cognis;

and mixtures thereof.

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

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

Mention may also be made of the alkanes described in the Cognis patent applications WO 2007/068 371 or WO 2008/155 059 (mixtures of different alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut kernel or palm oil. Mention may be made of the mixtures of n-undecane (C11) and n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof.

Other volatile hydrocarbon-based oils, for instance petroleum distillates, notably those sold under the name Shell Solt® by the company Shell, may also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof.

The non-volatile silicone oils may be notably chosen from non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes including alkyl or alkoxy groups which are pendent and/or at the end of the silicone chain, these groups each containing from 2 to 24 carbon atoms, or phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxysilicates.

Volatile silicone oils that may be mentioned, for example, include volatile linear or cyclic silicone oils, notably those with a viscosity ≤ 8 centistokes (8×10^-6 m²/s) and notably containing from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may notably be made of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

Mention may also be made of linear volatile alkyltrisiloxanes such as:

3-butyl-1,1,1,3,5,5,5-heptamethyltrisiloxane,

3-propyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and

3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane.

Use may also be made of volatile fluoro oils, such as nonafluoromethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoro-pentane, and mixtures thereof.

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

Another fatty substance that may be present in the oily phase may be, for example:

- a fatty acid chosen from fatty acids including from 8 to 30 carbon atoms, different from the fatty-chain amino acids as defined previously, such as stearic acid, lauric acid, palmitic acid and oleic acid;

- a gum chosen from silicone gums (dimethiconol);

- a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, fatty acid triglycerides and derivatives thereof;

- and mixtures thereof.

The overall oily phase, including all the lipophilic substances of the composition capable of being dissolved in this same phase, including the lipophilic screening agents, represents from 20% to 60% by weight and preferentially from 25% to 45% by weight, relative to the total weight of the composition.

Aqueous phase

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

The aqueous phase contains water and optionally other water-soluble or water-miscible organic solvents.

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

The water-soluble or water-miscible solvents that are suitable for use in the invention comprise, besides the short-chain alcohols as defined previously, diols or polyols, such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol and sorbitol, and mixtures thereof.

According to one particular form of the invention, the overall aqueous phase, including all the hydrophilic substances of the composition which are capable of being dissolved in this same phase, including hydrophilic screening agents, represents from 40% to 80% by weight and preferably from 55% to 75% by weight relative to the total weight of the composition.

Cosmetic active ingredients

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

As examples of cosmetic active agents, mention may be made of moisturizing agents such as protein hydrolysates, polyglycerol-3; natural extracts; vitamins such as vitamin A (retinol), vitamin E (tocopherol), vitamin C (ascorbic acid), vitamin B5 (panthenol), vitamin B3 (niacinamide), and derivatives of said vitamins (in particular esters) and mixtures thereof; urea; caffeine; salicylic acid and derivatives thereof; α-hydroxy acids such as lactic acid or glycolic acid and derivatives thereof; retinoids such as carotenoids and vitamin A derivatives; extracts of algae, fungi, plants, yeasts and bacteria; enzymes; tensioning agents; agents acting on the microcirculation, and mixtures thereof.

According to a particular embodiment of the invention, the composition comprises at least one moisturizer. Said moisturizer is preferably polyglycerol-3.

A person skilled in the art can readily adjust the amount of cosmetic active principle according to the intended use of the composition according to the present invention.

Additional adjuvants or additives

The composition of the present invention may also comprise conventional cosmetic adjuvants or additives, for example fragrances, chelating agents (for example, tetrasodium glutamate diacetate and disodium EDTA), preserving agents (for example, chlorphenesin and phenoxyethanol) and bactericides, additional thickeners (such as acrylamide/sodium acryloyldimethyltaurate copolymer, polysaccharides other than carrageenans, notably xanthan gum), pH regulators (for example triethanolamine, citric acid and sodium hydroxide), fillers (for example aluminium starch octenylsuccinate and polymethylsilsesquioxane) and mixtures thereof.

