Solid cosmetic composition
A solid cosmetic composition using a polymerized castor oil and natural waxes addresses the environmental and stability issues of synthetic waxes, offering a stable, sustainable, and comfortable cosmetic solution.
Patent Information
- Application Number
- PCT/EP2025/071862
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-07-30
- Filing Date
- 2025-07-29
- Publication Date
- 2026-02-05
AI Technical Summary
Existing synthetic waxes, particularly paraffins, pose environmental and safety concerns due to their non-biodegradability and potential toxicity, and natural or naturally derived waxes face issues with stability and sensory texture, making them unsuitable replacements in cosmetic applications.
A solid cosmetic composition comprising a lipophilic gelling agent, such as a polymerized castor oil, and a combination of natural or naturally derived waxes, along with minimal synthetic and mineral waxes, to achieve a hardness and stability comparable to synthetic waxes, ensuring the composition is anhydrous and free of petroleum-based components.
The composition provides adequate hardness, stability, and sensory comfort, eliminating issues of breakage, exudation, and oxidation, while being environmentally friendly and sustainable.
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Abstract
Description
Description Title: Solid cosmetic composition technical field
[0001] This description concerns a solid cosmetic composition based on natural or naturally derived waxes. It also concerns a preparation process and a process for the treatment or makeup of keratinous materials that utilizes this composition. Previous technique
[0002] Synthetic waxes are products derived from petroleum. Paraffins constitute the first category of synthetic waxes: they are hydrocarbon compounds derived from petroleum. They have a solid to semi-solid consistency at room temperature. They are generally characterized by a melting point between 40 and 90°C, excellent oxidation and temperature stability, odor neutrality, and clarity.
[0003] Other synthetic waxes can be obtained by chemical synthesis from petroleum derivatives. These include polymers, which generally have a higher melting point than paraffins.
[0004] These properties of texture, visual appearance and olfactory neutrality make synthetic waxes highly sought-after products for many applications such as the manufacture of cosmetic products and in particular the manufacture of solid cosmetic products, for example poured into pots or pans or in stick form.
[0005] However, the synthetic waxes currently available on the market pose problems in terms of environmental impact and safety.
[0006] Indeed, paraffins, including MOSH (mineral oil saturated hydrocarbons) and / or MOAH (mineral oil aromatic hydrocarbons), are suspected of toxicity, particularly of carcinogenic effect, so that regulations now require limiting their concentration in food products.
[0007] Furthermore, due to their origin, paraffins contribute negatively to the increase of anthropogenic carbon dioxide. In addition, synthetic waxes are not biodegradable and lead to bioaccumulation in the environment.
[0008] This is why many sectors are looking for environmentally friendly, biodegradable and sustainable substitute products to replace synthetic waxes.
[0009] Natural waxes or waxes derived from nature, of plant or animal origin, such as beeswax, candelilla or carnauba wax, offer a renewable alternative to synthetic waxes, especially paraffins.
[0010] In the context of the invention, an ingredient "of natural origin" is understood to mean an ingredient that is either "natural" or "derived from natural" as defined below, and in accordance with the definition given by ISO 16128.
[0011] For the purposes of this application, a "natural" ingredient is defined as an ingredient of plant or animal origin that has not undergone any chemical transformation. In the field of cosmetics, a natural ingredient may have undergone physical modifications, such as extraction by traditional mechanical means. Its naturalness index is 1, meaning that it consists solely of natural components.
[0012] For the purposes of this application, a "naturally derived" ingredient is defined as an ingredient of plant or animal origin that has undergone chemical transformations, meaning its natural state has been altered to make it suitable for use in cosmetics. A naturalness index can be calculated for these ingredients. An ingredient will be considered "naturally derived" if its naturalness index is greater than 0.5, meaning that more than 50% of its constituent components are derived from nature. The naturalness index of an ingredient with less than 50% of its constituent components being derived from nature will be 0.
[0013] Calculating the naturalness index of an ingredient, particularly if it contains wax, falls within the general knowledge of a person skilled in the art. The naturalness index calculation is generally established and provided by the raw material supplier. Therefore, for the same ingredient with a given chemical structure, different naturalness indices can be obtained depending on the preparation process.
[0014] However, in many applications, natural or naturally derived waxes cannot completely replace paraffins or other synthetic waxes.
[0015] Recent scientific work has investigated the possibility of replacing paraffins in lipstick formulations with mixtures of naturally derived lipids, specifically a mixture of linear C35-C38 alkenones from algal resources. However, low stability was observed (Huynh, A. et al. Evaluation of alkenones, a renewablely sourced, plant-derived wax as a structuring agent for lipsticks. Int. J. Cosmet. Sci. 42, 146-155 (2020)).
[0016] Other scientific work has recently shown that in the field of lipsticks, the substitution of synthetic waxes of petroleum origin with waxes of plant origin poses problems of product stability, lipstick solidity, exudation, incompatibilities and / or oxidation, with which increasingly demanding consumers are not prepared to deal, (de Clermont-Gallerande et al. Substitution of synthetic waxes by plant-based waxes in lipsticks, OCL, 2022, 29, 19).
[0017] Thus, this study shows that when the composition obtained with vegetable waxes is solid, it has too low hardness values which result in too frequent breakage during application in the case of sticks.
[0018] Furthermore, the stability over time is not satisfactory. This can result in the appearance of an exudation phenomenon, polymorphism, a change in the appearance of the surface of the product such as the appearance of inhomogeneities, with the presence of matte surface area(s), or film-forming area(s), or even an evolution of the sensory experience during application over time (decrease in meltability, glide).
[0019] Furthermore, natural plant-based waxes with a high melting point, around 80°C, do not allow for sufficiently sensorial textures: they are very rigid, lack flexibility, and the sensation upon application to the skin or lips is unpleasant. Finally, plant-based waxes with a melting point below 80°C do not allow for sufficient structuring of the composition to mold lipsticks into sticks.
[0020] There is therefore a real need to find natural or naturally derived substitute products, particularly plant-based, ecological and sustainable ones to replace paraffins.
[0021] A solid cosmetic composition based on natural or naturally derived ingredients, particularly plant-derived ingredients, has now been developed. Its physicochemical characteristics, including hardness, texture, and / or melting point, are very close to those obtained with existing synthetic waxes. In particular, this solid composition, free of petroleum-based synthetic waxes, does not present problems with stability, strength (i.e., excessive breakage in the case of sticks), exudation, incompatibilities, and / or oxidation.
[0022] Thus, according to a first aspect, the invention relates to a solid cosmetic composition comprising: a lipophilic gelling agent selected from functionalized castor oils, in particular a polymer of castor oil functionalized with isophorone diisocyanate, and at least 3.5% by weight of at least one natural or naturally derived wax; at least one polar non-volatile oil; less than 3% by weight of mineral and / or synthetic wax, preferably less than 1% by weight of mineral and / or synthetic wax, preferably the composition being free of mineral and / or synthetic wax, the percentages being expressed in relation to the total weight of the solid cosmetic composition. SOLID
[0023] According to the invention, "solid composition" refers to a composition exhibiting, at a temperature of 20°C and atmospheric pressure (760 mm Hg), a hardness greater than 30 Nm⁻¹, preferably greater than 40 Nm⁻¹, and preferably between 55 Nm⁻¹ and 315 Nm⁻¹. Hardness can be measured at 20°C using the "butter cutter" method, which assesses the firmness of a lipstick by measuring, in particular, its resistance to cutting the product into a stick. This measurement is performed 24 hours after formulation, using a texture analyzer (TAXTPIus, MicroStable Systems, UK) equipped with a 5 kg load cell and its Butter Cutter A / BC probe (Swantech, MicroStable Systems, UK). It allows the maximum resistance force of the stick during the penetration of the butter-cutting wire to a depth of 9 mm at a speed of 1.6 mm / s.To ensure the reproducibility of the measurements, the analysis is repeated on 6 sticks, and the relative difference between measurements must not exceed 10%, ideally 5%. For each type of product, a reference (target) range is established to guarantee the mechanical properties of the stick. For example, for a stick with a diameter of 12.7 mm (0.0127 m), a hardness expressed in Nm⁻¹ is calculated by multiplying the hardness expressed in grams by a factor of 0.01 (where 1 g = 0.01 N) and dividing the result by the diameter 0.0127 m.
[0024] The solid composition according to the invention will generally have a hardness greater than or equal to 50g for a stick in a guided pack, because its base is held in the packaging when the user uses it and it is therefore more resistant to breakage during use.
[0025] The solid composition according to the invention will generally have a hardness greater than or equal to 70g, in particular greater than or equal to 90g, for example ranging from 100g to 400g, and preferably ranging from 140g to 300g and even more preferably ranging from 175g to 250g for a stick in an unguided pack.
[0026] Such compositions (corresponding in particular to cast sticks in standard format of approximately 12.7mm) exhibit adequate stability and hardness: the stick is sufficiently rigid and solid, does not break during application and is thus compatible with packaging in stick form or in another solid form and with application by friction on the surface to be treated and / or made up; they are also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture.
[0027] Solid cosmetic compositions can be in the form of a stick or a composition packaged in a cup.
[0028] The solid cosmetic composition can be a skincare cosmetic composition of keratinous materials, a perfume or a makeup composition of keratinous materials. ANHYDROUS
[0029] Preferably the solid cosmetic composition of the invention is anhydrous.
[0030] By "anhydrous composition," it is understood, in particular, that water is preferably 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 may comprise less than 4% by weight of water, preferably less than 3%, preferably less than 2%, more preferably less than 1%, and even more preferably less than 0.5% by weight of water, relative to the total weight of said composition, or may even be completely free of water. According to a particular embodiment, the composition is free of water. POLYMERIC LIPOPHILIC GELDING AGENT DERIVED FROM CASTOR OIL
[0031] By "lipophilic gelling agent" according to the invention, we mean a compound capable of gelling the fatty phase of a composition.
