WO2009086513A1

WO2009086513A1 - Cosmetic composition containing a polar modified wax and a low melting point polyolefin wax

Info

Publication number: WO2009086513A1
Application number: PCT/US2008/088434
Authority: WO
Inventors: Hy Si Bui; Yoriko Kawaratani; Michell Chen
Original assignee: L'oreal S.A.
Priority date: 2007-12-28
Filing date: 2008-12-29
Publication date: 2009-07-09

Abstract

The present invention is directed to a method of making up keratinous substrates involving applying onto the keratinous substrate a composition containing (a) a polar modified wax; (b) a film forming agent, preferably an alkyl silsesquioxane resin; (c) a low melting point polyolefin wax; (d) a liquid fatty phase; and (e) optionally, a colorant. Also disclosed is the composition for application to the keratinous substrate.

Description

COSMETIC COMPOSITION CONTAINING A POLAR MODIFIED WAX AND A LOW MELTING POINT POLYOLEFIN WAX

[0001] BACKGROUND OF THE INVENTION [0002] Currently in the cosmetic market there is a demand for cosmetics that give long lasting effects, are transfer-resistant and/or are comfortable to wear or use. However, generally speaking, the majority of long wearing and transfer resistant products have had to sacrifice comfort, and for example are dry or sticky after application. Attempts have been made to provide comfort with long wear and transfer resistance through the use of a two step system. This renders the process of make up a little more cumbersome, inconvenient and time consuming. Other attempts have been made with the use of different volatile solvents such as cyclomethicone or isododecane and various film formers, yet the feel and texture of such compositions can be unacceptable.

[0003] It has been surprisingly discovered that the use of a film former and a combination of waxes provides remarkable properties of long wear, transfer resistance and comfort in cosmetic compositions.

[0004] BRIEF SUMMARY OF THE INVENTION

[0005] A first aspect of the present invention is directed to a method of making up keratinous substrates involving applying onto the keratinous substrates a composition containing (a) a polar modified wax;(b) a film former, preferably an alkyl silsesquioxane resin; (c) a low melting point polyolefin wax; (d) a liquid fatty phase; and (e) optionally, a colorant.

[0006] A second aspect of the present invention is directed to a composition for making up keratinous substrates containing (a) a polar modified wax;(b) a film former, preferably an alkyl silsesquioxane resin; (c) a low melting point polyolefin wax; (d) a liquid fatty phase; and (e) optionally, a colorant. [0007] DETAILED DESCRIPTION OF THE INVENTION

[0008] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term "about".

[0009] POLAR MODIFIED WAX

[0010] According to the present invention, compositions comprising at least one polar modified wax are provided. "Polar modified wax" as used herein refers to waxes made using metallocene catalysis which have been modified to include polar groups or units. Suitable polar modified waxes include those disclosed in U.S. patent application publication no. 20070031361 , the entire contents of which is hereby incorporated by reference.

[0011] Preferably, the polar modified wax is based upon a homopolymer and/or copolymer wax of ethylene and/or propylene monomers having a weight-average molecular weight Mw of less than or equal to 25 000 g/mol, preferably of 1000 to 22 000 g/mol and particularly preferably of 4000 to 20,000 g/mol, a number-average molecular weight Mn of less than or equal to 15 000 g/mol, preferably of 500 to 12 000 g/mol and particularly preferably of 1000 to 5000 g/mol, a molar mass distribution Mw/Mn in the range from 1.5 to 10, preferably from 1.5 to 5, particularly preferably from 1.5 to 3 and especially preferably from 2 to 2.5, which have been obtained by metallocene catalysis. In the case of a copolymer wax, it is preferable to have, based on the total weight of the copolymer wax, 0.1 to 30.0% by weight of structural units originating from the one monomer and 70.0 to 99.9% by weight of structural units originating from the other monomer. Such homopolymer and copolymer waxes can be made, for example, by the process described in EP 571 882, the entire contents of which is hereby incorporated by reference, using the metallocene catalysts specified therein. Suitable preparation processes include, for example, suspension polymerization, solution polymerization and gas-phase polymerization of olefins in the presence of metallocene catalysts, with polymerization in the monomers also being possible. [0012] Polar modified waxes can be produced in a known manner from the homopolymers and copolymers described above by oxidation with oxygen-containing gases, for example air, or by graft reaction with polar monomers, for example maleic acid or acrylic acid or derivatives of these acids. The polar modification of metallocene polyolefin waxes by oxidation with air is described, for example, in EP 0 890 583 A1 , and the modification by grafting is described, for example, in U.S. Pat. No. 5,998,547, the entire contents of both of which are hereby incorporated by reference in their entirety.

