LONG-LASTING COMPOSITIONS

Abstract

LONG-LASTING COMPOSITIONS The invention provides compositions comprising (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound. It also provides lip makeup processes using these compositions. Figure for abstract: none

Description

Title of the invention: LONG-LASTING COMPOSITIONS FIELD OF INVENTION

[0001] The present invention relates to long-lasting compositions comprising

[0002] (1) at least one copolymer containing a segment of silicone resin and at least one fluid silicone segment and (2) at least one hydrophobically modified pullulan compound. DISCUSSION OF THE CONTEXT

[0003] Many cosmetic compositions, particularly pigmented cosmetics such as foundations, mascaras, and lipsticks, have been formulated with the aim of possessing long-lasting properties upon application. Unfortunately, many of these compositions generally lack good long-lasting / transfer resistance properties, as well as good application properties, good comfort properties, and / or good appearance or stability properties (e.g., consistency or uniformity of color over time).

[0004] For example, with regard to lip compositions, commercial products containing silicone resins such as MQ resins are known. These products are known to offer good long-lasting properties and / or transfer resistance. However, these products have poor application properties and / or an unpleasant feel upon application (e.g., a rough feel). Sometimes, a second composition (topcoat) is applied separately over these products to improve the poor properties of the compositions in order to make the products acceptable to consumers. Furthermore, the topcoat composition must be continually reapplied in order for the product to remain acceptable to consumers, which means that the products are not effectively "long-lasting" because they require constant maintenance and reapplication.Indeed, even with a distinct topcoat composition, it is still difficult to achieve superior properties.

[0005] There remains a need for improved compositions having improved cosmetic properties, in particular good properties such as minimal or no desquamation or cracking, good resistance to oil and / or water and / or good resistance to transfer properties after application.

[0006] Consequently, one aspect of the present invention is a skincare and / or makeup and / or treatment composition for keratinous materials which has one or more of the aforementioned properties after application. Summary of the invention

[0007] The present invention relates to compositions comprising (1) at least one copolymer containing a segment of silicone resin and at least one segment of fluid silicone and (2) at least one hydrophobically modified pullulan compound.

[0008] According to some embodiments, (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound are present in a weight ratio, A:B, which is greater than 1:1, such as greater than about 2:1, such as greater than about 3:1, such as greater than 1:1 to about 10:1. According to some embodiments, (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound collectively constitute a major fraction of a film-forming component of the composition.

[0009] In some other embodiments, the composition is anhydrous. In some other embodiments, the composition is liquid. In some other embodiments, the composition further includes at least one coloring agent. In some other embodiments, the composition further includes at least one volatile oil. In still other embodiments, the composition includes from about 10% to about 60% by weight of at least one volatile oil and wherein (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound are present in a total weight percentage of about 2% to about 20%, wherein all percentages are relative to the total composition.

[0010] In yet other embodiments, the composition may satisfy one, a plurality, or even all of the limitations described above.

[0011] According to another aspect, a lip makeup process includes the application of any of the compositions described above to the lips in sufficient quantity to make up the lips.

[0012] It must be understood that both the preceding general description and the following detailed description are provided by way of example and explanation only, and do not limit the invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] In the following description of the invention and the claims annexed thereto, it shall be understood that the terms used have their ordinary and usual meanings in the art, unless otherwise specified.

[0014] Except for the operating examples, or unless otherwise indicated, all numbers expressing quantities of ingredients (e.g., concentrations, ratios, etc.) and / or reaction conditions should be understood as being modified in certain embodiments by the term "approximately", meaning within the limits of 10% to 15% of the number indicated (for example, "approximately 10%" means from 8.5% to 11.5%, in particular from 9% to 11%, and approximately 2% means from 1.7% to 2.3%, in particular from 1.8% to 2.2%).

[0015] Similarly, for ratios, the modifier "approximately" means to the nearest 10% or 15% of the ratio. For example, approximately 4:1 means from 3.4:1 to 4.6:1, preferably from 3.6:1 to 4.4:1. As a person skilled in the art will readily understand, when the first ingredient in a ratio is less than the second, then a ratio can be expressed "inversely." For example, if a second ingredient, B, is present in an amount or at a concentration 2.5 times greater than that of ingredient A, this can be identified as an A:B ratio of 1:2.5. "Approximately 1:10" means from 1:8.5 to 1:11.5, preferably from 1:9 to 1:11. As a person skilled in the art will understand, the modifier "approximately" also encompasses the exact number or ratio specified. Unless otherwise stated, all concentrations indicated as percentages are concentrations by weight and, unless otherwise stated, refer to the entire composition.

[0016] “At least one” means one or more and thus includes components individual products as well as mixtures / combinations.

[0017] The numeric ranges include the bounds and are intended to include all combinations and subcombinations. In particular, from approximately 5%, 10%, or 15% to approximately 20%, 50%, or 60% can denote from approximately 5% to approximately 20%, from approximately 5% to approximately 50%, from approximately 5% to approximately 60%, from approximately 10% to approximately 20%, from approximately 10% to approximately 50%, from approximately 10% to approximately 60%, from approximately 15% to approximately 20%, from approximately 15% to approximately 50%, or from approximately 15% to approximately 60%. As used here, a ratio range is intended to include each specific ratio within the subranges and a combination of subranges between the given ranges.

[0018] “Film-forming”, “film-forming polymer” or “film-forming agent” as used herein means a polymer or resin that leaves a film on the substrate to which it is applied, for example, after a solvent accompanying the film-forming agent has evaporated, been absorbed into the substrate and / or dissipated on it.

[0019] “Wax” as used herein means a lipophilic fatty compound that is solid at room temperature (25 °C) and changes from solid to liquid reversibly, having a melting point above 30 °C and, for example, above 45 °C and a hardness above 0.5 MPa at room temperature.