[0032] For the purposes of this application, the term "gelling agent" refers to a compound characterized in that it exhibits: - a measurable gelling temperature and / or - an elastic modulus G' greater than its viscous modulus G”, measured at 20°C after solubilization in a lipophilic solvent and / or - an elastic modulus G' and viscous modulus G” greater than those of a non-gelled lipophilic solvent.
[0033] Gelling temperature:
[0034] The lipophilic gelling agent according to the invention differs from a non-gelling compound, particularly a polymer, in that it exhibits a measurable gelling temperature when mixed with a lipophilic solvent. Conversely, a non-gelling compound does not gel the lipophilic solvent with which it is mixed.
[0035] According to one embodiment, the gelation temperature can be measured by preparing a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, and increasing the temperature of the mixture until gelation occurs.
[0036] The gelation temperature can be measured according to the following protocol, using the TA Instruments DHR-2 rheometer:
[0037] - The temperature of the solution or mixture is increased up to 70°C to create the conditions for solubilization and gel formation.
[0038] - The temperature of 70°C is maintained for 1 minute to continue gelling under stirring;
[0039] - Next, the temperature is decreased to 20°C at a rate of 10°C / min,
[0040] - The gelation temperature is recorded at the temperature at which G' increases.
[0041] The lipophilic gelling agent according to the invention is characterized by a gelling temperature between 45°C and 70°C, preferably between 50°C and 65°C, even more preferably between 55°C and 62°C, when it is put into a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, more preferably caprylic / capric acid triglyceride.
[0042] Values of G' (elastic modulus) > G” (viscous modulus):
[0043] The elastic modulus G' provides information on the degree of gelation (and therefore, the amount of solid gelled portion) of the binary compound / solvent mixture. The higher the value of G', the more solid and thus gelled the composition.
[0044] In contrast, the viscous modulus G” gives an indication of the ungelled portion of the solvent after the addition of the compound, and when considered in relation to G'. Provided that G” is greater than G', the higher the value of G”, the more liquid and therefore ungelled the composition.
[0045] According to one embodiment, the lipophilic gelling agent according to the invention can also be characterized by an elastic modulus G' greater than its viscous modulus G”, after solubilization in a lipophilic solvent.
[0046] According to one embodiment, the elastic and viscous moduli G' and G” can be measured by preparing a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, at a given temperature.
[0047] G' and G” can be measured using the following protocol:
[0048] The viscoelastic behavior of solutions can be evaluated on a TA Instruments DHR-2 rheometer at 20°C with a hot rheology process in which the rheometer is used with an imposed strain of 0.1%, at a frequency of 1 Hz and equipped with a metal plane-plane geometry with an air gap of 500 pm.
[0049] The average modulus G' in the sense of the present invention is the elastic modulus in the linear domain of the curve G'.
[0050] The average G” modulus in the sense of the present invention is the viscous modulus in the linear domain of the G curve”.
[0051] In particular, the elastic modulus G', measured at 70°C for a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, more preferably caprylic / capric acid triglyceride, is between 6 and 13 Pa, preferably between 7 and 12 Pa, even more preferably between 8 and 11 Pa.
[0052] According to another embodiment, the lipophilic gelling agent according to the invention is characterized by a G' value measured at 20°C for a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, more preferably caprylic / capric acid triglyceride, between 3000 and 4000 Pa, preferably between 3200 and 3800 Pa, even more preferably between 3400 and 3700 Pa.
[0053] According to yet another embodiment, the lipophilic gelling agent according to the invention is characterized by a G” value measured at 20°C for a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, more preferably caprylic / capric acid triglyceride, between 80 and 160 Pa, preferably between 100 and 140 Pa, even more preferably between 110 and 130 Pa.
[0054] According to a preferred embodiment, the lipophilic gelling agent according to the invention is characterized by an elastic modulus G' at least 10 times greater than its viscous modulus G”, preferably at least 20 times greater than G”, even more preferably at least 30 times greater than G”, when G' and G” are measured at 20°C for a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, more preferably caprylic / capric acid triglyceride.
[0055] G' and G” are greater than those of a non-gelled lipophilic solvent:
[0056] According to one embodiment, the lipophilic gelling agent of the invention can be characterized by an elastic modulus G' and viscous modulus G” greater than those of a non-gelled lipophilic solvent. The elastic and viscous moduli G' and G” can be measured according to the method described above.
[0057] In particular, the moduli G' and G”, measured at 20°C for a binary mixture consisting of 30% of the lipophilic gelling agent and 70% of a lipophilic solvent, preferably a non-volatile oil, more preferably caprylic / capric acid triglyceride, are greater than the moduli G' and G”, measured at 20°C for caprylic / capric acid triglyceride.
[0058] As an example, the moduli G' and G” measured at 20°C for the lipophilic solvent used in the examples of this application, ungelled caprylic / capric acid triglyceride, are respectively 0.02 Pa and 0.1 Pa.
[0059] A "polymeric lipophilic gelling agent" is defined as a polymer capable of gelling the oil phase of a composition. This polymer is defined as a relatively large molecule, typically with a weight-average molecular weight of 2,000 daltons or more, composed of reaction products of smaller, repeating chemical units. The "oil phase" refers to lipophilic compounds such as oils, waxes, butters, and pastes.
[0060] According to a particular embodiment, the composition of the invention comprises at least one castor oil polymer functionalized with isophorone diisocyanate. Preferably, the castor oil is of natural origin, also known as 'bio-based'. The naturally sourced castor oil has the following composition, shown in Table 1:
[0061] Table 1:
[0062] The lipophilic gelling agent chosen from the functionalized castor oils obtained exhibits improved adhesion properties on keratinous materials, film-forming properties and stability.
[0063] One example is the castor oil polymer functionalized with isophorone diisocyanate. It has a naturalness index of 0.91. While not bound by any specific theory, the inventors believe that the gel formation is based on supramolecular chemistry: the polymer molecules associate with each other through hydrogen bonds. These bonds are weak and reversible.
[0064] Such a castor oil polymer functionalized with isophorone diisocyanate can be obtained according to the following chemical reaction described in US patent 5707612:
[0065] The stoichiometric use of two moles of castor oil for one mole of isophorone diisocyanate gives a preferred embodiment indicated above.
[0066] The lipophilic gelling agent is marketed by ALZO INC. under the trade name POLYDERM PPI-CCO®. Its chemical name is castor oil polymer with 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and its INCI name is CASTOR OIL / IPDI COPOLYMER with a CAS number 68955-90-8.
[0067] The lipophilic gelling agent with the INCI name CASTOR OIL / IPDI COPOLYMER or & CASTOR OIL / IPDI COPOLYMER, CAPRYLIC I CAPRIC TRIGLYCERIDE, is marketed under the name ESTOGEL E® or ESTOGEL M® by the company POLYMEREXPERT, preferably ESTOGEL M®. It is a lipophilic gelling agent, more than 90% bio-based, intended for polar oils.
[0068] ESTOGEL E® or ESTOGEL M® is distinct from the non-siliconized elastomer distributed under the reference "Gransense TC-21X-C" by Grant Industries Inc., bearing the INCI name: TRIHEPTANOIN (AND) COCO-CAPRYLATE / CAPRATE (AND) DILINOLEIC ACID / BUTANEDIOL COPOLYMER (AND) CASTOR OIL / IPDI COPOLYMER ELASTOMER and described in patent application FR 3124728 A1.
[0069] Indeed, as demonstrated in the experimental part of this application, the product "Gransense TC-21X-C" is not a gelling agent.
[0070] The composition of the invention shall generally comprise from 0.9% to 50%, in particular 2% to 40%, preferably even from 4% to 12% by weight of the functionalized lipophilic gelling agent, the percentages being expressed by weight relative to the total weight of the composition. WAXES
[0071] The term "wax" refers to a lipophilic fatty compound, solid at room temperature (15-25°C) and atmospheric pressure (760 mmHg), whose solid-to-liquid phase change is reversible. Waxes generally have a melting point above 30°C (sometimes reaching up to 200°C) and exhibit anisotropic crystalline structure in their solid state. At its melting point, wax becomes miscible with oils and can form a microscopically homogeneous mixture. When the mixture is cooled to room temperature, the wax can recrystallize within the oils of the mixture. NATURAL WAXES OR WAXES DERIVED FROM NATURAL PRODUCTS
[0072] Advantageously, the waxes used in the composition according to the invention are natural or natural waxes, solid at room temperature (i.e. at a temperature ranging from about 15 to 25°C).
[0073] In the context of the invention, waxes of natural origin are selected from natural waxes or waxes derived from nature. As previously defined, natural waxes or waxes derived from nature are waxes of vegetable or animal origin. In particular, waxes Mineral waxes are not natural waxes or waxes derived from natural sources within the meaning of this application.
[0074] Naturally derived ingredients can be cosmetic ingredients obtained through defined chemical and / or biological processes aimed at chemically modifying them. They can be chemical compounds or substances produced by living organisms, i.e., found in nature. For the purposes of this invention, ingredients of natural origin are considered to include ingredients such as waxes, butters, or oils derived from plants, or products resulting from the hydrogenation or esterification of naturally derived oils, preferably of vegetable origin.
[0075] The combination of natural or naturally derived waxes according to the invention allows for the structuring of the composition, particularly hot-poured solid compositions in stick, cup, or any other type of support. The waxes used in the compositions according to the invention may be hydrocarbon-based. The waxes used in the compositions according to the invention are of natural origin, preferably of vegetable origin.
[0076] By "derived from" we mean an ingredient that has undergone a chemical modification.
[0077] The natural or naturally derived waxes used in the compositions according to the invention can be obtained from the hydrogenation of oils of natural origin, preferably vegetable such as castor oil (the wax of natural origin is then hydrogenated castor oil).
