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WO2023208523A1 - Composition with a polyphenol, an aqueous dispersion of wax, a nonionic surfactant with an hlb of greater than or equal to 8 and an uncoated iron oxide - Google Patents

Composition with a polyphenol, an aqueous dispersion of wax, a nonionic surfactant with an hlb of greater than or equal to 8 and an uncoated iron oxide Download PDF

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Publication number
WO2023208523A1
WO2023208523A1 PCT/EP2023/058549 EP2023058549W WO2023208523A1 WO 2023208523 A1 WO2023208523 A1 WO 2023208523A1 EP 2023058549 W EP2023058549 W EP 2023058549W WO 2023208523 A1 WO2023208523 A1 WO 2023208523A1
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WO
WIPO (PCT)
Prior art keywords
equal
weight
composition
wax
composition according
Prior art date
Application number
PCT/EP2023/058549
Other languages
French (fr)
Inventor
Philippe Ilekti
Grégory Plos
Original Assignee
L'oreal
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Publication date
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Publication of WO2023208523A1 publication Critical patent/WO2023208523A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin

Definitions

  • Makeup compositions for keratin materials generally comprise pigments. They usually contain thickening polymers in order to have a composition that is homogeneous and stable over time. Specifically, the presence of a thickening polymer makes it possible to control the homogeneity of the composition and also the homogeneity of the colour in the deposit. However, the presence of such a thickening polymer in the composition substantially increases the viscosity and unfavourably modifies the sensory effect on application. The deposits are in particular thicker and therefore more present on the keratin material. The absence of thickening polymer results in a settling of the pigments, which requires the consumer to have to shake the composition before any application in order to rehomogenize the composition.
  • At least one pigment of uncoated iron oxide type at least one pigment of uncoated iron oxide type.
  • the composition does not contain any water-soluble or water-dispersible thickening polymer.
  • a “thickening polymer” is understood to mean any polymer capable of increasing the viscosity of the composition.
  • room temperature means 25°C.
  • a “polyphenol” is understood to mean any compound having in its chemical structure at least two benzene compounds, in free or fused form, each benzene compound comprising at least one hydroxyl (OH) group, preferably at least 2 hydroxyl groups, or even 3 hydroxyl groups.
  • non-flavonoids examples include curcuminoids such as curcumin or tetrahydrocurcumin; stilbenoids such as astringin, resveratrol or rhaponticin; aurones such as aureusidin; and mixtures thereof.
  • the polyphenol is tannic acid, such as the commercial product sold under the name Brewtan F® by Anijomoto Omnichem NV.
  • Aqueous dispersions of wax are also described in application EP 0 394 078 together with the processes for preparing same.
  • These particles are constituted of a wax or of a mixture of waxes.
  • the hardness is determined by measuring the compressive force, measured at 20°C using the texturometer sold under the name TA-TX2i by the company Rheo, equipped with a stainless-steel cylinder with a diameter of 2 mm, travelling at a measuring speed of 0.1 mm/second, and penetrating the wax to a penetration depth of 0.3 mm.
  • the wax is melted at a temperature equal to the melting point of the wax + 20°C.
  • the molten wax is poured into a container 30 mm in diameter and 20 mm deep.
  • the wax is recrystallized at room temperature (25°C) for 24 hours, and the wax is then stored for at least 1 hour at 20°C before performing the hardness measurement.
  • the hardness value is the compressive force measured divided by the area of the texturometer cylinder in contact with the wax.
  • hydrocarbon-based waxes such as beeswax, lanolin wax; rice bran wax, carnauba wax, candelilla wax, ouricury wax, Japan wax, berry wax, shellac wax and sumac wax; montan wax.
  • m is an integer ranging from 18 to 38.
  • a wax is especially sold under the names Kester Wax K 82 P® and Kester Wax K 80 P® by the company Koster Keunen.
  • composition of the invention comprises at least one nonionic surfactant with an HLB of greater than or equal to 8.
  • x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
  • - ALK which may be identical or different, represent a C 1 -C 6 and in particular C 1 -C 4 alkylene group, preferably ethylene,
  • - x is an integer other than 0 and preferably between 1 and 200.
  • the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, is (are) chosen from:
  • alcohols that may comprise from 20 to 200 oxyethylene and/or oxypropylene units, preferably from 20 to 100 oxyethylene units, in particular polyethoxylated fatty alcohols, notably C 8 -C 24 , and preferably C 12 -C 18 fatty alcohols, such as Steareth-20, for instance the product BRIJ 78® sold by CRODA, and Ceteareth-30, for instance the product Eumulgin B 3® sold by BASF;
  • Polyglyceryl-6 Stearate for instance the product sold under the name Nikkol Hexaglyn 1-SV® by NIKKO CHEMICALS; Polyglyceryl-6 Isostearate sold under the name Plurol Isostearique® by GATEFOSSE; Polyglyceryl-10 Stearate for instance the product sold under the name Nikkol Decaglyn 1-SVEX® and Polyglyceryl-10 Isostearate for instance the product sold under the name Nikkol Decaglyn 1-ISV® by NIKKO CHEMICALS, Polyglyceryl-10 Laurate for instance the product sold under the name Dermofeel G 10 L® by Dr Straetmans, Polyglyceryl-10 Myristate for instance the commercial product Nikkol Decaglyn 1-M® sold
  • the nonionic surfactant(s) with an HLB of greater than or equal to 8 of the invention is (are) present in an amount of greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0% by weight relative to the total weight of the composition.
  • pigment means particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify the resulting composition and/or deposit.
  • the pigments have a size characterized by a D[50] greater than 100 nm and possibly ranging up to 10 ⁇ m, preferably from 200 nm to 5 ⁇ m and more preferentially from 300 nm to 1 ⁇ m.
  • oil means a fatty substance that is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e. 101 325 Pa).
  • the oil may be volatile or non-volatile.
  • silicon oil is understood to mean an oil comprising at least one Si-O group, and more particularly an organopolysiloxane.
  • hydrocarbon-based oil is understood to mean an oil containing mainly carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether or carboxyl functions.
  • volatile hydrocarbon-based oils such as petroleum distillates, in particular those sold under the name Shell Solt by Shell
  • volatile linear alkanes such as those described in the patent application DE10 2008 012 457 from Cognis and for instance the one sold under the trade name Cetiol Ultimate® by BASF. Mention may also be made of the dodecane/tetradecane mixture in the 85/15 weight ratio sold by Biosynthis under the reference Vegelight 1214® and of the mixture of C9-C12 volatile linear alkanes having the INCI name: C9-12 Alkane such as the product sold by the company Biosynthis under the reference Vegelight Silk®.
  • fatty alcohols containing from 12 to 26 carbon atoms for instance octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol and oleyl alcohol;
  • the total amount of non-volatile oil(s) is less than or equal to 10% by weight, more preferentially less than or equal to 5.0% by weight, or even less than 2.0% by weight, relative to the total weight of the composition.
  • the present invention also relates to an assembly, or kit, for packaging and applying a cosmetic composition for coating keratin materials, comprising:
  • Said applicator may be integrally attached to a gripping member forming a cap for said packaging device.
  • said applicator may be mounted in a removable position on said device between a closed position and an open position of a dispensing aperture of the device for packaging said composition.
  • An assembly for coating keratin materials suitable for the invention may comprise an applicator configured for applying said cosmetic composition for coating keratin materials and, where appropriate, a packaging device suitable for receiving said composition.
  • a method for applying the composition according to the invention to the eyelashes or the eyebrows may also include the following steps:
  • the applicator may form a product container.
  • a container may, for example, be provided in the gripping member and an internal channel can internally connect this gripping member to the application elements in relief.
  • composition 1 according to the invention remained stable and homogeneous at 25°C, 24 hours after its preparation whereas composition 2 outside the invention obtained without tannic acid was unstable, resulting in phase separation. In the case of composition 2, settling of the pigment in the bottom of the composition and a white supernatant were observed.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Cosmetics (AREA)

Abstract

The present invention relates to a composition comprising, preferably in a physiologically acceptable medium: (1) at least one polyphenol comprising at least two different phenol groups; (2) at least one aqueous dispersion of wax particles; (3) at least one nonionic surfactant with an HLB of greater than or equal to 8; and (4) at least one pigment of uncoated iron oxide type. The invention also relates to a method for coating keratin materials, in particular the skin, and keratin fibres, such as the eyelashes and/or the eyebrows, comprising a step of applying to said keratin materials at least one composition as defined above.