[0020] “Surfactant” and “emulsifier” are used interchangeably throughout throughout this patent memorandum.

[0021] “Polymer” as used herein means a compound that is made up of at least two monomers.

[0022] “Keratinous materials” include materials containing keratin such as hair, skin, eyebrows, lips and nails.

[0023] “Substituted” in this document (unless otherwise specified) means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen-containing groups, ester groups, thiol groups, sulfonate groups, thiosulfate groups, siloxane groups, hydroxyalkyl groups, and polysiloxane groups. The substituent(s) may, in addition, be substituted.

[0024] “Volatile”, as used here, means having a flash point less than about 100°C.

[0025] “Non-volatile”, as used here, means having a flash point greater than approximately 100°C.

[0026] “Anhydrous” means that the compositions contain less than 1% water. Preferably, the compositions of the present invention contain less than 0.5% water, and preferably no water (water-free).

[0027] “Transfer” as used herein means the movement of a fraction of a A composition that has been applied to a keratinous material through contact with another substrate, whether of the same or a different nature. For example, when a composition such as liquid lipstick has been applied, the composition can be transferred to another person's teeth, hands, or cheek. Regardless of the type of composition, it can also be transferred from the keratinous material to which it was applied to another substrate such as towels, collars, glasses, cups, or other containers.

[0028] “Transfer resistance” as used herein refers to the quality exhibited by A composition with respect to transfer resistance. To determine transfer resistance, the amount of composition transferred from a keratinous material to a substrate can be evaluated and compared. For example, a composition may be transfer-resistant if, after application to a keratinous material such as lips, skin, or eyelashes and contact with a substrate, a majority of the composition remains on the wearer. Furthermore, the amount transferred can be compared to that transferred by other compositions, such as commercially available compositions. In a preferred embodiment of the present invention, little or no composition is transferred from the keratinous material to the substrate.

[0029] The term “long-lasting” compositions, as used herein, refers to compositions where, after application to a keratinous material, they do not transfer or stain upon contact with another substrate and maintain a consistent appearance on the keratinous material for an extended period. “Long-lasting” compositions, as used herein, may also refer to compositions where the color remains the same or substantially the same as at the time of application, as seen with the naked eye, after an extended period of time. Long-lasting properties may be evaluated by any method known in the art for evaluating such properties. For example, long-lasting properties may be evaluated by a test involving the application of a composition to keratinous materials such as skin, eyelashes, or lips and evaluating the color of the composition after an extended period of time.For example, the color of a composition can be evaluated immediately after application to keratinous materials, and these characteristics can then be re-evaluated and compared after a certain period. Furthermore, these characteristics can be evaluated against other compositions, such as commercially available ones. In addition, long-lasting properties can be assessed by applying a sample, allowing it to dry, and then abrading it to determine shrinkage / loss of the sample.

[0030] The composition of the present invention may be in any form, liquid or non-liquid (semi-solid, soft solid, solid, etc.). For example, it may be a paste, a solid, a gel, or a cream. It may be an emulsion, such as an oil-in-water or water-in-oil emulsion, a multiple emulsion, such as an oil-in-water-in-oil or water-in-oil-in-water emulsion, or a solid, rigid, or flexible gel. The composition of the invention may, for example, include an external or continuous oily phase.

[0031] “Exempt” or “substantially exempt” or “devoid of”, as used herein, means that although it is preferable that no quantity of the specific component be present in the composition, it is possible that there may be very small quantities of it in the compositions of the invention provided that such quantities do not materially affect at least one, preferably most, of the advantageous properties of the compositions of the invention.Thus, for example, "free from ingredients of animal origin" means that an effective amount (i.e., greater than trace amounts) of ingredients of animal origin is omitted from the composition (i.e., approximately 0% by weight), "substantially free from ingredients of animal origin" means that one or more ingredients of animal origin are present in amounts not exceeding 0.1% by weight, and "free from ingredients of animal origin" means that one or more ingredients of animal origin are present in amounts not exceeding 0.25% by weight, relative to the total weight of the composition. Thus, . For example, "surfactant-free" means that an effective amount of surfactant is omitted from the composition (i.e., 0% by weight), "substantially surfactant-free" means that a surfactant is present in amounts not exceeding 0.1% by weight, and "surfactant-free" means that a surfactant is present in amounts not exceeding 0.25% by weight, relative to the total weight of the composition. The same nomenclature applies to all other ingredients identified throughout the application and in this paragraph, such as wax (the compositions of the invention that are "wax-free," "substantially wax-free," and "wax-free" have meanings consistent with the consideration given in this paragraph), even if this is not specifically stated for each identified ingredient.The examples cited of the use of such language as that in this paragraph are intended to be provided as examples, not as limitations.

[0032] “Physiologically acceptable” means compatible with keratinous material and having a pleasant color, odor, and feel, and which does not cause unacceptable discomfort likely to discourage a consumer from using the composition. Acceptable pH levels for the compositions of the present invention are preferably acidic, namely, less than 7, preferably 6.5 or less, preferably 6.0 or less, preferably 5.5 or less, including all intermediate ranges and sub-ranges, such as, for example, 3 to 5, 4 to 6, 3 to 4.5, etc. The compositions of the present invention may be in the form of a gel composition.

[0033] “Natural compound” means any compound derived directly from a natural substance such as a plant without having undergone any chemical modification.

[0034] “Compound of natural origin” refers to any compound derived from a a natural compound that has undergone one or more chemical modifications, for example by organic synthesis reaction, without the properties of the natural compound being modified.

[0035] “Synthetic compound” refers to any compound that is not a neither a natural compound nor a compound of natural origin.

[0036] “Ambient temperature” means 25 °C.

[0037] “Atmospheric pressure” means 760 mmHg, i.e. 105 pascals.

[0038] “Liquid” means a composition that can conform to a container in which She is in place.

