Solid oleogel cosmetic composition
A solid anhydrous cosmetic composition using a combination of L-glutamic acid amides, polyamide-type polycondensates, and either polyurethane gelling agents or modified clays addresses stability issues in solid cosmetic compositions, achieving improved stability and performance.
Patent Information
- Application Number
- FR2023014924
- Authority / Receiving Office
- FR · FR
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-12-21
- Publication Date
- 2025-06-27
AI Technical Summary
Current solid cosmetic compositions, such as stick lipsticks, face stability issues due to the use of synthetic waxes, which are non-biodegradable and have stability problems at room temperature. Additionally, gelled oil formulations are sensitive to storage temperature variations, leading to quality issues like oily film formation.
A solid anhydrous cosmetic composition is developed using a combination of three lipophilic gelling agents: L-glutamic acid amides, polyamide-type polycondensates, and either polyurethane gelling agents or modified clays. This combination stabilizes the oleogelified system, allowing for the creation of solid gels in stick form without the need for waxes.
The composition achieves improved stability and desired properties such as hardness, structure, and sensoriality, making it suitable for care, makeup, and makeup removal applications in various solid anhydrous galenic forms.
Abstract
Description
Title of the invention: Oleogel-formed solid cosmetic composition FIELD OF THE INVENTION
[0001] The present invention relates to the cosmetic field and in particular to solid anhydrous compositions for the care, makeup or removal of makeup from keratin materials, in particular from the skin and / or lips. STATE OF THE ART
[0002] Current cosmetic products in solid form, such as stick lipsticks, are mainly anhydrous formulations composed of solid, pasty and liquid fatty substances at room temperature. The fatty substances that are solid at room temperature used in cosmetics have varied melting points, which allow structuring by crystallization. Among these solid fatty substances, waxes are widely used, but many synthetic waxes are considered non-biodegradable plastic beads, and waxes of natural origin also have stability problems at temperatures close to room temperature.
[0003] We therefore seek to reduce their content in the compositions, or to substitute them with other compounds. One of the technical approaches consists of solidifying the oils, not by crystallization but by gelling, thanks to the use of lipophilic gelling agents. But the major problem with this type of formulation by gelling is the sensitivity to variations in storage temperature. Thus, fatty substances in liquid form structured by gelling and not by crystallization tend to form an oily film on the surface of the formats cast in cups, pots, sticks. This phenomenon is reversible but it can cause quality problems.
[0004] There therefore remains a need to develop new gelled solid anhydrous compositions (also referred to as oleogelled solid compositions), exhibiting improved stability.
[0005] It is in this context that the Applicant has demonstrated that the use of a 3rd gelling agent of polyurethane or modified clay type, in association with two lipophilic gelling agents chosen for their oil gelling properties, makes it possible to stabilize the oleogelified system. In particular, it has shown that the association of a first lipophilic gelling agent of L-glutamic acid amide type, and a second lipophilic gelling agent of polyamide polycondensate type, allows the formation of a solid gel in stick form, but that the addition of a 3rd gelling agent chosen specifically from a lipophilic polyurethane or a modified clay, was necessary for the stabilization of this system.
[0006] The combination of the 3 lipophilic gelling agents according to the invention in an oily phase therefore allows the development of solid anhydrous gelled cosmetic products, where appropriate without waxes, but nevertheless presenting the desired properties in terms of hardness, structure and sensoriality on application, for applications in care, makeup and makeup removal and for all types of solid anhydrous galenics in stick, pot or jar form. Summary of the invention
[0007] A first subject of the invention therefore relates to a solid anhydrous cosmetic composition for care, makeup or makeup removal of keratin materials comprising, in a physiologically acceptable medium, at least: i. A non-volatile hydrocarbon oil, ii. A first lipophilic gelling agent chosen from L-glutamic acid amides, iii. A second lipophilic gelling agent chosen from polyamide-type polycondensates, and iv. A third lipophilic gelling agent chosen from polyurethane gelling agents (iva or iva'), modified clays (ivb), and mixtures thereof, preferably polyurethane gelling agents (iva or iva').
[0008] The invention also relates to a cosmetic process for caring for and / or making up keratin materials, in particular the skin and / or the lips, preferably the lips, comprising the application to said keratin materials of a composition as defined according to the invention.
[0009] Another subject of the invention is a process for removing makeup from made-up keratin materials, in particular from the lips, comprising the application to said keratin materials of a composition as defined according to the invention, then wiping the keratin materials in order to remove the makeup film.
[0010] The present invention thus constitutes a real advance in the formulation of gelled solid anhydrous products, preferably without waxes. DETAILED DESCRIPTION OF THE INVENTION
[0011] The invention therefore relates in particular to a solid anhydrous cosmetic composition for caring for, making up or removing make-up from keratin materials comprising, in a physiologically acceptable medium, at least: i. A non-volatile hydrocarbon oil, ii. A first lipophilic gelling agent chosen from L-glutamic acid amides, iii. A second lipophilic gelling agent chosen from polyamide-type polycondensates, and iv. A third lipophilic gelling agent chosen from polyurethane gelling agents (iva or iva'), modified clays (ivb), and their mixtures, preferably polyurethane gelling agents (iva or iva').
[0012] By "cosmetic composition" is meant any composition for cosmetic purposes, that is to say aesthetic, which can be brought into contact with the superficial parts of the human body and more particularly with keratin materials, in particular human skin and / or lips.
[0013] By "physiologically acceptable medium" is meant any excipient suitable for topical use, in contact with keratin materials, without risk of toxicity, incompatibility, instability and / or allergic response.
[0014] By "anhydrous composition" is meant in particular that water is not deliberately added to the composition of the invention but may be present in trace amounts in the various compounds used in the composition. In particular, the composition according to the invention comprises less than 4% by weight of water, preferably less than 3%, preferably less than 2%, more preferably less than 1%, even more preferably less than 0.5% by weight of water, relative to the total weight of said composition, or even is completely free of water. According to a particular embodiment, the composition is free of water.
[0015] By "solid composition" according to the invention, we mean a composition which does not flow under its own weight, at 20°C and at atmospheric pressure (760 mm Hg), as opposed to so-called liquid compositions.
[0016] The composition may in particular be in the form of a stick or a composition packaged in a cup.
[0017] The hardness of the compositions of the invention, in particular the sticks, can be measured at 20°C by the so-called "butter wire cutting" method, which consists of transversely cutting a stick of product with a diameter of between 10 and 12 mm, preferably cylindrical in revolution, using a rigid metal wire with a diameter of 250 μm, moving the wire relative to the stick at a speed of 60 mm / min. The hardness of the samples is expressed in Gram force (Gf) and can be measured using a texturometer of the Texturometer TAXT Plus type. For a stick of a composition intended to be applied to the lips, the minimum value obtained is greater than 30 Gf. According to a particular and preferred embodiment, the hardness of the sticks according to the invention will range from 50 to 110 Gf, preferably from 60 to 100 Gf, in particular from 70 to 90 Gf, even better from 75 to 90 Gf.
[0018] A person skilled in the art will know how to adapt the method of shaping the stick from the composition of the invention according to its hardness. In particular when the hardness is less than 1000gf, shaping the stick by a so-called "back-fill" method, consisting of pouring and cooling the composition directly in the mechanism of the pack will be preferred over shaping consisting of pouring and cooling the composition position in a mold then stick the stick into the mechanism.
[0019] By "keratin materials" according to the invention, we mean the skin and / or its appendages, and more particularly the human skin and / or lips. In particular, this will be the skin of the face and / or neck and / or body, and the lips. The keratin materials in the context of the invention are healthy, that is to say not presenting any troubles or disorders which would be part of a pathological state ("non-healthy" subjects, suffering from a pathology). We will speak indifferently of healthy skin and / or lips or skin and / or lips in the remainder of the description.
[0020] According to a particular embodiment, the composition of the invention comprises less than 5% by weight of waxes relative to the total weight of the composition, preferably less than 3% of waxes, or even is free of waxes. Non-volatile hydrocarbon oils (compound (i))
[0021] The composition of the invention therefore comprises a gelled oily phase comprising one or more oils, in particular one or more hydrocarbon oils.
[0022] By “oil” is meant a fatty substance, insoluble in water, liquid at 25°C and atmospheric pressure.
[0023] By "hydrocarbon oil" is meant according to the invention an oil containing mainly hydrogen and carbon atoms, in particular being neither silicone nor fluorinated.
[0024] According to the invention, the term “non-volatile oil” means an oil that does not meet the definition of “volatile oil” defined below.
[0025] By "volatile oil" is meant according to the invention an oil having lost more than 20% of its mass at 60 minutes, according to the protocol below.
[0026] METHODOLOGY: 20 mg of the oil to be studied is weighed onto a 5 cm x 5 cm PMMA plate using a micropipette and a precision balance. This material is spread with the finger over the entire plate. Then, it is placed in a ventilated chamber thermostatically controlled at 33°C and 50% humidity. For each material, the test is carried out 3 times. The mass loss during drying is measured after 60 minutes. The mass lost is expressed according to the following calculation:
[0027] [Math.l] % musse ærdw — ------— X 100 With mtx corresponding to the remaining mass at the measured time (tôOmin) and mt0 corresponding to the mass applied initially.
