FR2848421A1 - Cosmetic composition in the form of a water-in-oil-in-water emulsion, useful as a make-up product, comprises a pigment dispersed on one or both aqueous phases in the presence of a dispersant - Google Patents

Abstract

Cosmetic composition in the form of a water-in-oil-in-water emulsion comprises a pigment dispersed on one or both aqueous phases in the presence of a dispersant. An Independent claim is also included for production of a composition in the form of a triple emulsion by dispersing an aqueous phase in an oil phase to form a primary emulsion and dispersing the primary emulsion in an aqueous phase, where a pigment paste comprising 30-85 wt.% pigment and 0.1-5 wt.% dispersant is predispersed on one or both aqueous phases in an amount of 1-15% by weight of the emulsion.

Description

<Desc / Clms Page number 1>

 The present invention relates to a cosmetic composition in the form of a multiple emulsion comprising at least one internal aqueous phase, an intermediate oily phase and an external aqueous phase, and at least one pigment dispersed in the presence of a dispersant in the aqueous phase. internal and / or external. The invention also relates to a process for preparing the composition. This composition is particularly intended for the makeup of keratin materials, especially the skin, as well as the face of the human body, eyelashes, eyebrows, lips, or the nails of human beings.

 Multiple emulsions such as triple water-oil-water emulsions are emulsions in which water microglobules (internal phase) are encapsulated in oil globules (intermediate phase) themselves dispersed in an aqueous medium (external phase ).

 The triple water-oil-water emulsions make it possible to introduce active compounds or various ingredients into the different phases separately without being in direct contact in the same phase. But these emulsions are difficult to achieve especially because of stability problems over time. These problems occur particularly when we introduce conventional pigments whose particles agglomerate and form large aggregates that destabilize the emulsion. The destabilized triple emulsion then loses its multiple character and is found in the form of a simple water-in-oil emulsion. The risk of destabilization increases with the content of pigments.

 It has already been attempted to introduce solid particles such as pigments or fillers into the aqueous phases of a multiple emulsion, but the introduction of these solid particles frequently leads to problems of instability by re-agglomeration of the particles. especially when the solid particle content is high.

 Also, patent FR 92/08532 describes a cosmetic composition in the form of triple water / silicone oil / gelled water emulsion. The description

<Desc / Clms Page number 2>

 exemplifies a tinted triple emulsion for the face, containing 0.14% by weight of pigments in the internal aqueous phase.

 GB 2 242 358 discloses a composition comprising an aqueous gel in which a water-in-oil emulsion is introduced to form an immiscible mixture. Pigments are dispersed in the aqueous gel at a content of less than 0.1% by weight of the total weight of the composition.

 The object of the invention is therefore to obtain multiple emulsions, in particular triple emulsions, comprising at least one aqueous phase in which are dispersed pigments, which are stable, even for high levels of pigment. In particular, tinted multiple emulsions which are stable at 25 ° C. for two months are sought.

 It has surprisingly been found that it is possible to formulate a cosmetic composition which overcomes the drawbacks of the prior art by dispersing in the internal and / or external aqueous phase a multiple emulsion of the pigments in the presence of dispersant, in particular in the presence of using an aqueous pigment paste comprising from 30% to 80% by weight of at least one pigment based on the total weight of the pigment paste and a dispersant.

 The invention therefore relates to a cosmetic composition in the form of a multiple emulsion comprising at least one internal aqueous phase, an intermediate oily phase and an external aqueous phase and at least one pigment dispersed in the internal and / or external aqueous phase of the aqueous phase. emulsion, characterized in that the pigment is dispersed in the presence of a dispersant.

 The invention also relates to a process for preparing such an emulsion.

 By multiple emulsion comprising an internal aqueous phase, an intermediate oily phase and an external aqueous phase is meant an emulsion emulsion in which micro-globules of water are dispersed in globules of oils, themselves dispersed in a aqueous medium.

<Desc / Clms Page number 3>

Advantageously, the multiple emulsion is a triple water-in-oil-in-water emulsion.

 The pigments may be all pigments conventionally used for the formulation of cosmetic compositions. The pigments can be inorganic, organic or pigmented materials.

 Among the inorganic pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, and chromium hydrate. and ferric blue. In particular, mention may be made of TiO 2, FeO, Fe 2 O 3, Fe 3 O 4, FeO (OH), ZnO, Cr 2 O 3, ZrO 2, V 2 O 5, Nb 2 O 5, and mixtures thereof.

 Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, or aluminum.

