WO2023180256A1 - Composition comprising ethyl cellulose, a monoalcohol, a volatile hydrocarbon-based oil, a non-volatile alkane oil, a mono- or di-ester of a fatty acid and of polyglycerol and an ester oil - Google Patents

Abstract

The present invention relates to an anhydrous care and/or makeup composition comprising: a) ethyl cellulose; and b) at least one linear or branched monoalcohol including from 2 to 6 carbon atoms, and c) at least one monoester or diester of a linear or branched C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 glycerol units; and d) a liquid fatty phase comprising i) at least one volatile hydrocarbon-based oil; and ii) at least one non-volatile alkane oil; and iii) at least one particular non-volatile ester oil of the ester type of formula RICOOR2 in which R₁COO represents a linear or branched, saturated or unsaturated, acyclic or cyclic, aromatic or non-aromatic carboxylic acid residue including from 1 to 40 carbon atoms and R₂ represents a linear or branched alkyl radical containing from 1 to 40 carbon atoms.

Description

Composition comprising ethyl cellulose, a monoalcohol, a volatile hydrocarbon-based oil, a non-volatile alkane oil, a mono- or di-ester of a fatty acid and of polyglycerol and an ester oil

The present invention is directed towards providing for the field of caring for and/or making up keratin materials such as the skin, notably the facial areas, in particular the eyelids. It also relates to a process for caring for and/or making up human keratin materials, such as the skin, notably the facial areas, in particular the eyelids, in which said composition is applied.

Cosmetic makeup compositions are commonly used to give an aesthetic colour to keratin materials such as the skin, but also to enhance the beauty of irregular skin, by making it possible to hide marks and dyschromias, and to reduce the visibility of relief imperfections such as pores and wrinkles. Many formulations have been developed to date.

The vast majority of eyeshadows (or blushers) on the cosmetics market are products in the form of powders whose sheen is provided exclusively by reflective particles, notably interference pigments such as nacres having a natural substrate such as mica or a synthetic substrate such as a synthetic borosilicate or fluorphlogopite. These types of compositions do not provide sufficiently intense sheen.

Other current eyeshadow formulations include
- anhydrous creams with a high content of fatty substances such as oils or waxes, for instance the commercial product Longwear Cream Eyeshadow® from Chanel;
- compact powders with a high content of oil binders, for instance the products Longwear Powder Eyeshadow® and Ombre Première Cruise Gloss Top Coat Eyeshadow® from Chanel;
- hot-cast solid anhydrous formulas, notably in the form of pencils based on ester oils and waxes, such as the commercial product Jumbo Crayon® from Nyx;

- gloss-type formulas such as the commercial product Eye Gloss Smudger® from Yves Saint-Laurent, similar to the glosses used for lips, whether coloured or uncoloured, and generally containing a high content of hydrogenated polybutene, polyisobutene and/or polydecene.

In all these types of anhydrous presentation forms, the gloss effect is provided by oils (esters, silicones, hydrogenated polyisobutene, isododecane), in the presence or absence of reflective particles such as nacres or glitter flakes. Despite providing good sheen, these products tend to produce an uncomfortable tacky effect, and to migrate easily into the creases of the eyelid or to transfer and consequently have poor staying power.

There are also liquid water-based formulas in the form of a more or less gelled oil-in-water emulsion, such as the commercial products Eye Tint Liquid Eyeshadow® from Georgio Armani, Ombre Première Laque® from Chanel and Glitter & Glow Liquid Eyeshadow® from Stila Styles, which are based on a high content of oils and nacres. However, the wet sheen provided by the water when these products are applied generally disappears after a few moments, leaving only a particulate sheen due to the nacres after drying, the residual deposit of the formula itself being matt.

To date, the only category of cosmetic products with a fast-drying, transfer-resistant, high-gloss deposit without the aid of reflective particles is nail varnish. However, these products are unsuitable for application to the face, notably to the eyelids. Indeed, such products could lead to tolerance problems and would produce a film after application with an uncomfortable strong rigidity.

There is still a need to find novel compositions for caring for and/or making up keratin materials, in particular eyeshadows or blushers, which make it possible to obtain an intense sheen without necessarily using reflective particles, which have a good lasting effect, which have very little or even no tacky effect and which do not transfer or migrate into the creases of the eyelid very quickly after application.

In the course of its research, the Applicant has discovered, unexpectedly, that these objectives could be met with an anhydrous composition for caring for and/or making up keratin materials such as the skin, notably the facial areas, in particular the eyelids, comprising, preferably in a physiologically acceptable medium:
a) ethyl cellulose; and
b) at least one linear or branched monoalcohol including from 2 to 6 carbon atoms, and

c) at least one monoester or diester of a linear or branched C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 and preferably 2 or 3 glycerol units; and

d) a liquid fatty phase comprising
i) at least one volatile hydrocarbon-based oil; and
ii) at least one non-volatile alkane oil; and
iii) at least one non-volatile ester oil of the ester type of formula R₁COOR₂ in which R₁COO represents a linear or branched, saturated or unsaturated, acyclic or cyclic, aromatic or non-aromatic carboxylic acid residue including from 1 to 40 carbon atoms and R₂ represents a linear or branched alkyl radical containing from 1 to 40 carbon atoms; said non-volatile ester oil being chosen such that the composition has at 25°C:
1) a tack value of less than or equal to 0.01 N.s (newton-seconds), preferably less than or equal to 0.005 N.s; and

2) a gloss of greater than or equal to 50 gloss units at 60°, preferably ranging from 60 to 85 gloss units; and

3) a setting time of the surface of the film formed by the composition on the keratin material or a synthetic substrate, preferably of less than 1 minute, more preferentially less than or equal to 30 seconds;
said composition being in the form of a gel whose modulus G* (viscoelastic modulus) is between 100 and 3000 Pa for a phase shift angle of between 30 and 60.

This discovery forms the basis of the invention.

The present invention relates to an anhydrous composition for caring for and/or making up keratin materials such as the skin, notably the facial areas, in particular the eyelids, comprising, preferably in a physiologically acceptable medium:
a) ethyl cellulose; and
b) at least one linear or branched monoalcohol including from 2 to 6 carbon atoms, and

c) at least one monoester or diester of a linear or branched C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 and preferably 2 or 3 glycerol units; and

d) a liquid fatty phase comprising
i) at least one volatile hydrocarbon-based oil; and
ii) at least one non-volatile alkane oil; and
iii) at least one non-volatile ester oil of formula R₁COOR₂ in which R₁COO represents a linear or branched, saturated or unsaturated, acyclic or cyclic, aromatic or non-aromatic carboxylic acid residue including from 1 to 40 carbon atoms and R₂ represents a linear or branched alkyl radical containing from 1 to 40 carbon atoms; said non-volatile ester oil being chosen such that the composition has at 25°C:
1) a tack value of less than or equal to 0.01 N.s (newton-seconds), preferably less than or equal to 0.005 N.s; and

2) a gloss of greater than or equal to 50 gloss units at 60°, preferably ranging from 60 to 85 gloss units; and

3) a setting time of the surface of the film formed by the composition on the keratin material or a synthetic substrate, preferably of less than 1 minute, more preferentially less than or equal to 30 seconds;
said composition being in the form of a gel whose modulus G* (viscoelastic modulus) is between 100 and 3000 Pa for a phase shift angle of between 30 and 60.

The invention relates to a process for coating keratin materials, such as the skin, notably the facial areas, in particular the eyelids, characterized in that it comprises the application to the keratin materials of a composition as defined previously.

The invention more particularly relates to a process for making up and/or caring for keratin materials such as the skin, notably the facial areas, in particular the eyelids, characterized in that it comprises the application to the skin of a composition as defined previously.

Definitions

In the context of the present invention, the term “keratin materials” means the skin, notably the facial areas, more particularly the eyelids.