[0028] In particular, the non-volatile hydrocarbon oils are chosen from oils esters, C15-C21 alkanes, triglycerides of vegetable origin, oils of vegetable origin, C10-C26 alcohol oils, and mixtures thereof.
[0029] Among the ester oils, we can notably cite:
[0030] - esters of fatty alcohols and C8-C18 fatty acids, in particular coco-caprylate caprate which is an ester of naturally occurring fatty alcohol (e.g. coconut), caprylic acid and capric acid,
[0031] - fatty acid esters, in particular of 4 to 22 carbon atoms,
[0032] - synthetic esters such as oils of formula RiCOOR2 in which Ri re has the residue of a linear or branched fatty acid containing from 4 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched one, containing from 4 to 40 carbon atoms provided that Ri+R2 is >16, such as for example isononyl isononanoate, 2-ethylhexyl palmitate, octyldodecyl neopentanoate, isodecyl neopentanoate, 2-octyldodecyl stearate, isostearyl isostearate, 2-octyldodecyl benzoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyl-decyl, 2-octyldodecyl myristate, 2-diethyl-hexyl succinate;
[0033] - linear fatty acid esters having a total carbon number ranging from 35 to 70;
[0034] - hydroxylated esters, preferably having a total carbon number ranging from 35 to 70, such as polyglyceryl-2 triisostearate, polyglyceryl-10 pentaisostearate, polyglyceryl 10 nonaisostearate, isostearyl lactate, octyldodecyl hydroxystearate, diisostearyl malate, glycerin stearate; diethylene glycol diisononanoate;
[0035] - esters of aromatic acids and alcohols comprising 4 to 22 atoms;
[0036] - esters of fatty alcohol or branched C24-C28 fatty acids;
[0037] - esters of amino acid derivatives; we can cite in particular Di (phytosteryl octyldodecyl)N-Lauroyl-L-glutamate (e.g. Eldew®);
[0038] - and their mixtures.
[0039] Among the C15-C21 alkanes, the following commercial references may be cited in particular: - VEGELIGHT 1618LC from the company Biosynthis, with INCI name C15-19 ALKANE (and) COCO-CAPRYLATE CAPRATE; - VEGELIGHT 1820 from the company Biosynthis, with INCI name Cl8-21 ALKANE; EMOGREEN L19 from the company SEPPIC, with INCI name C15-19 ALKANE.
[0040] As triglycerides of plant origin, mention may in particular be made of glycerol trihexanoate, glycerol triheptanoate (triheptanoin), glycerol trioctanoate, coco-caprylate / caprate, and mixtures thereof, preferably coco-caprylate / caprate.
[0041] As oils of vegetable origin, we can cite in particular: Sunflower oil, jojoba oil, castor oil, sweet almond oil, argan oil, and mixtures thereof.
[0042] As C10-C26 alcohol oils, more particularly C10-C24, and preferably C12-C22, more particularly monoalcohols, mention may be made in particular of lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecyl pentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol and mixtures thereof.
[0043] According to a preferred embodiment, the composition of the invention comprises at least one ester oil chosen from: - esters of fatty alcohols and C8-C18 fatty acids, in particular coco-caprylate caprate which is an ester of fatty alcohol of natural origin (e.g. coconut), caprylic acid and capric acid, - hydroxylated esters, preferably having a total carbon number ranging from 35 to 70, such as polyglycerol-2 triisostearate, Polyglyceryl-10 Pentaisostearate, Polyglyceryl 10 Nonaisostearate, isostearyl lactate, octyldodecyl hydroxystearate, diisostearyl malate, glycerin stearate; diethylene glycol diisononanoate, - and their mixtures.
[0044] More preferably, the composition comprises coco-caprylate caprate and polyglycerol-2 triisostearate.
[0045] Preferably, the total content of non-volatile hydrocarbon oils (compound i) will generally range from 30 to 90%, preferably from 35 to 85%, more preferably from 35 to 80%, better still from 40 to 75% by weight relative to the total weight of the composition.
[0046] The composition according to the invention further comprises at least 3 particular lipophilic gelling agents, as defined below.
[0047] Indeed, the Applicant has shown that the combination of a first lipophilic gelling agent of the L-glutamic acid amide type, and a second lipophilic gelling agent of the polyamide polycondensate type, allowed the formation of a solid gel in stick form, but that the addition of a 3rd gelling agent chosen specifically from a lipophilic polyurethane or a modified clay, was necessary for the stabilization of this system.
[0048] The term “lipophilic gelling agent” means a liposoluble or lipodispersible compound capable of gelling the fatty (or oily) phase of the composition according to the invention.
[0049] By liposoluble or lipodispersible is meant the possibility of dissolving the gelling agent (polymeric or not) or of dispersing it homogeneously in at least one oil, at room temperature or by heating where appropriate to a temperature below the flash point of said oil, and at a mass percentage generally less than or equal to 80% by weight of gelling agent.
[0050] First gelling agent: glutamic or aspartic acid amide (compound ii)
[0051] The first lipophilic gelling agent used in the composition according to the invention is chosen among the amides of L-glutamic acid or aspartic acid, preferably the amides of L-glutamic acid (glutamides).
[0052] Such an amide of glutamic acid used in the composition of the invention is notably described in patent application FR 2 820 739 by Ajinomoto, and corresponds to a compound represented by the following formula (I):
[0053] [Chem.l] $ XCHjVconhr1 JL A ® H
[0054] where R1 and R2 independently represent a hydrocarbon group having 1 to 26 carbon atoms, R3 represents a hydrocarbon group having 7 to 10 carbon atoms, n represents 1 or 2, provided that the acidic amino acid residue in the molecule is an L-aspartic acid residue when n is 1 and is an L-glutamic acid residue when n is 2.
[0055] Preferably, R1 and R2 independently represent a linear or branched alkyl group having 1 to 26 carbon atoms, R3 represents a linear or branched alkyl group having 7 to 10 carbon atoms and n represents 2. More preferably, R1 and R2 independently represent a linear or branched alkyl group having 3 to 5 carbon atoms, preferably an n-butyl group, R3 represents a linear or branched alkyl group having 7 to 9 carbon atoms and n represents 2. Preferably the group represented by R3-CO is selected from an octanoyl, decanoyl or 2-ethylhexanoyl group, more preferably a 2-ethylhexanoyl group.
[0056] Most particularly preferably, the compound represented by the general formula (I) is chosen from N-2-ethylhexanoyl-L-glutamic acid dibutylamide (otherwise called dibutyl ethylhexanoyl glutamide), N-octanoyl-L-glutamic acid dibutylamide (otherwise called dibutyl octanoyl glutamide), N-decanoyl-L-glutamic acid dibutylamide glutamic acid (otherwise called dibutyl decanoyl glutamide), and mixtures thereof.
[0057] According to a particular and preferred embodiment, the gelling agent is in the form of a mixture of a compound of formula (I) as described above and N-lauroyl-L-glutamic acid dibutylamide (otherwise known as dibutyl lauroyl glutamide). A preferred mixture comprises dibutyl ethylhexanoyl glutamide as the compound of formula (I) and dibutyl lauroyl glutamide. According to this latter embodiment, the mass ratio of the compound represented by the general formula (I) to dibutyl lauroyl glutamide will generally range from 35:5 to 5:35.
[0058] Thus, the amides of L-glutamic acid (glutamides) or of aspartic acid used as first gelling agent according to the invention preferably comprise at least an alkyl group comprising from 6 to 14 carbon atoms, for example 8 or 12 carbon atoms. The glutamides are preferably chosen from dibutyl lauroyl glutamide, dibutyl ethylhexanoyl glutamide, and their mixture, and may be for example one of the products of the brands EB-21, GP-1, AJK-OD2046, AJK-BG2055, and AJK-CE2046, manufactured by the company Ajinomoto.
[0059] According to a particular and preferred embodiment, the composition of the invention comprises the compound with the INCI name: OCTYLDODECANOL and DIBUTYL LAUROYL GLUTAMIDE and DIBUTYL ETHYLHEXANOYL GLUTAMIDE, marketed under the name AJK OD-2046 by the company AJINOMOTO. The amide or mixture of amides, in particular glutamide(s), will generally represent from 0.5 to 15% by weight, in particular from 1% to 10% by weight, or even from 1.5 to 5% by weight of active materials relative to the total weight of the composition.
[0060] Second gelling agent: polyamide-type polycondensate (compound iii)
[0061] The composition according to the invention comprises at least one lipophilic polycondensate of polyamide type, as a second lipophilic gelling agent of the oily phase.
[0062] Polyamide-type polycondensates can form a three-dimensional network by hydrogen bonding type interactions, in which lipophilic oils have an affinity for acidic dimer chains. Applied to the surface of the skin and / or lips, they form a highly structured network resistant to external stresses (friction, contact, etc.) and which reforms quickly after shearing, while remaining comfortable.