[0039] The compositions and methods of the present invention may include, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredient, component, or limitation described herein or otherwise useful. For example, the film-forming system or The film-forming component may consist essentially of (1) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment, and (2) at least one hydrophobically modified pullulan compound. Similarly, the oily system or oily component may consist essentially of, or consist of, silicone oils (volatile or non-volatile) or volatile oils (silicone or hydrocarbon).

[0040] For the purposes of the present invention, the "fundamental and innovative property" associated with the compositions, components and processes which "consist essentially of" identified ingredients or actions is "long-lasting and flexible."

[0041] Reference is made herein to trade names of materials including, but not limited to, polymers and optional components. The inventors do not intend to limit themselves herein to the materials described and referenced by a particular trade name. Equivalent materials (for example, those obtained from a different source under a different name or catalogue (reference) number) to those referenced by a trade name may be substituted and used in the processes described and claimed herein.

[0042] Unless otherwise stated, all percentages and ratios are calculated by weight. Unless otherwise stated, all percentages are calculated relative to the total weight of a composition. Furthermore, all component or composition levels refer to the active level of that component or composition and are understood to exclude impurities, for example, residual solvents or derivatives, which may be present in commercially available sources.

[0043] Copolymer containing a silicone resin segment and a fluid silicone segment

[0044] According to the first aspect of the present invention, the composition comprises at least one copolymer containing a silicone resin segment and a fluid silicone segment, also referred to as "silicone copolymer" in the present application.

[0045] The silicone copolymer is derived from the reaction between a silicone resin and a fluid silicone. These copolymers are described in patent applications WO 03 / 026 596, WO 2004 / 073 626, WO 2007 / 051 505 and WO 2007 / 051 506 for various cosmetic applications on hair and nails and for pharmaceutical applications on the skin.

[0046] Such copolymers are also described, for example, in "Silicone Pressure Sensitive Adhesive", Sobieski and Tangney, Handbook of Pressure Sensitive Adhesive Technology (D. Satas Ed.), Van Nostrand Reinhold, New York.

[0047] Silicone resin segment

[0048] According to one embodiment of the present invention, the silicone resin segment of the copolymer is an MQ-type silicone resin. Examples of Such MQ silicone resins include, but are not limited to: (i) alkyl siloxysilicates of formula [(RI)3SiO1 / 2]x(SiO4 / 2)y, (MQ motifs) in which x and y are integers from 50 to 80, and the RI group represents a hydrocarbon-based radical containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group, and is preferably an alkyl group containing from 1 to 8 carbon atoms, preferably a methyl group, and (ii) phenylalkyl siloxysilicate resins, the alkyl of the phenylalkyl being as defined above, such as phenylpropyldimethyl siloxysilicate.

[0049] Examples of such MQ type silicone resins include, but are not limited to, trimethyl siloxysilicate type, such as those sold under the reference SR1000 by General Electric, under the reference TMS 803 by Wacker, or under the name KF-7312J by Shin-Etsu, or DC749 or DC593 by Dow Corning.

[0050] Examples of such MQ type silicone resins further include, but are not limited to, MQ siloxysilicate motifs, such as phenylalkylsiloxysilicate resins such as phenylpropyldimethylsiloxysilicate (Silshine 151 sold by General Electric).

[0051] Fluid silicone segment

[0052] According to one embodiment of the present invention, the fluid silicone segment of the copolymer according to the present invention carries a terminal OH functional group.

[0053] Preferably, the fluid silicone segment is a diorganopolysiloxane bearing OH terminal groups, having a viscosity between 100 and 100,000 cSt at 25 °C (determined with a Brookfield viscometer using the ASTMD-445 procedure), wherein the diorganopolysiloxane substituent(s) is / are selected independently from the methyl, ethyl, propyl, and vinyl radicals. The diorganopolysiloxanes are preferably linear polymers. Examples of diorganopolysiloxanes may include, but are not limited to, polydimethylsiloxane, ethylmethyl polysiloxane, a copolymer of dimethylsiloxane and methylvinylsiloxane, and mixtures of such polymers or copolymers containing OH terminal groups. The preferred diorganopolysiloxane is a polydimethylsiloxane.

[0054] For example, the copolymers according to the present invention can be prepared by heating the following mixture:

[0055] - from 45% to 75% by mass of a silicone resin, which is the product of condensation of SiO2 and R3(SiO)1 / 2 motifs for which each R group is independently chosen from the methyl, ethyl, propyl and vinyl radicals and for which the ratio between the SiO2 and R3(SiO)1 / 2 functions of the silicone resin ranges from 0.6 to 0.9;

[0056] - from 25% to 55% by mass of a fluid diorganopolysiloxane containing functions OH terminals, having a viscosity between 100 and 100,000 cSt at 25 °C (determined with a Brookfield viscometer using the ASTMD-445 procedure), wherein the diorganopolysiloxane substituents are independently selected from the methyl, ethyl, propyl, and vinyl radicals; and

[0057] - from 0.001% to 5% of a suitable catalyst, which is preferably a compound organic aliphatic amine preferably selected from primary amines, secondary amines, tertiary amines, carboxylic acid salts of the aforementioned amines and quaternary ammonium salts.

[0058] The mixture is heated to a temperature between 80°C and 160°C until the adhesive character of the resulting silicone copolymer is achieved.

[0059] In the copolymer, the silicone resin is present at a weight concentration ranging from about 0.5%, 1%, 2.5% or 5% to about 15%, 17.5%, 20% or 25% by weight, including all intermediate ranges and sub-ranges.