[0078] In particular, the natural or naturally derived waxes used in the compositions according to the invention have a melting point above 55°C, preferably between 58°C and 95°C, preferably between 58°C and 92°C at atmospheric pressure.
[0079] In particular, the wax of natural origin may be chosen from the group including beeswax, sunflower wax, carnauba wax, candelilla wax, cottonseed wax, rice bran wax, berry wax, Chinese insect wax, kapok wax, sugar cane wax, jojoba wax, shellac wax; the wax derived from natural sources may be chosen from the group including lanolin and its alcohol derivatives, acetylated, esterified, polyethoxylated natural waxes or a mixture thereof.
[0080] Naturally derived waxes may also be vegetable ester waxes selected from the group comprising the mixture of jojoba esters, polyglycerin-3, Acacia decurrens flower wax, and sunflower seed wax, said mixture being marketed by Gattefosse under the trade name Acticire®, and the mixture of sunflower wax and hydrogenated castor oil marketed by Brasca under the trade name ABWAX REVOWAX, jojoba esters marketed by Floratech under the trade name Floraesters 60 or Floraesters 70, hydrogenated alkyl esters or hydrogenated alkyl esters marketed by Sophim under the trade name Phytowax, such as hydrogenated lauroyl oleate esters marketed under the name Phytowax Olive 12L44, tribehenin marketed by Croda under the trade name Syncrowax HRC-PA(RB).
[0081] In a particular embodiment, the natural or naturally derived wax of vegetable origin may be chosen from: - sunflower wax alone or combined with hydrogenated castor oil, or - candelilla wax or one of their mixtures.
[0082] For example, the naturalness index of sunflower wax is 1, the naturalness index of candelilla wax is 1, the naturalness index of sunflower wax combined with castor oil is 0.99.
[0083] The mixture may therefore include sunflower wax combined with hydrogenated castor oil, sunflower wax combined with candelilla wax, candelilla wax combined with hydrogenated castor oil, or sunflower wax combined with hydrogenated castor oil and candelilla wax.
[0084] In a particular embodiment, sunflower wax alone or combined with hydrogenated castor oil, candelilla wax or a mixture thereof represents between 50% and 99%, preferably between 70% and 99% and even more preferably between 80% and 99% by weight of said mixture in relation to the total weight of wax(s).
[0085] When the solid cosmetic composition is in the form of a product poured into a cup, it may comprise from 3.5% to 12% by weight, preferably between 4% and 6% by weight of at least one natural or naturally derived wax according to the invention, relative to the total weight of the composition.
[0086] When the solid cosmetic composition is in the form of a stick, it may comprise from 3.5% to 20% by weight, preferably between 7% and 17% by weight of at least one natural or naturally derived wax according to the invention, relative to the total weight of the composition.
[0087] Preferably the total wax content is between 7% and 20%, preferably between 8% and 18% and more preferably between 10% and 14% by weight, relative to the total weight of the solid cosmetic composition.
[0088] In a particular embodiment, the composition of the invention has a weight ratio between the lipophilic gelling agent / natural or natural wax, preferably of vegetable origin, of between 0.01-2, preferably between 0.1 and 1 and, more preferably, between 0.5-0.7, for example around 0.67.
[0089] The solid cosmetic compositions according to the invention may further comprise other ingredients, in particular additional solid fats, including pasty fats. MINERAL OR SYNTHETIC WAX
[0090] Preferably, the solid cosmetic compositions according to the invention comprise less than 3% by weight of mineral and / or synthetic wax, in particular less than 1% by weight, the percentages being expressed by weight relative to the total weight of the composition, and even better the composition is free of mineral and / or synthetic wax.
[0091] By "synthetic wax" we mean a wax that is not natural or derived from nature.
[0092] Among the mineral waxes, we can mention in particular montan wax, ceresins, ozokerites, microcrystalline waxes, mineral paraffins.
[0093] Examples of synthetic waxes include: - synthetic beeswaxes, such as those marketed by Koster Keunen under the trade name Kester Wax K82H, or one of their mixtures; - polyethylene wax, such as that marketed by New Phase Technologies under the name Performalène 400 (P400) or by Jeen International Corporation under the name Jeenate 3H, - a mixture of high molecular weight linear polyethylene and ethylene / propylene copolymer, marketed by Safi-Alcan under the trade name Lipwax® PZ80-20, - a synthetic wax like the one marketed by Sasol under the name Sasol Wax C80; - mixtures of synthetic waxes and vegetable waxes, such as for example a mixture of synthetic wax and carnauba wax (Copernica cerifera) marketed by Strahl & Pitsch under the name Smart wax 202, a mixture of synthetic wax, Candelilla wax and carnauba wax (Copernica cerifera) marketed by Strahl & Pitsch under the name Smartwax 7743S, - Fischer Tropsch waxes such as those marketed by Cirebelle under the name Cirebelle 303, or one of their mixtures. PASTY
[0094] The solid cosmetic compositions according to the invention may include an additional pasty fatty substance.
[0095] For the purposes of this invention, "pasty fat" means a lipophilic fatty compound with a reversible solid / liquid change of state, exhibiting an anisotropic crystalline organization in the solid state, and comprising, at a temperature of 23 °C, a liquid fraction and a solid fraction.
[0096] In other words, the initial melting point of the solid fat can be below 23°C. The liquid fraction of the solid fat measured at 23°C can represent 9 to 97% by weight of the solid fat. This liquid fraction at 23°C preferably represents between 15 and 85%, and even more preferably between 40 and 85% by weight.
[0097] For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in ISO 11357-3; 1999. The melting point of a pasty fat can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by TA Instruments.
[0098] The measurement protocol is as follows:
[0099] A 5 mg sample of pasty fat placed in a crucible is first heated from -20 °C to 100 °C at a rate of 10 °C / minute, then cooled from 100 °C to -20 °C at a rate of 10 °C / minute, and finally heated a second time from -20 °C to 100 °C at a rate of 5 °C / minute. During this second heating cycle, the difference in power absorbed by the empty crucible and the crucible containing the pasty fat sample is measured as a function of temperature. The melting point of the pasty fat is the value of the temperature corresponding to the top of the peak of the curve representing the variation of the difference in absorbed power as a function of temperature.
[0100] The liquid fraction by weight of a solid fat at 23°C is equal to the ratio of the enthalpy of fusion consumed at 23°C to the enthalpy of fusion of the solid fat. The enthalpy of fusion of a solid fat is the enthalpy consumed by the fat to change from a solid to a liquid state. A solid fat is said to be in a solid state when its entire mass is in crystalline form. A solid fat is said to be in a liquid state when its entire mass is in liquid form.
[0101] The enthalpy of fusion of the pasty fat is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by TA instrument, with a temperature rise of 5 or 10 °C per minute, according to ISO 11357-3:1999.
[0102] The enthalpy of fusion of a fat in a paste form is the amount of energy required to change the fat in a paste form from a solid to a liquid state. It is expressed in J / g.
[0103] The enthalpy of fusion consumed at 23 °C is the amount of energy absorbed by the sample to change from the solid state to the state it presents at 23 °C consisting of a liquid fraction and a solid fraction.
[0104] The liquid fraction of the solid fat measured at 32 °C preferably represents 30 to 100% by weight of the solid fat, preferably 50 to 100%, and preferably 60 to 100% by weight of the solid fat. When the liquid fraction of the solid fat measured at 32 °C is equal to 100%, the temperature at the end of the melting range of the solid fat is less than or equal to 32 °C.
[0105] The liquid fraction of the solid fat measured at 32 °C is equal to the ratio of the enthalpy of fusion consumed at 32 °C to the enthalpy of fusion of the solid fat. The enthalpy of fusion consumed at 32 °C is calculated in the same way as the enthalpy of fusion consumed at 23 °C.
[0106] The paste-like fat is preferably chosen from synthetic fats and fats of vegetable origin. A paste-like fat can be obtained synthetically from starting materials of vegetable origin.
[0107] One such compound is a mixture of sterol esters, such as the cholesterol and lanosterol ester mixture available from the manufacturer CRODA under the trade name Super Sterol Ester®, - lanolin and its derivatives, - mixtures of beeswax and octyldodecanol such as that marketed under the name Zenibee Cream by the company Zenitech, - esters, - vegetable butters such as mango butter, shea butter, cocoa butter, cottonseed butter, avocado butter, or a mixture thereof.
[0108] Among the esters, we can notably use: - esters of an oligomeric glycerol, in particular diglycerol esters, especially adipic acid and glycerol condensates, in which part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid and 12-hydroxystearic acid, in particular those marketed under the Softisan 649 brand by the company Sasol, - arachidyl propionate, marketed under the brand name Waxenol 801 by Alzo, - phytosterol esters such as the product with the INCI name "bis-behenyl / isostearyl / phytosteryl dimer dilinoleyl dimer dilinoleate" marketed under the name Plandool-G by Nippon Fine Chemical Co, and "Phytosteryl / behenyl / octyldodecyl / isostearyl lauroyl glutamate" marketed under the name Eldew-PS308 by Ajinomoto, - fatty acid triglycerides and their derivatives, for example the mixture of stearyl heptanoate and stearyl caprylate marketed under the name DUB solid by the company Stéarinerie Dubois, - pentaerythritol esters, - non-crosslinked polyesters resulting from the polycondensation between a dicarboxylic acid or a linear or branched C4-C50 polycarboxylic acid and a diol or a C2-C50 polyol, - aliphatic esters of ester resulting from the esterification of an aliphatic hydroxycarboxylic acid ester by an aliphatic carboxylic acid such as cetyl lactate marketed under the name ceraphyl 28 by the company ISP (International Speciality Products), - polyesters resulting from the esterification, by a polycarboxylic acid, of an aliphatic hydroxycarboxylic acid ester, said ester comprising at least two hydroxyl groups such as the products Risocast DA-H ®, and Risocast DA-L ®, or one of their mixtures.