[0063] For the purposes of the invention, the term “polycondensate” means a polymer obtained by polycondensation, namely by chemical reaction between monomers having different functional groups chosen in particular from acid, alcohol and amine functions.
[0064] For the purposes of the invention, the term “polymer” means a compound having at least 2 repeating units, preferably at least 3 repeating units and better still 10 repeating units.
[0065] In the remainder of the description, we speak indifferently of 'polyamide polymer' or 'polyamide polycondensate' or 'lipophilic polyamide polycondensate' or 'lipophilic polycondensate of polyamide type' or 'lipophilic gelling polymer of polyamide type'.
[0066] The polyamide-type polycondensate is preferably chosen from ester-terminated polyamides, tertiary amide-terminated polyamides or polyalkyleneoxy-terminated polyamides or even ester-terminated poly(ester-amides).
[0067] In the context of the invention, the composition according to the invention advantageously comprises at least one ester-terminated polyamide and / or one ester-terminated poly(ester-amides).
[0068] According to a first preferred embodiment of the invention, the composition comprises at least one Ester-terminated polyamide obtained by condensation of a C36 diacid, more particularly a linoleic acid dimer (also called dilinoleic acid), with ethylenediamine, the remaining acid ends being esterified by cetyl alcohol (Cl6), stearyl alcohol (Cl8) or their mixture. The copolymer thus obtained has the INCI name: ETHYLENEDIAMINE / STEARYL DIMER DL LINOLEATE COPOLYMER.
[0069] These mixtures are also sold by the company CRODA under the trade name OLEOCRAFT LP-IO-PA-(MV) respectively at 99.7% (in active matter) with a preservative. They have a softening point of 88°C to 94°C. Its weight-average molecular mass is preferably 6000, even more preferably 4000.
[0070] According to a second particularly preferred embodiment of the invention, the composition comprises at least one poly(ester-amide) with an ester end obtained by condensation of a C36 diacid, more particularly a dimer of hydrogenated linoleic acid (also called hydrogenated dilinoleic acid) and neopentyl glycol, on ethylene diamine; the remaining acid ends being esterified by stearyl alcohol (C18).
[0071] The copolymer thus obtained is a dimer copolymer of ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl, having the INCI name: POLYAMIDE-8.
[0072] The copolymer with the INCI name POLYAMIDE-8 is, for example, marketed under the name OLEOCRAFT LP-20 by the company CRODA.
[0073] In general, the polymers as described below are in the form of polymer mixtures, these mixtures being able to further contain a synthetic product corresponding to a diester.
[0074] A mixture of lipophilic gelling agents among those described above is for example a mixture of ester-terminated poly(ester-amides) and polyalkyleneoxy-terminated polyamides whose molecular weights are approximately between 4,500 and 30,000 Daltons (Da).
[0075] According to a particular and preferred embodiment, the lipophilic polycondensate of polyamide type used in the composition of the invention is the compound with INCI name: POLYAMIDE-8 marketed under the name Oleocraft LP 20 by the company Croda.
[0076] According to a particular embodiment, the lipophilic polycondensate of polyamide type used according to the invention is present in the composition in an amount of active material ranging from 5% to 30% by weight, preferably from 7% to 25%, better still from 8 to 22% by weight relative to the total weight of the composition.
[0077] Third gelling agent: lipophilic polyurethane or modified clay (compound iv) Lipophilic polyurethane (compound iva and iva')
[0078] The term “lipophilic gelling agent” means a liposoluble or lipodispersible compound capable of gelling the fatty (or oily) phase of the composition according to the invention.
[0079] Liposoluble or lipodispersible means the possibility of dissolving the polymer or dispersing it homogeneously in at least one oil, at room temperature or by heating where appropriate to a temperature below the flash point of said oil, and at a mass percentage generally less than or equal to 80% by weight of film-forming polymer.
[0080] According to a particular embodiment, the lipophilic polyurethane (iva) comprises a hydrophobic segment (or part) (al) and a hydrophilic segment (or part) (a2).
[0081] The hydrophobic segment (al) advantageously comprises at least one unit derived from an isocyanate compound also called “isocyanate unit”. As isocyanate compound, mention may be made of 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanatomethyl) cyclohexane, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof. Preferably, the isocyanate compound is 1,6-hexamethylene diisocyanate.
[0082] The hydrophobic portion may further comprise at least one unit derived from a hydrogenated polyolefin polyol.
[0083] Examples of hydrogenated polyolefin polyols include hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol and mixtures thereof, in particular hydrogenated polybutadiene diol.
[0084] The hydrophobic portion preferably further comprises at least one unit derived from a dimer diol which can be hydrogenated. Examples of dimer diol include dimer dilinoleic alcohol, dimer dioleic alcohol and mixtures thereof, preferably dimer dilinoleic alcohol and better still hydrogenated dimer dilinoleic alcohol is particularly preferred.
[0085] The hydrophilic part (a2) preferably comprises a unit derived from a polyol, preferably a trio or diol, of low molecular weight, ranging for example from 50 to 800, better still from 60 to 700.
[0086] The low molecular weight diols may be chosen from ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, and mixtures thereof. As triol, mention may in particular be made of trimethylolpropane. Preferably, the low molecular weight polyol is chosen from ethylene glycol, 1,4-butylene glycol, trimethylolpropane and mixtures thereof.
[0087] According to one embodiment, the lipophilic polyurethane (iva') is derived from the condensation of a polyester polyol obtained by reaction of a polyol such as trimethylol propane with a lactone, such as hexyl lactone, and a diisocyanate compound as described above, in particular 1,6-hexamethylene diisocyanate.
[0088] According to advantageous embodiments, the lipophilic polyurethane can be chosen among the following compounds of (I) and (II):
[0089] Polyurethane (I) resulting from the reaction of at least (i) a hydrogenated polybutadiene having terminal isocyanate groups and at least (ii) a diol of formula HO-R 3-OH in which R3 represents a linear or branched C2-C6 alkylene group which may comprise an ether bond, and
[0090] Polyurethane (II) resulting from the reaction of at least (iii) a hydrogenated polybutadiene having terminal hydroxyl groups, at least (iv) a diisocyanate compound and at least (ii) a diol of formula HO-R 3 -OH as defined above.
[0091] The choice of the hydrogenated polybutadiene compound (i) is not particularly limited provided that it has terminal isocyanate groups.
[0092] The compound of formula (i) may be chosen from the compounds of formula (1) below:
[0093] in which:
[0094] R 1 and R 2 each independently represent a linear or branched alkylene group, C1 to C6, n is an integer ranging from 10 to 100 and n 1 and n 2 each independently represent 0 or 1
[0095] the C1 to C6 alkylene groups may be chosen from methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene and mixtures thereof.
[0096] Preferably, RI represents a C1 to C2 alkylene group.
[0097] Preferably, R2 represents a C5 to C6 alkylene group.
[0098] Preferably, n represents an integer ranging from 10 to 100, preferably 15 at 55 and ni and n 2 are each independently equal to 0 or 1.
[0099] In formula (1), the hydrogenated polybutadiene-derived group or repeating unit of formula (2) below may have different structures of formulas (3 a) to (3d) as follows: CH -Ç-
[0100] In the compound of formula (1), the hydrogenated polybutadiene-derived group may consist of a single type of repeating unit or several types of repeating units distributed statistically or randomly.
[0101] As an example of hydrogenated polybutadiene compounds with terminal isocyanate groups, mention may be made of the compounds of formula (4) below corresponding to the compounds of formula (1) in which:
[0102] n is an integer ranging from 10 to 100,
[0103] R 1 is an ethylene group,
[0104] R 2 is a hexamethylene group,
[0105] ni = n2=l. OO \Vt\ { i '\x ,'t I f! H 'B, ' f M i ''' -x' J e (4)
[0106] in which:
[0107] the diol compound (ii) of formula HO-R 3-OH (in which R3 represents a linear or branched C2-C6 alkylene group which may comprise an ether bond) may be chosen from ethylene glycol (HOCH 2 CH 2 OH), propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol), diethylene glycol and mixtures thereof.
[0108] The choice of hydrogenated polybutadiene having terminal hydroxyl groups (iii) is not particularly limited, as examples it can be chosen from the compounds of formula (6) below. OH (6)
[0109] in which
[0110] n is an integer ranging from 10 to 100 [YES] and the grouping
[0112] is as defined above.