Description

Composition with a polyphenol, an aqueous dispersion of wax, a nonionic surfactant with an HLB of greater than or equal to 8 and an uncoated iron oxide
The present invention relates to the field of caring for and/or making up keratin materials, and is directed towards proposing compositions more particularly intended for making up the skin, in particular the face, the eye contour, the eyelashes or the eyebrows.
Compositions intended for caring for and/or making up the skin such as foundations are commonly used to give the skin an aesthetic colour, but also to enhance the beauty of uneven skin, by making it possible to hide marks and dyschromias, to reduce the visibility of relief imperfections such as pores and wrinkles, and to conceal spots, acne marks and scars. In this regard, the coverage and the matt effect or "soft focus" effect are the main properties desired.
Compositions intended for making up keratin fibres, for example the eyelashes, such as mascaras, aim to densify the thickness and the visual perception of the eyelashes and ultimately the look. These mascaras are described as aqueous or cream mascaras when they are formulated in an aqueous base, and anhydrous mascaras when they are formulated as a dispersion in an organic solvent medium. A great diversity of cosmetic effects may be afforded by applying a mascara to keratin fibres and notably the eyelashes, for instance a volumizing, lengthening, thickening and more particularly loading makeup effect.
Makeup compositions for keratin materials generally comprise pigments. They usually contain thickening polymers in order to have a composition that is homogeneous and stable over time. Specifically, the presence of a thickening polymer makes it possible to control the homogeneity of the composition and also the homogeneity of the colour in the deposit. However, the presence of such a thickening polymer in the composition substantially increases the viscosity and unfavourably modifies the sensory effect on application. The deposits are in particular thicker and therefore more present on the keratin material. The absence of thickening polymer results in a settling of the pigments, which requires the consumer to have to shake the composition before any application in order to rehomogenize the composition.
The need thus remains to find novel compositions for caring for and/or making up keratin materials, which are based on pigments, with no thickening polymer, which are homogeneous and stable over time, and which produce, after application to the keratin material, both a homogeneous colour and pleasant sensory properties such as the perception of a very thin film. Said compositions should not result in a settling of the pigments requiring the consumer to have to shake the composition before any application in order to rehomogenize the composition.
Unexpectedly, the inventors have observed that it is possible to achieve these objectives by using a composition comprising, notably in a physiologically acceptable medium:
at least one polyphenol comprising at least two different phenol groups;
at least one aqueous dispersion of wax particles;
at least one nonionic surfactant with an HLB of greater than or equal to 8; and
at least one pigment of uncoated iron oxide type.
The inventors have also discovered that said polyphenol and said nonionic surfactant with an HLB of greater than or equal to 8 interact via hydrogen bonds to form a coating agent on the keratin material.
This discovery forms the basis of the invention.
Subjects of the invention
Thus, a first subject of the present invention is a composition comprising, preferably in a physiologically acceptable medium:
at least one polyphenol comprising at least two different phenol groups;
at least one aqueous dispersion of wax particles;
at least one nonionic surfactant with an HLB of greater than or equal to 8; and
at least one pigment of uncoated iron oxide type.
According to a preferential embodiment of the invention, the composition does not contain any water-soluble or water-dispersible thickening polymer.
A second subject of the present invention is a method for coating keratin materials consisting in applying to the surface of said materials at least one composition as defined previously.
In the context of the present invention, the term “keratin material” notably means the skin such as the face, the body, the hands, the cheeks, the eyelids, the contour of the eyes, keratin fibres such as the eyelashes, the eyebrows and body hair such as beard hair. For the purposes of the present invention, this term “keratin materials” also extends to synthetic false eyelashes and false eyebrows.
The term “physiologically acceptable” is intended to mean compatible with the skin and/or skin appendages, which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging or tautness) liable to discourage the consumer from using this composition.
A “composition not containing any water-soluble or water-dispersible thickening or gelling polymer” is understood to mean any composition containing less than 0.1% by weight relative to the total weight of the composition, or even free of water-soluble or water-dispersible thickening polymer.
A “polymer” is understood to mean any molecule comprising in its structure at least one chain formed by at least two identical units (monomers), preferably at least 3.
A “thickening polymer” is understood to mean any polymer capable of increasing the viscosity of the composition.
The term “room temperature” means 25°C.
The term “atmospheric pressure” means 760 mmHg, i.e. 101 325 pascals.
For the purposes of the invention, the term “hydrogen bonding” means an interaction involving a hydrogen atom of one of the two reagents and an electronegative heteroatom of the other reagent, such as oxygen, nitrogen, sulfur and fluorine. In the context of the invention, the hydrogen bonds are formed between the hydroxyl (OH) functions of the reactive phenol groups of the polyphenol and the group(s) (for example hydroxyl and/or ether groups) of the nonionic surfactant with an HLB of greater than or equal to 8 capable of forming hydrogen bonds with those of said phenol groups of the polyphenol.
Polyphenol
The polyphenols that may be used according to the present invention include in their structure at least two different phenol groups.
A “polyphenol” is understood to mean any compound having in its chemical structure at least two benzene compounds, in free or fused form, each benzene compound comprising at least one hydroxyl (OH) group, preferably at least 2 hydroxyl groups, or even 3 hydroxyl groups.
The term “different phenol groups” refers to phenol groups that are chemically different.
The polyphenols that can be used according to the invention may be synthetic or natural. They may be in isolated form or contained in a mixture, notably contained in a plant extract. Polyphenols are phenols comprising at least two phenol groups that are differently substituted on the aromatic ring.
The two classes of polyphenols are flavonoids and non-flavonoids.
Examples of flavonoids that may be mentioned include chalcones such as phloretin, phloridzin, aspalathin or neohesperidin; flavanols such as catechin, fisetin, kaempferol, myricetin, quercetin, rutin, procyanidins, proanthocyanidins, pyroanthocyanidins, theaflavins or thearubigins (or thearubins); dihydroflavonols such as astilbin, dihydroquercetin (taxifolin) or silibinin; flavanones such as hesperidin, neohesperidin, hesperetin, naringenin or naringin; anthocyanins such as cyanidin, delphinidin, malvidin, peonidin or petunidin; catechin tannins such as tannic acid; isoflavonoids such as daidzein or genistein; neoflavanoids; lignans such as pyroresorcinol; and mixtures thereof.
Among the natural polyphenols that may be used according to the invention, mention may also be made of lignins.
Examples of non-flavonoids that may be mentioned include curcuminoids such as curcumin or tetrahydrocurcumin; stilbenoids such as astringin, resveratrol or rhaponticin; aurones such as aureusidin; and mixtures thereof.
As polyphenols that can be used according to the invention, mention may also be made of chlorogenic acid, verbascoside; coumarins substituted with phenols.
According to a particular embodiment of the invention, the polyphenol will be chosen from catechin tannins such as gallotannins chosen from tannic acid; ellagitannins such as epigallocatechin, epigallocatechin gallate, castalagin, vescalagin, vescalin, castalin, casuarictin, castanopsinins, excoecarianins, grandinin, gradinin, roburins, pterocarinin, acutissimin, tellimagrandins, sanguiin, potentillin, pedunculagin, geraniin, chebulagic acid, repandusinic acid, ascorgeraniin, stachyurin, casuarinin, casuariin, punicacortein, coriariin, cameliatannin, isodehydrodigalloyl, dehydrodigalloyl, hellinoyl, punicalagin and rhoipteleanins.