[0060] Examples of copolymers containing a silicone resin segment and a fluid silicone segment that are important according to the present invention are sold by Dow Corning under the brand names Bio-PSA® and DOWSIL™. In particular, categories 7-4400, 7-4405, 7-4500, and 7-4600 for Bio-PSA® and FC-5001 CM Resin Gum, FC-5002 IDD Resin Gum, and FC-5004 DM Resin Gum for DOWSIL™ may be cited. The copolymer containing a silicone resin segment and a fluid silicone segment can be described by the INCI name Trimethylsiloxysiliate / Dimethiconol Crosspolymer (also referred to herein as "TMSS / DC").

[0061] Advantageously, the copolymer containing a silicone resin segment and a fluid silicone segment is present in an amount ranging from 0.5%, 1% or 2% to 10%, 15% or 25%, preferably from 0.8% to 8%, more preferably from 1% to 6%, relative to the weight of the composition.

[0062] Hydrophobically modified pullulan compound

[0063] According to the present invention, compositions including one or more hydrophobically modified pullulan compounds are proposed.

[0064] Pullulan is a natural polysaccharide produced from starch by the fungus Aureobasidium pullulans. Pullulan is an alpha-glucan primarily composed of repeated maltotriose units linearly linked by alpha 1,6-glycosidic bonds. Natural pullulan is readily soluble in cold or hot water, forming clear, viscous solutions.

[0065] Pullulan can be produced, for example, from the fermentation of partially hydrolyzed starch or by using sucrose, sugar cane, milk, potato and other sources for carbohydrate raw materials.

[0066] Preferably, the hydrophobically modified pullulan compounds of the present invention are oil-soluble. For example, the preferred pullulan compounds of the present invention have been modified with a hydrophobic group such as a siloxane group or a hydrocarbon group that confers oil solubility to the compound. Such modifications may include, for example, a silicone group such as a siloxysilyl group (-[-SiRR'-SiOR"R"'-]-), where R, R', R" and R'" are alkyl groups containing preferably 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms and preferably 1 to 3 carbon atoms), or may include hydrocarbon groups of C8 or higher (for example, hydrocarbon groups containing 8 to 24 carbon atoms, including intermediate ranges and sub-ranges such as 12 to 22 carbon atoms and 12 to 18 carbon atoms).

[0067] A preferred siloxane-modified pullulan compound has a structure corresponding to:

[0068] a pullulan-binder-siloxane group;

[0069] where the siloxane group is preferably a C1-C6 alkyl-substituted siloxysilyl group, such as, for example, a monoalkyl-substituted siloxysilyl group, a diacyl-substituted siloxysilyl group, or a trialkyl-substituted siloxysilyl group, where the C1-C6 alkyl group is linear, cyclic, or branched, substituted or unsubstituted; and

[0070] when the linker does not negatively affect either the film-forming properties or the oil solubility properties of the compound. Preferably, the linker is an alkyl (-C-), an ester or an ether (-O-), an amide or an amine (-N-), or a combination thereof, such as a carbamoyl group. Preferably, the linker is a carbamoyl group.

[0071] Preferably, the hydrophobically modified pullulan compound is a trialkylsiloxysilylcarbamoyl pullulan, a particularly preferred compound being trimethylsiloxysilylcarbamoyl pullulan. The hydrophobically modified pullulan compound may be described by the INCI name Trimethylsiloxysilylcarbamoyl Pullulan (also referred to as "TMSSCP" here).

[0072] Preferably, the hydrophobically modified pullulan compound(s) in the compositions of the present invention has a molecular weight of 50,000 to 10,000,000 daltons, preferably of 100,000 to 5,000,000 daltons, preferably of 250,000 to 1,000,000 daltons, including all intermediate ranges and sub-ranges including, for example, 200,000 to 7,600,000 daltons, 350,000 to 8,750,000 daltons, 225,000 to 700,000 daltons, etc.

[0073] Preferably, at least one hydrophobically modified pullulan compound is present in the compositions of the present invention in an amount ranging from about 0.5%, 1%, 2.5% or 5% to about 5%, 15%, 17.5%, 20% or 25% by weight, including all intermediate ranges and sub-ranges.

[0074] The inventors further observed that the ratio of the weight concentrations between (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound, A:B, is an important performance indicator. In some embodiments, the A:B ratio is from approximately 1:10 or 1:4 to approximately 4:1 or 10:1. According to some other embodiments, the A:B ratio is greater than 1:1, such as greater than approximately 2:1, such as greater than approximately 3:1. This ratio (A):(B) can be, for example, greater than 1:1 or from about 1.25:1, 1.5:1, 2:1 or 3:1 to about 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, such as, for example, greater than 1:1 to about 10:1, such as from about 2:1 or 3:1 to about 4:1, 5:1, 6:1 or 10:1.

[0075] According to certain embodiments, the film-forming polymers are primarily composed of (1) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment, and (2) at least one hydrophobically modified pullulan compound. In this embodiment, at least 50%, such as at least 75%, such as at least 90% by weight of all the film-forming polymers in the composition are derived from the aforementioned polymers.

[0076] According to other embodiments, the sum of the total weight concentration of (1) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and of (2) at least one hydrophobically modified pullulan compound is about 0.5%, 2%, 5%, 7.5% or 10% to about 15%, 17.5%, 20%, 22.5%, 25% or 30%. OILY PHASE

[0077] Preferred embodiments of the present invention provide compositions further comprising at least one fatty substance. Suitable fatty substances include oil(s) and / or wax(s). "Oil" means any non-aqueous medium that is liquid at room temperature (25 °C) and atmospheric pressure (760 mm Hg). A "wax," as used in this disclosure, is a lipophilic fatty compound that is solid at room temperature (25 °C) and reversibly transitions from solid to liquid, having a melting point above 30 °C and, for example, above 45 °C, up to 150 °C, a hardness above 0.5 MPa at room temperature, and an anisotropic crystalline structure in the solid state.By bringing the wax to its melting point, it is possible to use the wax(s) itself as a support(s) and / or it is possible to make the wax(s) miscible with oils to form a microscopically homogeneous mixture.