A person skilled in the art may select the amount of additional adjuvants or additives so as not to adversely affect the end use of the composition according to the present invention.

Presentation forms

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

According to a particular embodiment of the invention, the composition is in the form of an emulsion. It may notably 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 may be used are of the paddle or impeller, rotor-stator and HPH type.

In order to obtain stable emulsions with a low content of polymer (oil/polymer ratio > 25), it is possible to prepare the dispersion in concentrated phase and then to dilute the dispersion with the remainder of the aqueous phase.

It is also possible, via HPH (between 50 and 800 bar), to obtain stable dispersions with drop sizes that may be as low as 100 nm.

The emulsions may generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are chosen in an appropriate manner according to the emulsion to be obtained (W/O or O/W emulsion).

Examples of W/O emulsifying surfactants that may be mentioned include alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the name DC 5225 C® by the company Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyldimethicone copolyol, such as the product sold under the name Abil EM 90R® by the company Goldschmidt, and the mixture of cetyldimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, sold under the name Abil WE O9® by the company Goldschmidt. One or more coemulsifiers, which may be chosen advantageously from the group comprising polyol alkyl esters, may also be added thereto.

Mention may also be made of non-silicone emulsifying surfactants, notably alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars.

Polyol alkyl esters that may notably be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135® by the company ICI.

Examples of glycerol and/or sorbitan esters that may be mentioned include polyglyceryl isostearate, such as the product sold under the name Isolan GI 34® by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987® by the company ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986® by the company ICI, and mixtures thereof.

For the O/W emulsions, examples of nonionic emulsifying surfactants that may be mentioned include polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids and of glycerol, such as the polyethylene glycol stearic acid ester having the INCI name PEG-100 Stearate sold under the name Myrj S100-PA-(SG) by the company Croda; oxyalkylenated esters of fatty acids and of sorbitan; polyoxyalkylenated (in particular polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids, optionally in combination with an ester of fatty acid and of glycerol, such as the PEG-100 stearate/glyceryl stearate mixture sold, for example, by the company ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of fatty alcohol and of sugar, notably alkyl polyglucosides (APGs), such as decyl glucoside and lauryl glucoside, sold, for example, by the company Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol, sold, for example, under the name Montanov 68® by the company SEPPIC, under the name Tegocare CG90® by the company Goldschmidt and under the name Emulgade KE3302® by the company Henkel, and arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and of arachidyl glucoside sold under the name Montanov 202® by the company SEPPIC. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, for example as described in WO-A-92/06778.

As anionic surfactants allowing O/W emulsions to be produced, mention may be made of surfactants chosen from amino acids modified with at least one C₈-C₃₀, preferably C₈-C₂₄, hydrocarbon-based chain, and salts thereof, in particular acyl glutamic acids (INCI name: acyl glutamic acid) or a salt thereof (acyl glutamates), such as stearoyl glutamic acid or a salt thereof, notably sodium stearoyl glutamate (INCI name).

Such compounds are sold under the name Amisoft by the company Ajinomoto and notably under the references Amisoft CA, Amisoft LA, Amisoft HS 11 PF, Amisoft MK-11, Amisoft LK-11, Amisoft CK-11, or even under the name Eumulgin SG by the company Cognis.

As anionic surfactants allowing O/W emulsions to be produced, mention may also be made of hydrophobically modified polysaccharides, notably inulins modified with hydrophobic chains such as alkylcarbamate groups, in particular C8-C18 alkyl carbamate groups, and more particularly laurylcarbamate groups.

Examples of these compounds that may notably be mentioned include the product sold under the name Inutec SL1 by the company Creachem.

When it is an emulsion, the aqueous phase of this emulsion may comprise a nonionic 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, notably cosmetic treatments, for the skin, the lips and the hair, including the scalp, notably for protecting and/or caring for the skin, the lips and/or the hair, and/or for making up the skin and/or the lips.

Another subject of the present invention consists of the use of the compositions according to the invention as defined above for the manufacture of products for the cosmetic treatment of the skin, the lips, the nails, the hair, the eyelashes, the eyebrows and/or the scalp, notably care products, antisun products and makeup products.