According to a particular embodiment of the invention, the polyphenol is epigallocatechin, in particular a green tea extract having the INCI name Green Tea Extract, notably comprising at least 45% epigallocatechin relative to the total weight of said extract, for instance the commercial product sold under the name Dermofeel Phenon 90 M-C® sold by Evonik Nutrition & Care or the commercial product sold under the name Tea Polyphenols Green Tea Extract® by Tayo Green Power.
According to a particular embodiment of the invention, the polyphenol is a procyanidin or a mixture of procyanidins, in particular an extract of maritime pine bark having the INCI name Pinus pinaster Bark/Bud Extract, notably comprising at least 65% by weight of procyanidins relative to the total weight of said extract, such as the commercial product sold under the name Pycnogenol® sold by Biolandes Arômes.
According to a particular embodiment of the invention, the polyphenol is tannic acid, such as the commercial product sold under the name Brewtan F® by Anijomoto Omnichem NV.
Tannic acid will be used more particularly as polyphenol.
According to a particular embodiment, the polyphenol(s) of the invention is (are) present in an amount of greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0% by weight and more particularly greater than or equal to 2.0% by weight relative to the total weight of the composition.
According to a particular embodiment, the polyphenol(s) of the invention is (are) present in an amount ranging from 1.0% to 30.0% by weight, and more particularly ranging from 2.0% to 30% by weight relative to the total weight of the composition.
Aqueous dispersion of wax particles
The composition according to the invention comprises at least one aqueous dispersion of wax.
An aqueous dispersion of wax particles is understood to mean an aqueous dispersion of wax particles in which the mean size of said wax particles is less than or equal to 30 microns, preferably less than or equal to 10 microns, or even less than or equal to 5 microns.
According to one particular embodiment, the particles of the wax dispersion have mean dimensions of less than or equal to 1 μm, notably ranging from 0.02 μm to 1 μm.
The sizes are measured by static light scattering using a commercial MasterSizer 3000® particle size analyzer from Malvern, which makes it possible to determine the particle size distribution of all of the particles over a wide range which may extend from 0.01 µm to 1000 µm. The data are processed on the basis of the standard Mie scattering theory. This theory is the most suitable for size distributions ranging from submicron to multimicron; it allows an “effective” particle diameter to be determined. This theory is described in particular in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.
D[50] represents the maximum size exhibited by 50% by volume of the particles.
In the present application, a wax is a lipophilic compound, which is solid at room temperature (25°C), with a reversible solid/liquid change of state, with a melting point above or equal to 30°C, which may be up to 120°C. By bringing the wax to the liquid state (melting), it is possible to make it miscible with the oils and to form a microscopically homogeneous mixture, but on returning the temperature of the mixture to room temperature, recrystallization of the wax in the oils of the mixture is obtained.
The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC by the company Mettler. A sample of 15 mg of product placed in a crucible is subjected to a first temperature rise passing from 0°C to 120°C, at a heating rate of 10°C/minute, it is then cooled from 120°C to 0°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise passing from 0°C to 120°C at a heating rate of 5°C/minute. During the second temperature rise, the variation of the difference in power absorbed by the empty crucible and by the crucible containing the sample of product is measured as a function of the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
Aqueous dispersions of wax are stable dispersions of colloidal wax particles, and are described in particular in Microemulsions Theory and Practice, L.M. Prince Ed., Academic Press (1977) pages 21-32.
Aqueous dispersions of wax are also described in application EP 0 394 078 together with the processes for preparing same.
In particular, these wax dispersions may be obtained by melting the wax in the presence of a surfactant, and optionally of a portion of water, followed by gradual addition of hot water with stirring. Intermediate formation of an emulsion of the water-in-oil type is observed, followed by a phase inversion with final production of an emulsion of the oil-in-water type. On cooling, a stable dispersion of solid colloidal particles of wax is obtained. The wax dispersions may also be obtained by stirring the mixture of wax, surfactant and water using an agitation means such as ultrasonic waves, a high-pressure homogenizer or turbomixers.
These particles are constituted of a wax or of a mixture of waxes.
The wax or waxes used in the compositions of the invention are preferably polar waxes.
The term "polar wax" is intended to mean waxes comprising in their chemical structure, in addition to carbon and hydrogen atoms, at least one highly electronegative heteroatom, such as O, N or P.
They may, however, comprise a minor proportion of oily and/or pasty fatty additives and/or a common liposoluble active agent/additive.
The polar waxes that can be used in the compositions according to the invention are chosen from waxes that are solid and rigid at room temperature, of animal, plant, mineral or synthetic origin, and mixtures thereof. Preferably, the waxes that are incorporated into the composition have a melting point above 45°C, and in particular above 60°C. The wax may also have a hardness ranging from 0.05 MPa to 15 MPa, and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compressive force, measured at 20°C using the texturometer sold under the name TA-TX2i by the company Rheo, equipped with a stainless-steel cylinder with a diameter of 2 mm, travelling at a measuring speed of 0.1 mm/second, and penetrating the wax to a penetration depth of 0.3 mm. To perform the hardness measurement, the wax is melted at a temperature equal to the melting point of the wax + 20°C. The molten wax is poured into a container 30 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25°C) for 24 hours, and the wax is then stored for at least 1 hour at 20°C before performing the hardness measurement. The hardness value is the compressive force measured divided by the area of the texturometer cylinder in contact with the wax.
Mention may in particular be made of hydrocarbon-based waxes such as beeswax, lanolin wax; rice bran wax, carnauba wax, candelilla wax, ouricury wax, Japan wax, berry wax, shellac wax and sumac wax; montan wax.
Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains. Among these waxes, mention may especially be made of hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, bis(1,1,1-trimethylolpropane) tetrastearate sold under the name Hest 2T-4S by the company Heterene and bis(1,1,1-trimethylolpropane) tetrabehenate sold under the name Hest 2T-4B® by the company Heterene. The wax obtained by hydrogenation of olive oil esterified with stearyl alcohol, sold under the name Phytowax Olive 18L57® or else the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the names Phytowax ricin 16L64® and 22L73® by the company Sophim may also be used. Such waxes are described in patent application FR-A-2 792 190. Mention may also be made of waxes derived from the reaction of fatty acids on carbohydrates, for instance disaccharides of sucrose type, such as sucrose polybehenate sold by Croda under the reference Cromaderm B®. Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains.
Mention may also be made of a C20-C40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, in particular a C20-C40 alkyl 12-(12’-hydroxystearyloxy)stearate, of formula (I) below:
(I)
in which m is an integer ranging from 18 to 38. Such a wax is especially sold under the names Kester Wax K 82 P® and Kester Wax K 80 P® by the company Koster Keunen.
The waxes mentioned above generally have a starting melting point of less than 45°C.
Preferably, the polar waxes are chosen from hydrocarbon-based waxes such as beeswax, lanolin wax; rice bran wax, carnauba wax, candelilla wax, ouricury wax, Japan wax, berry wax, shellac wax and sumac wax; montan wax, hydrogenated castor oil, hydrogenated lanolin oil, waxes derived from the reaction of fatty acids on carbohydrates, for instance disaccharides of sucrose type, such as sucrose polybehenate, sold by Croda under the reference Cromaderm B® and C20-C40 alkyl (hydroxystearyloxy)stearate waxes such as those sold under the names Kester Wax K 82 P® and Kester Wax K 80 P® by the company Koster Keunen, and mixtures thereof.