The term “physiologically acceptable” means compatible with the skin and/or its integuments, which has a pleasant colour, odour and feel, and which does not cause any unacceptable discomfort (stinging or tautness) liable to discourage the consumer from using this composition.

For the purposes of the present invention, the term “anhydrous” refers to a composition comprising a content of less than or equal to 5.0% by weight, preferably less than or equal to 2.0% by weight, more preferentially less than or equal to 1.0% by weight, even more preferentially less than or equal to 0.5% by weight of water relative to the total weight of said composition, or is even free of water. Where appropriate, such small amounts of water may notably be introduced by ingredients of the composition that may contain residual amounts thereof.

Rheological properties of the product

The composition is in the form of a gel with a G* modulus (viscoelastic modulus) of between 100 and 3000 Pa for a phase shift angle of between 30 and 60, more particularly between 500 and 2800 Pa for a phase shift angle of between 30 and 50°.

Gels, like all polymerized systems, show viscoelastic behaviour.

This type of behaviour can be characterized by means of creep or relaxation experiments, or by dynamic tests where a sinusoidal stress (or strain) is applied. In the present case, the viscoelastic properties (G* and delta) are measured with an imposed-stress rheometer and the values are taken on the viscoelastic plateau at 25°C.

The measurements are taken with an imposed-stress rheometer (ARG2® from TA Instruments). The measurement geometry used is the sanded cone-plate with a diameter of 35 mm and an angle of 2°. The sample is loaded with sinusoidal stresses of increasing amplitude at a frequency of 1 hertz, over a stress range from 0.1 to 1000 Pa. The resistance of the sample to the imposed strain is used to obtain the curves of consistency G* and solid/liquid nature δ as a function of the stress τ. The main data collected are the G* at the plateau (consistency) and the delta phase shift angle (solid/liquid nature).

Protocol for measuring the tack

The composition is applied as a film in a silicone mould 2.5 cm wide and 5.5 cm long (for example a Silikomart 20.026.00.0060 SF026® cake mould). In the silicone mould, 1.70±0.02 g of the composition are weighed out. The product is spread with a flat spatula, for instance a Labo Moderne type spatula, BC3219 Spatula®, so as to obtain a homogeneous layer on the entire bottom of the mould. The mould is stored with the product in a draught-free space such as a cupboard drawer and is left to dry for 24 hours.

The film is gently removed from the silicone mould and is laid flat on a flexible sheet of Supplale® type, for instance that of the commercial reference Soudotique PG SARL® or DFSUP10075® Beige.

The assembly is placed on the platform of a texturometer such as the Stable Texturometer MicroSystem TA. XT Plus® texturometer equipped with a 5 kg sensor, an SMS P/5S® spherical traction mobile and Exponent Connect® software. The parameters of the compression tests with maintenance over time are as follows:

Approach speed (or pre-speed): 0.5 mm/s;
Speed (starting from detection of the contact): 0.1 mm/s;
Force (and corresponding pressure): 0.01 newton;
Penetration depth: 0.15 mm;
Maintenance time: 5 seconds;
Withdrawal speed (or post-speed): 2 mm/s.

Four successive measurements are taken, positioning the film so that the measurement points are evenly distributed over the film surface, avoiding the most irregular areas. For each test, the curve measuring the force exerted on the mobile as a function of time is plotted.

The tack is characterized by the separation force measured during the pressure reduction (pull phase).

The tack value of the composition, expressed in newton-seconds (N.s), corresponds to the average of the values of the areas of the four tack force measurements as a function of time during the movement of the mobile (the area delimited between the curve of the points measured during the ascent of the mobile - negative force values - and the x-axis, until this curve reaches a zero force value).

Protocol for measuring the gloss

The sample is spread as a 50.8 µm film on a Byko Chart 2A® or Penopac 1A® contrast card from the company Byk using an automatic film spreader of the Byko-Drive XL® type from the company Byk equipped with a film spreading bar such as a 5353® variable slit height square from the company Byk, set for a slit height of 50.8 µm.

The contrast card is placed on the applicator platform and the 50.8 µm slit bar is placed on the contrast card at the information area to be filled in. About 2 g of material are deposited directly in front of the bar. The automatic applicator is started and the bar is moved to ensure that an even film of the required thickness is deposited.

The film is left to dry at 25°C for 15 minutes.

The gloss of the film applied to the black areas of the contrast card is measured at an incident angle of 60° and expressed in Gloss Units.

The gloss unit is a gloss meter scale (example: Rhopoint IQ-S® from Konica Minolta), based on a reference standard of highly polished black glass with a defined refractive index and a specular reflectance of 100 gloss units at a given angle, with the minimum point set to 0 for a perfectly matt surface. This scale is suitable for most coatings and non-metallic materials such as paint and plastic).

The measurement can be repeated over time to evaluate the gloss persistence.

Protocol for evaluating the setting time

When the product is applied as a thin layer (to the skin or to a synthetic surface), the surface of the deposit sets slightly, forming a very thin, flexible but non-tacky film, which prevents the product from being transferred onto another surface. This can be considered as a drying time.

0.05 g ± 0.01 g of the sample is placed on the inside of the forearm and spread rapidly (in 2-3 seconds) as a thin layer by finger to form a film of uniform thickness over an area of about 8 cm².

The stopwatch is started and about every 10 seconds the setting of the surface of the deposit is assessed by lightly pressing the pad of the index finger on it and then observing the presence or absence of any trace of product that has transferred onto the index finger.

The setting time is the time after which no more product transfer from the forearm to the index finger is observed.

Ethylcellulose

As indicated previously, the composition according to the invention comprises a) at least ethylcellulose.

Ethylcellulose is a cellulose ethyl ether comprising a chain formed from β-anhydroglucose units linked together via acetal bonds. Each anhydroglucose unit contains three replaceable hydroxyl groups, all or some of these hydroxyl groups being able to react according to the following reaction: RONa + C₂H₅Cl ROC₂H₅ + NaCl, in which R represents a cellulose radical. Total substitution of the three hydroxyl groups would lead, for each anhydroglucose unit, to a degree of substitution of 3, in other words to a content of alkoxy groups, in particular ethoxy groups, of 54.88%.

The ethylcellulose polymers used in a cosmetic composition according to the invention are preferentially polymers with a degree of substitution with ethoxy groups ranging from 2.5 to 2.6 per anhydroglucose unit, in other words comprising a content of ethoxy groups ranging from 44% to 50%.

The average molar mass of the ethylcellulose is preferably chosen such that the viscosity of a 5% by weight solution in a mixture of 80/20 (toluene/ethanol) at 25°C ranges from 4 to 300 mPa.s, preferably from 5 to 200 mPa.s, for example from 5 to 150 mPa.s. (standard ASTM D 914).

The ethyl cellulose used in the composition according to the invention is more particularly found in powdered form.

It is sold, for example, under the trade names Ethocel Standard® from Dow Chemicals, notably including Ethocel Standard 7 FP Premium® and Ethocel Standard 100 FP Premium®. Other commercially available products, such as those sold by Ashland, Inc. under the trade names Aqualon Ethylcellulose® type-K, type-N and type-T, preferably type-N, such as N7, N100, are particularly suitable for performing the invention.

The ethylcellulose content preferably ranges from 10% to 30% by weight, more preferentially from 15% to 25% by weight, and more particularly from 18% to 25% by weight relative to the total weight of the composition.

Monoalcohol

The compositions of the invention comprise b) at least one linear or branched monoalcohol, including from 2 to 6 carbon atoms, and in particular from 2 to 4 carbon atoms.

The compositions of the invention may comprise one or more monoalcohols.

This monoalcohol may be represented, for example, by the formula R_aOH, in which R_a represents a linear or branched alkyl group comprising from 2 to 6 carbon atoms.

