CN104168874B

CN104168874B - Color changing composition with polyol

Info

Publication number: CN104168874B
Application number: CN201380014738.7A
Authority: CN
Inventors: C·莱莫恩; 楚娟
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2012-01-17
Filing date: 2013-01-16
Publication date: 2017-04-19
Anticipated expiration: 2033-01-16
Also published as: CN104168874A

Abstract

A changing color composition for caring for and/or making up keratin materials is disclosed. The composition comprises in a physiologically acceptable medium, at least: a) microcapsules containing one or more releasable colorant(s), said microcapsules comprising: a core comprising one organic material; at least one layered coating surrounding said core, the layered coating comprising at least one polymer, at least one colorant, and advantageously at least one lipid-based material, b) at least 10% by weight of polyol(s) and/or glycol(s) relative to the weight of the composition, c) at least one hydrophilic gelifying agent, d) and optionally 0.1 to 70% by weight relative to the weight of the composition, of additional cosmetic ingredient(s) selected from volatile and non-volatile silicon or hydrocarbon oils, surfactants, filler, thickening agents, film forming agents, polymers, preservatives, silicon elastomer, self-tanning agents, additional non-entrapped colorants, cosmetic actives, pH regulators, perfumes, and mixtures thereof.

Description

Color-changing composition with polyol

Technical Field

The present invention relates to a color-changing composition comprising at least one polyol and/or diol, in particular for the care, hygiene and/or make-up of keratin materials.

In particular, the color-changing composition according to the invention may be any type of cosmetic composition, such as a foundation, face powder, eye shadow, concealer product, blush, lipstick, lip gloss, lip pencil, eyeliner, mascara, body makeup, skin coloring product, skin care product such as skin cream, 'BB' product (concealer product capable of concealing imperfections), colored cream or sunscreen product, preferably a foundation or 'BB' product. The color-changing composition according to the present invention may be liquid, solid or powder.

The compositions of the invention are in particular compositions intended to be applied to keratin materials, in particular the skin, more particularly the skin of the ground, for example, skin care products or cosmetics for the face.

According to another embodiment, the composition of the invention is a mascara.

According to a further embodiment, the composition of the invention is a product for the lips, in particular a lip gloss, lip balm or lipstick.

Background

Cosmetic compositions, especially foundations, are commonly used to impart aesthetic color to the skin, but also to mask skin imperfections such as redness and/or scarring. In this regard, many formulations have been developed to date.

In this regard, there is increasing interest in cosmetics that provide a color change in response to an external stimulus, such as shear force.

Generally, this object is achieved by including microencapsulated colorants in a cosmetic composition, wherein the composition provides the desired color change when applied to the skin. More specifically, the color change is provided by microcapsules containing a colorant, which upon rupture by application of mechanical force release the entrapped colorant into the composition, thereby changing its color. Mechanical action, such as rubbing, spreads the topical composition and facilitates its penetration into the skin. The immediate change in color of the composition provides a visual aesthetic effect.

Different types of encapsulated colorants, more particularly microcapsules containing pigments, are already available. They differ mainly by the type of containment material and/or the type of encapsulation.

Thus, as the microencapsulated pigment by the polymer or copolymer of acrylic acid and/or methacrylic acid, for example, microcapsules comprising A copolymer of ethyl acrylate/ammonium methacrylate salt sold by tagar described in WO-A-01/35933 can be proposed. And alsoMention may be made of the name by TAGRA BIOTECHNOLOGIES Andencapsulated pigments are sold.

As pigments encapsulated by microspheres of cellulose derivatives, mention may be made, for example, of the pigments known by the company Inuchem under the nameSold spheres comprising cellulose, hydroxypropyl methylcellulose.

As microencapsulated pigments of polymers of the polyester type, polyaminomethacrylate type, polyvinylpyrrolidone type, hydroxypropylmethylcellulose type, shellac type and mixtures thereof, mention may be made in particular of the pigments described in application US 2011/0165208 to Biogenics and by Biogenics under the nameThose pigments sold.

As other microencapsulated pigments, mention may also be made of those pigments disclosed in JP2011-79804 by DAITO, and also of pigment-encapsulating double-layer microcapsules comprising three or more than three of the following materials: (a) mannitol, (b) hydrogenated lecithin, (c) polymethyl methacrylate, (d) cellulose and (e) shellac.

These double-layer microcapsules do not comprise, like one of the microcapsules preferably used according to the invention, an uncoloured core, but a coloured inner layer comprising the above-mentioned components, which are all mixed together and then granulated.

However, with some microcapsules containing a colorant, it is difficult to permanently retain the colorant over long periods of time, and when subjected to different environments and conditions. This is true of pigments, oil-soluble dyes, and water-soluble dyes. Thus, some of the microcapsules described in the patents and publications have been found: when tested at elevated temperatures for extended periods of time, the microcapsules gradually release the colorant, or "bleed out," over time. Bleeding occurs when the dye or pigment migrates through or out of the microspheres/microcapsules by contact with moisture and/or other components in the formulation, such as alcohols or glycols, surfactants, silicones, oils, preservatives, salts and other ingredients typically present in cosmetic formulations. Adsorption or bleeding of colorants in cosmetic compositions can impair the long-term visual impact of the cosmetic product in the container and on the substrate.

In addition, some microcapsules containing pigments can give less coverage than expected.

In addition, some microcapsules containing pigments burst immediately upon application, and therefore, although a sudden color change is interesting, it is not possible to achieve an intermediate stage of the color change or to adjust the tone scale.

In addition, some microcapsules comprising pigments may have some stability problems depending on the cosmetic composition and with respect to the relevant solvents/components.

In addition, some microcapsules containing pigments can have a grey appearance, which imparts an unattractive color to the body of the cosmetic composition.

Finally, some microcapsules can provide an uncomfortable and/or unpleasant feel when a cosmetic formulation comprising the microcapsules is applied to a keratin material.

More particularly, because of the lack of deformability and lack of softness of the microcapsules, some topical compositions containing microcapsules can provide a skin peeling or abrasion sensation to the user.

Disclosure of Invention

Therefore, there is a need to provide a cosmetic composition having microcapsules containing a colorant with improved color bleed resistance. In this regard, there is a need for microcapsules containing colorants that maintain good shatter resistance and have improved barrier properties. In cosmetic compositions, if the dye is not permanently retained, this can impair the long-term visual effect of the cosmetic.

It would also be desirable to provide cosmetic compositions that allow for the adjustment of the preferred coloration or tone scale pattern by varying the method or intensity of application to the skin, or the use of microcapsules containing different colorants.

There is also a need to provide cosmetic compositions that are stable with a wide array of associated solvents/components.

There is also a need to provide cosmetic compositions in which the microcapsules are visible or invisible within the body of the composition, depending on the desired appearance.

There is also a need for a cosmetic composition comprising pigment-encapsulated microcapsules that do not cause an uncomfortable feeling to the user when applied.

There is also a need to provide cosmetic compositions comprising pigment-encapsulated microcapsules which disintegrate quickly or even immediately upon application, produce a liquid feel on the skin and leave the colored composition without any grainy appearance. In particular, the composition may exhibit different shades or gradations depending on the frictional strength.

There is also a need to provide pigment encapsulated microcapsules that are sufficiently hard to be mixed in an industrial process without replacement. Advantageously, the hardness of the microcapsules does not significantly decrease during the preparation process.

There is also a need to provide a cosmetic composition that imparts and/or improves the deformability of microcapsules.

There is also a need to propose a cosmetic composition having microcapsules containing a colorant which softens the microcapsules to provide a comfortable feel and a soft feel to the user when applied on the skin.

There is also a need to provide a cosmetic composition having a good fresh feel, good spreading and gliding properties, while avoiding a greasy feel, tautness and friction effects.

Surprisingly and advantageously, the compositions according to the invention meet the needs of the prior art.

Thus, according to one aspect of the present invention, a subject of the present invention is a color-changing composition for caring for and/or making up keratin materials, comprising, in a physiologically acceptable medium, at least:

a) a plurality of microcapsules comprising one or more releasable colorants, the microcapsules comprising:

-a core comprising an organic material,

-at least one layer of coating surrounding the core, the at least one layer of coating comprising

At least one kind of polymer,

at least one kind of coloring agent is selected from the group consisting of,

and advantageously at least one lipid-based material,

b) at least 10% by weight, relative to the weight of the composition, of polyols and/or diols,

c) and optionally, from 0.1% to 70% by weight, relative to the weight of the composition, of another one or more cosmetic components selected from volatile and non-volatile silicone oils or hydrocarbon oils, surfactants, fillers, gelling agents, thickeners, film formers, polymers, preservatives, silicone elastomers, self-tanning agents, additional non-entrapped colorants, cosmetically active agents, pH adjusting agents, fragrances, and mixtures thereof.

Preferably, the microcapsules comprise at least two layers, preferably at least one organic inner layer and one organic outer layer of different colors.

Preferably, said core comprises as said organic material at least one monosaccharide or a derivative thereof, in particular a monosaccharide-polyol advantageously selected from mannitol, erythritol, xylitol, sorbitol and mixtures thereof, preferably mannitol.

Preferably, the coating layer surrounding the at least one layer of the core comprises at least one hydrophilic polymer selected from the group consisting of: polysaccharides and derivatives, preferably polysaccharides and derivatives comprising one saccharide type or more saccharide types, preferably more saccharide types comprising at least D-glucose units, especially starch and derivatives, cellulose or derivatives, more preferably starch and derivatives.

Preferably, the microcapsules comprise at least one lipid-based material, preferably having amphiphilic properties, such as lecithin, in particular hydrogenated lecithin.

Advantageously, the core represents from 1% to 50% by weight, preferably from 5% to 30% by weight, in particular from 10% to 20% by weight, relative to the total weight of the microcapsule.

Advantageously, the one or more colouring agents represent from 20% to 90%, preferably from 30% to 80%, in particular from 50% to 75% by weight with respect to the microcapsules.

Advantageously, the microcapsules have a size of 50 to 800 μm, in particular 60 to 600 μm, in particular 80 to 500 μm, in particular 100 to 400 μm.

In particular, the microcapsules comprise at least:

-an inner core made of monosaccharide-polyol, preferably mannitol,

-at least two layers of different colors,

-at least one hydrophilic polymer, preferably selected from polysaccharides or derivatives, more preferably from starch or derivatives,

and advantageously at least one lipid-based material, preferably an amphiphilic compound, more preferably a phospholipid, even more preferably a phosphoryl glycerol, such as hydrogenated lecithin.

Preferably, the microcapsule comprising one or more releasable colorants is a multilayer microcapsule comprising one or more releasable colorants, the microcapsule comprising:

-an uncolored core of an organic material, and

-a multilayer coating surrounding said core, said multilayer coating comprising at least one organic inner layer and one organic outer layer of different colors and respectively containing at least one colorant.

The composition may comprise at least 0.1% to 20%, preferably between 0.5% and 15%, in particular between 2% and 10% by weight of microcapsules relative to the total weight of the composition.

The present invention is also directed to a cosmetic process for caring for and/or making up keratin materials, comprising the application to the said keratin materials, in particular the skin, of a composition according to the invention.

The term "physiologically acceptable medium" is used to indicate a medium particularly suitable for applying the product of the invention to keratin materials, in particular the skin, more particularly the ground skin.

The "physiologically acceptable medium" comprises the aqueous phase used according to the invention.

For the purposes of the present invention, the term "keratin materials" is intended to cover the skin, mucous membranes, such as the lips, the nails and the eyelashes. According to the invention, the skin and lips, in particular the facial skin, are particularly considered.

As presented from the examples below, the compositions according to the invention prove to be advantageous in various respects.

The encapsulation of the colorant prevents undesirable reaggregation of the pigment during manufacture and long-term storage of the cosmetic composition.

Since the microcapsules of the invention are capable of swelling or softening upon contact with an aqueous phase as defined below, advantageously they are deformable when applied to keratin materials, thus providing a soft feel to the user. In addition, their small size helps not to create any uncomfortable or undesirable grainy sensation when applied.

However, the microcapsules of the present invention are soft enough to break to release their contents when subjected to very slight rubbing or squeezing on the skin, but they are durable enough to avoid coating damage during manufacture of the corresponding color-changing composition, even during industrial processes and storage.

In addition, the microcapsules of the present invention allow the preparation of the compositions of the present invention using conventional equipment, since no coloration of the equipment occurs during the manufacturing process.

Thus, the microcapsules of the present invention are particularly attractive because they mask the original color of the encapsulated colorant, enhance the stability of these colorants against degradation, and prevent the undesirable release of the encapsulated colorant into the composition during the manufacturing process and long term storage.

Finally, the compositions of the present invention also have the advantage of meeting consumer expectations in terms of cosmetics.

According to another aspect of the present invention, the subject of the present invention is also directed to a cosmetic process comprising at least a step consisting in applying at least part of the composition according to the invention to the surface of a keratin material, in particular the surface of the skin.

According to the invention, a "color-changing composition" refers to a composition which: wherein the color before application is different from the color after application, the difference being visible to the naked eye.

In particular, the color-changing composition can be associated with a color difference Δ Ε of CIE laboratory system 1976(Δ Ε pre-application/post-application) values.

Δ E is defined by the equation:

wherein L is₁、a₁、b₁Is a parameter in the chromaticity space of the first color (composition before application), and L₂、a₂、b₂Is a parameter in the chromaticity space of the second color (composition after application and homogenization on the keratin material).

These values can be measured by spectrophotometer or with a chromosphere (Chromasphere) (composition for application to the skin).

The color-changing composition according to the invention can be characterized as having a before/after application Δ Ε of greater than 1, in particular greater than or equal to 2, preferably greater than or equal to 3.

Colored microcapsules

The term "microcapsule" as used herein refers to spherical microcapsules of: the spherical microcapsule comprises at least one coating layer containing at least one colorant and surrounding a core chemically distinct from said coating layer. Microcapsules are distinguished from microspheres, which consist of a spherical homogeneous matrix.

According to an embodiment, the "at least one coating layer" is a multilayer coating, preferably an organic multilayer coating.

The term "multilayer microcapsule" refers to a microcapsule consisting of a core surrounded by a coating based on one or more inner layers and one outer layer. The inner layer or layers of the multilayer coating forming the multilayer microcapsule and the single outer layer of the microcapsule may be composed of the same or different wall-forming organic compounds.

The microcapsules according to the invention comprise a core, also called "inner core", surrounded by a coating based on one or more layers. In a preferred embodiment, the microcapsule is a 'multilayer' microcapsule comprising at least one inner layer and one outer layer. The inner layer or layers of the multilayer coating forming the multilayer microcapsule and the single outer layer of the microcapsule may be composed of the same or different wall-forming organic compounds.

In a particular embodiment, the inner layer and the outer layer are composed of the same organic wall-forming compound, so that the core is surrounded by a coating.

In one embodiment, the outer layer does not contain any colorant. In another embodiment, the outer layer comprises at least one colorant.

The term "wall-forming organic compound" refers to an organic compound or a combination of two or more different organic compounds as defined herein, which form a component of one or more layers of the microcapsule. In a preferred embodiment, the 'wall-forming organic compound' comprises at least one polymer.

The term "colorant" refers to: organic pigments such as any synthetic or natural dye selected from the well-known FD & C or D & C dyes; inorganic pigments such as metal oxides, or lakes, and any combination (blend) thereof. Thus, colorants useful according to the present invention may be oil soluble or oil dispersible or have limited solubility in water.

In a preferred embodiment, the colorant is an inorganic pigment, more preferably a metal oxide.

Generally, according to the present invention, an average particle diameter of up to about 800 μm in diameter of the colorant microcapsules is used. Preferably, for skin care applications, the average particle size is less than about 400 μm, based on the diameter of the colorant microcapsules. Advantageously, the average particle size is in the range of about 10 to 350 μm in diameter. Preferably, the average particle size will be from 50 μm to 800 μm, especially from 60 μm to 600 μm, especially from 80 μm to 500 μm, especially from 100 μm to 400 μm in diameter.

In particular, the average particle diameter may be 50 to 1000 mesh (about 400 to 10 μm), particularly 60 to 200 mesh (about 250 to 75 μm), as measured by a screening test method or observed by a microscope.

Preferably, the composition may comprise from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight of microcapsules relative to the total weight of the composition according to the invention.

Especially for the skin care composition according to the invention, the amount of microcapsules is from 0.1% to 5%, preferably from 0.2% to 3% by weight relative to the total weight of the composition.

Especially for the cosmetic composition according to the invention, the amount of microcapsules is from 0.5% to 20%, preferably from 1% to 15%, more preferably from 2% to 10% by weight relative to the total weight of the composition.

According to a particular embodiment, the encapsulated colorant may be present in the composition in an amount of from 0.5% to 20% by weight, in particular from 1% to 15% by weight, more particularly from 2% to 12% by weight, based on the active material encapsulating the pigment, of the total weight of the composition according to the invention.

The microcapsules will generally be incorporated into the cosmetic formulation during the final stage of formulation and after the filtration stage (if any), to avoid rupture of the microcapsules. Preferably, the microcapsules according to the invention are added and homogeneously mixed at a temperature of 50 ℃. The microcapsules were gently mixed using a stirring paddle instead of a homogenizer.

Microcapsules can be manufactured by a number of methods known to those skilled in the art in the field of coating or encapsulation, including spheronization, granulation, coating, and the like. For example, the microcapsules can be obtained by a process comprising mixing the compounds (active agents, pigments, polymers, solvents) and drying to form capsules as disclosed in WO01/35933 and WO2011/027960, or by a process comprising granulation and spray-dry coating as disclosed in FR2841155, or by a fluid bed technique which has long been used in the food and pharmaceutical industry for coating and encapsulating components. As mentioned, for example, in WO2008/139053, WO2008/139053 relates to the preparation of a spherical multilayered capsule comprising a sugar core and concentric layers of a pharmaceutically active agent. The immobilization of the pharmaceutically active agent on the core is achieved by dipping, crushing, or spraying, and then the first layer is dried before the second layer is applied.

For example, in the Fluid-Bed process disclosed by Teunou et al (Fluid-Bed Coating, Poncelet, 2005, D.food Science and Technology (Boca Raton, FL, United States), Vol.146, IssueEnencapsulated and Powdered Foods, p.197-212). A particular feature of the fluidized bed process is that it results in coated particles with a well encapsulated core compared to spray drying, which results in a matrix and a random dispersion of the core material in the polymer.

In a preferred embodiment, the microcapsules are obtained by a fluidized bed process.

According to this embodiment, at least one layer of microcapsules is preferably obtained by a fluidized bed process.

In a particular embodiment, the outer layer is obtained by a fluidized bed process.

In another particular embodiment, the at least one inner layer is obtained by a fluidized bed process.

Most preferably, all layers are obtained by a fluidized bed process.

The person skilled in the art knows how to adjust the amount of air, the amount of liquid, and the temperature that allow the reproduction of the capsules according to the invention.

Preferably, the fluidized bed process carried out according to the invention comprises the hurster process and/or the tangential spraying process. In contrast to the spheronization process, this process allows the production of spherical capsules, in which the core is surrounded by one or more surrounding layers.

When the entire process for manufacturing the layer surrounding the core of the microcapsules according to the invention is carried out by a fluidized bed process, the microcapsule layer is advantageously regular, concentric and exhibits a uniform thickness.

In the following description, different examples of the preparation of capsules according to the invention will be given.

I a) core

The core is made of at least an organic material. The core is preferably sized in the range of 500nm to 150 μm in diameter.

Preferably, the core is in solid form and/or crystalline form at room temperature.

In a particular embodiment, the organic material is selected from organic materials that are highly water soluble. Preferably, the core is water soluble or water dispersible.

In a particular embodiment, the core is uncolored, i.e. the core does not contain colorant material.

In a particular embodiment, the core is based on only one compound. The compound is organic and more preferably a natural compound.

According to a preferred embodiment, the core is a sugar-alcohol, preferably a monosaccharide-polyol advantageously selected from mannitol, erythritol, xylitol, sorbitol.

In a particular embodiment, the core is made of mannitol, more preferably only mannitol.

According to an alternative embodiment, the core comprises at least mannitol and at least one further ingredient, which is preferably a polymer selected from hydrophilic polymers. In particular, such a core may comprise mannitol and a hydrophilic polymer selected from the group consisting of cellulose polymers, starch polymers and mixtures thereof, preferably mixtures thereof.

In a preferred embodiment, the cellulose polymer is carboxymethyl cellulose and the starch polymer is an unmodified native starch, such as corn starch.

The core may be constituted by a seed (or crystal) of one of the above materials.

The core is preferably included in an amount of from 1% to 50% by weight, preferably from 4% to 40% by weight, in particular from 5% to 30% by weight and in particular from 10% to 20% by weight, relative to the total weight of the microcapsule.

Mannitol is preferably included in an amount of 2 to 100% by weight, preferably 5 to 100% by weight, in particular 100% by weight, relative to the total weight of the core.

