CN105848626A - Transparent composition containing oil and microcapsules - Google Patents

Abstract

Transparent compositions in the form of nanoemulsions or microemulsions comprise microcapsules containing releasable colorants. The composition comprises at least one fatty phase, at least one nonionic surfactant, at least one microcapsule comprising a releasable colorant, and water. Such compositions provide high cosmetic properties such as emolliency and high slippery feel while giving the consumer a discoloration sensation upon shearing.

Description

Transparent composition comprising oil and microcapsules

technical field

The present invention relates to compositions comprising oil and microcapsules. More particularly, the present invention relates to compositions in the form of microemulsions or nanoemulsions comprising microcapsules comprising releasable colorants.

Background technique

Cosmetic compositions are generally used to impart an aesthetically pleasing color to the skin and to conceal skin imperfections such as redness and/or blemishes. Many formulations have been developed to date. Furthermore, there is growing interest in cosmetic products that provide color changes in response to external stimuli such as shear forces.

Typically, this is achieved by including microencapsulated colorants in the composition, wherein the composition provides a color change after application to the skin. More particularly, the color change is provided by colorant-containing microcapsules which upon rupture by application of mechanical force release the entrapped colorant into the composition, thereby changing its color. Mechanical action such as friction spreads the topical composition and facilitates its penetration into the skin. The immediate change in color of the composition provides a visually pleasing effect.

It is known in the art to incorporate pigments into cosmetic compositions, especially compositions for skin care or for making up the skin which contain large amounts of water. These compositions are expected to have a fresh sensory effect after application and impart a suitable color shade to the skin. Furthermore, their ability to contain a large number of active ingredients is highly appreciated.

This refreshing sensory and optical effect is desired, for example, in "quick break" formulations, in face serums, in eye serums and in foundations.

However, introducing large amounts of pigments can impair the cooling effect: pigments tend to absorb water, causing the composition to dry out more quickly, thus making it more difficult to apply the composition evenly on the skin.

Thus, the color of such compositions after application to the skin does not meet the desired requirements with regard to uniformity. Furthermore, it is not always possible to remedy the problem once the composition has formed a dry film on the skin.

In order to provide transparent cosmetics, the following techniques have been used so far. This is a known practice in the field of cosmetics or dermatology: the use of oil-in-water (O/W) emulsions. These emulsions, which consist of an oil phase (or lipophilic phase) dispersed in an aqueous phase, have an external aqueous phase. Thus, the products are more pleasant to use due to the refreshing sensation they provide. However, they lack relative stability when large amounts of oil are present. For some applications, it is advantageous to have a large amount of oils, as the oils provide the skin with comfort, nourish it, and when these oils have makeup-removing properties, also remove makeup from the skin.

Furthermore, it is advantageous to have miniemulsions, i.e. emulsions in which the oil phase is in the form of very small droplets, i.e. droplets less than 4 μm in size, as these have a pleasing cosmetic feel and are generally more stable than macroemulsions .

These emulsions can be prepared especially by phase transition type temperature techniques (PIT emulsions), in which the average size of the globules constituting the oil phase is within given limits, namely 0.1 μm to 4 μm (100 nm to 4000 nm). The principle of phase change temperature (or PIT) emulsification is well known to those skilled in the art in theory; it was described by K.Shinoda in 1968 (J.Chem.Soc.Jpn., 1968, 89,435). It has been shown that this emulsification technique makes it possible to obtain stable miniemulsions (K. Shinoda and H. Saito, J. Colloid Interface Sci., 1969, 30, 258). As early as 1972, Mitsui et al applied this technology to cosmetics ("Application of the phase-inversion-temperature method to the emulsification of cosmetics"); T . Mitsui, Y. Machida and F. Harusawa, USA. Cosmet. Perfum., 1972, 87, 33).

The principle of this technique is as follows: an O/W emulsion (introduction of the water phase into the oil phase) is prepared at a temperature exceeding the phase transition type temperature of the system (i.e. the temperature at which equilibrium is reached between the hydrophilic and lipophilic properties of the emulsifier used) ; at higher temperatures, i.e. above the phase transition temperature (>PIT), the emulsion is water-in-oil and when it cools, the emulsion inverts at the phase transition temperature to become oil-in-water type emulsions, previously undergoing a microemulsion state. This method makes it possible to easily obtain emulsions with diameters typically smaller than 4 μm. Commonly used emulsifying surfactants of the oil-in-water type have an HLB (Hydrophile-Lipophile Balance) in the range of 8 to 18. These emulsifiers, due to their amphiphilic structure, are located at the oil/water phase interface and thus stabilize the dispersed oil droplets.

However, it is difficult to produce fine O/W emulsions containing a large amount of oil phase because of the tendency of such emulsions to destabilize leading to coalescence and separation of the water and oil phases, releasing the oil. To improve the stability of these emulsions, the concentration of emulsifiers can be increased; however, high concentrations of emulsifiers can lead to a rough, sticky (clingy or sticky) feel and cause harmless problems to the skin, eyes and scalp .

In particular, miniemulsions such as O/W nanoemulsions or microemulsions are of particular interest in cosmetic products due to their transparent or slightly translucent appearance.

For example, JP-A-H09-110635 discloses a miniemulsion formed by using a combination of polyglycerol fatty acid ester (as a surfactant) and C ₁₀ -C ₂₂ 2-hydroxy fatty acid. Furthermore, JP-A-H11-71256 discloses a miniemulsion formed by using a combination of polyglyceryl fatty acid ester and betaine.

Contents of the invention

technical problem

The object of the present invention is to provide a composition with a high amount of oil, which has the transparent or slightly translucent, preferably transparent appearance of an emulsion, has a color changing effect and has a high cosmeticity acceptable to many consumers.

problem solution

The above objects of the present invention can be achieved by a composition in the form of a nanoemulsion or microemulsion comprising (a) at least one fatty phase, (b) at least one nonionic surfactant, (c) comprising a releasable at least one microcapsule of colorant, and (d) an aqueous phase.

Brief description of the drawings

The accompanying drawings intended to illustrate the invention in a non-limiting manner and representing examples of microcapsules to be incorporated into the cosmetic composition according to the invention will be described below.

[ Fig. 1] Fig. 1 is a schematic diagram illustrating a typical structure of a color-changing microcapsule of the first embodiment of the present invention, wherein A1 represents a core and B1, C1, D1, and E1 are different layers concentrically surrounding the core.

[ Fig. 2] Fig. 2 is a schematic diagram showing a first embodiment of a microcapsule of a core-shell structure of a color-changing microcapsule B as used in Example 1 described below.

[Fig. 3] Fig. 3 is a schematic view illustrating a typical structure of a microcapsule according to a second embodiment of the present invention, wherein A2 represents a colored core, and B2, C2, D2, and E2 are different layers concentrically surrounding the core A2, and among these surrounding layers At least one of the layers is required and preferably includes titanium dioxide particles, while the other layers are optional.

[ Fig. 4] Fig. 4 is a schematic diagram showing the core-shell structure of the color-changing microcapsule of the second embodiment of the microcapsule comprising 3 layers: colored core-inner color layer-TiO ₂ particle layer. The pigment core contained in the right particle of FIG. 4 corresponds to the left particle, and the pigment core includes a pigment/lecithin layer (inner color layer) and an inner pigment powder (inner coloring core).

[ Fig. 5] Fig. 5 is a schematic diagram showing the core-shell structure of the color-changing microcapsule of the second embodiment of the microcapsule comprising 2 layers: colored core-TiO ₂ particle layer.

Implementation Description

Since the composition of the present invention may be transparent or slightly translucent, the composition may be preferably used for lotions and the like. Since the dispersed phase is finely divided, the compositions of the present invention provide an emollient texture as well as slipperiness. Furthermore, since the composition of the present invention contains microcapsules comprising a releasable colorant, the composition provides a color change sensation upon simultaneous application of shear or pressure by the consumer.

The composition of the invention has a dispersed phase which has a smaller diameter due to the presence of at least one microcapsule comprising a releasable colorant. Thus, the composition may be in the form of a clear or slightly translucent nanoemulsion or microemulsion.

Hereinafter, the composition of the present invention will be explained in a more detailed manner.

1-1. Fat phase

The compositions of the invention comprise at least one fatty phase consisting essentially of oil. Here, "oil" means a fatty compound or substance in liquid form at room temperature (25° C.) and atmospheric pressure (760 mmHg). Those oils commonly used in cosmetics may be used alone or in combination thereof. These oils may be volatile or nonvolatile, preferably nonvolatile. The oil can be polar or non-polar.

The oil may be a synthetic oil or a naturally occurring oil, such as vegetable and animal oils.

Vegetable oils can include, for example, linseed oil, camellia oil, macadamia oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil , Almond Oil, Canola Oil, Sesame Oil, Soybean Oil, and Peanut Oil.

Animal oils may include, for example, squalene and squalane.

The oil may be hydrocarbon oil, silicone oil or fluoro oil. Hydrocarbon oils may include paraffin oils, ester oils, ether oils and triglyceride oils.

Ester oils are preferably saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic monobasic or polyacids and saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic monohydric alcohols Or a liquid ester of a polyol having a total number of carbon atoms greater than or equal to 10. Preferably, for esters of monohydric alcohols, at least one of the alcohol portion and the acid portion of the ester is branched. Among the monoesters of monobasic acids and monohydric alcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dioctyl carbonate, alkyl myristates such as isopropyl myristate Or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate. Esters of C ₄ -C ₂₂ dicarboxylic or tricarboxylic acids and C ₁ -C ₂₂ alcohols can also be used, as well as monocarboxylic, dicarboxylic or tricarboxylic acids and non-sugar C ₄ -C ₂₆ dihydroxy, trihydroxy , esters of tetrahydric or pentahydric alcohols. Particular mention may be made of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; Di-n-propyl adipate; Dioctyl adipate; Bis(2-ethylhexyl) adipate; Diisostearyl adipate; Bis(2-ethylhexyl) maleate; Triisopropyl Citrate; Triisocetyl Citrate; Triisostearyl Citrate; Triglyceryl Triglyceride; Glyceryl Tricaprylate; Ester; Neopentyl Glycol Diheptanoate; Diethylene Glycol Diisononanoate. As ester oils one can use sugar esters and diesters of C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids. The term "sugar" means an oxygen-bearing hydrocarbon-based compound containing several alcohol functions, with or without aldehyde or ketone functions, and comprising at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides. Examples of suitable sugars that may be mentioned include sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof substances, especially alkyl derivatives, such as methyl derivatives, such as methylglucose. Sugar esters of fatty acids may especially be selected from the previously described esters or mixtures of sugars and linear or branched, saturated or unsaturated C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids. If they are unsaturated, these compounds may have from one to three conjugated or nonconjugated carbon-carbon double bonds. The esters may also be selected from monoesters, diesters, triesters, tetraesters and polyesters and mixtures thereof. These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, capric acid esters and arachidonic acid esters, or mixtures thereof such as, inter alia, mixed esters of oleopalmitate, oleostearate and palmitostearate, and pentaerythritol tetrakis(ethyl caproic acid) ester. More particularly mono- and diesters are used, and especially sucrose, glucose or methyl glucose mono- or di-oleate, stearate, behenate, oleyl palmitate, linoleic acid Esters, Linolenates and Oleostearates. An example that may be mentioned is the company Amerchol under the name The product sold, which is methyl glucose dioleate. As examples of preferred ester oils, mention may be made, for example, of diisopropyl adipate, dioctyl adipate, 2-ethylhexyl caproate, ethyl laurate, cetyl caprylate, octyl caprylate Lauryl Ester, Isodecyl Neopentanoate, Myristyl Propionate, 2-Ethylhexyl 2-Ethylhexanoate, 2-Ethylhexyl Octanoate, 2-Ethylhexyl Caprylate/Caprate , methyl palmitate, ethyl palmitate, isopropyl palmitate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, Isopropyl myristate, Isodecyl Oleate, Glyceryl Tris(2-Ethylhexanoate), Pentaerythritol Tetrakis(2-Ethylhexanoate), 2-Ethylhexyl Succinate, Disebacate Ethyl esters, and mixtures thereof.

Triglycerides may include artificial triglycerides such as, trimyristyl, tripalmitin, trilinolenate, trilaurin, tricaprin, tricaprylycerin, glycerin Tris(caprate/caprylate) and triglycerides(caprate/caprylate/linolenate).

As the silicone oil, there may be mentioned, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and the like; cyclic organopolysiloxanes Such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.; and mixtures thereof. Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aromatic group. These silicone oils may also be organomodified. Organomodified silicones usable according to the invention are silicone oils as defined above and comprising in their structure one or more organofunctional groups linked via hydrocarbon-based groups. Organopolysiloxanes are defined in more detail in Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press. They can be volatile or nonvolatile. Volatile or non-volatile silicone oils can be used, such as volatile or non-volatile polydimethylsiloxane (PDMS) containing linear or cyclic silicone chains, which are liquid or pasty at ambient temperature. ), especially cyclopolydimethylsiloxane (cyclopolydimethylsiloxane, cyclomethicone) such as cyclohexasiloxane; polydimethylsiloxane containing alkyl, alkoxy or phenyl Oxane, the alkyl, alkoxy or phenyl group is on the side chain or terminal of the silicone chain, said group has 2 to 24 carbon atoms; phenylsiloxane such as phenyltrimethicone Phenyl trimethicone, phenyl dimethicone, phenyl trimethylsiloxy diphenyl siloxane, diphenyl dimethyl polysiloxane, diphenyl phenylmethyldiphenyltrisiloxane, 2-phenylethyltrimethylsiloxysilicate and polymethylphenylsiloxane.

Paraffinic oils may be selected from:

- Linear or branched, optionally cyclic, C ₆ -C ₁₆ lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane and isoparaffins such as isohexadecane, isododecane and isodecane; and

- straight-chain or branched-chain hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petroleum jelly, polydecene and hydrogenated polyisobutene such as and squalane.

Preferably, paraffinic oils may include linear or branched chain hydrocarbons such as mineral oil (e.g., liquid paraffin), paraffin, petrolatum or petrolatum, naphthalene, and the like; hydrogenated polyisobutene, isoeicosane, and decene/butane vinyl copolymers; and mixtures thereof. Preferably, the oil may be selected from hydrocarbon oils which are in liquid form at room temperature and atmospheric pressure.

Preferably, the oil has a low molecular weight, e.g. below 700 g/mol, selected from ester oils with short hydrocarbon chains (C ₁ -C ₁₂ ) (e.g. isopropyl myristate, isopropyl palmitate, isononanoic acid isononyl and ethylhexyl palmitate), hydrocarbon oils (such as isododecane, isohexadecane and squalane), oils of the branched and/or unsaturated fatty alcohol (C ₁₂ -C ₃₀ ) type , such as octyldodecanol, oleyl alcohol, and ether oils such as dioctyl ether.

The oil may be selected from vegetable oils, animal oils, mineral oils, synthetic oils, silicone oils and hydrocarbon oils, preferably hydrocarbon oils selected from ester oils, ether oils, paraffin oils and triglyceride oils.

The amount of oil in the composition of the invention is not limited and may range from 0.1% to 50% by weight, preferably from 0.5% to 40% by weight, and more preferably from 5% to 30% by weight, relative to the total weight of the composition. in the weight % range.

1-2. Nonionic surfactant

The compositions of the present invention comprise at least one nonionic surfactant. A single type of nonionic surfactant may be used, but two or more different types of nonionic surfactants may be used in combination.

The nonionic surfactant is not limited, but may have an HLB (Hydrophile-Lipophile Balance) value of 8.0 to 14.0, preferably 9.0 to 13.5, and more preferably 10.0 to 13.0. If two or more nonionic surfactants are used, the HLB value is determined by weight average of the HLB values of all nonionic surfactants.

Nonionic surfactants may be selected from:

(1) Surfactants that are fluid at temperatures lower than or equal to 45°C, selected from esters of at least one polyol and at least one fatty acid selected from polyols containing 1 to 60 ethylene oxide units Ethylene glycol, sorbitan, glycerol containing 2 to 30 ethylene oxide units, polyglycerol containing 2 to ₁₂ glycerol units, the fatty acid containing at least one saturated or unsaturated, linear or branched C8 _-C22 Alkyl chain,

(2) Mixed esters of fatty acids or fatty alcohols, carboxylic acids and glycerol,

(3) Fatty acid esters of sugar and fatty alcohol ethers of sugar,

(4) A surfactant that is solid at a temperature lower than or equal to 45°C, selected from fatty acid esters of glycerol, fatty acid esters of sorbitan, and oxyethylenated fatty acid esters of sorbitan, ethoxylated Fatty ethers and ethoxylated fatty acid esters,

(5) block copolymers of ethylene oxide (A) and propylene oxide (B), and

(6) Silicone surfactants.