 Among the pigmented materials, mention may be made of pearlescent pigments which may be chosen from white pearlescent pigments, such as titanium-coated mica, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type.

 The pigment advantageously has an average particle size of less than or equal to 5 m.

 The pigment is dispersed in the inner and / or outer aqueous phase in the presence of a dispersant.

 The dispersant has the function of dispersing the pigment particles in the aqueous phase and protecting the dispersed pigment particles against agglomeration or flocculation. The pigment thus dispersed does not form aggregates greater than 20 m in size which destabilize the multiple emulsion. The dispersant may be a surfactant, an oligomer, a polymer or a mixture of several of them, bearing one or more groups having a strong affinity for the surface of the particle to be dispersed.

<Desc / Clms Page number 4>

 Among the dispersants that are suitable for the present invention, mention may be made of: the sodium salt of the maleic anhydride / diisobutylene copolymer sold under the name OROTAN 731 DP by the company Rohm & Haass, the methacrylic acid / methyl methacrylate copolymer sold under the name "ARLATONE 3315" by the company Uniquéma, the sorbitan monostearate oxyethylenated with 20 moles of ethylene oxide sold under the name "Polysorbate 80" by the company Wackherr.

 Such dispersants are commonly used for the preparation of aqueous pigment paste.

 In order to produce the inner and / or outer aqueous phase of the multiple emulsion according to the invention, it is possible to use an aqueous pigment paste containing the pigment and the dispersant.

 The term "aqueous pigment paste" means a concentrated, stable colloidal dispersion of pigments in an aqueous continuous medium, or dispersion medium.

 The colloidal dispersion may or may not comprise one or more dispersing agents promoting the stability of the dispersion.

 The term concentrated colloidal dispersion is understood to mean a suspension of particles of micron size, that is to say less than or equal to 5 m, in particular ranging from 500 nm to 5 m, in an aqueous continuous medium.

 The aqueous continuous medium may be water or a mixture of water and a water-miscible organic solvent at 25 ° C., such as polyols having from 2 to 8 carbon atoms, such as glycerine, glycol or propylene glycol. , butylene glycol. A water-glycerin mixture is preferably used.

 The pigment paste may comprise from 30% to 85% by weight, preferably from 50% to 75% by weight, of at least one pigment relative to the total weight of the pigment paste. It may also comprise from 0.1% to 5% by weight, preferably from 0.1% to 2% by weight, of dispersant, relative to the total weight of the pigment paste.

<Desc / Clms Page number 5>

 Pigment pastes are especially described in EP-A-974628, US-B-5663224, US-B-4089699.

 The multiple emulsion according to the invention may comprise from 0.3% to 12.75% by weight of pigment, based on the total weight of the emulsion, and preferably from 1% to 7.5% by weight.

 The multiple emulsion may comprise from 0.1% to 0.75% by weight of dispersant, based on the total weight of the emulsion, and preferably from 0.2% to 0.375% by weight.

 The multiple emulsion comprises a water-in-oil (W / O) primary emulsion and an external aqueous phase.

 The inner aqueous phase and the intermediate oily phase of the multiple emulsion constitute a primary water-in-oil emulsion. This primary emulsion preferably represents from 5% to 80% by weight of the total emulsion and in correspondence, the external aqueous phase then preferably represents from 20% to 95% by weight of the total emulsion.

 The primary emulsion comprises an oily phase and an internal aqueous phase. According to a preferred embodiment, the internal aqueous phase represents from 10% to 80% by weight of the primary emulsion and in correspondence, the oily phase then represents from 20% to 90% by weight of the primary emulsion.

 The internal aqueous phase of the primary emulsion according to the invention may comprise a stabilizing agent which may be chosen from salts, polyols, especially glycols, and sugars. The stabilizing agent modifies the osmotic pressure of the internal aqueous phase.

 The salts may especially be alkali metal or alkaline earth metal salts, and especially chlorides, sulphates, borates or citrates of alkali metal or alkaline earth metal. As a stabilizing agent, it is possible to use magnesium sulphate, sodium chloride, potassium chloride and sodium citrate.

 The glycols may be especially glycerine, butylene glycol, propylene glycol.

<Desc / Clms Page number 6>

 The stabilizing agent may be present in the composition in a content ranging from 0.01% to 10% by weight, relative to the total weight of the emulsion, and preferably ranging from 0.1% to 5% by weight.

 The oily phase may contain at least one oil chosen from oils of mineral, vegetable, animal, synthetic origin, in particular a hydrocarbon and / or silicone and / or fluorinated oil, and mixtures thereof.