Mannitol is preferably included in an amount of 1% to 50% by weight, preferably 4% to 40% by weight, in particular 5% to 30% by weight, and in particular 10% to 20% by weight, relative to the total weight of the microcapsule.

I b) outer layer or coating

As previously disclosed, the core is advantageously surrounded by a coating or outer layer, which preferably comprises at least one inner layer and one outer layer. In this latter case, the layers preferably extend concentrically with respect to the core.

The layer or layers are preferably organic, i.e. contain at least one organic compound as wall-forming material. Preferably, the inner layer and/or the outer layer comprise at least one polymer, in particular a hydrophilic polymer.

Polymer and method of making same

The composition according to the invention comprises one or more polymers. In a particular embodiment, the polymer is a hydrophilic polymer.

Such hydrophilic polymers may be dissolved or dispersed in water or alcohol compounds, especially alcohol compounds selected from the group consisting of lower alcohols, diols, polyols.

For the purposes of the present patent application, the term "hydrophilic polymer" refers to a (co) polymer capable of forming hydrogen bonds with water or alcohol compounds, in particular alcohol compounds selected from the group consisting of lower alcohols, diols, polyols. In particular, polymers capable of forming O-H, N-H and S-H bonds are of interest.

According to a particular embodiment of the invention, the hydrophilic polymer may swell or soften when contacted with water or an alcohol compound, in particular an alcohol compound selected from the group consisting of lower alcohols, diols, polyols.

The hydrophilic polymer may be selected from the following polymers:

homopolymers or copolymers of acrylic or methacrylic acid or salts and esters thereof, in particular: products sold under the name Versicol F or Versicol K by Allied Colloid company; the product sold under the name Ultrahold 8 by the company Ciba-Geigy; and polyacrylic acids of the Synthalen K type; and salts of polyacrylic acids, especially the sodium salt (corresponding to the INCI name sodium acrylate copolymer), more especially the crosslinked sodium polyacrylate sold by the company under the name Luvigel EM (corresponding to the INCI name sodium acrylate copolymer (and) caprylic/capric triglyceride);

copolymers of acrylic acid and of acrylamide in the form of their sodium salts, sold under the name Reten by the company Hercules, sodium polymethacrylate, sold under the name Darvan No.7 by the company Vanderbilt, and the sodium salt of a polyhydroxycarboxylic acid, sold under the name Hydagen F by the company Henkel;

-polyacrylic acid/alkyl acrylate copolymers, preferably modified or unmodified carboxyvinyl polymers; particularly preferred copolymers according to the invention are acrylates/C₁₀-C₃₀Alkyl acrylate copolymers (INCI name: acrylate/C)₁₀-C₃₀Alkyl acrylate crosspolymers), such as those sold under the trade names Pemulen TR1, Pemulen TR2, carbopol 1382, and carbopol ETD 2020 by Lubrizol corporation, even more preferably Pemulen TR-2;

-alkylacrylic/alkylmethacrylic acid copolymers and derivatives thereof, in particular salts and esters thereof, such as copolymers of ethyl acrylate, methyl methacrylate and low levels of methacrylic acid esters with quaternary ammonium groups, supplied under the trade name EUDRAGIT RSPO from Evonik Degussa;

AMPS (partially neutralized and highly cross-linked polyacrylamide-based methylpropanesulfonic acid with ammonia) sold by Clariant;

AMPS/acrylamide copolymers, such as the products Sepigel or Simulgel sold by the SEPPIC company, in particular the copolymers of polyacrylamide (and) isoparaffin C13-14 (and) laureth-7 under the INCI name;

types of polyoxyethylated AMPS/alkyl methacrylate copolymers (crosslinked or not), such as Aristoflex HMS sold by Clariant corporation;

polysaccharides and derivatives, such as:

-anionic, cationic, amphoteric or non-ionic chitin or chitosan polymers;

-cellulose polymers and derivatives, preferably selected from hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose, and carboxymethylcellulose, and quaternized cellulose derivatives, in addition to alkylcelluloses; in a preferred embodiment, the cellulosic polymer is carboxymethyl cellulose;

-finally modified starch polymers and derivatives; in a preferred embodiment, the starch polymer is native starch;

optionally modified polymers of natural origin, such as galactomannans and derivatives thereof, such as konjac gum, gellan gum, locust bean gum, fenugreek gum, carageenan gum, tragacanth gum, gum arabic, acacia gum, guar gum, hydroxypropyl guar modified with sodium methyl carboxylate groups (Jaguar XC97-1, Rhodia), guar hydroxypropyl trimonium chloride, and xanthan derivatives;

-alginates and carrageenans;

-glycosaminoglycans, hyaluronic acid and derivatives thereof;

mucopolysaccharides, such as hyaluronic acid and chondroitin sulfate, and mixtures thereof;

vinyl polymers, such as polyvinylpyrrolidone, copolymers of methyl vinyl ether and maleic anhydride, copolymers of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinylpyrrolidone and caprolactam, polyvinyl alcohol;

and mixtures thereof.

Preferably, the composition according to the invention, in particular the outer layer, comprises a hydrophilic polymer selected from polysaccharides and derivatives, homopolymers or copolymers of acrylic or methacrylic acid, or salts and esters thereof, and mixtures thereof.

The polymer is advantageously selected from (poly) (alkyl) (meth) acrylic acid and derivatives thereof, in particular (poly) (alkyl) (meth) acrylates and derivatives thereof, preferably from alkylacrylic/alkylmethacrylic acid copolymers and derivatives thereof, and most preferably copolymers of ethyl acrylate, methyl methacrylate and a low content of methacrylic acid esters having quaternary ammonium groups, supplied under the trade name EUDRAGIT RSPO from Evonik Degussa.

The polysaccharide and derivatives thereof are preferably selected from the group consisting of chitosan polymers, chitin polymers, cellulose polymers, starch polymers, galactomannans, alginates, carrageenans, mucopolysaccharides, and derivatives thereof, and mixtures thereof.

In a preferred embodiment, the outer layer is free of microcrystalline cellulose.

According to a particularly preferred embodiment, the polysaccharide and derivatives thereof are preferably selected from the group consisting of polysaccharides and derivatives thereof comprising one saccharide type or more, preferably more, especially at least D-glucose units as saccharides, preferably starch polymers, cellulose polymers, and derivatives thereof, and mixtures thereof.

According to a preferred embodiment, the microcapsules comprise at least one hydrophilic polymer chosen from: starch and its derivatives, in particular corn starch; cellulose and its derivatives; homopolymers and/or copolymers of methacrylic acid and/or methacrylic acid esters or copolymers of (alkyl) acrylic acid and/or (alkyl) methacrylic acid and derivatives thereof, preferably salts and esters thereof; in particular, the microcapsules comprise polymethyl methacrylate.

Starches useful according to the invention are typically produced from plant raw materials such as rice, soy, potato or corn. The starch may be unmodified or (in comparison to cellulose) modified. In a preferred embodiment, the starch is unmodified.

Preferred homopolymers and/or copolymers of methacrylic acid and/or methacrylic acid esters are those which are: wherein the copolymer of methyl methacrylate and ethyl acrylate has a molecular weight of from 750kDa to 850 kDa.

For example, cellulose derivatives include alkali cellulose, carboxymethyl cellulose (CMC), cellulose esters and cellulose ethers, and amino cellulose. In a particular embodiment, the cellulose is carboxymethyl cellulose (CMC).

According to a preferred embodiment, the microcapsules comprise at least a starch derivative (in particular corn starch), polymethyl methacrylate, a copolymer of (alkyl) acrylic acid and/or (alkyl) methacrylic acid and derivatives thereof (preferably salts and esters thereof), and/or cellulose derivatives.

Preferably, the microcapsules comprise a polymer that is not crosslinked.

The polymer may be in one layer or multiple layers.

In another embodiment, the polymer may be in the core.

The microcapsules may comprise a polymer in the core and/or a polymer in the layer.

In particular embodiments, the polymer is in the core as well as in the layers.

In an embodiment, the core comprises at least starch and/or cellulose derivatives as polymer. When starch is contained in the core, it represents the main component of such a core, i.e. the weight of starch is greater than the respective amounts of the other ingredients of the core.

The polymer may comprise from 0.5% to 20% by weight of the microcapsule, especially from 1% to 10% by weight, preferably from 2% to 8% by weight of the microcapsule.

The different layers forming the coating may be based on the same or different polymers. Advantageously, the different layers may be composed of the same polymer.

Instead, the layers are advantageously of different colors.

The different colors may be obtained by using different colorants, which may be obtained by using different concentrations of at least one colorant when the colorants used for the two layers are the same.

In a particular embodiment, the outer layer comprises at least one colorant.

In another embodiment, the outer layer does not contain any colorant.

Coloring agent

As previously mentioned, "colorant" includes any organic or inorganic pigment or colorant approved for use in cosmetics by CTFA (american cosmetic association) and FDA (food and drug administration) for use in cosmetic formulations.

Thus, the term "colorant" refers to: organic pigments such as synthetic dyes or natural dyes selected from any of the well-known FD & C or D & C dyes; inorganic pigments, such as metal oxides or lakes, such as lakes based on cochineal, barium, strontium, calcium or aluminum and any combination (blend) thereof. Such colorants are described in detail below.

In particular embodiments, the colorant may be water soluble or water dispersible.

In another embodiment, the colorants that may be used according to the present invention may be oil soluble or oil dispersible or have limited solubility in water.

Advantageously, the colouring agent of the multilayer microcapsules is a primary metal oxide selected from iron oxide, titanium dioxide, aluminum oxide, zirconium oxide, cobalt oxide, cerium oxide, nickel oxide, tin oxide or zinc oxide, or a composite oxide, more preferably an iron oxide selected from red, yellow or black iron oxide, or a mixture thereof.

One or more of the layers may also contain a lake corresponding to an organic colorant fixed to the substrate. Such one or more lakes are advantageously selected from the following materials and one or more mixtures thereof:

-cochineal red;

-organic pigments of azo colorants, anthraquinone colorants, indigo colorants, xanthene colorants, pyrene colorants, quinoline colorants, triphenylmethane colorants, fluoran colorants; among these organic pigments, mention may be made of the pigments known under the following commercial designations: d & C blue No. 4, D & C brown No. 1, D & C green No. 5, D & C green No. 6, D & C orange No. 4, D & C orange No. 5, D & C orange No. 10, D & C orange No. 11, D & C red No. 6, D & C red No.7, D & C red No. 17, D & C red No. 21, D & C red No. 22, D & C red No. 27, D & C red No. 28, D & C red No. 30, D & C red No. 31, D & C red No. 33, D & C red No. 34, D & C red No. 36, D & C violet No. 2, D & C yellow No.7, D & C yellow No. 8, D & C yellow No. 10, D & C yellow No. 11, FD & C blue No. 1, FD & C green No. 3, FD & C red No. 40, FD & C yellow No. 5, FD & C yellow No. 6;

water-insoluble salts of sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium of acidic colorants, for example azo colorants, anthraquinone colorants, indigo colorants, xanthene colorants, pyrene colorants, quinoline colorants, triphenylmethane colorants, fluoran colorants, which colorants may comprise at least one carboxylic acid group or sulfonic acid group.

The organic lake may also be protected by an organic vehicle such as rosin or aluminum benzoate.

Among the organic lakes, mention may be made in particular of those known under the following names: d & C Red No. 2 aluminum lake, D & C Red No. 3 aluminum lake, D & C Red No. 4 aluminum lake, D & C Red No. 6 barium/strontium lake, D & C Red No. 6 potassium lake, D & C Red No. 6 sodium lake, D & C Red No.7 aluminum lake, D & C Red No.7 barium lake, D & C Red No.7 calcium/strontium lake, D & C Red No.7 zirconium lake, D & C Red No. 8 sodium lake, D & C Red No. 9 aluminum lake, D & C Red No. 9 barium/strontium lake, D & C Red No. 9 zirconium lake, D & C No. 10 sodium lake, D & C Red No. 19 aluminum lake, D & C Red No. 19 barium lake, D & C Red & No. 19 barium lake, Aluminum lake D & C red No. 21, zirconium lake D & C red No. 21, aluminum lake D & C red No. 22, aluminum lake D & C red No. 27, aluminum/titanium/zirconium lake D & C red No. 27, barium lake D & C red No. 27, calcium lake D & C red No. 27, zirconium lake D & C red No. 27, aluminum lake D & C red No. 28, sodium lake D & C red No. 28, aluminum lake D & C red No. 30, calcium lake D & C red No. 31, aluminum lake D & C red No. 33, calcium lake D & C red No. 34, calcium lake D & C red No. 36, aluminum lake D & C red No. 40, aluminum lake D & C blue No. 1, aluminum lake D & C green No. 3, aluminum lake D & C No. 4, aluminum lake orange lake D & C No. 5, zirconium lake D & C No. 5, orange lake D & C, aluminum lake D & C10, barium lake D & C17, barium lake D & C red No. 17, aluminum lake D & C, D & C yellow No. 5 aluminum lake, D & C yellow No. 5 zirconium lake, D & C yellow No. 6 aluminum lake, D & C yellow No.7 zirconium lake, D & C yellow No. 10 aluminum lake, FD & C blue No. 1 aluminum lake, FD & C red No. 4 aluminum lake, FD & C red No. 40 aluminum lake, FD & C yellow No. 5 aluminum lake, FD & C yellow No. 6 aluminum lake.

Chemical materials corresponding to each of these organic colorants previously mentioned are mentioned in a book published by The Cosmetic, Toiletry, and Fragrance Association, entitled international Cosmetic Ingredient dictionary and Handbook (edition 1997, pages 371 to 386, and pages 524 to 528), The contents of which are incorporated by reference into The description of The present invention.

According to a preferred embodiment, the lake is selected from: cochineal red; and water insoluble salts of sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium of acidic colorants, e.g., azo colorants, anthraquinone colorants, indigo colorants, xanthene colorants, pyrene colorants, quinoline colorants, triphenylmethane colorants, fluoran colorants (it is contemplated that these colorants may include at least one carboxylic acid group or sulfonic acid group); and mixtures thereof.

According to a preferred embodiment, the lake is selected from: cochineal, water-insoluble salts of sodium, calcium, aluminum, and mixtures thereof.

As lake comprising carmine, mention may be made of the commercial code: CARMIN COVALAC W3508, CLOISONNERED 424C, and CHROMA-LITE MAGENTA CL 4505.

The water insoluble aluminum salt is preferably selected from the group consisting of FDC yellow No. 5 aluminum lake, le FDC blue No. 1 aluminum lake, le FDC red No. 40 aluminum lake, le FDC red No. 30 aluminum lake, le FDC green No. 5 aluminum lake, and mixtures thereof. As compounds containing such inorganic lakes, mention may be made, among others, of the commercial numbers: INTENZA FIREFLY C91-1211, INTENZA AZUREALLEURE C91-1251, INTENZA THINK PINK C91-1236.

Preferably, the water insoluble calcium salt is selected from red No.7 calcium lake. As compounds comprising such inorganic lakes, mention may be made, inter alia, of the commercial numbers: INTENZA MAGENITUDE C91-1234, INTENZA HAUTE PINK C91-1232, INTENZA RAZZLED ROSE C91-1231, INTENZA AMETHYST FORCE C91-7231, INTENZA PLUSHPLUM C91-7441, INTENZA ELECTRIC CORAL C91-1233, FLORASOMES-JOJOBA-SMS-10% CELLINI RED-NATURAL, and mixtures thereof.

Preferably, the water insoluble sodium salt is selected from red No. 6 sodium lake and red No. 28 sodium lake, and mixtures thereof. As compounds comprising such inorganic lakes, mention may be made, inter alia, of the commercial numbers: INTENZA MANGO TANGO C91-1221 and INTENZA NITRO PINK C91-1235.

In a preferred embodiment, the colorant is an inorganic colorant.

In a preferred embodiment, the colorant is a metal oxide. Such metal oxides are preferably selected from the group consisting of iron oxides, titanium oxides, and mixtures thereof.

The color-changing composition of the present invention may comprise a mixture of two or more colorants, the colorants being individually encapsulated in microcapsules and/or one or more mixtures of colorants being encapsulated in multi-layer microcapsules.

According to this particular embodiment, each layer of the microcapsules may comprise at least one particular colorant or a particular blend of colorants.

According to this particular embodiment, the colour-changing composition of the invention comprises two or more microcapsules of the invention having different colours.

One skilled in the art would know how to select colorants, and combinations of colorants, to produce a desired color effect or color change.

As previously mentioned, the microcapsules of the invention preferably comprise at least titanium dioxide and/or iron oxide, preferably at least titanium dioxide, in their coating.

In a preferred embodiment, the microcapsules of the invention preferably comprise at least titanium dioxide and iron oxide in the coating thereof.

According to a particular embodiment, the outer layer of the microcapsules comprises titanium dioxide, and more preferably as the only colorant.

According to these particular embodiments, the outer layer of the microcapsules comprises titanium dioxide as the only colouring agent, and the composition according to the invention is non-coloured, the "non-coloured" or "uncoloured" composition referring to a transparent or white composition.

According to a preferred embodiment, the composition according to the invention comprises microcapsules which are uncoloured, i.e. the outer layer is white or transparent and when the outer layer is transparent the visible inner layer is white.

For the purposes of the present invention, the term "transparent composition" refers to a composition which transmits at least 40% of light having a wavelength of 750nm without scattering it, i.e. a composition in which the scattering angle of the light is less than 5 °, better still about 0 °.

The transparent composition can transmit at least 50%, in particular at least 60%, in particular at least 70% of the light with a wavelength of 750 nm.

The transmission measurements were performed using a Cary 300 scanning UV-visible spectrophotometer from Varian corporation according to the following protocol:

-pouring the composition into a spectrophotometer cuvette having a square shape with a side of 10 mm;

-then, at 20 ℃, in a thermostatically regulated chamber, holding a sample of the composition for 24 hours;

-then measuring the light transmitted through the sample of the composition by scanning the wavelength from 700nm to 800nm on a spectrophotometer, the measurement being performed in transmission mode;

-then, determining the percentage of light transmitted through a sample of the composition at a wavelength of 750 nm.

Transparent compositions which, when placed 0.01m apart to face a black line drawn on a piece of white paper 2mm in diameter, allow the line to be seen; in contrast, opaque compositions, i.e., compositions that are not transparent, do not allow the line to be seen.

According to a particular embodiment, the outer layer of the microcapsule comprises an organic pigment or iron oxide.

The colorant is present in an amount of 20% to 90% by weight, preferably 30% to 80% by weight, more preferably 50% to 75% by weight, relative to the total weight of the microcapsule.

In a particular embodiment, the microcapsule comprises a metal oxide selected from iron oxide, titanium oxide, and mixtures thereof, present in an amount of 20% to 90% by weight, preferably 30% to 85% by weight, more preferably 50% to 85% by weight, relative to the total weight of the microcapsule.

In particular, the titanium oxide may be present in 28% to 80% by weight, preferably 30% to 75% by weight, more preferably 30% to 50% by weight, relative to the total weight of the microcapsule.

In particular, the iron oxide may be present in a range from 5% to 75% by weight, preferably from 8% to 65% by weight, relative to the total weight of the microcapsule. In a particular embodiment, the iron oxide is present in an amount higher than 15% by weight, preferably higher than 30% by weight, in particular from 40% to 65% by weight, relative to the total weight of the microcapsule.

In a preferred embodiment, the colorant is the predominant component in at least one layer, preferably in each layer, i.e., comprises at least 40% by weight of the layer, preferably at least 75% by weight of the layer, more preferably at least 95% by weight of the layer.

In a preferred embodiment, the titanium dioxide layer has an average thickness of 5 μm to 150 μm.

Grease-based material

The inner and/or outer layer may also advantageously comprise at least one lipid-based material.

According to particular embodiments of the present invention, such lipid-based materials may have amphiphilic properties, i.e., having a non-polar portion and a polar portion.

Such a lipid-based material may include at least one or more C₁₂-C₂₂For example, fatty acid chains selected from stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, and the like, and mixtures thereof. Preferably, these fatty acid chains are hydrogenated. Finally, these fatty acid chains may be the non-polar part of the lipid-based material.

Such lipid-based material is preferably selected from phospholipids. These phospholipids are preferably selected from phosphorylglycerol (phosphorylglycerol), more preferably from lecithins, especially hydrogenated lecithins.

The lipid-based material may comprise from 0.05% to 5% by weight of the microcapsules, in particular from 0.1% to 1% by weight of the microcapsules.

By combining three or more compounds (e.g., sugar alcohols, polymers, lipid-based materials) in microcapsules of different hardness and/or water solubility, the time required for the colorant-encapsulated microcapsules to rupture on the skin can be adjusted, so that by varying the method or intensity of application to the skin, the preferred coloration or tone scale pattern can be adjusted.

Thus, according to a preferred embodiment, the multilayer coating comprises at least starch as polymer and at least one lipid-based material, preferably lecithin.

According to an advantageous embodiment, the microcapsules according to the invention comprise at least one monosaccharide or derivative thereof and at least one polysaccharide or derivative thereof.