(1) Surfactants that are fluid at temperatures below or equal to 45°C may be, inter alia:

- isostearate of polyethylene glycol with a molecular weight of 400, sold under the name PEG 400 by the company Unichema;

- diglyceryl isostearate, sold by the company Solvay;

- glyceryl laurate containing 2 glycerol units, sold by the company Solvay;

- sorbitan oleate, sold under the name Span 80 by the company ICI;

- sorbitan isostearate, sold under the name Nikkol SI 10R by the company Nikko; and

- Alpha-Butyl Glucoside Cocoate or Alpha-Butyl Glucoside Caprate, sold by the company Ulice.

(2) Mixed esters of fatty acids or fatty alcohols, carboxylic acids and glycerol (which can be used as the above-mentioned nonionic surfactants) can be selected especially from fatty acids or fatty alcohols having an alkyl chain of 8 to 22 carbon atoms and α - Mixed esters of hydroxy acids and/or succinic acid with glycerol. The alpha-hydroxy acid may be, for example, citric, lactic, glycolic or malic acid and mixtures thereof.

The alkyl chains of the fatty acids or alcohols from which the mixed esters useful in the nanoemulsions of the invention are derived can be straight or branched and saturated or unsaturated. They may be especially stearates, isostearates, linoleates, oleates, behenates, arachidonates, palmitates, myristates, laurates, capric acids Esters, isostearyl, stearyl, linoleyl, oleyl, behenyl, myristyl, lauryl or octyl chains, and mixtures thereof.

As an example of a mixed ester that can be used in the nanoemulsion according to the invention, mention may be made of the mixed ester of glycerol and a mixture of citric, lactic, linoleic and oleic acids sold under the name Imwitor 375 by the company Hüls (CTFA name: Glyceryl Citrate/Lactate/Linoleate/Oleate); succinic acid and mixed esters of isostearyl alcohol and glycerol sold under the name Imwitor 780K by the company Hüls (CTFA name: Isostearyl Diglycerol succinate); citric and stearic acid mixed esters with glycerol sold under the name Imwitor 370 by the company Hüls (CTFA name: Glyceryl Stearate Citrate); sold under the name Lactodan B30 or Rylo LA30 by the company Danisco Mixed esters of lactic and stearic acids with glycerin (CTFA name: Glyceryl Stearate Lactate).

(3) Fatty acid esters of sugars (which can be used as the above-mentioned nonionic surfactants) may preferably be solid at a temperature lower than or equal to 45° C. and may be particularly selected from C ₈ -C ₂₂ fatty acids and sucrose, Esters or mixtures of esters of maltose, glucose or fructose, and esters or mixtures of esters of C ₁₄ -C ₂₂ fatty acids and methylglucose.

_The C8- _C22 or _C14 - _C22 fatty acid forming the fatty unit of the ester comprises a saturated or unsaturated linear alkyl chain containing 8 to 22 or 14 to 22 carbon atoms, respectively. The fatty units of the esters may in particular be chosen from stearates, behenates, arachidonates, palmitates, myristates, laurates and caprates, and mixtures thereof. Stearic acid esters are preferably used.

As examples of esters or mixtures of esters of fatty acids and sucrose, maltose, glucose or fructose, mention may be made of sucrose monostearate, sucrose distearate and sucrose tristearate and mixtures thereof, as sold by the company Croda Products sold under the names Crodesta F50, F70, F110 and F160; and examples of esters or mixtures of esters of fatty acids and methylglucose that may be mentioned are methylglucose polyglycerol sold under the name Tego-care 450 by the company Goldschmidt- 3 distearate. Mention may also be made of glucose or maltose monoesters such as methyl o-hexadecanoyl-6-D-glucoside and o-hexadecanoyl-6-D-maltoside .

(3) Fatty alcohol ethers of sugars (which can be used as the above-mentioned nonionic surfactants) can be solid at a temperature lower than or equal to 45° C. and can be selected especially from C ₈ -C ₂₂ fatty alcohols and glucose, maltose, Ethers or mixtures of ethers of sucrose or fructose, and ethers or mixtures of ethers of C ₁₄ -C ₂₂ fatty alcohols and methylglucose. These are especially alkyl polyglucosides.

The C ₈ -C ₂₂ or C ₁₄ -C ₂₂ fatty alcohols forming the fatty units of the ethers usable in the nanoemulsions of the invention comprise saturated or unsaturated linear chains containing 8 to 22 or 14 to 22 carbon atoms, respectively. Alkyl chain. The fatty units of the ethers may in particular be selected from decyl, cetyl, behenyl, arachidyl, stearyl, palmityl, myristyl, lauryl, octyl and palmityl units, and mixtures thereof, Such as cetearyl.

As fatty alcohol ethers of sugars, mention may be made, for example, of alkyl polyglucosides, such as decyl glucoside and lauryl glucoside, cetearyl glucoside, sold for example under the names Plantaren 2000 and Plantaren 1200, respectively, by the company Henkel (optionally as a mixture with cetearyl alcohol), for example sold under the name Montanov 68 by the company SEPPIC, Tego-care CG90 by the company Goldschmidt and Emulgade KE3302 by the company Henkel, and arachidyl glucoside , sold for example under the name Montanov 202 by the company SEPPIC in the form of arachidyl alcohol and a mixture of behenyl alcohol and arachidyl glucoside.

The surfactants used are more particularly sucrose monostearate, sucrose distearate or sucrose tristearate and mixtures thereof, methylglucose polyglyceryl-3 distearate and alkylpolyglucose glycosides.

(4) Fatty acid esters of glycerin which are solid at a temperature lower than or equal to 45° C. (which can be used as the above-mentioned nonionic surfactant) can be selected from at least one acid (which contains 12 to 22 a saturated linear alkyl chain of 2 carbon atoms) and an ester of 1 to 12 glycerol units. One or more of these fatty acid esters of glycerol can be used in the present invention.

These esters may in particular be chosen from stearates, behenates, arachidates and palmitates and mixtures thereof. Stearates and palmitates are more preferably used.

As surfactants usable in the present invention, for example, decaglyceryl monostearate, distearate, tristearate, and pentastearate (CTFA name: polyglyceryl-10 stearate, polyglyceryl-10 distearate, polyglyceryl-10 tristearate, polyglyceryl-10 pentastearate), such as Nikkol Decaglyn 1-S, 2 - the products sold as S, 3-S and 5-S, and diglyceryl monostearate (CTFA name: polyglyceryl-2 stearate), such as the product sold under the name Nikkol DGMS by the company Nikko.

(4) Fatty acid esters of sorbitan that are solid at a temperature lower than or equal to 45° C. (which can be used as the above-mentioned nonionic surfactant) may be selected from C ₁₆ -C ₂₂ fatty acids of sorbitan Esters and oxyethylenated C ₁₆ -C ₂₂ fatty acid esters of sorbitan. They are formed from at least one fatty acid comprising at least one saturated linear alkyl chain each containing 16 to 22 carbon atoms and sorbitol or ethoxylated sorbitol. The oxyethylenated esters generally contain 1 to 100 ethylene glycol units and preferably 2 to 40 ethylene oxide (EO) units.

These esters may in particular be chosen from stearates, behenates, arachidates, palmitates and mixtures thereof. Stearates and palmitates are preferably used.

As an example of the aforementioned nonionic surfactants that can be used in the present invention, mention may be made of sorbitan monostearate (CTFA name: sorbitan stearate), sold under the name Span 60 by the company ICI , sorbitan monopalmitate (CTFA name: sorbitan palmitate), sold by ICI Corporation under the name Span 40, and sorbitan tristearate 20EO (CTFA name: polysorbate 65), Sold under the name Tween 65 by ICI Corporation.

(4) The ethoxylated fatty ether (which can be used as the above-mentioned nonionic surfactant) which is solid at a temperature lower than or equal to 45° C. is preferably composed of 1 to 100 ethylene oxide units and at least one Ethers formed from fatty alcohol chains of 16 to 22 carbon atoms. The fatty chain of the ether may in particular be selected from behenyl, arachidyl, stearyl and cetyl units and mixtures thereof, such as cetearyl. Examples of ethoxylated fatty ethers that may be mentioned are behenyl ethers comprising 5, 10, 20 and 30 ethylene oxide units (CTFA names: Beheneth-5, Beheneth-10, Beheneth-20, Beheneth-30), such as the products sold by the company Nikko under the names Nikkol BB5, BB10, BB20 and BB30, and stearyl ethers comprising 2 ethylene oxide units (CTFA name : Steareth-2), such as the product sold under the name Brij 72 by the company ICI.

(4) Ethoxylated fatty acid esters solid at temperatures lower than or equal to 45°C (which can be used as the above-mentioned nonionic surfactants) are composed of 1 to 100 ethylene oxide units and at least one type containing Esters formed from fatty acid chains of 16 to 22 carbon atoms. The fatty chain in the ester may in particular be selected from stearate, behenate, arachidate and palmitate units and mixtures thereof. Examples of ethoxylated fatty acid esters that may be mentioned are esters of stearic acid comprising 40 ethylene oxide units, such as the product sold under the name Myrj 52 (CTFA name: PEG-40 Stearate) by the company ICI , and esters of behenic acid comprising 8 ethylene oxide units (CTFA name: PEG-8 behenate), such as the product sold under the name Compritol HD5ATO by the company Gattefosse.

(5) Block copolymers of ethylene oxide (A) and propylene oxide (B), which can be used as surfactants in the nanoemulsions according to the invention, can be selected especially from block copolymers of formula (I) and Its mixture:

[Formula (I)]

HO(C ₂ H ₄ O) _x (C ₃ H ₆ O) _y (C ₂ H ₄ O) _z H (I)

wherein x, y and z are integers such that x+z is in the range of 2 to 100 and y is in the range of 14 to 60, and is more particularly selected from formula (IV) having an HLB value in the range of 8.0 to 14 block copolymers.

As the (6) silicone surfactant usable according to the present invention, for example, those disclosed in documents US-A-5364633 and US-A-5411744 can be mentioned.

The (6) silicone surfactant as the above-mentioned nonionic surfactant may preferably be a compound of formula (II):

[Formula (II)]

in:

R ₁ , R ₂ and R ₃ independently represent C ₁ -C ₆ alkyl groups or groups

-(CH ₂ ) _x -(OCH ₂ CH ₂ ) _y -(OCH ₂ CH ₂ CH ₂ ) _z -OR ₄ , at least one of the groups R ₁ , R ₂ or R ₃ is not alkyl; R ₄ is hydrogen , alkyl or acyl;

A is an integer in the range of 0 to 200;

B is an integer in the range 0 to 50; provided that A and B are not simultaneously equal to zero;

x is an integer in the range 1 to 6;

y is an integer in the range 1 to 30;

z is an integer ranging from 0 to 5.

In a preferred embodiment, in the compound of formula (II), alkyl is methyl, x is an integer ranging from 2 to 6, and y is an integer ranging from 4 to 30.

As silicone surfactants of formula (II), for example, compounds of formula (III) may be mentioned:

[Formula (III)]

wherein A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10, and y is an integer ranging from 10 to 20.

As examples of silicone surfactants of formula (II), mention may also be made of compounds of formula (IV):

[Formula (IV)]

H-(OCH ₂ CH ₂ ) _y -(CH ₂ ) ₃ -[(CH ₃ ) ₂ SiO] _A' -(CH ₂ ) ₃ -(OCH ₂ CH ₂ ) _y -OH (IV)

where A' and y are integers in the range of 10 to 20.

Compounds of the invention which may be used are those sold by the company Dow Corning under the names DC 5329, DC7439-146, DC 2-5695 and Q4-3667. Said compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II), wherein, respectively, A is 22, B is 2, and y is 12; A is 103, B is 10, and y is 12; A is 27, B is 3, and y is 12.

Compound Q4-3667 is a compound of formula (III), wherein A is 15 and y is 13.

Preferably, nonionic surfactants may be selected from:

- macrogol isostearate or oleate (8 to 10 mol of ethylene oxide),

- polyethylene glycol isocetyl ether, behenyl ether or isostearyl ether (8 to 10 mol of ethylene oxide),

- polyglycerol monolaurate or dilaurate containing 3 to 6 glycerol units,

- polyglycerol mono(iso)stearate containing 3 to 6 glycerol units,

- polyglycerol monooleate comprising 3 to 6 glycerol units, and

- Polyglycerol dioleate comprising 3 to 6 glycerol units.

Preferably, the nonionic surfactant is selected from polyglycerol fatty acid esters and mono- or polyoxyalkylenated fatty acid esters.

Preferably, polyglycerol fatty acid esters include esters of fatty acids and polyglycerols containing 70% or more of polyglycerol with a degree of polymerization of 4 or more, preferably 60% or more of polyglycerol with a degree of polymerization between 4 and 11 fatty acid of polyglycerol and ester of polyglycerol, and more preferably contains fatty acid of polyglycerol and ester of polyglycerol with a degree of polymerization of 5 equal to or greater than 30%.

Polyglycerol fatty acid esters may be selected from saturated or unsaturated acids, preferably saturated acids, containing 2 to 30 carbon atoms, preferably 6 to 30 carbon atoms and more preferably 8 to 30 carbon atoms, such as lauric acid, Monoesters, Diesters and Triesters of Oleic, Stearic, Isostearic, Capric, Caprylic and Myristic Acids.

The polyglycerol fatty acid ester may have a polyglycerol moiety derived from 2 to 10 glycerols, more preferably 3 or 4 to 6 glycerols and still more preferably 5 or 6 glycerols.

Preferably, the polyglycerol (PG) fatty acid ester may be selected from PG-4 laurate, PG-5 laurate, PG-5 dilaurate, PG-5 oleate, PG-5 dioleate , PG-6 Tricaprylate, PG-5 Myristate, PG-5 Trimyristate, PG-5 Stearate, PG-5 Isostearate, PG-5 Trioleate , PG-6 Caprylate and PG-6 Tricaprylate.

Preferably, the monooxyalkylenated or polyoxyalkylenated fatty acid ester has a (poly)oxyalkylene moiety derived from 1 to 20 alkylene oxides, preferably 3 to 15 alkylene oxides, and more preferably 8 to 10 alkylene oxides .

The oxyalkylene moieties can be derived from alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexylene glycol, and the like. The oxyalkylene moiety may comprise between 1 and 100 and preferably between 2 and 50 moles of ethylene oxide and/or propylene oxide. Advantageously, the nonionic surfactant does not contain any oxypropylene units.

The monooxyalkylenated or polyoxyalkylenated fatty acid esters may be selected from saturated or unsaturated acids containing 2 to 30 carbon atoms, preferably 6 to 30 carbon atoms and more preferably 8 to 30 carbon atoms, preferably Monoesters and diesters of saturated acids such as lauric, oleic, stearic, isostearic, capric, caprylic and myristic acids.

Examples of monooxyalkylenated or polyoxyalkylenated fatty acid esters that may be mentioned include saturated or unsaturated, linear or branched C ₂ -C ₃₀ , preferably C ₆ -C ₃₀ and more preferably C ₈ - Esters of _C22 acids and polyethylene glycols.

Examples of monooxyalkylenated or polyoxyalkylenated fatty acid esters that may be mentioned include esters of ethylene oxide with lauric, myristic, palmitic, stearic, isostearic, oleic or behenic acids , and mixtures thereof, especially those containing 8 to 20 oxyethylene groups, such as PEG-8 to PEG-20 Laurate (as CTFA name: PEG-8 Laurate to PEG-20 Laurate esters); PEG-8 to PEG-20 myristate (as CTFA names: PEG-8 myristate to PEG-20 myristate); PEG-8 to PEG-20 palmitate (as CTFA Name: PEG-8 Palmitate to PEG-20 Palmitate); PEG-8 to PEG-20 Stearate (as CTFA name: PEG-8 Stearate to PEG-20 Stearate); PEG-8 to PEG-20 Isostearate (as CTFA Name: PEG-8 Isostearate to PEG-20 Isostearate); PEG-8 to PEG-20 Oleate (as CTFA Name : PEG-8 Oleate to PEG-20 Oleate); PEG-8 to PEG-20 Behenate (as CTFA names: PEG-8 Behenate to PEG-20 Behenate); and its mixture.

Preferably, polyethylene glycol fatty acid esters may be selected from PEG-8 isostearate, PEG-8 stearate, PEG-10 isostearate, PEG-10 oleate, PEG-10 isostearate Cetyl ether, PEG-10 behenyl ether or PEG-10 isostearyl ether and mixtures thereof. A preferred nonionic surfactant is polyglycerol (PG) fatty acid ester.

Preferably, the nonionic surfactant may be selected from monooxyalkylenated or polyoxyalkylenated fatty acid esters, polyglycerol fatty acid ester surfactants, and fatty acid esters of sugars, especially sucrose.

The amount of nonionic surfactant in the composition of the invention is not limited and may range from 0.1% to 30% by weight, preferably from 0.5% to 15% by weight and more preferably 1% by weight, relative to the total weight of the composition to within 10% by weight.