[0078] Suitable oils include volatile and / or non-volatile oils. These oils may be any acceptable oil, including, but not limited to, silicone oils and / or hydrocarbon oils.

[0079] According to certain embodiments, the compositions of the present invention preferably comprise one or more volatile silicone oils. Examples of these volatile silicone oils include linear or cyclic silicone oils having a viscosity at room temperature less than or equal to 6 cSt and possessing 2 to 7 silicon atoms, these silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. The specific oils that can be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Other volatile oils that can be used include KF 96A with a viscosity of 6 cSt, a commercial product from Shin Etsu with a flash point of 94°C.Preferably, volatile silicone oils have a flash point of at least 40°C.

[0080] Non-limiting examples of volatile silicone oils are listed in Table 1 below.

[0081] [Table 1] Table 1 Compound Flash Point (°C) Viscosity (cSt) Octyltrimethicone 93 1.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2 (cyclopentasiloxane or D5) - Octamethylcyclotetrasiloxane 55 2.5 (cyclotetramethylsiloxane or D4) - Dodecamethylcyclohexasiloxane (D6) 93 7 Decamethyltetrasiloxane (L4) 63 1.7 KF-96 A from Shin Etsu 94 6 PDMS (polydimethylsiloxane) DC 200 (1.5 cSt) from Dow Corning 56 1.5 - PDMS DC 200 (2 cSt) from Dow Corning 87 2

[0082] Furthermore, a linear volatile silicone oil may be used in the present invention. Suitable linear volatile silicone oils include those described in US patents No. 6,338,839 and WO 03 / 042221. In one embodiment, the linear volatile silicone oil is decamethyltetrasiloxane. In another embodiment, decamethyltetrasiloxane is further combined with another solvent that is more volatile than decamethyltetrasiloxane.

[0083] According to certain embodiments of the present invention, the composition preferably comprises one or more non-silicone volatile oils, which may be selected from volatile hydrocarbon oils, volatile esters, and volatile ethers such as those mentioned above. Examples of such volatile non-silicone oils include, but are not limited to, volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof, and in particular, C8-Ci6 branched alkanes such as C8-Ci6 isoalkanes (also known as isoparaffins) or C9-Ci2 alkanes, isohexadecane, isododecane, isodecane, and, for example, oils sold under the trade names Isopar or Permethyl. Preferably, the non-silicone volatile oils have a flash point of at least 40 °C.

[0084] Non-limiting examples of non-silicone volatile oils are given in Table 2 below.

[0085] [Table 2] Table 2 Compound Flash Point (°C) Isododecane 43 Propylene glycol N-butyl ether 60 Ethyl 3-Ethoxypropionate 58 Propylene glycol acetate methyl ether 46 Isopar L (Cn-Cu isoparaffin) 62 Isopar H (Cn-Cl2 isoparaffin) 56 Undecane 62 Tridecane 94 Isohexadecane 96

[0086] The volatility of solvents / oils can be determined using the evaporation rate, as described in US Patent No. 6,338,839. According to preferred embodiments, if present, at least one volatile oil is present in the compositions of the present invention in an amount ranging from approximately 10%, 15%, 20%, 25%, or 30% to approximately 30%, 35%, 40%, 50%, 60%, or 80% by weight, including all ranges and sub-ranges within those ranges. In some other embodiments, the concentration of the non-silicone volatile oil also lies within one or more of these specific ranges.

[0087] According to certain embodiments of the present invention, the composition comprises at least one non-volatile oil. Examples of non-volatile oils that may be used in the present invention include, but are not limited to, polar oils such as:

[0088] - high triglyceride-content hydrocarbon vegetable oils consisting in the fatty acid esters of glycerol, whose fatty acids can have different chain lengths, these chains being optionally linear or branched and saturated or unsaturated; These oils include wheat germ oil, corn oil, sunflower oil, shea butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, pumpkin seed oil, avocado oil, hazelnut oil, grapeseed oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passionflower oil or rosehip oil; or caprylic / capric acid triglycerides, for example those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

[0089] - synthetic oils or esters of formula R5COOR6 in which R5 represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms, including from 7 to 19 carbon atoms, and R6 represents a branched hydrocarbon chain containing from 1 to 40 carbon atoms, including from 3 to 20 carbon atoms, with R6 + R7 > 10, such as, for example, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, octyldodecyl neopentanoate, Ci2 to Ci5 alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate and the octanoates, decanoates or ricinoleates of alcohols or polyalcohols; hydroxylated esters, for example isostearyl lactate or diisostearyl malate; and pentaerythritol esters;

[0090] - synthetic ethers containing 10 to 40 carbon atoms;

[0091] - fatty alcohols in the C8 to C26 range, for example oleyl alcohol, cetyl alcohol, stearyl alcohol and cetearyl alcohol; and

[0092] - their mixtures.

[0093] In addition, examples of non-volatile oils that can be used in the present invention include, but are not limited to, non-polar oils such as branched and unbranched hydrocarbons and hydrocarbon waxes including polyolefins, in particular petrolatum, paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydrosqualene, and mixtures thereof.

[0094] In addition, examples of non-volatile oils that can be used in the present invention include, but are not limited to, silicone oils such as dimethicone (polydimethylsiloxane) of various viscosities, as well as phenylated silicone oils such as phenyltrimethicone and trimethylsiloxyphenyldim ethicone.

[0095] According to preferred embodiments, if present, at least one oil is present in the compositions of the present invention in an amount ranging from about 10%, 15%, 20%, 25% or 30% to about 60%, 65%, 70% or 80% by weight, including all ranges and sub-ranges within those ranges.

