CN108430433A - Composition for whitening or whitening keratin materials - Google Patents

Abstract

The composition in the form of an emulsion comprises an oil phase dispersed in an aqueous phase, and comprises (i) at least one white pigment; (ii) at least one silicone resin selected from MQT resins; and (iii) hollow particles. A method for caring for and/or making up keratinous materials is disclosed.

Description

Composition for whitening or whitening keratin materials

technical field

The present invention relates to compositions for whitening or lightening keratinous materials, especially human skin, and more particularly, the present invention relates to compositions comprising white pigment(s), silicone resin(s) and Composition of hollow particles.

current technology

An important function of cosmetics, especially color cosmetic products such as foundation, mascara, eyeliner, and lip products, is to bring aesthetic improvement to the skin. For this reason, when these products are applied to the skin, they often leave a film on the skin. The better the water resistance of the film, the better the longevity, or in other words, the better the product stays.

Attempts have been made to formulate compositions with good retention.

For example, WO2010149493 discloses a cosmetic composition comprising at least one fatty phase, at least one silicone resin and at least one styrene/acrylate copolymer. The composition itself claims to exhibit good staying power, such as the anhydrous lipsticks mentioned in the examples.

On the other hand, the compositions currently used for the care and/or makeup of keratinous materials, especially the skin, are usually composed of aqueous dispersion continuous It is in the form of an oil-in-water (O/W) type emulsion composed of an oily dispersed discontinuous phase or a water-in-oil (W/O) type emulsion composed of an oily dispersed continuous phase and an aqueous dispersed discontinuous phase.

O/W emulsions are the most popular category in cosmetics because they contain an aqueous phase as the external phase, which gives them a fresher, less greasy and lighter feel than W/O emulsions when applied to the skin.

However, due to their natural properties, conventional oil-in-water emulsions are not entirely satisfactory, especially with regard to immediate and stable whitening or lightening of the skin, without compromising the comfort of use.

Attempts have been made to incorporate silicone resins, styrenic type copolymers as well as pigments and whitening actives into oil-in-water emulsions. However, the present inventors have found that it is difficult to obtain a composition with good skin lightening or lightening (that is, instant whitening or whitening) and long-lasting of the same strength.

Accordingly, there is a need to formulate compositions to overcome the above difficulties.

In particular, there is a need to formulate compositions in the form of emulsions, comprising an oily phase dispersed in an aqueous phase, with improved whitening or lightening of keratinous materials while maintaining good comfort in use. More particularly, there is a need for such compositions to be formulated and to be stable over time. More particularly, there is a need to formulate a composition that maintains a good whitening or whitening effect on the skin even under hot and humid conditions where a large amount of water and sebum are present on the skin. In particular, there is a need to formulate the above compositions with good water resistance and sebum resistance.

Summary of the invention

The inventors have found that by formulating a composition in the form of an emulsion comprising an oil phase dispersed in an aqueous phase and comprising white pigment(s), silicone selected from MQT resin(s) Resins and hollow particles can meet such needs.

Thus, the present invention relates to a composition in the form of an emulsion, comprising an oily phase dispersed in an aqueous phase, and comprising:

(i) at least one white pigment;

(ii) at least one silicone resin selected from MQT resins; and

(iii) Hollow particles.

The compositions of the present invention are advantageous in several respects.

Firstly, the compositions of the invention have an improved whitening or whitening effect on keratinous materials, especially the skin.

In particular, "whitening and whitening effect" means according to the invention an immediate and long-lasting whitening or whitening of keratinous materials, wherein the immediate effect is indicated by the L* _black value after application of the composition of the invention on the substrate, The long-lasting effect is evidenced by the change in L* _black over the course of 24 hours after application of the composition of the invention on the substrate.

The L* _black value is measured by a colorimeter sold under the trade name CHROMA METER CR-400 by the company KONICA MINOLTA.

For the present invention, the higher the L* _black value, the better the whitening or whitening effect of the composition; and for the persistence of the whitening or whitening effect, the smaller the change in L* _black indicates the better lasting effect.

Furthermore, the compositions according to the invention have good comfort in use.

"Use comfort" is intended to mean the feeling of softness, soothing, hydration and moisturization after application of the composition of the invention on keratin materials, without any greasy or dry feeling.

Furthermore, the compositions of the present invention are stable over time.

If no changes in its macroscopic or microscopic appearance and its physicochemical properties (droplet size, pH, viscosity) are observed after storage for 2 months at different temperatures (T = 4 °C, T _{room temperature} , 40 °C and 45 °C), Then the emulsion is stable.

Furthermore, the composition itself provides excellent in-use comfort to the skin, such as softness, soothing, hydration and freshness.

Preferably, the compositions of the present invention are water and sebum resistant. The composition of the present invention is capable of providing good whitening or whitening to the skin even under hot and humid conditions.

The water resistance and sebum resistance of the present invention were measured using a Chromasphere with a resolution of 410×410 pixels, and the results are represented by ΔE ₉₄ , which will be described in more detail below.