According to a preferred embodiment, the microcapsules comprise a core comprising a monosaccharide derivative and a coating comprising a polysaccharide (or derivative thereof) comprising one type of sugar or a plurality of types of sugar, preferably a plurality of types of sugar.

According to a more preferred embodiment, the microcapsule comprises: a core comprising monosaccharide polyol (preferably selected from mannitol, erythritol, xylitol, sorbitol); and a coating comprising a polysaccharide (or derivative thereof) comprising at least one or more D-glucose units as a saccharide.

According to a preferred embodiment, the microcapsules comprise three or more colorants in different layers.

According to a preferred embodiment, the microcapsules additionally comprise a lipid-based material selected from phospholipids, advantageously from phosphorylglycerols, in particular from lecithins.

In a particular embodiment, the core comprises mannitol, a starch polymer and a cellulose derivative and optionally a lipid-based material. In this case, the starch polymer is the main component, i.e. the weight number of starch is greater than the respective weight number of mannitol, cellulose derivative and lipid-based material of the core.

With reference to fig. 1, according to a preferred embodiment, the present invention advantageously provides a color-changing microcapsule, the size of which is 50 μm to 800 μm, preferably 60 μm to 500 μm, in diameter of the microcapsule, comprising:

i) a core (a), preferably sized in the range 500nm to 150 μm in diameter, preferably free of any coloring agent, comprising at least one organic core, preferably selected from at least one sugar alcohol, preferably a monosaccharide-polyol, advantageously selected from mannitol, erythritol, xylitol, sorbitol and mixtures thereof;

ii) a first layer (B) surrounding said core, comprising:

at least one colorant, preferably one or more iron oxides, and

-a binder selected from at least one polymer, at least one lipid-based material and mixtures thereof, preferably from mixtures thereof;

iii) a second layer (C) surrounding said first layer (B), preferably having a thickness of 5 μm to 500 μm, comprising:

-titanium dioxide particles, and

iv) optionally, a third layer (D) surrounding said second layer (C), comprising:

-at least one colorant, and

v) optionally, a fourth layer (E) surrounding said third layer (D) (if present) or surrounding said second layer (C), comprising:

-at least one wall-forming polymer, preferably selected from: polysaccharides, such as cellulose derivatives, especially cellulose ethers and cellulose esters; (poly) (alkyl) (meth) acrylic acid and derivatives thereof, especially (poly) (alkyl) (meth) acrylates and derivatives thereof; and preferably alkyl acrylic/alkyl methacrylic copolymers and derivatives thereof.

As examples of commercially available microcapsules for use in the composition of the present invention, there may be mentioned microcapsules produced by korea particle Technology KPT under the following trade names:

magic60-WP0105 from KPT: pink spherical microcapsules having a particle size of 60-200 mesh comprising titanium dioxide, mannitol, hydrogenated lecithin, synthetic fluorophlogopite, red 30 lake, corn starch, tin oxide;

magic50-BW0105 from KPT: light gray spherical microcapsule with particle size of 60-200 mesh and comprising mannitol, ferrite red, iron oxide yellow, iron oxide black, hydrogenated lecithin, titanium dioxide, and corn starch.

In the composition according to the invention, the microcapsules suitable for the invention are preferably stable at high temperatures, for example at a temperature of greater than or equal to 40 ℃, for example in an oven at 45 ℃ for 1 month, better still for two months, better still for three months; or can be stabilized in an oven at 60 deg.C for 15 days.

In a preferred embodiment, the microcapsules according to the invention exhibit suitable softening kinetics.

Preferably, the hardness of the microcapsules is advantageously between 5 and 50 grams, more preferably between 6 and 20 grams, more preferably between 7 and 10 grams, at least three hours after contact with the other compounds in the formulation. This hardness is consistent with the industrial process used to prepare cosmetic compositions comprising such microcapsules.

Such values of softening kinetics and hardness allow to provide not only aesthetic microcapsules, but also compositions which are generally aesthetic.

In particular, the composition may cause different shades or gradations depending on the intensity of the rubbing. The composition may advantageously exhibit a high chroma C measured in CIE laboratory system 1976.

Aqueous phase

Polyols and diols

As previously mentioned, the claimed composition comprises at least 10% by weight of polyols and/or diols relative to the total weight of the composition.

The composition according to the invention may advantageously comprise at least 10%, preferably between 10% and 45%, in particular between 10% and 40% by weight of polyols and/or diols, preferably one C, based on the weight of the composition₂-C₃₂Polyalcohol and/or/and/or (B)Or a diol.

The composition according to the invention may advantageously comprise at least 10%, preferably from 12% to 50%, in particular from 13% to 40%, more preferably from 14% to 35%, better still from 15% to 30% by weight of polyols and/or diols, based on the weight of the composition.

The composition according to the invention may advantageously comprise at least 10%, preferably from 12% to 50%, in particular from 13% to 40%, more preferably from 14% to 35%, better still from 15% to 30% by weight of polyols and/or diols, based on the weight of the aqueous phase.

Preferably, the polyol is C₂-C₃₂Polyols and/or diols.

For the purposes of the present invention, the term "polyol" is understood to mean any organic molecule comprising at least two free hydroxyl groups. The term "polyol" according to the present invention does not cover the monosaccharide-alcohols disclosed above.

Preferably, the polyols according to the invention are present in liquid form at room temperature.

The polyol/diol is a humectant or moisturizer.

They may have an effect on the stability of the other components of the composition, in particular the microcapsules of the prior art.

Therefore, there is a need to have a stable composition with any use, comprising the color-changing microcapsules in a physiological medium comprising polyols and/or glycols, since these compositions exhibit a significant moisturizing or moisturizing effect.

The composition according to the invention solves this technical problem.

The polyols suitable for use in the present invention may be compounds of the linear, branched or cyclic, saturated or unsaturated alkyl type, carrying at least two-OH functions, in particular at least three-OH functions, and more in particular at least four-OH functions, on each alkyl chain.

Polyols advantageously suitable for formulating the composition according to the invention are polyols containing in particular from 2 to 32 carbon atoms, preferably from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, advantageously from 2 to 10 carbon atoms, more advantageously from 2 to 6 carbon atoms.

According to another embodiment, the polyols suitable for use in the present invention may advantageously be selected from polyethylene glycols.

According to one embodiment, the composition of the present invention may comprise a mixture of polyols.

Advantageously, the polyol or diol may be chosen from polyols, preferably C₂-C₈More preferably C₃-C₆The polyol of (1). The polyol or diol may be selected from: glycerol, pentaerythritol, trimethylolpropane, ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 3-propanediol, pentanediol, hexanediol, isoprene glycol, dipropylene glycol, diethylene glycol and diglycerol, ethylhexyl glycerol, octyl glycol, and mixtures thereof; glycerol and its derivatives; polyglycerols, such as glycerol oligomers, such as diglycerol and polyethylene glycol; glycol ethers (in particular containing 3 to 16 carbon atoms), such as monopropylene glycol (C)₁-C₄) Alkyl ether, dipropylene glycol (C)₁-C₄) Alkyl ethers or tripropylene glycol (C)₁-C₄) Alkyl ethers, monoethylene glycol (C)₁-C₄) Alkyl ether, diethylene glycol (C)₁-C₄) Alkyl ethers or triethylene glycols (C)₁-C₄) An alkyl ether; and mixtures thereof.

In particular, the polyol or diol is selected from: glycerol; glycols, preferably propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, ethylhexylglycerin, octylene glycol; glycol ethers, preferably monopropylene glycol (C)₁-C₄) Alkyl ether, dipropylene glycol (C)₁-C₄) Alkyl ethers or tripropylene glycol (C)₁-C₄) Alkyl ethers, or monoethylene glycol (C)₁-C₄) Alkyl ether, diethylene glycol (C)₁-C₄) Alkyl ethers or tri-sEthylene glycol (C)₁-C₄) An alkyl ether; and mixtures thereof.

According to a preferred embodiment of the present invention, the polyol or diol is selected from the group consisting of ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, butylene glycol, glycerol, polyglycerol and polyethylene glycol, and mixtures thereof.

In particular embodiments, the polyol is selected from: glycerol; a glycol selected from propylene glycol, butylene glycol, ethylhexylglycerin, octylene glycol; and mixtures thereof.

According to a particular embodiment, the composition of the invention comprises at least butylene glycol, glycerol or a mixture thereof.

In a preferred embodiment, the composition comprises at least glycerin.

According to a particular embodiment, the composition of the invention comprises glycerol as the sole polyol.

Advantageously, the composition may comprise from 1% to 10%, preferably from 2% to 8% by weight of glycerol, based on the total weight of the composition.

Advantageously, the composition may comprise from 1% to 10%, preferably from 2% to 8% by weight of butanediol, based on the total weight of the composition.

Advantageously, the composition may comprise from 1% to 10%, preferably from 2% to 8% by weight of propylene glycol, based on the total weight of the composition.

When the composition comprises glycerol and at least one diol, the weight ratio glycerol/diol is advantageously from 1/2 to 3/2, preferably from 2/3 to 1/1, more preferably about 1.

In a preferred embodiment, the composition comprises glycerol and at least one diol selected from propylene glycol, butylene glycol, ethylhexylglycerol, octylethylene glycol, advantageously in a weight ratio glycerol/diol from 1/2 to 3/2, preferably from 2/3 to 1/1, more preferably about 1.

Advantageously, the weight ratio of polyol and glycol/composition is from 1/10 to 1/2, preferably from 1/8 to 1/3, more preferably from 1/6 to 1/4. More particularly, the weight ratio of polyol and glycol/aqueous phase is from 1/10 to 1/2, preferably from 1/8 to 1/3, more preferably from 1/6 to 1/4.

These compounds are particularly advantageous for imparting and/or improving the deformability of the microcapsules of the invention. They may also be referred to as bulking or softening agents.

Advantageously, the composition of the invention comprises an aqueous phase comprising water, at least one compound selected from the group consisting of polyols, glycols, and optionally at least one C2-C8 alcohol, and mixtures thereof.

Advantageously, the aqueous phase acts as a swelling agent or softening agent with respect to the microcapsules without rupturing the microcapsules. The microcapsules are not inactive when placed in the aqueous phase, they swell (their diameter increases significantly with optional softening of the microcapsules); or the microcapsules soften significantly without increasing in diameter, they become more malleable and more prone to rupture when applied to the skin.

The aqueous phase used in the composition according to the invention is capable of contributing to the softening kinetics of the microcapsules, and more particularly it allows to obtain a good balance between softening kinetics and hardness.

The above compounds, polyols and/or glycols and optionally C2-C8 alcohols in the aqueous phase play an important role in the softening of the microcapsules. In particular, the softening kinetics can be advantageously controlled by adjusting the amount of the above-mentioned compounds. Thus, a composition is obtained in which the microcapsules (immediately after preparation) are still hard and stable enough for industrial processing of the freshly prepared composition and for a time sufficient (e.g. 3 to 4 hours) to enable conventional industrial processes such as encapsulation without premature rupture of the microcapsules. More advantageously, once the composition is prepared and encapsulated, for example after about 24 hours, the microcapsules will soften so that the composition does not exhibit a granular sensation due to the hard capsules when applied on the keratin materials.

Where appropriate, the aqueous phase also includes a water-soluble solvent.

In the present invention, the term "water-soluble solvent" means a compound that is liquid at room temperature and miscible with water (miscibility with water of more than 50% by weight at atmospheric pressure and at 25 ℃).

Water soluble solvents useful in the compositions of the present invention may also be volatile.

As said, the composition of the invention comprises an aqueous phase comprising water and at least one polyol, glycol, optionally at least one C₂-C₈And mixtures thereof. It may also comprise C₄Ketone and C₂-C₄The aldehyde of (a).

Advantageously, the aqueous phase may be present in a content ranging from 30% to 99% by weight, preferably from 40% to 95% by weight, more preferably from 50% to 90% by weight, relative to the total weight of the composition.

Advantageously, water is present in an amount of at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, relative to the weight of the composition. Water is generally present in an amount of from 30% to 90% by weight, preferably from 40% to 85% by weight, more preferably from 50% to 80% by weight, relative to the weight of the composition.

Advantageously, this aqueous phase acts as a swelling or softening agent with respect to the microcapsules, preferably without rupturing the microcapsules or causing leakage of the colorant.

The compositions according to the invention may advantageously comprise at least one lower monoalcohol, in particular at least one C₂-C₈The mono-alcohol of (1).

The compound selected from water and C2-C8 monoalcohols, preferably C2-C8 monoalcohols, is present in an amount of at least 3%, preferably at least 5%, more preferably at least 8%, advantageously at least 10% by weight relative to the weight of the composition.

The composition of the invention generally comprises an amount by weight of from 3% to 50%, preferably from 5% to 45%, more preferably from 10% to 45%, of a compound selected from water, a monoalcohol of C2-C8, preferably a monoalcohol of C2-C8, relative to the total weight of the composition.

The mono-or lower alcohols suitable for use in the present invention may be compounds of the linear, branched or cyclic, saturated or unsaturated alkyl type, bearing only one-OH function.

Advantageously, C₂-C₈The monoalcohols of (A) are acyclic monoalcohols, preferably they are C₂-C₅Of (2), preferably C₂-C₃The mono-alcohol of (1).

Lower monoalcohols advantageously suitable for use in formulating the compositions according to the invention are lower monoalcohols comprising in particular from 2 to 8 carbon atoms, more preferably from 2 to 5 carbon atoms, such as ethanol, propanol, butanol, isopropanol, isobutanol, preferably ethanol and/or isopropanol, more preferably at least ethanol.

Preferably, the lower monoalcohol is selected from the group consisting of ethanol, isopropanol and mixtures thereof.

The composition may comprise at least 1% by weight, preferably at least 2%, more preferably from 2% to 15%, advantageously from 3% to 10% by weight, better from 3% to 8% by weight, preferably from 4% to 6% by weight of the monoalcohol(s), relative to the total weight of the composition of the invention.

In a preferred embodiment, the composition comprises ethanol and/or isopropanol, more preferably at least ethanol, in a total concentration from 2% to 15% by weight, more preferably from 3% to 10% by weight, relative to the total weight of the composition of the invention.

In the field of make-up and/or care of keratin materials, lower monoalcohols such as ethanol can be advantageously used in various ways.

Such compounds are particularly useful for providing a fresh feel to the user when the user applies the composition of the present invention to the skin.

In addition, such a refreshing sensation that is pleasant for the user can also advantageously activate the blood circulation in the skin that feels refreshed, in particular in the skin that forms a particularly good blood supply area around the eye. Thus, the fresh sensation associated with the application of these lower mono-ols reduces edema and dark circles that occur in the facial portion due to high vascularity and thinness in the facial portion.

The use of lower mono-alcohols may also advantageously avoid the need to apply other cooling agents around the eye, such as methanol, menthane carboxamide ethyl amine, menthyl lactate, menthoxypropanediol, which are typically eye-irritating raw materials.

There is also a need for compositions with any use of the colour-changing microcapsules contained in a physiological medium comprising a lower alcohol, since some cosmetic ingredients are particularly soluble in hydroalcoholic media.

In addition, lower monoalcohols (such as ethanol) allow the dissolution of active agents, in particular keratolytic agents, such as salicylic acid and its derivatives.

Some microcapsules of the prior art burst rapidly in hydroalcoholic media, and there is therefore a need to have a composition comprising colour-changing microcapsules that is stable in hydroalcoholic media for any use.

Finally, the monoalcohols act in particular as swelling agents or softeners.

One or more hydrophilic gelling agents

Hydrophilic gelling agents which may be mentioned in particular include water-soluble or water-dispersible thickening polymers. These polymers may be chosen in particular from:

modified or unmodified carboxyvinyl polymers, such as: products sold under the name Carbopol (CTFA name: carbomer) by Goodrich corporation; a polyacrylate ester, a polyacrylate,

polymethacrylates, such as the products sold under the name Lubrajel and Norgel by the company Guardian or under the name Hispagel by the company Hispano Chimica;

-a polyacrylamide; optionally crosslinked and/or

Neutral 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, such as poly (2-acrylamido-2-methylpropanesulfonic acid) sold under the name Hostacerin AMPS by the company Clariant (CTFA name: ammonium polyacryloyldimethyltaurate);

crosslinked anionic copolymers of acrylamide and AMPS in the form of W/O emulsions, such as the products sold under the name Sepigel 305(CTFA name: polyacrylamide/C13-14 isoparaffin/laureth-7) and under the name Simulgel 600(CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by the company SEPPIC;

polysaccharide biopolymers, such as xanthan gum, guar gum, locust bean gum, acacia gum, scleroglucan (scleroglucans), chitin and chitosan derivatives, carrageenan, gellan gum, alginates,

cellulose, such as microcrystalline cellulose, carboxymethyl cellulose, hydroxymethyl cellulose and hydroxypropyl cellulose; and mixtures thereof. Preferably, these polymers may be selected from acrylate/C10-30 alkyl acrylate crosspolymers, such as Carbopol ultrez 20, Carbopol ultrez 21, Permulen TR-1, Permulen TR-2, Carbopol 1382, Carbopol ETD 2020, carbomers such as Synthalen K, Carbopol 980, ammonium acryloyldimethyltaurate/steareth-8 methacrylate copolymers such as Aristoflex SNC, acrylate copolymers such as Carbopol Aqua SF-1, ammonium acryloyldimethyltaurate/steareth-25 methacrylate crosspolymers such as Aristoflex HMS, ammonium acryloyldimethyltaurate such as arisflex AVC, and xanthan gum such as Keltrol CG, and the like, may also be any polymer which not only helps to maintain a suitable viscosity, thereby making the balloon suspendable excellent and thereby stabilizing the balloon over its shelf life, but also helps to provide transparency.

According to a particular embodiment, the aqueous phase of the composition comprises at least one neutral 2-acrylamido-2-methylpropanesulfonic acid polymer and copolymer and one polysaccharide biopolymer.

Preferably, hydrophilic gelling agents suitable for use in the present invention include: carboxyvinyl polymers, e.g. carbopol products (carbomers), such as carbopol Ultrez 20 sold by LubrizolAnd Pemulen products (acrylates/C)₁₀-C₃₀-alkyl acrylate copolymers); polyacrylamide, for example under the trademark Sepigel 305 by SEPPIC (CTFA name: Polyacrylamide/C)_13-14Isoparaffin/laureth 7) or Simulgel 600(CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate 80); 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, which are optionally crosslinked and/or neutral, such as poly (2-acrylamido-2-methylpropanesulfonic acid) sold by Hoechst under the trademark Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyltaurate) or the product sold by SEPPIC under the trademark Simulgel 800(CTFA name: sodium polyacryloyldimethyltaurate/polysorbate 80/sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulfonic acid and ethyl hydroxyacrylate, such as Simulgel NS and Sepinov EMT 10 sold by SEPPIC; cellulose-based derivatives such as hydroxyethyl cellulose; polysaccharides and in particular gums such as xanthan gum; and mixtures thereof.

More preferably, the hydrophilic gelling agent is selected from acrylates/C₁₀-C₃₀-alkyl acrylate copolymers, carbomer, xanthan gum, carboxyvinyl polymers synthesized in dichloromethane, and ammonium polyacryloyldimethyltaurate, and mixtures thereof.

These gelling agents may be present in an amount of 0.001% to 10% by weight, preferably 0.01% to 5% by weight, more preferably 0.05% to 3% by weight, relative to the total weight of the composition.

Cosmetic medium and additional ingredients

The composition according to the invention is cosmetically acceptable, i.e. it comprises a medium that is physiologically acceptable, non-toxic and suitable for application on human keratin materials.

In the sense of the present invention, "cosmetically acceptable" means a composition having a pleasant appearance, smell or feel.

The "physiologically acceptable medium" is generally suitable for such forms: the composition is intended to be constrained in this form.

In particular, the nature and amount of the components are adjusted, for example, depending on whether the composition is formulated as a solid, fluid, or powder.

Depending on the form and purpose of the skin-care or cosmetic preparation, the composition according to the invention will comprise, in addition to the microcapsules comprising the colouring agent, one or more further cosmetic components, such as cosmetic components selected from volatile and non-volatile silicone oils or hydrocarbon oils, surfactants, fillers, gelling agents, thickeners, film formers, polymers, preservatives, silicone elastomers, sunscreens, further non-entrapped colouring agents, active agents, UV-filtering substances, fragrances, pH regulators and mixtures thereof.

The pH of the cosmetic composition according to the invention is preferably from 6.5 to 7.5. The preferred base for changing the pH is triethanolamine.

It is a matter of routine practice for the person skilled in the art to adjust the nature and amount of the additives present in the composition according to the invention so that the desired cosmetic properties of the composition are not affected.

Some of these conventional components are described in detail below.

Liquid fatty phase

The composition according to the invention may therefore comprise at least one fatty phase which is liquid at room temperature and at atmospheric pressure, in particular at least one oil as mentioned hereinafter.

In particular, the presence of at least one oil has hitherto been advantageous in that it facilitates application of the composition and provides a softening effect.