[0113] The diisocyanate compound (iv) may be chosen from diisocyanate of 1,6-hexamethylene, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)benzene and mixtures thereof, preferably diisocyanate 1,6-hexamethylene of formula (7)
[0114] According to a preferred embodiment, the lipophilic polyurethane is chosen from: polyurethanes of formula (I) resulting from the reaction of at least (i) a hydrogenated poly-butadiene having terminal isocyanate groups and at least (ii) a diol of formula HO-R 3-OH, as defined above, in a molar ratio (i): (ii) = 1: 4 to 4: 1, preferably (i): (ii) = 2: 3 to 3: 2, better still (i): (ii) = 4: 5 to 4: 3, and even better still (i): (ii) = 9: 10 to 10: 9;
[0115] in this case, the weight average molecular weight (Mw) of (i) preferably ranges from 1,000 to 3,000;
[0116] and polyurethanes of formula (II) resulting from the reaction of at least (iii) a hydrogenated poly-butadiene having terminal hydroxyl groups, at least (iv) a diisocyanate compound and at least (ii) a diol of formula HO-R 3 -OH, as defined above, in a molar ratio (iii): (ii) = 1: 4 to 4: 1, preferably (iii): (ii) = 2: 3 to 3: 2, better 4: 5 to 4: 3, and even better 9: 10 to 10: 9.
[0117] The polyurethane of formula (I) or (II) may have a weight-average molecular mass (Mw) ranging from 10,000 to 150,000, preferably from 15,000 to 130,000, and better still from 20,000 to 110,000.
[0118] Thus, according to a particular and preferred embodiment, the lipophilic polyurethane (iva) used in the composition of the invention comprises a hydrophobic segment (al) and a hydrophilic segment (a2), in which the hydrophobic segment (al) comprises at least one unit derived from an isocyanate compound, preferably 1,6-hexamethylene diisocyanate, at least one unit derived from a hydrogenated polyolefin-polyol, preferably hydrogenated polybutadiene diol and at least one unit derived from a dimer diol capable of being hydrogenated, preferably hydrogenated dilinoleic alcohol dimer, and the hydrophilic segment (a2) comprises at least one unit derived from a low molecular weight diol, preferably 1,4-butylene glycol and mixtures thereof
[0119] According to another particular and preferred embodiment, the lipophilic polyurethane (iva') is derived from the condensation of a polyester polyol obtained by reaction of a polyol such as trimethylol propane with a lactone, such as hexyl lactone, and a diisocyanate compound as described above, in particular 1,6-hexamethylene diisocyanate.
[0120] As a lipophilic polyurethane according to the present invention, mention may in particular be made of the copolymer formed by reacting hydrogenated polybutanediol, 1,6-hexamethylene diisocyanate, hydrogenated dilinoleyl alcohol, and 1,4-butanediol, and which is capped with stearyl alcohol, such as that sold under the reference OilkemiaTM 5S Polymer by the company Lubrizol Corporation (INCI name: Polyurethane-69), and the crosslinked copolymer HDI / Trimethylol Hexyllactone sold under the reference OilkemiaTM 5S CC Polymer by the company Lubrizol Corporation (INCI name: HDI / TRIMETHYLOL HEXYLLACTONE CROSSPOLYMER).
[0121] According to a particular and preferred embodiment, the composition of the invention comprises a lipophilic polyurethane with the INCI name: Caprylic / Capric Triglyceride (and) Hydrogenated C6-20 Polyolefin (and) HDI / Trimethylol Hexyllactone Crosspolymer, marketed under the name OILKEMIA 5S CC PALM FREE by the company Lubrizol.
[0122] Thus, according to a particular and preferred embodiment, the composition according to the invention comprises, as third gelling agent (iva or iva'), the gelling agent with INCI name Poly-urethane-69 or Caprylic / capric triglyceride (and) hydrogenated C6-20 polyolefin (and) HDI / trimethylol hexyllactone crosspolymer.
[0123] The content of lipophilic polyurethane (iva) or (iva') in the composition of the invention will in particular range from 0.5 to 15% by weight, preferably from 1.5 to 10%, better still from 2 to 7% by weight relative to the total weight of the composition. Modified clays (compound ivb)
[0124] According to another embodiment, the 3rd lipophilic gelling agent is chosen from modified clays (otherwise called organomodified clays) which are clays treated with compounds chosen in particular from quaternary amines and tertiary amines, preferably quaternary amines.
[0125] The clays are in particular natural or synthetic clays chosen from bentonites, in particular hectorites and montmorillonites. Preferably, they will be hectorites. Even more preferably, a hectorite modified with a quaternary alkylammonium chloride is used, said ammonium being substituted by at least one, and preferably at least two Cl4-C20 alkyl radicals, such as dis-teardimonium hectorite in which the ammonium comprises two methyls and two stearyls.
[0126] As preferred modified clay, mention may in particular be made of a modified hectorite dispersed in an oil, for example the product with the INCI name: COCO-CAPRYLATE / CAPRATE (and) DISTEARDIMONIUM HECTORITE (and) PROPYLENE
[0127]
[0128]
[0129]
[0130]
[0131] CARBONATE marketed under the name BENTONE GEL CCC V MB by the company Elementis. The modified clay content, when present in the composition of the invention, will range in particular from 0.1 to 5% by weight, preferably from 0.2 to 3%, better still from 0.25 to 1% by weight relative to the total weight of the composition. According to a particular and preferred embodiment, the 3rd gelling agent is a lipophilic polyurethane as described previously. The total content of gelling agents (sum of the contents of the 3 gelling agents (ii), (iii) and (iv) mentioned above) will range in particular from 5 to 40% by weight, in particular from 12 to 35% by weight, even better from 15 to 30% relative to the total weight of the composition. According to a particular and preferred embodiment, in the composition of the invention: - the non-volatile hydrocarbon oil(s) (i) are chosen from ester oils, C15-C21 alkanes, triglycerides of vegetable origin, oils of vegetable origin, C10-C26 alcohol oils, and mixtures thereof, preferably in a content ranging from 40 to 60% by weight relative to the total weight of the composition, - the first gelling agent (ii) is an amide of L-glutamic acid comprising at least one C6-C14, preferably C8-C12, alkyl group, such as dibutyl lauroyl glutamide, dibutyl ethylhexanoyl glutamide, and mixtures thereof, preferably in an active ingredient content ranging from 1.5 to 5% by weight relative to the total weight of the composition, - the second gelling agent (iii) is an ester-terminated polyamide and / or ester-terminated poly(ester-amides), preferably an ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl dimer copolymer with INCI name: Polyamide-8, preferably with an active ingredient content ranging from 7 to 25% by weight relative to the total weight of the composition, and - the third gelling agent (iv) is chosen from: a lipophilic polyurethane (iva) comprising a hydrophobic segment (al) and a hydrophilic segment (a2) wherein the hydrophobic segment (al) comprises at least one unit derived from an isocyanate compound, preferably 1,6-hexamethylene diisocyanate, at least one unit derived from a hydrogenated polyolefin polyol, preferably hydrogenated polybutadiene diol and at least one unit derived from a diol dimer capable of being hydrogenated, preferably hydrogenated dilinoleic alcohol dimer, and the hydrophilic segment (a2) comprises at least one unit derived from a low molecular weight diol, preferably 1,4-butylene glycol and mixtures thereof, a lipophilic polyurethane (iva') resulting from the condensation of a polyester polyol obtained by reaction of a polyol such as trimethylol propane with a lactone, such as hexyl lactone, and a diisocyanate compound, in particular 1,6-hexamethylene diisocyanate, a hectorite modified (ivb) by a quaternary alkylammonium chloride, preferably in a content ranging from 0.5 to 10% by weight relative to the total weight of the composition, and - their mixtures,
[0132] preferably lipophilic polyurethane (iva or iva') with INCI name Polyurethane-69 or Caprylic / capric triglyceride (and) hydrogenated C6-20 polyolefin (and) HDI / trimethylol hexyllactone crosspolymer.
[0133] In a particular mode of composition: - the non-volatile hydrocarbon oil(s) (i) are chosen from esters of fatty alcohols and C8-C18 fatty acids, in particular coco-caprylate caprate, C35-C70 hydroxylated esters, preferably polyglycerol-2 triisostearate, and mixtures thereof, - the first gelling agent (ii) is a mixture of dibutyl lauroyl glutamide and dibutyl ethylhexanoyl glutamide, and mixtures thereof, - the second gelling agent (iii) is a dimer copolymer of ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl with INCI name: Polyamide-8, and - the third gelling agent (iv) is a lipophilic polyurethane (iva or iva') with the INCI name Polyurethane-69 or Caprylic / capric triglyceride (and) hydrogenated C6-20 polyolefin (and) HDI / trimethylol hexyllactone crosspolymer.
[0134] In another particular mode of composition: - the non-volatile hydrocarbon oil(s) (i) are chosen from esters of fatty alcohols and C8-C18 fatty acids, in particular coco-caprylate caprate, C35-C70 hydroxylated esters, preferably polyglycerol-2 triisostearate, and mixtures thereof, - the first gelling agent (ii) is a mixture of dibutyl lauroyl glutamide and dibutyl ethylhexanoyl glutamide, and mixtures thereof, - the second gelling agent (iii) is a dimer copolymer of ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl with INCI name: Polyamide-8, and - the third gelling agent (iv) is a modified clay (ivb) with INCI name: Coco-Caprylate / Caprate (And) Disteardimonium Hectorite (And) Propylene Carbonate. Additional ingredients (optional)
[0135] The composition of the invention may further comprise one or more in- additional cosmetic ingredients, chosen in particular from agents promoting the adhesion and / or shine of the composition, coloring materials, fillers, antioxidants, perfumes and their mixtures.