According to another aspect, the present invention also relates to a method for caring for and/or making up keratinous materials, in particular human skin, comprising at least one step of applying to said keratinous materials a composition according to the invention.

A further aspect of the present invention relates to the use of the above composition for whitening or whitening keratinous materials.

For the purposes of the present invention, the term "keratin material" is intended to cover skin, mucous membranes (eg lips), nails. According to the invention, the skin, especially the facial skin, is most particularly considered.

A detailed evaluation method will be described below.

Instructions attached

In the description below will be described the accompanying drawings intended to describe the invention in a non-limiting manner, which represent examples of microcapsules to be incorporated in the compositions of the invention.

Figure 1 is the change in L* _black value over the course of 24 hours after application of a composition of the invention on a substrate.

Detailed description of the invention

white paint

The compositions of the invention comprise at least one white pigment.

For the purposes of the present invention, such pigments are not interference pigments.

The specific pigment(s) used in the composition of the invention refers to mineral or organic particles insoluble in aqueous solution, said particles being white, coated or uncoated, spherical or non-spherical, and porous or non-porous.

Thus, the pigments of the present invention may be selected from titanium dioxide, zinc oxide, mica, guanine, sericite, talc, kaolin, cornstarch esterified with octenyl succinic anhydride, and aluminum salts (as described by National Starch under the name Dry Product sold by FloPlus (INCI name: Aluminum Starch Octenylsuccinate).

The white pigment preferably used according to the invention is titanium dioxide, which can especially be in the rutile or anatase form and can be coated or uncoated, provided that the titanium dioxide retains its properties used in this patent application.

The pigments according to the invention may thus be formed from a substrate selected in particular from the above-mentioned list of pigments, preferably titanium dioxide, covered with one or more pigments selected from the group consisting of polydimethylsiloxane (PDMS), aluminum oxide, Coatings of silicon, compounds of trimethylolpropane or even combinations of these compounds.

The pigments according to the invention advantageously have a refractive index of greater than or equal to 1.6, preferably greater than or equal to 1.8, preferably of 1.6 to 2.7.

The pigments according to the invention may have a volume size of less than 30 microns and preferably less than 15 microns.

Preferably, the pigments according to the invention may have a volume size of 500 nm to 30 μm and especially of 1 μm to 15 μm.

In particular, said pigment is advantageously in the form of a white powder.

As white pigments suitable for use in the present invention, mention may be made of the pigment sold under the name Hombitan FFPharma by the company Sachtleben, consisting of titanium dioxide, and the product sold by Miyoshi Kasei under the designation SA-TAO-77891, made of Titanium dioxide (TiO ₂ ) composition of methylsiloxane (PDMS). Mention may also be made of TiO ₂ surface-treated with alumina/silica/trimethylolpropane sold under the designation Tipaque PF671 by Ishihara Sangyo.

The white pigment is present in the composition of the invention in a content of 0.1% to 4% by weight, preferably 0.5% to 3% by weight, based on the total weight of the composition.

Colorimetric definition of white pigment of the present invention

Colorimetric measurements of lightness (L*) and saturation (c*) of pigments in the CIE Lab 1976 colorimetric space can be performed using the CR400 ^® Colorimetric Colorimeter from Minolta.

For this purpose, the pigment is first dispersed in the following cosmetic vehicle:

This pigment dispersion is then introduced into a tank with a volume of 15 ml (caliber: 1.9 cm; depth: 1.8 cm). The surface of the cosmetic medium introduced was smoothed by leveling with a glass slide. The cuvette is then placed in contact with the surface and the colorimetric parameters are determined.

The CR400 ^® colorimeter is calibrated on the one hand with a white reference (white calibration sheet of the Spectralon type) to values of luminance L*=100 and saturation c*=0, and on the other hand with a light trap .

According to a preferred mode, according to the aforementioned scheme, the white pigments of the invention will in particular have an L* value greater than or equal to 95 and a c* value less than or equal to 3.

silicone resin

The composition of the invention comprises at least one silicone resin selected from MQT resins.

The term "resin" as used herein refers to a crosslinked or uncrosslinked three-dimensional structure. "Silicone resins" are also referred to as "silicone resins".

The terminology of silicone resins is known under the name MDTQ, which describes the resin according to the various siloxane monomer units it contains, the letters MDTQ each characterizing the type of unit.

The letter M designates, for example, a monofunctional unit of the formula (CH ₃ ) ₃ SiO _1/2 , the silicon atom being bonded to only one oxygen atom in a polymer comprising such a unit.

The letter D refers to a difunctional unit, eg (CH ₃ ) ₂ SiO _2/2 , where the silicon atom is bonded to two oxygen atoms.

The letter T denotes, for example, a trifunctional unit of formula (CH ₃ )SiO _3/2 .