 As oils that can be used in the composition of the invention, mention may be made, for example, of: hydrocarbon-based oils of animal origin, such as perhydrosqualene; hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn or soybean oils, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor oil, avocado, triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names Miglyol 810,812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil; linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®; isoparaffins such as isohexadecane and isodecane.

esters and synthetic ethers, in particular of fatty acids, such as the oils of formulas R1COOR2 and R'OR2 in which R1 represents the residue of a fatty acid comprising from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain , branched or unbranched, containing from 3 to 30 carbon atoms, for example purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, stearate of octyl-2-dodecyl, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate,

<Desc / Clms Page number 7>

 octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetraisostearate; fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-n-butylpentadecanol, oleic alcohol or linoleic alcohol; alkyl and especially ethoxylated fatty alcohols such as oleth-12; partially fluorinated hydrocarbon oils and / or silicone oils such as those described in document JP-A-2-295912; as fluorinated oils, mention may also be made of perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names "FLUTEC PC1" and "FLUTEC PC3" by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names "PF 5050" and "PF 5060" by the company 3M, or bromoperfluorooctyl sold under the name "Foralkyl" by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 5052" by the company 3M; silicone oils such as volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular cyclopoly-dimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones,

<Desc / Clms Page number 8>

 diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes; - their mixtures.

 Preferably, the oily phase contains at least one C10-C20 alkane, for example isohexadecane.

 The oily phase may also contain one or more emulsifiers intended to stabilize the primary emulsion W / H, called the first emulsifier.

The first emulsifier may be chosen from emulsifiers having a HLB (hydrophilic / lipophilic balance) of less than or equal to 6, in particular ranging from 4 to 6. Examples of the first emulsifiers include fatty esters of polyol, in particular glycerol or sorbitol, and in particular isostearic, oleic and ricinoleic esters of polyol, such as the mixture of petrolatum, polyglyceryl-3 oleate, glyceryl isostearate, hydrogenated castor oil and ozokerite, sold under the name Protegin W # by GOLDSCHMIDT, sorbitan isostearate, polyglyceryl diisostearate, polyglyceryl-2 sesquioisostearate; ose esters and ethers such as "Methyl glucose dioleate"; fatty esters such as magnesium lanolate; dimethicone copolyols and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Coming 5200 Formulation Aid by the company Dow Corning and cetyl dimethicone copolyol sold under the name Abil EM 90 # by the company GOLDSCHMIDT; and their mixtures.

 The emulsifiers for stabilizing the primary emulsion W / O preferred according to the invention are dimethicone copolyols, better alkyl dimethicone copolyols of general formula:

<Desc / Clms Page number 9>

dans laquelle : p est un entier de 7 à 17 x est un entier de 1 à 100 y est un entier de 1 à 40 z est un entier de 0 à 200
PE est (C2H40)a-(C3H6O)b-H de poids moléculaire compris entre 250 et 2000.

where: p is an integer from 7 to 17 x is an integer from 1 to 100 y is an integer from 1 to 40 z is an integer from 0 to 200
PE is (C2H40) a- (C3H6O) bH of molecular weight between 250 and 2000.

 The oily phase of the triple emulsion may comprise a wax, thickeners of oily media well known to those skilled in the art.

 According to another embodiment of the invention, the external aqueous phase of the emulsion is gelled and contains at least one gelling agent.

 Gelling agents of the aqueous phases are well known in the art. There may be mentioned in particular carboxyvinyl polymers and copolymers, (alkyl) acrylic polymers and copolymers, (alkyl) acrylamide polymers and copolymers, biosaccharides, polysaccharides, cellulosic polymers, natural gums such as xanthan gums, guar, carob, scleroglucans, chitin or chitosan derivatives, carrageenans, clays, and mixtures thereof.

 As examples of aqueous phase gelling agents, SEPIGEL 305 sold by the company SEPPIC, FUCOGEL 1000 PP marketed by the company SOLABIA, SYNTHALEN K sold by the company 3V SA and LUVISKOL VA 64 P may be mentioned. marketed by the company BASF, the HOSTACERIN AMPS marketed by the company

<Desc / Clms Page number 10>

 CLARIANT, the PEMULENTR1 sold by the company GOODRICH, the LUBRAGEL MS marketed by the GUARDIAN company, the SATIAGEL # K80 marketed by the SANOFI company, the KELTROL marketed by the company KELCO.

 The gelling agent generally represents from 0.05% to 20% by weight of the aqueous phase, preferably from 0.5% to 10%.