[0013] In accordance with the present invention, particularly preferred polar modified waxes are hydrophilically modified waxes (that is, waxes which have been modified to provide the waxes with hydrophilic properties). Suitable examples include, but are not limited to, homopolymers and copolymers of hydrophobic groups such as C2-C30 groups, for example ethylene, propylene, C18-C30, etc. which have been modified with hydrophilic units such as, for example, maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc. Particularly preferred hydrophilically modified waxes are ethylene and propylene homopolymers and copolymers which have been modified with acrylate and/or maleic anhydride units.

[0014] In accordance with the present invention, particularly preferred polar modified waxes also include hydrophobically modified waxes (that is, waxes which have been modified to provide the waxes with hydrophobic properties). Suitable examples include, but are not limited to, hyrdrophilic homopolymers and copolymers of maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc. which have been modified with hydrophobic groups such as C2-C30 groups, for example ethylene, propylene, C18-C30, etc.

[0015] Particularly preferred polar modified waxes for use in the present invention are polypropylene-maleic anhydride modified waxes ("PPMA") commercially available from Clariant under the trade name LICOCARE, and C26-C28 alpha olefin maleic acid anhydride copolymer modified waxes. Such waxes are also known as polypropylene-ethylene-maleic anhydride copolymers and C26-C28 alpha olefin-ethylene-maleic anhydride copolymers due to inclusion of ethylene group(s) resulting from the reaction of the hydrophobic group with the hydrophilic maleic anhydride group. Specific examples of such waxes include products marketed by Clariant under the LicoCare name having designations such as PP207 LP3349, CM401 LP3345, CA301 LP 3346, and CA302 LP 3347.

[0016] According to particularly preferred embodiments in which the composition is a lip composition, it is preferred that the polar modified waxes have low crystallinity as determined by differential scanning calorimetry. Preferably, the polar modified waxes have a crystallinity of less than 40%, more preferably less than 30%, and most preferably less than 25%. For example, LicoCare PP207 LP3349 has approximately 11 % crystallinity. Such waxes possess improved clarity which, in turn, results in less reduction in gloss of the lip composition.

[0017] Preferably, the polar modified wax(es) represent from about 0.1 % to about 30% of the total weight of the composition, more preferably from about 0.5% to about 20% of the total weight of the composition, and most preferably from about 1 % to about 15%, including all ranges and subranges therebetween such as, for example, about 5% to about 15% and about 10% to about 20%.

[0018] LOW MELTING POINT POLYOLEFIN WAX

[0019] According to the present invention, compositions comprising at least one low melting point polyolefin wax are provided. As used herein, the phrase "low melting point" refers to polyolefin waxes having a melting point of less than 8O⁰C, preferably less than 75⁰C, most preferably between about 5O⁰C and 75°C, including all ranges and subranges therebetween.

[0020] Preferably, the polyolefin wax used in accordance with the present invention results from the polymerization, and in particular from the homopolymerization, of an alpha-olefin corresponding to the general formula: R-CH=CH₂, in which R denotes an alkyl radical having at least 10 carbon atoms, preferably from 10 to 50 carbon atoms and more preferably from 25 to 50 carbon atoms. R is preferably a linear alkyl radical. According to the invention, the term "homopolymerization of an alpha-olefin" is understood to mean the polymerization of monomers composed essentially of an alpha-olefin or a mixture of alpha-olefins as defined above. Such waxes also include hyperbranched polyolefin waxes such as Performa V 343 produced by New Phase Technologies.

[0021] Preferably, the polyolefin wax has a number-average molecular weight ranging from 400 to 3000, more preferably from 2000 to 3000, and better still from 2500 to 2700. Suitable examples of such polyolefins are disclosed in U.S. Pat. Nos. 6,641 ,821 , 6,464,967, 4,060,569, and 4,239,546, the disclosures of all of which are specifically incorporated by reference herein. Commercial examples of such waxes are sold in particular under the name of "Performa V (Reg) 103", "Performa (Reg)253" and "Performa V (Reg) 260" by New Phase Technologies.

[0022] Preferably, the polyolefin wax(es) represent from about 0.01 % to about 40% of the total weight of the composition, more preferably from about 0.1 to about 30%, more preferably from about 0.5% to about 20%, more preferably from about 1 % to about 15%, including all ranges and subranges therebetween such as, for example, about 5% to about 15% and about 10% to about 20%.