1-3. Water phase

The compositions of the invention comprise at least one aqueous phase. The aqueous phase contains water as a main component. The amount of water is not limited and may be 5% to 99% by weight, preferably 10% to 95% by weight and more preferably 15% to 90% by weight relative to the total weight of the composition.

The aqueous phase may further comprise at least one organic solvent, preferably a water-miscible organic solvent. As the organic solvent, there may be mentioned, for example, C ₁ -C ₄ alkanols such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol and phenoxyethanol; analogous products thereof; and mixtures thereof. The amount of the water-miscible organic solvent may be less than 10% by weight, preferably 5% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the composition.

1-4. Microcapsules comprising a releasable coloring agent

The term "microcapsule" as used herein refers to a spherical microcapsule comprising at least one lamellar coating embedding at least one colorant and surrounding a core, which is chemically distinct from the coating. Microcapsules differ from microspheres, which consist of a spherical uniform matrix.

In an embodiment, said "at least one layered coating" 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 an outer layer. The one or more inner layers forming the multilayer coating of the multilayer microcapsules and the single outer layer of the microcapsules may be formed from the same or different wall-forming organic compounds.

The microcapsules comprise a core, also called "inner core", surrounded by a coating based on one or more layers. In a preferred embodiment, the microcapsules are "multilayered" microcapsules comprising at least one inner layer and one outer layer. The one or more inner layers of the multilayer coating forming the multilayer microcapsules and the single outer layer of the microcapsules may be formed from the same or different wall-forming organic compounds.

In a particular embodiment, the inner and outer layers are formed from the same wall-forming organic compound, and the core is then surrounded by a coating.

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

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

In a particular embodiment, the encapsulated colorant may range from 0.5 wt. Amounts ranging from wt. % to 12 wt. % are present in the compositions of the invention.

Microcapsules will usually be incorporated into the cosmetic formulation at the last stage of formulation and after the filtration stage (if any) to avoid microcapsule breakage. Preferably, the microcapsules are added at a temperature below 50°C and mixed uniformly. Mix them gently with a paddle instead of a homogenizer.

Microcapsules may have the ability to break up more easily on contact with an aqueous phase, preferably a hydrophilic agent (eg, water, polyols, diols, alcohols). Advantageously, the microcapsules are swellable on contact with such hydrophilic agents as defined below. Advantageously, the microcapsules are deformable when applied to keratin materials and thereby provide a soft feel to the user. Furthermore, their small size contributes to application without any discomfort or unpleasant sensations.

However, the microcapsules are soft enough to rupture to release their contents when very lightly rubbed or pressed against the skin, but are nevertheless durable enough to avoid damage to the coating during manufacture and storage of the corresponding composition.

Furthermore, microcapsules allow the use of conventional equipment to prepare the compositions of the present invention, since essentially no coloration of the device occurs during the manufacturing process.

Microcapsules are thus of particular interest because they can mask the original color of the encapsulated colorants during the manufacturing process and during prolonged storage, increase the stability of these colorants against degradation and prevent undesired release of the encapsulated colorants into the composition middle.

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

A preferred constitution of the microcapsules will be described in detail below.

1-4-1. First Embodiment of Microcapsules Containing Releasable Coloring Agent

In a first embodiment, typically the microcapsules have an average particle size of less than 800 μm, more preferably less than about 400 μm, advantageously 1 to 300 μm, especially 5 to 200 μm and more particularly 10 to 100 μm in diameter.

Microcapsules containing a releasable colorant are multilayered microcapsules. The microcapsules contain:

- core, preferably unpigmented core, comprises an organic material, preferably consists of an organic material, and

- At least one layered coating surrounding said core, said layered coating comprising at least one polymer, and at least one colorant. Advantageously, it contains at least one binder.

Preferably, the microcapsules comprise at least two layers, preferably at least one organically colored inner layer and one organic outer layer, said organic outer layer being of a different color than said organically colored inner layer.

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

Advantageously, this layered coating surrounding the core comprises at least one hydrophilic polymer selected from polysaccharides and their derivatives, preferably comprising one type of ose or several types of ose, preferably comprising at least Polysaccharides of several types of sugars of D-glucose units and their derivatives, especially starch and derivatives, cellulose or its derivatives, and more preferably starch and derivatives.

Preferably, the microcapsules comprise at least one lipid-based material, preferably of amphipathic nature, such as lecithin, and especially hydrogenated lecithin.

Advantageously, the core represents 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 30% to 70% by weight, and still more preferably 40% to 60% by weight, relative to the total weight of the microcapsules %.

Advantageously, the colorant represents 20% to 90% by weight, preferably 30% to 80% by weight and especially 50% to 75% by weight, relative to the microcapsules.

In particular, the microcapsules at least include:

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

- at least two layers of different colors from each other,

- at least one hydrophilic polymer, preferably selected from polysaccharides or derivatives thereof, and more preferably from starch or derivatives, and advantageously at least one lipid-based material, preferably an amphiphile, and More preferred are phospholipids, even more preferred phosphoacylglycerols, such as hydrogenated lecithin.

In one embodiment, each layer from the microcapsules comprises at least one specific colorant or a specific blend of colorants. In one embodiment, the outer layer from the microcapsules comprises at least one specified colorant or a specified blend of colorants. In particular, said colorants are pigments, preferably selected from metal oxides. In one embodiment, one layer from the microcapsules comprises iron oxide and titanium dioxide (TiO ₂ ) as colorants. In one embodiment, one layer from the microcapsules contains only _TiO2 as colorant.

The composition according to the invention may also comprise from 0.1% to 70% by weight, relative to the weight of the composition, of additional cosmetic ingredients selected from volatile and non-volatile silicone or hydrocarbon oils, surfactants, fillers, Additional gelling agents, thickeners, film formers, polymers, preservatives, silicone elastomers, self-tanning agents, additional non-entrapping colourants, cosmetic active agents, pH adjusters, fragrances, UV filters, and mixtures thereof.

1-4-1-1. Nuclear

In a first embodiment of the invention, the core is made of at least an organic material. The size of the core is preferably in the range of 500 nm to 150 μm in diameter. Preferably, the core is in solid and/or crystalline form at room temperature and atmospheric pressure. In certain embodiments, the organic material may have high water solubility.

Preferably, the core is water soluble or water dispersible.

In a particular embodiment, the core is unpigmented, ie it does not contain colorant material.

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

In 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, and more preferably only of mannitol. In an alternative embodiment, the core comprises at least mannitol and at least one additional ingredient, preferably a polymer selected from hydrophilic polymers. In particular, such a core may comprise mannitol and a hydrophilic polymer selected among cellulosic polymers, starch polymers and mixtures thereof, preferably mixtures thereof. In a preferred embodiment, the cellulosic polymer is carboxymethyl cellulose and the starch polymer is unmodified native starch, such as corn starch.

The core may consist of a seed (or crystal) of one of the above materials.

Preferably in an amount of 1% to 50% by weight, preferably 4% to 40% by weight, especially 5% to 30% by weight, and more particularly 10% to 20% by weight, relative to the total weight of the microcapsules including nuclei.

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

Manna is preferably included in an amount of 1% to 50% by weight, preferably 4% to 40% by weight, especially 5% to 30% by weight, and especially 10% to 20% by weight, relative to the total weight of the microcapsules sugar alcohol.

1-4-1-2. External layer (external layer)

As previously disclosed, the core is advantageously surrounded by an outer layer, which preferably comprises at least one inner layer and one outer layer). In a first embodiment, the layers preferably extend concentrically with respect to the core. The layer is preferably organic, ie contains at least one organic compound as wall-forming material. Preferably, the inner and/or outer layer comprises at least one polymer, and especially a hydrophilic polymer.

(a) polymer

In a first embodiment, the microcapsules, and especially the outer layer, comprise a hydrophilic polymer selected from polysaccharides and derivatives, acrylic or methacrylic acid homopolymers or copolymers or salts and esters thereof, and mixtures thereof .

In a preferred embodiment, the microcapsules, and especially the outer layer, comprise a hydrophilic polymer selected from polysaccharides and derivatives, and especially starch polymers.

The polymer is advantageously selected from (poly)(alkyl)(meth)acrylic acids and their derivatives, especially (poly)(alkyl)(meth)acrylates and their derivatives, preferably from Alkyl acrylic acid/alkyl methacrylic acid copolymers and their derivatives, and most preferably ethyl acrylate, methyl methacrylate and low content of methacrylates with quaternary ammonium groups from Evonik Degussa under the trade name EUDRAGIT RSPO copolymer.

Polysaccharides and derivatives are preferably selected from chitosan polymers, chitin polymers, cellulose polymers, starch polymers, galactomannans, alginates, carrageenans, mucopolysaccharides, and their derivatives , and mixtures thereof.

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

In a particularly preferred embodiment, the polysaccharides and their derivatives are preferably selected from those comprising one type of sugar or several types of sugars, preferably several types of sugars, especially at least as D-glucose units of sugars , preferably starch polymers, cellulose polymers and derivatives, and mixtures thereof.

In a preferred embodiment, the microcapsules comprise at least one hydrophilic polymer selected from starch and its derivatives, especially corn starch; cellulose and its derivatives; methacrylic acid and/or Homopolymers and/or copolymers of methacrylates or copolymers of (alk)acrylic acid and/or (alk)methacrylic acid and their derivatives, preferably their salts and their esters; and especially , capsules containing polymethylmethacrylate.

In a preferred embodiment, the microcapsules comprise at least one hydrophilic polymer selected from starch and its derivatives, especially corn starch.

The starches usable according to the invention are generally produced from plant raw materials such as rice, soybeans, potatoes or corn. The starch can be unmodified or (in analogy with cellulose) modified starch. In preferred embodiments, the starch is unmodified.

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

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

In a preferred embodiment, the capsule comprises at least starch derivatives (especially corn starch), polymethylmethacrylate, copolymers of (alk)acrylic acid and/or (alk)methacrylic acid and their derivatives ( Preference is given to their salts and their esters), and/or cellulose derivatives.

Preferably, the microcapsules comprise non-crosslinked polymers. The polymers can be in one layer or in several layers. In another embodiment, the polymer can be in the core. Microcapsules may contain polymers in the core and/or layers. In particular embodiments, the polymer is in the core as well as the layers. In an embodiment, the core comprises at least starch and/or cellulose derivatives as polymers. When starch is contained within a core, it represents the main constituent of such a core, ie the weight of starch is greater than the respective amounts of the other compounds of the core. The polymer may represent 0.5% to 20% by weight of the microcapsules, especially 1% to 10% by weight and preferably 2% to 8% by weight of the microcapsules.

The different layers forming the coating can be based on the same or different polymers. Advantageously, they will be formed from the same polymer. Rather, the layers will advantageously be differently colored. The different colors can be obtained by using different colorants and, when the colorants used for the two layers will be the same, by using different concentrations of at least one colorant.

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

(b) Colorant

In a first embodiment, the microcapsules and in particular the outer layer comprise a colorant.

The term "colorant" includes any organic or inorganic pigment or colorant approved for use in cosmetics by the CTFA and FDA for cosmetic formulations. Thus, the term "colorant" refers to: organic pigments, such as synthetic or natural dyes selected from any of the well-known FD&C or D&C dyes; inorganic pigments, such as metal oxides, or color lakes such as those based on carmine, barium, Lakes of strontium, calcium or aluminum, and any combination (blend) thereof. Such colorants are described in detail hereinafter. In particular embodiments, colorants can be water soluble or water dispersible. In another embodiment, colorants useful according to the 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. Advantageously, the colorant 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 The composite oxide is more preferably an iron oxide selected from red iron oxide, yellow iron oxide, or black iron oxide, or a mixture thereof.

The layer may also comprise a lake corresponding to the organic colorant fixed to the substrate. Such lakes are advantageously selected from the following materials, and mixtures thereof:

- carmine;

-Organic pigments of azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane, fluorane colorants; among the organic pigments, mention may be made of those known under the following trademark numbers: 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&CRed No.40, FD&C Yellow No.5 and FD&C Yellow No.6;

- Acidic colorants such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane, and water-insoluble sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium, and fluoran colorants Salts, these colorants may contain at least one carboxylic or sulfonic acid group.

Organic lakes can also be protected by organic vehicles such as rosin or aluminum benzoate.

Among the organic lakes we may mention in particular those known under the 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 Aluminum Lake, D&C Red No.6 Barium Lake, D&C Red No.6 Barium/Strontium Lake, D&C Red No.6 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 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 Lake, D&C Red No.9 Barium/Strontium Lake, D&C Red No.9 Zirconium Lake, D&C Red No. .10 sodium lake, D&CRed No.19 aluminum lake, 20D&C Red No.19 barium lake, D&C Red No.19 zirconium lake, D&C RedNo.21 aluminum lake, D&C Red No.21 zirconium lake, D&C Red No.22 Aluminum Lake, D&C Red No.27 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.28 Aluminum Lake, D&C Red No.28 Sodium Lake, D&C Red No.30 Lake, 25D&C Red No.31 Calcium Lake, D&C Red No.33 Aluminum Lake , D&C Red No.34 Calcium Lake, D&C Red No.36 Lake, D&C Red No.40 Aluminum Lake, D&C BlueNo.1 Aluminum Lake, D&C Green No.3 Aluminum Lake, D&C Orange No.4 Aluminum Lake Lake, D&C Orange No.5 Aluminum Lake, D&C Orange No.5 Zirconium Lake, D&C Orange No.10 Aluminum Lake, D&C Orange No.17 Barium Lake, D&C Yellow No.5 Aluminum Lake, D&C Yellow No. 5 Zirconium Lake, D&C YellowNo.6 Aluminum Lake, D&C Yellow No.7 Zirconium Lake, D&C Yellow No.10 Aluminum Lake, FD&C BlueNo.1 Aluminum Lake, FD&C Red No.4 Aluminum Lake, FD&C Red No.40 Aluminum Lake, FD&C Yellow No.5 Aluminum Lake and FD&C Yellow No.6 Aluminum Lake.

Chemical materials corresponding to each of these previously mentioned organic colorants are described in <The Cosmetic, Toiletry, and Fragrance Association> published by <The Cosmetic, Toiletry, and Fragrance Association> called <International Cosmetic Raw Materials <International Cosmetic Ingredient Dictionary and Handbook> (<International Cosmetic Ingredient Dictionary and Handbook>) (1997 Edition), pages 371 to 386 and pages 524 to 528, the contents of which are hereby incorporated by reference into this specification.

In a preferred embodiment, the color lake is selected from the group consisting of: cochineal; and water-insoluble colorants of acidic colorants such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane, and fluorane colorants. sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium salts (taking into account that these colorants may include at least one carboxylic or sulfonic acid group); and mixtures thereof.

In a preferred embodiment, the lake is selected from the group consisting of cochineal and water insoluble sodium, calcium, aluminum salts, and mixtures thereof.

As a lake combined with carmine we may mention the article numbers:

CARMIN COVALAC W 3508, CLOISONNE RED 424C, and CHROMA-LITEMAGENTA CL4505.

The water-insoluble aluminum salt is preferably selected from FDC Yellow No.5 aluminum lake, FDC Blue No.1 aluminum lake, FDC Red No.40 aluminum lake, FDC Red No.30 aluminum lake, FDC Green No.5 aluminum lake starches, and their mixtures. As compounds incorporating such inorganic lakes, mention may especially be made of the article numbers: INTENZAFIREFLY C91-1211, INTENZA AZURE ALLURE C91-1251, INTENZA THINKPINK C91-1236.

The water insoluble calcium salt is preferably selected from Red No. 7 calcium lakes. As compounds incorporating such inorganic lakes, mention may especially be made of the product numbers: INTENZA MAGENTITUDE C91-1234, INTENZAHAUTE PINK C91-1232, INTENZA RAZZLED ROSE C91-1231, INTENZAAMETHYST FORCE C91-7231, INTENZA PLUSH PLUM C91-7441, INTENZAELECTRIC CORAL 30C91-1233, FLORASOMES-JOJOBA-SMS-10% CELLINIRED-NATURAL and mixtures thereof.

The water insoluble sodium salt is preferably selected from Red No. 6 sodium lakes and Red No. 28 sodium lakes and mixtures thereof. As compounds incorporating such inorganic lakes, mention may especially be made of the product numbers: INTENZA MANGOTANGO C91-1221 and INTENZA NITRO PINK C91-1235.

In an embodiment, the colorant present in the microcapsules is selected from inorganic pigments, organic pigments and mixtures thereof, preferably at least one inorganic pigment, more preferably at least a mixture of inorganic pigments, even more preferably selected from metal oxides, and Especially selected from iron oxides, titanium dioxide particles and mixtures thereof, preferably mixtures thereof.

The compositions of the present invention may comprise a mixture of two or more colorants encapsulated individually in microcapsules and/or a blend of one or more colorants encapsulated in multilayer microcapsules Inside. In this particular embodiment, each layer of the microcapsules may comprise at least one specified colorant or a specified blend of colorants. In this particular embodiment, the composition of the invention comprises two or more microcapsules of different colours.