The external aqueous phase of the triple emulsion may comprise one or more emulsifiers intended to stabilize the O / W emulsion, called the second emulsifier. The second emulsifier may be chosen from emulsifiers having an HLB of greater than or equal to 8, in particular ranging from 8 to 25. As examples of second emulsifiers, mention may be made, for example, of the following emulsifiers: * as amphoteric emulsifiers, N-acylamines amino acids such as
N-alkylaminoacetates and disodium cocoamphodiacetate and amine oxides such as stearamine oxide; as anionic emulsifiers, acylglutamates such as "disodium hydrogenated tallow glutamate" (Amisoft HS-21 marketed by the company AJINOMOTO); carboxylic acids and their salts such as sodium stearate; phosphoric esters and their salts such as "DEA oleth-10 phosphate"; sulfosuccinates such as "Disodium PEG-5 citrate lauryl sulfosuccinate" and "Disodium ricinoleamido MEA sulfosuccinate"; as cationic emulsifiers, alkylimidazolidiniums such as isostearyl ethylimidonium ethosulphate; ammonium salts such as N, N, N-trimethyl-1-docosanaminium chloride (Behentrimonium chloride); as nonionic emulsifiers, esters and ether esters such as sucrose stearate, sucrose cocoate, and the mixture of sorbitan stearate and sucrose cocoate sold by the company ICI under the name Arlatone 2121; polyol esters, especially glycerol or sorbitol, such as glyceryl stearate, stearate of

<Desc / Clms Page number 11>

 polyglyceryl-2, sorbitan stearate; glycerol ethers; oxyethylenated and / or oxypropylenated ethers, such as the oxyethylenated, oxypropylene ether of oxyethylenated lauric alcohol and oxypropylene groups (CTFA name "PPG-25 laureth-25") and the oxyethylenated ether of the mixture of C12-C15 fatty alcohols having 7 oxyethylenated groups (CTFA name "C12-C15 Pareth-7"); ethylene glycol polymers, such as PEG-100; block copolymers of ethylene oxide and propylene oxide, such as SYNPERONIC PE F127 sold by ICI; and their mixtures.

 According to a particular embodiment of the invention, the multiple emulsion defined above is a triple water-in-oil-in-water emulsion.

 The composition according to the invention may additionally contain conventional adjuvants such as perfumes, dyes, preservatives, sequestering agents (EDTA), pH adjusters (acids or bases), cosmetic active agents and mixtures thereof.

 By cosmetic active is meant a compound intended to improve the qualities of the skin, lips and integuments such as moisturizers (for example polyols and especially glycerine), sunscreens, vitamins (A, B3, C, E and F) and specific care assets (ahydroxyacids).

 These adjuvants may be present in amounts ranging preferably from 0.01 to 20% by weight relative to the total weight of the composition.

 The composition of the invention may be in the form of a makeup product, in particular a colored product, of the skin, in particular a tinted skincare cream, a foundation, optionally having care properties, a blush, a blush, an eyeliner, an eyeliner, an eyeliner; a lip makeup product such as a lipstick, possibly with care properties, a lip gloss, a lip pencil; a make-up product for integuments such as

<Desc / Clms Page number 12>

 nails, eyelashes especially in the form of a mascara and eyebrows in the form of a pencil; a body make-up product.

 The subject of the invention is also a process for preparing a composition in the form of a triple emulsion comprising the following steps: a) dispersion of at least one aqueous pigment paste (as defined above) in an aqueous phase phase phase internal and / or external aqueous; b) dispersing the internal aqueous phase comprising or not the aqueous pigment paste in an oily phase forming the intermediate oily phase to form a primary emulsion; c) dispersion of the primary emulsion in an aqueous phase forming the external aqueous phase comprising or not the aqueous pigment paste.

The dispersed aqueous pigment pastes may represent from 1% to 15% by weight of the total weight of the emulsion, and preferably from 2% to 10% by weight.

 The following example illustrates a cosmetic composition according to the invention.

Example 1 a) An aqueous pigment paste having the following composition (per 100 g) was prepared: - Uncoated brown iron oxide: 70 g - Water: 14.36 g - Glycerine: 14.35 g - Orotan 731 PD * from Rhom & Haas: 0.49 g - antifoam (BYK 024 from BYK CERA): g * maleic anhydride copolymer and diisobutylene in the form of sodium salt

<Desc / Clms Page number 13>

 b) Then a triple water-in-oil-in-water emulsion was prepared, the inner aqueous phase of which comprises the pigment paste.