[0136] Advantageously, the composition may further comprise at least (v) an agent promoting the adhesion and / or shine of the composition on keratin materials chosen from: - sugar esters, preferably sucrose acetate isobutyrate, - dimer diol and dimer diacid esters, optionally esterified on their alcohol or free acid function(s) by acid or alcohol radicals, and oligomeric polyesters of dimers obtained by reaction between a fatty alcohol and a dimer fatty acid, we can cite in particular the dimer dilinoleate esters and in particular dimerdilinoleyl dimerdilinoleate, - hydrogenated castor oil esters, in particular hydrogenated castor oil dimer dilinoleate,
[0137] and mixtures thereof.
[0138] Thus, according to a particular and preferred embodiment, in the composition of the invention: - the non-volatile hydrocarbon oil(s) (i) are chosen from ester oils, C15-C21 alkanes, triglycerides of vegetable origin, oils of vegetable origin, C10-C26 alcohol oils, and mixtures thereof, preferably in a content ranging from 30 to 90% by weight, preferably 40 to 75% by weight relative to the total weight of the composition, - the first gelling agent (ii) is an amide of L-glutamic acid comprising at least one C6-C14, preferably C8-C12, alkyl group, such as dibutyl lauroyl glutamide, dibutyl ethylhexanoyl glutamide, and mixtures thereof, preferably in a content ranging from 0.5 to 15% by weight, preferably from 1.5 to 5% by weight relative to the total weight of the composition, - the second gelling agent (iii) is an ester-terminated polyamide and / or ester-terminated poly(ester-amides), preferably an ethylenediamine bis-stearyl ethylenediamine dibenzoate dimer copolymer / neopentyl glycol / stearyl with INCI name: Polyamide-8, preferably in a content ranging from 5 to 30% by weight, preferably from 8 to 22% by weight relative to the total weight of the composition, - the third gelling agent (iv) is chosen from a lipophilic polyurethane (iva) comprising a hydrophobic segment (al) and a hydrophilic segment (a2), in which the hydrophobic segment (al) comprises at least one unit derived from an isocyanate compound, preferably 1,6-hexamethylene dii-isocyanate, at least one unit derived from a hydrogenated polyolefin-polyol, preferably hydrogenated polybutadiene diol and at least a unit derived from a diol dimer capable of being hydrogenated, preferably the dimer of hydrogenated dilinoleic alcohol, and the hydrophilic segment (a2) comprises at least one unit derived from a low molecular weight diol, preferably 1,4-butylene glycol and mixtures thereof,
[0139] a lipophilic polyurethane (iva') resulting from the condensation of a polyester polyol obtained by reaction of a polyol such as trimethylol propane with a lactone, such as hexyl lactone, and a diisocyanate compound, in particular 1,6-hexamethylene diisocyanate, a hectorite modified (ivb) by a quaternary alkylammonium chloride, and
[0140] their mixtures,
[0141] preferably the lipophilic polyurethane of INCI name Polyurethane-69 or Caprylic / capric triglyceride (and) hydrogenated C6-20 polyolefin (and) HDI / trimethylol hexyllactone crosspolymer,
[0142] preferably in a total content of third gelling agent(s) (iv) ranging from 0.5 to 15% by weight, preferably from 2 to 7% by weight relative to the total weight of the composition,
[0143] and - the agent promoting the adhesion and / or shine of the composition on keratin materials chosen from sugar esters, preferably sucrose acetate isobutyrate, dimer diol and dimer diacid esters, optionally esterified on their free alcohol or acid function(s) by acid or alcohol radicals, and oligomeric polyesters of dimers obtained by reaction between a fatty alcohol and a dimer fatty acid, mention may in particular be made of dimer dilinoleate esters and in particular dimerdilinoleyl di-merdilinoleate, and mixtures thereof, preferably in a content ranging from 1 to 25% by weight, preferably 2 to 20% by weight relative to the total weight of the composition.
[0144] As a sugar ester, mention may be made in particular of sucrose acetate isobutyrate marketed under the name EASTMAN SUSTANE SAIB by the company EASTMAN. This compound can be prepared by known techniques of reaction between a sucrose and acetic and isobutyric anhydrides, followed by extensive purification by vacuum distillation. The degree of esterification is almost complete (degree of substitution greater than 7.5 for a maximum degree of substitution of 8), with an acetate:isobutyrate ester ratio of 2:6. US patent 3,096,324 gives an example of the preparation of SAIB.
[0145] As esters of dimer diol and dimer diacid, optionally esterified on their free alcohol or acid function(s) by acid or alcohol radicals, and oligomeric polyesters of dimers obtained by reaction between a fatty alcohol and a dimer fatty acid, mention may in particular be made of dimer dilinoleate esters, such as the products following:
[0146] - polyglyceryl-2 isostearate / dimer dilinoleate copolymer (Hailucent ISDA of Estenity);
[0147] - bis-behenyl / isostearyl / phytosteryl dimerdilinoleyl dimerdilinoleate (Plandool G of Estenity), or phytosteryl / isosteryl / cetyl / stearyl / behenyl dimerdilinoleate (Plandool H or Plandool S),
[0148] - dimerdilinoleyl dimerdilinoleate (Lusplan DDA7 from Unipex),
[0149] - Octyldodecanol And Dimer Dilinoleyl Dimer Dilinoleate marketed under the name VISCOPLAST 25 000 SHINE
[0150] - Dilinoleic Acid / Butanediol Copolymer marketed under the name VISCOPLAST 14436H
[0151] - Dilinoleic Acid / Butanediol Copolymer And C15-19 Alkane And Coco- Caprylate / Caprate marketed under the name VISCOPLAST WR-2 1618
[0152] - Helianthus Annuus (Sunflower) Seed Oils And Dimer Dilinoleyl Dimer Dilinoleate marketed under the name VISCOPLAST 30 000 SHINE,
[0153] and mixtures thereof.
[0154] As esters of hydrogenated castor oil, mention may in particular be made of hydrogenated castor oil dimer dilinoleate, with the INCI name Hydrogenated Castor Oil Dimer Dilinoleate, for example that marketed under the name RISOCAST-DA-L by Estenity.
[0155] According to a particular and preferred embodiment, the composition of the invention comprises a sugar ester and preferably a sucrose acetate isobutyrate (SAIB) ester.
[0156] According to another particular and preferred embodiment, the composition of the invention comprises a dimerdilinoleyl dimerdilinoleate (Lusplan DDA7 from Unipex).
[0157] The content of agents promoting adhesion and / or shine in the composition of the invention, when present, will generally range from 1 to 25% by weight, in particular 2 to 20% by weight relative to the total weight of the composition.
[0158] Thus, in a particular mode of composition: - the non-volatile hydrocarbon oil(s) (i) are chosen from esters of fatty alcohols and C8-C18 fatty acids, in particular coco-caprylate caprate, C35-C70 hydroxylated esters, preferably polyglycerol-2 triisostearate, and mixtures thereof, - the first gelling agent (ii) is a mixture of dibutyl lauroyl glutamide and dibutyl ethylhexanoyl glutamide, and mixtures thereof, - the second gelling agent (iii) is a dimer copolymer of ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl with INCI name: Polyamide-8, - the third gelling agent (iv) is a lipophilic polyurethane (iva or iva') by name INCI Polyurethane-69 or Caprylic / capric triglyceride (and) hydrogenated C6-20 polyolefin (and) HDI / trimethylol hexyllactone crosspolymer, and - the adhesion and / or gloss promoting agent is a sucrose ester, preferably sucrose acetate isobutyrate (SAIB).
[0159] In a particular mode of composition: - the non-volatile hydrocarbon oil(s) (i) are chosen from esters of fatty alcohols and C8-C18 fatty acids, in particular coco-caprylate caprate, C35-C70 hydroxylated esters, preferably polyglycerol-2 triisostearate, and mixtures thereof, - the first gelling agent (ii) is a mixture of dibutyl lauroyl glutamide and dibutyl ethylhexanoyl glutamide, and mixtures thereof, - the second gelling agent (iii) is a dimer copolymer of ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl with INCI name: Polyamide-8, - the third gelling agent (iv) is a lipophilic polyurethane (iva or iva') with the INCI name Polyurethane-69 or Caprylic / capric triglyceride (and) hydrogenated C6-20 polyolefin (and) HDI / trimethylol hexyllactone crosspolymer, and - the adhesion and / or shine promoting agent is a dimerdilinoleyl dimerdi-linoleate.
[0160] In another particular mode of composition: - the non-volatile hydrocarbon oil(s) (i) are chosen from esters of fatty alcohols and C8-C18 fatty acids, in particular coco-caprylate caprate, C35-C70 hydroxylated esters, preferably polyglycerol-2 triisostearate, and mixtures thereof, - the first gelling agent (ii) is a mixture of dibutyl lauroyl glutamide and dibutyl ethylhexanoyl glutamide, and mixtures thereof, - the second gelling agent (iii) is a dimer copolymer of ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl with INCI name: Polyamide-8, - the third gelling agent (iv) is a modified clay (ivb) with INCI name: Coco-Caprylate / Caprate (And) Disteardimonium Hectorite (And) Propylene Carbonate, and - the adhesion and / or shine promoting agent is a sucrose ester, preferably sucrose acetate isobutyrate (SAIB).