[0109] Among the additional pasty fats, phytosterol esters such as the product with the INCI name "bis-behenyl / isostearyl / phytosteryl dimer dilinoleyl dimer dilinoleate" marketed under the name Plandool-G by Nippon Fine Chemical Co, "Phytosteryl / behenyl / octyldodecyl / isostearyl lauroyl glutamate" marketed under the name Eldew-PS308 by Ajinomoto, or a mixture of these, are preferred.
[0110] The compositions may include additional fats having a melting point between 25°C and 55°C. The fat having a melting point between 25°C and 55°C is chosen from among hydrogenated oils solid at 25°C or fatty esters solid at 25°C and mixtures thereof.
[0111] Among the solid hydrogenated oils at 25°C, we can mention hydrogenated castor oil, hydrogenated palm oil, hydrogenated tallow, hydrogenated coconut oil such as that available under the trade name hydrobase 32-34 by the company Prod'Hyg.
[0112] Examples of solid fatty esters at 25°C include propylene glycol myristate, myristyle myristate, and cetyl alcohol.
[0113] The fatty constituent with a melting point between 25°C and 55°C is preferably hydrogenated coconut oil.
[0114] According to embodiments, the cosmetic compositions according to the invention comprise less than 3% by weight of pasty fats of mineral and / or synthetic origin, in particular less than 1% by weight, the percentages being expressed by weight relative to the total weight of the composition.
[0115] Preferably, cosmetic compositions are free from pasty fats of mineral and / or synthetic origin.
[0116] Among the pasty fats of mineral and / or synthetic origin, we can mention petroleum jelly, also called petrolatum. - vinyl polymers, in particular homopolymers and copolymers of olefins, homopolymers and copolymers of hydrogenated dienes, linear or branched oligomers, homo or copolymers of alkyl (meth)acrylates preferably having an alkyl group at C8-C30, homo and copolymer oligomers of vinyl esters having alkyl groups at C8-C30, homo and copolymer oligomers of vinyl ethers having alkyl groups at C8-C30, - liposoluble polyethers resulting from polyetherification between one or more C2-C100 diols, preferably C2-C50, According to embodiments, the solid cosmetic compositions according to the invention comprise less than 3% by weight of silicone and / or fluorinated pasty fats, in particular less than 1% by weight, the percentages being expressed by weight relative to the total weight of the composition.
[0117] Preferably, cosmetic compositions are free from silicone and / or fluorinated paste-like fats. POLAR NON-VOLATILE OIL
[0118] For the purposes of the present invention, "oil" means a compound which has a lipophilic character and which, when introduced at a rate of at least 1% by weight into water at 20°C, is not at all soluble in water, or soluble to a rate of less than 10% by weight, relative to the weight of oil introduced into the water.
[0119] For the purposes of the present invention, a polar non-volatile oil may be natural or derived from nature.
[0120] The term "non-volatile oil" refers to an oil which has a boiling point generally above 300°C under 760 mm Hg (101325 Pa) and which has little or no vapor pressure.
[0121] The composition according to the invention may comprise one or more non-volatile oils miscible with each other.
[0122] The definition of the solubility parameters in the three-dimensional solubility space of HANSEN are described in the article by CM HANSEN: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967).
[0123] According to this Hansen space: 5D characterizes the London dispersion forces arising from the formation of induced dipoles during molecular collisions; 5P characterizes the DEBYE interaction forces between permanent dipoles as well as the KÉESOM interaction forces between induced dipoles and permanent dipoles; ôh characterizes the specific interaction forces (hydrogen bonding, acid / base, donor / acceptor type, etc.)
[0124] These three parameters can be treated as the coordinates of a point in three dimensions within Hansen space. The closer the solvents are in this three-dimensional space, the more likely they are to dissolve in one another. This is based on the affinity of the molecules for each other, the principle of "like dissolves like."
[0125] The parameters 5D, 5P, 5h are expressed in (MPa)1 / 2, unit equivalent to (J / cm3)1 / 2.
[0126] The Hansen solubility parameters are calculated using HSPiP software version V5.3.06 from a chemical structure; the method selected in the software is Y-MB or Yamamoto-Molecular Break.
[0127] This software is available for download via the official Hansen parameters and HSPiP software website at www.hansen-solubility.com.
[0128] The Log Kow or LogP, is a measure of the differential solubility of molecules in water and in octanol; P is the octanol / water partition coefficient.
[0129] LogP = Log(Coct / Ceau).
[0130] This value allows us to understand whether the molecule is hydrophilic or lipophilic.
[0131] If the LogP is positive and very high, the molecule is much more soluble in octanol than in water, reflecting its lipophilic nature. Conversely, if the LogP is negative, the molecule is hydrophilic. A LogP of zero means the molecule is soluble in both solvents.
[0132] Preferably, the oils used according to the present invention have a LogP greater than 0.
[0133] For the purposes of this invention, "polar oil" means an oil whose chemical structure is essentially formed, or even made up, of carbon and hydrogen atoms, and comprising at least one strongly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.
[0134] Preferably, the non-volatile polar oils used according to the present invention have a 5P between 2 and 8 (J / cm3)1 / 2.
[0135] The non-volatile polar oil may be chosen from fatty alcohols, fatty acid triglycerides, dialkyl carbonates, the two alkyl chains being identical or different, diols, vegetable hydrocarbon oils, synthetic esters, polyol polyesters other than fatty acid triglycerides, in particular esters pentaerythritol, higher fatty acids, C2-C16 dicarboxylic acid diesters, butylene glycol diesters, and mixtures thereof.
[0136] Fatty alcohols are, in particular, alcohols that are liquid at room temperature, with a linear or branched carbon chain, saturated or unsaturated, having 12 to 26 carbon atoms, preferably 16 to 22 carbon atoms, and even better 18 to 20 carbon atoms, such as octyldodecanol or isostearyl alcohol. Preferably, the fatty alcohol is octyldodecanol, marketed under the name Eutanol G® by INOLEX.
[0137] Fatty acid triglycerides consist of a glycerol residue esterified by three fatty acid residues, whose chain lengths can vary from 0.4 to 24 C. These chains can be linear or branched, saturated or unsaturated. Fatty acid triglycerides can be chosen from among capric and / or caprylic acid triglycerides, such as those marketed under the name DUB MOT 5545 by STEARINERIE DUBOIS, or triheptanoin, which is marketed under the name Sustoléo MOT® by Index.
[0138] Dialkyl carbonate comprises two alkyl chains, which may be identical or different. Dicaprylyl carbonate is preferred. It is notably marketed under the name Cetiol CC® by BASF.
[0139] Diols are notably compounds comprising two liquid alcohol functions at room temperature, with a linear or branched carbon chain, saturated or unsaturated, having 12 to 26 carbon atoms, preferably 16 to 22 carbon atoms, even better 18 to 20 carbon atoms, such as caprylyl glycol. - hydrocarbon oils of vegetable origin: - cranberry, chia, hibiscus, camellia, sunflower, rapeseed, castor, jojoba, shea, sweet almond, argan, avocado, olive, soybean, corn, apricot, camelina oils, and meadowfoam seed oil (Limnanthes alba), - polyglyceryl-3 diisostearate such as that marketed by Croda under the trade name Cithrol® PG32IS - triethyl citrate - coco-caprylate / caprate such as that marketed by BASF under the trade name Cetiol® C5C - synthetic esters such as oils with the formula R1COOR2 in which R1 represents the remainder of a linear or branched fatty acid containing from 1 to 40 atoms of carbon and R2 represents a particularly branched hydrocarbon chain containing from 1 to 40 carbon atoms provided that the sum of Ri and R2 is greater than or equal to 10.Esters can be chosen from among other types of esters, particularly fatty acid esters such as cetostearyl octanoate, esters of isopropyl alcohol and C8-C18 fatty acids, preferably C12-C16 such as isopropyl palmitate, ethyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and in particular isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, octanoate of cetyl, tridecyl octanoate, 4-diheptanoate, propylene glycol diethyl 2-hexanoate and mixtures thereof, hexyl laurate, hydroxylated esters such as isostearyl lactate, diisostearyl malate; - polyol polyesters other than fatty acid triglycerides, in particular pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate / tetraisostearate such as SALACOS 168EV marketed by SACI CFPA EUROS, or Pentaerythrityl Adipate / Caprate / Caprylate / Heptanoate such as LEXFEEL 700 MB marketed by INOLEX, whose INCI name is polyester-4; - higher fatty acids such as oleic acid, linoleic acid, linolenic acid and their mixtures, - C2-C16 dicarboxylic acid diesters, preferably C8-C12, and C1-C4 monoalcohol diesters, preferably C3-C4 branched monoalcohol diesters; preferably sebacic acid and isopropyl alcohol diesters such as diisopropyl sebacate marketed under the name DUB DIS by Stéarineries Dubois or marketed under the name Schercemol DIS ester by LUBRIZOL, - Butylene glycol diesters such as butylene glycol dicaprylate / dicaprate marketed under the name Dermofeel® BGC by Dr. Straetmanns.
[0140] According to embodiments, the composition according to the invention comprises at least one polar non-volatile oil selected from octyldodecanol, capric and / or caprylic acid triglycerides, dipentaerythritol tetrahydroxystearate / tetraisostearate, polyglyceryl-3 diisostearate or a mixture thereof.
[0141] Preferably, the non-volatile polar oil represents at least 20% by weight of the composition, in particular from 30% to 70% of the composition.
[0142] The composition may also include one or more non-polar oils, distinct from the aforementioned polar oils.
[0143] For the purposes of this invention, "non-polar oil" means an oil whose 5P parameter as defined above is less than 2 (J / cm3)1 / 2, preferably a 5P less than 1, even better less than 0.5.