EXAMPLES

The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the invention.

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

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

The sample is prepared by preparing 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. After visual inspection, the sample appears to be totally dissolved in the solvent.

The sample prepared was analysed using two polypore 300×7.5 mm columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, a tetrahydrofuran mobile phase and detection by refractive index. The sample was filtered through a 0.45 µm nylon filter, before being injected into the liquid chromatograph. The standards used for the 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 the 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 various molecular weights were performed 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 the standards ASTM E791 and ASTM D 34182 and the DSC calibration is performed according to standard ASTM E 9672.

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

In a 4-necked flask equipped with a side-blade mixer, an internal thermometer, two funnels, a reflux condenser, and an extension for two other 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, over the course of 60 minutes at 80°C, to 40 g of isopropanol, with stirring, after having removed the oxygen from the system by means of a nitrogen flush for 20 minutes. The mixture was stirred at 80°C for 3 hours. The solvent was then 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, a stream of demineralized water was added and the mixture was then stirred. The water was removed by vacuum distillation.

Molecular weight: Mn = 7300 g/mol, Mw = 21 000, 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 mixer, an internal thermometer, two funnels, a reflux condenser, and an extension for two other 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, over the course of 90 minutes at 80°C, to 50 g of isopropanol, with stirring, after having removed the oxygen from the system by means of a nitrogen flush for 20 minutes. The mixture was stirred at 80°C for 3 hours. The solvent was then 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, a stream of demineralized water was added and the mixture was then stirred. The water was removed by vacuum distillation.

Molecular weight: Mn = 7500 g/mol, Mw = 19 000, Mw/Mn = 2.6

Melting point: 49°C

B/ Formulation examples

In these examples, the amounts of the ingredients present in the compositions are given as weight percentages of starting materials, relative to the total weight of the composition.

Application protocol:

The application of an antisun product in the context of a photoprotection test is an important step, as it has a significant impact on the SPF result. It must therefore be standardized and performed under the most favourable conditions possible.

This application is performed on the backs of three to ten volunteers.

Areas of 30 cm² on the back will be selected between the shoulder blades and the lower back for application of the products.

These areas must be free of spots, hairs, fuzz, moles or scars and must have a uniform colour.

When positioning the volunteer, the back must be perfectly flat.

It is possible to spread the product onto dry skin and also onto wet skin, so as to observe the homogeneity of the product on contact with water.

There must be a minimum gap of 1 cm between each area. These areas, each measuring 30 cm², should be drawn between the shoulder blades and the lower back. Before taking up any sample, and unless otherwise indicated, it is important to shake the product well so as to obtain good homogenization of the emulsion.

Saturation of the sampling instrument (pipette or syringe) must be performed for taring. Double weighing is necessary so as to ensure that the correct amount of product is applied. The application pre-tests allowed the amount of product to be taken up to be evaluated, so as to ensure that 2 mg/cm² ± 2.5% are indeed applied.

It is possible to apply the product with or without a finger stall. In the case of application with a finger stall, this must be tautly stretched over the pad of the finger so as to avoid excessive loss of product and to perform the application under optimum conditions.

It is possible to perform the application with or without a finger stall for the product, but the water will always be applied with the finger stall. Throughout the application, it is recommended to use light pressure, not to retrace the movement or to remove the finger, and to adhere to an application time of between 20 and 50 seconds.

On dry skin:

The drops of product to be applied must be deposited evenly over the entire area and be of a uniform size. Care should be taken to ensure that the drops are not too close to the edges of the area to avoid excessive over-running during application.

During application, a certain number of factors need to be taken into account: the pressure applied must be light, and circular movements are essential. Ideally, it is necessary to start with small circles and widen them within the area, always in the same direction, moving gradually towards the other end of the area. To avoid excessive concentration of product in the centre, care must be taken to ensure that the product is drawn right up to the edge. Linear movements, for the finishing step, must be straight. It is recommended to perform this step quickly so as not to impair the homogeneity of the deposit.