In the M, D and T units exemplified above as examples, at least one methyl group may be substituted. In some embodiments, the at least one silicone resin comprising at least one trifunctional unit of the formula (R)SiO _3/2 is selected from silsesquioxanes of the formula: ((R')SiO _3/2 ) _x , wherein x is from 100 to 500, and R' is independently selected from a trifunctional unit, a hydrocarbon-based group containing 1 to 10 carbon atoms, or a hydroxyl group, provided that at least one R' is hydrocarbon-based group. In some embodiments, the hydrocarbon-based group containing 1 to 10 carbon atoms is methyl. In some embodiments, the at least one silicone resin comprising at least one trifunctional unit of the formula (R)SiO _3/2 is selected from silsesquioxanes of the formula: ((R')SiO _3/2 ) _x , wherein x is 100 to 500, and R' is independently selected from CH ₃ , a hydrocarbon-based group containing 2 to 10 carbon atoms, or a hydroxyl group, with the proviso that at least one R' is a hydrocarbon-based group.

Finally, the letter Q refers to the tetrafunctional unit SiO _4/2 , in which the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer.

Various resins with different properties can be obtained from these different units. The properties of these polymers vary with the type of monomer (or unit), the type and number of substituent groups, the length of the polymer chain, the degree of branching and the size of the side chain. And change.

According to the invention, the resin is selected from MQT resins.

“MQT resins” means silicone resins comprising MQT units, known in particular from the document US 5 110 890 .

A preferred form of MQT-type resin is the MQT-propyl (also known as MQTpr) resin.

Such resins which can be used in the composition of the invention are in particular those described and prepared in patent application WO2005/075542, the content of which is hereby incorporated by reference.

The MQ-T-propyl resin preferably comprises the following units:

(i) (R1 ₃ SiO _1/2 ) _a

(ii) (R2 ₂ SiO _2/2 ) _b

(iii) (R3SiO _3/2 ) _c and

(iv) (SiO _4/2 ) _d

in

R1, R2 and R3 independently represent a hydrocarbon-based group containing 1 to 10 carbon atoms (especially an alkyl group), phenyl, phenylalkyl or hydroxyl, and preferably an alkane group containing 1 to 8 carbon atoms base or phenyl,

a is 0.05 to 0.5,

b is 0 to 0.3,

c is greater than 0,

d is 0.05 to 0.6,

a + b + c + d = 1, and a, b, c and d are mole fractions,

The proviso is that more than 40 mole % of the groups R3 of the silicone resin are propyl groups.

Preferably, the silicone resin comprises the following units:

(i) (R1 ₃ SiO _1/2 ) _a

(iii) (R3SiO _3/2 ) _c and

(iv) (SiO _4/2 ) _d

in

R1 and R3 independently represent an alkyl group containing 1 to 8 carbon atoms,

R1 is preferably methyl and R3 is preferably propyl,

a is from 0.05 to 0.5, preferably from 0.15 to 0.4,

c is greater than 0, preferably 0.15 to 0.4,

d is 0.05 to 0.6, preferably 0.2 to 0.6, or 0.2 to 0.55,

a + b + c + d = 1, and a, b, c and d are mole fractions,

The proviso is that more than 40 mole % of the groups R3 of the silicone resin are propyl groups.

The silicone resins that can be used according to the invention can be obtained via a process involving the reaction of:

A) MQ resins comprising at least 80 mol % of units (R1 ₃ SiO _1/2 ) _a and (SiO _4/2 ) _d ,

R1 represents an alkyl group, aryl group, methanol group or amino group containing 1 to 8 carbon atoms,

a and d are greater than 0,

a ratio a/d of 0.5 to 1.5; and

B) T-propyl resins comprising at least 80 mol % of units (R3SiO _3/2 ) _c ,

R3 represents an alkyl group, aryl group, methanol group or amino group containing 1 to 8 carbon atoms,

c is greater than 0,

with the proviso that at least 40 mole % of the groups R3 are propyl groups,

Wherein the mass ratio A/B is 95/5 to 15/85.

Advantageously, this mass ratio A/B is from 95/5 to 15/85. Preferably, the mass ratio A/B is less than or equal to 70/30. These preferred ratios have proven to be able to obtain a comfortable deposit due to the absence of percolation of the hard particles of the MQ resin in the deposit.

Mention may be made of MQT resins, such as those sold by the company Dow Corning under the trade name Dow ^Corning® MQ-1640 FlakeResin, which is a 65/35 ratio of trimethylsiloxysilicate and polypropylsilsesquioxane of blends.

The silicone resin is preferably present in the composition according to the invention in an amount of 0.05% to 7% by weight, preferably 0.1% to 5% by weight, based on the total weight of the composition.

hollow particles

The compositions of the present invention comprise hollow particles.

The hollow spherical particles of the present invention may have a particle size of generally 100 to 450 nm, preferably 100 to 380 nm, preferably 150 to 375 nm, as measured by a Brookhaven BI-90 photon correlation spectrometer.

For a given particle size, the hollow particles of the present invention generally have a maximum hollow fraction. The hollow particles preferably have a void fraction of 0.1% to 50%, and more preferably 5% to 50%. The void fraction is determined by comparing the volume occupied by hollow particles that have been compacted in a centrifuge from a diluted dispersion with the volume of void-free particles in the same composition.