[0161] In these embodiments, the contents of each compound are those described previously.
[0162] Preferably, the composition of the invention comprises less than 5% by weight of silicone compound relative to the total weight of the composition, preferably less than 3% by weight of silicone compound, or even is free of silicone compound.
[0163] According to a particular embodiment of the invention, the composition of the invention is a transparent or translucent composition.
[0164] By “transparent or substantially transparent” is meant that the composition lets light through and makes it possible to distinguish objects or alphanumeric characters.
[0165] By “translucent” we mean that the composition lets light through but does not allow objects or alphanumeric characters to be distinguished.
[0166] In the case of transparent compositions, lipophilic polyurethane (iva or iva') as described above will advantageously be used as the 3rd gelling agent.
[0167] According to a particular embodiment, in particular in the case of a makeup composition according to the invention, the composition of the invention further comprises coloring materials, in particular pigments.
[0168] For the purposes of the present invention, the term "coloring matter" means a compound capable of producing a colored optical effect when formulated in sufficient quantity in a suitable cosmetic medium. The coloring matters are conventionally chosen from pigments (insoluble in the oily phase) and liposoluble dyes.
[0169] The coloring materials can be of mineral, synthetic or natural origin.
[0170] According to a particular embodiment, the coloring materials are of mineral or synthetic origin.
[0171] Said coloring materials may or may not be treated with a lipophilic treatment agent. The lipophilic treatment agent is in particular chosen from the group consisting of metallic soaps, N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; diisostearyl sebacate; natural vegetable or animal waxes, polar synthetic waxes; fatty esters; phospholipids, and mixtures thereof, in particular N-acylated amino acids or their salts.
[0172] These coloring materials, in particular when they are pigments, are generally pre-dispersed in a dispersing agent, before incorporation into the composition.
[0173] By “pigments” we mean white or colored particles, mineral or organic, insoluble in an aqueous solution, intended to color and / or opacify the resulting deposit.
[0174] According to a particular embodiment, the pigment(s) are in particular chosen from mineral and / or organic pigments, composite pigments (based on mineral and / or organic materials), nacres or pearlescent pigments, and mixtures thereof.
[0175] Among the “mineral pigments”, we can cite, as examples, dioxide of titanium (rutile or anatase), possibly surface-treated; black, yellow, red and brown iron oxides; manganese violet; ultramarine blue; chromium oxide; hydrated chromium oxide and ferric blue.
[0176] Among the "organic dyes and pigments (e.g. lakes)", we can cite, for example, Blue 1, Yellow 5, Yellow 6, Yellow 10, Yellow 11, Red 4, Red 6, Red 7, Red 9, Red 19, Red 13, Red 17, Red 21, Red 22, Red 27, Red 28, Red 30 and Red 33, Red 34, Red 36, Red 40, Green 3, Orange 4, Violet 2, carmine, Green 5, Orange 5, Orange 10, Green 6, Sudan red, Sudan brown, Orange 5, and quinoline yellow, their salts, such as a sodium or barium salt, or even lakes comprising at least one of said organic dyes or pigments, for example those having the name Blue 1 lake (CI 42090); Yellow 5 lake (CI 19140); Yellow 6 lake (CI 15985), Yellow 10 lake (CI 47005), Yellow 11 Lake, Red 6 lake (15850); Red 7 lake (CI 15850); Red 21 lake (CI 45380);Red 22 lake (CI 45380), Red 27 lake (CI 45410), Red 28 lake (CI 45410), Red 30 lake (CI 73360), Red 33 lake (CI 15880), Red 34 lake (CI 15880), Red 40 Lake (CI 16035), and / or their sodium or barium salts, in particular Red 6 Na Sait Lake, Red 6 Ba Sait Lake, and mixtures thereof. “Lakes” are organic pigments comprising at least one organic dye precipitated on an inert support (otherwise known as a “base”). In particular, use will be made of lakes comprising a base chosen from alumina (Al), barium sulfate (Ba), or calcium rosinate (Ca) bases. For example, Red 28 Al lake is a lake comprising an alumina base on which the Red 28 dye is precipitated. ;
[0177] According to a particular embodiment, the composition of the invention comprises at least pigments chosen from iron oxides, organic dyes and pigments, and mixtures thereof. Preferably, the composition of the invention, when it is colored and intended for making up keratin materials, will comprise at least iron oxides.
[0178] The content of coloring materials, when present, may range from 0.005 to 20% by weight, in particular from 0.01 to 10% by weight relative to the total weight of the composition.
[0179] According to a particular embodiment, in particular in the case of a makeup removal composition according to the invention, the composition will generally comprise less than 0.5% by weight, in particular less than 0.1% by weight relative to the total weight of the composition, or even be free of coloring materials.
[0180] In the case of a makeup composition according to the invention, the composition may generally comprise from 0.5 to 20% by weight, in particular from 5 to 15% by weight of coloring materials relative to the total weight of the composition. Formulations
[0181] The composition of the invention is in solid form.
[0182] According to a particular embodiment, the composition of the invention is in the form of a stick or a composition packaged in a pot or a cup.
[0183] According to a particular embodiment, it will be a lip balm, a lip stick, an eyebrow pencil, an eye shadow or eyeshadow, a blush or cheek shadow, a foundation stick, a complexion corrector or concealer, preferably a lip stick.
[0184] According to a first embodiment, it will be a solid composition for caring for keratin materials, in particular the skin and / or the lips, preferably the lips.
[0185] According to a first embodiment, it will be a solid composition for making up keratin materials, in particular the skin and / or the lips, preferably the lips.
[0186] According to yet another embodiment, it will be a solid composition for removing makeup from made-up keratin materials, in particular from the skin and / or the lips, preferably the lips.
[0187] By 'make-up removal composition', according to the invention, is meant a composition intended to remove makeup from a made-up keratin material. Indeed, the Applicant has observed that the composition according to the invention, in particular when it contains little or no coloring matter and knowing that it contains a high oil content, allows, when it is applied to a made-up keratin material, to form an oily film which is easily removable by wiping off the makeup film, for example using a cotton pad.
[0188] A makeup removal composition according to the invention will in particular comprise at least: i. A non-volatile hydrocarbon oil, ii. A first lipophilic gelling agent chosen from L-glutamic acid amides and aspartic acid, iii. A second lipophilic gelling agent chosen from polyamide-type polycondensates, and iv. A third lipophilic gelling agent chosen from (iva) polyurethane gelling agents, (ivb) modified clays, and mixtures thereof, preferably polyurethane gelling agents,
[0189] characterized in that the total content of non-volatile hydrocarbon oils is greater than or equal to 40%, better still greater than 50% by weight, in particular ranges from 45 to 90% by weight, in particular from 50 to 85%, even better from 70 to 80% by weight relative to the total weight of the composition, and in that it comprises less than 0.5% by weight, preferably less than 0.1% by weight relative to the total weight of the composition, or even is free of coloring matters.
[0190]
[0191]
[0192]
[0193]
[0194]
[0195] According to a particular embodiment, in the makeup removal composition according to the invention: - the non-volatile hydrocarbon oil(s) (i) are chosen from ester oils, C15-C21 alkanes, triglycerides of plant origin, oils of plant origin, C10-C26 alcohol oils, and mixtures thereof, preferably in a content ranging from 45 to 90% by weight, in particular 50 to 85% by weight relative to the total weight of the composition, - the first gelling agent (ii) of the L-glutamic acid amide type comprises at least one C6-C14, preferably C8-C12, alkyl group, such as dibutyl lauroyl glutamide, dibutyl ethylhexanoyl glutamide, and mixtures thereof, preferably in a content ranging from 0.5 to 15% by weight, preferably from 1.5 to 5% by weight relative to the total weight of the composition, - the second gelling agent (iii) is an ester-terminated polyamide and / or ester-terminated poly(ester-amides), preferably an ethylenediamine bis-stearyl ethylenediamine dibenzoate dimer copolymer / neopentyl glycol / stearyl with INCI name: Polyamide-8, preferably in a content ranging from 5 to 30% by weight, preferably from 8 to 22% by weight relative to the total weight of the composition, - the third gelling agent (iv) is chosen from a lipophilic polyurethane (iva) in which the hydrophobic segment (al) comprises at least one unit derived from an isocyanate compound, preferably 1,6-hexamethylene diisocyanate, at least one unit derived from a hydrogenated polyolefin polyol, preferably hydrogenated polybutadiene diol and at least one unit derived from a diol dimer which can be hydrogenated, preferably hydrogenated dilinoleic alcohol dimer, and the hydrophilic segment (a2) comprises at least one unit derived from a low molecular weight diol, preferably 1,4-butylene glycol and mixtures thereof, a lipophilic polyurethane (iva') resulting from the condensation of a polyester polyol obtained by reaction of a polyol such as trimethylol propane with a lactone, such as hexyl lactone, and a diisocyanate compound, in particular 1,6-hexamethylene diisocyanate, a hectorite modified (ivb) by a quaternary alkylammonium chloride, and their mixtures, preferably in a total content of third gelling agent(s) (iv) ranging from 0.5 to 15% by weight, preferably from 2 to 7% by weight relative to the total weight of the composition. Cosmetic process Makeup process Another subject of the invention is a cosmetic process for the care and / or makeup of keratin materials, in particular the skin and / or the lips, preferably the lips, comprising the application to said keratin materials of a composition as defined according to the invention.