[0144] Non-polar oils can be volatile or non-volatile. Non-polar, non-volatile oils
[0145] Examples of non-polar, non-volatile oils include hydrocarbon oils of mineral or synthetic origin, such as: - squalane, phytosqualane and their mixtures. - synthetic esters selected from 2-ethylhexyl palmitate, neopentanic acid esters such as isodecyl neopentanate, isotridecyl neopentanate, isostearyl neopentanate, octyldodecyl neopentanate, isononanoic acid esters such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate; - copolymers of polyols and diacid dimers, and their esters, such as Hailucent ISDA marketed by KOKAYA ALCOHOL.
[0146] Preferably, the weight content of polar oil in the composition is predominant compared to that of non-polar oil.
[0147] Preferably, the composition according to the invention comprises less than 20% by weight of nonpolar oil relative to the weight of the composition, preferably less than 10% by weight, in particular less than 3% by weight, even better less than 1% by weight of nonpolar oil relative to the weight of the composition, or even the composition is free of nonpolar oil.
[0148] The composition of the invention may include a coloring agent. COLORING AGENT
[0149] The coloring agent can be chosen from among water-soluble or fat-soluble dyes, pigments, mother-of-pearl, lacquers or mixtures thereof.
[0150] These coloring agents may optionally be surface-treated with a hydrophobic agent such as silanes, silicones, fatty acid soaps, C9-15 fluoroalcohol phosphates, acrylate / dimethicone copolymers, or mixed C9-15 fluoroalcohol copolymers. Phosphates, silicones, lecithins, carnauba wax, polyethylene, chitosan, and possibly acylated amino acids such as lauroyl lysine, disodium stearoyl glutamate, and aluminum acyl glutamate. Pigments may be mineral or organic, natural or synthetic.
[0151] Examples of mineral pigments include titanium dioxide, zinc oxide, iron, zinc or chromium oxides, manganese violets, ultramarines, ferric ferrocyanide known as Prussian Blue, as well as composite pigments and goniochromatic, pearlescent, interference, photochromic or thermochromic pigments, without this list being exhaustive.
[0152] Examples of organic pigments that can be used in the invention include carbon black, D&C type pigments, carmine-based lakes, barium, strontium, calcium or aluminum lakes, and diketopyrrolopyrrole (DPP) described in documents EP-A-542669, EP-A-787730, EP-A-787731 and WO-A-96 / 08537.
[0153] The pearlescent pigments can be chosen from those commonly found in makeup products, such as mica / titanium dioxide. Alternatively, they can be mica / silica / titanium dioxide-based pigments, synthetic fluorphlogopite / titanium dioxide-based pigments (MAPRECOS' SUNSHINE®), calcium sodium borosilicate / titanium dioxide-based pigments (ENGELHARD's REFLECKS®), or calcium aluminum borosilicate / silica / titanium dioxide-based pigments (MERCK's RONASTAR®). Bismuth oxychloride is another option.
[0154] Advantageously, when it contains one or more pigments, the composition according to the invention further contains at least one dispersant such as diisostearyl malate, polyglyceryl-3 diisostearate such as, for example, that marketed by CRODA under the name Cithrol PG32IS, or pentaerythrityl adipate / caprate / caprylate / heptanoate marketed by Index under the name LEXFEEL 700 EX-LO MB having the INCI name polyester-4.
[0155] Colouring agents are present in the composition in a content of between 0.1% and 15%, the percentages being percentages by weight relative to the total weight of the composition.
[0156] The composition of the invention may include a charge. CHARGES
[0157] These fillers are preferably colorless or white.
[0158] The particles that make it up can be porous or not, and can be in various forms, including platelet, spherical or oblong, regardless of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.).
[0159] In particular, the filler can be chosen from cellulose, especially microcrystalline cellulose, or cellulose microbeads such as those marketed under the trade name Cellulobeads by Daito. Other options include silica, kaolin, lauroyl lysine, boron nitride, silicone microbeads such as those marketed under the name Tospearl by Toshiba, precipitated calcium carbonate, hydroxyapatite, elastomeric polyorganosiloxane particles, glass or ceramic microcapsules, zinc myristate, magnesium myristate, magnesium stearate, magnesium carbonate, magnesium aluminum silicate such as that marketed under the trade name Neusilin ULF2 by Fuji Chemical Industry, natural mica, fluorphlogopite, sericite, starch, clay, or mixtures thereof.
[0160] The starch can be chosen, for example, from rice, tapioca, potato, or corn starch. Rice starch is preferred, particularly that with the INCI name distarch phosphate, marketed as "Rice PO4 Natural" by the company Agrana Starch.
[0161] Clay can be natural or synthetic. It is rendered lipophilic by treatment with an alkyl ammonium salt, such as a C10 to C22 ammonium chloride, for example, di-stearyl dimethyl ammonium chloride. It can be selected from bentonites, particularly hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, and vermiculites. Preferably, the clay is chosen from the hectorite family. Examples of hectorite include the product sold under the name Bentone 38V CG by ELEMENTIS SPECIALTIES (INCI name disteardimonium hectorite) and the product sold under the name Bentone Gel EUG V by ELEMENTIS SPECIALTIES.
[0162] The cosmetic compositions according to the invention may further comprise an additional lipophilic gelling agent, a film-forming polymer, or a volatile oil. ADDITIONAL LIPOPHILE GELDING AGENT
[0163] The term "lipophilic gelling agent", in the context of this application, refers to a substance capable of solidifying or gelatinizing the oil present in the composition of the invention.
[0164] Among the lipophilic gelling agents used, we can mention in particular organic or mineral polymeric or molecular lipophilic gelling agents.
[0165] Another type of organic polymeric lipophilic gelling agent, other than sucrose polyester, consists of dextrin esters. Examples include dextrin and fatty acid esters, such as dextrin palmitate.
[0166] Another type of organic polymeric lipophilic gelling agent consists of glyceryl esters. One example is the diester of eicosadiotic acid and glycerol esterified with behenic acid. It is notably available under the trade name NOMCORT® HK-G from NISSHIN OILLIO.
[0167] As a lipophilic mineral gelling agent, one can cite fumed silica, possibly with a hydrophobic surface treatment, whose particle size is less than 1 µm. It is indeed possible to chemically modify the surface of silica through a chemical reaction that reduces the number of silanol groups present on the silica surface. In particular, silanol groups can be replaced by hydrophobic groups, resulting in hydrophobic silica. The hydrophobic groups can be: - trimethylsiloxyl groups, which are notably obtained by treating fumed silica in the presence of hexamethyldisilazane. Silicas treated in this way are called "Silica silylate" according to the CTFA (8th edition, 2000). They are marketed, for example, under the references Aerosil R812® by the company DEGUSSA, and CAB-O-SIL TS-530® by the company CABOT, - dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas treated in this way are called "Silica dimethyl silylate" according to the CTFA (8th edition, 2000). They are marketed, for example, under the references Aerosil R972® and Aerosil R974® by the company DEGUSSA, and CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by the company CABOT.
[0168] Hydrophobic pyrogenated silica in particular has a particle size that can be nanometric to micrometric, for example ranging from about 5 to 200 nm.
[0169] Organic polymeric lipophilic gelling agents include, for example, partially or fully cross-linked elastomeric organopolysiloxanes with a structure three-dimensional, such as those marketed under the names KSG6®, KSG16® and KSG18® by SHIN-ETSU, Trefil E-505C® and Trefil E-506C® by DOW-CORNING, Gransil SR-CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® by GRANT INDUSTRIES, SF 1204® and JK 113® by GENERAL ELECTRIC; ethylcellulose such as that sold under the name Ethocel® by DOW CHEMICAL; galactomannans having from one to six, and in particular from two to four, hydroxyl groups per sugar, substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated by alkyl chains in C1 to C6, and in particular in C1 to C3 or one of their mixtures.Sequenced copolymers of the "dibloc", "tribloc" or "radial" type of polystyrene / polyisoprene, polystyrene / polybutadiene such as those marketed under the name Luvitol HSB® by BASF, of the polystyrene / copoly(ethylene-propylene) type such as those marketed under the name Kraton® by SHELL CHEMICAL CO or of the polystyrene / copoly(ethylene-butylene) type, mixtures of tribloc and radial (star) copolymers in isododecane such as those marketed by PENRECO under the name Versagel® such as for example the mixture of tribloc copolymer butylene / ethylene / styrene and star copolymer ethylene / propylene / styrene in isododecane (Versagel M 5960) or in hydrogenated polyisobutene (Versagel ME 2000).
[0170] Another type of organic polymeric lipophilic gelling agent consists of polyamide resins or poly(ester-amide) resins, such as ester-terminated polyamides (ETPA), ester-terminated poly(ester-amides) (ETPEA), tertiary amide-terminated polyamides (ATPA), polyalkyleneoxy-terminated polyamides (PAOPA), or polyether polyamides (PEPA).
[0171] Examples of ester-terminated polyamides (ETPA) are those identified by the INCI name "Ethylenediamine / Stearyl Dimer Dilinoleate Copolymer" and available, for example, under the trade name Uniclear® 100VG from Arizona Chemical.
[0172] Examples of ester-terminated poly(ester-amides) (ETPEA) are those identified by the INCI name polyamide-8 which are "Ethylenediamine bis-stearyl dibenzoate dimer copolymers ethylenediamine / neopentylglycol / stearyl" and available, for example, under the trade name Oloecraft® LP-20-PA-MV from the company Croda.
[0173] Examples of tertiary amide-terminated polyamides (ATPAs) are those identified by the INCI name "Ethylenediamine / Dimer Diilinoate Copolymer" hydrogenated Bis-Di-C14-18 Alkyl Amide" and available, for example, under the trade name Sylvaclear® A200V or Sylvaclear® A2614V from Arizona Chemical or those identified by the INCI name "diisostearyl malate and bis-dioctadecylamide dimer dilinoleic acid / ethylenediamine" and available, for example, under the trade name Haimalate PAM from Kokyu Alcohol Kogyo.