Use will more particularly be made of carnauba wax (INCI name: COPERNICA CERIFERA (CARNAUBA) WAX).
According to a preferential embodiment, the wax(es) is (are) present in an amount of greater than or equal to 5.0% by weight, more preferentially greater than or equal to 8.0%, in particular ranging from 8% to 25% by weight, relative to the total weight of the composition.
Nonionic surfactant with an HLB ≥ 8
The composition of the invention comprises at least one nonionic surfactant with an HLB of greater than or equal to 8.
Within the meaning of the present invention, a “surfactant” is understood to mean an amphiphilic surfactant compound, i.e. one which has two parts of different polarity. Generally, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). Surfactants are characterized by the value of their HLB (hydrophilic-lipophilic balance), the HLB being the ratio of the hydrophilic part to the lipophilic part in the molecule. The term “HLB” is well known to a person skilled in the art and is described, for example, in “The HLB System. A Time-Saving Guide to Emulsifier Selection” (published by ICI Americas Inc.; 1984). The HLB of the surfactant(s) used according to the invention can be determined by the Griffin method or the Davies method.
For the purposes of the present invention, a “nonionic surfactant” is understood to mean any surfactant having no ionic (anionic or cationic) charge in its structure.
According to a preferred embodiment of the invention, the nonionic surfactant(s) used according to the invention have a molar mass of greater than 350 g/mol.
According to a preferred embodiment of the invention, the nonionic surfactant(s) with an HLB greater than 8 are polyoxyalkylenated, monoglycerolated and/or polyglycerolated.
For the purposes of the present invention, a “polyoxyalkylenated compound” is understood to mean any molecule comprising in its chemical structure at least one chain comprising oxyalkylene units, in particular -(OCH2CH2)n oxyethylene and/or -(OCH2CH2CH2)p oxypropylene units.
For the purposes of the present invention, a “monoglycerolated or polyglycerolated compound” is understood to mean any molecule comprising in its chemical structure a glycerol group or a chain comprising -(O-CH2-CHOH-CH2OH)m glycerol units.
According to one particular embodiment of the invention, the nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8 correspond to formula (II) below:
[Chem 2]
(ALK-[C(O)]a-[O]b)c-X (II)
in which:
- ALK is a C7-C23, preferably C11-C21 and more preferentially C15-C17 alkyl group,
- a and b are integers ranging from 0 to 100,
- c is an integer ranging from 1 to 100, in particular from 1 to 3, preferably equal to 1, a and b preferably being equal to 0,
- X is a (poly)oxyalkylene group optionally substituted and/or terminated with a hydroxyl group, X preferably being an oxyethylene group (CH2CH2O)n or (OCH2CH2)n in which n is greater than or equal to 1, for example ranging from 1 to 200, said (poly)oxyalkylene group preferably being a polyethylene glycol or being the result of at least one substitution of a hydroxyl group, preferably chosen from (poly)glycerols.
The group X is preferably chosen from:
i) those of formula (III) below:
[Chem 3]
HO-(ALK-O)z-CH2-CH[(OALK)y-OH]-CH2-(O-ALK)x-(*) (III)
in which:
- ALK, which may be identical or different, represent a C1-C6 and in particular C1-C4 alkylene group, preferably ethylene,
- x, y and z being an integer between 0 and 200, it being understood that x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
ii) those of formula (IV) or (V) below:
[Chem 4]
H-(ALK-O)x-(*) (IV)
or
[Chem 5]
H-(O-ALK)x-(*) (V)
in which:
- ALK, which may be identical or different, represent a C1-C6 and in particular C1-C4 alkylene group, preferably ethylene,
- x is an integer other than 0 and preferably between 1 and 200.
Preferably, X is an H-(O-ALK)x-(*) group.
The nonionic surfactant(s) with an HLB value at 25°C of greater than or equal to 8, preferably greater than or equal to 10, is (are) chosen from:
- polyoxyalkylenated, in particular oxypropylenated and optionally oxyethylenated, glycerol ethers that may comprise from 20 to 200 oxyalkylene units such as PPG-50 Glyceryl Ether sold under the trade name Newpol GP-3000® and PPG-67 Glyceryl Ether sold under the trade name Newpol GP-4000® by Sanyo Chemical; PPG-70 Glyceryl Ether sold under the trade name Uniol TG-4000R® by NOF Corporation; and PPG-24-Glycereth-24 sold under the trade name Nikkol SG-G2424® by Nikko Chemicals;
- polyoxyalkylenated, in particular polyoxyethylenated and/or polyoxypropylenated,
alcohols that may comprise from 20 to 200 oxyethylene and/or oxypropylene units, preferably from 20 to 100 oxyethylene units, in particular polyethoxylated fatty alcohols, notably C8-C24, and preferably C12-C18 fatty alcohols, such as Steareth-20, for instance the product BRIJ 78® sold by CRODA, and Ceteareth-30, for instance the product Eumulgin B 3® sold by BASF;
- polyoxyalkylenated fatty acid esters, in particular esters of a fatty
acid, notably a C8-C24 and preferably C16-C22 fatty acid, and of polyethylene glycol (or PEG) which may comprise from 20 to 200 oxyethylene units, such as PEG-50 Stearate sold under the trade name Myrj S50® and PEG-40 Stearate sold under the name Myrj S40® by CRODA;
- esters of a fatty acid, notably a C8-C24 and preferably C16-C22 fatty acid, and of (poly)oxyalkylenated, in particular oxyethylenated and/or oxypropylenated glycerol ethers that may comprise from 20 to 200 oxyethylene and/or oxypropylene units, such as PEG-200 Glyceryl Stearate sold under the name Simulsol 220® by SEPPIC; PEG-30 Glyceryl Stearate such as the product TAGAT S® sold by EVONIK, PEG-20 Glyceryl Oleate such as the product TAGAT O2V® sold by EVONIK, and PEG-20 Glyceryl Laurate such as the product TAGAT L2® from EVONIK;
- esters of a fatty acid, notably a C8-C24 and preferably C16-C22 fatty acid, and of (poly)oxyalkylenated, in particular oxyethylenated and/or oxypropylenated, sorbitol ethers that may comprise from 20 to 200 oxyethylene and/or oxypropylene units such as Polysorbate-20 sold under the name Tween 20®, Polysorbate-21 sold under the name Tween 21®, Polysorbate-40 sold under the name Tween 40®, Polysorbate-60 sold under the name Tween 60® and Polysorbate-80 sold under the name TWEEN-80-LQ® by CRODA;
- esters of a C12-C20 fatty acid and of a polyglycerol comprising from 3 to 12 glycerol groups, preferably from 6 to 10 glycerol groups such as Polyglyceryl-6 Stearate, for instance the product sold under the name Nikkol Hexaglyn 1-SV® by NIKKO CHEMICALS; Polyglyceryl-6 Isostearate sold under the name Plurol Isostearique® by GATEFOSSE; Polyglyceryl-10 Stearate for instance the product sold under the name Nikkol Decaglyn 1-SVEX® and Polyglyceryl-10 Isostearate for instance the product sold under the name Nikkol Decaglyn 1-ISV® by NIKKO CHEMICALS, Polyglyceryl-10 Laurate for instance the product sold under the name Dermofeel G 10 L® by Dr Straetmans, Polyglyceryl-10 Myristate for instance the commercial product Nikkol Decaglyn 1-M® sold by NIKKO CHEMICALS, Polyglyceryl-10 Oleate for instance the commercial product Nikkol Decaglyn 1-OV® sold by NIKKO CHEMICALS;
- and mixture(s) thereof.
Use will more particularly be made of esters of a C12-C20 fatty acid and of a polyglycerol comprising from 3 to 12 glycerol groups, preferably from 6 to 10 glycerol groups, in particular PEG-30 Glyceryl Stearate.
In particular, the composition of the invention comprises an aqueous dispersion of carnauba wax containing 27% by weight of said wax, 10% by weight of ethanol, 7% by weight of PEG-30 Glyceryl Stearate surfactant and 56% by weight of water relative to the total weight of the dispersion, such as the commercial product sold under the name MEXORYL SAP® by NOVEAL.
According to a preferential embodiment, the nonionic surfactant(s) with an HLB of greater than or equal to 8 of the invention is (are) present in an amount of greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0% by weight relative to the total weight of the composition.
According to a preferential embodiment, the nonionic surfactant(s) with an HLB of greater than or equal to 8 of the invention is (are) present in an amount of less than or equal to 15% by weight, preferably less than or equal to 12% by weight, and more particularly ranging from 1% to 8% by weight relative to the total weight of the composition.