Those skilled in the art know how to select colorants and combinations of colorants to produce the desired color effect or color change. As stated previously, the microcapsules preferably comprise in their coating at least titanium dioxide and/or iron oxide, preferably at least titanium dioxide. In a preferred embodiment, the microcapsules comprise at least titanium dioxide and iron oxide in their coating. In a particular embodiment, the outer layer of the microcapsules comprises titanium dioxide, more preferably as the sole colorant.

In certain embodiments, the outer layer of the microcapsules comprises organic pigments or iron oxides.

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

In a particular embodiment, the microcapsules comprise a metal oxide selected from iron oxides and titanium oxides in an amount ranging from 20% to 90% by weight, preferably from 30% to 85% by weight, relative to the total weight of the microcapsules and More preferably present in an amount ranging from 50% to 85% by weight.

In particular, titanium oxide may be present in an amount of 28% to 80% by weight, preferably 30% to 75% by weight and more preferably 30% to 50% by weight, relative to the total weight of the microcapsules. In a particular embodiment, the titanium oxide may be present in 50% to 80% by weight, specifically 55% to 70% by weight and more particularly 55% to 65% by weight relative to the total weight of the microcapsules.

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

In a preferred embodiment, in at least one layer, and preferably in each layer, the colorant is a major constituent, i.e. representing at least 40% by weight of the layer, preferably at least 75% by weight of the layer, more preferably 1% of the total weight of the layer At least 95% by weight.

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

(c) Adhesives or lipid-based materials

The inner and/or outer layer may also advantageously comprise at least one binder, preferably a lipid-based material. In particular embodiments of the invention, such lipid-based materials may be amphiphilic in nature, ie have a non-polar part and a polar part.

Such lipid-based materials may comprise _{at least one or several C12-C22 fatty} acid chains, eg, those selected from stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, etc., and mixtures thereof. Preferably, these fatty acid chains are hydrogenated. Ultimately, these fatty acid chains can be the non-polar part of the lipid-based material.

Such lipid-based materials are preferably selected from phospholipids. These phospholipids are preferably selected from phosphoacylglycerols, more preferably from lecithins, and especially hydrogenated lecithins.

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

By combining three or more compounds (e.g. sugar alcohols, polymers, lipid-based materials) with different hardness and/or water solubility in the microcapsules, it is possible to modulate the rate at which microcapsules encapsulating colorants rupture on the skin. Over time, it is possible to adjust the preferred coloration or gradation pattern by varying the method or intensity of application to the skin.

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

In an advantageous embodiment, the microcapsules comprise at least one monosaccharide or derivative thereof and at least one polysaccharide or derivative thereof.

In 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 several types of sugar , preferably several types of sugars.

In a more preferred embodiment, the microcapsules comprise a core comprising a monosaccharide polyalcohol (preferably selected from mannitol, erythritol, xylitol, sorbitol), and a core comprising a polysaccharide (or a derivative thereof) Coating, the polysaccharide (or derivative thereof) comprises at least one or more D-glucose units as sugar.

In preferred embodiments, the microcapsules include three or more colorants in different layers.

In a preferred embodiment, the microcapsules additionally comprise a binder, for example a lipid-based material selected from phospholipids, advantageously from phosphoacylglycerols and especially from lecithins.

In particular embodiments, microcapsules include mannitol, starch polymers, and lipid-based materials.

With reference to Fig. 1, in a preferred embodiment, the present invention advantageously provides color-changing microcapsules, comprising:

i) core (A), preferably having a diameter of less than 800 μm, more preferably less than about 400 μm, advantageously 1 to 300 μm, in particular 5 to 200 μm, and more particularly 10 to 100 μm in size, which preferably does not contain any coloring and comprising at least one organic core preferably selected from at least one sugar alcohol, preferably a monosaccharide-polyol, advantageously selected from mannitol, erythritol, xylitol and sorbitol;

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

- at least one colorant, preferably iron oxide, and

- a binder selected from polymers and lipid-based materials, preferably mixtures thereof;

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

- titanium dioxide particles, and

- a binder selected from polymers and lipid-based materials, preferably mixtures thereof;

iv) Optionally, a third layer (D) surrounding the second layer (C), comprising:

- at least one colorant, and

- a binder selected from polymers and lipid-based materials, preferably mixtures thereof;

v) Optionally, a fourth layer (E) surrounding the third layer (D) (if present) or surrounding the 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 selected from alkacrylic acid/alkylmethacrylic acid copolymers and their derivatives.

In a preferred embodiment, the polymer is a hydrophilic polymer selected from starch and its derivatives, especially corn starch.

As examples of commercially available microcapsules for use in the composition of the invention, we may mention the following microcapsules produced by Korea Particle Technology KPT under the following trade names:

- Magic50-BW0105 from KPT: light gray spherical microcapsules containing mannitol, iron oxide red, iron oxide yellow, iron oxide black, hydrogenated lecithin, titanium dioxide, maize (corn) starch, with 60-200 Mesh particle size.

1-4-2. Second Embodiment of Microcapsules Containing Releasable Coloring Agent

In a second embodiment, the microcapsules comprise:

- a kernel comprising at least one coloring kernel and finally at least one inner color layer, and

- A shell having at least one pressure-breakable wall layer surrounding said core, an optional outer color layer and an optional outermost shell.

In a preferred embodiment, the microcapsules comprise a colorant selected from inorganic pigments, preferably from metal oxides, such as iron oxides and titanium oxides.

Preferably, the coloring nucleus comprises at least one inorganic pigment, advantageously chosen from at least one metal oxide, more advantageously at least one iron oxide.

Preferably, the crushable wall layer comprises at least one inorganic pigment, advantageously selected from at least one metal oxide, more advantageously selected from at least one titanium oxide.

Preferably, such iron oxides are located at least in the colored core and titanium oxides are located at least in the crushable wall layer surrounding said core.

The microcapsules comprise at least 70% by weight of colorants, preferably inorganic pigments, preferably mixtures of inorganic pigments, preferably metal oxides such as iron oxides and titanium oxides, relative to the total weight of the microcapsules.

Typically, an average colorant microcapsule size (diameter) of up to about 800 microns is used in accordance with the present invention. For skin care applications, the average particle size (diameter) of the colorant microcapsules is preferably less than about 400 microns. Advantageously, the average particle size (diameter) is in the range of about 10 to 350 microns. Preferably the average particle size will be from 50 μm to 800 μm, and especially from 60 μm to 400 μm.

Advantageously, the microcapsules have an average particle size of about 18 to 270 mesh (about 1000 μm to 53 μm), in particular about 25 to 170 mesh (about 710 μm to 90 μm).

In particular for the skin care compositions of the invention, the amount of microcapsules will range from 0.1% to 5% by weight, preferably from 0.2% to 3% by weight, relative to the total weight of the composition.

In particular for the cosmetic compositions according to the invention, the amount of microcapsules will be between 0.5% and 20% by weight, preferably between 1% and 15% by weight, more preferably between 2% and 10% by weight, relative to the total weight of the composition % range.

In particular embodiments, the encapsulated colorant may range from 0.5% to 20% by weight, in particular from 1% to 15% by weight, and more particularly Amounts ranging from 2% to 12% by weight are present in the compositions of the invention.

They will usually be incorporated into the cosmetic formulation at the final stage of formulation and after the filtration stage (if any) to avoid breakage. Preferably, the microcapsules of the present invention are added and uniformly mixed at a temperature below 50°C. Mix them lightly with a paddle, not a homogenizer.

In a particular aspect of the invention, more than 60%, preferably more than 70%, especially more than 80%, and more especially more than 90% of the microcapsules will be pressed, rubbed, wiped and/or scrubbed with hands or tools. within 1 minute, preferably 1 to 40 seconds, especially 1 to 30 seconds, and more particularly 1 to 20 seconds, to release the internal colorant. However, the ratio and time limit are not critical in the present invention.

1-4-2-1. Core (colorant and binder or lipid-based material)

In a second embodiment, the core of the microcapsule comprises a colored core comprising at least one colorant and advantageously at least one binder, for example a lipid-based material.

The colorant is not particularly limited, and the above-described kinds are preferably used.

The binder is preferably selected from at least one hydrophilic polymer, at least one lipid-based material and mixtures thereof, preferably mixtures thereof. Generally, it is difficult to form a coating layer by using only colorant components or particles without using any binder. Furthermore, even if it is difficult to form a coating layer without a binder, such a coating layer may be easily damaged or cracked or any components or particles may be easily removed from the coating layer. Therefore, adhesives can be used to facilitate the coating process and improve the durability of the coating layer. This binder is selected from sticky polymeric materials which can function as wall-forming material (wall-forming polymeric material).

In the present invention, the binder is preferably selected from at least one wall-forming material, lipid-based material and mixtures thereof. More preferably, the binder is a mixture comprising both a polymer as wall forming material and a lipid based material as coating base.

Coating substrates refer to hydrophilic coating substrates, hydrophobic coating substrates or lipid-based coating substrates. Since a hydrophilic coating base can be extracted together with the colorant and a hydrophobic coating base can give a perception of the presence of foreign substances due to its too strong film properties, it is preferable to use a lipid-based coating base.

In certain embodiments, such lipid-based materials may be amphiphilic in nature, ie, have a non-polar portion and a polar portion.

Such lipid-based materials may comprise at least one or several chains of C ₁₂ -C ₂₂ fatty acids, eg selected from stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, etc. and mixtures thereof. Preferably, these fatty acid chains are hydrogenated. Ultimately, these fatty acid chains can be the non-polar part of the lipid-based material.

Lipid-based materials are amphiphilic materials having both a polar portion and a non-polar portion in one molecule, and include, for example, selected from the group consisting of stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid and Its mixture of C ₁₂ -C ₂₂ fatty acid chains. The fatty acid chains can be hydrogenated and optionally form the non-polar portion of the lipid-based material.

The lipid-based material may be selected from phospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidic acid or phosphatidylserine, sphingolipids such as sphingosine-1-phosphate or sphingomyelin and ceramides, preferably ceramides or lecithins, It is a mixture of phospholipids, especially hydrogenated lecithin.

The amount of lipid-based material can be determined by taking into account the type and amount of wall-forming polymers as well as other components such as colorants and/or titanium dioxide particles. In general, however, the amount of lipid-based material may be selected from 0.1% to 30% by weight, in particular 0.2% to 25% by weight, preferably 0.3% to 20% by weight, with respect to the total weight of the layers. % by weight and more preferably 0.4% by weight to 20% by weight. When the amount of lipid-based material is less than 0.1% by weight, breakability or dissolving ability may decrease, and when it exceeds 25% by weight, durability may decrease or stability during processing and storage may decrease.

In the present invention, the wall-forming polymer is selected from hydrophilic polymers. The term "hydrophilic polymer" refers to polymers capable of forming hydrogen bonds with water or alcoholic compounds, especially those selected from lower alcohols, diols and polyols, especially those having O-H, N-H and S-H bonds in the molecule .

The hydrophilic polymer may be selected from the following polymers or mixtures thereof:

- acrylic or methacrylic acid homopolymers or copolymers or salts and esters thereof, and in particular: products sold under the name Versicol F or Versicol K by the company Allied Colloid; products sold under the name Ultrahold 8 by the company Ciba-Geigy; and polyacrylic acid of the Synthalen K type; and salts of polyacrylic acid, especially the sodium salt (corresponding to the INCI name Sodium Acrylate Copolymer), and more particularly the crosslinked sodium polyacrylate sold under the name Luvigel EM by the company BASF (corresponding to In the INCI name Sodium Acrylate Copolymer (and) Caprylic/Capric Triglyceride);

- Copolymers of acrylic acid and acrylamide sold under the name Reten by the company Hercules in the form of their sodium salts, sodium polymethacrylate sold under the name Darvan No. Sodium salts of hydroxycarboxylic acids;

- polyacrylic acid/alkyl acrylate copolymers, preferably modified or unmodified carboxyvinyl polymers; most particularly preferred copolymers are acrylates/C ₁₀ -C ₃₀ alkyl acrylate copolymers (INCI name : Acrylates/C _10-30 Alkyl Acrylate Crosspolymer), such as the products sold by the company Lubrizol under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382 and Carbopol ETD2020, Carbopol Ultrez 21, and even more preferably Pemulen TR -2;

- Alkacrylic acid/alkylmethacrylic acid copolymers and their derivatives, especially their salts and their esters, such as ethyl acrylate, methyl methacrylate and low content of methacrylate copolymers with quaternary ammonium groups;

- AMPS (polyacrylamidomethylpropanesulfonic acid partially neutralized and highly cross-linked with ammonia) sold by the company Clariant;

- AMPS/acrylamide copolymers, such as the products Sepigel or Simulgel sold by the company SEPPIC, especially copolymers of INCI name polyacrylamide (and) C ₁₃ -C ₁₄ isoparaffin (and) laureth-7;

- polyoxyethylated AMPS/alkylmethacrylate copolymers (crosslinked or non-crosslinked) of the type Aristoflex HMS as sold by the company Clariant;

- anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;

- cellulosic polymers and their derivatives, preferably selected from hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, ethyl hydroxyethyl cellulose and carboxyl cellulose in addition to alkyl cellulose methylcellulose, and also quaternized cellulose derivatives; in a preferred embodiment, the cellulose polymer is carboxymethylcellulose;

- final modified starch polymers and their derivatives; in a preferred embodiment the starch polymers are native starches;

- 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, vinylpyrrolidone and Copolymers of caprolactam, polyvinyl alcohol;

- optionally modified polymers of natural origin, such as galactomannan and its derivatives, such as konjac gum, gellan gum, locust bean gum, couma gum, karaya gum , gum tragacanth, gum arabic, acacia gum, guar gum, hydroxypropyl guar gum, hydroxypropyl guar gum modified with sodium methyl carboxylate groups (Jaguar XC97-1, Rhodia), guar hydroxypropyltrimonium chloride, and xanthan gum derivatives;

- alginate and carrageenan;

- glycosaminoglycans (glycoaminoglycan), hyaluronic acid and their derivatives; and

- Mucopolysaccharides, such as hyaluronic acid and chondroitin sulfate, and mixtures thereof.

Preferably, the hydrophilic polymer of the present invention may be selected from polysaccharides and their derivatives, homopolymers and/or copolymers of acrylic acid or methacrylic acid or salts and esters thereof, and mixtures thereof.

Polysaccharides and their derivatives may be selected from chitosan polymers, chitin polymers, cellulose polymers, starch polymers, galactomannans, alginates, carrageenans, mucopolysaccharides, and their derivatives, and mixtures thereof.

Polysaccharides and their derivatives are preferably selected from starch polymers.

Preferably, the hydrophilic polymer may be selected from corn starch, polymethyl methacrylate, cellulose or its derivatives such as carboxymethyl cellulose (CMC), cellulose esters and ethers and amino cellulose, and mixtures thereof .

Preferably, the hydrophilic polymer may be selected from cornstarch, polymethylmethacrylate, their derivatives, and mixtures thereof.

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

The hydrophilic polymers used as wall-forming materials in the present invention are not cross-linked.

The amount of polymer or wall-forming polymer can be determined by considering the type and amount of colorant, titanium dioxide particles, and/or lipid-based material. In general, however, the amount of polymer or wall-forming polymer in each layer may be selected from 0.1% to 30% by weight, in particular 0.2% to 25% by weight, with respect to the total weight of the layers, preferably 0.3% to 20% by weight and more preferably 0.4% to 20% by weight. When the content of the lipid-based material is less than 0.1% by weight, breakability or dissolving ability may decrease, and when it exceeds 25% by weight, durability may decrease or stability during processing and storage may decrease. Such hydrophilic polymers described in this section can be used as both shell-forming polymers and binders.

The core can be obtained as granules, powders, granules, for example by spray-drying or fluidized-bed processes of a solution comprising at least one colorant, at least one polymer as wall-forming material and at least one lipid-based material in a solvent. (granule), microspheres and microcapsules.

The coloring core, and more generally the size of the core is not particularly limited and can be appropriately selected according to the final desired microcapsules. For example, the coloring nuclei, and more generally the nuclei, may have a size greater than 20 μm or greater, especially 30 μm or greater, preferably 40 μm or greater, more preferably 50 μm or greater, and less than 800 μm or less, especially 700 μm or less, preferably 600 μm or less, more preferably 500 μm or less.

The radius of the core is greater than 50%, especially greater than 60%, preferably greater than 70%, and more preferably greater than 80%, relative to the total radius of the microcapsule. For example, the ratio between core radius and shell thickness may be 1:0.05 to 1:0.5.

Alternatively, the amount of core may be greater than 30 wt%, especially greater than 40 wt%, preferably greater than 50 wt%, and more preferably greater than 60 wt%, relative to the total weight of the microcapsules. Therefore, microcapsules have a large loading of colorants in the particles.

The core may have one or more inner color layers surrounding the shading core. The inner color layer can be every layer located between the color core and the crushable wall layer.