[0023] LIQUID FATTY PHASE

[0024] The cosmetic composition of the present invention comprises a liquid fatty phase. The liquid fatty phase may contain at least one oil chosen from a volatile silicone oil, a volatile hydrocarbon oil, a non-volatile silicone oil, a non-volatile hydrocarbon oil, and mixtures thereof.

[0025] Suitable volatile silicone oils include linear or cyclic silicone oils having a viscosity at room temperature less than or equal to 6cSt and having from 2 to 7 silicon atoms, these silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Examples of volatile silicone oils that may be used include, but are not limited to, octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and their mixtures. Preferably, the volatile silicone oils have a flash point of at least 4O⁰C.

[0026] Suitable volatile hydrocarbon oils include, but are not limited to, those having from 8 to 16 carbon atoms and their mixtures and in particular branched C₈ to Ci₆ alkanes such as C₈ to C-iβ isoalkanes (also known as i so pa raff ins), isododecane, isodecane, isohexadecane, and for example, the oils sold under the trade names of lsopar or Permethyl, the C₈ to C-16 branched esters such as isohexyl or isodecyl neopentanoate and their mixtures. Preferably, the volatile hydrocarbon oils have a flash point of at least 40⁰C.

[0027] Suitable non-volatile silicone oils that may be used include, but are not limited to, linear polydimethylsiloxanes (PDMSs), that are liquid at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent and/or at the end of a silicone chain, these groups each containing from 2 to 24 carbon atoms; phenylsilicones, for instance phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicat.es, trimethyl pentaphenyl trisiloxane, tetramethyl hexaphenyl trisiloxane.

[0028] Suitable non-volatile hydrocarbon oils which can be used in the compositions of the present invention include, but are not limited to, polar oils such as:

[0029] - hydrocarbon-based plant oils with a high triglyceride content consisting of fatty acid esters of glycerol, the fatty acids of which may have varied chain lengths, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially wheat germ oil, corn oil, sunflower oil, karite 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, marrow oil, avocado oil, hazelnut oil, grape seed oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; or caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

[0030] - synthetic oils or esters of formula R²COOR³ in which R² represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms, including from 7 to 19 carbon atoms, and R³ represents a branched hydrocarbon-based chain containing from 1 to 40 carbon atoms, including from 3 to 20 carbon atoms, with R² + R³ MO, such as, for example, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, Ci₂ to C₁₅ alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate, and octanoates, decanoates or ricinoleates of alcohols or of polyalcohols; hydroxylated esters, for instance isostearyl lactate or diisostearyl malate; and pentaerythritol esters;

[0031] - synthetic ethers containing from 10 to 40 carbon atoms;

[0032] - C₈ to C₂6 fatty alcohols, for instance oleyl alcohol; and

[0033] - mixtures thereof.

[0034] The liquid fatty phase is present in the composition of the present invention in an amount of from greater than 0% to about 80% by weight, based on the weight of the composition.

[0035] Film Forming Agents

According to particularly preferred embodiments of the present invention, compositions further comprising at least one film forming agent (film former) are provided. Acceptable film forming agents are known in the art and include, but are not limited to, those disclosed in U.S. patent application publication no. 2004/0170586, the entire contents of which is hereby incorporated by reference. Non-limiting representative examples of such film forming agents include silicone resins such as, for example, MQ resins (for example, trimethylsiloxysilicates), T-propyl silsesquioxanes and MK resins (for example, polymethylsilsesquioxanes), silicone esters such as those disclosed in U.S. Pat. Nos. 6,045,782, 5,334,737, and 4,725,658, the disclosures of which are hereby incorporated by reference, polymers comprising a backbone chosen from vinyl polymers, methacrylic polymers, and acrylic polymers and at least one chain chosen from pendant siloxane groups and pendant fluorochemical groups such as those disclosed in U.S. Pat. Nos. 5,209,924, 4,693,935, 4,981 ,903, 4,981 ,902, and 4,972,037, and WO 01/32737, the disclosures of which are hereby incorporated by reference, polymers such as those described in U.S. Pat. No. 5,468,477, the disclosure of which is hereby incorporated by reference (a non-limiting example of such polymers is poly(dimethylsiloxane)-g-poly(isobutyl methacrylate), which is commercially available from 3M Company under the tradename VS 70 IBM). According to preferred embodiments, the film former, when present, is present in the composition in an amount ranging from 0.1% to 30% by weight relative to the total weight of the composition. Preferably, the film former is present in an amount ranging from 0.5% to 20% by weight relative to the total weight of the composition, and more preferably from 2% to 15%, including all ranges and subranges therebetween. One of ordinary skill in the art will recognize that the film former of the present invention may be commercially available, and may come from suppliers in the form of a dilute solution. The amounts of the film former disclosed herein therefore reflect the weight percent of active material.