According to a preferential embodiment of the invention, the mole ratio of the hydroxyl (OH) groups of the polyphenol which are reactive via a hydrogen bonding interaction to the reactive groups (i.e. hydroxyl and/or ether groups) of the nonionic surfactant with an HLB of greater than or equal to 8 capable of forming hydrogen bonds with the hydroxyl groups of the polyphenol, ranges from 1/3 to 20, more preferentially from 1/2 to 15 and more particularly from 3/4 to 3.
Pigment
The composition according to the invention comprises at least one pigment of iron oxide type (INCI name: Iron Oxide).
The term “pigment” means particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify the resulting composition and/or deposit.
The term “uncoated pigment” means any pigment not treated by a surface agent that covers it partially or completely while being absorbed, adsorbed or grafted onto said pigment.
According to a preferential embodiment, the pigment(s) is (are) present in an amount ranging up to 35.0% by weight, more preferentially ranging up to 25.0% by weight and more particularly ranging from 4% to 25% by weight, relative to the total weight of the composition.
According to one particular embodiment , the uncoated pigments used according to the invention are chosen from yellow iron oxides (CI 77492), red iron oxides, black iron oxides (CI47499), and mixtures thereof.
The size of the pigment of use in the context of the present invention is generally greater than 100 nm and can range up to 10 µm, preferably from 200 nm to 5 µm and more preferentially from 300 nm to 1 µm.
According to a particular form of the invention, the pigments have a size characterized by a D[50] greater than 100 nm and possibly ranging up to 10 µm, preferably from 200 nm to 5 µm and more preferentially from 300 nm to 1 µm.
The sizes are measured by static light scattering using a commercial MasterSizer 3000® particle size analyzer from Malvern, which makes it possible to determine the particle size distribution of all of the particles over a wide range which may extend from 0.01 µm to 1000 µm. The data are processed on the basis of the standard Mie scattering theory. This theory is the most suitable for size distributions ranging from submicron to multimicron; it allows an “effective” particle diameter to be determined. This theory is described in particular in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.
D[50] represents the maximum size exhibited by 50% by volume of the particles.
In the context of the present invention, the pigments are more particularly black iron oxides (CI 77499).
Cosmetic composition
The composition may be manufactured via the known processes generally used in the cosmetics field.
The composition of the invention is a composition with a continuous aqueous phase.
The term “aqueous phase” means a phase comprising water and also optionally all the water-soluble or water-miscible solvents and ingredients (miscibility with water of greater than 50% by weight at 25°C), for instance lower monoalcohols containing from 2 to 8 carbon atoms such as ethanol or isopropanol, polyols containing from 3 to 8 carbon atoms such as propylene glycol, 1,3-butylene glycol, caprylyl glycol, pentylene glycol, glycerol, and dipropylene glycol; C3-C4 ketones and C2-C4 aldehydes.
The expression “composition with a continuous aqueous phase” means any composition having a conductivity, measured at 25°C, of greater than 23 µS/cm (microSiemens/cm), the conductivity being measured, for example, using an MPC227® conductivity meter from Mettler Toledo and an Inlab730® conductivity measuring cell. The measuring cell is immersed in the composition so as to remove the air bubbles that might be formed between the two electrodes of the cell. The conductivity reading is taken once the conductivity meter value has stabilized. A mean is determined on at least three successive measurements.
The composition of the invention may contain a demineralized water or alternatively a floral water such as cornflower water and/or a mineral water such as Vittel water, Lucas water or La Roche Posay water and/or a spring water.
The pH of the composition is preferably below 6, more preferentially between 2 and 6, and more particularly between 2 and 5.
The amount of water is preferably greater than or equal to 30% by weight, and more preferentially ranges from 35% to 85% by weight, and more particularly from 40% to 65% by weight, relative to the total weight of the composition.
Oily phase
According to a particular embodiment of the invention, the aqueous composition according to the invention may additionally comprise an oily phase.
It may notably be in the form of an oil-in-water emulsion, which is a dispersion of the oily phase in the form of droplets of oil in the aqueous phase so as to form a composition which is macroscopically homogeneous to the naked eye.
The term “oily phase” refers to a phase which is liquid at room temperature (25°C) and at atmospheric pressure, comprising oils, waxes or pasty substances and also optionally all the organic solvents and ingredients that are soluble or miscible in said phase.
The oil(s) may be chosen from mineral, plant or synthetic oils, in particular chosen from volatile or non-volatile hydrocarbon-based oils and/or silicone oils and/or fluoro oils, and mixtures thereof.
The term “oil” means a fatty substance that is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e. 101 325 Pa). The oil may be volatile or non-volatile.
Within the meaning of the present invention, the term “silicone oil” is understood to mean an oil comprising at least one Si-O group, and more particularly an organopolysiloxane.
The term “fluoro oil” refers to an oil comprising at least one fluorine atom.
The term “hydrocarbon-based oil” is understood to mean an oil containing mainly carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether or carboxyl functions.
For the purposes of the invention, the term “volatile oil” refers to any oil that is capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, which is liquid at room temperature, notably having a non-zero vapour pressure, at room temperature and atmospheric pressure, notably having a vapour pressure ranging from 2.66 Pa to 40 000 Pa, in particular ranging from 2.66 Pa to 13 000 Pa and more particularly ranging from 2.66 Pa to 1300 Pa.
The term “non-volatile oil” refers to an oil that remains on the skin or the keratin fibre at room temperature and atmospheric pressure for at least several hours, and that notably has a vapour pressure of less than 2.66 Pa, preferably less than 0.13 Pa. By way of example, the vapour pressure may be measured via the static method or via the effusion method by isothermal thermogravimetry, depending on the vapour pressure (standard OCDE 104).
Volatile hydrocarbon-based oils
As examples of volatile hydrocarbon-based oils that may be used in the invention, mention may be made of:
- hydrocarbon-based oils containing from 8 to 16 carbon atoms, and notably C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane) and isohexadecane, for example the oils sold under the trade names Isopar® or Permethyl®, branched C8-C16 esters and isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon-based oils, such as petroleum distillates, in particular those sold under the name Shell Solt by Shell, can also be used; volatile linear alkanes, such as those described in the patent application DE10 2008 012 457 from Cognis and for instance the one sold under the trade name Cetiol Ultimate® by BASF. Mention may also be made of the dodecane/tetradecane mixture in the 85/15 weight ratio sold by Biosynthis under the reference Vegelight 1214® and of the mixture of C9-C12 volatile linear alkanes having the INCI name: C9-12 Alkane such as the product sold by the company Biosynthis under the reference Vegelight Silk®.
Non-volatile hydrocarbon-based oils
As examples of non-volatile hydrocarbon-based oils that can be used in the invention, mention may be made of:
- linear or branched hydrocarbons, of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, polybutenes or polyisobutenes, which are optionally hydrogenated such as Parleam, or squalane;
- synthetic ethers containing from 10 to 40 carbon atoms, such as dicaprylyl ether;
- triglycerides constituted of fatty acid esters of glycerol, in particular the fatty acids of which may have chain lengths ranging from C4 to C36, and notably from C18 to C36, these oils possibly being linear or branched, and saturated or unsaturated; these oils may notably be heptanoic or octanoic triglycerides, wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil (820.6 g/mol), corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil or musk rose oil; shea oil; or alternatively caprylic/capric acid triglycerides, for instance those sold by Stéarinerie Dubois or those sold under the names Miglyol 810®, 812® and 818® by Dynamit Nobel;