Monoalcohols that may be mentioned include include ethanol, isopropanol, propanol or butanol.

According to one embodiment, the compositions of the invention comprise ethanol.

According to an advantageous embodiment, the amount of monoalcohol(s) ranges from 10% to 25% by weight, preferably from 12% to 18% by weight relative to the total weight of said composition.

C ₁₀ -C ₂₄ carboxylic acid monoester or diester of polyglycerol

The composition of the invention comprises c) at least one monoester or diester of a linear or branched C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 and preferably 2 or 3 glycerol units.

Among the monoesters or diesters of a linear or branched C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 glycerol units that may be used in the compositions of the invention, mention may be made, by way of example, of polyglyceryl-2 diisostearate, polyglyceryl-3 diisostearate, polyglyceryl-6 diisostearate, polyglyceryl-3 dilaurate polyglyceryl-6 diisostearate, polyglyceryl-3 dilaurate, polyglyceryl-4 dilaurate, polyglyceryl-5 dilaurate, polyglyceryl-6 dipalmitate, polyglyceryl-2 distearate, polyglyceryl-3 distearate, polyglyceryl-4 distearate, polyglyceryl-6 distearate, polyglyceryl-2 isopalmitate, polyglyceryl-2 isostearate polyglyceryl-3 isostearate, polyglyceryl-4 isostearate, polyglyceryl-5 isostearate, polyglyceryl-6 isostearate, polyglyceryl-2 laurate, polyglyceryl-3 laurate, polyglyceryl-4 laurate, polyglyceryl-5 laurate, polyglyceryl-6 laurate, polyglyceryl-2 myristate, polyglyceryl-3 myristate polyglyceryl-5 myristate, polyglyceryl-6 myristate, polyglyceryl-2 palmitate, polyglyceryl-3 palmitate, polyglyceryl-6 palmitate, polyglyceryl-2 stearate, polyglyceryl-3 stearate, polyglyceryl-4 stearate, polyglyceryl-5 stearate, polyglyceryl-6 stearate and mixtures thereof.

According to a preferred embodiment, the composition according to the invention comprises at least one linear or branched diester of a C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 glycerol units, preferably 2 or 3 glycerol units, in particular those chosen from polyglyceryl-2 diisostearate polyglyceryl-3 diisostearate, polyglyceryl-6 diisostearate, polyglyceryl-3 dilaurate, polyglyceryl-4 dilaurate, polyglyceryl-5 dilaurate, polyglyceryl-6 dipalmitate, polyglyceryl-2 distearate, polyglyceryl-3 distearate, polyglyceryl-4 distearate, polyglyceryl-6 distearate, and mixtures thereof.

According to a particularly preferred form, polyglyceryl-3 distearate such as the commercial products sold under the following names are used:
AEC Polyglyceryl-3 Diisostearate® (A & E Connock Perfumery & Cosmetics) Ltd.);
Cithrol PG32IS® (Croda Europe, Ltd.);
Cremer COOR PG3 DIS® (IOI Oleo GmbH);
Dub ISO G3® (Stéarinerie Dubois Fils);
Lameform TGI® (BASF Corporation);
Plurol Diisostearique® (Gattefossé);
Risorex PGIS32® (Kokyu Alcohol Kogyo Co., Ltd.).

According to an advantageous embodiment, the amount of monoester or diester of a C₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 glycerol units ranges from 5% to 45% by weight, preferably from 20% to 35% by weight relative to the total weight of said composition.

Liquid fatty phase

A composition according to the invention contains a liquid fatty phase comprising
i) at least one volatile hydrocarbon-based oil; and
ii) at least one non-volatile alkane oil; and
iii) at least one non-volatile ester oil of formula R1COOR2 in which R1COO represents a linear or branched, saturated or unsaturated, acyclic or cyclic, aromatic or non-aromatic carboxylic acid residue including from 1 to 40 carbon atoms and R2 represents a linear or branched alkyl radical containing from 1 to 40 carbon atoms; said ester oil being chosen such that the composition has at 25°C:
1) a tack value of less than or equal to 0.01 N.s, preferably less than or equal to 0.005 N.s; and

2) a gloss of greater than or equal to 50 gloss units at 60°, preferably ranging from 60 to 85 gloss units; and
3) a setting time of the surface of the film formed by the composition on the keratin material or a synthetic substrate, preferably of less than 1 minute, more preferentially less than or equal to 30 seconds.

Such a liquid fatty phase is an organic phase that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg), non-aqueous and water-immiscible.

The term “hydrocarbon-based oil” refers to an oil mainly containing carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

The term “non-volatile oil” refers to 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 2.66 Pa, preferably less than 0.13 Pa. By way of example, the vapour pressure may be measured via the static method or via the effusion method by isothermal thermogravimetry, depending on the vapour pressure (standard OCDE 104).

For the purposes of the invention, the term “volatile oil” refers to any oil that is capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, which is liquid at room temperature, notably having a non-zero vapour pressure, at room temperature and atmospheric pressure, notably having a vapour pressure ranging from 2.66 Pa to 40 000 Pa, in particular ranging from 2.66 Pa to 13 000 Pa and more particularly ranging from 2.66 Pa to 1300 Pa.

i) Volatile hydrocarbon-based oil

The volatile hydrocarbon-based oils i) that may be used in the compositions according to the invention may be chosen from branched C₈-C₁₆ alkanes.

The term “alkane” means any compound comprising a saturated, linear hydrocarbon-based chain consisting exclusively of carbon atoms and hydrogen atoms.

Mention may notably be made of C₈-C₁₆ isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and isohexadecane, for example the oils sold under the trade names Isopar® or Permethyl®, branched C₈-C₁₆ esters and isohexyl neopentanoate, and 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.

The volatile hydrocarbon-based oils that may be used in the compositions according to the invention may also be chosen from volatile linear alkanes comprising from 6 to 14 carbon atoms.

As examples of linear alkanes that are suitable for use in the invention, mention may be made of the alkanes described in the patent applications by the company Cognis WO 2007/068371 or WO 2008/155059 (mixtures of different alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut kernel oil or palm oil.

As examples of linear C₆-C₁₄ alkanes that are suitable for use in the invention, mention may be made of n-hexane (C₆), n-heptane (C₇), n-octane (C₈), n-nonane (C₉), n-decane (C₁₀), n-undecane (C₁₁), n-dodecane (C₁₂), n-tridecane (C₁₃) and n-tetradecane (C₁₄), and mixtures thereof.

Mention may also be made of n-dodecane (C₁₂) and n-tetradecane (C₁₄) sold by Sasol under the respective references Parafol 12-97® and Parafol 14-97®, and also mixtures thereof.

According to another embodiment, a mixture of n-dodecane and n-tetradecane is used. It is in particular possible to use the dodecane/tetradecane mixture in an 85/15 weight ratio sold by the company Biosynthis under the reference Vegelight 1214®.

According to yet another embodiment, use is made of a mixture of volatile linear C₉-C₁₂ alkanes of INCI name: C9-12 Alkane such as the product sold by the company Biosynthis under the reference Vegelight Silk®.

According to yet another embodiment, use is made of a mixture of n-undecane (C₁₁) and of n-tridecane (C₁₃) as obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis and the product sold under the trade name Cetiol Ultimate® by the company BASF.

According to a particularly preferred embodiment, the volatile hydrocarbon-based oil is isododecane.

The volatile hydrocarbon-based oil(s) i) are preferably present in the composition of the invention in contents of less than or equal to 25.0% by weight and more preferentially ranging from 5% to 15% by weight relative to the total weight of said composition.

ii) Non-volatile alkane oil

The non-volatile alkane oils ii) that may be used in the compositions according to the invention may be chosen from linear or branched alkanes including from 20 to 40 carbon atoms, notably chosen from
- liquid linear or branched paraffins comprising from 18 to 32 carbon atoms,
- squalane (C₃₀) of the following structure
[Chem 1]

- isoeicosane (C₂₀);
- mixtures thereof.