[0036] According to particularly preferred embodiments, the composition of the present invention contains an alkyl silsesquioxane resin. Alkyl silsesquioxane resins are silsesquioxane homopolymers and/or copolymers having an average siloxane unit of the general formula R¹ _nSiO(_4- _n)/2, wherein each R¹ is independently chosen from a hydrogen atom and a Cr Cio alkyl group, wherein more than 80 mole % of R¹ represent a C₃-Ci₀ alkyl group, n is a value of from 1.0 to 1.4, and more than 60 mole % of the copolymer comprises R¹SiO_3/2 units.

[0037] Preferably, the silsesquioxane resin used is one where R¹ is a C₁-C₁₀, preferably a CrC₄ alkyl group, and more preferably a propyl group. Examples of alkyl silsesquioxane resins suitable for use in the present invention are propyl silsesquioxane resins. One such propyl silsesquioxane resin is commercially available from Dow-Corning as Dow Corning® 670 Fluid.

[0038] The alkyl silsesquioxane resin is preferably present in the cosmetic composition of the present invention in an amount ranging from about 3% to about 50% by weight, such as from about 5% to about 30% by weight, based on the weight of the composition.

[0039] TACKIFIER

[0040] According to preferred embodiments, the composition of the present invention may also contain a tackifier. Generally, a tackifier is a low molecular weight resin with a glass transition temperature T₉ above room temperature, such as above 25⁰C. By low molecular weight, it is meant a molecular weight below 10,000, such as below 5,000.

[0041] Examples of suitable tackifiers, include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, hydrogenated rosin acids, hydrogenated rosin esters, polyisoprene, partially or fully hydrogenated polyisoprene, polybutenediene, partially or fully hydrogenated polybutenediene, and the like. As is evidenced by some of the cited examples, the tackifier may be fully or partially hydrogenated. The tackifier may also be non-polar. (Non-polar meaning that the tackifier is substantially free of monomers having polar groups. Preferably, the polar groups are not present, however, if they are present, they are preferably present in an amount of up to about 5% by weight, preferably up to about 2% by weight, and more preferably up to about 0.5% by weight.)

[0042] In some embodiments, the tackifier may have a softening point (Ring and Ball, as measured by ASTM E-28) of 8O⁰C to 15O⁰C, preferably 10O⁰C to 13O⁰C. In other embodiments the tackifier may be liquid and have an R and B softening point of between about -7O⁰C and 7O⁰C.

[0043] In some embodiments, the tackifiers are hydrogenated hydrocarbon resins such as a hydrogenated styrene/methyl styrene/indene copolymer e.g., styrene/methyl styrene/indene copolymers which include R1090, R1100, R7100, S1100, and S5100, all which are commercially available from Eastman Chemical under the trade name Regalite^®. In other embodiments, aliphatic or aromatic hydrocarbon-based tackifying resins, for instance the resins sold under the name "Piccotac®" and "Hercotac®" from Hercules or "Escorez®" from Exxon®, may also be used. It is also to be understood that mixtures of tackifiers may also be employed without departing from the spirit of the invention. [0044] A particularly preferred tackifier for use in the present invention is a hydrogenated hydrocarbon resin such, for example, a hydrogenated styrene/methyl styrene/indene copolymer, commercially available from Eastman under the tradename Regalite I R1100.

[0045] The tackifier is present in the cosmetic composition of the present invention in an amount ranging from about 2% to about 50% by weight, such as from about 10% to about 40% by weight, based on the weight of the composition.

[0046] COLORANT

[0047] The cosmetic compositions of the present invention may also contain at least one cosmetically acceptable colorant such as a pigment or dyestuff. Examples of suitable pigments include, but are not limited to, inorganic pigments, organic pigments, lakes, pearlescent pigments, irhdescent or optically variable pigments, and mixtures thereof. A pigment should be understood to mean inorganic or organic, white or colored particles. Said pigments may optionally be surface-treated within the scope of the present invention but are not limited to treatments such as silicones, perfluorinated compounds, lecithin, and amino acids.