[0196] Compositions for caring for or making up keratin materials and in particular the skin and / or the lips, preferably the lips, which can be used in the cosmetic process according to the invention are as described above.
[0197] Make-up removal process
[0198] The present invention also relates to a method for removing makeup from made-up keratin materials, in particular from the lips, comprising the application to said keratin materials of a composition as defined according to the invention, then wiping the keratin materials in order to remove the makeup film.
[0199] The makeup film can be wiped off with cotton or a woven material, used dry or possibly soaked.
[0200] The invention will now be illustrated in the following non-limiting examples. The % are expressed as % by weight of ingredient relative to the total weight of the composition, unless otherwise indicated. EXAMPLES
[0201] Example 1: Selection of polymeric organic oily gelling agents in association 1.1 Tests of gelling agents alone
[0202] Different polymeric organic oily gelling agents were tested in an anhydrous composition comprising non-volatile oils, and the resulting composition was evaluated for its hardness and stability properties, as well as for its glide and gloss properties upon application.
[0203] The compositions prepared and evaluated are detailed in the following Table 1:
[0204] [Tables 1] Ingrédients (nom INCI et nom commercial) % % % % % SP OLEOCRAFT LP-20 MBAL-PA-(MV) MB POLYAMIDE-8 30 AJK-OD2046 MB OCTYLDODECANOL and DIBUTYL LAUROYL GLUTAMIDE and DIBUTYL ETHYLHEXANOYL GLUTAMIDE 30 OILKEMIA 5S CC PALM FREE Caprylic / Capric Triglycéride (and) Hydrogenated C6-20 Po-lyolefin (and) HDI / Trimethylol Hexyllactone Crosspolymer 30 ESTOGEL GREEN HYDROGENATED CASTOR OIL / SEBACIC ACID COPOLYMER 30 ESTOGEL M CASTOR OIL / IPDI COPOLYMER, CAPRYLIC CAPRIC TRIGLYCERIDE 30 SAIB 100 Sucrose acetate isobutyrate 15 15 15 15 15 Pigments TiO2 et oxydes de fer dans le TRIMETHY-LOLPROPANE TRIL SOSTEARATE Polyglyceryl-2 triisostearate 31 31 31 31 31 POLYGLYCERYL-2 TRII SOSTEARATE MB 5 5 5 5 5 CETIOL C 5C MB COCO-CAPRYLATE / CAPRA TE Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100 Hardness OK Liquid when hot but sets immediately at RT so cannot be poured into stick KO KO KO Slip + / +++ - ++ Shine ++ / +++ + ++ Stability Exudation (even at RT) / OK Exudation (even at RT) Exudation (even at RT)
[0205] The compositions were prepared according to the following procedure:
[0206] The gelling agent is heated in a water bath if its melting temperature is lower than 90-95°C, or in an oil bath if its melting temperature is higher than 95°C.
[0207] Add the remaining ingredients one by one, while stirring, until a smooth and homogeneous mixture is obtained.
[0208] The mixture is then poured into a stick and left to cool to room temperature.
[0209] The compositions were evaluated for stick hardness, glide on application, shine and stability.
[0210] The hardness is measured 24 hours after casting, at a temperature of 25°C by the so-called “butter wire cutting” method, which consists of transversely cutting a stick of product with a diameter of between 10 and 12 mm, preferably cylindrical in revolution, using a rigid metal wire with a diameter of 250 μm, moving the wire relative to the stick at a speed of 60 mm / min. The hardness of the samples is expressed in Gram force (Gf) and can be measured using a texturometer of the Texturometer TAXT Plus type.
[0211] A conforming hardness in the range of 80 to 100g is noted as “OK” when evaluation, a hardness value outside this range is noted as “KO”.
[0212] Stability is assessed according to the following protocol:
[0213] The compositions are placed in ovens at different temperatures (room temperature Tamb, T4°C, T40°C, T45°C, with alternating cycles 40 / 4°C (24h) and oven at T40°C 80% humidity). Observations are made 2 hours after removal from the oven and return to room temperature.
[0214] The assessment is rated “OK” or “KO” as follows:
[0215] Stability OK: no exudation or exudation that is reabsorbed after returning to T ambient without leaving any traces;
[0216] KO stability: exudation without reabsorption after returning to ambient T or which leaves traces.
[0217] The glide and shine criteria are evaluated by a panel of cosmetic formulation experts and are rated from - to +++ as follows:
[0218] +++ very slippery or very shiny
[0219] ++slippery or shiny
[0220] + not very slippery or not very shiny
[0221] - not slippery and not shiny
[0222] These results show that the gelling agents tested do not, alone, allow the desired performance to be obtained. The polyurethane gel (Oilkemia 5S CC), which gives the best scores, allows a stable gel to be obtained, but the structuring is not sufficient to allow its use alone in a formula.
[0223] Combinations of gelling agents were therefore tested. 1.2 Gelling agent association tests
[0224] Different combinations of oily gelling agents (combinations of 2 or 3 gelling agents) were tested in an anhydrous composition similar to that of Example 1.1, and the composition obtained was evaluated for its hardness and stability properties, as well as for its glide and gloss properties on application.
[0225] The compositions prepared and evaluated are detailed in the following Table 2:
[0226] [Tables2] Ingredients (INCI name) % Comparative % Comparative % Invention % Comparative % Comparative % inventio n SP OLEOCRAFT LP-20 MBAL-PA-(MV) MB (polyamide-8) (1st gelling agent) 20 20 12 20 12 20 AJK-OD2046 MB (octyldodecanol and dibutyl lauroyl glutamide and dibutyl ethylhexanoyl glutamide at 20% in MA*) (2nd gelling agent) 10 0 12 0 12 10 OILKEMIA 5S CC PALM FREE (Caprylic / Capric Triglyceride (and) Hydrogenated C6-20 Polyolefin (and) HDI / Trimethylol Hexyllactone Crosspolymer at 30% in MA*)) (3rd gelling agent) 0 10 12 0 0 0 ESTOGEL GREEN HYDROGENATED CASTOR O1E / SEBAC1C ACID COPOEYMER 0 0 0 10 0 0 ESTOGEL M CASTOR OIUIPDI 0 0 0 0 12 0 COPOLYMER, CAPRYLIC CAPRIC TRI GLYCERIDE at 80% in MA BENTONE GEL CCC V MB (coco-caprylate / caprate (and) disteardimonium hectorite at 15% in MA* (and) propylene carbonate) (3rd gelling agent) 0 0 0 0 0 2.5 SAIB 100 (Sucrose acetate iso-butyrate) 15 15 15 15 15 15 TiO2 pigments and iron oxides in trimethy-lolpropane triisostearate Polyglyceryl-2 triisostearate (35 to 60% pigments) 31 31 31 31 31 31 POLYGLYCERYL-2 TRIISOSTEARATE MB 5 5 5 5 5 5 COCO-CAPRYLATE / C APRATE Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100 EVALUATIONS Hardness KO KO OK KO KO OK Slip +++ +++ +++ ++ + + Shine +++ +++ +++ ++ ++ - Stability KO KO OK KO KO OK
[0227] *MA = active ingredients
[0228] The compositions were prepared according to the same procedure and evaluated according to the same protocols as in Example 1.1 above.