On wet skin:

The application procedure for wet skin is identical to that for dry skin.

Water is first applied in an amount of 1.7 mg/cm² and the product in an amount of 2 mg/cm² ± 2.5%.

Apply the water evenly over the entire test area, 1.7 mg/cm² of water (40 cm² = 68 mg), in the form of regular micro-droplets. Using a finger inserted in a finger stall, spread the drops quickly (between 10 and 15 seconds maximum), using circular movements followed by a single linear stroke (following the length of the area).

When applying the antisun product, the skin should still appear damp (micro-droplets visible on the surface). The antisun product to be tested should be applied immediately according to the method described previously.

Protocol for evaluating the spreading:

Checking of the amount applied must be performed immediately after application.

Observation under a Wood lamp is necessary and allows the homogeneity of the deposit to be visualized. This evaluation is performed immediately, and then 15 minutes before UV exposure (differences may be observed at 15-minute intervals). In certain cases, an improvement in the homogeneity of the screening agents or a diffusion of the product may be found.

Protocol for evaluating the SPF in vivo on dry and wet skin

The evaluation of the Sun Protection Factor (SPF) of the compositions on dry skin and on wet skin is performed in vivo according to the method ISO/EN 24444 “Cosmetics - Sun protection test methods - in-vivo determination of the sun protection factor (SPF) (2019)”.

Composition preparation method

Place phases A1, A2 and A3 successively in a stainless steel beaker. Place the beaker on a hotplate at 55°C with Rayneri blending. Once the phase is clear, add phase A4 to the beaker and then phases A5 and A6. Leave to homogenize for a few minutes until no more white grains are visible. Finish by adding phase A7, gradually increasing the stirring speed of the Rayneri blender. Once the phase is gelled and grain-free, pour it into the cos and then switch on the paddle stirrer. The jacket should be set to 60-65°C so as to maintain the temperature.

Weigh out the fatty phase B1 in a beaker, then place it on a hotplate until it reaches 80°C and the phase is clear. Switch off the heating, add phase B2 and leave to homogenize for a few minutes.

Then, using a funnel, pour phase B1 into the cos while at the same time turning on and increasing the speed of the impeller up to 40%. Switch off the heating to the jacket.

After 10 minutes of emulsifying, start cooling so as to reach a temperature of 55°C. Once this temperature has been reached, open the COS and add phase C, which has been homogenized using a spatula. Reactivate the blades and the impeller for 10 minutes. If necessary, add 5 or 10 minutes of stirring.

When the formula is smooth and homogeneous, continue cooling while still mixing with the impeller, but at 30%, until it reaches 35°C. Add phase E by opening the COS, and start stirring (blades and impeller at 40%) for 5 minutes. Add another 5 minutes if necessary so as not to have any deposit on the walls or blades. Continue cooling until a temperature of about 30°C is reached. Add phase F through the funnel, with continued stirring, for 5 minutes.

Example 1 - Composition 1 according to the invention

Composition 1 below is prepared.