[0174] Examples of polyalkyleneoxy terminated polyamides (PAOPA) are those identified by the INCI name Polyamide-3 and available, for example, under the name Sylvaclear® AF1900V, Sylvaclear® PE1800V and Sylvaclear® PA1200V from Arizona Chemical.
[0175] Examples of polyether polyamides (PEPA) are those identified by the INCI name Polyamide-6 and available, for example, under the name Sylvaclear® PE400V from the company Arizona Chemical.
[0176] Another type of organic polymeric lipophilic gelling agent consists of N-acylglutamic acid diamides. Examples include N-acylglutamic acid diamides with a straight-chain alkyl group, such as dibutyl lauroyl glutamide, and N-acylglutamic acid diamides with a branched-chain alkyl group, such as dibutyl ethylhexanoyl glutamide. Dibutyl lauroyl glutamide is commercially available as GP-1, and dibutyl ethylhexanoyl glutamide is commercially available as EB-21; both are marketed by Ajinomoto.
[0177] Among lipophilic gelling agents, sucrose and fatty acid esters, dextrin esters and glyceryl esters are preferred. FILMOGEN
[0178] The composition according to the invention may also include at least one film-forming polymer.
[0179] Among the film-forming polymers that can be used in the compositions of the present invention, we can mention synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and their mixtures.
[0180] By radical film-forming polymer, we mean a polymer obtained by polymerization of monomers with unsaturation, particularly ethylenic, each monomer being capable of homopolymerizing (unlike polycondensates).
[0181] Radical-type film-forming polymers can include vinyl polymers or copolymers, particularly acrylic polymers.
[0182] Vinyl film-forming polymers can result from the polymerization of ethylenically unsaturated monomers having at least one acid group and / or esters of these acid monomers and / or amides of these acid monomers.
[0183] Unsaturated α,β-ethylenic carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid can be used as the monomer bearing the acid group. Preferably, (meth)acrylic acid, itaconic acid, and crotonic acid are used, and itaconic acid is preferred (for example, a metal salt of poly(itaconic acid) such as that marketed under the trade name REVCARE NE 100S by Itaconix).
[0184] Acid monomer esters are advantageously chosen from among the esters of (meth)acrylic acid (also called (meth)acrylates), in particular alkyl (meth)acrylates, especially C1-C30 alkyl, preferably C1-C20, aryl (meth)acrylates, especially C6-C10 aryl, hydroxyalkyl (meth)acrylates, especially C2-C6 hydroxyalkyl.
[0185] Examples of alkyl (meth)acrylates include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethyl-2-hexyl methacrylate, lauryl methacrylate, and cyclohexyl methacrylate.
[0186] Examples of hydroxyalkyl (meth)acrylates include hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.
[0187] Among the aryl (meth)acrylates, we can mention benzyl acrylate and phenyl acrylate.
[0188] The particularly preferred esters of (meth)acrylic acid are the alkyl (meth)acrylates.
[0189] According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, that is to say that some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.
[0190] Examples of amides of acidic monomers include (meth)acrylamides, and in particular N-alkyl (meth)acrylamides, especially those with a C2-C12 alkyl group. Examples of N-alkyl (meth)acrylamides include N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide, and N-undecylacrylamide.
[0191] Vinyl film-forming polymers can also result from the homopolymerization or copolymerization of monomers selected from vinyl esters and styrenic monomers. In particular, these monomers can be polymerized with acid monomers and / or their esters and / or amides, such as those mentioned previously.
[0192] Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate, and t-butyl vinyl benzoate.
[0193] Examples of styrenic monomers include styrene and alpha-methylstyrene.
[0194] We can also mention styrene / butadiene block copolymers such as the products of the Kraton company, or OLEOFLEX EG 200 from the APPLECHEM company.
[0195] Examples of film-forming polycondensates include polyurethanes, polyesters, polyester amides, polyamides, epoxy ester resins, and polyureas.
[0196] Polyurethanes can be chosen from anionic, cationic, non-ionic or amphoteric polyurethanes, acrylic polyurethanes, polyurethanes-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and their mixtures.
[0197] Polyesters can be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, particularly diols.
[0198] Dicarboxylic acid can be aliphatic, alicyclic, or aromatic. Examples of such acids include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers can be used alone or in combination with at least two other dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid, and terephthalic acid are preferred.
[0199] The diol can be chosen from aliphatic, alicyclic, or aromatic diols. Preferably, a diol is used from among the following: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, and 4-butanediol. Other polyols that can be used include glycerol, pentaerythritol, sorbitol, and trimethylol propane.
[0200] Polyester amides can be obtained in a manner similar to polyesters, by polycondensation of diacids with diamines or amine alcohols. Ethylenediamine, hexamethylenediamine, and meta- or para-phenylenediamine can be used as diamines. Monoethanolamine can be used as an amino alcohol. Another example of a polyamide resin is the one with the INCI name DIISOSTEARYL MALATE & BIS DIOCTADECYLAMIDE DIMER DILINOLEIC ACID / ETHYLENE DIAMINE COPOLYMER, marketed as Haimalate PAM by Kokyu Alcohol Kogyo.
[0201] The polyester may further comprise at least one monomer bearing at least one -SO3M group, where M represents a hydrogen atom, an ammonium ion NH4+, or a metal ion, such as Na+, Li+, K+, Mg2+, Ca2+, Cu2+, Fe2+, or Fe3+. In particular, a bifunctional aromatic monomer bearing such a -SO3M group may be used.
[0202] The aromatic ring of the bifunctional aromatic monomer further bearing an -SO3M group as described above can be chosen, for example, from the rings of benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl, and methylenediphenyl. Examples of bifunctional aromatic monomers further bearing an -SO3M group include sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, and 4-sulfonaphthalene-2,7-dicarboxylic acid.
[0203] Copolymers based on isophthalate / sulfoisophthalate can be used, and more particularly copolymers obtained by condensation of di-ethylene glycol, cyclohexane di-methanol, isophthalic acid, sulfoisophthalic acid.
[0204] Naturally derived polymers, possibly modified, can be chosen from shellac resin, sandarac gum, gum arabic (ACACIA SENEGAL GUM), dammars, elemis, copals, cellulosic polymers, polymers extracted from the fruit of Caesalpinia spinosa and / or the algae Kappaphycus alvarezii (such as the product Filmexel® marketed by Silab), and mixtures thereof. A natural polymer such as Filmexel® notably improves the strength of the film obtained from of the composition according to the invention. Other examples include film-forming polymers with the INCI names SHOERA ROBUSTA RESIN + BEESWAX, SHOERA ROBUSTA RESIN + SUNFLOWER OIL, ARAUCARIA + SUNFLOWER OIL, ARAUCARIA + CASTOR OIL, and SHOERA ROBUSTA + OCTYLDODECANOL. Rosin esters such as glyceryl rosinate, available under the trade name NatPure GR from Gattefossé, may also be mentioned.
[0205] We can also mention phytosterols marketed under the name TECHNOL SD by YOKOZEKI, and esters and polyesters of a diol dimer and a monocarboxylic or dicarboxylic acid, such as the esters of dilinoleic diacids and dilinoleyl diol dimers marketed under the names Lusplan DD-DA5® and DD-DA7® by the company Nippon Fine Chemical.
[0206] According to one embodiment, the film-forming polymer can be a polymer solubilized in a liquid fatty phase comprising oils or organic solvents (the film-forming polymer is then said to be a liposoluble polymer).
[0207] Examples of fat-soluble polymers include vinyl ester copolymers (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (whose alkyl group has from 2 to 18 carbon atoms), or an allylic or methallylic ester (having a saturated hydrocarbon radical, linear or branched, of 1 to 19 carbon atoms, linked to the carbonyl of the ester group).
[0208] These copolymers can be crosslinked using crosslinkers which can be either vinyl, allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and divinyl octadecanedioate.
[0209] Examples of these copolymers include: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecyl vinyl ether, vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, vinyl stearate / allyl acetate, and 2,2-dimethyl octanoate. vinyl / vinyl laurate, dimethyl-2,2 allyl pentanoate / vinyl laurate, dimethyl vinyl propionate / vinyl stearate, dimethyl allyl propionate / vinyl stearate, vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, dimethyl vinyl propionate / vinyl laurate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / allyl stearate crosslinked with 0.2% divinyl benzene.
[0210] As examples of liposoluble film-forming polymers, we can also mention liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters having 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the allyl radicals having 10 to 20 carbon atoms.
[0211] Such liposoluble copolymers may be selected from vinyl polystearate copolymers, vinyl polystearate crosslinked with divinylbenzene, diallylether or diallyl phthalate, stearyl poly(meth)acrylate copolymers, vinyl polylaurate, lauryl poly(meth)acrylate, these poly(meth)acrylates being crosslinked with methylene glycol dimethacrylate or tetraethylene glycol.
[0212] The liposoluble copolymers defined above are known and in particular described in application FR-A-2232303; they can have an average molecular weight by weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000.
[0213] We can also mention liposoluble homopolymers, and in particular those resulting from the homopolymerization of vinyl esters having 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having 2 to 24 carbon atoms.
[0214] Examples of liposoluble homopolymers include vinyl polylaurate and lauryl poly(meth)acrylates, these poly(meth)acrylates being able to be crosslinked using ethylene glycol dimethacrylate or tetraethylene glycol.