[0229] These results show that the presence of a 3rd gelling agent, chosen from a polyurethane type gelling agent and a modified hectorite type mineral gelling agent, is necessary to stabilize the oily gel formed by the non-volatile hydrocarbon oils, a first lipophilic gelling agent chosen from L-glutamic acid amides, and a second lipophilic gelling agent chosen from polyamide type polycondensates. Example 2: Formulations
[0230] Illustrative and non-limiting examples of formulations are described below. 2.1 Lipstick stick
[0231] [Tables3] Phase Ingredient (INCI name) % Al AJK-OD2046 MB (OCTYLDODECANOL and DIBUTYL LAUROYL GLUTAMIDE and DIBUTYL ETHYLHEXANOYL GLUTAMIDE) 12.0 A2 OILKEMIA 5S CC PALM FREE (Caprylic / Capric Triglyceride (and) Hydrogenated C6-20 Po-lyolefin (and) HDI / Trimethylol Hexyllactone Crosspolymer) 12.0 A2 SP OLEOCRAFT LP-20 MBAL-PA-(MV) MB (POLYAMIDE-8) 12.0 A2 Sucrose acetate isobutyrate 15.0 A2 COCO-CAPRYLATE / CAPRATE QsplOO B TiO2 pigments and iron oxides in TRIMETHY-LOLPROPANE TRIISOSTEARATE Polyglyceryl-2 triisostearate (35 to 60% of pigments) 31.0 C Polyglyceryl-2 triisostearate 5.0
[0232] The composition is prepared according to the following protocol: - The Al phase is melted in an oil bath at 110°C - Phase A2 is melted in a water bath at 95°C and homogenized - Phase A2 is added to phase Al in the oil bath and the mixture is homogenized - Phase B is added and the mixture is homogenized - Phase C is added and the mixture is homogenized
[0233] The composition obtained is stable, with a consistent hardness. It is easily applied to the lips (gliding properties on application) and has good shine properties. 2.2 Lipstick stick
[0234] [Tables4] Phase Ingredient (INCI name) % Al AJK-OD2046 MB (OCTYLDODECANOL and DIBUTYL LAUROYL GLUTAMIDE and DIBUTYL ETHYLHEXANOYL GLUTAMIDE) 10.0 A2 SP OLEOCRAFT LP-20 MBAL-PA-(MV) MB (POLYAMIDE-8) 20.0 A2 Sucrose acetate isobutyrate 15.0 A2 COCO-CAPRYLATE / CAPRATE QsplOO A2 BENTONE GEL CCC V MB COCO-CAPRYLATE / CAPRATE (and) DISTEAR-DIMONIUM HECTORITE (and) PROPYLENE CARBONATE 2.5 B TiO2 pigments and iron oxides in TRIMETHY-LOLPROPANE TRIISOSTEARATE Polyglyceryl-2 trii-sostearate (35 to 60% pigments) 31.0 C Polyglyceryl-2 triisostearate 5.0
[0235] The composition is prepared according to the protocol described in example 1.1.
[0236] The composition obtained is stable, with a hardness of between 80 and 100 gr. It is easily applied to the lips (gliding properties on application) and has good shine properties.
[0237] 2.3 Solid composition for removing lip makeup
[0238] [Tables5] Phase Ingredient (INCI name) % Al AJK-OD2046 MB (OCTYLDODECANOL and DIBUTYL LAUROYL GLUTAMIDE and DIBUTYL ETHYLHEXANOYL GLUTAMIDE) 12.0 A2 OILKEMIA 5S CC PALM FREE (Caprylic / Capric Triglyceride (and) Hydrogenated C6-20 Po-lyolefin (and) HDI / Trimethylol Hexyllactone Crosspolymer) 12.0 A2 SP OLEOCRAFT LP-20 MBAL-PA-(MV) MB (POLYAMIDE-8) 12.0 A2 LUSPLAN DIMER DILINOLEYL DIMER DILINOLEATE 5.0 A2 COCO-CAPRYLATE / CAPRATE QsplOO B TiO2 pigments and iron oxides in TRIMETHY-LOLPROPANE TRIISOSTEARATE Polyglyceryl-2 trii-sostearate (35 to 60% pigments) 0.0144 C Polyglyceryl-2 triisostearate 5.0
[0239] The composition is prepared according to the protocol described in example 1.1.
[0240] The composition obtained is stable, with a conformal hardness of between 80 and 100 gr.
[0241] After application to the lips, it forms an oily film which allows all traces of makeup to be easily removed after using a cotton pad.
Claims
Claims
1. Solid anhydrous cosmetic composition for care, makeup or makeup removal of keratin materials comprising, in a physiologically acceptable medium, at least: i. A non-volatile hydrocarbon oil, ii. A first lipophilic gelling agent chosen from amides of L-glutamic acid and aspartic acid, iii. A second lipophilic gelling agent chosen from polycondensates of polyamide type, and A third lipophilic gelling agent chosen from polyurethane gelling agents (iva or iva'), modified clays (ivb), and mixtures thereof, preferably polyurethane gelling agents (iva or iva').
2. Composition according to claim 1, characterized in that it comprises less than 5% by weight of waxes relative to the total weight of the composition, preferably less than 3% of waxes, or even is free of waxes.
3. Composition according to claim 1 or claim 2, characterized in that: - the non-volatile hydrocarbon oil(s) (i) are chosen from ester oils, C15-C21 alkanes, triglycerides of vegetable origin, oils of vegetable origin, C10-C26 alcohol oils, and mixtures thereof, - the first gelling agent (ii) is an amide of L-glutamic acid comprising at least one C6-C14, preferably C8-C12, alkyl group, such as dibutyl lauroyl glutamide, dibutyl ethylhexanoyl glutamide, and mixtures thereof, - the second gelling agent (iii) is an ester-terminated polyamide and / or ester-terminated poly(ester-amides), preferably an ethylenediamine bis-stearyl ethylenediamine dibenzoate / neopentyl glycol / stearyl dimer copolymer with INCI name : Polyamide-8, - the third gelling agent (iv) is chosen from: a lipophilic polyurethane (iva) comprising a hydrophobic segment (al) and a hydrophilic segment (a2),in which the hydrophobic segment (al), comprises at least one unit derived from an isocyanate compound, preferably 1,6-hexamethylene diisocyanate, at least one unit derived from a hydrogenated polyolefin polyol, preferably hydrogenated polybutadiene diol and at least one unit derived from a diol dimer which can be hydrogenated, preferably hydrogenated dilinoleic alcohol dimer, and the hydrophilic segment (a2) comprises at least one unit derived from a low molecular weight diol, preferably 1,4-butylene glycol and mixtures thereof, a lipophilic polyurethane (iva') resulting from the condensation of a polyester polyol obtained by reaction of a polyol such as trimethylol propane with a lactone, such as hexyl lactone, and a diisocyanate compound in particular 1,6-hexamethylene diisocyanate, a hectorite modified (ivb) by a quaternary alkylammonium chloride, and mixtures thereof.
4. Composition according to any one of claims 1 to 3, in which the third gelling agent (iv) is chosen from lipophilic polyurethanes (iva or iva') with INCI name polyurethane -69 or Caprylic / capric triglyceride (and) hydrogenated C6-20 polyolefin (and) HDI / trimethylol hexyllactone crosspolymer.
5. Composition according to any one of claims 1 to 4, in which the first lipophilic gelling agent (ii) chosen from amides of L-glutamic acid and aspartic acid represents from 0.5 to 15% by weight, in particular from 1% to 10% by weight, or even from 1.5 to 5% by weight of active materials relative to the total weight of the composition.
6. Composition according to any one of claims 1 to 5, in which the second lipophilic gelling agent (iii) chosen from polyamide-type polycondensates is present in an amount of active material ranging from 5% to 30% by weight, preferably from 7% to 25%, better still from 8 to 22% by weight relative to the total weight of the composition.
7. Composition according to any one of claims 1 to 6, in which the third gelling agent (iv) of lipophilic polyurethane type (iva or iva') is present in an active material content ranging from 0.5 to 15% by weight, preferably from 1.5 to 10%, better still from 2 to 7% by weight relative to the total weight of the composition, and the third gelling agent (iv) of modified clay type (ivb), when present, is in a content ranging from 0.1 to 5% by weight, preferably from 0.2 to 3%, better still from 0.25 to 1% by weight relative to the total weight of the composition.
8. Composition according to any one of claims 1 to 7, characterized in that it further comprises at least (v) an agent promoting the adhesion and / or shine of the composition on keratin materials chosen from: - sugar esters, preferably sucrose acetate isobutyrate, - dimer diol and dimer diacid esters, optionally esterified on their free alcohol or acid function(s) by acid or alcohol radicals, and oligomeric polyesters of dimers obtained by reaction between a fatty alcohol and a dimer fatty acid, in particular dimer dilinoleate esters and in particular dimerdilinoleyl dimerdilinoleate, - hydrogenated castor oil esters, in particular hydrogenated dimer dilinoleate castor oil, - and mixtures thereof.
9. Composition according to any one of claims 1 to 8, characterized in that it comprises less than 5% by weight of silicone compound relative to the total weight of the composition, preferably less than 3% by weight of silicone compound, or even is free of silicone compound.
10. Composition according to any one of claims 1 to 9, characterized in that it is a transparent or translucent composition.
11. Composition according to any one of claims 1 to 10, characterized in that it further comprises coloring materials, in particular pigments.
12. Cosmetic composition according to any one of claims 1 to 11, characterized in that it is in the form of a stick or a composition packaged in a pot or a cup.
13. Cosmetic composition according to any one of claims 1 to 12, characterized in that it is a lip balm, a lip stick, an eyebrow pencil, an eye shadow or eyeshadow, a blush or cheek shadow, a foundation stick, a complexion corrector or concealer, preferably a lip stick.
14. Cosmetic process for caring for and / or making up keratin materials, in particular the skin and / or the lips, preferably the lips, comprising the application to said keratin materials of a composition as defined in any one of claims 1 to
15. 13. Method for removing make-up from made-up keratin materials, in particular from the lips, comprising the application to said keratin materials of a composition as defined in any one of claims 1 to 13, then wiping the keratin materials in order to remove the make-up film.
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