[0096] According to preferred embodiments of the present invention, the compositions of the present invention further comprise at least one wax.Appropriate examples of waxes that may be used in accordance with this disclosure include those commonly used in cosmetics: these include those of natural origin, such as beeswax, carnauba wax, candelilla wax, ouricoury wax, Japanese wax, cork fiber wax or sugar cane wax, rice bran wax, rice wax, montan wax, paraffin wax, lignite wax or microcrystalline wax, ceresin or ozokerite, and hydrogenated oils such as hydrogenated castor oil or jojoba oil; synthetic waxes such as polyethylene waxes obtained by polymerization or copolymerization of ethylene, and Fischer-Tropsch waxes, or fatty acid esters, such as octacosanyl stearate, glycerides which are solid at 30 °C, for example at 45 °C.

[0097] According to certain embodiments of the present invention, the compositions of the present invention may include at least one silicone wax. Examples of suitable silicone waxes include, but are not limited to, silicone waxes such as alkyl- or alkoxydimethicones having an alkyl or alkoxy chain of 10 to 45 carbon atoms, poly(di)methylsiloxane esters that are solid at 30 °C and whose ester chain comprises at least 10 carbon atoms, di(l,l,l-trimethylolpropane tetrastearate), which is marketed or manufactured by Heterene under the name HEST 2T-4S;Alkylated silicone acrylate copolymer waxes comprising at least 40 mol% of siloxy motifs of formula (R2 R'SiO1 / 2)x(R"SiO2 s / 2)y, where x and y have a value of 0.05 to 0.95, R is an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group, R is a monovalent hydrocarbon having 9-40 carbon atoms, R" is a monovalent hydrocarbon group having 1 to 8 carbon atoms, an aryl group such as those disclosed in US patent application No. 2007 / 0149703, a particular example being C30-C45 alkyldimethylsilyl polypropylsilsesquioxane; and mixtures thereof.

[0098] According to preferred embodiments, the compositions of the present invention contain less than 1% wax.

[0099] According to preferred embodiments, the compositions of the present invention contain less than 0.5% wax.

[0100] According to preferred embodiments, the compositions of the present invention do not contain wax.

[0101] If present, the wax(s) may be present in an amount from 1 to 30% by weight relative to the total weight of the composition, for example from 2 to 20%, and for example from 3 to 10%, including all intermediate ranges and sub-ranges. COLORING AGENTS

[0102] According to embodiments of the present invention, the compositions of the present invention may optionally include at least one coloring agent. According to this embodiment, the coloring agent(s) is / are preferably chosen from pigments, dyes, pearlescent pigments, pearlescent agents, and mixtures thereof.

[0103] Representative fat-soluble dyes that can be used according to the present invention include Sudan Red, DC Red 17, DC Green 6, beta-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, annatto, and quinoline yellow. The fat-soluble dyes, if present, generally have a concentration of up to 40% by weight of the total weight of the composition, such as from 0.0001% to 30%, including all intermediate ranges and sub-ranges.

[0104] The pearlescent pigments that can be used according to the present invention can be selected from colored pearlescent pigments, such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment selected from those mentioned above, and pearlescent pigments based on bismuth oxychloride. If present, the pearlescent pigments are included in the composition at a concentration of up to 50% by weight of the total weight of the composition, for example, from 0.0001% to 40%, preferably from 0.001% to 30%, including all intermediate ranges and sub-ranges.

[0105] The pigments that can be used according to the present invention can be selected from white, colored, inorganic, organic, polymeric, and non-polymer pigments. Representative examples of mineral pigments include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, and ferric blue. Representative examples of organic pigments include carbon black, D&C type pigments, and lakes based on cochineal carmine, barium, strontium, calcium, and aluminum.

[0106] If present, the coloring agents may be present in the composition at a concentration of up to 50% by weight of the total weight of the composition, such as from 0.0001% to 40%, and furthermore such as from 0.001% to 30%, including all intermediate ranges and sub-ranges. AQUEOUS PHASE

[0107] The compositions of the present invention may also optionally contain water. When the compositions of the present invention contain water, they are preferably in the form of an emulsion. Preferably, when the compositions of the present invention contain water, they are in the form of an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion. Preferably, when in the form of an emulsion, the oil phase consists mainly of silicone oils (Si / W or W / Si emulsion) or hydrocarbon oils. If present, the water is preferably present in an amount of approximately 10% to approximately 80% by weight, preferably approximately 20% to approximately 70% by weight, preferably approximately 35% to approximately 65% ​​by weight, including all intermediate ranges and sub-ranges, all weights being based on the total weight of the composition.

[0108] According to preferred embodiments, however, the compositions of the present invention are water-free, substantially water-free, or water-free as defined herein. Preferably, the compositions of the present invention are anhydrous.

[0109] The composition of the invention may also include any additive commonly used in the field concerned. For example, additional film-forming agents other than at least one and at least one (1) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (2) at least one hydrophobically modified pullulan compound, dispersants such as poly(12-hydroxystearic acid), antioxidants, essential oils, sunscreens, preservatives, perfumes, fillers, neutralizing agents, cosmetic and dermatological active agents such as, for example, emollients, moisturizers, vitamins, essential fatty acids, surfactants, silicone elastomers, thickening agents, gelling agents, particles, paste compounds, viscosity-increasing agents may be added.A non-exhaustive list of these ingredients is available in US patent application publication no. 2004 / 0170586. Other examples of suitable additional components can be found in the other references cited in this application.

[0110] A person skilled in the art shall ensure that the optional additional additives and / or their quantity are chosen so that the advantageous properties of the composition according to the invention are not, or substantially not, compromised by the envisaged addition.

[0111] These substances can be chosen in various ways by a person skilled in the art to prepare a composition that has the desired properties, for example, consistency or texture.

[0112] These additives may be present in the composition in a proportion of 0% to 99% (such as 0.01% to 90%) relative to the total weight of the composition and furthermore such as 0.1% to 50% by weight (if present), including all intermediate ranges and sub-ranges.