According to the invention, the term "oil" refers to a non-aqueous compound immiscible with water that is liquid at room temperature (25 ℃) and atmospheric pressure (760 mmHg).

The oily phase suitable for preparing the anhydrous cosmetic compositions according to the invention may comprise hydrocarbon-based oils, silicone oils, fluoro oils or non-fluoro oils, or mixtures thereof.

The oil may be volatile or non-volatile.

They may be oils of animal, vegetable, mineral or synthetic origin. According to one embodiment variant, oils of vegetable origin are preferred.

The term "volatile oil" refers to any non-aqueous medium that is capable of evaporating upon contact with the skin or lips in less than 1 hour at room temperature and atmospheric pressure. The volatile oil is cosmetic volatile oil, which is liquid at room temperature. More specifically, the volatile oil has a concentration of 0.01mg/cm²Min and 200mg/cm²Evaporation rate between/min, limits included.

The term "fixed oil" refers to an oil that is maintained on the skin or keratinous fibers at room temperature and atmospheric pressure. More particularly, the non-volatile oil has a viscosity of strictly less than 0.01mg/cm²Evaporation rate per minute.

To measure the evaporation rate, 15g of the oil or oil mixture to be tested are placed in a crystallization dish with a diameter of 7cm, the evaporation dish is placed at a temperature adjusted to 25 ℃ and humidity adjusted to the phaseAbout 0.3m at 50% humidity³On a large indoor scale. The liquid was allowed to evaporate freely without stirring the liquid, while ventilation was provided by a fan (Papst-Motoren, No. 8550N, spinning at 2700 rpm) placed in a vertical position above the crystallization dish containing the oil or the mixture, with the blade directed towards the dish and 20cm from the bottom of the dish. The mass of oil remaining in the crystallization dish was measured at regular intervals. Evaporation rate in terms of per unit area (cm)²) And mg of oil evaporated per unit time (min).

For the purposes of the present invention, the term "silicone oil" refers to 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-based oil" refers to an oil comprising primarily hydrogen and carbon atoms.

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

Advantageously, the anhydrous composition of the invention may comprise from 10% to 50% by weight, preferably from 20% to 40% by weight, of one or more oils, relative to the total weight of the composition.

a) Essential oils

The volatile oil may be selected from hydrocarbon-based oils containing 8 to 16 carbon atoms, especially C₈-C₁₆Branched alkanes (also known as isoparaffins) such as isododecane (also known as 2,2,4,4, 6-pentamethylheptane), isodecane and isohexadecane, for example under the trade namesOrSold oils, or especially straight chain C₈-C₁₄Of (a) an alkane.

Volatile oils that may also be used include volatile silicones, such as volatile linear or cyclic silicone oils, especially those having a viscosity of 8 centistokes (cSt) (8 × 10)^-6m²Per s), and in particular silicone oils containing from 2 to 10 silicon atoms, in particular containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils which can be used in the present invention, mention may be made in particular of polydimethylsiloxanes having viscosities of 5cSt and 6cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

Volatile fluoro oils such as nonafluoromethoxybutane or perfluoromethylcyclopentane, and mixtures thereof, may also be used.

Advantageously, the liquid fatty phase may comprise from 1% to 50% by weight, preferably from 2% to 40% by weight, better still from 5% to 30% by weight of volatile oils, relative to the total weight of the liquid fatty phase of the invention.

b) Non-volatile oils

The non-volatile oil may be chosen in particular from non-volatile hydrocarbon-based oils, fluoro oils and/or silicone oils.

Non-volatile hydrocarbon-based oils that may be mentioned in particular include:

-a hydrocarbon-based oil of animal origin,

-hydrocarbon-based oils of vegetable origin, such as vegetable stearyl esters (phytostearyl esters), such as vegetable stearyl oleate, vegetable stearyl isostearate, and lauroyl/octyldodecyl/vegetable stearyl glutamate (Ajinomoto, Eldew PS203), triglycerides formed from fatty acid esters of glycerol, in particular wherein the fatty acids may have C₄To C₃₆Chain length of (2), especially C₁₈To C₃₆Of a chain length ofThe oils may be straight or branched chain, saturated or unsaturated; these oils may be, inter alia, triglycerides of heptanoic or octanoic acids, shea butter, alfalfa oil, poppy oil, millet oil, barley oil, rye oil, Chinese gooseberry oil (cardlenut oil), passion flower oil, shea butter, aloe oil, sweet almond oil, peach oil (peach oil), peanut oil, argan oil, avocado oil, kapok oil, borage oil, broccoli seed oil, calendula oil, camellia oil, canola oil (canola oil), carrot oil, safflower oil, linseed oil, rapeseed oil, cottonseed oil, coconut oil, pumpkin seed oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, corn oil, meadowfoam seed oil, san john's wort oil, creeper oil (monoil), extracted almond oil, walnut oil, olive oil, evening primrose oil, palm oil, black currant seed oil, macadamia oil, grape seed oil, hazelnut oil, grape seed oil, and grape seed oil, Pistachio oil, squash oil, pumpkin oil, quinoa oil, musk rose oil, sesame oil, soybean oil, sunflower oil, castor oil and watermelon oil, and mixtures thereof, or alternatively a triglyceride of caprylic/capric acid, such as the products sold by the company Stearineries Dubois or under the name Miglyol by the company Dynamit NobelMiglyolAnd MiglyolThe product being sold;

linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffin and its derivatives, vaseline, polydecenes, polybutenes, hydrogenated polybutenes such as Parleam, and squalane,

-synthetic ethers containing 10 to 40 carbon atoms, such as dioctanoyl ether;

-synthetic esters of formula R₁COOR₂The oil of (a), wherein,R₁represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms, R₂Represents a particularly branched hydrocarbon-based chain comprising from 1 to 40 carbon atoms, with the proviso that R₁+R₂Not less than 10. The ester may be chosen in particular from: esters of alcohols and fatty acids, such as cetearyl octanoate; esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl stearate; hydroxylated esters, such as isostearic acid ester, octyl hydroxystearate, ricinoleate of alcohols or polyols, hexyl laurate; pivalate esters such as isodecyl pivalate, isotridecyl pivalate; and isononanoates, such as isononyl isononanoate and isotridecyl isononanoate.

Polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate/tetraisostearate,

esters of dimer diol and dimer diacid, such as those described in patent application US 2004-175338 and sold by the company Nippon Fine Chemical by LusplanAnd Lusplan

Copolymers of dimer diol and dimer diacid and esters thereof, for example dimer dilinonediol/dimer dilinoleic acid and esters thereof, such as planchool-G,

copolymers of polyols and dimer diacids and esters thereof, for example copolymers of Hailuscent ISDA or dilinoleic/butanediol,

fatty alcohols which are liquid at room temperature, having branched and/or unsaturated carbon-based chains containing from 12 to 26 carbon atoms, such as, for example, 2-octyldodecanol, isostearyl alcohol and oleyl alcohol,

-C₁₂-C₂₂is highA lower fatty acid, such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof,

dialkyl carbonates, the two alkyl chains being identical or different, such as by Cognis under the name CetiolThe amount of dioctyl carbonate sold is that of dioctyl carbonate,

high molar mass oils, in particular oils having a molar mass of from about 400g/mol to about 2000g/mol, in particular from about 650g/mol to about 1600 g/mol. As high molar mass oils which can be used in the present invention, mention may be made in particular of: linear fatty acid esters having a total carbon number of 35 to 70, such as pentaerythritol tetrapelargonate; hydroxylated esters, such as polyglyceryl-2 triisostearate; aromatic esters such as tridecyl trimellitate; c of a branched chain₂₄-C₂₈Esters of fatty alcohols or fatty acids, such as those described in patent US 6491927, and pentaerythritol esters, in particular triisoeicosanol citrate, triisostearin, tri (2-decyl) tetradecanoate, polyglyceryl-2 tetraisostearate or pentaerythritol tetrakis (2-decyl) tetradecanoate; phenyl silicones such as Belsil PDM 1000 from Wacker (MM 9000 g/mol); non-volatile Polydimethylsiloxane (PDMS), which comprises alkyl or alkoxy groups, respectively comprising from 2 to 24 carbon atoms, pendant and/or at the end of a silicone chain; phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxy silicates, polydimethylsiloxanes or phenyl trimethicones (wherein the viscosity is less than or equal to 100cSt), and mixtures thereof; and mixtures of these different oils, and

-mixtures thereof.

According to one embodiment, the composition of the invention comprises at least one non-volatile oil chosen from non-volatile hydrocarbon-based oils, such as:

-hydrocarbon-based oils of animal origin;

-hydrocarbon-based oils of vegetable origin;

-synthetic ethers comprising 10 to 40 carbon atoms;

synthetic esters, e.g. of the formula R₁COOR₂Wherein R is₁Represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms, R₂Represents a particularly branched hydrocarbon-based chain comprising from 1 to 40 carbon atoms, with the proviso that R₁+R₂≥10；

-polyol esters and pentaerythritol esters;

-fatty alcohols that are liquid at room temperature, having a branched and/or unsaturated carbon-based chain comprising from 12 to 26 carbon atoms;

-dialkyl carbonates, the two alkyl chains being the same or different;

-oils of high molar mass; and

-mixtures thereof.

Advantageously, the liquid fatty phase may comprise at least 40% by weight, preferably at least 60% by weight, or even 100% by weight of non-volatile oil, relative to the total weight of the liquid fatty phase of the invention.

The composition according to the invention may be anhydrous or non-anhydrous.

In the anhydrous composition according to the invention, "at least one selected from polyols and/or diols, and optionally C, relative to the weight of the composition₂-C₈The compound of the monoalcohols, and mixtures thereof "is present in an amount of at least 3% by weight, preferably at least 5% by weight, more preferably at least 8% by weight, advantageously at least 10% by weight, and the composition is devoid of water.

By "water-deficient" it is meant that the composition comprises less than 3%, preferably less than 1%, more preferably less than 0.5% water, especially no water.

Such small amounts of water may, where appropriate, be introduced, inter alia, by components of the composition that may contain residual amounts of water.

In the non-anhydrous composition according to the invention, "at least one selected from polyols and/or diols, and optionally C, with respect to the weight of the composition₂-C₈The compound "of the monoalcohols, and mixtures thereof, is advantageously present in an amount of at least 10% by weight, preferably at least 12% by weight, more preferably at least 15% by weight.

Tanning agent

For the purposes of the present invention, the expression "skin tanning agent" refers to a compound capable of undergoing a coloring reaction, when in contact with the skin, with the free amino functions present in the skin (for example amino acids, peptides or proteins).

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

The self-tanning agents are generally selected from certain mono-or polycarbonyl compounds, such as isatin, alloxan, ninhydrin, glyceraldehyde, meso-tartaric aldehyde, glutaraldehyde, erythrulose, pyrazoline-4, 5-dione derivatives as described in patent applications FR 2466492 and WO 97/35842, Dihydroxyacetone (DHA), and 4, 4-dihydroxypyrazoline-5-one as described in patent application EP 903342. Preferably DHA will be used.

DHA may be used in free form and/or in encapsulated form, for example in lipid vesicles, such as liposomes, as described in particular in patent application WO 97/25970.

The self-tanning agent is generally present in a proportion of from 0.1% to 15% by weight, preferably from 0.2% to 10% by weight, more preferably from 1% to 8% by weight, relative to the total weight of the composition.

Silicone elastomer

According to the invention, the composition may comprise at least one silicone elastomer. Any suitable silicone elastomer may be used in accordance with the present invention. Suitable silicone elastomers include, for example: emulsifying silicone elastomers, such as polyglycerolated and/or hydrophilic emulsifying silicone elastomers, such as alkoxylated silicone elastomers; and non-emulsifying silicone elastomers. Such silicone elastomers may be spherical or non-spherical.

Polyglycerolated silicone elastomers

Suitable polyglycerolated silicone elastomers include, for example, crosslinked elastomeric organopolysiloxanes obtainable by a crosslinking addition reaction of a diorganopolysiloxane comprising at least one silicon-bonded hydrogen atom with a polyglycerolated compound containing ethylenic unsaturation, especially in the presence of a platinum catalyst.

Polyglycerolated silicone elastomers that may be used include, but are not limited to, the polyglycerolated silicone elastomers sold by Shin-Etsu company under the names "KSG-710", "KSG-810", "KSG-820", "KSG-830" and "KSG-840". Suitable polyglycerolated silicone elastomers are also disclosed in U.S. serial No. 11/085,509 (published as U.S. patent application publication No. 2005/0220728), filed on 22/3/2005, the entire disclosure of which is incorporated herein by reference.

Hydrophilic emulsified silicone elastomer

The term "hydrophilic emulsifying silicone elastomer" refers to a silicone elastomer comprising at least one hydrophilic chain different from the polyglycerolated chains described above.

In particular, the hydrophilic emulsifying silicone elastomer may be chosen from polyoxyalkylenated silicone elastomers.

Suitable polyoxyalkylenated elastomers are described in U.S. Pat. No. 5,236,986, U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793, and U.S. Pat. No. 5,811,487.

Suitable polyoxyalkylenated silicone elastomers that may be used include: products sold by the company Shin-Etsu under the names "KSG-21", "KSG-20", "KSG-30", "KSG-31", "KSG-32", "KSG-33", "KSG-210", "KSG-310", "KSG-320", "KSG-330", "KSG-340" and "X-226146"; or products sold under the names "DC 9010" and "DC 9011" by the company Dow Corning.

Suitable hydrophilic emulsifying silicone elastomers are also disclosed in U.S. serial No. 11/085,509 (published as U.S. patent application publication No. 2005/0220728), filed on 22/3/2005.

Non-emulsifying silicone elastomers

The term "non-emulsifying" defines an elastomer that does not contain hydrophilic chains (e.g. polyoxyalkylene units or polyglycerolated units).

The non-emulsifying silicone elastomer is preferably a crosslinked organopolysiloxane of an elastomer obtainable by: a crosslinking addition reaction of a diorganopolysiloxane containing at least one silicon-bonded hydrogen atom with a diorganopolysiloxane containing silicon-bonded ethylenically unsaturated groups, especially in the presence of a platinum catalyst; or a dehydrocrosslinking coupling reaction between a diorganopolysiloxane containing hydroxyl end groups and a diorganopolysiloxane containing at least one silicon-bonded hydrogen, especially in the presence of an organotin compound; or a cross-coupling reaction of a diorganopolysiloxane containing hydroxyl end groups and a hydrolyzable organopolysilane; or thermal crosslinking of the organopolysiloxane, especially in the presence of an organic peroxide catalyst; or crosslinking of the organopolysiloxane by means of high-energy radiation, such as gamma rays, ultraviolet rays, or electron beams.

Suitable non-emulsifying silicone elastomers are described in patent applications JP 61-194009A, EP 0242219A, EP 0295886A and EP 0765656A.

Suitable non-emulsifying silicone elastomers that may be used include, but are not limited to, the non-emulsifying silicone elastomers sold by Dow Corning under the names "DC 9040", "DC 9041", "DC 9509", "DC 9505" and "DC 9506".

Suitable non-emulsifying silicone elastomers are also disclosed in U.S. serial No. 11/085,509 (published as U.S. patent application publication No. 2005/0220728), filed on 22/3/2005.

The non-emulsifying silicone elastomer may also be a crosslinked organopolysiloxane powder coated with an elastomer of a silicone resin, particularly a silsesquioxane resin, for example as described in U.S. Pat. No. 5,538,793, the entire contents of which are incorporated herein by reference. Such elastomers are sold by the company Shin-Etsu under the names "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104" and "KSP-105".

Other elastomeric crosslinked organopolysiloxanes in powder form include: hybrid silicone powders functionalized by fluoroalkyl groups, in particular the product sold under the name "KSP-200" by the company Shin-Etsu; hybrid silica powders functionalized by phenyl groups, such as the product sold under the name "KSP-300" by the company Shin-Etsu.

The silicone elastomer may be present in the composition in an amount of from 0.1% to 95% by weight, preferably from 0.1% to 75% by weight, more preferably from 0.1 to 50% by weight, more preferably from 0.1% to 40% by weight, more preferably from 0.5% to 30% by weight, more preferably from 0.5% to 25% by weight, more preferably from 1% to 20% by weight, more preferably from 1% to 15% by weight, even more preferably from 3% to 10% by weight, based on the weight of the composition of the invention.

Film forming agent

Silicone polyamides

The composition according to the invention comprises at least one silicone polyamide.

The silicone polyamide of the composition is preferably solid at room temperature (25 ℃) and at atmospheric pressure (760 mmHg).

The silicone polyamide of the composition of the invention may be A polymer of the polyorganosiloxane type, such as those described in documents U.S. Pat. No. 4, 5874069, U.S. Pat. No. 3, 5919441, U.S. Pat. No. 3, 6051216 and U.S. Pat. No. 5981680. According to the invention, the silicone polymers can belong to the following two families:

(1) a polyorganosiloxane comprising at least two amide groups located in the polymer chain, and/or

(2) Polyorganosiloxane comprising at least two amide groups, the amide groups being located on a graft or branch.

A) According to a first variant, the silicone polymer is a polyorganosiloxane as described above in which the amide units are located in the polymer chain.

The silicone polyamide may in particular be a polymer comprising at least one unit corresponding to formula I:

1) wherein, when G represents-C (O) -NH-Y-NH-, G' represents C (O); and G' represents-NH-when G represents-NH-C (O) -Y-C (O) -and,

2)R⁴、R⁵、R⁶and R⁷And, which may be identical or different, represent a group selected from:

-linear, branched or cyclic, saturated or unsaturated C₁To C₄₀May contain one or more oxygen, sulfur and/or nitrogen atoms in their chain and may be partially or fully substituted with fluorine atoms,

-C₆-C₁₀aryl of (C)₆-C₁₀Optionally substituted by one or more C₁-C₄Is substituted with an alkyl group of (a),

polyorganosiloxane chains which may contain one or more oxygen, sulfur and/or nitrogen atoms,

3) the radicals X, which may be identical or different, represent straight-chain or branched C₁To C₃₀Alkylene diyl (alkylene) of (a), which may contain one or more oxygen atoms and/or nitrogen atoms in its chain;

4) y is saturated or unsaturated C₁To C₅₀A divalent radical of a linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group of (a), which may comprise one or more oxygen atoms, sulfur atoms and/or nitrogen atoms, and/or which may carry as substituents one of the following atoms or groups of atoms: fluorine, hydroxy, C₃To C₈Cycloalkyl radical, C₁To C₄₀Alkyl radical, C₅To C₁₀Aryl, optionally with 1 to 3C₁To C₃Alkyl-substituted phenyl, C₁To C₃Hydroxyalkyl and C₁To C₆Aminoalkyl, or

5) Y represents a group corresponding to the formula:

wherein:

-T represents a linear or branched, saturated or unsaturated C₃To C₂₄A trivalent or tetravalent hydrocarbon-based group optionally substituted with a polyorganosiloxane chain and which may contain one or more atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and Al, and

-R⁸represents a linear or branched C₁-C₅₀May contain one or more ester groups, amide groups, urethane groups, thiourethane groups, urea groups, thiourea groups and/or sulfonamide groups, with which it is possible to reactAnother chain linkage of the polymer;

6) n is an integer from 2 to 500, preferably from 2 to 200, and m is an integer from 1 to 1000, preferably from 1 to 700, better still from 6 to 200.

According to the invention, the radical R of the polymer⁴、R⁵、R⁶And R⁷Preferably 80% of (a) are selected from methyl, ethyl, phenyl and 3,3, 3-trifluoropropyl groups. According to another embodiment, the group R of the polymer⁴、R⁵、R⁶And R⁷80% of them are methyl groups.

According to the invention, Y can represent various divalent groups, additionally optionally comprising one or two free valencies to establish a link with other parts of the polymer or copolymer. Preferably, Y represents a group selected from:

a) straight chain C₁To C₂₀Preferably C₁To C₁₀The alkylene group of (a) is,

b) c of a branched chain₃₀To C₅₆May comprise a cyclic and non-conjugated unsaturated alkylene group,

c)C₅-C₆the cyclic alkylene group of (a) is,

d) optionally by one or more C₁To C₄₀An alkyl-substituted phenylene group of (a) a,

e) c comprising 1 to 5 amide groups₁To C₂₀The alkylene group of (a) is,

f) containing one or more groups selected from hydroxy, C₃To C₈Cycloalkanes, C₁To C₃Hydroxyalkyl and C₁To C₆C of substituents of alkylamino groups₁To C₂₀An alkylene group or a substituted alkylene group,

g) polyorganosiloxane chains of formula:

or

Wherein R is⁴、R⁵、R⁶、R⁷T and m are as defined above.