[0215] Other examples of usable liposoluble film-forming polymers in the invention include polyalkylenes, particularly C2-C20 alkene copolymers such as polybutene; alkylcelluloses with a linear or branched alkyl radical, saturated or unsaturated in the C1-C8 range, such as ethylcellulose and propylcellulose; vinylpyrrolidone (VP) copolymers, particularly vinylpyrrolidone and C2-C40 alkene copolymers, and preferably C3-C20 copolymers. As an example of a usable VP copolymer in Examples of the invention include VP / vinyl acetate copolymer, VP / ethyl methacrylate, butylated polyvinylpyrolidone (PVP), VP / ethyl methacrylate / methacrylic acid, VP / eicosene (ANTARON V220 marketed by Ashland), VP / hexadecene (ANTARON V216 marketed by Ashland), VP / triacontene, VP / styrene, and VP / acrylic acid / lauryl methacrylate.
[0216] Other examples include dextrin esters, and in particular: - dextrin isostearate & isostearic acid marketed under the name UNIFILMA HVY by Chiba Flour Milling - dextrin palmitate / ethylhexanoate marketed under the name RHEOPEARL TT by Chiba Flour Milling - dextrin myristate marketed under the name RHEOPEARL MKL2 by Chiba Flour Milling
[0217] We can also mention sugar esters and in particular sucrose acetate isobutyrate marketed under the name EASTMAN SUSTANE SAIB by the EASTMAN company.
[0218] Silicone resins, generally soluble or swellable in silicone oils, can also be mentioned; these are cross-linked polyorganosiloxane polymers. The nomenclature for silicone resins is known as "MDTQ," where the resin is described according to the different siloxane monomeric units it comprises, with each letter "MDTQ" characterizing a specific type of unit.
[0219] Examples of commercially available polymethylsilsesquioxane resins include those marketed by Wacker under the reference Resin MK, such as Belsil PMS MK, and by SHIN-ETSU under the references KR-220L, or silform flexible resin.
[0220] Examples of siloxysilicate resins include trimethylsiloxysilicate (TMS) resins such as those marketed under the reference SR1000 by General Electric or under the reference TMS 803 by Wacker. Other examples include trimethylsiloxysilicate resins marketed in a solvent such as cyclomethicone, sold under the name "KF-7312J" by Shin-Etsu, "DOWSIL™ RSN-0749", and "DOWSIL™ 593 Fluid" by Dow Corning.
[0221] We can also mention copolymers of silicone resins such as those cited above with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers marketed by Dow Corning under the reference BIO-PSA and described in US patent 5,162,410, or silicone copolymers resulting from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane as described in document WO 2004 / 073626.
[0222] One can also use copolymers with a non-siliconized organic skeleton grafted by monomers containing a polysiloxane motif, such as for example the butyl acrylate / hydroxypropyl dimethicone acrylate copolymer marketed under the name GRANACRYSIL BAS by the company GRANT.
[0223] Finally, we can mention acrylate / polytrimethylsiloxymethacrylate copolymers comprising a carbosiloxane dendrimer structure grafted onto a vinyl skeleton, commercially available under the references DOWSIL FA 4002 ID or DOWSIL FA 4001 CM.
[0224] One can also use silicone polyamides of the polyorganosiloxane type such as those described in documents US-A-5,874,069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680.
[0225] As film-forming agents, natural resins such as phytosterols and esters and polyesters of a diol dimer, dextrin esters and rosin esters are preferred.
[0226] In a preferred embodiment, the composition according to the invention comprises from 1 to 40% by weight of a film-forming polymer, preferably 5 to 36% by weight of at least one film-forming polymer. Oil
[0227] For the purposes of the present invention, "oil" means a liquid compound at room temperature (20°C). When introduced at a rate of at least 1% by weight into water at 25°C, the oil is either completely insoluble in water, or soluble to a degree of less than 10% by weight, relative to the weight of oil introduced into the water. VOLATILE OIL
[0228] According to an advantageous embodiment of the invention, the composition contains no (0%) or very little (maximum 5% by weight relative to the total weight of the composition) volatile oil.
[0229] By "volatile oil" we mean an oil that is likely to evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure.
[0230] Volatile oil is a volatile cosmetic oil, liquid at room temperature, having in particular a non-zero vapor pressure at room temperature and atmospheric pressure, specifically having a vapor pressure between 0.13 Pa and 40 000 Pa (0.001 to 300 mm Hg), preferably between 1.3 Pa and 13,000 Pa (0.01 to 100 mm Hg), and even more preferably between 1.3 Pa and 1,300 Pa (0.01 to 1000 mm Hg).
[0231] Volatile oils may include volatile hydrocarbon oils.
[0232] Regarding volatile hydrocarbon oil, we can more specifically mention a short-chain hydrocarbon oil, volatile linear alkanes such as, for example, described in document FR2933865 incorporated by reference.
[0233] Examples of short-chain hydrocarbon oil(s) may include those chosen from the group including isododecane, isodecane, isohexadecane, dodecane or mixtures thereof.
[0234] Examples of volatile linear alkanes include those with hydrocarbon chains in the following forms: - C9-C17, C10-C14, such as a mixture of undecane and tridecane, marketed by BASF Care Creations under the name Cetiol® Ultimate, - C15-19, such as those marketed by Seppic under the name Emogreen L15, - C12-14, such as those marketed by Biosynthis under the name Vegelight 1214LC, - C9-12 alkane, such as those marketed by Daito under the name Makigreen D10. ADDITIONAL ADDITIVES
[0235] Apart from the aforementioned constituents, the composition according to the invention may contain various ingredients, such as a UV filter, a vegetable or synthetic butter, a sweetening agent, an antioxidant, a sequestering agent, a pH adjuster, a preservative, perfumes, vitamins, moisturizing agents, or a mixture thereof.
[0236] UV filters can be chosen from among organic and inorganic filters, or mixtures thereof. Examples of organic filters include dibenzoylmethane derivatives (such as butyl methoxydibenzoylmethane), cinnamic acid derivatives (such as ethylhexyl methoxycinnamate), salicylates, para-aminobenzoic acids, β,β'-diphenyl acrylates, benzophenones, benzylidene camphor derivatives, phenylbenzimidazoles, triazines, phenylbenzotriazoles, and anthranilic derivatives. Examples of inorganic filters include... based on mineral oxides in the form of pigments or nanopigments, coated or not, and in particular based on titanium dioxide or zinc oxide.
[0237] The composition according to the invention may also contain one or more sweetening agents such as sorbitol, sucrose, xylitol, acesulfame K and sodium saccharin; antioxidants such as alkylated or phosphorylated esters of ascorbic acid, or tocopherol and its esters; sequestrants such as EDTA salts; pH adjusters; preservatives; perfumes; vitamins; moisturizing agents; or a mixture thereof.
[0238] Examples of such adjuvants are cited in particular in the CTFA Dictionary (International Cosmetic Ingredient Dictionary and Handbook published by The Cosmetic, Toiletry and Fragrance Association, 11th Edition, 2006).
[0239] According to a second aspect, the invention relates to a process for preparing a solid cosmetic composition comprising the following steps: dispersion of polar non-volatile oils under agitation at a temperature greater than or equal to 85°C, preferably between 90°C and 95°C; addition of a lipophilic gelling agent chosen from functionalized castor oils alone until it is totally dispersed; addition of waxes and dispersion until a homogeneous mixture is obtained; addition, if present, of film-forming and paste-forming agents, of pigments previously ground in a pigment dispersant while maintaining the temperature at 95°C and agitation; of fillers, mother-of-pearl, active ingredients, perfume and antioxidant, pouring into molds at a temperature greater than or equal to 85°C, preferably between 90°C and 95°C, storing the molds at a temperature less than 0°C, preferably between -10°C and -30°C for a period of between 2 and 20 minutes, demolding.
[0240] Preferably, the mussels should be stored at -20°C for 10 minutes.
[0241] Preferably, the solid cosmetic composition is according to the first aspect.
[0242] According to a third aspect, the invention relates to a method for the care, perfumement or makeup of keratinous materials comprising the application of the composition solid cosmetic according to the first aspect or of the solid cosmetic composition obtained according to the process of the second aspect on the skin, mucous membranes or hair appendages. EXAMPLES Example 1
[0243] Protocol
[0244] The lipstick formulations in Table 2 were prepared as follows: The polar non-volatile oils were dispersed under stirring (150 rpm) in a beaker in a water bath at 95°C. When present, the functionalized castor oil, used as the sole lipophilic gelling agent, was dispersed in the polar oils at 95°C for 30 minutes until completely dispersed. Then, maintaining the temperature at 95°C and stirring, the waxes were added and allowed to disperse until a completely homogeneous mixture was obtained; then the film-forming agents and finally the pastes were added. This yielded a completely molten white body in the form of a homogeneous and clear mixture into which the pigments, previously ground in polyglyceryl-3-diisostearate (Cithrol PG32IS, marketed by Croda), were incorporated. Next, while maintaining the temperature at 95°C and stirring (150 rpm), the fillers, mother-of-pearl, active ingredients, perfume and antioxidant (if present) are added.We pour it into molds at 85°C.
[0245] The molds are placed at -20°C for 10 minutes then unmolded. [Table 2]
[0246] The lipstick formulations were subjected to breakage tests on lips. The results of these tests are excellent, as none of the 20 lipsticks in Example 1 of the invention formulated with functionalized castor oil broke.
[0247] The 20 lipsticks in comparative example 1, in which functionalized castor oil was replaced by polar non-volatile oil (caprylic / capric triglyceride), the formula being otherwise identical to that of example 1, were all broken during the test.
[0248] None of the 20 lipsticks in comparative example 2, in which functionalized castor oil was replaced by ABWAX REVOWAX wax, the formula otherwise being identical to that of example 1, were broken.
[0249] Exudation tests were also performed. Exudation is a phenomenon of seepage resulting in the appearance of oily deposits on the surface of the anhydrous product in the form of micro-pitting, droplets, or oily patches. For this test, 12 lipsticks were placed at different temperatures (27°C, 30°C, 35°C, and 45°C) and examined after 1 hour, 4 hours, and 24 hours to determine if any exudation was visible.