Isoeicosane is notably sold under the following trade names:
Creasil IE CG® (C.I.T. Sarl);
Creasil IE Sethic® (The Innovation Company);
Fancol IE® (Elementis Specialities);
OriStar IES® (Orient Stars LLC);
Permethyl 102A® (Presperse Corp).

According to a particularly preferred form, the non-volatile alkane oil ii) is squalane notably sold under the following trade names:
ABS Amaranthus Squalane® (Active Concepts LLC);
AEC Squalane® (A & E Connock Perfumery & Cosmetics) Ltd.);
Botanessential Olivane® (Botanigenics, Inc);
Cosbiol® (Laserson);
Creanatural Vegetable Squalane® (C.I.T. Sarl);
Dermane® (Universal Preserv-A-Chem, Inc.);
Fitoderm® (BASF Corporation);
Keteol N® (Laboratoires Prod’Hyg);
Keteol V® (Laboratoires Prod’Hyg);
Nikkol Olive Squalane® (Nikko Chemicals Co., Ltd.);
Nikkol Squalane® (Nikko Chemicals Co., Ltd.);
Nikkol Sugar Squalane® (Nikko Chemicals Co., Ltd.);
Olive Squalane® (Kokyu Alcohol Kogyo Co., Ltd.);
OriStar Squalane® (Orient Stars LLC);
Phytosqualan® (Sophim);
Phytosqual Hydrogen® (Vevy Europe SpA);
Plantec Olive Squalane® (CRM International);
Pripure 3759®;
Salacos RS® (The Nisshin Oil Group, Ltd.);
Sophiderm® (Sophim);
Neossance Squalane® (Amyris).

The non-volatile alkane oil(s) ii) are preferably present in the composition of the invention in contents of less than or equal to 15% by weight and more preferentially ranging from 3% to 12% by weight relative to the total weight of said composition.

iii) Non-volatile ester oil

The liquid fatty phase of the composition according to the invention comprises iii) at least one volatile ester oil of formula R1COOR2 in which R1COO represents a linear or branched, saturated or unsaturated, acyclic or cyclic, aromatic or non-aromatic carboxylic acid residue including from 1 to 40 carbon atoms and R2 represents a linear or branched alkyl radical containing from 1 to 40 carbon atoms; said ester oil being chosen such that the composition has at 25°C:
1) a tack value of less than or equal to 0.01 N.s, preferably less than or equal to 0.005 N.s; and

2) a gloss of greater than or equal to 50 gloss units at 60°, preferably ranging from 60 to 85 gloss units; and
3) a setting time of the surface of the film formed by the composition on the keratin material or a synthetic substrate, preferably of less than 1 minute, more preferentially less than or equal to 30 seconds.

Preferably, the composition according to the invention comprises at least one non-volatile ester oil chosen from
- esters of benzoic acid and of a linear or branched C₈-C₂₂ fatty alcohol;
- C₁₆-C₂₂ dialkyl carbonates;
- unsaturated esters of linoleic acid or oleic acid and of a linear or branched C₁-C₁₀ alkanol;
- mixtures thereof.

The term “alkanol” means any saturated alkane compound bearing a hydroxyl (OH) function in its structure.

The term “unsaturated ester” means any ester including at least one double bond -CH₂=CH₂- in the main chain.

I/ Esters of benzoic acid and of a linear or branched C ₈ -C ₂₂ fatty alcohol

The ester oils of benzoic acid and of a linear or branched C₈-C₂₂ fatty alcohol may notably be chosen from a mixture of lauryl benzoate and myristyl benzoate (INCI name: Lauryl/Myristyl Benzoate), a mixture of C₁₂-C₁₅ alkyl benzoates (INCI name: C12-15 Alkyl Benzoate), a mixture of C₁₆-C₁₇ alkyl benzoates (INCI name: C16-17 Alkyl Benzoate), stearyl benzoate, isostearyl benzoate, hexyldecyl benzoate, butyloctyl benzoate, octyldodecyl benzoate, behenyl benzoate, and mixtures thereof.

A mixture of C₁₆-C₁₇ alkyl benzoates (INCI name: C16-17 Alkyl Benzoate) is notably sold under the trade name Corum 5014® by the company Corum Inc.

According to a particularly preferred form, the non-volatile ester oil iii) is a mixture of C₁₂-C₁₅ alkyl benzoates (INCI name: C12-15 Alkyl Benzoate) such as those sold under the following trade names:
AEC C12-15 Alkyl Benzoate® (A & E Connock (Perfumery & Cosmetics) Ltd.);

Botanester AB® (Botanigenics, Inc);
Cetiol AB® (BASF Corporation);
Crodamol AB® (Croda Europe, Ltd.);
Crodamol AB® (Croda, Inc.);
Dub B1215® (Stéarinerie Dubois Fils);
Finsolv TN® (Innospec Performance Chemicals);
Hest 25B® (Global Seven Inc.);
Liponate NEB® (Vantage Personal Care);

OriStar AKB® (Orient Stars LLC);

Saboderm AB® (Sabo s.p.a.);

Tegosoft TN® (Evonik Nutrition & Care GmbH);

Tegosoft TN 2® (Evonik Nutrition & Care GmbH).

II/ C16-C22 Dialkyl carbonates

The ester oils of the C₁₆-C₂₂ dialkyl carbonate type are preferably chosen from those corresponding to the formula R¹COOR² in which R¹ and R², independently, denote a linear or branched alkyl radical containing from 1 to 16 atoms such that the total number of carbon atoms present in the radicals R¹ and R² is from 16 to 22.

Among the C₁₆-C₂₂ dialkyl carbonates, mention may be made of
- bis(2-ethylhexyl) carbonate (C₁₇) such as the product sold under the trade name Tegosoft DEC® by the company Evonik Nutrition & Care GmbH;
- dicaprylyl carbonate (C₁₇) such as the products sold under the trade names Cetiol CC® (BASF Corporation) and OriStar DCC® (Orient Stars LLC);
- a mixture of C₁₄-C₁₅ dialkyl carbonates (INCI name: C₁₄-C₁₅ Dialkyl Carbonate) such as the products sold under the trade names Lialcarb SR-1000/R® by the company EniChem SpA and OriStar C14-15 DAC® by the company Orient Stars LLC;
- dipropylheptyl carbonate (C₂₁) such as the product sold under the trade name Cetiol 4 All® by the company BASF.

According to a particularly preferred form, the dialkyl carbonate oil is dicaprylyl carbonate.

III/ Unsaturated esters of linoleic acid or oleic acid and of a linear or branched C ₁ -C ₁₀ alkanol

Among the linoleic acid esters in accordance with the invention, mention may be made of:
- Methyl Linoleate such as the products sold under the following trade names:
AEC Methyl Linoleate® (A & E Connock Perfumery & Cosmetics) Ltd.);
Dub LIM® (Stéarinerie Dubois Fils);
- Ethyl Linoleate such as products sold under the following trade names:
AEC Ethyl Linoleate® (A & E Connock Perfumery & Cosmetics) Ltd.);
Dub Omega 6 EE® (Stéarinerie Dubois Fils);
Nikkol VF-LINO® (Nikko Chemicals Co., Ltd.);
Safester A-75® (Givaudan Active Beauty);
Synovea EL (Sytheon, Ltd.);
-Isopropyl Linoleate such as the product sold under the trade name:
AEC Isopropyl Linoleate® (A & E Connock Perfumery & Cosmetics Ltd.);
- and mixtures thereof.