B) According to a second variant, the silicone polyamide may be a polymer comprising at least one unit corresponding to formula (II):

wherein:

-R⁴and R⁶Which may be identical or different, as defined above for formula (I),

-R¹⁰represents for R as defined above⁴And R⁶Or represents the formula-X-G' -R¹²Wherein X is as defined above for formula (I), R¹²Represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated C₁-C₅₀Based on hydrocarbon (C)₁-C₅₀Optionally containing in its chain one or more atoms selected from O, S and N, optionally substituted with one or more fluorine atoms and/or one or more hydroxyl groups), or optionally with one or more C₁-C₄A phenyl group substituted with an alkyl group,

and G' represents-C (O) NH-and-HN-C (O) -,

-R¹¹is represented by the formula-X-G' -R¹²Wherein X, G' and R¹²As defined above, the above-mentioned,

-m₁is an integer of 1 to 998, and

-m₂is an integer from 2 to 500.

According to the invention, the silicone polymer may be a homopolymer, i.e. a polymer comprising a plurality of identical units, in particular units of formula (I) or formula (II).

According to the invention, it is also possible to use silicone polymers formed from copolymers comprising a plurality of different units of formula (I), i.e. where the group R⁴、R⁵、R⁶、R⁷At least one of X, G, Y, m and n is a different polymer in one of the units. The copolymers may also be formed from units of the formula (II) in which the radical R⁴、R⁶、R¹⁰、R¹¹、m₁And m₂At least one of which differs in at least one cell.

Polymers comprising at least one unit of formula (I) and at least one unit of formula (II), which may be the same as or different from each other, may also be used.

These copolymers may be block polymers or graft polymers.

In this first embodiment of the invention, the silicone polymer may also consist of a graft copolymer. Thus, the polyamide comprising silicone units may be grafted and optionally crosslinked with amide group-containing silicone chains. Such polymers can be synthesized using trifunctional amines.

According to an advantageous embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of the formulae-C (O) NH-and-HN-C (O) -. In this case, the structuring agent may be a polymer comprising at least one unit of formula (III) or formula (IV):

or

Wherein R is⁴、R⁵、R⁶、R⁷X, Y, m and n are as defined above.

In these polyamides of formula (III) or formula (IV), m is in the range of 1 to 700, in particular 15 to 500, in particular 50 to 200, and n is in particular in the range of 1 to 500, preferably 1 to 100, better still 4 to 25.

X is preferably a linear or branched alkylene chain comprising from 1 to 30 carbon atoms, especially from 1 to 20 carbon atoms, especially from 5 to 15 carbon atoms, more especially 10 carbon atoms, and

y is preferably an alkylene chain which is linear or branched or may contain rings and/or unsaturations, comprising from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms, better still from 2 to 6 carbon atoms, in particular 6 carbon atoms.

In formula (III) and formula (IV), the alkylene group representing X or Y can optionally comprise at least one of the following in its alkylene moiety:

1)1 to 5 amide groups, urea groups, urethane groups, or urethane groups,

2)C₅or C₆A cycloalkyl group of, and

3) optionally substituted by 1 to 3 identical or different C₁To C₃Alkyl-substituted phenylene radicals.

In formula (III) and formula (IV), the alkylene group may be further substituted with at least one member selected from the group consisting of:

-a hydroxyl group,

-C₃to C₈A cycloalkyl group,

-1 to 3C₁To C₄₀An alkyl group, a carboxyl group,

optionally 1 to 3C₁To C₃A phenyl group substituted with an alkyl group,

-C₁to C₃Hydroxyalkyl radicals, and

-C₁to C₆An aminoalkyl group.

In these formulae (III) and (IV), Y may also represent:

wherein R is⁸Represents a polyorganosiloxane chain and T represents a group of formula:

wherein a, b and c are independently integers from 1 to 10, R¹³Is a hydrogen atom or such as for R⁴、R⁵、R⁶And R⁷A defined group.

In the formulae (III) and (IV), R⁴、R⁵、R⁶And R⁷Preferably independently represent a linear or branched C₁To C₄₀Alkyl, preferably CH₃、C₂H₅、n-C₃H₇Or isopropyl, a polyorganosiloxane chain or a phenyl group optionally substituted with 1 to 3 methyl or ethyl groups.

As seen previously, the polymer may comprise the same or different units of formula (III) or formula (IV).

Thus, the polymer may be a polyamide comprising a plurality of units of formula (III) or formula (IV) of different lengths, i.e. a polyamide corresponding to formula (V):

wherein, X, Y, n and R⁴To R⁷Having the meaning given above, m₁And m₂Different and selected from the range of 1 to 1000, and p is an integer from 2 to 300.

In this formula, the units may be structured to form a block copolymer, or a random copolymer, or an alternating copolymer. In the copolymer, the units may not only have different lengths, but also different chemical structures, for example comprising different groups Y. In this case, the polymer may correspond to formula VI:

wherein R is⁴To R⁷、X、Y、m₁、m₂N and p have the meanings given above, Y¹Different from Y but selected from the groups defined for Y. As previously described, the individual units may be structured to form block copolymers, or random or alternating copolymers.

In this first embodiment of the invention, the structuring agent may also consist of a graft copolymer. Thus, the polyamide comprising silicone units may be grafted and optionally crosslinked with amide group-containing silicone chains. Such polymers can be synthesized using trifunctional amines.

In this case, the polymer may comprise at least one unit of formula (VII):

wherein, the same or different X¹And X²Having the given meaning for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I), R¹⁴To R²¹Is selected from the group consisting of⁴To R⁷Radicals of the same radicals, m₁And m₂Is a number in the range of 1 to 1000, and p is an integer in the range of 2 to 500.

In formula (VII), preferred are:

-p is in the range of 1 to 25, better still 1 to 7,

-R¹⁴to R²¹Is a methyl group, and the compound is,

-T corresponds to one of the following formulae:

wherein R is²²Is a hydrogen atom or is selected from the group consisting of⁴To R⁷Radical of a group as defined, R²³、R²⁴And R²⁵Independently linear or branched alkylene, more preferably corresponding to the formula:

in particular, R²³、R²⁴And R²⁵represents-CH₂-CH₂-，

-m₁And m₂In the range of 15 to 500, preferably 15 to 45,

-X¹and X²Represents- (CH)₂)₁₀-, and

-Y represents-CH₂-。

These polyamides comprising grafted silicone units of formula (VII) can be copolymerized with polyamide-silicones of formula (II) to form block, alternating or random copolymers. The weight percentage of grafted silicone units (VII) in the copolymer may be from 0.5% to 30% by weight.

According to the invention, the siloxane units may be in the main chain or in the backbone of the polymer, as previously described, but they may also be present in the graft chain or in the pendant chain. In the backbone, the siloxane units may be in the form of segments as described above. In the pendant chain or graft chain, the siloxane units may occur individually or in fragments.

According to one embodiment variant of the invention, it is possible to use copolymers of silicone polyamides and of hydrocarbon-based polyamides, or copolymers comprising units of formula (III) or (IV) and of hydrocarbon-based polyamide units. In this case, the polyamide-silicone unit may be located at the terminal of the hydrocarbon-based polyamide.

According to a preferred embodiment, the silicone polyamide comprises units of formula III, preferably wherein the group R⁴、R⁵、R⁶And R⁷Represents a methyl group, one of X and Y represents an alkylene group of 6 carbon atoms, the other represents an alkylene group of 11 carbon atoms, and n represents the degree of polymerization DP of the polymer.

Examples of such silicone polyamides that may be mentioned include the compounds sold under the names DC 2-8179(DP100) and DC 2-8178(DP 15) by the company Dow Corning under the name INCI Nylon-611/Dimethicone copolymer.

Advantageously, the silicone polyamide is a compound having the INCI name nylon-611/polydimethylsiloxane copolymer.

Advantageously, the composition according to the invention comprises at least one polydimethylsiloxane block polymer of formula (I) in which the coefficient m is about 100. The coefficient "m" corresponds to the degree of polymerization of the silicone portion of the polymer.

More preferably, the composition according to the invention comprises at least one polymer comprising at least one unit of formula (III) wherein m is in the range of 50 to 200, especially 75 to 150, more especially about 100.

Also preferably, in formula (III), R⁴、R⁵、R⁶And R⁷Independently represent straight-chain or branchedC of the chain₁-C₄₀Alkyl, preferably CH₃、C₂H₅、n-C₃H₇Or an isopropyl group.

As an example of A polymer which can be used, mention may be made of one of the silicone polyamides obtained according to examples 1 to 3 of document US-A-5981680.

Preferably, a nylon-611/polydimethylsiloxane copolymer sold by Dow Corning as number DC 2-8179 is used as the silicone polyamide.

The silicone polyamide may be present in the composition in a total content ranging from 0.5% to 45% by weight, preferably from 1% to 30% by weight, better still from 2% to 20% by weight, relative to the total weight of the composition.

Silicone resin

Examples of such silicone silicones that may be mentioned include:

a siloxane-based silicate which may be of the formula [ (CH)₃)₃SiO]_x(SiO_4/2)_y(units MQ) wherein x and y are integers in the range of from 50 to 80,

-formula (CH)₃SiO_3/2)_x(unit T) wherein x is greater than 100 and at least one of its methyl groups can be substituted by a group R as defined above,

polymethylsilsesquioxane, which is a polysilsesquioxane: wherein no methyl group is substituted by another group. Such polymethylsilsesquioxanes are described in document US 5246694.

As examples of commercially available polymethylsilsesquioxane resins, the following products sold can be mentioned:

products sold under the number Resin MK by Wacker corporation, such as Belsil PMS MK: comprising CH₃SiO_3/2Polymers of repeating units (units T), which polymers are also suitableMay contain up to 1% by weight of (CH)₃)₂SiO_2/2Units (unit D) and having an average molecular weight of about 10000g/mol, or

A product sold under the number KR-220L by the company Shin-Etsu, of formula CH₃SiO_3/2And comprises Si-OH (silanol) end groups; the product sold under the number KR-242A, comprising 98% of units T and 2% of dimethyl units D and comprising Si-OH end groups; alternatively, the product sold under the number KR-251, which comprises 88% of units T and 12% of dimethyl units D and comprises Si-OH end groups.

Mention may be made of siloxanylsilicate resins including trimethylsiloxysilicate resins (TMS), optionally in powder form. These resins are sold under the number SR1000 by Momentive Performance Materials or under the number TMS 803 by Wacker. Mention may also be made of trimethylsiloxysilicate resins sold under the name KF-7312J by the company Shin-Etsu or sold under the names DC 749 and DC 593 by the company Dow Corning in solvents such as cyclomethicone.

Advantageously, the silicone resin, for example trimethylsiloxysilicate resin, is present in a content ranging from 0.5% to 30%, better still from 1% to 25%, or even better still from 5% to 25%, relative to the total weight of the composition.

Preferably, nylon-611/polydimethylsiloxane is used as the silicone polyamide and trimethylsiloxysilicate resin is used as the silicone resin.

According to another embodiment, the silicone resin is a propylphenylsilsesquioxane resin.

Silsesquioxane resins are a specific form of film-forming silicone resin. Silicone resins are crosslinked organopolysiloxanes that are solid at room temperature and are typically soluble in organic solvents. When they are dissolved in volatile solvents, silicone resins are capable of forming films once the solvent evaporates. In addition, if a solvent dissolving the silicone resin is adsorbed on a substrate coated with the silicone resin, the silicone resin remaining on the substrate may also form a film.

The composition of the present invention comprises a propylphenylsilsesquioxane resin which has been disclosed in patent publication WO2005/090444 published on 9/29 in 2005, US20040180011 published on 9/16 in 2004, and US20040156806 published on 8/12 in 2004.

The propylphenylsilsesquioxane resin comprises at least about 70 mole percent of propylsiloxane-based units (C), based on the total mole percent of siloxane-based units of the resin₃H₇SiO_3/2) And up to about 30 mole percent of phenylsiloxane-based units (C), based on the total mole percent of siloxane-based units of the resin₆H₅SiO_3/2)。

The mole percentage of propylsiloxanyl units to phenylsiloxanyl units can be adjusted depending on the intended application. Thus, there may be a propylphenylsilsesquioxane resin having propylsiloxane-based units: the molar percentage of phenylsiloxane-based units is about 70:30 to about 100:0, e.g., 70:30, 80:20, 90:10, and 100:0, and subranges therebetween. When the mole percentage of propylsiloxane-based units is about 100 mole%, the propylphenyl silsesquioxane resin is referred to as a propylsilsesquioxane resin.

Suitable examples of propylphenylsilsesquioxane resins for use in the cosmetic compositions of the present invention include, but are not limited to, propylsilsesquioxane resins available from Dow-Corning under the trade name DC 670 Fluid.

The propylphenylsilsesquioxane film-forming resin may be present in an amount ranging from about 0.5% to about 50% by weight, such as from about 1% to about 40% by weight, such as from about 2% to about 30% by weight, such as from about 3% to about 20% by weight, such as from about 4% to about 10% by weight, all weights based on the weight of the entire composition.

Silicone acrylate copolymers

The compositions of the present invention may comprise a silicone acrylate copolymer.

Silicone acrylate copolymers are another specific form of film-forming silicone resin. They may be used as silicone acrylate copolymers having a (meth) acrylate skeleton grafted with a silicone chain, or having a silicone skeleton grafted with a (meth) acrylate, or having a silicone acrylate dendrimer.

Silicone acrylate dendrimers, such as those described and claimed in U.S. patent No. 6,280,748, the entire contents of which are incorporated herein by reference, are preferred for use in the compositions of the present invention. The silicone acrylate dendrimers are composed of vinyl polymers with carbosiloxane dendrimer structures in their side molecular chains. It is characterized by a vinyl-type polymer having a carbosiloxane dendrimer structure in its side molecular chain. The term "carbosiloxane dendrimer structure" is a structure having high molecular weight groups branched with high regularity in the radial direction from a single center.

The vinyl polymer backbone is composed of vinyl type monomers containing a basic polymerizable vinyl group. In the broadest definition, there is no particular limitation on the type of such monomers. Particularly preferred vinyl polymers are (meth) acrylates.

The number average molecular weight of the silicone acrylate dendrimers used in the compositions of the present invention is from about 3,000 to about 2,000,000, such as from about 5,000 to about 800,000.

Particularly preferred silicone acrylate dendrimers for use in the compositions of the present invention are FA-4001CM silicone acrylate (30% solution in cyclomethicone) and FA-4002ID silicone acrylate (40% solution in isododecane) available from Dow Corning under the INCI designation acrylate/polytrimethylsiloxanylmethacrylate copolymer.

The silicone acrylate copolymer may be present in the compositions of the present invention in an amount in the range of from about 0.5% to about 20% by weight (e.g., from about 0.7% to about 15% by weight, such as from about 1% to about 10% by weight), all weights being based on the weight of the entire composition.

Phase of powder form

The composition of the invention may comprise a pulverulent phase material in addition to the microcapsules defined above.

The composition may comprise at least 1% by weight, in particular at least 5% by weight, of pulverulent phase relative to the total weight of the composition according to the invention.

More particularly, the composition may comprise at least 15% by weight, in particular at least 20% by weight, of pulverulent phase relative to the total weight of the composition according to the invention.

For the purposes of the present invention, the pulverulent phase may comprise, in addition to the desired microcapsules according to the invention, at least one non-inclusive particulate material chosen from fillers, pigments, nacres, particles having a metallic tone, and mixtures thereof.

Thus, the composition may advantageously comprise from 1% to 70% by weight, preferably from 5% to 60% by weight, better still from 10% to 50% by weight of pulverulent phase, relative to the total weight of the composition according to the invention.

Thus, the composition may advantageously comprise from 15% to 70% by weight, preferably from 20% to 60% by weight, better still from 25% to 50% by weight of pulverulent phase, relative to the total weight of the composition according to the invention.

a) Uncontained packing

For the purposes of the present invention, the term "filler" is understood to mean any form of solid particles, colorless or white, which are in insoluble and dispersed form in the medium of the composition.

These mineral or organic fillers, of natural or synthetic nature, provide softness to the composition comprising them and matte effect and uniformity to the cosmetic result.

The composition may comprise from 0.5% to 50% by weight, preferably from 1% to 30% by weight, of filler relative to the total weight of the composition according to the invention.

The amount of filler does not include the amount of hollow particles required in parallel according to the invention.

Among the mineral fillers that can be used in the composition according to the invention, mention may be made of natural or synthetic mica, talc, kaolin, natural or synthetic sericite, silica, hydroxyapatite, boron nitride, calcium carbonate, hollow silica microspheres (silica beads from maprocs), Glass or ceramic microcapsules, composites of silica and titanium dioxide (such as the TSG series sold by Nippon Sheet Glass) and mixtures thereof.

Among the organic fillers which can be used in the compositions according to the invention, mention may be made of: polyamide powder (from Atochem)Orgasol, poly- β -alanine powder, polyethylene powder, polytetrafluoroethylene (PTFE) Powder; lauroyl lysine; tetrafluoroethylene polymer powder; spherical powders of crosslinked elastomeric organopolysiloxanes, such as those sold under the name Trefil Powder E2-506C or DC9506 or DC9701 by the company Dow Corning, are described in particular in document JP-A-02-243612; silicone resins which are the product of the hydrolysis and polycondensation of a siloxane mixture of the formulae (R)3SiOHCH3 and Si (OCH3)4, R representing an alkyl group containing from 1 to 6 carbon atoms (e.g. KSP100 from Shin-Etsu); silicone beads (e.g., from Toshiba))，L200(Chemdal corporation); polyurethane powder, in particular cross-linked polyurethane powder comprising a copolymer comprising trimethylolcaprolactone, for example under the name Plastic powder by the company ToshikiOr Plastic PowderPolymers of hexamethylene diisocyanate/trimethylol caprolactone sold; and mixtures thereof.

Among the other organic fillers that can be used in the compositions according to the invention, mention may be made of starch-based or cellulose-based powders. Examples of such fillers that may be mentioned include the Dry Flo product sold by Akzo Nobel and the Cellubeads product sold by DaitoKasei Corp.

Advantageously, the filler according to the invention is a mineral filler, preferably selected from mica, sericite, kaolin, talc and silica, and mixtures thereof.

c) Uncontained particulate materials for coloring purposes

These additional coloured particulate materials may be present in a proportion of from 0 to 40% by weight, preferably from 1 to 30% by weight, or even from 5 to 30% by weight, relative to the total weight of the composition comprising the additional coloured particulate materials.

They may be, in particular, pigments, nacres and/or particles of products having a metallic tone, these materials being surface-treated.

The term "pigment" is understood to mean a white or coloured, mineral or organic particle insoluble in aqueous solutions, the pigment being used to colour and/or opacify the composition comprising the pigment.

The composition may comprise from 0.01% to 40% by weight, preferably from 0.1% to 20% by weight, better still from 1% to 15% by weight of pigment relative to the total weight of the composition according to the invention.

The pigments may be white or coloured, mineral and/or organic.

As mineral pigments which can be used in the present invention, mention may be made of titanium oxides, titanium dioxide, zirconium oxides, zirconium dioxide, cerium oxides or cerium oxides and also zinc oxides, iron oxides or chromium oxides, iron blue, manganese violet, ultramarine blue and chromium hydroxide, and mixtures thereof.

According to a particular embodiment, the composition of the invention comprises at least an uncontained inorganic pigment chosen from titanium dioxide, zinc oxide, cerium oxide and/or a filler chosen from bismuth oxychloride or boron nitride, in order to improve the whiteness of the composition.

According to a particular embodiment, the composition of the invention comprises at least an uncontained TiO₂。

The pigment may also be a pigment having a structure of, for example, sericite/brown iron oxide/titanium dioxide/silica type. For example, such pigments are sold under the number Coverleaf NS or Coverleaf JS by Chemicals and Catalysts, Inc., and have a contrast of about 30.

The pigment may also be a pigment having a structure such as silica microsphere type comprising iron oxide. An example of a pigment having this structure is sold under the number PC Ball PC-LL-100P by the company Miyoshi, which pigment consists of silica microspheres containing yellow iron oxide.

Advantageously, the pigment according to the invention is an iron oxide and/or titanium dioxide.

The term "nacres" is understood to mean any shape of shiny or non-shiny coloured particles, in particular produced by some mollusk within its shell, or else synthesized, and which have a chromatic effect by optical interference.

The composition may comprise from 1% to 80% by weight, preferably from 5% to 60% by weight, better still from 10% to 40% by weight of nacres relative to the total weight of the composition of the invention.

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

Examples of nacres which may also be mentioned include natural mica coated with titanium oxide, iron oxide, natural pigments or bismuth oxychloride.

Among the nacres available on the market, mention may be made of: nacre Timica, Flamenco and Duochrome (based on mica) sold by Engelhard; timiron mica sold by Merck corporation; the nacres sold by Eckart corporation based on Prestige mica; and mother-of-pearl sold by Sun Chemical company based on Sunshine synthetic mica.

The nacres may in particular have a yellow, pink, red, bronze, orange, brown, gold and/or copper colour or hue.