Phase	Composition	1 (invention)
A1	Water/Aqua	29.65
A2	Water/Aqua	10
A2	Trisodium ethylenediaminedisuccinate	0.31
A2	Caprylyl glycol	0.3
A2	Sodium chloride	0.11
A2	Glycerol	3
A2	Terephthalylidenedicamphorsulfonic acid (Mexoryl SX from Noveal)	1
A2	Phenylbenzimidazolesulfonic acid (Eusolex 232 from Merck)	1.5
A3	Propanediol	3
A4	Acrylates copolymer (Carbopol Aqua SF-1 from Lubrizol)	2
A5	Water/Aqua	2
A6	Triethanolamine	1.86
A7	Carrageenan (Satiagum VPCN410 from Cargill)	0.31
A7	Carrageenan (Genuvisco Carrageenan CG-131 from CP Kelco)	0.31
B1	Butylmethoxydibenzoylmethane (Parsol 1789 from DSM Nutritional Products)	4.5
B1	Bis(ethylhexyloxyphenol)methoxyphenyltriazine (Tinosorb S from BASF)	5
B1	Drometrizole trisiloxane (Mexoryl XL from Noveal)	0.5
B1	Diethylamino hydroxybenzoyl hexyl benzoate (Uvinul A Plus Granular from BASF)	0.5
B1	Ethylhexyl triazone (Uvinul T150 from BASF)	4.7
B1	C12-C-22 Alkyl acrylate/hydroxyethyl acrylate copolymer (Polymer 1)	1
B1	Isopropyl palmitate	7
B1	Diisopropyl sebacate	4
B1	Diisopropyl adipate	4
B1	Dicaprylyl ether	5
B1	Preserving agent	0.5
B2	Fragrance	0.6
B2	Tocopherol	1
C	Xanthan gum	0.1
C	Hydroxyethylcellulose	0.1
C	Acrylates/C10-30 alkyl acrylate crosspolymer (Pemulen TR-2 from Lubrizol)	0.15
E	Oxidized starch acetate	1
F	Denat. alcohol	5

Results obtained

Composition 1 in accordance with the invention applies easily and uniformly to both dry and wet skin.

Example 2 - Compositions 2 to 4 according to the invention

Compositions 2 to 4 below are prepared.

Phase	Composition	2 (invention)	3 (invention)	4 (invention)
A1	Water/Aqua	25.65	26.65	27.65
A2	Water/Aqua	10	10	10
A2	Trisodium ethylenediaminedisuccinate	0.31	0.31	0.31
A2	Caprylyl glycol	0.3	0.3	0.3
A2	Sodium chloride	0.11	0.11	0.11
A2	Glycerol	3	3	3
A2	Terephthalylidenedicamphorsulfonic acid (Mexoryl SX from Noveal)	1	1	1
A2	Phenylbenzimidazolesulfonic acid (Eusolex 232 from Merck)	1.5	1.5	1.5
A3	Propanediol	3	3	3
A4	Acrylates copolymer (Carbopol Aqua SF-1 from Lubrizol)	2	2	2
A5	Water/Aqua	2	2	2
A6	Triethanolamine	1.86	1.86	1.86
A7	Carrageenan (Satiagum VPCN410 from Cargill)	0.31	0.31	0.31
A7	Carrageenan (Genuvisco Carrageenan CG-131 from CP Kelco)	0.31	0.31	0.31
B1	Butylmethoxydibenzoylmethane (Parsol 1789 from DSM Nutritional Products)	4.5	4.5	4.5
B1	Bis(ethylhexyloxyphenol)methoxyphenyltriazine (Tinosorb S from BASF)	5	5	5
B1	Drometrizole trisiloxane (Mexoryl XL from Noveal)	0.5	0.5	0.5
B1	Diethylamino hydroxybenzoyl hexyl benzoate (Uvinul A Plus Granular from BASF)	0.5	0.5	0.5
B1	Ethylhexyl triazone (Uvinul T150 from BASF)	4.7	4.7	4.7
B1	Oryza sativa (rice) bran wax/Oryza sativa cera	1	1	1
B1	C12-C-22 Alkyl acrylate/hydroxyethyl acrylate copolymer (Polymer 1)	1	1	1
B1	Isopropyl palmitate	7	7	7
B1	Diisopropyl sebacate	4	4	4
B1	Diisopropyl adipate	4	4	4
B1	Copernicia cerifera (carnauba) wax	1	-	1
B1	Dicaprylyl ether	5	5	5
B1	Preserving agent	0.5	0.5	0.5
B2	Fragrance	0.6	0.6	0.6
B2	Tocopherol	1	1	1
C	Dimethicone (and) acrylates/dimethicone copolymer (KP-545L from Shin-Etsu)	2	2	-
C	Xanthan gum	0.1	0.1	0.1
C	Hydroxyethylcellulose	0.1	0.1	0.1
C	Acrylates/C10-30 alkyl acrylate crosspolymer (Pemulen TR-2 from Lubrizol)	0.15	0.15	0.15
E	Oxidized starch acetate	1	1	1
F	Denat. alcohol	5	5	5

Results obtained

The results of the application tests on dry and wet skin and the in vivo SPF tests are as follows.