Among the oleic acid esters in accordance with the invention, mention may be made of:
- Butyl Oleate such as the product sold under the trade name
AEC Butyl Oleate® (A & E Connock Perfumery & Cosmetics Ltd.);
- Decyl Oleate such as the products sold under the following trade names:
AEC Decyl Oleate® (A & E Connock Perfumery & Cosmetics Ltd.);
Ceraphyl 140® (Ashland Inc.);
Ceraphyl 140A® (Ashland Inc.);
Cetiol V® (BASF Corporation);
Cremer COOR DO® (IOI Oleo GmbH);
Dermol DO® (Alzo International Inc.);
Dermol V® (Fabriquimica S.R.L.);
Dub OD® (Stéarinerie Dubois Fils);
Jeechem DO® (Jeen International Corporation);
Pelemol DO® (Phoenix Chemical, Inc.);
Radia 7336® (Oleon NV);
Saboderm DO (Sabo s.p.a.);
Tegosoft DO® (Evonik Nutrition & Care GmbH);
Unimul-CTV® (Universal Preserv-A-Chem, Inc.);
Unitolate V® (Universal Preserv-A-Chem, Inc.);
- Ethylhexyl Oleate such as the products sold under the following trade names:
AEC Ethylhexyl Oleate® (A & E Connock Perfumery & Cosmetics Ltd.);
Saboderm EO® (Sabo s.p.a.);
AEC Ethyl Oleate (A & E Connock (Perfumery & Cosmetics) Ltd.);
- Ethyl Oleate, such as the products sold under the following trade names:
Crodamol EO® (Croda Europe, Ltd.);
Dub OE HP® (Stéarinerie Dubois Fils);
- Isobutyl Oleate such as the product sold under the trade name Clearbright IB-81S® (NOF Corporation);
- Isodecyl Oleate such as the products sold under the following trade names:
AEC Isodecyl Oleate® (A & E Connock Perfumery & Cosmetics Ltd.);

Dermol IDO® (Alzo International Inc.);
Pelemol IDO® (Phoenix Chemical, Inc.);
Schercemol IDO Ester® (Lubrizol Advanced Materials, Inc.);
- Isopropyl Oleate such as the product sold under the trade name AEC Isopropyl Linoleate (A & E Connock Perfumery & Cosmetics Ltd.);
- Methyl Oleate, such as the products sold under the following trade names:
AEC Methyl Oleate® (A & E Connock Perfumery & Cosmetics Ltd.);
Dub OM HTO® (Stéarinerie Dubois Fils); and mixtures thereof.

According to a particularly preferred embodiment, the composition of the invention comprises ethyl linoleate.

The non-volatile ester oil(s) iii) are preferably present in the composition of the invention in contents of less than or equal to 25.0% by weight and preferably from 5% to 20% by weight relative to the total weight of said composition.

Pigments

According to a particular embodiment of the invention, the composition also comprises at least one pigment.

The term “pigments” means white or coloured, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify the resulting composition and/or deposit. These pigments may be white or coloured, and mineral and/or organic. They may or may not be coated with a surface-treating agent.

Preferably, the composition comprises at least 0.01% by weight, more preferentially from 0.1% to 3% by weight, in particular from 0.2% to 1% by weight and preferably from 0.2% to 0.5% by weight of pigments relative to the total weight of said composition.

According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, and metal powders, for instance aluminium powder or copper powder. The following mineral pigments may also be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, ZrO₂ as a mixture with TiO₂, ZrO₂, Nb₂O₅, CeO₂, ZnS.

The size of the pigment that is useful in the context of the present invention is generally greater than 100 nm and may range up to 10 µm, preferably from 200 nm to 5 µm and more preferentially from 300 nm to 1 µm.

According to a particular form of the invention, the pigments have a size characterized by a D[50] of greater than 100 nm and possibly ranging up to 10 µm, preferably from 200 nm to 5 µm and more preferentially from 300 nm to 1 µm.

The sizes are measured by static light scattering using a commercial MasterSizer 3000® particle size analyser from Malvern, which makes it possible to determine the particle size distribution of all of the particles over a wide range which may extend from 0.01 µm to 1000 µm. The data are processed on the basis of the standard Mie scattering theory. This theory is the most suitable for size distributions ranging from submicron to multimicron; it allows an “effective” particle diameter to be determined. This theory is notably described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.

D[50] represents the maximum size exhibited by 50% by volume of the particles.

In the context of the present invention, the mineral pigments are more particularly coated or uncoated iron oxides and/or titanium dioxide.

As mineral pigments that may be used in the invention, mention may also be made of nacres.

The term “nacres” should be understood as meaning coloured particles of any form, which may or may not be iridescent, notably produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.

The nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride. They may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.

Examples of nacres that may also be mentioned include natural mica covered with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.

Among the nacres available on the market, mention may be made of the Timica®, Flamenco® and Duochrome® nacres (based on mica) sold by the company Engelhard, the Timiron® nacres sold by the company Merck, the Prestige® mica-based nacres, sold by the company Eckart, and the Sunshine® synthetic mica-based nacres, sold by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery colour or tint.

As illustrations of the nacres that may be used in the context of the present invention, mention may be made of gold-coloured nacres sold notably by the company Engelhard under the name Brilliant Gold 212G® (Timica), Gold 222C® (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X® (Cloisonne); the bronze nacres sold notably by the company Merck under the names Bronze Fine (17384)® (Colorona) and Bronze (17353)® (Colorona) and by the company Engelhard under the name Super Bronze (Cloisonne); the orange nacres sold notably by the company Engelhard under the names Orange 363C® (Cloisonne) and Orange MCR 101® (Cosmica) and by the company Merck under the names Passion Orange (Colorona) and Matte Orange (17449)® (Microna); the brown-tinted nacres sold notably by the company Engelhard under the names Nu-Antique Copper 340XB® (Cloisonne) and Brown CL4509® (Chromalite); the nacres with a copper tint sold notably by the company Engelhard under the name Copper 340A® (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna Fine® (17386) (Colorona); the nacres with a yellow tint sold notably by the company Engelhard under the name Yellow (4502)® (Chromalite); the red-coloured nacres with a golden tint sold notably by the company Engelhard under the name Sunstone G012® (Gemtone); the pink nacres sold notably by the company Engelhard under the name Tan Opal G005® (Gemtone); the black nacres with a golden tint sold notably by the company Engelhard under the name Nu Antique Bronze 240 AB® (Timica); the blue nacres sold notably by the company Merck under the name Matte Blue (17433)® (Microna); the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver; and the golden-green pinkish-orange nacres sold notably by the company Merck under the name Indian Summer® (Xirona), and mixtures thereof.

Among the pigments that may be used according to the invention, mention may also be made of those having an optical effect different from a simple conventional colouring effect, i.e. a unified and stabilized effect such as produced by conventional dyestuffs, for instance monochromatic pigments. For the purposes of the invention, the term “stabilized” means lacking the effect of variability of the colour with the angle of observation or in response to a temperature change.

For example, this material may be chosen from particles with a metallic tint, goniochromatic colouring agents, diffractive pigments, thermochromic agents, optical brighteners, and also fibres, notably interference fibres. Needless to say, these various materials may be combined in order simultaneously to afford two effects, or even a novel effect in accordance with the invention.

The particles with a metallic tint that may be used in the invention are chosen in particular from:

- particles of at least one metal and/or of at least one metal derivative;

- particles including a single-material or multi-material organic or mineral substrate, at least partially coated with at least one layer with a metallic tint comprising at least one metal and/or at least one metal derivative; and

- mixtures of said particles.

Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr and mixtures or alloys thereof (for example, bronzes and brasses) are preferred metals.

The term “metal derivatives” denotes compounds derived from metals, notably oxides, fluorides, chlorides and sulfides.

Illustrations of these particles that may be mentioned include particles of aluminium, such as those sold under the names Starbrite 1200 EAC® by Silberline and Metalure® by Eckart.