As an illustration of the nacres that can be used in the context of the present invention, mention may be made of: gold mother-of-pearl sold in particular by the company Engelhard under the names bright Gold (Brillant Gold)212g (Timica), Gold (Gold)222c (cloisonne), Sparkle Gold (Sparkle Gold) (Timica), Gold (Gold)4504(Chromalite) and Monarch Gold (Monarch Gold)233x (cloisonne); in particular the Bronze nacres sold by the company Merck under the name fine Bronze (Bronze) (17384) (Colorona) and Bronze (Bronze) (17353) (Colorona) and sold by the company Engelhard under the name Super Bronze (clousone); in particular, the Orange nacres sold by the company Engelhard under the names Orange (Orange)363c (cloisonne) and Orange (Orange) MCR 101 (cosmoca) and by the company Merck under the names intense Orange (page Orange) (Colorona) and matt Orange (mate) 17449 (micron); in particular brown nacres sold by the company Engelhard under the names antique copper (nuanique copper)340xb (cloisonne) and Bronze (Bronze) CL4509 (Chromalite); in particular nacres with a Copper tint sold by the company Engelhard under the name Copper (cooper) 340a (timica); in particular mother-of-pearl sold by the company Merck under the name tiny brown (Siennafine) (17386) (Colorona) with a red hue; in particular mother-of-pearl with a Yellow tint sold by the company Engelhard under the name Yellow (Yellow) (4502) (Chromalite); in particular the red nacre sold by the company Engelhard under the name heliostone G012(Gemtone) with a gold hue; in particular the pink nacre sold by the company Engelhard under the name brown-white (Tan opale) G005 (Gemtone); especially black nacre with a gold tone sold by the company Engelhard under the name antique bronze (Nu anti quebronze)240ab (timica); in particular the blue mother-of-pearl sold by the company Merck under the name matt blue (mate blue) (17433) (micron); in particular white nacres with a Silver hue sold by the company Merck under the name of herona Silver (Xirona Silver); and in particular the mother-of-pearl sold by the company Merck under the name Indian summer (Xirona) under the name turquoise red-orange; and mixtures thereof.

Advantageously, the nacres according to the invention are mica coated with titanium dioxide or iron oxides and with bismuth oxychloride.

Within the meaning of the present invention, the term "particles having a metallic hue" denotes particles whose properties, size, structure and surface state allow them to reflect incident light, in particular in a non-glittering manner.

The composition may comprise from 1% to 50% by weight, preferably from 1% to 20% by weight, relative to the total weight of the composition according to the invention, of particles having a metallic hue.

Particles having a substantially flat outer surface are also suitable, since they are more prone to strong specular reflection if their size, structure and surface state allow, which may be referred to as a mirror effect.

Particles having a metallic hue useful in the present invention, for example, can reflect light in all components of the viewable area without significantly absorbing one or more wavelengths. The spectral reflectance of these particles may for example be greater than 70%, better at least 80%, or even 90% or 95% in the range of 400nm-700 nm.

The thickness of these particles is generally less than or equal to 1 μm, in particular less than or equal to 0.7 μm, in particular less than or equal to 0.5. mu.m.

The particles having a metallic hue useful in the present invention are chosen in particular from:

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

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

a mixture of said particles.

Among the metals that may be present in the 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 and Cr and mixtures or alloys thereof (e.g. bronze and brass) are preferred metals.

The term "metal derivative" is used to denote compounds derived from metals, in particular oxides, fluorides, chlorides and sulfides.

Among the metal derivatives that may be present in the particles, mention may be made in particular of: metal oxides, e.g. titanium oxides, especially TiO₂(ii) a Iron oxides, especially Fe₂O₃(ii) a Tin oxide; chromium oxide(ii) a Barium sulfate; and the following compounds: MgF₂、CrF₃、ZnS、ZnSe、SiO₂、Al₂O₃、MgO、Y₂O₃、SeO₃、SiO、HfO₂、ZrO₂、CeO₂、Nb₂O₅、Ta₂O₅、MoS₂And mixtures or alloys thereof.

Examples of such particles that may be mentioned include aluminum particles, such as under the name Starbrite1200 by SiberineSold aluminum pellets and known by the Eckart companyAluminum pellets are sold.

Mention may also be made of: metal powders of copper or alloy mixtures, such as the product sold under the number 2844 by the company radius Bronze; metallic pigments, such as aluminum or bronze, such as the product sold under the name Rotosafe 700 by the company Eckart; silica coated aluminum particles sold by the Eckart corporation under the name Visaire Bright Silver; and metal alloy particles such as silica coated bronze (an alloy of copper and zinc) powder sold by the Eckart company under the name vision air Bright Natural Gold.

As an illustration of the second type of particles, mention may be made in particular of:

glass particles coated with ｃA metal layer, in particular those described in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

As an illustration of these particles comprising a glass substrate, mention may be made of: a product sold under the name Microglass Metashine by Nippon Sheet Glass company coated in the form of a foil of silver, gold or titanium respectively. The particles with a silver-coated glass substrate in flake form are particles sold under the name Microglass Metashine REFSX 2025PS by Toyal corporation. Particles having a glass substrate coated with a nickel/chromium/molybdenum alloy are the particles sold by the same company under the names CrystalStar GF550 and CrystalStar GF 2525. Those particles coated with brown iron or titanium oxides, tin oxides or mixtures thereof are, for example, those sold under the name refleks by the Engelhard company or under the name Metashine MC 2080GP by the Nippon Sheet Glass company.

These metal-coated Glass particles may be coated with silica, such as those sold by Nippon Sheet Glass company under the name Metastone series PSS1 or GPS 1.

Particles comprising a spherical glass substrate optionally coated with a metal, in particular those sold under the name Prizmalilite Microsphere by Prizmalilite industries.

Metastine 1080R range pigments sold by Nippon Sheet Glass Inc. are also suitable for use in the present invention. These pigments, in particular those described in patent application JP 2001-11340, are those comprising from 65% to 72% of SiO₂Coated with rutile type titanium oxide (TiO)₂) Medium alkali glass flakes of the layer. These glass flakes had an average thickness of 1 micron and an average size of 80 microns, i.e. a ratio of average size/average thickness of 80. According to TiO₂The thickness of the layers, which have a blue, green, or yellow hue or shade of silver.

Particles comprising a silver-coated borosilicate substrate are also referred to as "white nacres".

Particles comprising a metal substrate in flake form, such as aluminum, copper or bronze, are sold under the trade name Starbrite by Silberline and Visuaire by Eckart.

Particles comprising a synthetic mica substrate coated with titanium dioxide, and particles of synthetic mica (fluorophlogopite) substrate coated with titanium dioxide, for example, having a size of between 80 μm and 100 μm, comprising 12% by weight of the total weight of the particle, sold under the name promience by the company Nihon Koken.

The particles having a metallic hue may also be selected from particles formed from a laminate of at least two layers having different refractive indices. These layers may be of polymeric or metallic nature and may include, inter alia, at least one polymeric layer.

Thus, the particles having a metallic effect may be particles produced from a multilayer polymer film.

The materials used to construct the various layers of the multilayer structure are obviously selected to provide the desired metallic effect on the particles so formed.

Such particles are described in particular in WO 99/36477, US 6299979 and US 6387498 and are identified in particular in the goniochromatic part hereinafter.

Advantageously, the particles having a metallic hue according to the present invention are particles having a spherical or aspherical glass substrate as well as particles having a metallic substrate.

According to a particular embodiment, the composition according to the invention comprises at least reflective particles, in particular selected nacres, particles having a metallic tone, and bismuth oxychloride and mixtures thereof.

As examples of particles of this second type, mention may be made in particular of:

particles comprising a synthetic mica substrate coated with titanium dioxide, or particles comprising a spherical Glass substrate optionally coated with brown iron oxide or titanium oxide, tin oxide or mixtures thereof, such as those sold under the name refleks by the Engelhard company, or those sold under the name Metashine MC 2080GP by the Nippon Sheet Glass company. Such particles are described in detail in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

-particles comprising a metal-coated mineral substrate having a metallic effect. It may be particles with a silver-coated borosilicate substrate, which is also referred to as "white nacre".

Particles comprising a spherical glass substrate coated with silver, in particular particles sold by TOYAL under the name microglass glass REFSX 2025 PS. Particles comprising a spherical glass substrate coated with a nickel/chromium/molybdenum alloy, in particular particles sold by the same company under the names CRYSTAL STAR GF550, CRYSTAL STAR GF 2525.

Particles with a metallic effect and having a metallic compound on the surface, known by the company NIPPON SHEET GLASS under the name NIPPONLE 2040PS、5MC5090PS orMC280GP (2523) optionally coated; by ENGELHARD corporation under the name SPHERICAL SILVERDC 100、SILVERJV 6 or GOLDA1570, optionally coated granules sold; manufactured by ENERGY STRATEGY ASSOCIATES INC under the name STARLIGHT REFLECTIONS(ii) sold optionally coated particles; is known under the name BRIGHT by MEADOWBROK INVENTIONSOptionally granulated sold as 1E 0.008X 0.008; by the company ECKART under the name(ALUMINUM POUDRE FINE LIVING), and the name COSMETIC METALLIC POWDER VISION NEREBRIGHT SILVERCOSMETIC METALLIC POWDER VISIONAIRE NATURAL(60314) Or COSMETIC metal POWDER VISIONAIRE560316 ° sold as optionally coated granules.

More preferably, the reflective particles are selected from the group consisting of bismuth oxychloride particles, titanium oxide coated mica particles, and mixtures thereof.

According to a particular embodiment, the composition of the invention comprises at least bismuth oxychloride (CI 77163).

Advantageously, the composition of the invention may also comprise at least nacres comprising a borosilicate substrate coated with silver, also known as "white nacres". Such particles are sold under the trade name Xirona Silver by MERCK.

The composition may include reflective particles pre-dispersed in an oil selected from the group consisting of mineral oil, vegetable oil, and ester oil.

According to a preferred embodiment, these reflective particles are present in the composition of the invention in the form of a predispersion in at least one oil chosen from:

-a mineral oil;

-vegetable oils, such as sweet almond oil, wheat germ oil, jojoba oil, almond oil, soybean oil, canola oil, castor oil;

esters, e.g. octyldodecanol, octyldodecanol pivalate, caprylic/capric triglyceridePentaerythritol tetraisostearate, isodecyl neopentanoate, diisopropyl sebacate, and C₁₂-C₁₅Alkyl benzoates, ethyl hexyl hexanoate, ethyl hexyl hydroxystearate;

-and mixtures thereof.

More preferably, the oil is selected from ethyl (2) hexyl hydroxystearate, or castor oil, preferably ethyl (2) hexyl hydroxystearate.

Thus, according to a particular and preferred embodiment, the composition according to the invention comprises, in a physiologically acceptable medium, a compound of formula (I)

(i) At least microcapsules of the invention, and

(ii) reflective particles at least in the form of pre-dispersed in at least one oil selected from ethyl (2) hexyl hydroxystearate and castor oil, preferably ethyl (2) hexyl hydroxystearate.

Advantageously, the reflective particles are chosen from bismuth oxychloride particles and mica particles coated with titanium oxide, said particles being pre-dispersed ethyl (2) hexyl hydroxystearate.

According to a particular embodiment, the composition of the invention comprises a predispersion comprising 68% to 72% by weight of bismuth oxychloride in 28% to 32% by weight of ethyl (2) hexylhydroxystearate, relative to the total weight of the predispersion, i.e. a weight ratio bismuth oxychloride/oil greater than or equal to 2, preferably in the range from 2 to 2.6.

Such a dispersion is available under the trade name Xirona Silver from MERCKProducts sold by Liquid Silver.

Additional moisturizing agent

For specific care applications, the composition according to the invention may comprise at least one additional humectant (also known as a humectant).

The humectant may be present in the composition at a level of from 0.1% to 15% by weight, especially from 0.5% to 10% by weight, or even from 1% to 6% by weight, relative to the total weight of the composition.

Polyhydric alcohols, preferably C₂-C₈Polyhydric alcohol of (2), more preferably C₃-C₆Are known as humectants or moisturizers, preferably, for example, glycerol, propylene glycol, 1, 3-butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol and diglycerol, and mixtures thereof, glycerol and derivatives thereof.

The composition according to the invention may also comprise additional humectants or humectants.

Such additional humectants or wetting agents that may be particularly mentioned include: sorbitol; glycol ethers (especially containing 3 to 16 carbon atoms), such as monopropylene glycol (C)₁-C₄) Alkyl ether, dipropylene glycol (C)₁-C₄) Alkyl ethers or tripropylene glycol (C)₁-C₄) Alkyl ethers, monoethylene glycol (C)₁-C₄) Alkyl ether, diethylene glycol (C)₁-C₄) Alkyl ethers or triethylene glycols (C)₁-C₄) An alkyl ether; urea and its derivatives, especially hydroxyethyl urea (hydro) sold by National Starch (2-hydroxyethyl urea); lactic acid; hyaluronic acid; fruit acids (AHA); salicylic acid (BHA); sodium pyridonate; xylitol; serine; sodium lactate; trehalase and its derivatives; chitosan and its derivatives; collagen protein; plankton; an extract of Imperata cylindrica (Imperata cylindra) sold under the name Moist 24 by Sederma corporation; acrylic acid homopolymers, such as Lipidure-β -dextran, in particular sodium carboxymethyl β -dextran from Mibelle-AG-Biochemistry, by Nestle under the nameMixtures of passion flower oil, almond oil, corn oil and rice bran oil which are sold, C-glycoside derivatives such as those described in patent application WO 02/051828, in particular C- β -D-xylopyranoside-2-hydroxypropane in the form of a solution containing 30% by weight of active material in a water/propylene glycol mixture (60%/40% by weight), such as that sold by Chimex under the trade name MexorylThe product of manufacture; muscat rose oil sold by Nestle; spheres of collagen and chondroitin sulphate of Marine origin (Atelocollagen) sold under the name Marine Filling Spheres by the company Engelhard Lyon; hyaluronic acid spheres, such as those sold by Engelhard Lyon; arginine; argan oil; and mixtures thereof.

It will be preferred to use a compound selected from glycerol, urea and derivatives thereof (especially sold by National Starch)) C-glycoside derivatives (such as those described in patent application WO 02/051828), in particular C- β -D-xylopyranoside-2-hydroxypropane in the form of a solution containing 30% by weight of active material in a water/propylene glycol mixture (60%/40% by weight), such as that sold under the trade name Mexoryl by ChimexProducts sold), argan oil, and mixtures thereof.

More preferably, glycerol will be used.

Sunscreen/sunblock agent

Sunscreens are important skin care products for the prevention of photoaging and skin cancer. There are two groups of sunscreens: a UVA sunscreen which blocks UV radiation in the wavelength range of about 320nm to 400 nm; and a UVB sunscreen that blocks radiation in the range of 290nm to 320 nm.

The composition according to the invention comprises hydrophilic and/or lipophilic, organic and/or inorganic UV sunscreen components effective in the UV-a region and/or the UV-B region.

In particular, the UV sunscreen component according to the present invention may have a solubility parameter in the range of 8.0 to 9.5. The UV light-blocking component has a good plasticizer function.

Advantageously, the UV sunscreen according to the invention may have a molecular weight of 150g/mol to 500g/mol and comprise hydrophobic sites and a benzene nucleus or electron resonance group attached to a polar site.

The hydrophilic and/or lipophilic organic UV sunscreen component is selected in particular from dibenzoylmethane derivatives, cinnamic acid derivatives, salicylic acid derivatives, benzophenone derivatives, β -diphenylacrylate derivatives, p-aminobenzoic acid (PABA) derivatives, benzylidenecamphor derivatives, and mixtures thereof.

As examples of organic UV sunscreen components, mention may be made of sunscreen components hereinafter denoted by their INCI names:

-para-aminobenzoic acid derivatives:

-PABA，

-an ethyl group PABA,

-an ethyl dihydroxypropyl PABA,

-ethylhexyldimethylPABA, in particular sold by ISP under the trademark "Escalol 507",

-a glyceryl PABA,

-dibenzoylmethane derivatives:

butyl methoxydibenzoylmethane, in particular sold by Hoffmann-LaRoche under the trademark "Parsol 1789",

-isopropyl dibenzoylmethane,

-salicylic acid derivatives:

trimethylcyclohexyl salicylate, in particular sold by Rona/EM Industries under the trademark "Eusolex HMS",

ethylhexyl salicylate, sold under the trademark "Neo Heliopan OS" by Haarmann & Reimer,

dipropylene glycol salicylate, sold by Scher under the trademark "Dipsal",

TEA salicylate, sold under the trademark "Neo Heliopan TS" by Haarmann & Reimer,

-cinnamic acid derivatives:

-ethylhexyl methoxycinnamate, in particular sold by Hoffmann-LaRoche under the trademark "Parsol MCX",

-an isopropyl methoxycinnamate ester,

isopentylmethoxy cinnamate, sold under the trademark "Neo Heliopan E1000" by Haarmann & Reimer,

-a salt of cinoxate or a salt thereof,

-DEA-methoxycinnamate,

-a compound of formula (I) or (II) or (III),

-glyceryl ethylhexanoate dimethoxycinnamate,

-beta, beta-diphenylacrylate derivatives:

octocrylene, in particular sold by BASF under the trademark "Uvinul N539",

etorine (Etocrylene), in particular BASF, sold under the trademark "Uvinul N35",

-benzophenone derivatives:

benzophenone-1, sold by BASF under the trademark "Uvinul 400",

benzophenone-2, sold by BASF under the trademark "Uvinul 50",

benzophenone-3 or oxybenzone, sold by BASF under the trademark "Uvinul M40",

benzophenone-4, sold by BASF under the trademark "Uvinul MS 40",

-a benzophenone-5 and a benzophenone-c,

benzophenone-6, sold under the trademark "Helisorb 11" by Norquay,

and mixtures thereof;

-benzylidenecamphor derivatives:

-p-xylylene dicamphor sulfonic acid,

-4-methylbenzylidenecamphor.

-and mixtures thereof.

Preferred UV sunscreen components are selected from cinnamic acid derivatives, beta-diphenylacrylate derivatives, salicylic acid derivatives, and mixtures thereof.

Preferred UV sunscreen components are selected from, inter alia, ethylhexyl methoxycinnamate, octocrylene and ethylhexyl salicylate, and mixtures thereof.

Mention may in particular be made of: under the trade mark UVINUL MC by BASFEthyl hexyl methoxycinnamate sold; under the trademark NEO HELIOPAN by SYMRISEEthyl hexyl salicylate sold; and NEO HELIOPAN brand by SYMRISE IncSold octocrylene.

The composition may comprise from 0.1% to 30% by weight, such as from 0.5% to 20% by weight, such as from 1% to 15% by weight, such as at least 1% by weight of UV sunscreen component relative to the total weight of the composition according to the invention.

According to an exemplary embodiment, the composition may comprise microcapsules and at least one UV sunscreen component in a weight ratio of the microcapsules and the at least one UV sunscreen component [ mineral filler/UV sunscreen component ] in the range of 0.20 to 10, such as 1 to 9.5, preferably 3 to 9.

Advantageously, the composition of the invention comprises at least one UV filter and eventually an active agent.

Active agent

For use in particular for caring for the skin or making up the skin, the composition according to the invention may comprise at least one active agent chosen from:

according to an advantageous embodiment, the composition according to the invention may be combined with one or more supplementary cosmetic active agents.

These active agents may be selected from anti-wrinkle agents vitamins (especially B3, B8, B12 and B9), moisturizers, desquamating agents, anti-aging actives, depigmenting agents, antioxidants, and the like.

These active agents may be present in the composition at a content ranging from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight, more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.

An anti-wrinkle agent: mention may be made of: ascorbic acid and its derivatives, such as magnesium ascorbyl phosphate and ascorbyl glucoside; tocopherols and their derivatives, such as tocopheryl acetate; nicotinic acid and its precursors, such as nicotinamide; ubiquinone; glutathione and its precursors, such as L-oxothiazoline-4-carboxylic acid; c-glycoside compounds and derivatives thereof, such as plant extracts (in particular extracts of cumin and olive leaves) and plant proteins and hydrolysates thereof (such as protein hydrolysates of rice or soya), seaweed extracts (in particular extracts of kelp), as described in particular hereinafter; a bacterial extract; sapogenins, such as diosgenin and extracts of Dioscorea (Dioscorea) plants containing sapogenin, especially extracts of Dioscorea batatas; an alpha-hydroxy acid; beta-hydroxy acids such as salicylic acid and 5-n-octanoylsalicylic acid; oligopeptides and pseudodipeptides and acyl derivatives thereof, in particular {2- [ acetyl- (3-trifluoromethylphenyl) amino ] -3-methylbutyrylamino } acetic acid and the lipopeptides sold under the trade names Matrixyl 500 and Matrixyl 3000 by the company Sederma; lycopene; manganese and magnesium salts, especially manganese gluconate and magnesium gluconate; and mixtures thereof;

peeling agent: mention will be made of beta-hydroxy acids, in particular salicylic acid and its derivatives other than 5-n-octanoylsalicylic acid; urea; glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; 4- (2-hydroxyethyl) piperazine-1-propanesulfonic acid (HEPES); extract of camellia japonica; honey; n-acetylglucosamine; sodium methylglycinate diacetate, Alpha Hydroxy Acids (AHA), Beta Hydroxy Acids (BHA), and mixtures thereof;

depigmenting agents which may be mentioned are ceramides, vitamin C and its derivatives, in particular vitamin CG, CP and 3-O-ethyl vitamin C, α -arbutin and β -arbutin, ferulic acid, kojic acid, resorcinol and its derivatives, calcium D-pantetheine sulfonate, lipoic acid, ellagic acid, vitamin B3, phenylethyl resorcinol, such as Symwhite from SymriseKiwi (kiwi) juice sold by Gattefosse; extract of peony (Paeoniausufructcusa) root, as obtained by Ichimaru Pharcos under the name Botanpi LiquidThe product being sold; brown sugar (sugar cane, sugar cane of ficinarum) extract, such as Molasses, sold under the name Molasses Liquid by the company Taiyo Kagaku; mixtures of undecylenic acid and undecylenoylphenylalanine, e.g. Sepiwhite from Seppic

Antioxidant: mention may in particular be made of: tocopherols and esters thereof, especially tocopheryl acetate; EDTA; ascorbic acid and its derivatives, especially magnesium ascorbyl phosphate and ascorbyl glucoside; chelating agents, such as BHT, BHA, N' -bis (3,4, 5-trimethoxybenzyl) ethylenediamine and salts thereof; and mixtures thereof.