The composition of the emulsion is given in Table 1
Table 1

<Tb>
<tb> Compounds <SEP> Content <SEP> (in <SEP> g)
<tb> Phase <SEP> aqueous <SEP> internal <SEP> Water <SEP> 53.6
<tb> Paste <SEP> pigmentary <SEP> according to <SEP> a) <SEP> 4
<tb> Oil <SEP>phase>SEP> Isohexadecane <SEP> 19.2
<tb> Alkyl <SEP> Dimethicone <SEP> 3,2
<tb> copolyol <SEP> (Abil <SEP> EM <SEP> 90 <SEP>)
<tb> Goldschmidt)
<tb><SEP> Water Phase <SEP> External <SEP><SEP> Copolymer Sequence <SEP> to <SEP> 0.8
<tb> oxide <SEP> sequences
<tb> of ethylene <SEP> and <SEP> oxide <SEP> of
<tb> propylene
<tb> (SYNPERONIC <SEP> PE / F <SEP> 127
<tb> from ICI)
<tb> Conservative <SEP> Qs
<tb> Water <SEP> qsp <SEP> 100
<Tb>

The pigment paste comprising the pigments is dispersed in the internal aqueous phase with vigorous stirring. This is then added to the oily phase with stirring. The stirring is carried out using a turbine rotating at 700 rpm and is maintained for 45 minutes at room temperature. A colored primary emulsion is obtained. The external aqueous phase is then added to the primary emulsion, with stirring by a turbine at 1200 rpm. A triple water-in-oil emulsion is obtained in colored water.

Claims (10)

Cosmetic composition in the form of a multiple emulsion comprising at least one internal aqueous phase, an intermediate oily phase and an external aqueous phase and at least one pigment dispersed in the internal and / or external aqueous phase of the emulsion, characterized in that the pigment is dispersed in the presence of a dispersant.  2. Cosmetic composition according to claim 1, characterized in that the pigments are selected from inorganic pigments, organic pigments, pearlescent pigments.  3. Cosmetic composition according to any one of the preceding claims, characterized in that the pigments are selected from TiO 2, FeO, Fe 2 O 3, Fe 3 O 4, FeO (OH), ZnO, Cr 2 O 3, ZrO 2, V 2 O 5, Nb 2 O 5 and mixtures thereof.  4. Composition according to any one of the preceding claims, characterized in that it comprises from 0.3% to 12.75% by weight of pigment, relative to the total weight of the emulsion, and preferably 1% at 7.5% by weight.  5. Composition according to any one of the preceding claims, characterized in that the dispersant is chosen from: - the sodium salt of maleic anhydride / diisobutylene copolymer; the methacrylic acid / methyl methacrylate copolymer; sorbitan monostearate oxyethylenated with 20 moles of ethylene oxide.  6. Composition according to any one of the preceding claims, characterized in that it comprises from 0.1% to 0.75% by weight of dispersant, relative to the total weight of the emulsion, and preferably from 0, 2% to 0.375% by weight.  7. Cosmetic composition according to any one of the preceding claims, characterized in that the internal aqueous phase and the intermediate oily phase constitute a primary emulsion water in oil <Desc / Clms Page number 15>  representing 5 to 80% by weight of the total emulsion, the external aqueous phase representing 20% to 95% by weight of the total emulsion.  8. Cosmetic composition according to any one of the preceding claims, characterized in that the internal aqueous phase comprises a stabilizing agent chosen from salts, polyols, sugars.  9. Cosmetic composition according to any one of the preceding claims, characterized in that the multiple emulsion is a triple water-in-oil-in-water emulsion.  10. A process for preparing a composition in the form of a triple emulsion comprising the following steps: a) dispersing at least one aqueous pigment paste in an aqueous phase forming the internal and / or external aqueous phase; b) dispersing the internal aqueous phase comprising or not the aqueous pigment paste in an oily phase forming the intermediate oily phase to form a primary emulsion; c) dispersion of the primary emulsion in an aqueous phase forming the external aqueous phase comprising or not the aqueous pigment paste. the aqueous pigment paste comprising from 30% to 85% by weight, preferably from 50% to 75% by weight, of at least one pigment relative to the total weight of the pigment paste, and comprising from 0.1% to 5% by weight; % by weight, preferably from 0.1% to 2% by weight, of dispersant, relative to the total weight of the pigment paste, the dispersed pigment paste (s) representing from 1% to 15% by weight of the total weight of the emulsion, preferably from 2% to 10% by weight.