Mention may also be made of metal powders of copper or of alloy mixtures such as the references 2844 sold by the company Radium Bronze, metallic pigments, for instance aluminium or bronze, such as those sold under the names Rotosafe® 700 from the company Eckart, silica-coated aluminium particles sold under the name Visionaire Bright Silver® from the company Eckart, and metal alloy particles, for instance the silica-coated bronze (alloy of copper and zinc) powders sold under the name Visionaire Bright Natural Gold® from the company Eckart.

They may also be particles including a glass substrate, such as those sold by the company Nippon Sheet Glass under the name Microglass Metashine®.

The goniochromatic colouring agent may be chosen, for example, from multilayer interference structures and liquid-crystal colouring agents.

Examples of symmetrical multilayer interference structures that may be used in the compositions prepared in accordance with the invention are, for example, the following structures: Al/SiO₂/Al/SiO₂/Al, pigments having this structure being sold by the company Dupont de Nemours; Cr/MgF₂/Al/MgF₂/Cr, pigments having this structure being sold under the name Chromaflair® by the company Flex; MoS₂/SiO₂/Al/SiO₂/MoS₂; Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O_3,and Fe₂O₃/SiO₂/Fe₂O₃/SiO₂/Fe₂O₃, pigments having these structures being sold under the name Sicopearl® by the company BASF; MoS₂/SiO₂/mica-oxide/SiO₂/MoS₂; Fe₂O₃/SiO₂/mica-oxide/SiO₂/Fe₂O₃; TiO₂/SiO₂/TiO₂ and TiO₂/Al₂O₃/TiO₂; SnO/TiO₂/SiO₂/TiO₂/SnO; Fe₂O₃/SiO₂/Fe₂O₃; SnO/mica/TiO₂/SiO₂/TiO₂/mica/SnO, pigments having these structures being sold under the name Xirona® by the company Merck (Darmstadt). By way of example, these pigments may be the pigments of silica/titanium oxide/tin oxide structure sold under the name Xirona Magic® by the company Merck, the pigments of silica/brown iron oxide structure sold under the name Xirona Indian Summer® by the company Merck and the pigments of silica/titanium oxide/mica/tin oxide structure sold under the name Xirona Caribbean Blue® by the company Merck. Mention may also be made of the Infinite Colors pigments from the company Shiseido. Depending on the thickness and the nature of the various coats, different effects are obtained. Thus, with the Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O₃ structure, the colour changes from greenish gold to reddish grey for SiO₂ layers of 320 to 350 nm; from red to gold for SiO₂ layers of 380 to 400 nm; from violet to green for SiO₂ layers of 410 to 420 nm; from copper to red for SiO₂ layers of 430 to 440 nm.

As examples of pigments with a multilayer polymeric structure, mention may be made of those sold by the company 3M under the name Color Glitter®.

Examples of liquid-crystal goniochromatic particles that may be used include those sold by the company Chenix and also the product sold under the name Helicone® HC by the company Wacker.

Hydrophobic coated pigments

According to a particular embodiment of the invention, the compositions according to the invention comprise at least one pigment coated with at least one lipophilic or hydrophobic compound and notably as detailed below.

This type of pigment is particularly advantageous insofar as it may be considered in large amount together with a large amount of water. What is more, insofar as they are treated with a hydrophobic compound, they show predominant affinity for an oily phase, which can then convey them.

Needless to say, the compositions according to the invention may in parallel contain uncoated pigments.

The coating may also comprise at least one additional non-lipophilic compound.

For the purposes of the invention, the “coating” of a pigment according to the invention generally denotes the total or partial surface treatment of the pigment with a surface agent, absorbed, adsorbed or grafted onto said pigment.

The surface-treated pigments may be prepared according to surface treatment techniques of chemical, electronic, mechanochemical or mechanical nature that are well known to those skilled in the art. Commercial products may also be used.

The surface agent may be absorbed, adsorbed or grafted onto the pigments by evaporation of solvent, chemical reaction and creation of a covalent bond.

According to one variant, the surface treatment consists in coating the pigments.

The coating may represent from 0.1% to 20% by weight and in particular from 0.5% to 10% by weight relative to the total weight of the coated pigment.

The coating may be produced, for example, by adsorption of a liquid surface agent onto the surface of the solid particles by simple mixing with stirring of the particles and of said surface agent, optionally with heating, prior to the incorporation of the particles into the other ingredients of the makeup or care composition.

The coating may be produced, for example, by chemical reaction of a surface agent with the surface of the solid pigment particles and creation of a covalent bond between the surface agent and the particles. This method is notably described in patent US 4 578 266.

The chemical surface treatment may consist in diluting the surface agent in a volatile solvent, dispersing the pigments in this mixture and then slowly evaporating off the volatile solvent, so that the surface agent is deposited on the surface of the pigments.

Lipophilic or hydrophobic treatment agent

According to a particular embodiment of the invention, the pigments may be coated according to the invention with at least one compound chosen from silicone surface agents; fluoro surface agents; fluorosilicone surface agents; metal soaps; N-acylamino acids or salts thereof; lecithin and derivatives thereof; isopropyl triisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

According to a particular embodiment of the invention, the hydrophobic treatment agent may be chosen from metal soaps such as aluminium dimyristate, and the aluminium salt of hydrogenated tallow glutamate.

Metal soaps that may notably be mentioned include metal soaps of fatty acids containing from 12 to 22 carbon atoms and in particular those containing from 12 to 18 carbon atoms.

The metal of the metal soap may notably be zinc or magnesium.

Metal soaps that may be used include zinc laurate, magnesium stearate, magnesium myristate and zinc stearate, and mixtures thereof;

The hydrophobic treatment agent may also be chosen from ii) fatty acids such as lauric acid, myristic acid, stearic acid and palmitic acid.

According to a particular embodiment of the invention, the hydrophobic treatment agent may be chosen from N-acylamino acids or salts thereof which may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.

The amino acid may be, for example, lysine, glutamic acid or alanine.

The salts of these compounds may be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts.

Thus, according to a particularly preferred embodiment, an N-acylamino acid derivative may notably be a glutamic acid derivative and/or a salt thereof, and more particularly a stearoyl glutamate, for instance aluminium stearoyl glutamate.

According to a particular mode of the invention, the hydrophobic treatment agent may be chosen from lecithin and derivatives thereof.

According to a particular embodiment of the invention, the hydrophobic treatment agent may be isopropyl triisostearyl titanate.

As examples of isopropyl titanium triisostearate (ITT)-treated pigments, mention may be made of those sold under the commercial references BWBO-I2® (iron oxide CI77499 and isopropyl titanium triisostearate), BWYO-I2® (iron oxide CI77492 and isopropyl titanium triisostearate) and BWRO-I2® (iron oxide CI77491 and isopropyl titanium triisostearate) by the company Kobo.

The hydrophobic treatment agent may also be vi) isostearyl sebacate.

According to a particular embodiment of the invention, the hydrophobic treatment agent may be isostearyl sebacate.

According to a particular embodiment of the invention, the hydrophobic treatment agent may be chosen from natural plant or animal waxes or polar synthetic waxes.

According to a particular embodiment of the invention, the hydrophobic treatment agent may be chosen from fatty esters, in particular jojoba esters.

According to a particular embodiment of the invention, the hydrophobic treatment agent may be chosen from phospholipids.

According to a particular embodiment, the pigments may be coated with an N-acylamino acid and/or a salt thereof, in particular with a glutamic acid derivative and/or a salt thereof, notably a stearoyl glutamate, for instance aluminium stearoyl glutamate. Examples of coated pigments according to the invention that may be mentioned more particularly include titanium dioxides and iron oxide coated with aluminium stearoyl glutamate, sold, for example, under the reference NAI® by Miyoshi Kasei.