- linear aliphatic hydrocarbon-based esters of formula RCOOR’ in which RCOO represents a carboxylic acid residue including from 2 to 40 carbon atoms, and R’ represents a hydrocarbon-based chain containing from 1 to 40 carbon atoms, such as cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, diisopropyl adipate, heptanoates, and notably isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate and palmitate, alkyl benzoate, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate and 2-octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate and octyl isononanoate, oleyl erucate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate and isostearyl behenate;
- polyesters obtained by condensation of unsaturated fatty acid dimer and/or trimer and of diol, such as those described in patent application FR 0 853 634, in particular such as of dilinoleic acid and of 1,4-butanediol. Mention may notably be made in this respect of the polymer sold by Biosynthis under the name Viscoplast 14436H® (INCI name: Dilinoleic Acid/Butanediol Copolymer) or else copolymers of polyols and of diacid dimers, and esters thereof, such as Hailuscent ISDA®,
- dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name
Cetiol CC® by Cognis;
- linear fatty acid esters with a total carbon number ranging from 35 to 70, for instance pentaerythrityl tetrapelargonate;
- aromatic esters such as tridecyl trimellitate, C12-C15 alcohol benzoate, the 2-phenylethyl ester of benzoic acid, and butyloctyl salicylate;
- esters and polyesters of diol dimer and of monocarboxylic or dicarboxylic acid, such as esters of diol dimer and of fatty acid and esters of diol dimer and of dicarboxylic acid dimer, such as Lusplan DD-DA5® and Lusplan DD-DA7® sold by the company Nippon Fine Chemical and described in patent application US 2004-175 338, the content of which is incorporated into the present application by reference;
- fatty alcohols containing from 12 to 26 carbon atoms, for instance octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol and oleyl alcohol;
- dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name
Cetiol CC® by Cognis;
- and mixtures thereof.
Non-volatile silicone oils
Among the non-volatile silicone oils, mention may be made of silicone oils such as non-volatile polydimethylsiloxanes (PDMS); phenyl silicones such as phenyl trimethicones, phenyl dimethicones, diphenyl dimethicones, trimethylpentaphenyltrisiloxanes, tetramethyltetraphenyltrisiloxanes, trimethylsiloxyphenyl dimethicones, diphenylsiloxyphenyl trimethicones, and also mixtures thereof.
Linear or cyclic volatile silicone oils
Linear volatile silicone oils that may be mentioned include octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.
Cyclic volatile silicone oils that may be mentioned include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, and mixtures thereof.
According to a preferential embodiment of the invention, the total amount of non-volatile oil(s) is less than or equal to 10% by weight, more preferentially less than or equal to 5.0% by weight, or even less than 2.0% by weight, relative to the total weight of the composition.
According to one particular embodiment of the invention, the composition of the invention may be free of non-volatile oil.
According to a preferential embodiment of the invention, the total amount of volatile oil(s) is less than or equal to 10% by weight, more preferentially less than or equal to 5.0% by weight, relative to the total weight of the composition.
According to one particular embodiment of the invention, the composition of the invention may be free of volatile oil.
The composition may be manufactured via the known processes generally used in the cosmetics field.
Cosmetic additives
The compositions of the invention may contain additives that are common in cosmetics. Mention may notably be made of antioxidants, preserving agents, neutralizers, cosmetic active agents, for instance emollients, moisturizers, vitamins and mixtures thereof.
The composition used according to the invention may be a composition for caring for and/or for making up the skin.
More especially, the composition according to the invention is a makeup product for the face such as a foundation, for the cheeks or for the eyelids such as face powders and eyeshadows.
The composition used according to the invention may be a composition for caring for and/or making up the eyes, notably the contour of the eye or keratin fibres such as the eyelashes or eyebrows.
More specifically, the composition according to the invention is a makeup product for the eyelashes such as a mascara, a makeup product for the eyebrows or a product for the contour of the eyes such as an eyeliner.
It may be a makeup base, also known as base coat, a composition to be applied onto makeup, also known as topcoat, or else a composition for treating keratin materials.
Such compositions are in particular prepared according to the general knowledge of a person skilled in the art.
Packaging and application assembly or kit
The present invention also relates to an assembly, or kit, for packaging and applying a cosmetic composition for coating keratin materials, comprising:
- a device for packaging said cosmetic composition for coating keratin materials, as described above,
- an applicator for said composition.
Said applicator may be integrally attached to a gripping member forming a cap for said packaging device. In other words, said applicator may be mounted in a removable position on said device between a closed position and an open position of a dispensing aperture of the device for packaging said composition.
An assembly for coating keratin materials suitable for the invention may comprise an applicator configured for applying said cosmetic composition for coating keratin materials and, where appropriate, a packaging device suitable for receiving said composition.
Packaging device
The packaging device comprises a container intended for housing the composition for coating keratin materials. This composition may then be withdrawn from the container by immersing the applicator therein.
This applicator may be firmly attached to an element for closing the container. This closing element may form a member for gripping the applicator. This gripping member may form a cap to be removably mounted on said container by any suitable means, such as by screwing, click-fastening, coupling, etc. Such a container may thus reversibly house said applicator.
This container may be optionally equipped with a wiper suitable for removing surplus product taken up by the applicator.
A method for applying the composition according to the invention to the eyelashes or the eyebrows may also include the following steps:
- forming a deposit of the cosmetic composition on the keratin materials,
- leaving the deposit on the keratin materials, it being possible for the deposit to dry.
It should be noted that, according to another embodiment, the applicator may form a product container. In such a case, a container may, for example, be provided in the gripping member and an internal channel can internally connect this gripping member to the application elements in relief.
Finally, it should be noted that the packaging and application assembly may be in the form of a kit, it being possible for the applicator and the packaging device to be housed separately in the same packaging article.
The expressions “between ... and ...”, and “ranging from ... to ...” should be understood as meaning limits included, unless otherwise specified. In the description and the examples, the percentages are weight percentages, unless otherwise indicated. The percentages are thus expressed by weight relative to the total weight of the composition. The ingredients are mixed in the order and under the conditions that are readily determined by a person skilled in the art.
The invention will now be described by means of examples which are present for purely illustrative purposes and should not be interpreted as examples that limit the invention.
Examples 1 and 2
Phase Ingredients 1
(invention) 		2
(outside the invention)
65% by weight of pigment paste comprising 40% of iron oxide, 10% or 0% by weight of tannic acid and the remainder being water, namely in each of the compositions:
A
Tannic acid
(Brewtan F® - Anijomoto Omnichem NV)		 6.5 -
Black iron oxide (CI 77499)
SUNPURO C33-7001 from SUN		 26 26
Water 32.5 39
B
35% by weight of aqueous dispersion of wax
containing 27% of carnauba wax, 10% of ethanol, 7% of PEG-30 Glyceryl Stearate surfactant and 56% of water
(MEXORYL SAP ® from NOVEAL) namely in each of the compositions:
Carnauba wax 9.45 9.45
PEG-30 glyceryl stearate 2.45 2.45
Ethanol 3.5 3.5
Water 19.6 19.6