The hollow particles of the invention can be obtained from particles comprising at least one polymer for the core and at least one polymer for the shell. The core polymer and the shell polymer can be obtained from a single polymerization step, or from a sequence of polymerization steps.

The hollow particles of the present invention can be prepared by conventional techniques of emulsion polymerization. Such methods are described inter alia in patents US 4,427,836, US 4,469,825, US 4,594,363, US 4,677,003, US 4,920,160 and US 4,970,241, or prepared by conventional polymerization techniques as described in the following patents and patent applications: EP267726, EP331421, US 490,229 and US 5,157,084.

The monomer used for the shell of the hollow particle preferably consists of one or more unsaturated nonionic ethylenic monomers. Optionally, one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group can be polymerized in the shell.

The monomers making up the shell can be selected so that they exhibit a glass transition temperature (Tg) high enough to withstand the voids of the hollow particle. The glass transition temperature is preferably greater than 50°C, more preferably greater than 60°C, even more preferably greater than 70°C. This temperature Tg can be measured by DSC (differential scanning calorimetry).

The monomers used in the emulsion polymerization in the core polymer of the hollow particles of the invention preferably consist of one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group. The core preferably comprises at least 5% by weight of monoethylenically unsaturated monomers containing at least one carboxylic acid group, based on the total weight of the core monomers.

The core polymer is obtained, for example, by emulsion homopolymerization of a monoethylenically unsaturated monomer containing at least one acid group, or by copolymerization of two or three monoethylenically unsaturated monomers containing at least one acid group get. Monoethylenically unsaturated monomers containing at least one acid group are preferably copolymerized with one or more ethylenically unsaturated nonionic monomers.

The core polymer or the shell polymer may contain from 0.1% to 20% by weight, preferably from 0.1% to 3% by weight, of a polyethylenically unsaturated monomer, such as ethylene glycol di(methyl ) acrylate, allyl (meth)acrylate, 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(methyl) Acrylates or divinylbenzene. Alternatively the core polymer or the shell polymer may optionally contain from 0.1% to 60% by weight of butadiene, based on the total weight of the core polymer.

Monoethylenically unsaturated monomers containing at least one carboxylic acid group include, for example: acrylic acid, methacrylic acid, acryloxypropionic acid, (meth)acryloxypropionic acid, itaconic acid, aconitic acid, Maleic acid or maleic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate.

More particularly monomers selected from acrylic acid and methacrylic acid are used.

The monoethylenically unsaturated nonionic monomers include, for example: styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, (meth)acrylic C ₁ -C ₂₀ alkyl esters and (C ₃ -C ₂₀ ) alkenyl esters of (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate and (meth)acrylic acid stearyl esters. According to the invention, the term (meth)acrylic acid shall mean a general expression covering methacrylic acid or acrylic acid. The term (meth)acrylate shall mean a general expression covering either methacrylate or acrylate.

The void portion of the core of the hollow particle is preferably created by swelling the core with a swelling agent comprising one or more volatile compounds. The reagent penetrates the shell to swell the core. Volatile components of the swelling agent can subsequently be removed by drying the hollow particles, thereby creating voids in the particles. The reagent is preferably an aqueous base. Mention may be made, for example, of ammonia, ammonium hydroxide, alkali metal hydroxides such as sodium hydroxide, and volatile amines such as trimethylamine or triethylamine.

The hollow particles can be incorporated into the composition of the invention together with a swelling agent. In this case, the volatile compounds are removed when the composition is dried. The hollow particles can also be added to the composition after the volatile compounds of the swelling agent have been removed.

Hollow particles that can be used according to the invention are those described in patent US 5,663,213 and patent application EP 1092421 .

According to a particular embodiment of the invention, the hollow particles used are those consisting of copolymers of styrene and (meth)acrylic acid or one of their C ₁ -C ₂₀ alkyl esters, whose INCI name is styrene/acrylate A copolymer, such as that sold under the tradename Sunspheres ^™ Powder by Rohm & Haas, which contains 86% styrene/acrylate copolymer with 11% PEG-8 laurate, 2.5% water, and 0.5% Sodium dodecylbenzene sulfonate mixed.

Advantageously, the composition of the invention comprises the hollow particle(s) in an amount ranging from 0.1% to 5% by weight, preferably from 0.5% to 4% by weight, relative to the total weight of the composition.

According to a preferred embodiment, the composition according to the invention relates to a composition for the care and/or makeup of keratin materials in the form of an oil-in-water emulsion, comprising an oily phase dispersed in an aqueous phase, comprising:

(i) 0.5% to 3% by weight of at least one selected from the group consisting of one or more compounds selected from polydimethylsiloxane, alumina, silica, trimethylolpropane or combinations thereof layer of titanium dioxide white pigment;

(ii) 0.1% to 5% by weight of at least one MQT-propyl resin;

(iii) 0.5% to 4% by weight of hollow particles selected from copolymers of styrene and (meth)acrylic acid or one of their C ₁ -C ₂₀ alkyl esters;

The amounts stated herein are relative to the total weight of the composition.