When the major active ascorbyl glucoside is present in the cosmetic composition according to the invention, it is present in an amount lower than 0.05% by weight, more preferably 0.01% by weight, relative to the total weight of the composition.

Galenic preparation

The composition according to the invention may be in the form of a make-up and/or care composition for keratin materials, in particular for the skin or the lips. In particular, the composition according to the invention may be a BB product or a foundation, intended in particular for application to the face or neck, a product intended to cover the dark circles under the eyes, a concealer product, a coloured cream, a coloured composition intended to care for the skin or make up the skin (in particular for the face or body), or an after-sun composition.

In a preferred embodiment, the composition according to the invention is a leave-on composition: the composition is not intended to be rinsed after application to the skin.

In another preferred embodiment, the composition according to the invention is not contained in a dispenser comprising a pump. This is advantageous as it avoids the risk of microcapsule rupture. In fact, when such a dispenser is used, the microcapsules may be broken up before application to the keratin materials.

It is understood that the composition according to the invention may be in any galenic form normally used for topical application, in particular in the form of a milk type of liquid or semi-liquid consistency, or in the form of a cream or gel type of soft, semi-solid or solid consistency, or alternatively an emulsion obtained by dispersing the fatty phase in the aqueous phase (O/W), an emulsion obtained by dispersing the aqueous phase in the fatty phase (W/O), a multiple emulsion (W/O/W, O/W/O), or a foam.

In particular, the composition is in a form selected from: gels, especially clear gels; a water-in-oil emulsion; an oil-in-water emulsion; and a foaming agent.

Surface active agent

The compositions according to the invention may comprise at least one surfactant (emulsifier) chosen in particular from amphoteric, anionic, cationic and nonionic surfactants, used alone or as a mixture.

The surfactant is generally present in the composition in a proportion ranging, for example, from 0.3% to 20% by weight, in particular from 0.5% to 15% by weight, in particular from 1% to 10% by weight, relative to the total weight of the composition.

Needless to say, the surfactants are chosen so as to effectively stabilize the emulsion, in particular the emulsion considered according to the invention, i.e. the emulsion of the O/W, W/O or O/W/O type. Such a selection is within the ability of the person skilled in the art.

For example, when the emulsifier potassium cetyl phosphate is present in the cosmetic composition according to the invention, the proportion of this emulsifier may range, for example, from 0.2% to 3% by weight, in particular from 0.5% to 1.5% by weight, more preferably from 0.8% to 1.2% by weight, even more preferably 1% by weight, relative to the total weight of the composition.

O/W emulsifier

Examples which may be mentioned for the O/W emulsion include nonionic surfactants, in particular: esters of polyols and fatty acids having a saturated or unsaturated chain containing, for example, from 8 to 24 carbon atoms, better still from 12 to 22 carbon atoms, and oxyalkylenated derivatives thereof, i.e. containing oxyethylenesDerivatives of alkylene units and/or oxypropylene units, e.g. C₈-C₂₄Glycerol esters of fatty acids and oxyalkylenated derivatives thereof; c₈-C₂₄Polyethylene glycol esters of fatty acids and their oxyalkylenated derivatives; c₈-C₂₄Sorbitol esters of fatty acids and their oxyalkylenated derivatives; c₈-C₂₄Sugar (sucrose, glucose or alkyl glucose) esters of fatty acids and their oxyalkylenated derivatives; a fatty alcohol ether; c₈-C₂₄Sugar ethers of fatty alcohols; and mixtures thereof.

Glycerides of fatty acids which may be mentioned in particular include glyceryl stearate (glyceryl monostearate, glyceryl distearate and/or glyceryl tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate, and mixtures thereof.

Polyethylene glycol esters of fatty acids which may be mentioned in particular include polyethylene glycol stearate (polyethylene glycol monostearate, polyethylene glycol distearate, and/or polyethylene glycol tristearate), more particularly polyethylene glycol 50OE monostearate (CTFA name: PEG-50 stearate) and polyethylene glycol 100OE monostearate (CTFA name: PEG-100 stearate), and mixtures thereof.

Mixtures of these surfactants may also be used, for example the product comprising glyceryl stearate and PEG-100 stearate sold under the name Arlacel 165 by the Uniqema company, and the product comprising glyceryl stearate (glyceryl mono-distearate) and potassium stearate sold under the name Tegin (CTFA name: glyceryl stearate SE) by the Goldschmidt company.

Fatty acid esters of glucose or alkylglucose which may be mentioned include in particular: glucose palmitate; alkyl glucose sesquistearate, such as methyl glucose sesquistearate; alkyl glucose palmitate such as methyl glucose palmitate or ethyl glucose palmitate; fatty esters of methyl glucoside, especially the diesters of methyl glucoside and oleic acid (CTFA name: methyl glucose dioleate); mixed esters of methyl glucoside and oleic acid/hydroxystearic acid mixtures (CTFA name: methyl glucose dioleate/hydroxystearate); esters of methylglucoside and isostearic acid (CTFA name: methylglucose isostearate); esters of methyl glucoside and lauric acid (CTFA name: methyl glucose laurate); a mixture of mono-and diesters of methylglucoside and isostearic acid (CTFA name: methylglucose sesquiisostearate); mixtures of mono-and diesters of methylglucoside and stearic acid (CTFA name: methylglucose sesquistearate), in particular the product sold under the name Glucate SS by the company Amerchol; and mixtures thereof.

Examples of fatty acids and oxyethylenated ethers of glucose or alkylglucose which may be mentioned include: oxyethylenated ethers of fatty acids and of methyl glucose, in particular polyethylene glycol ethers of methyl glucose and of diesters of stearic acid containing about 20mol of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate), such as the product sold under the name GlucamE-20 distearate by the company Amerchol; polyethylene glycol ethers of methyl glucose and mixtures of mono-and diesters comprising about 20 moles of ethylene oxide stearic acid (CTFA name: PEG-20 methyl glucose sesquistearate), especially the product sold under the name Glucamate SSE-20 by the company Amerchol, and the product sold under the name GrillosoSESE-20 by the company Goldschmidt; and mixtures thereof.

Examples of sucrose esters that may be mentioned include sucrose palmitate stearate, sucrose stearate and sucrose monolaurate.

Examples of fatty alcohol ethers which may be mentioned include: polyethylene glycol ethers of fatty alcohols containing from 8 to 30 carbon atoms, in particular from 10 to 22 carbon atoms, for example polyethylene glycol ethers of cetyl alcohol, stearyl alcohol or cetostearyl alcohol (mixtures of cetyl alcohol and stearyl alcohol). Examples which may be mentioned include ethers containing from 1 to 200 oxyethylene groups, preferably from 2 to 100 oxyethylene groups, such as the CTFA names ceteareth-20 and ceteareth-30, and mixtures of ethers.

Sugar ethers which may be mentioned in particular are alkyl polyglucosides, for example: decyl glucoside, such as the product sold under the name Mydol 10 by Kao Chemicals, the product sold under the name Plantaren 2000 by Henkel, and the product sold under the name Oramix NS 10 by SEPPIC; octanoyl/decanoyl glucosides such as the product sold under the name Oramix CG 110 by the company SEPPIC or the product sold under the name Lutensol GD 70 by the company BASF; lauryl glucoside, such as the products sold under the names Plantaren 1200N and Plantacare 1200 by Henkel corporation; coco glucoside, such as the product sold under the name Plantacare 818/UP by the Henkel company; cetearyl glucoside, optionally as a mixture with cetearyl alcohol, such as the product sold under the name Montanov 68 by SEPPIC, the product sold under the name Tego-Care CG90 by the company Goldschmidt and the product sold under the name EmulgadeKE3302 by the company Henkel; arachidyl glucoside, such as the product sold under the name Montanov 202 by the company SEPPIC as a mixture of arachidyl alcohol and behenyl alcohol and arachidyl alcohol glucoside; cocoylethylglucoside, for example the product sold under the name Montanov 82 by the company SEPPIC in the form of a mixture of cetyl alcohol and stearyl alcohol (35/65); and mixtures thereof.

W/O emulsifier

For the W/O emulsifier, a hydrocarbon-based surfactant or a silicone surfactant may be used.

According to one embodiment variant, hydrocarbon-based surfactants are preferred.

Examples of hydrocarbon-based surfactants that may be mentioned include polyester polyols such as PEG-30 dipolyhydroxystearate sold under the number Arlacel P135 by the Uniqema company and polyglyceryl-2 dipolyhydroxystearate sold under the number DehymulsPGPH by the Cognis company.

Examples of silicone surfactants that may be mentioned include: alkyl dimethicone copolyols such as lauryl dimethicone copolyol sold under the name Dow Corning 5200Formulation Aid by the company Dow Corning and cetyl dimethicone copolyol sold under the name Abil EM 90 by the company Goldschmidt or a mixture of polyglyceryl-4 isostearate/cetyl dimethicone copolyol/hexyl laurate sold under the name Abil WE 09 by the company Goldschmidt.

One or more co-emulsifiers may also be added thereto. The co-emulsifier may advantageously be selected from the group comprising polyol alkyl esters. Polyol alkyl esters which may be mentioned in particular include: glyceryl esters and/or sorbitan esters (such as polyglyceryl-3 diisostearate sold under the name Lameform TGI by the Cognis company); polyglyceryl-4 isostearate (such as the product sold under the name Isolan GI 34 by Goldschmidt corporation); sorbitan isostearate (such as the product sold under the name Arlacel 987 by ICI corporation); sorbitan isostearic acid glyceride (for example the product sold under the name Arlacel986 by ICI company); and mixtures thereof.

These compositions are prepared according to conventional methods.

Compositions of this type may be in the form of face and/or body care or make-up products and may be formulated, for example, as an in-can cream or in-can fluid.

The composition according to the invention may be a solid or more or less fluid and have the appearance of a cream, a gel (especially a transparent gel), an ointment, an emulsion, a lotion, a serum, a paste, a foam (with or without an associated propellant), a patch.

According to an embodiment, the composition is in the form of a gel (in particular a transparent gel) and comprises from 1% to 10% by weight of microcapsules relative to the weight of the composition.

The composition according to the invention may also be in the form of a gel (in particular a transparent gel, or a translucent gel), comprising one or more hydrophilic gelling agents and comprising from 1% to 10%, preferably from 1% to 5%, by weight of microcapsules, relative to the weight of the composition.

Preferably, the gel according to the invention has a viscosity, measured at 25 ℃ Rheomat, greater than or equal to 20UD (rotor No. 3 (Mobile)).

The viscosity is measured, generally at 25 ℃, using a viscometer RHEOMAT RM180 with a spindle number 3 (spindle selected for measurement with a UD unit deviation between 10 and 90) suitable for the viscosity of the product to be tested, the measurement being carried out after rotating the spindle within the composition for 10 minutes, with a shear rate of 200s^-1. Then, the UD value can be converted into poise (1 poise ═ 0.1Pa · s) using the corresponding table.

More preferably, the composition comprises a gelled aqueous phase.

Hydrophilic gelling agents (also referred to as hydrophilic gelling agents) that may be mentioned in particular include those listed above.

More preferably, the water-based gel is transparent.

The expression "transparent aqueous medium" refers to a matrix that allows light to pass through without causing refraction or reflection-induced deflection. The clarity of an aqueous medium can be measured using a turbidimeter. Portable Turbimidetimeter from HACH may be usedThe model number, for example, is used to measure the transparency range of the composition. The composition is considered transparent when the turbidity measurement is between 0 and 250NTU, and translucent when the turbidity measurement is between 250NTU and 1000 NTU.

When a transparent composition is placed in front of a 0.01m thick black line drawn on a white paper sheet with a diameter of 2mm, the transparent composition reveals the black line, in contrast to an opaque composition, that is, an opaque composition does not allow the black line to be revealed.

The color-changing composition in the form of a transparent gel according to the present invention preferably comprises water and a plurality of multi-layer microcapsules comprising releasable colorant(s).

In a first preferred embodiment, the transparent gel according to the invention comprises at least one hydrophilic or lipophilic gelling agent, and at least one water-soluble emollient and/or one or more lipids with a polar moiety.

In a first preferred embodiment, the transparent gel according to the invention comprises at least two types of different multilayer microcapsules comprising one or more releasable colorants.

The transparent gel according to the invention, which is preferably a BB product or a foundation, provides a very strong moisturizing sensation, a transparent, clean body appearance with a very pleasant feel during application and a completely natural makeup result after application. These features help provide skin care benefits feel (moisturized, and transparent) and make-up benefits (proper coverage).

Advantageously, the transparent gel comprises a swelling agent which allows better swelling of the microcapsules, making them more susceptible to rupture during application. Water, alcohols, glycols, polyols may be used as swelling agents. Examples of swelling agents are disclosed above.

Moisturizing may be further enhanced by the incorporation of one or more water-soluble emollients and/or one or more lipids with polar moieties. PEG-modified silanes and silicones (e.g., bis-PEG-18 methyl ether dimethylsilane) and/or PEG-modified esters (e.g., PEG-7 olive oleate, PEG-7 glyceryl cocoate, PEG-30 glyceryl cocoate, PEG-80 glyceryl cocoate) may be used to enhance moisturization.

Solubilizers may also be added to maintain the properties of the transparent gel upon storage, in particular to dissolve the softener in the aqueous phase, to make and maintain the gel transparent and stable over shelf life. Polysorbate 20, PEG-60 hydrogenated castor oil may be mentioned as examples of solubilizers.

The transparent gel according to the invention presents a very aesthetic, clean and tidy appearance, wherein the pigments are released during application without any perception of particles. After application, a perfect and uniform cosmetic effect is provided.

A preferred embodiment of the transparent gel according to the invention comprises:

at least one polymer selected from the group consisting of: acrylate/C10-30 alkyl acrylate crosspolymers, such as Permulen TR-1, Permulen TR-2, carbopol 1382, carbopol ETD 2020, preferably at a concentration of 0 to 10% by weight, more preferably 0 to 2% by weight; carbomers, such as Synthalen K, carbopol 980, preferably in a concentration of 0 to 10 wt%, more preferably 0 to 2 wt%; ammonium acryloyldimethyltaurate/steareth-8 methacrylate copolymers, such as Aristoflex SNC, preferably in concentrations of from 0 to 10% by weight, more preferably from 0 to 2% by weight; acrylate copolymers, such as carbopol Aqua SF-1, preferably at a concentration of 0 to 10 wt.%, more preferably 0 to 2 wt.%; ammonium acryloyldimethyltaurate/steareth-25 methacrylate crosspolymer, such as Aristoflex HMS, preferably at a concentration of 0 to 10 wt%, more preferably 0 to 2 wt%; acryloyldimethyl taurate ammonium, such as Arisfoflex AVC, preferably at a concentration of 0 to 10 wt%, more preferably 0 to 4 wt%; and xanthan gum, such as Keltrol CG, preferably at a concentration of 0 to 10 wt%, more preferably 0 to 4 wt%.

In addition, the transparent gel may comprise at least one of the following swelling agents: water, such as deionized water, preferably at a concentration of 0 to 90 wt.%, more preferably at a concentration of 30 to 70 wt.%; an alcohol, preferably at a concentration of 0 to 50 wt.%, more preferably at a concentration of 1 to 20 wt.%; glycols, such as propylene glycol, butylene glycol, preferably in a concentration of 0 to 50 wt.%, more preferably in a concentration of 1 to 15 wt.%; polyols, such as glycerol, tetrols, are preferably at concentrations of 0 to 50 wt.%, more preferably 1 to 10 wt.%.

Further, the transparent gel may comprise: at least one water-soluble softening agent selected from the group consisting of bis-PEG-18 methyl ether dimethylsilane, PEG-7 olive oleate, PEG-7 glyceryl cocoate, PEG-30 glyceryl cocoate, PEG-80 glyceryl cocoate, at a concentration of 0 to 20% by weight, more preferably at a concentration of 0 to 5% by weight; and at least one solubilizer, such as polysorbate 20, PEG-60 hydrogenated castor oil, at a concentration of 0 to 10 wt.%, more preferably at a concentration of 1 to 5 wt.%.

After gel fabrication, microcapsules (such as Magic60-WP0105 and Magic50-BW0105 from Korea Particle Technology) at concentrations of 0.1 to 30 wt.%, more preferably 1 to 10 wt.%, can be introduced in the final step with gentle agitation, without the need for a side-glazer.

For care compositions, the composition comprises from 0.1% to 5% by weight, preferably from 0.1% to 3% by weight of microcapsules relative to the total weight of the composition according to the invention.

The resulting transparent gel and microcapsules present a pure and clean appearance with excellent stability: -20/20 ℃ (5 cycles), room temperature (25 ℃,2 months), 37 ℃ (2 months) and 45 ℃ (2 months). During application, the microcapsules release the pigment without any perception of the particles. After application, a perfect and uniform cosmetic effect is provided.

The clear gel may also be lightly colored.

In this case, the transparent gel comprises at least one non-inclusive colorant, preferably in an amount of less than 1% by weight, based on the total weight of the total composition.

The composition may also be in the form of a gel-like cream or emulsified gel, comprising an oil and a surfactant.

According to another embodiment, the color-changing composition according to the invention is in the form of a foam comprising 1% to 30% by weight of microcapsules, relative to the weight of the composition.

The term "composition in the form of a foam" and the term "formulation of the foam type" have the same meaning and are understood to mean a composition comprising a gaseous phase (for example air) in the form of bubbles; another equivalent term is "volume expanded composition".

In one embodiment, the foam composition (non-aerosol foam) is obtained without the use of any propellant.

In another preferred embodiment, a propellant is used to obtain a foam composition (aerosol foam).

The composition according to the invention in the form of a foam can be obtained from the composition according to the invention as a "base composition" packaged in a product. In addition to the base composition, the product may also contain a propellant.

Accordingly, the present invention also relates to a product comprising:

a. a container defining at least one chamber;

b. a composition of the invention contained within the chamber;

c. a propellant for pressurizing the composition within the chamber; and

d. a dispensing head having an opening, the dispensing head being selectively in fluid communication with the chamber to deliver the pressurized composition in the form of a foam.

According to another embodiment, the invention relates to a cartridge containing one of the products defined above and an applicator.

The composition in the form of foam according to the present invention is stably formed into a form of mousse using the composition of the present invention and air or inert gas.

The air or inert gas may especially represent from 10% to 500%, preferably from 20% to 200%, for example from 30% to 100% by volume of the composition in the form of a foam.

The volume can be calculated by comparing the density of the base composition to the density of the composition in foam form.

The gas which allows obtaining the composition in the form of a foam, in addition to air, is in particular an inert gas, such as nitrogen, carbon dioxide, nitrogen oxides, noble gases or mixtures of said gases. When the composition comprises an oxidation-sensitive compound, it is preferred to use a non-oxygen containing gas, such as nitrogen or carbon dioxide.

The amount of gas introduced into the base composition helps to adjust the density of the composition in the form of a foam to a desired value, for example less than or equal to 0.12g/cm³。

The composition of the invention in the form of a foam may have, for example, a density of less than or equal to 0.12g/cm³A density of, for example, 0.02g/cm³To 0.11g/cm³Preferably 0.06g/cm³To 0.10g/cm³In the range of (a), the density is measured at a temperature of about 20 ℃ and at atmospheric pressure according to the following protocol.

Density measurement

For polishing introduced into 50mlCup (V)₁) 50ml of the composition in (1) was tested, the polishingThe cup defines a cylindrical fill space 30mm high with a bottom of 46mm diameter. The cup has a bottom wall of 10mm thickness and side walls of 12mm thickness.