[0113] It goes without saying that the composition of the invention must be cosmetically or dermatologically acceptable, namely that it must contain a physiologically acceptable non-toxic carrier and must be able to be applied to keratinous materials of human beings such as, for example, lips, skin or eyelashes.

[0114] In particular, suitable gelling agents for the oil phase include, but are not limited to, lipophilic or hydrophilic clays.

[0115] The term "hydrophilic clay" refers to a clay capable of swelling in water; this clay swells in water and, after hydration, forms a colloidal dispersion. Clays are silicates containing a cation that can be selected from among calcium, magnesium, aluminum, sodium, potassium, and lithium cations, and mixtures thereof. Examples of such products include clays of the smectite family, such as montmorillonite, hectorite, bentonite, beidellite, and saponite, as well as those of the vermiculite family, stevensite, and chlorite. These clays can be of natural or synthetic origin.

[0116] Hydrophilic clays that may be cited include synthetic hectorites (also called laponites), for example the products sold by the Laporte company under the names Laponite XLG, Laponite RD and Laponite RDS (these products are sodium-magnesium silicates and in particular sodium-lithium-magnesium silicates); bentonites, for example the product sold under the name Bentone HC by the Rheox company; magnesium-aluminium silicates, in particular hydrated, for example the products sold by the Vanderbilt company under the names Veegum Ultra, Veegum HS and Veegum DGT, or calcium silicates, and in particular the synthetic product sold by the company under the name Micro-cel C.

[0117] The term "lipophilic clay" refers to a clay capable of swelling in a lipophilic medium; this clay swells in the medium and thus forms a colloidal dispersion. Examples of lipophilic clays that may be mentioned include modified clays such as modified magnesium silicate (Rheox's Bentone Gel VS38), and hectorites modified with a C22 fatty acid ammonium chloride, for example, hectorite modified with distearyldimethylammonium chloride (CTFA name: disteardimonium hectorite) sold under the name Bentone 38 CE by Rheox or Bentone 38V® by Elementis.

[0118] In particular, among the gelling agents that can be used, silica particles may be mentioned. Preferably, the silica particles are sublimed silica particles.

[0119] Suitable silicas include, but are not limited to, hydrophobic silicas, such as fumed silica optionally with a hydrophobic surface treatment, having a particle size of less than 1 micron, preferably less than 500 nm, preferably less than 100 nm, preferably from 5 nm to 30 nm, including all intermediate ranges and sub-ranges. It is indeed possible to chemically modify the silica surface by a chemical reaction that reduces the number of silanol groups present on the silica surface. In particular, the silanol groups can be replaced by hydrophobic groups, resulting in hydrophobic silica. The hydrophobic groups can be:

[0120] trimethylsiloxyl groups, obtained in particular by treatment of pyrogenic silica in the presence of hexamethyldisilazane. The silicas thus treated are called "Silica silylate" according to the CTFA (6th edition, 1995). They are marketed for example under the references "AEROSIL R812®" by the company Degussa, "CAB-O-SIL TS-530 ®" by the company Cabot;

[0121] dimethylsilyloxyl or polydimethylsiloxane groups, obtained in particular by treating pyrogenic silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. The silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are marketed, for example, under the references "AEROSIL R972®", "AEROSIL R974®" by the company Degussa, "CAB-O-SIL TS-610®", "CAB-O-SIL TS-720®" by the company Cabot.

[0122] Preferably, the gelling agent, if present, is present in the composition of the present invention in amounts of active material generally ranging from about 0.1% to about 10%, preferably from about 0.25% to about 5%, and more preferably from about 0.5% to about 3.5%, by weight, relative to the total weight of the composition, including all intermediate ranges and sub-ranges.

[0123] Preferred embodiments of the present invention provide methods for treating, caring for, and / or coloring keratinous material by applying compositions of the present invention to the keratinous material in a sufficient quantity to treat, care for, and / or color the keratinous material. Preferably, the "coloring" of the keratinous material includes the application of at least one coloring agent to the keratinous material in a sufficient quantity to provide color to the keratinous material.

[0124] Still other preferred embodiments propose methods for improving the appearance of a keratinous material by applying compositions of the present invention to the keratinous material in a sufficient quantity to improve the appearance of the keratinous material.

[0125] In accordance with previous preferred embodiments, the compositions of the present invention are applied topically to the desired area of ​​keratinous material in a sufficient quantity to treat, care for, and / or conceal the keratinous material, to cover or mask defects associated with the keratinous material, or to improve the appearance of the keratinous material. The compositions can be applied to the desired area as needed, preferably once a day, and then preferably allowed to dry before being subjected to contact, such as with clothing or other objects. Preferably, the composition is allowed to dry for about 4 minutes or less, more preferably for about 2 minutes or less.

[0126] In preferred embodiments, lip makeup processes are proposed, wherein the process includes the application of compositions proposed herein to the lips of users in a quantity sufficient to make up the lips.

[0127] Unless otherwise stated, all numbers expressing quantities of ingredients, reaction conditions, etc., used in the patent memorandum and claims are to be understood as modified in all cases by the term "approximately." Accordingly, unless otherwise stated, the numerical parameters presented in the following patent memorandum and the attached claims are approximations that may vary depending on the desired properties that one seeks to obtain by means of the present invention.

[0128] Although the numerical ranges and parameters defining the general scope of the invention are approximations, the numerical values ​​given in the specific examples are reported as accurately as possible. However, every numerical value inherently contains some errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without thereby limiting its scope. Percentages are given on a weight basis.