Weight ratio of white pigment (i) to hollow particles (iii)

According to a preferred embodiment, the weight ratio of white pigment (i) to hollow particles (iii) is from 0.1 to 3.

More advantageously, the weight ratio of white pigment (i) to hollow particles (iii) is from 0.5 to 1.5.

For the purposes of the present invention, the composition is intended to whiten or whiten keratinous materials while maintaining hydration and a fresh feel after application.

The above-mentioned preferable weight ratio can obtain the best effect in both the above-mentioned aspects.

water box

The compositions of the present invention comprise at least one continuous aqueous phase.

The aqueous phase of the composition of the invention comprises water and optionally one or more water-miscible or at least partially water-miscible compounds, such as _C2 to _C8 lower polyols or monoalcohols, such as ethanol and isopropanol.

The term "polyol" is understood to mean any organic molecule comprising at least two free hydroxyl groups. Examples of polyhydric alcohols that may be mentioned include glycols such as butylene glycol, propylene glycol and isoprene glycol, glycerol and polyethylene glycol.

The aqueous phase may also contain any of the common water-soluble or water-dispersible additives as described below.

The aqueous phase may represent 30% to 98% by weight, preferably 30% to 95% by weight, better 50% to 90% by weight and even better 60% to 90% by weight of the total weight of the composition.

oil phase

The compositions of the invention comprise at least one oily phase dispersed in an aqueous phase as described above.

The nature of the oily phase of the emulsions of the invention is not critical.

In particular, the oily phase comprises at least one oil.

The term oil refers to any body of fat that is in liquid form at room temperature (20-25°C) and atmospheric pressure. These oils may be of animal, vegetable, mineral or synthetic origin. The oil can be volatile or nonvolatile.

The term "volatile oil" refers to any non-aqueous medium capable of evaporating from the skin or lips in less than one hour at room temperature (20-25°C) and atmospheric pressure (760 mmHg). Essential oils are volatile cosmetic oils that are liquid at room temperature. More specifically, the volatile oil has an evaporation rate of 0.01 to 200 mg/cm2/min inclusive.

The term "fixed oil" is intended to mean an oil that remains on keratin materials at room temperature and atmospheric pressure. More specifically, fixed oils have an evaporation rate strictly below 0.01 mg/cm2/min.

In order to measure this evaporation rate, 15 grams of the oil or oil mixture to be tested are placed in a crystallization dish with a diameter of 7 cm, which is placed in a large room with a temperature adjusted at 25 °C and a humidity adjusted at 50% relative humidity. 0.3 m3 on the balance in the chamber. Allow the liquid to evaporate freely without stirring while providing ventilation with a fan (PAPST-MOTOREN, reference 8550 N, rotating at 2700 rpm) placed vertically above the crystallization dish containing the solvent, with the blades facing the crystallization dish at a distance of 20 cm from the bottom of the crystallization dish . Periodically measure the mass of oil left in the crystallization dish. The evaporation rate is expressed in milligrams of oil evaporated per unit area (cm2) and per unit time (minutes).

Oils suitable for the present invention may be hydrocarbon-based, silicone-based or fluorine-based.

According to the invention, the term "silicone oil" means an oil comprising at least one silicon atom, in particular at least one Si-O group.

The term "fluoro oil" refers to an oil comprising at least one fluorine atom.

The term "hydrocarbon oil" means an oil mainly comprising hydrogen and carbon atoms.

The oil may optionally contain oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid groups.

Among the hydrocarbon-based oils, non-volatile hydrocarbon-based oils are preferably used in the present invention. Mention may be made of these types of oils, such as mono- or diesters of carboxylic acid residues containing 2 to 30 carbon atoms and alcohol residues representing hydrocarbon-based chains containing 1 to 30 carbon atoms, such as isononanoic acid Isononyl, isotridecyl isononanoate, diisostearyl malate, oleyl erucate or 2-octyldodecyl pivalate, isopropyl myristate or ethyl palmitate Hexyl ester.

More preferably, mention may be made, for example, of ethylhexyl palmitate, sold under the trade name Cegesoft C24 by the company BASF.

As silicone oils, mention may be made, for example, of linear or cyclic volatile silicone oils, especially of a viscosity less than or equal to 8 centistokes (cSt) (8×10 ^-6 m ² /s), and especially containing 2 to 10 silicon atoms and especially are those of 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups containing 1 to 10 carbon atoms; linear or cyclic non-volatile polydimethylsiloxanes (PDMS); containing Alkyl, alkoxy or phenyl polydimethylsiloxanes as pendant groups or at the end of the silicone chain, these groups containing 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicone Dimethicone, Phenyl Dimethicone, Phenyltrimethylsiloxydiphenylsiloxane, Diphenyl Dimethicone, Diphenylmethyldiphenyl trisiloxane and 2-phenylethyltrimethylsiloxysilicate; or mixtures thereof.

Mention may preferably be made of polydimethylsiloxanes, which are available under the trademark Xiametrer ^® PMX-200 siliconefluid 10cs from the company Dow Corning, or Belsil ^® DM 10 sold by the company Wacker.