[0048] Representative examples of inorganic pigments useful in the present invention include those selected from the group consisting of rutile or anatase titanium dioxide, coded in the Color Index under the reference Cl 77,891 ; black, yellow, red and brown iron oxides, coded under references Cl 77,499, 77, 492 and, 77,491 ; manganese violet (Cl 77,742); ultramarine blue (Cl 77,007); chromium oxide (Cl 77,288); chromium hydrate (Cl 77,289); and ferric blue (Cl 77,510) and mixtures thereof.

[0049] Representative examples of organic pigments and lakes useful in the present invention include, but are not limited to, D&C Red No. 19 (Cl 45,170), D&C Red No. 9 (Cl 15,585), D&C Red No. 21 (Cl 45,380), D&C Orange No. 4 (Cl 15,510), D&C Orange No. 5 (Cl 45,370), D&C Red No. 27 (Cl 45,410), D&C Red No. 13 (Cl 15,630), D&C Red No. 7 (Cl 15,850), D&C Red No. 6 (Cl 15,850), D&C Yellow No. 5 (Cl 19,140), D&C Red No. 36 (Cl 12,085), D&C Orange No. 10 (Cl 45,425), D&C Yellow No. 6 (Cl 15,985), D&C Red No. 30 (Cl 73,360), D&C Red No.3 (Cl 45,430) and the dye or lakes based on cochineal carmine (Cl 75,570) and mixtures thereof.

[0050] Representative examples of pearlescent pigments useful in the present invention include those selected from the group consisting of the white pearlescent pigments such as mica coated with titanium oxide, mica coated with titanium dioxide, bismuth oxychloride, titanium oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue, chromium oxide and the like, titanium mica with an organic pigment of the above-mentioned type as well as those based on bismuth oxychloride and mixtures thereof.

[0051] The precise amount and type of colorant employed in the compositions of the present invention will depend on the color, intensity and use of the cosmetic composition and, as a result, will be determined by those skilled in the art of cosmetic formulation.

[0052] WAXES

[0053] In some embodiments, it may be desirable to formulate cosmetic compositions in accordance with the present invention with waxes which are not low melting point polyolefin waxes. Suitable waxes are those generally used in cosmetics and dermatology. Examples thereof include, but are not limited to, those of natural origin such as beeswax, carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fiber wax, sugar cane wax, paraffin wax, lignite wax, microcrystalline waxes, lanolin wax, montan wax, ozokerites and hydrogenated oils such as hydrogenated jojoba oil. Examples of suitable synthetic waxes include, but are not limited to, fatty acid esters and glycerides that are solid at 40⁰C, for example, at above 55°C, silicone waxes such as alkyl- and alkoxy-poly(di)methylsiloxanes and/or poly(di)methyl- siloxane esters that are solid at 4O⁰C, for example, at above 55⁰C.

[0054] The waxes may be present in the composition of the present invention in an amount of from greater than 0% to 40% by weight, based on the weight of the composition.

[0055] EMULSIFIERS [0056] The composition of the present invention may contain at least one compound useful as an emulsifier. Suitable emulsifiers that can be used according to the present invention include, but are not limited to, nonionic, cationic, anionic, and zwitterionic emulsifiers. Suitable emulsifiers according to the present invention include, but are not limited to, acyl lactylates, alkyl phosphates, carboxylic acid copolymers, esters and ethers of glucose, esters of glycerin, esters of propylene glycol, esters of sorbitan anhydrides, esters of sorbitol, ethoxylated ethers, ethoxylated alcohols, fatty acid amides, fatty acid esters of polyethylene glycol, fatty esters of polypropylene glycol, polyoxyethylene fatty ether phosphates, soaps, alkoxylated polydimethylsiloxanes, and mixtures thereof.

[0057] Additional compounds suitable as emulsifiers include, but are not limited to, emulsifying crosslinked siloxane elastomers such as Dimethicone/PEG-10/15 Crosspolymer available as KSG-210®, Dimethicone/Polyglycerin-3 Crosspolymer available as KSG 710®, Lauryl PEG-15 Dimethicone/ Vinyl Dimethicone Crosspolymer available as KSG- 31®, PEG-12 Dimethicone Crosspolymer, available as DC 9011®. In one embodiment, the compound useful as an emulsifier is Dimethicone/PEG- 10/15 Crosspolymer. For examples of other suitable emulsifiers that can be used according to the present invention, see, for example, McCutcheon's, Detergents and Emulsifiers, North American Edition (2003), Allured Publishing Corporation, the entire contents of which are hereby incorporated by reference.