The inner color layers include, for example, a first inner color layer, a second inner color layer, a third inner color layer, etc., wherein the colorants and binders contained in the respective inner color layers are the same as or different from each other. In preferred embodiments, the colored core may comprise one or two inner color layers, preferably one inner color layer.

When the core has a colored core and an inner color layer, the colored core can be formed by granulation of a solution of a colored core comprising at least one colorant and preferably at least one binder, Preferably a solution of the inner colored layer of at least one binder coats the colored core to form the inner colored layer. The coating process can be performed by a fluidized bed coating method.

The thickness of the inner color layer is not particularly limited and can be properly selected according to the final required microcapsules. For example, the coloring nucleus, and more generally the thickness of the nucleus may be greater than 20 μm or greater, especially 40 μm or greater, preferably 60 μm or greater, more preferably 80 μm or greater, and less than 200 μm or less, especially 160 μm or less, preferably 120 μm or less, more preferably 100 μm or less.

Alternatively, the amount of the inner color layer may be 20% to 80% by weight, especially 30% to 70% by weight, and preferably 40% to 60% by weight, relative to the total weight of the core.

In a particular embodiment, the colored core is free of binder and surrounded by an inner color layer comprising colorant and binder, whereby the pigment contained in the core will disperse more easily upon rupture of the microcapsules.

In the coloring core, the binder can be used in an amount in which the coloring agent does not scatter or separate from the layer during the coating process and/or after removal of the solvent, and with respect to the total weight of the coloring core, it can usually be selected from 1 wt. % to 30% by weight, preferably 2% to 25% by weight, especially 5% to 20% by weight, and more particularly 5% to 15% by weight.

In a preferred embodiment, the colorants, and preferably pigments, even more preferably iron oxides, are present in an amount of at least 70% by weight, especially at least 75% by weight, preferably at least 80% by weight, more preferably at least 85% by weight, relative to the total weight of the core %, such as 80% to 99% by weight, is present in the core.

In a preferred embodiment, the colorants, and preferably pigments, more preferably iron oxides, are present in an amount of at least 30% by weight, especially at least 35% by weight, preferably at least 40% by weight, such as 40% by weight, relative to the total weight of the microcapsules. An amount of 60% by weight is present.

The amount of iron oxide particles in the microcapsules may be 20% to 60% by weight, preferably 25% to 55% by weight, more preferably 30% to 50% by weight, relative to the total weight of the microcapsules. More preferably, the amount of iron oxide particles in the microcapsules may be 30% to 58% by weight, preferably 35% to 55% by weight, and more preferably 40% to 50% by weight, relative to the total weight of the microcapsules. weight%.

1-4-2-2. Crushable wall layer or titanium dioxide particle layer

The microcapsules have a crushable wall layer comprising at least one colorant. The colorant is preferably selected from inorganic pigments, more preferably from metal oxides, and still more preferably from titanium dioxide particles.

Preferably, the colorants contained in the crushable wall layer are different from the colorants contained in the color core, for example both are different metal oxides from each other.

In a preferred embodiment, titanium dioxide particles are dispersed discontinuously in the layer and are interconnected by a binder.

The term "crushable" or "crushable" means that a rupture can be easily made when pressed, rubbed, wiped and/or scrubbed by hand or with an implement such as a cloth, sponge or paper.

The crushable layer of titanium dioxide particles may comprise titanium dioxide particles and a binder, and the binder may comprise wall forming material.

In the crushable wall layer of the present invention, it is believed that the titanium dioxide particles embedded in the wall forming material will irreversibly damage the crushable wall layer and facilitate or enhance the disintegration or dissolution of said wall layer. In addition, titanium dioxide particles are also expected to play an important role with regard to the strength, durability, crushability and feel of the wall layer.

For example, the crushable wall layer can be formed by the following steps:

(a) dissolving or dispersing titanium dioxide particles and binder in a suitable solvent to produce a solution comprising titanium dioxide particles and binder,

(b) coating particles having an internal color layer with the solution obtained in (a) above, and

(c) Optionally drying the resulting granules obtained in (b) above.

The coating can be performed by using a fluidized bed method, but other coating methods can also be utilized if necessary. As suitable solvents usable in the above steps, water or low boiling point solvents such as dichloromethane, methanol and ethanol may be mentioned.

The layer of titanium dioxide particles (the thickness of which can vary depending on the amount of titanium dioxide used and/or the type of binder) can have a thickness of 10 μm or greater, preferably 20 μm or greater, more preferably 30 μm or greater, especially 40 μm or greater , usually 300 μm or less, preferably 250 μm or less, more preferably 200 μm or less, and especially 150 μm or less in thickness.

The amount of titanium dioxide particles in the crushable wall layer is preferably selected from 50% to 99% by weight, more preferably 60% to 98% by weight, even more preferably 70% by weight, with respect to the total weight of the crushable wall layer % to 97% by weight, and especially 80% to 95% by weight. Preferably, the amount of said colorant, and especially titanium dioxide particles, represents less than 100% of the crushable wall layer.

The amount of titanium dioxide particles in the microcapsules is preferably selected from 20% to 60% by weight, preferably 25% to 55% by weight, and more preferably 30% to 50% by weight, relative to the total weight of the microcapsules.

The coloring agent (preferably iron oxide) in the coloring core and the coloring agent (preferably titanium dioxide particles) in the crushable wall layer are present in the microcapsules in respective total amounts such as (such as) the coloring agent in the coloring core ( and preferably iron oxide) relative to the colorant (preferably titanium dioxide particles) in the crushable wall layer is greater than or equal to 1 by weight.

Both iron oxide and titanium dioxide particles are present in the microcapsules in their respective total amounts such that the weight ratio of iron oxide to titanium dioxide particles is greater than or equal to 1.

The average diameter or size of titanium dioxide particles is not particularly limited, but has an average diameter of generally 10 nm to 20 μm, preferably 50 nm to 10 μm, more preferably 100 nm to 5 μm, and especially 150 nm to 5 μm. An average diameter or size of titanium dioxide particles of less than 10 nm may result in reduced crushability, and an average diameter of more than 20 μm may make it difficult to form a layer of titanium dioxide particles. Titanium dioxide particles having a first particle size smaller than the aforementioned range but having a second particle size falling within the aforementioned particle size range are suitable for use in the present invention.

1-4-2-3. Optional external color layer

The microcapsules additionally comprise an optional outer layer of color on the layer of crushable titanium dioxide particles. The outer color layer may be formed by coating a layer of titanium dioxide particles with a solution having a colorant and a binder, for example by a fluidized bed method. Colorants and binders used in the outer color layer may be the same as or different from those used in the inner color layer.

Generally, the outer color layer is provided to impart a visual color different from the white color produced by the titanium dioxide particle layer and/or the color of the inner color layer. Therefore, the colorant in the outer color layer can be used in an amount that does not interfere with the color developed by the inner color layer when the microcapsules are scrubbed.

The amount of the outer color layer may be 1% to 60% by weight, preferably 2% to 50% by weight, more preferably 3% to 40% by weight, and especially 4% to 30% by weight, relative to the total weight of the core %. However, the amount of the colorant in the outer color layer may be 0.01% by weight to 5% by weight, preferably 0.05% by weight to 4.5% by weight, more preferably 0.1% by weight to 4% by weight, relative to the total weight of the colorant in the inner color layer. % by weight, and especially 0.5% by weight to 3.5% by weight.

The amount of colorant in the outer color layer can be increased additionally if the color of the outer color layer will not interfere with the color of the inner color layer. Those skilled in the art can select the color and amount of the colorant in the outer color layer in an appropriate manner by considering the color and amount of the colorant contained in the inner color layer and the desired color to be finally developed.

The thickness of the outer color layer is not particularly limited and can be properly selected according to the final required microcapsules. For example, the outer color layer may have a thickness greater than 20 μm, especially 40 μm, preferably 60 μm, and more preferably 80 μm, and less than 200 μm, especially 150 μm, preferably 120 μm, and more preferably 100 μm.

1-4-2-4. Outermost shell

The microcapsules may comprise a protective outermost shell on a layer of crushable titanium dioxide particles or an additional outer color layer to protect the microcapsules from moisture in the air during storage or to secure the microcapsules in a carrier, especially in Long-term stability in solution.

The outermost shell may be made of at least one polymer, and preferably may be made of at least one polymer selected from polysaccharides and their derivatives, acrylic or methacrylic acid homopolymers or copolymers or salts thereof and Esters, polystyrene-maleic anhydride copolymers, and mixtures thereof, such as poly(meth)acrylates, cellulose ethers, cellulose esters, and derivatives thereof, and mixtures thereof.

The amount of the outermost shell is selected from 0.1% to 20.0% by weight and preferably from 0.5% to 15% by weight, relative to the total weight of the microcapsules. When the amount of the outermost shell is less than 0.1% by weight, the shell coating may be meaningless, and when it exceeds 20.0% by weight, it may cause a feeling that foreign substances are present.

The thickness of the outermost shell is not particularly limited and may be appropriately selected according to the final desired microcapsules. For example, the outermost shell may have a thickness greater than 20 μm, especially 30 μm, preferably 40 μm and more preferably 50 μm and less than 200 μm, especially 150 μm, preferably 120 μm and more preferably 90 μm.

Further examples of polymers that can be implemented as the outermost shell will be given later during the description of binders that can be used in the microcapsules of the present invention.

1-4-3. Method

Microcapsules can be produced by conventional methods known in the art within the coating or encapsulation domain, including pelletization, granulation, coating, and the like. For example, microcapsules can be obtained by comprising a mixture of compounds (active agent, pigment, polymer, solvent) as disclosed in WO01/35933 and WO2011/027960 and drying to form capsules, or by The disclosed granulation and is obtained by spray-drying coating steps, or by fluidized bed techniques already used in the food and pharmaceutical industries. The example in WO 08/139053 may be cited for the preparation of multilayered spheroids comprising a sugar core and concentric layers of pharmaceutically active agent. Immobilization of the pharmaceutically active agent on the core is carried out by dipping or pulverizing or spraying, with subsequent drying of the first layer before applying the second layer.

Preferably, the microcapsules incorporated into the composition of the invention are obtainable, and preferably obtained, at least in part, by the fluidized bed technique described hereinafter. The fluidized bed process is characterized in that it results in true capsules in contrast to spray drying which gives granular particles formed by particle agglomeration or a matrix in which the core material is randomly dispersed into the polymer. In particular, the use of a fluidized bed process allows substantially spherical microcapsules with a substantially spherical core, said microcapsules being composed of at least one layer circumferentially surrounding said core and preferably at least one of an inner layer Outer surround.

For example, in 'Fluid-Bed Coating, Teunou, E.; Poncelet, 2005, D. Food Science and Technology (Boca Raton, FL, United States), Vol. 146, Issue (Issue) Encapsulated and Powdered Foods, pp. 197-212 A fluidized bed process is disclosed. A person skilled in the art knows how to adjust the amount of air, liquid and temperature that allow the reproduction of the microcapsules according to the invention.

Preferred fluidized bed methods include the Würster method and/or the tangential spray method. Unlike spheronization methods, such methods allow spherical capsules with a core surrounded by one or more circumferential layers.

By combining two or more compounds (e.g., polymers, lipid-based materials) with different hardness and/or water solubility with titanium dioxide particles in the microcapsules, it is possible to modulate the rate at which microcapsules encapsulating colorants rupture on the skin. Over time, it is possible to adjust the preferred coloring or gradation pattern by varying the method or intensity of application to the skin.

Preferably, the multilayer coating comprises at least starch as polymer, and at least one lipid-based material and preferably lecithin.

Preferably, the microcapsules additionally comprise a lipid-based material selected from phospholipids, advantageously from phosphoacylglycerols and especially lecithin.

Preferably, the microcapsules comprise three or more different colorants (in terms of color). More preferably, the colorant is an inorganic pigment, and even more preferably a metal oxide.

In the present invention, an organic solvent may be used in the preparation of the coating solution used in the fluidized bed coating method. The organic solvent is not particularly limited, but preferably includes methylene chloride, methanol, ethanol and mixtures thereof. Any organic solvent may be used as long as it can dissolve or disperse the polymer and/or lipid-based material, has a boiling point less than that of water, and has low residual toxicity.

Microcapsules for use in the present invention are obtainable, and preferably obtained, by the following steps:

(a-1) preparing particles of colored cores (A-1) comprising at least one colorant and at least one binder, and

(a-2) Optionally coat the coloring core prepared in the above step (a-1) with a solution in which the same or different coloring agents as those used in the above step (a-1) are dissolved or dispersed. Colorants and binders to form the inner color layer (A-2),

(b) coating the particles prepared in step (a-1) or (a-2) above with a solution in which titanium dioxide particles and a binder form a crushable wall layer (B),

(c-1) optionally coating the particles obtained in the above step (b) with a solution in which the same as those used in the above step (a-1) or (a-2) are dissolved or dispersed or different colorants and binders to form the outer color layer (C-1),

(c-2) Optionally coating the particles obtained in the above step (b) or (c-1) with a solution in which the shell polymer is dissolved or dispersed to form the outermost shell.

The present invention will be further explained by the following examples, without being limited to them.

Properties of 1-4-4 microcapsules

The microcapsules are stable in the compositions of the invention, preferably at elevated temperatures, such as at temperatures greater than or equal to 40°C, such as in an oven at 45°C for 1 month, better for two months, and still more Good for three months; or stable for 15 days in an oven at 60°C.

Preferably, the microcapsules exhibit suitable softening kinetics. More preferably, the hardness of the microcapsules is advantageously from 5 to 50 grams, more preferably from 6 to 20 grams, and even more preferably from 7 to 10 grams, after at least three hours of contact with the other compounds in the formulation. This hardness is compatible with the industrial processes used to prepare compositions comprising such microcapsules. Such values of softening kinetics and hardness allow to provide not only aesthetically pleasing microcapsules, but also overall aesthetically pleasing compositions.

In particular, the composition may result in different shades or color gradations depending on the intensity of the rubbing. The composition may advantageously exhibit a high color C* as determined in the CIE Test System 1976.

1-5. Additional surfactants

In addition to (b) above, the composition of the present invention may further comprise at least one additional surfactant. A single type of additional surfactant may be used, but two or more different types of additional surfactant may be used in combination.

As additional surfactant, at least one ionic surfactant can be used. The ionic surfactant may be selected from cationic surfactants, anionic surfactants and amphoteric surfactants, preferably selected from anionic surfactants and amphoteric surfactants and more preferably anionic surfactants.

1-5-1. Cationic surfactant

Cationic surfactants are not limited. The cationic surfactant may optionally be selected from polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts and mixtures thereof.

Examples of quaternary ammonium salts that may be mentioned include, but are not limited to, those of the following general formula (V):

[Formula (V)]

wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and are selected from straight and branched chain aliphatic groups containing 1 to 30 carbon atoms and optionally containing heteroatoms such as oxygen, nitrogen, sulfur and halogen . The aliphatic group may be selected from, for example, alkyl, alkoxy, C ₂ -C ₆ polyoxyalkylene, alkylamide, (C ₁₂ -C ₂₂ )alkylamide (C ₂ -C ₆ ) Alkyl, (C ₁₂ -C ₂₂ ) alkyl acetate and hydroxyalkyl; and aromatic groups such as aryl and alkylaryl; and X ^- selected from the group consisting of halides, phosphates, acetates, Lactates, (C ₂ -C ₆ )alkylsulfates and alkyl- or alkylaryl-sulfonates; quaternary ammonium salts of imidazolines; diquaternary ammonium salts; and quaternary ammonium salts containing at least one ester function Salt.

The above-mentioned quaternary ammonium salts that can be used in the composition according to the present invention include, but are not limited to, tetraalkylammonium chlorides, such as dialkyldimethylammonium chloride and alkyltrimethylammonium chloride, wherein The alkyl group contains about 12 to 22 carbon atoms, such as behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride and benzyl dimethyl stearyl ammonium chloride. Tatyl ammonium chloride; palmitamidopropyl trimethyl ammonium chloride; and stearamidopropyl dimethyl (myristyl acetate) ammonium chloride sold by the Van Dyk Company under the name sell.

In one embodiment, the cationic surfactants which may be used in the compositions of the invention are selected from quaternary ammonium salts, for example, selected from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, Quaternium-83, Quaternium-87, Quaternium-22, Behenamidopropyl-2,3-Dihydroxypropyl Dimethyl Ammonium Chloride, Palmitomidopropyl Trimethyl Ammonium Chloride and Stearamidopropyl Dimethyl Ammonium Chloride Methylamine.

1-5-2. Anionic surfactant

Anionic surfactants are not limited. Anionic surfactants may in particular be selected from anionic derivatives of proteins of vegetable origin or silk proteins, phosphates and alkyl phosphates, carboxylates, sulphosuccinates, amino acid derivatives, alkyl Anion of alkyl sulphate, alkyl ether sulphate, sulphonate, isethionate, taurate, alkyl sulphoacetate, polypeptide, alkyl polyglucoside derivatives, and mixtures thereof.