[0250] No exudation phenomenon was observed with the lipsticks of example 1 of the invention formulated with functionalized castor oil, just like those formulated with comparative example 2 in which the functionalized castor oil was replaced by ABWAX REVOWAX wax.
[0251] However, an exudation phenomenon was observed with the lipsticks in comparative example 1, in which functionalized castor oil was replaced by a polar non-volatile oil (caprylic / capric triglyceride). Indeed, droplets of oil appeared on the surface of the stick and did not disappear after returning to room temperature, indicating the instability of these sticks.
[0252] Sensory tests were conducted on 25 trained volunteers to evaluate the glide. The results of these tests are excellent, as the lipsticks of Example 1 of the invention, formulated with functionalized castor oil, exhibit very good glide upon application.
[0253] The lipsticks in comparative example 1, in which functionalized castor oil has been replaced by polar non-volatile oil (caprylic / capric triglyceride), exhibit a glide similar to that felt for the lipsticks in example 1 of the invention.
[0254] In contrast, the lipsticks in comparative example 2, in which functionalized castor oil has been replaced by ABWAX REVOWAX wax, exhibit a significantly reduced glide.
[0255] Stability tests were performed on the lipsticks. Different lipstick sticks were incubated at various temperatures (4°C, 20°C, 40°C, and 45°C). The lipsticks were then observed on days 1, 15, 30, and 60. The lipsticks in Example 1 of the invention, formulated with functionalized castor oil, maintained their good hold, smooth application, and shine throughout the incubation period.
[0256] The results of butter-cutting wire measurements are presented in Table 3.
[0257] [Table 3]
[0258] Hardness is measured at 20°C using the "butter cutter wire" method, which assesses the firmness of a lipstick by measuring, in particular, its resistance to being cut into a stick. This measurement is taken 24 hours after formulation, using a texture analyzer (TAXTPIus, MicroStable Systems, UK) equipped with a 5 kg force cell and its Butter Cutter A / BC probe (Swantech, MicroStable Systems, UK). It measures the maximum resistance force of the stick when the butter cutter wire penetrates to a depth of 9 mm at a speed of 1.6 mm / s. To ensure the reproducibility of the measurements, the analysis is repeated on 6 sticks and the relative difference between the measurements should not exceed 10%, ideally 5%.
[0259] The solid composition according to the invention exhibits adequate stability and hardness: the stick is sufficiently rigid and solid, does not break during application and is thus compatible with packaging in stick form or in another solid form and with application by friction on the surface to be treated and / or made up; it is also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture.
[0260] Example 2
[0261] We prepared the following 3 formulations: - a mixture comprising 30% by weight of a lipophilic gelling agent according to the invention (Estogel M marketed by POLYMEREXPERT) and 70% by weight of a non-volatile oil (caprylic / capric acid triglyceride marketed under the trade reference "DU B MOT 5545" by the company Stéarinerie Dubois, - a mixture comprising 30% by weight of a non-siliconized elastomer (Gransense TC-21X-C) marketed by Grant Industries Inc. and 70% by weight of a non-volatile oil (caprylic / capric acid triglyceride marketed under the trade reference "DUB MCT 5545" by Stéarinerie Dubois), - a composition consisting solely of non-volatile oil (caprylic / capric acid triglyceride identical to that of the two previous mixtures.
[0262] The gelation temperatures and the elastic moduli G' and viscous moduli G” of these three formulations were measured.
[0263] Gelation temperature measurement protocol:
[0264] The gelation temperature can be measured according to the following protocol, using the TA Instruments DHR-2 rheometer:
[0265] - The temperature of the solution or mixture is increased up to 70°C to create the conditions for solubilization and gel formation.
[0266] - The temperature of 70°C is maintained for 1 minute to continue gelling under stirring;
[0267] - Next, the temperature is decreased to 20°C at a rate of 10°C / min,
[0268] - The gelation temperature is recorded at the temperature at which G' increases.
[0269] Measurement protocol for G' and G":
[0270] The viscoelastic behavior of solutions can be evaluated on a TA Instruments DHR-2 rheometer at 20°C with a hot rheology process in which the rheometer is used with an imposed strain of 0.1%, at a frequency of 1 Hz and equipped with a metal plane-plane geometry with an air gap of 500 pm.
[0271] The average modulus G' in the sense of the present invention is the elastic modulus in the linear domain of the curve G'.
[0272] The average G” modulus in the sense of the present invention is the viscous modulus in the linear domain of the G curve”.
[0273] The results obtained are summarized in Table 4 below: [Table 4]
[0274] The results show that Estogel M has a gelling temperature of 59.1°C, while "Gransense TC-21X-C" does not have a gelling temperature.
[0275] The results presented in Table 4 above show that for the third formulation consisting solely of non-volatile oil (triglyceride of acid caprylic I capric), G” > G’ at 20°C, which indicates that this solution is indeed liquid and that there is no gelation.
[0276] The mixture “Gransense TC-21X-C” / caprylic / capric acid triglyceride also exhibits a viscosity modulus G” > G’, regardless of the temperature at which G’ and G” were measured. This indicates the complete absence of gelation of the mixture, which is confirmed by visual observation showing that the mixture remains liquid at room temperature. Finally, for the composition according to the invention in which Estogel M is mixed with caprylic / capric acid triglyceride, G' > G”. At 20°C, G' is approximately 30 times greater than G”. These results show that the Estogel M / caprylic / capric acid triglyceride mixture is solid and gelled, contrary to what is observed for the “Gransense TC-21X-C” / caprylic / capric acid triglyceride mixture or for the caprylic / capric acid triglyceride solution alone.
Claims
Demands
1. Solid cosmetic composition comprising: a lipophilic gelling agent selected from functionalized castor oils, in particular a castor oil polymer functionalized with isophorone diisocyanate, and at least 3.5% by weight of at least one natural or naturally derived wax; at least one polar non-volatile oil; less than 3% by weight of mineral and / or synthetic wax, preferably less than 1% by weight of mineral and / or synthetic wax, preferably the composition being free of mineral and / or synthetic wax, the percentages being expressed in relation to the total weight of the solid cosmetic composition.
2. Composition according to claim 1, characterized in that it is anhydrous.
3. Composition according to any one of claims 1 to 2, characterized in that it is in the form of a stick.
4. Composition according to any one of claims 1 to 3 characterized in that the content of the lipophilic gelling agent selected from the functionalized castor oils is between 0.9% and 50% by weight, preferably between 2% and 40% by weight, and even more preferably between 4% and 12% by weight, the percentages being expressed in relation to the total weight of the solid cosmetic composition.
5. Composition according to any one of claims 1 to 4 characterized in that said at least one natural or natural derived wax is a wax of vegetable origin.
6. Composition according to any one of claims 1 to 5 characterized in that the wax of vegetable origin is selected from: sunflower wax alone or combined with hydrogenated castor oil, candelilla wax or a mixture thereof.
7. Composition according to any one of claims 1 to 6, characterized in that the total wax content is between 7% and 20% by weight, of Preference between 8% and 18% by weight and more preferred between 10% and 14% by weight, the percentages being expressed in relation to the total weight of the solid cosmetic composition.
8. Composition according to any one of claims 1 to 7 characterized in that the weight ratio between the lipophilic gelling agent / natural or naturally derived wax of vegetable origin is between 0.01-2, preferably between 0.1 and 1 and more preferably between 0.5-0.7 for example around 0.
67.
9. Composition according to any one of claims 1 to 8 characterized in that the non-volatile polar oil is selected from oils of polarity between 2 and 8 according to the Hansen method.
10. Composition according to any one of claims 1 to 9 characterized in that the non-volatile polar oil is selected from fatty alcohols, fatty acid triglycerides, di-alkyl carbonates, the 2 alkyl chains being identical or different, diols, vegetable hydrocarbon oils, synthetic esters, polyol polyesters other than fatty acid triglycerides, in particular pentaerythritol esters, higher fatty acids, C2-C16 dicarboxylic acid diesters, butylene glycol diesters, and mixtures thereof.
11. Composition according to any one of claims 1 to 10 characterized in that the polar non-volatile oil is selected from octyldodecanol, capric and / or caprylic acid triglycerides, dipentaerythritol tetrahydroxystearate / tetraisostearate, polyglyceryl-3 diisostearate or a mixture thereof.
12. Composition according to any one of claims 1 to 11 characterized in that the content of polar non-volatile oil is between 30% and 70% by weight relative to the total weight of the composition.
13. Composition according to any one of claims 1 to 12 characterized in that it further comprises a pasty compound.
14. Composition according to any one of claims 1 to 13 characterized in that it further comprises an additional gelling agent.
15. Composition according to any one of claims 1 to 14 characterized in that it further comprises a coloring agent.
16. Composition according to any one of claims 1 to 15 characterized in that it further comprises a charge.
17. Composition according to any one of claims 1 to 16 characterized in that it further comprises a film-forming agent.
18. Composition according to any one of claims 1 to 17 characterized in that it further comprises a volatile oil.
19. A method for preparing a composition according to claims 1 to 18 comprising the following steps: -dispersion of non-volatile polar oils under agitation at a temperature greater than or equal to 85°C, preferably between 90 and 95°C; -addition of a lipophilic gelling agent chosen from the functionalized castor oils alone until it is totally dispersed. -add the waxes and disperse until a homogeneous mixture is obtained; -addition, if present, of film-forming and paste-like substances, pigments previously ground in a pigment dispersant while maintaining the temperature at 95°C and stirring; fillers, mother-of-pearl, active ingredients, perfume and antioxidant -pouring into molds at a temperature of 85°C or higher, preferably between 90°C and 95°C, -storage of the molds at a temperature below 0°C, preferably between -10°C and -30°C, for a period of between 2 and 20 minutes -demolding.
20. A method for the care, perfumement or makeup of keratinous materials comprising the application of the solid cosmetic composition according to any one of claims 1 to 18.
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