[0129] Example 1 - Sample compositions of the invention

[0130] The following compositions can be prepared:

[0131] [Tables3] Ingredient General range (active ingredient content) Specific range (active ingredient content) Copolymer containing a silicone resin segment and a se 0.5%-25% 2%-15% Fluid silicone compound (e.g., TMSS / DC) Hydrophobically modified pullulan compound (e.g., TMSSCP) 0.5%–25% 0.5%–5% Volatile oil 10%–80% 25%–60% Colorant 0.1%–30% 5%–20% Other (e.g., preservatives, waxes, active agents, etc.) 0%–10% 0.1%–5% Example 2 - Test Procedures Example 2A#: Extended Wear Test Procedure

[0132] One ml samples (below) were taken from abrasive paper and left at room temperature for 24 hours to dry and form a film. Two drops of liquid (olive oil, artificial saliva, or acetic acid) were placed on the film of each sample, taking care not to overlap the drops. The drops were left to stand for the times indicated below and then wiped 15 times with a cotton pad. This procedure was repeated twice to obtain an average score.

[0133] Allow the 1 ml sample of test composition on the abrasive paper to rest on the bench at room temperature for 24 hours to dry.

[0134] Use a piece of ASTM tape to cover the right side of the film, press lightly with fingers along the film and, at a 180-degree angle, gently pull the film to remove it.

[0135] On the sample, place drops onto the sampling film. 2 drops of olive oil and repeat for artificial saliva and acetic acid, taking care not to overlap the drops.

[0136] Let the drops rest for 10 minutes, then wipe 15 times with a cotton pad for each category.

[0137] The above procedure was repeated for each sample for each liquid (olive oil, artificial saliva, acetic acid).

[0138] Finally, on a film on which no liquid has been applied, pass a piece of ASTM tape over the film, applying slight pressure with the fingers and remove it at an angle of 180 degrees.

[0139] Rating: The cotton disc and substrate are visualized and rated according to the quantity of product remaining. A numerical rating on a scale of 1 to 3 was assigned. where 1 = least transfer / best film property and 3 = most transfer / worst film property. An average score from two measurements was obtained and recorded in the table below – where “Oil” refers to the substrate for the oil experiment; “KW oil” refers to the cotton pad for the oil experiment; “Saliva” refers to the substrate for the saliva experiment; “KW saliva” refers to the cotton pad for the saliva experiment; “Acetic acid” refers to the substrate for the acetic acid experiment; “AA wipe” refers to the cotton pad for the acetic acid experiment. The average scores are also reported. Example 2B#: Stretch Test Procedure

[0140] Each sample (below) was taken from a 3x1 window on a 4x2 section of nitrile glove with a 1 / 2" border on all sides created using tape, and each sample was left to dry overnight and then the tape was removed. Each sample was then stretched 10 times by a total of 6 inches to determine the impact on flexibility, using the following rating scale:

[0141] [Tables4] Rating scale: 0 No break 1 Minimal break 2 Some break 3 Partial break 4 Major break 5 Total break Example 3#: Tests

[0142] The compositions were prepared as follows:

[0143] [Tables5] Exl Ex 2 Ex3 Cl C2 Ingredient Trimethylsiloxysilicate / dimethiconol crosspolymer (Trimethylsiloxysilicate / Dimethiconol Crosspolymer (TMSS / DC)) 9.6 6.0 2.4 12.0 0 Trimethylsiloxysilylcarbamoyl Pullulane (TMSSCP) 2.4 6.0 9.6 0 12.0 Tributyl acetyl citrate 2.0 2.0 2.0 2.0 2.0 Disteardimonium hectorite and propylene carbonate 4.0 4.0 4.0 4.0 4.0 Pigment 10.0 10.0 10.0 10.0 10.0 Isododecane QSQS QS QS QS Total TMSS / DC+TMSSCP 12 12 12 12 12 Ratio (A:B) TMSS / DC:TMSSCP 4:1 1:1 1:4 ___ ___

[0144] These compositions were tested for prolonged hold and flexibility according to the procedures of Example 2, where the drops were left to stand for 10 minutes. The results of these tests are presented below:

[0145] [Tableauxô] Sample n Oil Oil KW Saliva Saliva KW Acetic acid Wipe AA Average score Stretch Ex 1 1.25 2.00 1.00 1.25 1.00 1.00 1.25 0.5 Ex 2 1.00 1.63 1.00 1.25 1.00 1.25 1.19 1.0 Ex 3 1.00 1.50 1.00 1.25 1.00 1.50 1.21 2.0 Cl 1.75 2.00 1.00 1.00 1.00 1.00 1.00 1.29 0.5 C2 1.80 1.50 1.00 1.25 1.00 1.50 1.27 4.0

[0146] Comparing examples Exl, Ex 2, and Ex3 with Cl and C2, it can be seen that all the inventive compositions provide surprisingly better average strength scores (and considerably better for the "oil" challenge) than polymer (A) or (B) alone. Furthermore, it can also be seen that the (A:B) ratio of 4:1, and not the 1:1 or 1:4 ratios, also remarkably maintains the excellent stretch properties present in the "all-TMSS / DC" system (Cl).

Claims

Demands

1. Composition comprising (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound.

2. Composition according to claim 1, wherein (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound are present in a weight ratio, A:B, which is greater than 1:

1.

3. Composition according to any one of the preceding claims, wherein the composition is anhydrous.

4. Composition according to any one of the preceding claims, wherein the composition is liquid.

5. Composition according to any one of the preceding claims, wherein the composition comprises at least one coloring agent.

6. Composition according to any one of the preceding claims, wherein the composition further comprises from about 10% to about 60% by weight of at least one volatile oil and wherein (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound are present in a total weight percentage of about 2% to about 20%, wherein all percentages are relative to the total composition.

7. Composition according to any one of the preceding claims, wherein (A) at least one copolymer containing a silicone resin segment and at least one fluid silicone segment and (B) at least one hydrophobically modified pullulan compound are present in a weight ratio, A:B, which is greater than 1:1 up to about 10:

1.

8. A method for making up lips comprising the application of the composition of any one of the preceding claims.