1) Anionic derivatives of proteins of vegetable origin are protein hydrolysates comprising hydrophobic groups for which they may naturally occur in proteins or which result from the combination of proteins and/or protein hydrolysates with hydrophobic compounds React and join. The protein is of vegetable origin or derived from silk, and the hydrophobic group may in particular be an aliphatic chain, for example an alkyl chain containing 10 to 22 carbon atoms. As anionic derivatives of proteins of vegetable origin, mention may be made more particularly of apple, wheat, soybean or oat protein hydrolysates comprising alkyl chains having 10 to 22 carbon atoms, and their salts. The alkyl chain may in particular be a lauryl chain, and the salt may be a sodium, potassium and/or ammonium salt.

Thus, as protein hydrolysates comprising hydrophobic groups, mention may be made, for example, of salts of protein hydrolysates, wherein said protein is silk protein modified with lauric acid, such as the product sold under the name Kawa Silk by Kawaken; protein hydrolysates Salts of products wherein the protein is a wheat protein modified with lauric acid, such as the potassium salt sold under the name Aminofoam W OR by Croda (CTFA name: Potassium Lauroyl Wheat Amino Acid) and Proteol LW 30 by Seppic (CTFA name: sodium lauroyl wheat amino acid); salts of protein hydrolysates, wherein the protein is oat protein comprising alkyl chains having 10 to 22 carbon atoms, and more especially salts of protein hydrolysates , wherein the protein is oat protein modified with lauric acid, such as the sodium salt sold by Seppic under the name Proteol OAT (30% in water) (CTFA name: sodium lauroyl oat amino acid); or contains A salt of an apple protein hydrolyzate of an alkyl chain of atoms, such as the sodium salt sold by Seppic under the name Proteol APL (30% solution in water/glycol) (CTFA name: sodium cocoyl apple amino acid). Mention may also be made of the mixture of lauroyl amino acids (aspartic acid, glutamic acid, glycine, alanine) neutralized with sodium N-methylglycinate sold under the name Proteol SAV50S by Seppic (CTFA name: Cocoyl amino acid sodium).

2) As phosphates and alkyl phosphates, mention may be made, for example, of mono- and di-alkyl phosphates, as produced by Kao Chemicals under the name Lauryl monophosphate, potassium salt of lauryl phosphate, sold by Cognis under the name Mixtures of monoesters and diesters (mainly diesters) sold by Cognis under the name A mixture of octyl phosphate mono- and diesters sold by Condea under the name Mixtures of ethoxylated (7 mol of EO) 2-butyloctyl phosphate mono- and diesters sold by Uniqema under the code and The potassium or triethanolamine salts of mono(C ₁₂ -C ₁₃ ) alkyl phosphates sold by Rhodia Chimie under the name Potassium lauryl phosphate, and potassium cetyl phosphate sold under the name Arlatone MAP 160K by Uniqema.

3) As carboxylates there may be mentioned:

- Amido ether carboxylates (AEC), such as sodium lauryl amido ether carboxylate (3EO), sold by Kao Chemicals under the name sell;

- Polyoxyethylenated carboxylates, such as oxyethylenated (6EO) sodium lauryl ether carboxylate (65/25/10C ₁₂ -C ₁₄ -C ₁₆ ), sold by Kao Chemicals under the name Sold, polyoxyethylated and carboxymethylated fatty acids derived from olive oil, by Biologia E Tecnologia under the name Sold, or sodium oxyethylenated (6EO) tridecyl ether carboxylate, by Nikkol under the name sell; and

- Fatty acids with _C6 to _C22 alkyl chains neutralized with organic or inorganic bases such as potassium hydroxide, sodium hydroxide, triethanolamine, N-methylglucamine, lysine and arginine salt (soap).

4) As amino acid derivatives, mention may especially be made of alkali metal salts of amino acids, such as:

- Sarcosinates, such as sodium lauroyl sarcosinate, marketed by Ciba under the name sold by or by Seppic under the name Sold, Sodium Myristoyl Sarcosinate, by Nikkol under the name Sold, or sodium palmitoyl sarcosinate, by Nikkol under the name sell;

- Alanine salts, such as sodium N-lauroyl-N-methylamidopropionate, sold by Nikkol under the name sold by or by Kawaken under the name Sold, or N-lauroyl-N-methylalanine triethanolamine, by Kawaken under the name sell;

-Glutamates, such as triethanolamine monococoyl glutamate, by Ajinomoto under the name Sold, Triethanolamine Lauroyl Glutamate, by Ajinomoto under the name sell;

- Aspartate, such as a mixture of N-lauroyl aspartic acid triethanolamine and N-myristoyl aspartic acid triethanolamine, manufactured by Mitsubishi under the name sell;

- Glycine derivatives (glycine salts), such as sodium N-cocoyl glycinate, by Ajinomoto under the name and Amilite GCK 12 for sale;

- citrates, such as oxyethylenated (9 mol) citrate monoester of cocoyl alcohol, sold under the name Witconol EC 1129 by Goldschmidt; and

- Galacturonates, such as sodium dodecyl D-galactoside uronate, sold by Soliance.

5) As sulfosuccinates, mention may be made, for example, of oxyethylenated (3EO) lauryl (70/30C ₁₂ /C ₁₄ ) alcohol monosulfosuccinate, sold by Witco under the name and Sold, disodium salt of hemisulfosuccinates of C ₁₂ -C ₁₄ alcohols, by Zschimmer Schwarz under the name Sold, disodium oxyethylenated (2EO) oleamide sulfosuccinate, by Cognis under the name Sold, oxyethylenated (5EO) lauramide monosulfosuccinate, by Sanyo under the name Sold, disodium salt of oxyethylenated (10EO) lauryl citrate monosulfosuccinate, by Witco under the name Sold, or ricinoleic acid monoethanolamide monosulfosuccinate, by Witco under the name sell. Dimethicone sulfosuccinates such as PEG-12 disodium dimethicone sulfosuccinate sold under the name Mackanate-DC 30 by MacIntyre may also be used.

6) As alkyl sulfates, mention may be made, for example, of triethanolamine lauryl sulfate (CTFA name: TEA lauryl sulfate), such as the product sold under the name Empicol TL40FL by Huntsman or Texapon T42 by Cognis , the product is 40% in aqueous solution. Mention may also be made of ammonium lauryl sulphate (CTFA name: ammonium lauryl sulphate), such as the product sold under the name Empicol AL 30FL by Huntsman, which is 30% in aqueous solution.

7) As alkyl ether sulfates, mention may be made, for example, of sodium lauryl ether sulfate (CTFA name: sodium laureth sulfate), as sold by Cognis under the names Texapon N40 and Texapon AOS 225UP, or lauryl ether sulfate Ammonium sulfate (CTFA name: Ammonium Laureth Sulfate), as sold under the name Standapol EA-2 by Cognis.

8) As sulfonates, mention may be made, for example, of α-olefin sulfonates, such as sodium α-olefin sulfonate (C ₁₄ -C ₁₆ ), described by Stepan under the name Sold by Witco under the name and sold by or by Stepan under the name Sold, secondary sodium olefin sulfonate (secondary sodium olefinsulphonate), by Clariant under the name or linear alkylaryl sulfonates such as sodium xylene sulfonate sold by Manro under the name and sell.

9) As isethionates, mention may be made of acyl isethionates, such as sodium cocoyl isethionate, as described by Jordan under the name products for sale.

10) As taurine, mention may be made of the sodium salt of palm kernel oil methyl taurine, sold by Clariant under the name Sold; N-acyl-N-methyl taurates such as sodium N-cocoyl-N-methyl taurate sold by Clariant under the name sold by or by Nikkol under the name Sold by Nikkol under the name Sodium methyl stearoyl taurate sold under the name Sodium Palmitoyl Methyl Taurate For Sale.

11) Anionic derivatives of alkyl polyglucosides can be obtained in particular from citrates, tartrates, sulfosuccinates, carbonates and glyceryl ethers of alkyl polyglucosides. Mention may be made, for example, of the sodium salt of cocoyl polyglucoside (1,4) tartrate, sold by Cesalpinia under the name Sold, disodium salt of cocoyl polyglucoside (1,4) sulfosuccinate, by Seppic under the name sold, or sodium salt of cocoyl polyglucoside (1,4) citrate, by Cesalpinia under the name sell.

Preferably, the amino acid derivative may be an acylglycine derivative or a glycine derivative, especially an acylglycine salt.

The acylglycine derivative or glycine derivative may be selected from acyl glycine salt or acyl glycinate or glycine salt or glycinate, and is particularly selected from the following.

i) Acylglycine salts of formula R-HNCH ₂ COOX

in

-R represents an acyl group R'C=O, wherein R' represents a saturated or unsaturated, straight or branched hydrocarbon chain, preferably comprising 10 to 30 carbon atoms, more preferably 12 to 22 carbon atoms, even more preferably 14 to 22 carbon atoms and better 16 to 20 carbon atoms, and

-X represents a cation selected from, for example, ions of alkali metals (such as Na, Li or K, preferably Na or K), ions of alkaline earth metals (such as Mg), ammonium groups, and mixtures thereof.

The acyl group may in particular be selected from lauroyl, myristoyl, behenoyl, palmitoyl, stearoyl, isostearoyl, olivoyl, cocoyl or oleoyl groups and mixtures thereof.

Preferably, R is cocoyl.

ii) Glycinate salts of the following formula (VI):

[Formula (VI)]

in:

-R represents _a saturated or unsaturated, linear or branched hydrocarbon chain comprising 10 to 30 carbon atoms, preferably 12 to 22 carbon atoms and better ₁₆ to 20 carbon atoms; R advantageously selected from lauryl, myristyl, palmityl, stearyl, cetyl, cetearyl or oleyl and mixtures thereof, and preferably from stearyl and oleyl,

-R groups, which are the same or different, represent a R"OH group, R" being an alkyl group containing ₂ to 10 carbon atoms, preferably 2 to 5 carbon atoms.

As compounds of formula (VI), mention may be made, for example, of compounds having the INCI name Sodium Cocoyl Glycinate, such as, for example, Amilite GCS-12 sold by Ajinomoto, or Potassium Cocoyl Glycinate, such as, for example, Cocoyl Glycinate from Ajinomoto Amilite GCK-12.

As the compound of formula (VI), dihydroxyethyl oleyl glycinate or dihydroxyethyl stearyl glycinate can be used.

1-5-3. Amphoteric surfactants

Amphoteric surfactants are not limited. Amphoteric or zwitterionic surfactants may be, for example (non-limiting list), amine derivatives such as aliphatic secondary or tertiary amines, and optionally quaternized amine derivatives, wherein the aliphatic group is comprised of 8 to A straight or branched chain of 22 carbon atoms and containing at least one water-soluble anionic group (eg, carboxylate, sulfonate, sulfate, phosphate or phosphonate).

Among the amidoamine carboxylated derivatives, mention may be made of the product sold under the name Miranol, as described in US Patent Nos. 2,528,378 and 2,781,354 and classified in the CTFA Dictionary, Third Edition, 1982 (the disclosure of Incorporated herein by reference), under the names amphocarboxyglycinate and amphocarboxypropionate, the respective structures are:

R ₁ -CONHCH ₂ CH ₂ -N ⁺ (R ₂ )(R ₃ )(CH ₂ COO ^- )

where: R1 represents the alkyl, heptyl, nonyl or undecyl group _of the acid R1 _- COOH present in hydrolyzed coconut oil,

R2 represents β _- hydroxyethyl, and

_R represents carboxymethyl; and

R ₁ '-CONHCH ₂ CH ₂ -N(B)(C)

Among them: B stands for -CH ₂ CH ₂ OX',

C represents -(CH ₂ ) _z -Y', where z=1 or 2,

X' represents a -CH ₂ CH ₂ -COOH group, -CH ₂ -COOZ', -CH ₂ CH ₂ -COOH, -CH ₂ CH ₂ -COOZ' or a hydrogen atom,

Y' represents -COOH, -COOZ', -CH ₂ -CHOH-SO ₃ Z' or -CH ₂ -CHOH-SO ₃ H groups,

Z' represents an ion of an alkali or alkaline earth metal such as sodium, ammonium or an ion derived from an organic amine, and

R1' represents the alkyl, alkyl, e.g. C7, _C9 , _C11 or _C13 alkyl, _C17 alkyl and its isomeric forms of _the acid _R1' -COOH present in coconut oil or hydrolyzed linseed oil , or an unsaturated C ₁₇ group.

Preferably the amphoteric surfactant is selected from (C ₈ -C ₂₄ )-alkyl amphomonoacetates, (C ₈ -C ₂₄ ) alkyl amphodiacetates, (C ₈ -C ₂₄ )alkane (C ₈ -C ₂₄ )alkylamphodipropionates.

These compounds are classified in the CTFA Dictionary, 5th Edition, 1993, Disodium Cocoamphodipropionate, Disodium Lauroamphodiacetate, Disodium Octylamphodiacetate ( Disodium Caprylamphodiacetate), Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroylamphodiacetate, Disodium Caprylamphodiacetate, Caprylamphodiacetate disodium dipropionate, lauroamphodipropionate and cocoamphodipropionate.

By way of example, mention may be made of the Rhodia Chimie company under the trade name Cocoamphodiacetate sold in concentrate.

Preferably, the amphoteric surfactant may be betaine.

Betaine-type amphoteric surfactants are preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, alkylsultaines, alkylphosphobetaines and alkylamidoalkylsultaines Bases, especially (C ₈ -C ₂₄ ) alkyl betaines, (C ₈ -C ₂₄ ) alkyl amido (C ₁ -C ₈ ) alkyl betaines, (C ₈ -C ₂₄ ) alkyl sulfo Betaines, and (C ₈ -C ₂₄ )alkylamido(C ₁ -C ₈ )alkylsultaines. In one embodiment, the betaine-type amphoteric surfactant is selected from (C ₈ -C ₂₄ )alkyl betaines, (C ₈ -C ₂₄ )alkylamido (C ₁ -C ₈ )alkylsulfo Betaines, (C ₈ -C ₂₄ ) alkyl sultaines and alkyl (C ₈ -C ₂₄ ) phosphate betaines.

Non-limiting examples that may be mentioned include coco betaine, lauryl betaine, cetyl betaine, coco/oleamidopropyl betaine, Cocamidopropyl Betaine, Palmamidopropyl Betaine, Stearamidopropyl Betaine, Cocamidoethyl Betaine, Cocamidopropyl Hydroxysultaine, Oleamido Compounds under the names Propyl Hydroxysultaine, Cocoyl Hydroxysultaine, Lauryl Hydroxysultaine and Cocosultaine, alone or as a mixture.

Betaine-type amphoteric surfactants are preferably alkylbetaines and alkylamidoalkylbetaines, especially cocobetaines and cocamidopropyl betaines.

Additional surfactants, if used, may be present in amounts of 0.01% to 20%, preferably 0.10% to 10%, and more preferably 1% to 5% by weight relative to the total weight of the composition.

1-5-4. Polyols

The compositions of the invention may also comprise at least one polyol. A single type of polyol may be used, but two or more different types of polyols may be used in combination.

The term "polyol" here refers to alcohols having two or more hydroxyl groups and does not cover sugars or derivatives thereof. Derivatives of sugars include sugar alcohols obtained by reducing one or more carbonyl groups of sugars, and wherein one or more hydrogen atoms in one or more of its hydroxyl groups have been replaced by at least one substituent (e.g., alkyl, hydroxy Alkyl, alkoxy, acyl or carbonyl) substituted sugars or sugar alcohols.

The polyol may be a C ₂ -C ₁₂ polyol, preferably a C _2-9 polyol, comprising at least 2 hydroxyl groups, and preferably 2 to 5 hydroxyl groups.

The polyols may be natural or synthetic polyols. The polyol may have a linear, branched or cyclic molecular structure.

The polyhydric alcohol may be selected from glycerol and glycols, more preferably propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, ethylhexylglycerin, caprylyl glycol , glycol ether, preferably monopropylene glycol, dipropylene glycol or tripropylene glycol alkyl (C ₁ -C ₄ ) ether or monoethylene glycol, diethylene glycol or triethylene glycol alkane (C ₁ -C ₄ ) ethers, and mixtures thereof, even more preferably the polyol is glycerol and/or butanediol.

The polyol may be present in an amount ranging from 0.01% to 30% by weight, and preferably from 0.1% to 20% by weight, such as 1% to 10% by weight, relative to the total weight of the composition.

1-5-5. Thickener

The compositions of the invention may also comprise at least one thickener. A single type of thickener may be used, but two or more different types of thickeners may be used in combination.