According to a particularly preferred embodiment, the composition according to the invention comprises at least one selected from the group consisting of esters whose carboxylic acid residues contain from 2 to 30 carbon atoms, linear or cyclic non-volatile polydimethylsiloxanes or mixtures thereof. of oil.

More preferably, the composition comprises at least one oil selected from ethylhexyl palmitate, linear non-volatile polydimethylsiloxanes or mixtures thereof.

The amount of the oil phase in the composition of the present invention is less than 35% of the total weight of the composition, preferably less than or equal to 34% of the total weight of the composition.

The amount of oily phase may be, for example, 1% to 35% by weight, preferably 2% to 35% by weight and better 4% to 30% by weight, based on the total weight of the composition.

As stated above, the amount of oil phase does not include the amount of emulsifier.

additive

In a known manner, the compositions according to the invention may also contain one or more additives customary in cosmetics or dermatology.

Examples of auxiliaries that may be mentioned include emulsifiers, gelling agents, active agents, preservatives, antioxidants, fragrances, solvents, salts, additional fillers, opacifiers (=UV-screening agents), additional dyes, alkaline agents (triethanolamine, diethanolamine or sodium hydroxide) or acidic agents (citric acid) as well as lipid vesicles or any other type of carrier (nanocapsules, microcapsules, etc.), and mixtures thereof.

These additives are used in proportions customary in the cosmetic field, for example 0.01% to 30% of the total weight of the composition, and depending on their nature, they can be introduced into the aqueous or oily phase of the composition, or into capsules vesicles or any other type of carrier.

These additives and their concentrations must be such that they do not alter the desired properties of the emulsions of the invention.

Depending on the desired viscosity of the compositions according to the invention, it is possible to incorporate one or more hydrophilic gelling agents therein.

Examples of hydrophilic gelling agents that may be mentioned include modified or unmodified carboxyvinyl polymers such as those sold under the name ^Carbopol® by the company Lubrizol (INCI name: Carbopol); polyacrylamides, For example Ultrez ^10® , ^20® and ^21® from the company Lubrizol; acrylates/C10-30 alkyl acrylate crosspolymers such as those sold under the tradename Permulen TR-1 by the company Lubrizol; derived from 2-propene Homopolymers of amido-2-methylpropanesulfonic acid, such as the product sold under the tradename Hostacerin ^AMPS® by the company Clariant (CTFA name: ammonium polyacryloyldimethyltaurate); polysaccharide biopolymers, such as Gellan gum (such as sold under the tradename Kelcogel ^® CG LA by the company CP Kelco), xanthan gum, guar gum, alginates, and modified or unmodified cellulose; and mixtures thereof.

When present, these gelling agents must be introduced in such an amount that they do not alter the properties of the composition of the invention.

Preferably, the gelling agent is selected from carbomer, acrylate/C10-30 alkyl acrylate crosslinked polymer, ammonium polyacryloyl dimethyl taurate, xanthan gum or a mixture thereof.

The gelling agent is present in an active material content of from 0.05% to 10% by weight and preferably from 0.1% to 5% by weight of the total weight of the composition.

The composition of the invention may be in the form of any galenic form, eg an emulsion comprising an oily phase dispersed in an aqueous phase.

Preferably, the compositions of the invention are in the form of oil-in-water emulsions, for example in the form of serums, emulsions or creams, and they are prepared according to conventional methods.

method and use

The composition which is the subject of the present invention is intended for topical application and constitutes in particular intended, for example, for the care (anti-wrinkle, anti-ageing, moisturizing, sun protection, etc.), treatment, cleansing and makeup of keratinous materials, especially human skin Compositions.

Furthermore, a subject of the present invention is a method for caring for and/or making up keratin materials, characterized in that a composition as defined above is applied to said keratin materials.

In particular, the invention relates to a cosmetic method for whitening or whitening keratinous material, in particular human skin, comprising the step of applying to said keratinous material a composition as defined above.

The invention also relates to the use of the above-mentioned composition for whitening or whitening keratinous materials, especially human skin.

The invention is illustrated in more detail by the examples described below, which are given as non-limiting illustrations.

Percentages are by weight of active ingredient or active material.

In the following examples, the weight percentages are described based on the total weight of the composition.

Example

Preparation of Inventive and Comparative Formulas

Preparation of Inventive Formulation D and Comparative Formulations K, L and M:

.

Comparative formulations K, L and M each contained a film former comprising silicone, but were outside the definition of ingredient (ii) of the present invention.

making process:

Heat phase A to 80°C until dissolved, add A1 to phase A and homogenize for 30 minutes;

Heat phase B to 75°C until dissolved, add B1 to phase B and homogenize for 8 minutes;

Mix phase C by stirring until dissolved, heating to 75 °C;

Mix phases B and C into phase A and homogenize for 10 minutes;

The mixture obtained above was cooled to 60° C., phase D was added to the mixture separately and homogenized for 15 minutes;

The mixture was cooled to 35°C, phases E and F were added to the mixture with stirring until homogeneous.