Composition	2 (invention)	3 (invention)	4 (invention)
Application on dry skin	Easily applied. Production of a uniform film on the skin.	Easily applied. Production of a uniform film on the skin.	Easily applied. Production of a uniform film on the skin.
Application on wet skin	Easily applied. Production of a uniform film on the skin.	Some mottling and streaking throughout the area.	Some mottling and streaking throughout the area.
in vivo SPF on dry skin	65.8 ± 5.8	78.2 ± 3.0	67.7 ± 2.3
in vivo SPF on wet skin	68.1 ± 5.9	46.7 ± 5.8	51.6 ± 5.3

Compositions 2, 3 and 4 in accordance with the invention are easily applied to both dry and wet skin. The spread obtained and observed under a Wood lamp is acceptable on both dry and wet skin, with a high level of sun protection. The result is optimal with composition 2, which comprises the combination of a carnauba wax with an acrylate/dimethicone copolymer.

Comparative Example 3 - Compositions 5 to 7

Compositions 5 to 7 below are prepared.

Phase	Composition	5 (invention)	6 (comparative)	7 (comparative)
A1	Water/Aqua	25.65	26.65	26.27
A2	Water/Aqua	10	10	10
A2	Trisodium ethylenediaminedisuccinate	0.31	0.31	0.31
A2	Caprylyl glycol	0.3	0.3	0.3
A2	Sodium chloride	0.11	0.11	0.11
A2	Glycerol	3	3	3
A2	Terephthalylidenedicamphor-sulfonic acid (Mexoryl SX from Noveal)	1	1	1
A2	Phenylbenzimidazolesulfonic acid (Eusolex 232 from Merck)	1.5	1.5	1.5
A3	Propanediol	3	3	3
A4	Acrylates copolymer (Carbopol Aqua SF-1 from Lubrizol)	2	2	2
A5	Water/Aqua	2	2	2
A6	Triethanolamine	1.86	1.86	1.86
A7	Carrageenan (Satiagum VPCN410 from Cargill)	0.31	0.31	-
A7	Carrageenan (Genuvisco Carrageenan CG-131 from CP Kelco)	0.31	0.31	-
B1	Butylmethoxydibenzoylmethane (Parsol 1789 from DSM Nutritional Products)	4.5	4.5	4.5
B1	Bis(ethylhexyloxyphenol) methoxyphenyltriazine (Tinosorb S from BASF)	5	5	5
B1	Drometrizole trisiloxane (Mexoryl XL from Noveal)	0.5	0.5	0.5
B1	Diethylamino hydroxybenzoyl hexyl benzoate (Uvinul A Plus Granular from BASF)	0.5	0.5	0.5
B1	Ethylhexyl triazone (Uvinul T150 from BASF)	4.7	4.7	4.7
B1	Oryza sativa (rice) bran wax/Oryza sativa cera	1	1	1
B1	C12-C-22 Alkyl acrylate/hydroxyethyl acrylate copolymer (Polymer 1)	1	-	1
B1	Isopropyl palmitate	7	7	7
B1	Diisopropyl sebacate	4	4	4
B1	Diisopropyl adipate	4	4	4
B1	Copernicia cerifera (carnauba) wax	1	1	1
B1	Dicaprylyl ether	5	5	5
B1	Preserving agent	0.5	0.5	0.5
B2	Fragrance	0.6	0.6	0.6
B2	Tocopherol	1	1	1
C	Dimethicone (and) acrylates/dimethicone copolymer (KP-545L from Shin-Etsu)	2	2	2
C	Xanthan gum	0.1	0.1	0.1
C	Hydroxyethylcellulose	0.1	0.1	0.1
C	Acrylates/C10-30 alkyl acrylate crosspolymer (Pemulen TR-2 from Lubrizol)	0.15	0.15	0.15
E	Oxidized starch acetate	1	1	1
F	Denat. alcohol	5	5	5