The thickener can be selected from the following:

(i) associative thickeners, which are amphiphilic thickeners comprising both hydrophilic and hydrophobic units, for example comprising at least one C8- _C30 fatty chain and _at least one hydrophilic unit ;

(ii) a crosslinked acrylic acid homopolymer;

(iii) crosslinked copolymers of (meth)acrylic acid and (C ₁ -C ₆ ) alkyl acrylates;

(iv) nonionic homopolymers and copolymers comprising at least one of ethylenically unsaturated ester monomers and ethylenically unsaturated amide monomers;

(v) ammonium acrylate homopolymers and copolymers of ammonium acrylate and acrylamide;

(vi) C ₁₂ -C ₃₀ fatty alcohols;

(vii) (un)modified carboxyvinyl polymers such as the products sold under the name Carbopol (CTFA name: Carbomer) by the company Goodrich; polyacrylates;

(viii) Polymethacrylates such as those sold under the names Lubrajel and Norgel by the company Guardian and Hispagel by the company Hispano Chimica;

(ix) polyacrylamide, optionally crosslinked;

(x) Neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, such as those sold under the name Hostacerin AMPS (CTFA name: Ammonium Polyacryloyldimethyltaurate) by the company Clariant Poly(2-acrylamido-2-methylpropanesulfonic acid);

(xi) Cross-linked anionic copolymers of acrylamide and AMPS in the form of W/O emulsions, such as those sold by the company SEPPIC under the name Sepigel 305 (CTFA name: Polyacrylamide/C ₁₃ -C ₁₄ Isoparaffin/Lauryl Alcohol-7) and those sold under the name Simulgel 600 (CTFA name: Acrylamide/Sodium Acryloyldimethyltaurate Copolymer/Isohexadecane/Polysorbate 80);

(xii) Polysaccharide biopolymers such as xanthan gum, guar gum, carob gum, acacia gum, scleroglucan, chitin and chitosan derivatives, carrageenan, gellan gum, alginates ;

(xiii) Cellulose such as microcrystalline cellulose, carboxymethyl cellulose, hydroxymethyl cellulose and hydroxypropyl cellulose, and mixtures thereof, preferably selected from acrylates/C ₁₀ -C ₃₀ alkyl acrylate crosslinks Polymers such as Carbopolltrez 20, Carbopol ultrez 21, Permulen TR-1, Permulen TR-2, Carbopol 1382, Carbopol ETD 2020, carbomers such as Synthalen K, carbopol 980, ammonium acryloyldimethyltaurate/stearate Aleth-8 methacrylate copolymers such as Aristoflex SNC, acrylate copolymers such as Carbopol Aqua SF-1, Acryloyldimethylammonium taurate/steareth-25 methacrylate crosspolymerization substances such as Aristoflex HMS, ammonium acryloyldimethyl taurate such as Arisfoflex AVC, and xanthan gum such as Keltrol CG; Any polymer that further contributes to making it stable with respect to shelf life, and which contributes to clarity.

The thickener is preferably selected from associative thickeners, polysaccharides and (un)modified carboxyvinyl polymers such as starch, xanthene gum and carbomer.

The viscosity of the composition of the present invention is not particularly limited. Viscosity can be measured at 25°C with a viscometer or a rheometer, preferably with cone-plan geometry. Preferably, the viscosity of the composition of the invention at 25°C and 1 s ⁻¹ may for example be in the range of 1 Pa.s to 2000 Pa.s, and preferably 1 Pa.s to 1000 Pa.s.

The thickener may be present in an amount ranging from 0.001% to 10% by weight, and preferably from 0.01% to 10% by weight, and still more preferably from 0.1% to 5% by weight relative to the total weight of the composition.

1-5-6. Active agent

For applications, in particular for caring for the skin or making up the skin, the compositions according to the invention may comprise at least one active agent.

These active agents may be selected from moisturizers, sunscreen/sunblock agents, anti-wrinkle agents, vitamins (such as B3, B8, B12 and B9), desquamating agents, depigmenting agents, antioxidants, etc. .

For example, humectants (or humectants) that may in particular be mentioned include sorbitol, polyols, preferably C ₂ -C ₈ , and more preferably C ₃ -C ₆ polyols, preferably eg glycerol, propylene glycol, 1,3 -Butanediol, pentanediol, hexanediol, dipropylene glycol, diethylene glycol and diglycerol, mixtures thereof, glycerol and its derivatives, glycol ethers (especially containing 3 to 16 carbon atoms) , such as monopropylene glycol, dipropylene glycol or tripropylene glycol (C ₁ -C ₄ ) alkyl ethers, monoethylene glycol, diethylene glycol or triethylene glycol (C ₁ -C ₄ ) Alkyl ethers, urea and its derivatives, especially Hydrovance (2-hydroxyethylurea), lactic acid, hyaluronic acid, AHA, BHA, sodium pidolate, xylitol sold by National Starch , serine, sodium lactate, ectoin and its derivatives, chitosan and its derivatives, collagen, plankton, extracts of Imperata cylindra sold under the name Moist24 by the company Sederma, acrylic acid homopolymers, e.g. From NOF Corporation Beta-glucan and especially sodium carboxymethyl beta-glucan from Mibelle-AG-Biochemistry; sold by Nestle under the name Mixtures of passionflower oil, apriot oil, corn oil and rice bran oil sold; C-glycoside derivatives, such as those described in patent application WO 02/051 828, and especially in water/propylene glycol mixtures C-β-D-xylopyranoside-2-hydroxypropane in the form of a solution containing 30% by weight of active material in (60/40% by weight), as sold by Chimex under the trade name Manufactured product; musk rose oil sold by Nestle; spheres of collagen and chondroitin sulfate of marine origin (Atelocollagen) sold under the name Marine FillingSpheres by the company Engelhard Lyon; hyaluronic acid spheres such as by the company Engelhard Lyon Those sold; arginine, argan oil, and mixtures thereof.

Preferably, a humectant selected from the group consisting of glycerin, urea and their derivatives, sold especially by National Starch will be used C-glycoside derivatives, such as those described in patent application WO 02/051 828, and in particular C- β-D-Xylopyranoside-2-hydroxypropane, as sold by Chimex under the tradename Manufactured products; Argan oil and mixtures thereof.

More preferably glycerol will be used.

The humectant may be present in the composition in an amount ranging from 0.1% to 15% by weight, in particular from 0.5% to 10% by weight or even from 1% to 6% by weight, relative to the total weight of the composition.

Sunscreens (or sunscreens) are important skin care products used to prevent photoaging and skin cancer. There are two classes of sunscreens: UVA sunscreens, which generally block UV radiation in the wavelength range of 320 to 400 nm, and UVB sunscreens, which generally block radiation in the wavelength range of 290 to 320 nm.

The compositions of the invention comprise organic and/or inorganic UV sunscreen ingredients active in the UVA and/or UVB region, which are hydrophilic and/or lipophilic. In particular, the UV sunscreen composition of the present invention may have a solubility of 8.0 to 9.5. Such UV sunscreen ingredients have good plasticizer function.

Advantageously, the UV sunscreens of the invention may have a molecular weight of 150 to 500 g/mol and contain hydrophobic sites and benzene nuclei or electron resonance groups bound to polar sites.

Hydrophilic and/or lipophilic organic UV sunscreen ingredients are selected especially from dibenzoylmethane derivatives; cinnamic acid derivatives; salicylic acid derivatives; benzophenone derivatives; derivatives; para-aminobenzoic acid (PABA) derivatives; and mixtures thereof.

As examples of organic UV sunscreen ingredients, mention may be made of the following, indicated by their INCI names:

- p-aminobenzoic acid derivatives:

-PABA,

- PABA ethyl ester,

- dihydroxypropyl PABA ethyl ester,

- Ethylhexyl dimethyl PABA sold especially under the trademark "Escalol 507" by ISP,

- PABA glycerides,

-Dibenzoylmethane derivatives:

- Butylmethoxydibenzoylmethane sold especially under the trademark "Parsol 1789" by Hoffmann-LaRoche,

- Isopropyldibenzoylmethane,

- Salicylic acid derivatives:

- Homosalate sold under the trademark "Eusolex HMS" by Rona/EM Industries,

- Ethylhexyl salicylate sold under the trademark "Neo Heliopan OS" by Haarmann and Reimer,

- Dipropylene glycol salicylate sold under the trademark "Dipsal" by Scher,

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

- Cinnamic acid derivatives:

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

- Isopropyl methoxycinnamate,

- Isoamyl methoxycinnamate sold under the trademark "Neo Heliopan E 1000" by Haarmann and Reimer,

- Cinoxate,

- DEA methoxycinnamate,

- Diisopropyl methyl cinnamate,

- Glyceryl ethylhexanoate dimethoxycinnamate,

-β,β-Diphenylacrylate derivatives:

- octocrylene sold by BASF especially under the trademark "Uvinul N539";

- etocrylene sold under the trademark "Uvinul N35" by BASF,

- Benzophenone derivatives:

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

- Benzophenone-2 sold under the trademark "Uvinul D50" by BASF,

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

- Benzophenone-4 sold under the trademark "Uvinul MS40" by BASF,

- Benzophenone-5,

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

and their mixtures.

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

Preferred UV sunscreen ingredients are especially selected from ethylhexyl methoxycinnamate, octocrylene and ethylhexyl salicylate, and mixtures thereof.

Special mention may be made by BASF Corporation under the trade name Ethylhexyl methoxycinnamate sold under the trade name Ethylhexyl salicylate sold by the company SYMRISE under the trade name octocrylene for sale.

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

Anti-wrinkle agents: Mention may be made of ascorbic acid and its derivatives, such as magnesium ascorbyl phosphate and ascorbyl glucoside; tocopherol and its derivatives, such as tocopheryl acetate; niacin and its precursors, such as niacinamide; ubiquinone; Glutathione and its precursors, such as L-2-oxothiazoline-4-carboxylic acid; C-glycosidic compounds and their derivatives, as described inter alia in: Plant extracts, and especially sea fennel and olive leaf extracts; and also vegetable proteins and their hydrolysates, such as rice or soybean protein hydrolysates; seaweed extracts, and especially extracts of kelp; bacterial extracts; sapogenins, such as dioscin Dioscorea and extracts of plants of the genus Dioscorea containing sapogenins, especially wild yam; alpha-hydroxy acids; beta-hydroxy acids such as salicylic acid and 5-n-octanoyl salicylic acid; oligopeptides and pseudodipeptides and their acyl derivatives, especially {2-[acetyl-(3-trifluoromethylphenyl)amino]-3-methylbutyrylamino}acetic acid and Sederma under the trade names Matrixyl500 and Lipopeptide sold in Matrixyl 3000; lycopene; manganese and magnesium salts, especially manganese and magnesium gluconate; and mixtures thereof;

Peeling agents: mention may be made of beta-hydroxy acids, especially salicylic acid and its derivatives other than 5-n-octanoylsalicylic acid; urea; glycolic, citric, lactic, tartaric, malic or mandelic acids; 4-(2-Hydroxyethyl)piperazine-1-propanesulfonic acid (HEPES); Saphora japonica extract; honey; N-acetylglucosamine; sodium methylglycine diacetate, alpha-hydroxy acid ( AHA), beta-hydroxy acids (BHA), and mixtures thereof;

Depigmenting agents: mention may be made of ceramides, vitamin C and its derivatives, especially vitamin CG, vitamin CP and 3-O ethyl vitamin C; alpha- and beta-arbutin; ferulic acid; kojic acid; m-benzene Diphenols and their derivatives; calcium D-pantetheinate; lipoic acid; ellagic acid; vitamin B3; phenylethylresorcinol, e.g. from the company Symrise Kiwifruit (Actinidia chinensis) juice sold by Gattefosse, peony (Paeonia suffructicosa) root extract as sold by the company Ichimaru Pharcos under the name Products sold, brown sugar (Sugar cane, Saccharum officinarum) extract, such as molasses extract sold under the name Molasses Liquid by the company Taiyo Kagaku, a mixture of undecylenic acid and undecylenoylphenylalanine, such as from Seppic of

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

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

1-6. Preparation and Properties of Compositions

The composition of the present invention can be prepared by mixing the above-mentioned ingredients according to a conventional method. Conventional methods include mixing with a high pressure homogenizer (high energy method). Alternatively, the composition can be prepared by low energy methods such as phase change temperature method (PIT), phase change concentration (PIC), self-emulsification, and the like. Preferably, the compositions are prepared by low energy methods.

The ratio of nonionic surfactant to oil may be from 0.25 to 6, preferably from 0.3 to 3, and more preferably from 0.4 to 1.5.

The compositions of the invention are in the form of nanoemulsions or microemulsions. "Microemulsion" can be referred to in two ways, namely in a broader sense and in a narrower sense. That is, there is a case where a microemulsion refers to a thermodynamically stable isotropic single liquid phase comprising a ternary system having three components of an oily component, an aqueous component, and a surfactant ("in the narrow sense Microemulsions"), and another case where, in typical emulsion systems that are thermodynamically unstable, microemulsions additionally include those such emulsions that, due to their smaller particle size, exhibit a transparent or translucent appearance ("Microemulsion in a broad sense") (Satoshi Tomomasa et al., Oil Chemistry, Vol. 37, No. 11 (1988), pp. 48-53). "Microemulsion" as used herein refers to a "microemulsion in the narrow sense", ie a thermodynamically stable isotropic single liquid phase.

Microemulsion refers to an O/W (oil-in-water) type microemulsion in which oil is dissolved through micelles, a W/O type (water-in-oil) type microemulsion in which water is dissolved through reverse micelles, or a surfactant molecule in which Any state in a bicontinuous microemulsion in which the number of associations becomes so large that both the water phase and the oil phase have a continuous structure.

The microemulsion may have a dispersed phase having a number average diameter measured by laser granulometry of 100 nm or less, preferably 50 nm or less, and more preferably 20 nm or less.

"Nanoemulsion" here means an emulsion characterized by a dispersed phase having a size of less than 350 nm, which is passed through a non-ionic surfactant which may optionally form a lamellar-type liquid crystal phase at the dispersed phase/continuous phase interface The crown (crown) to stabilize. In the absence of specific opacifying agents, the transparency of nanoemulsions results from the small size of the dispersed phase, which is obtained by means of the use of mechanical energy and in particular a high-pressure homogenizer.

Nanoemulsions can be distinguished from microemulsions by their structure. In particular, microemulsions are thermodynamically stable dispersions formed, for example, of oil-filled micelles of nonionic surfactants. Furthermore, microemulsions do not require large amounts of mechanical energy to prepare.

The microemulsion may have a dispersed phase having a number average diameter measured by laser granulometry of 300 nm or less, preferably 200 nm or less, and more preferably 150 nm or less.

The composition of the invention may be in the form of an O/W nano- or micro-emulsion, a W/O nano- or micro-emulsion or a bicontinuous emulsion. Preferably, the composition of the invention is in the form of an O/W nanoemulsion or microemulsion.

In a preferred embodiment, the composition of the present invention may be in the form of an O/W emulsion. In this case, the oil may be in the form of droplets having a number average particle diameter of 300 nm or less, preferably 10 nm to 200 nm, and more preferably 20 nm to 150 nm.

The average size of the oil phase droplets was determined by light diffraction using a Mastersizer 2000 particle sizer (sold by Malvern Instruments). These assays were performed on emulsions diluted in a solution of 1% SDS (sodium dodecyl sulfate) in water. A computer program makes it possible to obtain the mean diameter D[4.3] (μm) by volume (see Operator's Guide, Malvern Instruments, December 1998, pp. 61-67).

The average size D[4.3] (μm) of the droplets of the oil phase of the composition of the invention is in the range of 10 nm to 150 nm, and more preferably 20 nm to 140 nm.

The compositions of the invention are particularly stable, especially during 2 months at room temperature and even at 37°C or 45°C, atmospheric pressure, and they exhibit optimal cosmetic properties. In fact, the compositions of the invention exhibit suitable fluidity: they are easy to handle and also easy to apply and spread on the skin.

These compositions also exhibit the desired texture for cosmetic use: they are not sticky, soft to the touch and impart a bouncy feel. Thus, the compositions of the present invention also have the advantage of meeting consumer expectations in terms of cosmetic properties such as lower viscosity and better emolliency.

The compositions of the present invention may be "color changing compositions". The term "color changing composition" refers to a composition in which the color before application differs 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 ΔE according to the CIE Laboratory System 1976 (ΔE before/after application) value. ΔE is defined by the equation:

[Math.1]

${\mathrm{<span\; class="notranslate">\; \&Delta;E</span>}}^{<span\; class="notranslate">\; *</span>}<span\; class="notranslate">\; =</span>\sqrt{<span\; class="notranslate">\; (</span>{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; L</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; L</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; a</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; a</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; b</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; b</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}<span\; class="notranslate">\; :</span>$

where L ₁ , a ₁ , b ₁ are parameters in the chromaticity space of the first color (the composition before application), and L ₂ , a ₂ , b ₂ are the second color (after application to the keratin material and Composition after homogenization on keratin material) parameters. These values can be determined spectrophotometrically or using a Chromasphere (for compositions applied to the skin). The color changing composition of the invention may be characterized as having a pre-application/post-application ΔE greater than 1, especially greater than or equal to 2, preferably greater than or equal to 3.