Appearance of the composition at rest at 25°C, 24 hours after its preparation 		The composition remained stable, the colour remains black and homogeneous. The composition phase separated very quickly. The pigments have settled. Two distinct phases were observed: a white phase on top and a black-coloured phase on the bottom.
Preparation protocol
The pigment phase A was prepared at 25°C by mixing the pigment in water in the presence or absence of tannic acid. Once the mixture is homogeneous, 65% by weight of this pigment preparation was added to 35% by weight of the dispersion of carnauba wax MEXORYL SAP® from NOVEAL.
The appearance of the composition at rest 24 hours after preparation was observed.
In the presence of tannic acid, composition 1 according to the invention remained stable and homogeneous at 25°C, 24 hours after its preparation whereas composition 2 outside the invention obtained without tannic acid was unstable, resulting in phase separation. In the case of composition 2, settling of the pigment in the bottom of the composition and a white supernatant were observed.

Claims (33)

  1. Composition comprising, preferably in a physiologically acceptable medium:
    (1) at least one polyphenol comprising at least two different phenol groups;
    (2) at least one aqueous dispersion of wax particles;
    (3) at least one nonionic surfactant with an HLB of greater than or equal to 8; and
    (4) at least one pigment of uncoated iron oxide type.
  2. Composition according to Claim 1, not comprising any water-soluble or water-dispersible thickening or gelling polymer.
  3. Composition according to Claim 1, in which the polyphenol is chosen from catechin tannins, notably chosen from gallotannins and ellagitannins.
  4. Composition according to Claim 1 or 2, in which the polyphenol is epigallocatechin, notably a green tea extract comprising at least 45% by weight of epigallocatechin relative to the weight of said extract.
  5. Composition according to Claim 1, in which the polyphenol is a procyanidin or a mixture of procyanidins, in particular an extract of maritime pine bark, notably comprising at least 65% by weight of procyanidins relative to the total weight of said extract.
  6. Composition according to Claim 1 or 2, in which the polyphenol is tannic acid.
  7. Composition according to any one of the preceding claims, in which the polyphenol(s) is (are) present in an amount of greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0% by weight and more particularly greater than or equal to 2.0% by weight relative to the total weight of the composition.
  8. Composition according to any one of the preceding claims, in which the polyphenol(s) is (are) present in an amount ranging from 1.0% to 30.0% by weight, and more particularly ranging from 2.0% to 30% by weight relative to the total weight of the composition.
  9. Composition according to any one of the preceding claims, in which the nonionic surfactant(s) with an HLB of greater than or equal to 8 is (are) polyoxyalkylenated, monoglycerolated and/or polyglycerolated.
  10. Composition according to any one of the preceding claims, in which the nonionic surfactant(s) with an HLB of greater than or equal to 8 correspond(s) to formula (II) below:
    (ALK-[C(O)]a-[O]b)c-X (II)
    in which:
    - ALK is a C7-C23, preferably C11-C21 and more preferentially C15-C17 alkyl group,
    - a and b are integers ranging from 0 to 100,
    - c is an integer ranging from 1 to 100, in particular from 1 to 3, preferably equal to 1, a and b preferably being equal to 0,
    - X is a (poly)oxyalkylene group optionally substituted and/or terminated with a hydroxyl group, X preferably being an oxyethylene group (CH2CH2O)n or (OCH2CH2)n in which n is greater than or equal to 1, for example ranging from 1 to 200.
  11. Composition according to Claim 9, in which the nonionic surfactant(s) with an HLB of greater than or equal to 8 of formula (II) is (are) such that the group X is chosen from
    i) those of formula (III) below:
    HO-(ALK-O)z-CH2-CH[(OALK)y-OH]-CH2-(O-ALK)x-(*) (III)
    in which:
    - ALK, which may be identical or different, represent a C1-C6 and in particular C1-C4 alkylene group, preferably ethylene,
    - x, y and z being an integer between 0 and 200, it being understood that x+y+z is other than 0, x+y+z preferably being inclusively between 1 and 150 and in particular between 20 and 60;
    ii) those of formula (IV) or (V) below:
    H-(ALK-O)x-(*) (IV)
    or
    H-(O-ALK)x-(*) (V)
    in which:
    - ALK, which may be identical or different, represent a C1-C6 and in particular C1-C4 alkylene group, preferably ethylene,
    - x is an integer other than 0 and preferably between 1 and 200.
  12. Composition according to any one of the preceding claims, in which the nonionic surfactant(s) with an HLB of greater than or equal to 8 is (are) chosen from:
    - (poly)oxyalkylenated, in particular oxyethylenated and/or oxypropylenated, glycerol ethers
    that may comprise from 20 to 200 oxyethylene and/or oxypropylene units such as PPG-50 Glyceryl Ether, PPG-67 Glyceryl Ether, PPG-70 Glyceryl Ether and PPG-24-Glycereth-24;
    - polyoxyalkylenated, in particular polyoxyethylenated and/or polyoxypropylenated, alcohols
    that may comprise from 20 to 200 oxyethylene and/or oxypropylene units, preferably from 20 to 100 oxyethylene units, in particular ethoxylated fatty alcohols, notably C8-C24, and preferably C12-C18 fatty alcohols, such as Steareth-20 and Ceteareth-30;
    - polyoxyalkylenated fatty acid esters, in particular esters of a fatty
    acid, notably a C8-C24 and preferably C16-C22 fatty acid, and of polyethylene glycol (or PEG) that may comprise from 20 to 200 oxyethylene units, such as PEG-50 Stearate and PEG-40 Stearate;
    - esters of a fatty acid, notably a C8-C24 and preferably C16-C22 fatty acid, and of (poly)oxyalkylenated, in particular oxyethylenated and/or oxypropylenated, glycerol ethers that may comprise from 20 to 200 oxyethylene and/or oxypropylene units such as PEG-200 Glyceryl Stearate; PEG-30 Glyceryl Stearate; PEG-20 Glyceryl Oleate, and PEG-20 Glyceryl Laurate;
    - esters of a fatty acid, notably a C8-C24 and preferably C16-C22 fatty acid, and of (poly)oxyalkylenated, in particular oxyethylenated and/or oxypropylenated, sorbitol ethers, that may comprise from 20 to 200 oxyethylene and/or oxypropylene units such as Polysorbate-20, Polysorbate-21, Polysorbate-40, Polysorbate-60 and Polysorbate-80;
    - esters of a C12-C20 fatty acid and of a polyglycerol comprising from 3 to 12 glycerol groups, preferably from 6 to 10 glycerol groups such as Polyglyceryl-6 Stearate; Polyglyceryl-6 Isostearate; Polyglyceryl-10 Stearate; Polyglyceryl-10 Isostearate; Polyglyceryl-10 Laurate; Polyglyceryl-10 Myristate; and Polyglyceryl-10 Oleate; and
    - mixture(s) thereof.
  13. Composition according to any one of the preceding claims, in which the nonionic surfactant(s) with an HLB of greater than or equal to 8 is (are) chosen from esters of a C12-C20 fatty acid and of a polyglycerol comprising from 3 to 12 glycerol groups, preferably from 6 to 10 glycerol groups, in particular the nonionic surfactant with an HLB of greater than or equal to 8 is PEG-30 Glyceryl Stearate.
  14. Composition according to any one of the preceding claims, in which the nonionic surfactant(s) with an HLB of greater than or equal to 8 is (are) present in an amount of greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0% by weight relative to the total weight of the composition.
  15. Composition according to any one of the preceding claims, in which the nonionic surfactant(s) with an HLB of greater than or equal to 8 is (are) present in an amount of less than or equal to 15% by weight, preferably less than or equal to 12% by weight, and more particularly ranges from 1% to 8% by weight relative to the total weight of the composition.
  16. Composition according to any one of the preceding claims, in which the mole ratio of the hydroxyl (OH) groups of the polyphenol which are reactive via a hydrogen bonding interaction to the reactive groups of the nonionic surfactant with an HLB of greater than or equal to 8 ranges from 1/3 to 20, more preferentially from 1/2 to 15 and more particularly from 3/4 to 3.
  17. Composition according to any one of the preceding claims, in which the mean size of the wax particles is less than or equal to 30 microns, preferably less than or equal to 10 microns, or even less than or equal to 1 micron.
  18. Composition according to any one of the preceding claims, in which the mean size of the wax particles is less than or equal to 1 μm, notably ranges from 0.02 μm to 1 μm, more preferentially is less than or equal to 0.5 μm, in particular ranges from 0.051 μm to 0.5 μm.
  19. Composition according to any one of the preceding claims, in which the wax or waxes are polar, and preferably are chosen from beeswax, lanolin wax; rice bran wax, carnauba wax, candelilla wax, ouricury wax, Japan wax, berry wax, shellac wax and sumac wax; montan wax, hydrogenated castor oil, hydrogenated lanolin oil, waxes derived from the reaction of fatty acids on carbohydrates, for instance disaccharides of sucrose type, such as sucrose polybehenate, and C20-C40 alkyl (hydroxystearyloxy)stearate waxes and mixtures thereof.
  20. Composition according to any one of the preceding claims, in which the wax is carnauba wax (INCI name: COPERNICA CERIFERA (CARNAUBA) WAX).
  21. Composition according to any one of the preceding claims, in which the wax(es) is (are) present in an amount of greater than or equal to 5.0% by weight, more preferentially greater than or equal to 8.0%, in particular ranging from 8% to 25% by weight, relative to the total weight of the composition.
  22. Composition according to any one of the preceding claims, comprising an aqueous dispersion of carnauba wax containing 27% by weight of said wax, 10% by weight of ethanol, 7% by weight of PEG-30 Glyceryl Stearate surfactant and 56% by weight of water relative to the total weight of the dispersion.
  23. Composition according to any one of the preceding claims, in which the uncoated iron oxide(s) is (are) present in an amount ranging up to 35.0% by weight, more preferentially ranging up to 25.0% by weight and more particularly ranging from 4% to 25% by weight relative to the total weight of the composition.
  24. Composition according to any one of the preceding claims, in which the pigment(s) is (are) iron oxides.
  25. Composition according to any one of the preceding claims, in which the amount of water is less than or equal to 30% by weight, and more preferentially varies from 5% to 30% by weight, and more particularly from 8% to 25% relative to the total weight of the composition.
  26. Composition according to any one of the preceding claims, further comprising an oily phase.
  27. Composition according to any one of the preceding claims, which is in the form of an oil-in-water emulsion.
  28. Composition according to Claim 26 or 27, in which the total amount of non-volatile oil(s) is less than or equal to 10% by weight, more preferentially less than or equal to 5.0% by weight, or even less than 2.0% by weight relative to the total weight of the composition, or even free of non-volatile oil relative to the total weight of the composition.
  29. Composition according to Claim 26 or 27, in which the total amount of volatile oil(s) is less than or equal to 10% by weight, more preferentially less than or equal to 5.0% by weight, relative to the total weight of the composition, or even free of volatile oil relative to the total weight of the composition.
  30. Composition according to any one of the preceding claims, in the form of a makeup product for the face such as a foundation, for the cheeks or for the eyelids such as face powders and eyeshadows.
  31. Composition according to any one of the preceding claims, in the form of a makeup product for the eyelashes such as a mascara, an eyebrow product or a product for the contour of the eyes, such as an eyeliner.
  32. Assembly, or kit, for packaging and applying a cosmetic composition for coating keratin fibres, comprising:
    - a packaging device comprising the composition as defined in any one of the preceding claims;
    - an applicator for said composition.
  33. Process for coating keratin materials, in particular the skin, keratin fibres such as the eyelashes and/or the eyebrows, comprising a step of applying to said keratin materials at least one composition as defined in any one of Claims 1 to 31.
PCT/EP2023/058549 2022-04-28 2023-03-31 Composition with a polyphenol, an aqueous dispersion of wax, a nonionic surfactant with an hlb of greater than or equal to 8 and an uncoated iron oxide WO2023208523A1 (en)