The homogenizer used in this method is sold by the company VMI.

Evaluate inventive and comparative formulations

The whitening or whitening effect of the inventive and comparative formulations was evaluated using the following in vitro protocol:

Films of 125 μm thickness of the formulation were applied respectively on comparative cards (ERICHSEN Typ 24/5 sold by BYK company), the cards with the formulation were dried at room temperature (20-25° C.) for 24 hours, and subsequently passed by KONICA MINOLTA The L* _black value is measured with a colorimeter manufactured by the company under the trade name CHROMA METER CR-400.

The L* _black value was evaluated during 24 hours after application of the formulation on the card to obtain the change in L* _black over time.

The L* _black value indicates the whitening or whitening effect of the skin, with higher values being preferred.

For the present invention, a lower change in L* _black value over time is preferred.

The evaluation results are presented in Figure 1.

Subsequently, the whitening or whitening effect of the inventive formula D under hot and humid conditions was evaluated through a Chromasphere with a resolution of 410×410 pixels according to the following protocol:

Measurements were carried out in a standardized manner at 20°C and 45% humidity and at 37°C and 60% humidity after applying the inventive formulation D with bare fingers to the skin of the model.

By measuring the mean values of C* (chroma, distance from neutral axis - saturation), H* (hue, angle/direction over 360 degrees) and L* (lightness) on a panel of 16 female models respectively Colorimetric measurements of the skin before and after application of inventive formulation D were performed.

For each of the 16 female models, images were captured using a Chromasphere with a resolution of 410×410 pixels. Results are expressed in the following way: Color is quantified by C* (chroma, distance from neutral axis - saturation), H* (hue, angle/direction over 360 degrees) and L* (lightness) analyzed by the camera.

Whitening and whitening effects were calculated by ΔE ₉₄ after application of the inventive and comparative formulations. The ΔE, dE or ΔE ₉₄ is defined as a measure of the difference between two colors. As shown below, the formula was published by the CIE Technical Committee in 1995 (TC1-29):

K _L , K ₁ and K ₂ are weighting factors;

L ₁ *, C ₁ * and H ₁ * are the coordinates of the first color to be compared in the colorimetric space, and L ₂ *, C ₂ * and H ₂ * are the coordinates of the second color.

The measurements were carried out in a group of 16 female phantoms who were kept for 30 minutes in air conditioning (temperature 21 °C +/- 1 °C, humidity 45% +/- 5%). Images of T ₀ were taken on the bare skin of the female model using Chromasphere.

Approximately 200 mg of Inventive Formula D was weighed out into a watch glass and applied with bare fingers to half of the face of a female model, on which the measurements were taken.

Images of the cheeks with inventive formulation D were acquired using Chromasphere 10 minutes after application of inventive formulation D. This image enables the measurement of color immediately after application of inventive formulation D ( _Timmediately ). The female model was then left in a steam room (temperature 37°C +/- 1°C, humidity 60% +/- 5%) for 1 hour. Then they went back to the air-conditioned room and waited for 1 hour. Finally, an image of the cheek with Invention Formula D was taken using the Chromasphere. This image enables the measurement of the color (T _2h ) of a female model exposed to hot and humid conditions for 1 hour, and for a total of 2 hours after application of inventive formula D on the cheeks.

Each image obtained using the camera was processed by coxellography. Computes the standard deviation for each monochromatic plane. The product of three standard deviations equals the coxellographic index. This parameter is used for statistical calculations. The more uniform the skin, the smaller the standard deviation. The coxellographic index changes in the same way, since it is the product of the standard deviations of the three planes C* (chroma), H* (hue) and L* (lightness).

The result is as follows:

project T _instant vs T ₀ T _2h vs T ₀ T _2h vs T _Immediately ΔE ₉₄ in hot and humid conditions 2.38±0.44 2.43±0.50 0.78±0.46

in conclusion

It is observed from Figure 1 that Inventive Formulation D shows improved whitening or whitening effect compared to Comparative Formulations K, L and M, and this effect is long-lasting. Comparative formulas K, L and M had low whitening or whitening values and the values decreased over time.

Inventive formulation D and comparative formulations K, L and M all had good application comfort on the skin, the skin was hydrated and refreshed.

In addition, it can be observed from ΔE ₉₄ that the inventive formula D still has a good whitening or whitening effect in a hot and humid environment. In other words, Invention Formula D has good water resistance and sebum resistance.