[0058] The emulsifier may be present in the cosmetic composition of the present invention in an amount ranging from greater than 0% to 10% by weight, based on the total weight of the composition.

[0059] Non-Emulsifying Silicone Elastomers

[0060] The composition of the present invention may contain non-emulsifying silicone elastomers.

[0061] The term "non-emulsifying" defines silicone elastomers not containing a hydrophilic chain, such as polyoxyalkylene or polyglycerolated units. [0062] The non-emulsifying silicone elastomer is preferably an elastomeric crosslinked organopolysiloxane that may be obtained by a crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen linked to silicon and of diorganopolysiloxane containing ethylenically unsaturated groups linked to silicon, especially in the presence of a platinum catalyst; or by dehydrogenation crosslinking coupling reaction between a diorganopolysiloxane containing hydroxyl end groups and a diorganopolysiloxane containing at least one hydrogen linked to silicon, especially in the presence of an organotin compound; or by a crosslinking coupling reaction of a diorganopolysiloxane containing hydroxyl end groups and of a hydrolysable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of an organoperoxide catalyst; or by crosslinking of organopolysiloxane via high-energy radiation such as gamma rays, ultraviolet rays or an electron beam.

[0063] The elastomeric crosslinked organopolysiloxanes may be conveyed in the form of a gel consisting of an elastomeric organopolysiloxane included in at least one hydrocarbon-based oil and/or one silicone oil. The elastomeric crosslinked organopolysiloxanes may also be in powder form.

[0064] Suitable non-emulsifying silicone elastomers for use in the composition of the present invention include, but are not limited to, those sold under the names "DC 9040®", "DC 9041®", "DC 9509®", "DC 9505®" and "DC 9506®" by the company Dow Corning, and KSG-6®, KSG-8®, KSG- 10®, KSG-14®, KSG-15®, and KSG-16® by the company Shin-Etsu; SFE- 168® and SFE-839® available from GE Silicones; and Gransil SR-SYC® available from Grant Industries.

[0065] The non-emulsifying silicone elastomer may also be in the form of elastomeric crosslinked organopolysiloxane powder coated with silicone resin, especially with silsesquioxane resin, as described, for example, in patent U.S. Pat. No. 5,538,793, the entire content of which is herein incorporated by reference. Such elastomers are sold under the names "KSP- 100®", "KSP-101®", "KSP-102®", "KSP-103®", "KSP-104®" and "KSP-105®" by the company Shin-Etsu.

[0066] Other elastomeric crosslinked organopolysiloxanes in the form of powders include hybrid silicone powders functionalized with fluoroalkyl groups, sold especially under the name "KSP-200®" by the company Shin- Etsu; hybrid silicone powders functionalized with phenyl groups, sold especially under the name "KSP-300®" by the company Shin-Etsu.

[0067 ] Additional elastomeric crosslinked organopolysiloxanes in the form of powders include cured silicone powder coated with microfine particles. These particles are described in US5,492,945, US5,756,568 and US5,945,471 , the entire contents of which are hereby incorporated by reference. Suitable cured silicone powder coated with microfine particles include, but are not limited to DC9701®, available from Dow Corning.

[0068] The silicone elastomer may be present in the cosmetic composition of the present invention in an amount ranging from greater than 0% to about 95% by weight, based on the weight of the composition.

[0069] GELLING AGENTS

[0070] The compositions of the invention may also be optionally gelled with an oil-phase gelling agent. The gelling agent increases the liquid fatty phase viscosity and leads to a solid or flowable composition when introduced in said fatty phase. The gelling agent does not encompass waxes, in the sense that it is not waxy. The at least one gelling agent may be chosen from gelling agents in polymeric form and gelling agents in mineral form. The gelling agent may be chosen from agents that gel via chemical cross-linking and agents that gel via physical cross-linking.

[0071] Modified clays may be used as gelling agents, examples of which include, but are not limited to, hectorites modified with an ammonium chloride of a C10 to C22 fatty acid, such as hectorite modified with distearyldimethylammonium chloride, also known as quatemium-18 bentonite, such as the products sold or made under the names Bentone 34® by the company Rheox, Claytone XL®, Claytone 34® and Claytone 40® sold or made by the company Southern Clay, the modified clays known under the name quatemium-18 benzalkonium bentonites and sold or made under the names Claytone HT®, Claytone GR® and Claytone PS® by the company Southern Clay, the clays modified with stearyldimethylbenzoylammonium chloride, known as stearalkonium bentonites, such as the products sold or made under the names Claytone APA® and Claytone AF® by the company Southern Clay, and Baragel 24® sold or made by the company Rheox. [0072] Other mineral gelling agents, which can be used in the invention, include silica, such as fumed silica. The fumed silica may have a particle size, which may be nanometric to micromethc, for example ranging from 5 nm to 200 nm.