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FR2203998A FR3134983A1 (en) 2022-04-28 2022-04-28 Composition with a polyphenol, an aqueous wax dispersion, a nonionic surfactant with HLB greater than or equal to 8 and an uncoated iron oxide
FRFR2203998 2022-04-28

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR853634A (en) 1938-04-29 1940-03-23 Ericsson Telefon Ab L M Measuring devices
EP0394078A1 (en) 1989-02-24 1990-10-24 L'oreal Cosmetic composition for hair treatment containing a microdispersion of wax
EP0507272B1 (en) * 1991-04-05 1995-07-05 Kao Corporation Hair cosmetic composition comprising a water soluble chitin derivative and a polyphenol
FR2787709A1 (en) * 1998-12-23 2000-06-30 Boots Co Plc NOVEL DERMATOLOGICAL COMPOSITION BASED ON TANNIC ACID AND A MICROBIAL PROLIFERATION INHIBITOR
FR2792190A1 (en) 1999-04-16 2000-10-20 Sophim Non-greasy wax-ester emollients for use in skin care preparations obtained by interesterification of triglycerides with an alcohol, distilling off residual alcohol, decolorizing and fridge or hydrogenating the product
US20040175338A1 (en) 2003-03-06 2004-09-09 L'oreal Cosmetic composition containing an ester and a pasty compound
DE102008012457A1 (en) 2007-06-19 2008-12-24 Cognis Ip Management Gmbh Hydrocarbon mixture, useful e.g. in decorative cosmetics, preferably lipsticks, lip gloss, eye shade, mascara, eye pencil, nail polish and make-up formulations and eye shade, comprises linear hydrocarbons
US20120064061A1 (en) * 2010-09-14 2012-03-15 Innotherapy Inc. Adhesive composition comprising tannin, poly(ethylene glycol), and water, lower alcohol or mixture thereof
US8562960B2 (en) * 2007-07-30 2013-10-22 Elc Management, Llc Cosmetic composition containing a polymer blend
US20180296444A1 (en) * 2017-03-29 2018-10-18 Dentsply Sirona Inc. Polyphenols/peg based hydrogel system for a dental varnish

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR853634A (en) 1938-04-29 1940-03-23 Ericsson Telefon Ab L M Measuring devices
EP0394078A1 (en) 1989-02-24 1990-10-24 L'oreal Cosmetic composition for hair treatment containing a microdispersion of wax
EP0507272B1 (en) * 1991-04-05 1995-07-05 Kao Corporation Hair cosmetic composition comprising a water soluble chitin derivative and a polyphenol
FR2787709A1 (en) * 1998-12-23 2000-06-30 Boots Co Plc NOVEL DERMATOLOGICAL COMPOSITION BASED ON TANNIC ACID AND A MICROBIAL PROLIFERATION INHIBITOR
FR2792190A1 (en) 1999-04-16 2000-10-20 Sophim Non-greasy wax-ester emollients for use in skin care preparations obtained by interesterification of triglycerides with an alcohol, distilling off residual alcohol, decolorizing and fridge or hydrogenating the product
US20040175338A1 (en) 2003-03-06 2004-09-09 L'oreal Cosmetic composition containing an ester and a pasty compound
DE102008012457A1 (en) 2007-06-19 2008-12-24 Cognis Ip Management Gmbh Hydrocarbon mixture, useful e.g. in decorative cosmetics, preferably lipsticks, lip gloss, eye shade, mascara, eye pencil, nail polish and make-up formulations and eye shade, comprises linear hydrocarbons
US8562960B2 (en) * 2007-07-30 2013-10-22 Elc Management, Llc Cosmetic composition containing a polymer blend
US20120064061A1 (en) * 2010-09-14 2012-03-15 Innotherapy Inc. Adhesive composition comprising tannin, poly(ethylene glycol), and water, lower alcohol or mixture thereof
US20180296444A1 (en) * 2017-03-29 2018-10-18 Dentsply Sirona Inc. Polyphenols/peg based hydrogel system for a dental varnish

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Microemulsions Theory and Practice", 1977, ACADEMIC PRESS, pages: 21 - 32
"The HLB System. A Time-Saving Guide to Emulsifier Selection", 1984, ICI AMERICAS INC.
VAN DE HULST, H.C.: "Light Scattering by Small Particles", 1957, WILEY

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