The compositions of the invention may have a transparent or slightly translucent appearance, preferably a transparent appearance. In other words, the compositions of the present invention comprise microcapsules comprising a releasable colorant in a transparent medium.

Transparency can be measured by measuring transmittance in the visible region with an absorption spectrometer (for example, transmittance as an average of visible light transmittance (between 400 and 800 nm) is measured with a V-550 (JASCO) having a 2 mm wide cell) . The assays are performed on undiluted compositions. Blanks were determined with distilled water.

The compositions of the invention may preferably have a transparency of greater than 50%, preferably greater than 60%, more preferably greater than 70%, and even more preferably greater than 75%.

In a preferred embodiment, the composition of the invention comprises microcapsules; preferably unpigmented microcapsules, 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 750 nm without scattering light, i.e. wherein the light is scattered at an angle of less than 50° and better about 5° combination. The transparent composition transmits at least 50%, especially at least 60% and especially at least 70% of light having a wavelength of 750 nm.

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

- Pour the composition into a square-sided spectrophotometer cuvette with a side length of 10 mm;

-then, keep the composition sample in a thermostatic chamber at 20°C for 24 hours;

- then, on a spectrophotometer, the light transmitted through the sample of the composition is measured by scanning wavelengths in the range from 700 nm to 800 nm, this determination being carried out in transmission mode;

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

Transparent compositions, when they are placed 0.01m in front of a black line with a diameter of 2mm thick drawn on a white paper, allow the line to be seen; line is seen.

The compositions of the invention, preferably cosmetic foundations or skin coloring products, provide an intense moisturizing feel, a creamy texture with a very pleasant feel during application and a completely natural cosmetic result after application. In the end, all these characteristics help to provide a very good balance of skin care efficacy perception (creaminess and moisturizing) and cosmetic efficacy (decent coverage and natural shine). In addition, the compositions of the present invention can exhibit a light-shielding effect. Advantageously, the microcapsules are deformable in the presence of an aqueous phase. Advantageously, the microcapsules inside the composition are breakable under the pressure applied to the keratin material.

2. Methods and uses

The present invention also relates to a cosmetic method of applying the composition described above to the skin, hair, mucous membranes, nails, eyelashes, eyebrows or scalp.

The present invention also relates to the composition described hereinbefore as or for use as a care product for body and/or face skin and/or mucous membranes and/or scalp and/or hair and/or nails and/or eyelashes and/or eyebrows and and/or use of cleansing products and/or makeup products and/or makeup removers.

In other words, the composition of the present invention can be used as the above products as they are. Alternatively, the composition of the present invention may be used as an element of the above products. For example, the compositions of the present invention may be added to or combined with any other ingredients to form the above products.

These compositions are prepared according to conventional methods. Compositions of this type may be in the form of face and/or body care or cosmetic products, and may be formulated, for example, as a cream in a jar or as a fluid in a tube or pump bottle.

In particular embodiments, the composition comprises at least one neutralized 2-acrylamido-2-methylpropanesulfonic acid polymer and copolymer and a polysaccharide biopolymer.

The expression "transparent aqueous medium" means a medium which allows light to pass through without causing deviations by refraction or reflection. The clarity of aqueous media can be determined using a nephelometer. For example a portable Model to determine the transparency range of the composition. The composition is considered transparent when the turbidity measurement is between 0 and 250 NTU, and translucent for turbidity values between 250 and 1000 NTU.

When placed in front of a 0.01 m thick black line of 2mm diameter drawn on white paper, this composition reveals the black line, in contrast to the opaque composition, that is to say the opaque composition will not reveal the black line. The compositions of the invention preferably comprise water and multilayered microcapsules comprising a releasable colourant. In a preferred embodiment, the composition according to the invention comprises at least one hydrophilic or lipophilic gelling agent and at least one water-soluble emollient and/or lipid with polar moieties. In a preferred embodiment, the composition of the invention comprises at least two types of different multilayered microcapsules comprising a releasable colorant.

The microcapsules can be introduced with gentle agitation in the final step without destroying the microcapsules after preparation of the gel.

The transparent composition with microcapsules thus obtained exhibited a pure and clean appearance at -20/20°C (5 cycles), room temperature (25°C, 2 months), 37°C (2 months) and 45°C ( 2 months), perfect stability at atmospheric pressure. The microcapsules release the pigment without feeling any particles during application. Provides a flawless and even makeup result after application.

The compositions of the invention are preferably clear, and may also be slightly colored. In this case, the composition according to the invention comprises at least one non-entrapped colorant, preferably in an amount of less than 1% by weight, based on the total weight of the entire composition.

The compositions of the invention may also be in the form of gel creams or emulsifying gels comprising oils and surfactants.

In another embodiment, the invention relates to a kit comprising one of the above defined products and an applicator. The applicator may be selected from conventionally used applicators.

Compositions of the invention can be applied, for example, with the fingers or using an applicator. The container is preferably used in combination with an applicator comprising at least one application component configured to apply said composition to keratinous substances.

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

Throughout the specification (including the claims), the terms "comprising a" and "comprising a" are to be understood as being synonymous with "comprising at least one" and "comprising at least one", respectively, unless mentioned otherwise.

The terms "between" and "from to" are to be understood as including upper and lower limits unless specified otherwise.

The invention is illustrated in more detail by the following examples. Unless mentioned otherwise, the indicated amounts are expressed as mass percent of active material.

Example

The present invention will be described in more detail by way of examples, however, the examples should not be construed as limiting the scope of the present invention.

recipe example

1: SUNSOFT A-121E (provided by Taiyo Kagaku)

2: MAGIC30-BW0105 (provided by KPT)

(1) Preparation of the composition

Preparation Example 1 and Comparative Example 1 according to the following methods:

Prepare the oil phase (mixture of ethylhexyl palmitate + polyglyceryl-5 laurate + preservatives) and heat the oil phase to about 75°C. Next, an aqueous phase (water+sodium methylstearyl taurate+glycerin+butylene glycol) was prepared, and the aqueous phase was heated to about 75°C. Then, add the water phase to the oil phase. After complete emulsification, the thickener phase (Acrylates/C10-30 Alkyl Acrylate Crosspolymer) was added to the mixture. Then, the mixture was cooled to room temperature. For Example 1, MAGIC30-BW0105 was added to the mixture at room temperature.

Comparative Example 2 was prepared according to the following method:

Prepare the aqueous phase (water+glycerin+butanediol) and heat the aqueous phase to about 75°C. Add the thickener phase (Acrylates/C10-30 Alkyl Acrylate Crosspolymer) to the mixture. The mixture was then cooled to room temperature. Add MAGIC30-BW0105 to the mixture at room temperature.

(2) Evaluation of technical effects

(i) Observation (appearance)

Appearance was evaluated by visual observation.

(ii) Transparency of bodies without MAGIC30-BW0105

Transparency was measured using a V-550 (JASCO) with a 2 mm wide cell. Transparency = average of visible light transmission (between 400 and 800 nm).

(iii) Particle size

The particle size was measured under undiluted conditions using VASCO-2 (CORDOUAN TECHNOLOGIES). A computer program makes it possible to obtain the mean diameter by specifying the intensity.

(iv) Coverage

in black Applied color was determined at 1 mg/cm ³ thickness (thickness). This value is displayed by ΔL*. The lower the ΔL* value, the greater coverage is achieved.

(v) Sensory test

In order to evaluate cosmetic properties, a sensory test was conducted by 5 panelists. Panelists rated each composition on a 5-point scale for emolliency and moisture.

Emollient

5: very emollient

4: Quite emollient

3: Moisturizing

2: Non-emollient

1: Very non-emollient (skin feels rather hard)

humidity

5: very wet

4: fairly wet

3: wet

2: not wet

1: very dry

Table 1

Modes of application to keratin materials have observed technical effects

As is clear from the above results, the cosmetic composition in the form of an O/W emulsion according to the present invention was found to have smaller oil droplets, and thus, provided an appearance with better transparency in the presence of microcapsules.

Comparative Example 1 is a formulation for comparison with Example 1, in that Comparative Example 1 has no microcapsules. From the comparison between Example 1 and Comparative Example 1, it can be concluded that Example 1 according to the present invention obtains a transparent gel in the presence of microcapsules, and the transparency is equivalent to the formulation without microcapsules. The particle size of Example 1 is below 150nm, and the composition is a nanoemulsion.

Comparative Example 2 is a formulation containing an aqueous clear gel. This means that Example 1 (clear nanoemulsion gel) outperforms Comparative Example 2 (clear aqueous gel) in terms of coverage and sensory properties (emollient and wetness).

Claims (22)

1. nanoemulsions or the compositions of microemulsion form, comprising:

(a) at least one fat phase；

(b) at least one nonionic surfactant；

(c) at least one comprise the microcapsule of releasable coloring agent；With

(d) at least one aqueous phase.

Compositions the most according to claim 1, it is o/w emulsion.

Compositions the most according to claim 1 and 2, it also includes at least one polyhydric alcohol, is preferably selected from Glycerol and dihydroxylic alcohols, more preferably propylene glycol, butanediol, pentanediol, hexanediol, dipropylene glycol, a contracting Diethylene glycol, Sensiva SC50, Flos Magnoliae glycol, glycol ethers, preferably MPG, dipropylene glycol or Alkyl (the C of tripropylene glycol₁-C₄) ether or the alkyl of monoethylene glycol, diglycol or triethylene-glycol (C₁-C₄) ether, and mixture, the most described polyhydric alcohol is glycerol and/or butanediol.

Compositions the most according to any one of claim 1 to 3, wherein said nonionic surfactant Selected from single oxygen alkylene or polyoxyalkylenated fatty acid ester, polyglyceryl fatty acid ester surfactant and sugar particularly sugarcane The fatty acid ester of sugar.

Compositions the most according to claim 4, wherein said polyglyceryl fatty acid ester has derived from 4 to 6 The polyglycereol part of individual glycerol, more preferably 5 or 6 glycerol.

Compositions the most according to any one of claim 1 to 5, wherein total relative to described compositions Weight, the amount of nonionic surfactant be 0.1 weight % to 30 weight %, preferably 0.5 weight % to 15 weight %, And more preferably 1 weight % to 10 weight %.

Compositions the most according to any one of claim 1 to 6, wherein said fat include mutually oil phase and Described grease separation, from vegetable oil, animal oil, mineral oil, artificial oil, silicone oil and hydrocarbon ils, is preferably selected from ester oil, ether Oil, alkane oil, the hydrocarbon ils of triglyceride oil, even more preferably have the oil of the molecular weight of less than 700.

Compositions the most according to claim 7, wherein relative to the gross weight of described compositions, described oil Amount be 0.1 weight % to 50 weight %, preferably 0.5 weight % is to 40 weight %, and more preferably 5 weight % are to 30 Weight %.

Compositions the most according to any one of claim 1 to 8, it also includes thickening agent, preferably selects From:

(i) associative thickeners；(ii) acrylate homopolymer cross-linked；(iii) (methyl) acrylic acid and (C₁-C₆) alkyl The copolymer of the crosslinking of acrylate；(iv) ethylenic beta-unsaturated esters monomer and ethylenic unsaturated amides list are comprised The nonionic homopolymer of at least one in body and copolymer；(v) acrylate homopolymers and ammonium acrylate and third The copolymer of acrylamide；(vi)C₁₂-C₃₀Fatty alcohol；(vii) (not) modified carboxy vinyl polymer；(viii) poly-first Base acrylate；(ix) polyacrylamide, optionally crosslinking；X 2-acrylamido-2-methyl-prop sulphur that () neutralizes Acid polymer and copolymer；(xi) anionic copolymer of the crosslinking of acrylamide and AMPS, it is W/O Emulsion form；(xii) polysaccharide biopolymer；(xiii) cellulose, is more preferably selected from (i) associative thickeners, (vii) (not) modification carboxy vinyl polymer and (ix) polysaccharide.

Compositions the most according to any one of claim 1 to 9, wherein total relative to described compositions Weight, water with in 5 weight % to 99 weight %, preferably 10 weight % to 95 weight % and even more preferably 15 weight % Amount to 90 weight % exists.

11. compositionss according to any one of claim 1 to 10, wherein said microcapsule includes:

(A) core, the most uncoloured core, it includes a kind of organic material, and

(B) surround at least one stratiform coating of described core, layered coating include at least one polymer, At least one coloring agent and advantageously at least one binding agent.

12. according to the compositions according to any one of claim 1 to 11, relative to the gross weight of described compositions Amount, it include 0.1 weight % to 20 weight %, and preferably 0.5 weight % is to 15 weight %, and more preferably 2 weight % To (c) microcapsule described in 10 weight %.

13. according to the compositions according to any one of claim 1 to 12, wherein said (c) microcapsule described Core includes that at least one monosaccharide or derivatives thereof, as described organic material, is particularly advantageously selected from mannose Monosaccharide-the polyhydric alcohol of alcohol, erythritol, xylitol, Sorbitol and mixture thereof, preferably mannitol.

14. at least wrap according to the compositions according to any one of claim 1 to 13, wherein said (c) microcapsule Include:

-the kernel be made up of the preferred mannitol of monosaccharide-polyhydric alcohol,

-there is at least two layer of mutually different colors,

-at least one hydrophilic polymer, is preferably selected from polysaccharide or their derivant, and is more preferably selected from Starch or derivatives thereof, and advantageously at least one material based on lipid, preferably amphipathic compound, more preferably Phospholipid, and even more preferably phosphate acyl glycerol such as hydrolecithin.

15. include according to the compositions according to any one of claim 1 to 14, wherein said (c) microcapsule:

A) core (A), preferably has diameter less than 800 μm, more preferably less than about 400 μm, is advantageously 1 μm To 300 μm, 5 μm to 200 μm especially, and the size of even more particularly 10 μm to 100 μm, it is excellent Choosing does not comprise any coloring agent, and includes at least one organic core, is preferably selected from least one sugar alcohol, preferably has Sharply selected from mannitol, erythritol, xylitol and the monosaccharide-polyhydric alcohol of Sorbitol；

B) ground floor (B) of described core is surrounded, comprising:

-at least one coloring agent, preferably iron oxides, and

-binding agent, it is selected from polymer and material based on lipid, preferably their mixture；

C) surround a second layer (C) of described ground floor (B), preferably there is 5 μm thickness to 500 μm, Comprising:

-titanium dioxide granule, and

-binding agent, it is selected from polymer and material based on lipid, preferably their mixture；

D) an optional third layer (D) of the described second layer (C) is surrounded, comprising:

-at least one coloring agent, and

-binding agent, it is selected from polymer and material based on lipid, preferably their mixture；

E) described third layer (D) is surrounded, if any, or surround optional one of the described second layer (C) 4th layer (E), comprising:

-at least one wall-forming polymer, it is preferably selected from polysaccharide such as cellulose derivative, particularly cellulose Ether and cellulose esters, selected from (gathering) (alkyl) (methyl) acrylic acid and derivant thereof, especially (gather) (alkyl) (methyl) Acrylate and derivant thereof, and be preferably selected from alkyl acrylic/alkyl methacrylate copolymer and they Derivant.

16. according to the compositions according to any one of claim 1 to 15, the institute within wherein said compositions It is rupturable for stating microcapsule under the pressure being administered to keratin material.

17. according to the compositions according to any one of claim 1 to 16, the most described microcapsule total Weight, described core represents 10 weight % to 90 weight %, preferably 20 weight % to 80 weight %, more preferably 30 weights Amount % to 70 weight %, and even more preferably 40 weight % to 60 weight %.

18. according to the compositions according to any one of claim 1 to 17, the most described microcapsule, Described coloring agent represents 20 weight % to 90 weight %, and preferably 30 weight % are to 80 weight %；And especially 50 weight % are to 75 weight %.

19. according to the compositions according to any one of claim 1 to 18, present in wherein said microcapsule Described coloring agent, selected from inorganic pigment, organic pigment and their mixture, is preferably at least a kind of inorganic pigment, The more preferably at least mixture of inorganic pigment, even more preferably selected from metal-oxide, and in particular selected from ferrum oxygen Compound, titanium dioxide granule and their mixture, preferably their mixture.

20. compositionss according to any one of claim 1 to 10, wherein said microcapsule includes:

(A) core, preferably has the size in 20 μm to 800 μ m, and it includes at least one coloring agent Preferably at least a kind of binding agent, described coloring agent preferably includes to be preferably selected from least one nothing of iron oxides Machine pigment, and

(B) surrounding the parietal layer crushed of described core, it includes at least one coloring agent and preferably at least Planting binding agent, described coloring agent preferably at least includes titanium dioxide granule,

Wherein, compared with the gross weight of described microcapsule, described microcapsule includes the coloring of at least 70 weight % Agent.

21. according to the compositions according to any one of claim 1 to 20, at least the one of wherein said microcapsule Individual layer is obtained by bed process.

22. for nursing and/or the cosmetic method of keratin material of making up, and it includes according to claim 1 It is administered on described keratin material particularly on skin to the compositions any one of 21.