According to a particularly preferred embodiment, the pigments are coated with a perfluoroalkyl trialkoxysilane such as Perfluorohexylethyl Triethoxysilane and Perfluorooctyl Triethoxysilane. As examples of pigments coated according to the invention, mention may be made more particularly of titanium dioxides and iron oxide, coated with Perfluorohexylethyl Triethoxysilane or Perfluorooctyl Triethoxysilane, for example sold under the references FHS-5 Sunpuro® by the company Daito Kasei Kogyo.

According to a particular embodiment, the composition of the invention may contain at least one organic pigment.

The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s Encyclopedia in the chapter on organic pigments. The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal-complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.

The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

These pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including a mineral core at least partially covered with an organic pigment and at least one binder for fixing the organic pigments to the core.

The pigment may also be a lake. The term “lake” means insolubilized dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

Among the organic dyes, mention may be made of cochineal carmine. Mention may also be made of the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

An example of a lake that may be mentioned is the product known under the name D&C Red 7 (CI 15 850:1).

Additives

The compositions according to the invention may also include additives commonly used in care and/or makeup products such as solar UV-screening agents; fatty alcohols such as octyldodecanol, moisturizers, for instance polyols such as glycerol, propanediol or pentylene glycol; fillers; liposoluble dyestuffs; thickeners or gelling agents for the fatty phase; antioxidants, preserving agents, fragrances and mixtures thereof.

Cosmetic compositions

The present invention also relates to a cosmetic composition comprising, in a physiologically acceptable medium, a composition as defined above.

The term “physiologically acceptable medium” is intended to denote a medium that is particularly suitable for the application of a composition according to the invention to the skin.

The physiologically acceptable medium is generally adapted to the nature of the support onto which the composition is to be applied, and also to the form in which the composition is to be packaged.

Applications

According to one embodiment, a composition of the invention may advantageously be in the form of a composition for caring for and/or making up keratin materials such as the skin, notably the facial areas, in particular the eyelids.

Thus, according to a sub-mode of this embodiment, a composition of the invention may advantageously be in the form of a makeup base composition.

A composition of the invention may advantageously be in the form of a composition for making up the skin and notably facial skin. It may thus be an eyeshadow or a blusher.

Such compositions are notably prepared according to the general knowledge of a person skilled in the art.

The expressions “between ... and ...”, and “ranging from ... to ...” should be understood as meaning limits included, unless otherwise specified.

The invention is illustrated in greater detail by the examples and figures presented below. Unless otherwise indicated, the amounts indicated are expressed as mass percentages.

Examples 1 and 3 (invention) and Examples 1a, 1b, 2a, 2b, 3a and 3b (outside the invention): eyeshadows

Compositions 1 to 3 according to the invention and compositions 1a, 1b; 2a, 2b, 3a and 3b outside the invention were prepared according to the preparation protocols described below.

Ingredients	Example 1 % by weight	Example 1a % by weight	Example 1b % by weight
Ethylcellulose (Aqualon EC N7 Pharm® - Ashland)	24.79	24.79	24.79
C12-15 Alkyl benzoate (C12/C15 Benzoate® (DUB B1215®) - Stéarinerie Dubois)	8.41	8.41
Neopentyl glycol dicaprate (Estemol N-01, Nisshin Oillio)			8.41
Polyglyceryl-3 diisostearate (Lameform TGI® – BASF)	33.57	33.57	33.57
Squalane (Neossance Squalane® - Amyris)	9.64	0	9.64
Alcohol	15	15	15
Isododecane	q.s. 100	q.s. 100	q.s. 100

Ingredients	Example 2 % by weight	Example 2a % by weight	Example 2b % by weight
Ethylcellulose (Aqualon EC N7 Pharm® - Ashland)	20	20	20
Dicaprylyl carbonate (Cetiol CC® - BASF)	10	10
Neopentyl glycol dicaprate (Estemol N-01, Nisshin Oillio)			10
Polyglyceryl-3 diisostearate (Lameform TGI® – BASF)	30	30	30
Squalane (Neossance Squalane® - Amyris)	10	0	10
Alcohol	15	15	15
Isododecane	q.s. 100	q.s. 100	q.s. 100

Ingredients	Example 3 % by weight	Example 3a % by weight	Example 3b % by weight
Ethylcellulose (Aqualon EC N7 Pharm® - Ashland)	24.79	24.79	24.79
Ethyl linoleate (vitamin F/EE® - Oleon)	8.41	8.41
Diisostearyl malate (Schercemol DISM Ester – Lubrizol)			8.41
Pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate (Tinoguard TT® – BASF)	0.25	0.25	0.25
Polyglyceryl-3 diisostearate (Lameform TGI® – BASF)	33.57	33.57	33.57
Squalane (Neossance Squalane® - Amyris)	9.64	0	9.64
Alcohol	15	15	15
Isododecane	q.s. 100	q.s. 100	q.s. 100

Protocol for preparing Examples 1 to 3 (invention) and Counter-Examples 1a, 1b, 2a, 2b, 3a and 3b outside the invention

The non-volatile ester oil polyglyceryl-3 diisostearate was introduced into a beaker and ethyl cellulose was then added. The mixture was then homogenized using a deflocculating stirrer, so as to deagglomerate and wet the polymer thoroughly. A thick, cream-white suspension was obtained at this stage. The alcohol was added and the mixture was then homogenized using a deflocculating stirrer until a more or less transparent, colourless to pale yellow gel was formed. Isododecane and, if necessary, squalane were added slowly in a steady stream so as to enable their gradual incorporation into the gel. Once all of these solvents were introduced, stirring was continued until a homogeneous gel was obtained.

The following characteristics of each composition were evaluated at 25°C for each of the Examples 1 to 3 (invention) and the Counter-Examples 1a, 1b, 2a, 2b, 3a and 3b outside the invention, according to the measurement protocols as detailed previously:

- the tack value

- the gloss at 60°, 15 minutes, 2 hours and 7 hours after application

- the setting time

The results are shown in the table below.

Measured characteristics	Tack value (Newton-seconds)	Gloss 60° (gloss units)			Setting time (seconds)
		at 15 minutes	at 2 hours	at 7 hours
Example 1 (invention) with C12-15 alkyl benzoate and squalane	0.3 ± 0.1	69 ± 4	68 ± 4	67 ± 4	15
Example 1a (outside the invention) with C12-15 alkyl benzoate without squalane	0.7 ± 0.1	82 ± 2	82 ± 2	80 ± 2	30
Example 1b (outside the invention) with squalane and neopentyl glycol dicaprate	0.3 ± 0.1	45 ± 5	47 ± 6	43 ± 4	30
Example 2 (invention) with dicaprylyl carbonate and squalane	0.4 ± 0.1	72 ± 4	72 ± 2	70 ± 4	20
Example 2a (outside the invention) with dicaprylyl carbonate without squalane	0.7 ± 0.1	81 ± 2	80 ± 2	79 ± 1	30
Example 2b (outside the invention) with neopentyl glycol dicaprate and squalane	Not measurable: the film tears	65 ± 3	63 ± 6	59 ± 6	80
Example 3 (invention) with ethyl linoleate and squalane	0.4 ± 0.1	63 ± 4	64 ± 5	64 ± 5	30
Example 3a (outside the invention) with ethyl linoleate without squalane	0.8 ± 0.1	77 ± 2	78 ± 2	76 ± 1	30
Example 3b (outside the invention) with diisostearyl Malate and squalane	0.3 ± 0.1	35 ± 3	34 ± 1	31 ± 3	120

The results showed that Examples 1 to 3 of the invention comprising ethyl cellulose, polyglyceryl-3 diisostearate, ethanol, isododecane, squalane and respectively as non-volatile ester oil C12-15 alkyl benzoate, dicaprylyl carbonate or ethyl linoleate respectively, produce after application a film with an intense gloss for 7 hours, satisfactory adhesion, a low tack effect and a short film-surface setting time of less than or equal to 30 seconds.