Results obtained

Composition	5 (invention)	6 (comparative)	7 (comparative)
Application on dry skin	Easily applied. Production of a uniform film on the skin.	Light streaking on application	Product missing here and there in the film
Application on wet skin	Easily applied. Production of a uniform film on the skin.	Product missing here and there in the film	Some mottling and missing product throughout the area.
in vivo SPF on dry skin	65.8 ± 5.8	41.3 ± 2.6	52.3 ± 2.6
in vivo SPF on wet skin	68.1 ± 5.9	37.0 ± 2.6	41.9 ± 3.7

Composition 5 in accordance with the invention is easily applied to both dry and wet skin. The spread obtained and observed under a Wood lamp is homogeneous. The level of sun protection obtained is high.

Comparative composition 6 which does not contain any lipophilic polymer comprising monomer units of formulae (A) and (B) (C12-22 alkyl acrylate/hydroxyethyl acrylate copolymer) and comparative composition 7 which does not contain any carrageenan are more difficult to spread, both on dry and wet skin, and the spread obtained and observed under a Wood lamp is not very homogeneous, which is reflected in a less effective level of sun protection on both dry and wet skin.

Claims

Composition, notably a cosmetic or dermatological composition, comprising:
a) at least one UV-screening agent;
b) at least one lipophilic polymer comprising monomer units of formulae (A) and (B):