The composition to be characterized and the cup were maintained at a temperature of about 20 ℃ prior to measurement. The tare weight of the cup was measured and the weight value (M) recorded₁). The composition in the form of a foam is then introduced into the cup to occupy the entire volume while avoiding the formation of air bubbles during filling of the cup. The device was allowed to stand for 10 seconds to allow the mousse to fully expand. Then, after weighing (M)₂) Previously, the top of the cup was skimmed. According to the rule ρ ═ M₂-M₁) And/50, evaluating the density.

Stability measurement

The composition in foam form according to the invention shows satisfactory stability, as measured by the volume of mousse remaining in the cup after 10 minutes (V) according to the protocol described above for density measurement₂) To calculate the stability.

Ratio V₂/V₁Corresponds to the ratio between the volume of the composition in the form of a foam after 10 minutes and the volume of the composition in the form of a foam after 10 seconds.

The expression "satisfactory stability" applies in particular to the ratioA composition in the form of a foam of more than 0.85, in particular more than 0.90, for example more than 0.95.

For a given weight of a composition in the form of a foam, the volume of the composition in the form of a foam is inversely proportional to the density of the composition in the form of a foam. Thus, the ratio between the density of the composition in foam form measured after 10 seconds and the density of the composition in foam form measured after 10 minutes may be greater than 0.85, in particular greater than 0.90, for example greater than 0.95.

In the composition according to the invention in the form of a foam, the air pause (air pause) may advantageously have a number average size in the range of 20 μm to 500 μm, preferably 100 μm to 300 μm.

The composition in the form of a foam may be obtained from the composition of the present invention in a dispenser. The dispenser may be a nebulizer, which nebulizer comprises a propellant in addition to the base composition.

The propellant may be less than 20% by weight of the base composition, in particular may be 1 to 10% by weight, for example 2 to 8% by weight, for example at least 5% by weight of the total weight of the base composition. Propellants which may be used may be selected from carbon dioxide, nitrogen, nitrous oxide, and volatile hydrocarbons (such as butane, isobutane, propane, ethane, pentane, isododecane, or isohexadecane) and mixtures thereof.

It may in particular be a propane/butane mixture (liquefied petroleum gas or LPG) with a weight ratio [ propane/butane ] in the range from 0.1 to 1, in particular 0.31.

The pressure of the propellant, e.g. the propane/butane mixture, in the nebulizer may be in the range 0.20MPa to 0.50MPa, e.g. 0.20MPa to 0.40MPa, especially 0.25MPa to 0.35 MPa.

The compositions in the form of foams employed in the present invention may be prepared by methods for mixing, agitating, or dispersing compressed gases (e.g., air, chlorofluorocarbon-based compounds, nitrogen, carbon dioxide, oxygen, or helium), methods for mixing and agitating in the presence of a foaming agent (e.g., a surfactant).

In particular, the composition in the form of a foam is prepared by: the components are mixed, usually under thermal conditions, with stirring, and then the volume is expanded under the action of a gas, which can be introduced during the phase of cooling the composition or after the preparation of the composition, for example using a device for expanding the volume of the Mondomix type, a stirrer of the Kenwood type, a scraped surface heat exchanger or a dynamic mixer (for example of the IMT type). The gas is preferably air or nitrogen.

The composition according to the invention may be packaged in a container defining at least one compartment containing said composition, said container being closed by a closure means. The container may be equipped with means for dispensing the product.

The container may be a can.

The container may be at least partially made of a thermoplastic. Mention may be made, as examples of thermoplastics, of polypropylene or polyethylene. Alternatively, the container is made of a non-thermoplastic material, in particular of glass or metal (or alloy).

The composition may be applied, for example, by the fingers or using an applicator.

The container is preferably used in combination with an applicator comprising at least one application member configured to apply the composition to the keratin materials.

According to another advantageous embodiment, the applicator comprises an application nozzle.

The composition comprises from 1% to 30% by weight, preferably from 3% to 10% by weight of microcapsules relative to the weight of the foam composition according to the invention. The resulting foam is fine (small bubbles) and contains colored microcapsules. The foam has a white appearance before application to keratin materials and a coloured appearance after application and homogenisation to keratin materials, in particular the skin.

When the foam composition comprises at least 3% by weight of microcapsules, relative to the weight of the composition, it preferably comprises a filler and/or a pigment, for example TiO₂ZnO, CeO, bismuth oxychloride, boron nitride, advantageously TiO₂。

The foam may also comprise calcium carbonate (CaCO)₃) To avoid coloration of the aqueous phase.

The foam according to the invention comprises from 1% to 10%, preferably from 3% to 8% by weight, relative to the weight of the composition, of fillers and/or pigments, advantageously TiO₂。

The foam according to the invention comprises from 0.5% to 5%, preferably from 1% to 3% by weight of calcium carbonate, relative to the weight of the composition.

To test the stability of the foams, they were vigorously shaken (1000 shakes), and the Δ E a, b between the colour of the body before and after shaking was less than 10, preferably less than 5.

According to another embodiment, the color-changing composition according to the present invention is an oil-in-water (O/W) emulsion.

The cosmetic composition, which is preferably a cosmetic BB product or foundation for the face, provides a very strong moisturizing sensation, a creamy texture with a very pleasant feel during application, and a completely natural makeup result after application. All these characteristics contribute to providing an excellent balance of skin care efficacy perception (creaminess and moisturization) and cosmetic efficacy (proper coverage and natural shine) after application. Advantageously, suitable opacifiers may be added.

The composition mainly comprises water, at least one non-volatile oil, at least one O/W emulsifier and microcapsules.

The non-volatile oil or oils used in this preferred embodiment are the oils previously described.

Advantageously, the O/W emulsion comprises an aqueous phase which allows better expansion of the microcapsules, making them more susceptible to rupture during application. Water, alcohols, glycols, polyols may be used as swelling agents.

Preferably, the O/W emulsion further comprises a co-emulsifier and/or a solubilizer.

Cetyl alcohol and stearyl alcohol may be referred to as co-emulsifiers.

Solubilizers are added to maintain the properties of the O/W emulsion upon storage, especially to dissolve the components of the aqueous phase, making and maintaining the composition stable over shelf life. Polysorbate 20, PEG-60 hydrogenated castor oil may be mentioned as examples of solubilizers.

An O/W emulsion is obtained with excellent stable capsules in storage, pigment release during application without any perception of particles. After application, a perfect and uniform cosmetic effect is provided.

Furthermore, the O/W emulsion may comprise at least one of the following agents: water, such as deionized water, preferably at a concentration of 0 to 90 wt.%, more preferably at a concentration of 30 to 70 wt.%; an alcohol, preferably at a concentration of 0 to 50 wt.%, more preferably at a concentration of 1 to 20 wt.%; glycols, such as propylene glycol, butylene glycol, preferably in a concentration of 0 to 50 wt.%, more preferably in a concentration of 1 to 15 wt.%; polyols, such as glycerol, tetrols, preferably in concentrations of 0 to 50 wt.%, more preferably in concentrations of 1 to 10 wt.%; coemulsifiers, such as cetyl alcohol and stearyl alcohol, at elevated temperatures above 60 ℃, preferably in concentrations of 0 to 20% by weight, more preferably 1% to 5% by weight; and a solubilizing agent, such as PEG-60 hydrogenated castor oil, at a concentration of 0 to 10 weight percent, more preferably 1 to 5 weight percent.

Additionally, the O/W emulsion may comprise at least two different types of microcapsules, for example three different types of microcapsules. Thus, the makeup effect can be modified to a natural and shiny appearance, further providing a makeup appearance with a white lining powder of uniform skin color.

After making the emulsion, microcapsules, such as Magic60-WP0105 and Magic50-BW0105 from Korea Particle Technology of KPT, preferably in concentrations of 0 to 30 wt.%, more preferably 0 to 10 wt.%, can be introduced in the final step by gentle stirring without the need for a side glazer.

An O/W emulsion can be obtained which has a pure and clean bulk appearance, with excellent stability: -20/20 ℃ (5 cycles), room temperature (25 ℃,2 months), 37 ℃ (2 months) and 45 ℃ (2 months). However, during application, the capsules will release the pigment without any perception of the particles. After application, a perfect and uniform makeup result is provided.

Additionally, organic solar-filtering materials can be added to the system and provide additional sun protection benefits.

Advantageously, the O/W emulsion contains at least TiO in an uncontained form₂. Unbound TiO₂Allowing for better coverage.

In particular, the composition in the form of an emulsion comprises at least TiO in an uncontained form₂And 1% to 30% by weight of microcapsules relative to the weight of the composition.

Throughout the description, including the claims, the terms "comprising" and "comprising" should be understood as being synonymous with "comprising at least one" unless otherwise indicated.

The terms "between … and …" and "in the range of … to …" should be understood to be inclusive unless otherwise indicated.

The present invention is illustrated in more detail by the examples according to the present invention described below. Unless otherwise indicated, the amounts indicated are expressed as mass percentages of the active substance.

Drawings

Fig. 1 is a schematic view showing a typical structure of the color-changing microcapsules of the present invention, wherein a represents a core, and B, C, D and E are different layers concentrically surrounding the core.

Fig. 2 to 10 represent schematic views showing the core-shell structures of the color-changing microcapsules prepared according to examples 6 to 14, respectively, which examples 6 to 14 are described later in this specification.

Detailed Description

Examples

I microcapsules

Different examples of the preparation of microcapsules according to the invention are described below to illustrate the invention.

Example 1: preparation of microcapsules with an internal brown coating and an external white coating

Mannitol (spray dried mannitol 100SD) was used as the core.

120.0g of ceramide (ceramide PC 104) and 120.0g of hydrogenated lecithin (lipid S100-3) were added to a mixed solution of 1600.0g of methylene chloride and 1600.0g of ethanol, and completely dissolved at 40 ℃. 1260.0g of iron oxide yellow, 252.0g of iron oxide red and 45.36g of iron oxide black were added to the resultant mixture, and sufficiently dispersed using a homogenizer to prepare an internal color coating solution.

347.70g of mannitol were introduced into a fluidized bed coating system (Glatt GPOG 1, bottom spray) as seed, and then subjected to coating of an internal color coating solution at a feed rate of 500ml/h to give granules having a mannitol core coated with an internal color layer.

Thereafter, 36.0g of ceramide and 36.0g of hydrogenated lecithin were added to a mixed solution of 720.0g of methylene chloride and 720.0g of ethanol, and dissolved at 40 ℃. 600.0g of titanium dioxide particles were added to the resultant mixture, and sufficiently dispersed using a homogenizer to prepare a titanium dioxide particle coating solution.

The coating with the resulting titanium dioxide particle coating solution is carried out by a fluidized bed process to obtain particles having an inner color layer coated with a titanium dioxide particle layer.

Then, 300.0g of shellac was dissolved in 3000g of ethanol to prepare an outer layer coating solution, which was coated on the above titanium dioxide particle layer to obtain a color-changing microcapsule having a titanium dioxide particle layer coated with an outer layer.

Example 2: preparation of microcapsules with an internal yellow coating and an external white coating

Microcapsules were prepared in the same manner as in example 1, except that 1557.36g of yellow iron oxide was used instead of a mixed colorant composed of yellow iron oxide, red iron oxide, and black iron oxide as an internal color in preparing an internal color coating solution.

Example 3: preparation of microcapsules with an inner red coating and an outer white coating

Microcapsules were prepared in the same manner as in example 1, except that 1557.36g of iron oxide red was used in preparing the internal color coating solution instead of the mixed colorant composed of iron oxide yellow, iron oxide red, and iron oxide black as the internal color.

Example 4: preparation of microcapsules with an internal black coating and an external white coating

Microcapsules were prepared in the same manner as in example 1, except that 1557.36g of black iron oxide was used in preparing the internal color coating solution instead of the mixed colorant composed of yellow iron oxide, red iron oxide, and black iron oxide as the internal color.

Example 5: preparation of microcapsules with an internal black coating and an external green coating

The same procedure as in example 4 was repeated until the step of forming a titanium dioxide particle layer.

Thereafter, 20.0g of ceramide and 20.0g of hydrogenated lecithin were added to a mixed solution of 400.0g of methylene chloride and 400.0g of ethanol, and dissolved at 40 ℃. 40.0g of chromium hydroxide green (CI77289) was added to the resulting reaction mixture, and sufficiently dispersed using a homogenizer to prepare a green coating solution.

Coating with the resulting green coating solution was effected by a fluidized bed process at a feed rate of 500ml/h of the coating solution to give particles having a layer of titanium dioxide particles coated with a green layer.

Then, 200.0g of polymethacrylate (Eudragit RSPO) was dissolved in 4000g of ethanol to prepare an outer coating solution. Coating with the obtained outer layer coating solution was effected by a fluidized bed process at a feed rate of the coating solution of 100ml/h to obtain color-changing microcapsules having a green layer coated with a polymer outer layer.

Example 6：

The color-changing microcapsules having a core and two layers as shown in fig. 2 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) mixed pigment (internal color): yellow: red: black 55.18:34.48:10.34

(2) The components are as follows: core seed-internal color layer-TiO₂Particle layer

The percentages represent weight percentages relative to the total microcapsule weight.

Example 7:

the color-changing microcapsules having a core and three layers as shown in fig. 3 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) mixed pigment (internal color): yellow: red: black-60.4: 23.8:11.4:4.4

(2) The components are as follows: core seed-internal color layer-TiO₂Particle layer-external color layer

Example 8:

the color-changing microcapsules having a core and two layers as shown in fig. 4 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) mixed pigment (internal color): yellow: red: 60.1:28.8:11.1

Example 9:

The color-changing microcapsules having a core and two layers as shown in fig. 5 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) the components are as follows: core seed-internal color layer-TiO₂Particle layer

Example 10：

The color-changing microcapsules having a core and three layers as shown in fig. 6 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) mixed pigment (internal color): yellow: red: black 55.18:34.48:10.34

Example 11：

The color-changing microcapsules having a core and three layers as shown in fig. 7 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) mixed pigment (internal color): white: yellow: red 92:6:2

Example 12：

The color-changing microcapsules having a core and three layers as shown in fig. 8 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) mixed pigment (internal color): white: yellow: red: 89:2:8:1, black ═ black

(3) Composition of the respective layers (details):

Example 13：

The color-changing microcapsules having a core and two layers as shown in fig. 9 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) the components are as follows: core seed-white TiO₂Particle layer-external color layer

(2) Composition of the respective layers (details):

Example 14：

The color-changing microcapsules having a core and three layers as shown in fig. 10 were prepared by a fluidized bed process by using the components and contents described in the following table:

(1) mixed pigment (internal color): white: yellow: red: black-84.3: 5.0:8.7:2

(2) The components are as follows: core seed-internal color layer-TiO₂Particle layer-outermost shell

II composition

In all examples, "alcohol" refers to "ethanol".

When not stated, the protocol used to prepare the compositions is conventional.

Example 1: transparent gel with brown microcapsules for cosmetic results

Preparation scheme

Premix B at 70 ℃ and mix until the solution is clear.

The main mixing

1. Phase a1 the polymer was fully expanded in water and then heated to 80-85 ℃;

2. adding A2, and mixing until completely dissolving;

3. adding phase B, dissolving completely, and cooling to RT;

4. adding to phase C at a temperature below 40 deg.C;

5. vacuum and slow mixing to reduce air bubbles in the body;

6. adding phases D1, D2;

7. vacuum and slow mixing until temperature to RT with few bubbles;

8. slowly add phase E (microcapsules) without blade mixing;

9. when the microcapsules were completely and uniformly dispersed, the mixing was stopped, the pH and viscosity were measured;

according to the protocol disclosed above, the viscosity of the gel, measured by rheostat RM180 at 25 ℃, is about 20UD (rotor No. 3).

Appearance and post-application evaluation of the compositions

The gel exhibited a transparent and fine appearance and also exhibited a covering makeup effect.

The inventors have obtained a gel of coloured microcapsules with a pure and clean appearance, which has excellent stability: -20/20 ℃ (5 cycles), room temperature (25 ℃,2 months), 37 ℃ (2 months) and 45 ℃ (2 months). The microcapsules release pigments during application to the skin, have a pleasant feel during application, and impart a natural cosmetic effect when the gel is used as a foundation, but at the same time have an excellent balance of skin care efficacy perception (moist, moisturizing and transparent) and cosmetic efficacy (proper coverage).

Practice ofExample 2: O/W emulsion with pink microcapsules

The preparation scheme is as follows:

1. mixed phase a1 to 75 deg.c

2. Adding A2 to A1

B3+ B4 roller mill

4. Blend B1+ B2+ B3+ B4 to 75 DEG C

5. Add phase B to phase A, homogenize (Rayneri 1000rpm, 10 minutes)

6. Cooled to 65 ℃ and phase C, phase D (1800rpm, 15 min) were added

7. Cooling to 45 deg.C, adding phase E

8. Changing Rayneri to Ekart, Using a mini-mixer, add phase F until the microcapsules are homogeneously dispersed

Appearance and post-application evaluation of the compositions

The resulting O/W emulsion exhibited a white-pink and fine appearance, but had a covering cosmetic effect when applied to the skin.

The O/W emulsion has a pure and clean appearance in the tank, which has excellent stability: -20/20 ℃ (5 cycles), room temperature (25 ℃,2 months), 37 ℃ (2 months) and 45 ℃ (2 months). The microcapsules release pigments during application to the skin, have a pleasant feel during application, and impart a natural cosmetic effect when the O/W emulsion is used as a foundation, but at the same time have an excellent balance of skin care efficacy perception (moist, moisturizing and transparent) and cosmetic efficacy (proper coverage).

Example 3: skin care gel

The gel was prepared according to the protocol disclosed in example 1.

After application on the skin, a natural cosmetic effect is obtained, with a good balance of skin care efficacy perception (moisturized, moisturized and transparent) and cosmetic efficacy (proper coverage).

Example 4: gel-like skin cream

The composition is obtained according to a classical process.

After application to the skin, a health effect is obtained, with a good balance of perception of skin care efficacy (moist, moisturized and transparent) and natural cosmetic effect.

Claims

1. Changing colour composition for caring for and/or making up keratin materials, comprising, in a physiologically acceptable medium, at least:

-a core comprising an organic material,

At least one kind of polymer,

at least one kind of coloring agent is selected from the group consisting of,

b) at least 10% by weight, relative to the weight of the composition, of a polyol,

c) at least one hydrophilic gelling agent which is capable of gelling,

wherein,

the core comprises at least one monosaccharide-polyol,

the core does not contain a colorant material;

the microcapsules comprise at least two layers of different colors.

2. The color-changing composition according to claim 1, wherein the at least 10% by weight percentage of the polyol in b) is a diol.

3. Changing color composition according to claim 1, wherein the microcapsules comprise an organic inner layer and an organic outer layer and the microcapsules are uncolored, i.e. the outer layer is white or transparent and when the outer layer is transparent the visible inner layer is white.

4. Changing color composition according to claim 1, wherein the microcapsules comprise at least:

-an inner core made of monosaccharide-polyol,

-at least two layers of different colors,

-at least one hydrophilic polymer.

5. Changing color composition according to claim 1 comprising from 0.1% to 20% by weight of microcapsules relative to the total weight of the composition.

6. The color-changing composition according to claim 1, wherein the polyol is selected from the group consisting of ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, butylene glycol, glycerol, polyglycerol, and polyethylene glycol, and mixtures thereof.

7. The color-changing composition of claim 1 comprising glycerol as the sole polyol.

8. The color-changing composition according to any one of claims 1 to 7 comprising 10 to 45% by weight percent of a polyol, based on the weight of the composition.

9. The color-changing composition according to any one of claims 1 to 7 comprising 10 to 45% by weight percent of a diol, based on the weight of the composition.

10. The color-changing composition of claim 1 further comprising at least one C2-C8 monoalcohol.

11. Changing color composition according to claim 1, wherein the hydrophilic gelling agent is selected from acrylates/C₁₀-C₃₀-alkyl acrylate copolymers, carbomers, xanthan gum, carboxyvinyl polymers synthesized in dichloromethane, and ammonium polyacryloyldimethyltaurate, and mixtures thereof.

12. The color-changing composition according to claim 1, wherein the microcapsules have a size of 50 to 800 μm in terms of microcapsule diameter, and comprise:

i) a core (A) comprising at least one organic core;

ii) a first layer (B) surrounding said core, said first layer (B) comprising:

-at least one colorant, and

-a binder selected from at least one polymer, at least one lipid-based material, and mixtures thereof;

iii) a second layer (C) surrounding said first layer (B), comprising:

-titanium dioxide particles, and

-a binder selected from at least one polymer, at least one lipid-based material, and mixtures thereof.

13. The color-changing composition according to claim 1 comprising water in an amount of at least 30% by weight percentage relative to the total weight of the composition.

14. Changing color composition according to claim 1, wherein at least one layer of the microcapsules is obtained by a fluidized bed process.

15. A non-therapeutic cosmetic process for caring for and/or making up keratin materials, comprising the application to the keratin materials of a composition according to claim 1.