The results showed that the Counter-Examples 1a, 2a and 3a outside the invention, containing no squalane, produce a more tacky film after application. They thus confirm the technical contribution of squalane towards reducing the tack of the film.

The results also showed that the Counter-Examples 1b and 2b outside the invention, in which the non-volatile ester oil used was neopentyl glycol dicaprate, produced after application a film with a longer surface setting time. Example 1b produced a substantially less glossy film. Example 2b did not demould as it tore due to lack of cohesion, making the tack measurement impossible.

The results also showed that the Counter-Example 3b outside the invention, in which the non-volatile ester oil used was diisostearyl malate, produced a low gloss film with a very long surface setting time: 2 minutes.

Claims (21)

1. Anhydrous composition for caring for and/or making up keratin materials such as the skin, notably the facial areas, in particular the eyelids, comprising, preferably in a physiologically acceptable medium:
   a) ethyl cellulose; and
   b) at least one linear or branched monoalcohol including from 2 to 6 carbon atoms, and
   c) at least one monoester or diester of a linear or branched C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 and preferably 2 or 3 glycerol units; and
   d) a liquid fatty phase comprising
   i) at least one volatile hydrocarbon-based oil; and
   ii) at least one non-volatile alkane oil; and
   iii) at least one non-volatile ester oil of the ester type of formula R1COOR2 in which R1COO represents a linear or branched, saturated or unsaturated, acyclic or cyclic, aromatic or non-aromatic carboxylic acid residue including from 1 to 40 carbon atoms and R2 represents a linear or branched alkyl radical containing from 1 to 40 carbon atoms; said non-volatile ester oil being chosen such that the composition has at 25°C:
   1) a tack value of less than or equal to 0.01 N.s, preferably less than or equal to 0.005 N.s; and
   2) a gloss of greater than or equal to 50 gloss units at 60°, preferably ranging from 60 to 85 gloss units; and
   3) a setting time of the surface of the film formed by the composition on the keratin material or a synthetic substrate, preferably of less than 1 minute, more preferentially less than or equal to 30 seconds;
   said composition being in the form of a gel with a G* modulus (viscoelastic modulus) of between 100 and 3000 Pa for a phase shift angle of between 30 and 60.
2. Composition according to Claim 1, in which the ethylcellulose content ranges from 10% to 30% by weight, preferably from 15% to 25% by weight and more particularly from 18% to 25% by weight, relative to the total weight of the composition.
3. Composition according to Claim 1 or 2, in which the C₂-C₆ monoalcohol is chosen from isopropanol, ethanol, butanol, and mixtures thereof, and more particularly ethanol.
4. Composition according to any one of the preceding claims, in which the amount of monoalcohol(s) ranges from 10% to 25% by weight, preferably from 12% to 18% by weight relative to the total weight of said composition.
5. Composition according to any one of the preceding claims, comprising at least one linear or branched diester of a C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 glycerol units, preferably 2 or 3 glycerol units, in particular those chosen from polyglyceryl-2 diisostearate, polyglyceryl-3 diisostearate, polyglyceryl-6 diisostearate, polyglyceryl-3 dilaurate, polyglyceryl-4 dilaurate, polyglyceryl-5 dilaurate, polyglyceryl-6 dipalmitate, polyglyceryl-2 distearate, polyglyceryl-3 distearate, polyglyceryl-4 distearate, polyglyceryl-6 distearate, and mixtures thereof, and more particularly polyglyceryl-3 diisostearate.
6. Composition according to any one of the preceding claims, in which the amount of monoester or diester of a C₁₂-C₁₈ carboxylic acid and of polyglycerol comprising from 2 to 6 glycerol units ranges from 5% to 45% by weight, preferably from 20% to 35% by weight relative to the total weight of said composition.
7. Composition according to any one of the preceding claims, in which the volatile hydrocarbon-based oil is chosen from branched C₈-C₁₆ alkanes, and more particularly is isododecane.
8. Composition according to any one of the preceding claims, in which the volatile hydrocarbon-based oil is chosen from linear C₆-C₁₄ alkanes, notably from n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane and n-tetradecane, and mixtures thereof.
9. Composition according to any one of the preceding claims, in which the volatile hydrocarbon-based oil(s) ii) are present in contents of less than or equal to 25.0% by weight and preferably ranging from 5% to 15% by weight relative to the total weight of said composition.
10. Composition according to any one of the preceding claims, in which the non-volatile alkane oil ii) is chosen from linear or branched alkanes including from 20 to 40 carbon atoms, notably chosen from
    - liquid linear or branched paraffins comprising from 18 to 32 carbon atoms;
    - squalane;
    - isoeicosane;
    - mixtures thereof; and more particularly is squalane.
11. Composition according to any one of the preceding claims, in which the non-volatile alkane oil(s) ii) are present in contents of less than or equal to 15.0% by weight and preferably ranging from 3% to 12% by weight relative to the total weight of said composition.
12. Composition according to any one of the preceding claims, comprising at least one non-volatile ester oil chosen from
    - esters of benzoic acid and of a linear or branched C₈-C₂₂ fatty alcohol;
    - C₁₆-C₂₂ dialkyl carbonates;
    - unsaturated esters of linoleic acid or oleic acid and of a linear or branched C₁-C₁₀ alkanol;
    - mixtures thereof.
13. Composition according to Claim 12, in which the non-volatile oil ester of benzoic acid and of a linear or branched C₈-C₂₂ fatty alcohol is chosen from a mixture of lauryl benzoate and myristyl benzoate, a mixture of C₁₂-C₁₅ alkyl benzoates, a mixture of C₁₆-C₁₇ alkyl benzoates, stearyl benzoate, isostearyl benzoate, hexyldecyl benzoate, butyloctyl benzoate, octyldodecyl benzoate, behenyl benzoate, and mixtures thereof; and more particularly is a mixture of C₁₂-C₁₅ alkyl benzoates of INCI name: C12-15 alkyl benzoate.
14. Composition according to Claim 12, in which the non-volatile C₁₆-C₂₂ dialkyl carbonate ester oil is chosen from bis(2-ethylhexyl) carbonate, dicaprylyl carbonate, a mixture of C₁₄-C₁₅ dialkyl carbonates, dipropylheptyl carbonate, and more particularly is dicaprylyl carbonate.
15. Composition according to Claim 12, in which the non-volatile oil unsaturated ester of linoleic acid is chosen from methyl linoleate, ethyl linoleate, isopropyl linoleate; and mixtures thereof, and more particularly is ethyl linoleate.
16. Composition according to Claim 12, in which the oleic acid ester oil is chosen from butyl oleate, decyl oleate, ethylhexyl oleate, ethyl oleate, isobutyl oleate, isodecyl oleate, isopropyl oleate, methyl oleate; and mixtures thereof.
17. Composition according to any one of the preceding claims, in which the non-volatile ester oil(s) iii) are present in contents of less than or equal to 25.0% by weight, preferably from 5% to 20% by weight relative to the total weight of said composition.
18. Composition according to any one of the preceding claims, which is in the form of a gel whose G* modulus (viscoelastic modulus) is between 500 and 2800 Pa, for a phase shift angle of between 30 and 50°.
19. Composition according to any one of the preceding claims, also comprising at least one white or coloured, mineral or organic, coated or uncoated pigment.
20. Composition according to Claim 19, comprising at least 0.01% by weight of pigment(s), more preferentially from 0.1% to 3% by weight of pigment(s), in particular from 0.2% to 1% by weight and preferably from 0.2% to 0.5% by weight of pigment(s), relative to the total weight of said composition.
21. Process for coating keratin materials, more particularly for making up and/or caring for keratin materials, such as the skin, notably the facial areas, in particular the eyelids, characterized in that it comprises the application to the keratin materials of a composition as defined in any one of the preceding claims.