in which:
R₁, independently of each other, are chosen from alkyl or alkenyl radicals;
with at least 60% by weight of the groups R₁ being radicals chosen from stearyl and behenyl radicals, the weight percentage being relative to the sum of all the groups R₁ present in the polymer;
the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the group R₁ ranges from 1:30 to 1:1; and
the sum of the total of units A and B is at least 95% by weight relative to the total weight of the polymer; and
the polymer having a number-average molecular weight Mn ranging from 2000 to 9000 g/mol; and
c) at least one carrageenan.
Composition according to Claim 1, in which the UV-screening agent(s) are chosen from lipophilic organic UV-screening agents, hydrophilic organic UV-screening agents and inorganic UV-screening agents.
Composition according to either of Claims 1 and 2, in which the lipophilic organic UV-screening agent(s) are chosen from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds; methylenebis(hydroxyphenyl)benzotriazole compounds; benzoxazole compounds; screening polymers and screening silicones; α-alkylstyrene-based dimers; 4,4-diarylbutadiene compounds and mixtures thereof; preferably salicylic compounds, dibenzoylmethane compounds, benzylidenecamphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof.
Composition according to any one of Claims 1 to 3, in which the hydrophilic organic UV screening agent(s) are chosen from water-soluble organic UV screening agents and water-dispersible organic UV screening agents.
Composition according to any one of Claims 1 to 4, in which the water-soluble organic UV screening agent(s) are chosen from benzene-1,4-bis(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid); benzene-1,4-bis(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid); and salts thereof.
Composition according to any one of Claims 1 to 5, in which the water-dispersible organic UV screening agent(s) are chosen from methylenebis(benzotriazolyl)tetra-methylbutylphenol in the form of an aqueous dispersion of micronized particles with a mean particle size ranging from 0.01 to 5 μm, more preferentially from 0.01 to 2 μm and more particularly from 0.020 to 2 μm, with at least one alkylpolyglycoside surfactant having the structure C_nH_2n+1O(C₆H₁₀O₅)_xH in which n is an integer from 8 to 16 and x is the mean degree of polymerization of the (C₆H₁₀O₅) unit and ranges from 1.4 to 1.6; methylenebis(benzotriazolyl)tetramethylbutylphenol in the form of an aqueous dispersion of micronized particles having a mean particle size ranging from 0.02 to 2 μm, more preferentially 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 polyglycerol ester with a degree of polymerization of glycerol of at least 5; bis(ethylhexyloxyphenol)methoxyphenyl triazine in its water-dispersible form having the INCI name Bis(ethylhexyloxyphenol)-methoxyphenyl triazine (and) acrylates/C12-22 alkyl methacrylate copolymer; symmetrical triazine screening agents substituted with naphthalenyl groups or polyphenyl groups used in micronized form (mean particle size of 0.02 to 3 µm), notably in aqueous dispersion form, notably 2,4,6-tris(biphenyl)triazine and 2,4,6-tris(terphenyl)triazine.
Composition according to any one of Claims 1 to 6, in which, in the lipophilic acrylic polymer R1 consists of an alkyl radical, preferably of a C₁₆-C₂₂ alkyl radical, and more preferentially of a behenyl or stearyl radical.
Composition according to any one of Claims 1 to 7, in which, in the lipophilic acrylic polymer, at least 70% by weight of the groups R1 are behenyl or stearyl radicals, preferentially at least 80% by weight, more preferentially at least 90% by weight.
Composition according to any one of Claims 1 to 8, in which, in the lipophilic acrylic polymer, all the groups R1 are stearyl or behenyl radicals.
Composition according to any one of Claims 1 to 9, in which, in the lipophilic acrylic polymer, the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the group R1 ranges from 1:15 to 1:1 and preferentially ranges from 1:10 to 1:4.
Composition according to any one of Claims 1 to 10, in which the lipophilic acrylic polymer has a number-average molecular weight Mn ranging from 5000 to 9000 g/mol.
Composition according to any one of Claims 1 to 11, in which the lipophilic acrylic polymer has a melting point ranging from 40°C to 70°C and preferentially ranging from 45°C to 67°C.
Composition according to any one of Claims 1 to 11, in which, in the lipophilic acrylic polymer, at least 60% by weight of the groups R1 are stearyl radicals, and said polymer has a melting point ranging from 40 to 60°C, and preferentially ranging from 45 to 55°C.
Composition according to any one of Claims 1 to 13, in which, in the lipophilic acrylic polymer, at least 60% by weight of the groups R1 are behenyl radicals, and said polymer has a melting point ranging from 60°C to 70°C, and preferentially ranging from 63°C to 67°C.
Composition according to any one of Claims 1 to 14, in which the lipophilic acrylic polymer(s) are present in an active material content ranging from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight and preferably from 0.2% to 2% by weight relative to the total weight of the composition.
Composition according to any one of Claims 1 to 15, comprising at least one carrageenan predominantly comprising ι forms, or exclusively in ι form.
Composition according to any one of Claims 1 to 16, comprising at least one carrageenan predominantly comprising λ forms, or exclusively in λ form.
Composition according to any one of Claims 1 to 17, comprising at least one carrageenan predominantly comprising ι forms, or exclusively in ι form and at least one carrageenan predominantly comprising λ forms, or exclusively in λ form.
Composition according to any one of Claims 1 to 18, comprising at least one wax, preferably a hard wax, and even more preferentially a polar hard wax.
Composition according to any one of Claims 1 to 19, comprising at least one wax of plant origin such as carnauba wax, candelilla wax, hydrogenated jojoba wax, sumac wax, the waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty-chain alcohols, or rice bran wax.
Composition according to any one of Claims 1 to 20, comprising one or more silicone copolymers resulting from the copolymerization of at least one monomer of carboxylic acid and alcohol ester type with a C6 to C30 fatty chain, with at least one monomer containing a polyalkylsiloxane chain.
Composition according to any one of Claims 1 to 21, comprising at least one silicone copolymer chosen from stearyl methacrylate, methyl methacrylate and propyl methacrylate copolymers containing a polydimethylsiloxane chain; methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and propyl methacrylate copolymers containing a polydimethylsiloxane chain; and mixtures thereof.
Composition according to any one of Claims 1 to 22, in the form of an emulsion, preferably in the form of an oil-in-water emulsion.
Non-therapeutic cosmetic process for caring for and/or making up a keratin material, comprising the application, to the surface of said keratin material, of at least one composition as defined in any one of Claims 1 to 23.