Claims (17)

1. A composition in the form of an emulsion comprising an oily phase dispersed in an aqueous phase, and comprising: (i) at least one white pigment; (ii) at least one silicone resin selected from MQT resins; and (iii) Hollow particles. 2. The composition of claim 1, wherein the white pigment is selected from white mineral or organic particles, insoluble in aqueous solution, coated or uncoated, spherical or non-spherical, porous or non-porous, or Mixture; preferably selected from titanium dioxide coated with one or more layers selected from compounds selected from polydimethylsiloxane, aluminum oxide, silicon dioxide, trimethylolpropane or combinations thereof; more preferably selected from coated Titanium dioxide coated with dimethicone. 3. The composition of claim 1 or 2, wherein the white pigment has a refractive index greater than or equal to 1.6, preferably greater than or equal to 1.8, preferably 1.6 to 2.7. 4. The composition of any one of the preceding claims 1 to 3, wherein the white pigment is present in the composition. 5. The composition of any one of the preceding claims 1 to 4, wherein the MQT resin is selected from MQT-propyl resins, preferably from MQT-propyl resins comprising the following units: (i) (R1 ₃ SiO _1/2 ) _a (ii) (R2 ₂ SiO _2/2 ) _b (iii) (R3SiO _3/2 ) _c and (iv) (SiO _4/2 ) _d in R1, R2 and R3 independently represent a hydrocarbon-based group containing 1 to 10 carbon atoms (especially an alkyl group), phenyl, phenylalkyl or hydroxyl, and preferably an alkane group containing 1 to 8 carbon atoms base or phenyl, a is 0.05 to 0.5, b is 0 to 0.3, c is greater than 0, d is 0.05 to 0.6, a + b + c + d = 1, and a, b, c and d are mole fractions, with the proviso that more than 40 mole % of the groups R3 of the silicone resin are propyl groups; Preferably, the siloxane resin comprises the following units: (i) (R1 ₃ SiO _1/2 ) _a (iii) (R3SiO _3/2 ) _c and (iv) (SiO _4/2 ) _d in R1 and R3 independently represent an alkyl group containing 1 to 8 carbon atoms, R1 is preferably methyl and R3 is preferably propyl, a is from 0.05 to 0.5, preferably from 0.15 to 0.4, c is greater than 0, preferably 0.15 to 0.4, d is 0.05 to 0.6, preferably 0.2 to 0.6, or 0.2 to 0.55, a + b + c + d = 1, and a, b, c and d are mole fractions, The proviso is that more than 40 mole % of the groups R3 of the silicone resin are propyl groups. 6. The composition of any one of the preceding claims 1 to 5, wherein the MQT resin is a blend of trimethylsiloxysilicate and polypropylsilsesquioxane. 7. The composition of any one of the preceding claims 1 to 6, wherein said MQT resin is present in said composition. 8. The composition of any one of the preceding claims 1 to 7, wherein the hollow particles have a particle size of 100 to 450 nm, preferably 100 to 380 nm, preferably 150 to 375 nm. 9. The composition of any one of the preceding claims 1 to 8, wherein the hollow particles are obtained from particles comprising at least one polymer for the core and at least one polymer for the shell, wherein the The polymer comprises unsaturated nonionic ethylenic monomers, preferably monoethylenically unsaturated monomers containing at least one carboxylic acid group; the polymer used for the core contains monoethylenically unsaturated monomers containing at least one carboxylic acid group saturated monomer. 10. The composition of claim 9, wherein the monoethylenically unsaturated monomer is selected from the group consisting of styrene, vinyl toluene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, C ₁ -C ₂₀ alkyl (meth)acrylates and (C ₃ -C ₂₀ )alkenyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palm (meth)acrylate esters and stearyl (meth)acrylate. 11. The composition of any one of the preceding claims 1 to 10, wherein the hollow particles are selected from copolymers of styrene and (meth)acrylic acid or one of their _C1 - _C20 alkyl esters. 12. The composition of any one of the preceding claims 1 to 11, wherein the hollow particles are present in the composition. 13. Composition for the care and/or makeup of keratinous materials in the form of an oil-in-water emulsion comprising an oily phase dispersed in an aqueous phase and comprising: (i) 0.5% to 3% by weight of at least one white pigment selected from titanium dioxide coated with one or more pigments selected from polydimethylsiloxane, aluminum oxide, silicon dioxide, trihydroxy Layers of compounds of methylpropane or combinations thereof; (ii) 0.1% to 5% by weight of at least one MQT-propyl resin; (iii) 0.5% to 4% by weight of hollow particles selected from copolymers of styrene and (meth)acrylic acid or one of their C ₁ -C ₂₀ alkyl esters; Wherein said amounts are relative to the total weight of said composition. 14. The composition of any one of the preceding claims 1 to 13, wherein the weight ratio of white pigment (i) to hollow particles (iii) is from 0.1 to 3, preferably from 0.5 to 1.5. 15. The composition of any one of the preceding claims 1 to 14, wherein said composition further comprises at least one oil selected from esters, linear or cyclic oils whose carboxylic acid residues contain from 2 to 30 carbon atoms Shaped non-volatile polydimethylsiloxanes or mixtures thereof; preferably selected from ethylhexyl palmitate, linear non-volatile polydimethylsiloxanes or mixtures thereof. 16. Cosmetic method for whitening or lightening keratinous material, especially human skin, comprising the step of applying a composition according to any one of the preceding claims 1 to 15 on said keratinous material. 17. Use of a composition according to any one of the preceding claims 1 to 15 for whitening or whitening keratinous material, especially human skin.