[0073] The fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in a hydrogen-oxygen flame, producing a finely divided silica. This process makes it possible to obtain hydrophilic silicas that have a large number of silanol groups at their surface. Such hydrophilic silicas are sold or made, for example, under the names "Aerosil 130®", "Aerosil 200®", "Aerosil 255®", "Aerosil 300®" and "Aerosil 380®" by the company Degussa, and "CAB-O-SIL HS-5®", "CAB-O-SIL EH- 5®", "CAB-O-SIL LM-130®", "CAB-O-SIL MS-55®" and "CAB-O-SIL M-5®" by the company Cabot.

[0074] It is thus possible to chemically modify the surface of the hydrophilic silica by chemical reaction, producing a reduction in the number of silanol groups. The silanol groups can be replaced, for example, with hydrophobic groups: this then gives a hydrophobic silica. The hydrophobic groups may be: trimethylsiloxyl groups, which are obtained in particular by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "silica silylate" according to the CTFA dictionary (6th edition, 1995). They are sold or made, 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 thus treated are known as "silica dimethyl silylate" according to the CTFA dictionary (6th edition, 1995). They are sold or made, 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; groups derived from reacting fumed silica with silane alkoxides or siloxanes. These treated silicas are, for example, the products sold or made under the reference "Aerosil R805®" by the company Degussa.

[0075] According to the invention, hydrophobic silica, such as fumed silica, may be used as a lipophilic gelling agent. The use of fumed silica makes it possible to obtain a translucent or even transparent composition, in particular in the form of a stick, which does not exude, in the absence of opacifying particles such as waxes, fillers and pigments (including nacres).

[0076] The at least one lipophilic gelling agent can allow the exudation of the composition to be limited and can allow its stability to be increased, while at the same time conserving the composition's glossy appearance, which is not possible with waxes such as those used conventionally in cosmetics and dermatology.

[0077] The at least one gelling agent, if used, will typically be present in the composition of the present invention in an amount of from greater than 0% to 20% by weight, based on the weight of the composition.

[0078] VOLATILE SOLVENTS

[0079] The composition of the present invention may also contain volatile solvents.

[0080] Examples of suitable volatile solvents include, but are not limited to, non-polar volatile hydrocarbon-based oils (which as used herein, refers to oil containing only hydrogen and carbon atoms), silicone oils (optionally comprising alkyl or alkoxy groups that are pendant or at the end of a silicone chain), and fluoro oils. Suitable hydrocarbon-based oils include, but are not limited to, isoparaffins, i.e., branched alkanes containing 8-16 carbon atoms, such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), and petroleum distillates. Suitable silicone oils may include linear or cyclic silicones containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. Examples of suitable silicone oils include, but are not limited to, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane and heptamethyloctyltrisiloxane, and mixtures thereof. Mixtures of these solvents may be used. Polar volatile solvents may also be used, examples of which include C₂ to C₅ alcohols, such as ethanol, ethyl 3-ethoxypropionate and isohexyl neopentanoate.

[0081] The volatile solvent may be present in the composition of the present invention in an amount generally ranging up to about 60%, such as from about 5% to about 50% by weight, such as from about 50% to about 40% by weight, based on the total weight of the composition.

[0082] ADDITIVES/AUXILIARY AGENTS

[0083] The compositions of the present invention may further comprise at least one cosmetically or dermatologically acceptable additive such as a thickener, a film former, a plasticizer, an antioxidant, an essential oil, a preserving agent, a fragrance, a filler, a pasty fatty substance, a waxy fatty substance, a neutralizing agent, and a polymer, and cosmetically active agents and/or dermatological active agents such as, for example, emollients, moisturizers, vitamins, essential fatty acids and medicaments.

[0084] While the use of a plasticizer is not necessary in the compositions of the present invention, it may, nevertheless, be desirable. Plasticizers are organic compounds added to a high polymer both to facilitate processing and to increase the flexibility and toughness of the final product by internal modification of the polymer molecule. Examples of suitable plasticizers include, but are not limited to, oils, cellulose esters, phthalate esters, adipate esters, sebacate esters, tricresyl phosphate, castor oil, glycol ethers, benzyl alcohol, triethyl citrate, and propylene carbonate.

[0085] Representative examples of preservatives include alkyl para-hydroxybenzoates, wherein the alkyl radical has from 1 , 2, 3, 4, 5 or 6 carbon atoms and preferably from 1 to 4 carbon atoms e.g., methyl parahydroxybenzoate (methylparaben), ethyl para-hydroxybenzoate (ethylparaben), propyl para-hydroxybenzoate (propylparaben), butyl parahydroxybenzoate (butylparaben) and isobutyl para-hydroxybenzoate (isobutylparaben). Mixtures of preservatives may certainly be used, e.g., the mixture of methyl-paraben, ethylparaben, propylparaben and butylparaben sold under the name Nipastat by Nipa, and the mixture of phenoxyethanol, methylparaben, ethylparaben, propylparaben and butylparaben sold under the name Phenonip, also by Nipa. These preservatives may be present in amounts ranging from about 0.01 to about 10% by weight, preferably from 0.5% to about 5% by weight, and more preferably from about 0.8 to about 3% by weight, based on the weight of the composition. [0086] Fillers that may be used in the compositions of the invention include, for example, silica powder; talc; polyamide particles and especially those sold under the name Orgasol by the company Atochem; polyethylene powders; microspheres based on acrylic copolymers, such as those based on ethylene glycol dimethacrylate/lauryl methacrylate copolymer sold by the company Dow Corning under the name Polytrap; expanded powders such as hollow microspheres and especially the microspheres sold under the name Expancel® by the company Kemanord Plast or under the name Micropearl F® 80 ED by the company Matsumoto; powders of natural organic materials such as crosslinked or noncrosslinked corn starch, wheat starch or rice starch, such as the powders of starch crosslinked with octenyl succinate anhydride, sold under the name Dry-Flo® by the company National Starch; silicone resin microbeads such as those sold under the name Tospearl® by the company Toshiba Silicone; clays (bentone, laponite, saponite, etc.) and mixtures thereof. These fillers may be present in amounts ranging from greater than 0% to 50% by weight, based on the weight of the composition.

[0087] The compositions of the present invention may further comprise a safe and effective amount of at least one active ingredient or pharmaceutically acceptable salt thereof. The term "safe and effective amount" as used herein, means an amount sufficient to modify the condition to be treated or to deliver the desired skin benefit, while at the same time avoiding serious side effects, at a reasonable benefit to risk ratio within the scope of sound medical judgment. What is a safe and effective amount of the active ingredient will vary with the specific active agent, the ability of the active agent to penetrate through the skin, the age, health and skin condition of the user, and other like factors. Typically, the active ingredient may be present in amounts ranging from greater than 0% to 20% by weight, based on the weight of the composition.

[0088] The active ingredients useful herein can be categorized by their therapeutic benefit or their postulated mode of action. However, it is to be understood that the active ingredients useful herein can in some instances provide more than one therapeutic benefit or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit the active ingredient to that particular application or applications listed. Also, pharmaceutically acceptable salts of these active ingredients are useful herein. The following active ingredients are useful in the compositions of the present invention.

[0089] The cosmetic compositions of the present invention may also contain sunscreens, which are chemical absorbers that actually absorb harmful ultraviolet radiation. It is well known that chemical absorbers are classified, depending on the type of radiation they protect against, as either UV-A or UV-B absorbers. UV-A absorbers generally absorb radiation in the 320 to 400 nm region of the ultraviolet spectrum. UV-A absorbers include anthranilates, benzophenones, and dibenzoyl methanes. UV-B absorbers generally absorb radiation in the 280 to 320 nm region of the ultraviolet spectrum. UV-B absorbers include p-aminobenzoic acid derivatives, camphor derivatives, cinnamates, and salicylates.

[0090] The sunscreens useful in the present invention typically comprise chemical absorbers, but may also comprise physical blockers. Exemplary sunscreens which may be formulated into the compositions of the present invention are chemical absorbers such as p-aminobenzoic acid derivatives, anthranilates, benzophenones, camphor derivatives, cinnamic derivatives, dibenzoyl methanes (such as avobenzone also known as Parsol^® 1789), diphenylacrylate derivatives, salicylic derivatives, triazine derivatives, benzimidazole compounds, bis-benzoazolyl derivatives, methylene bis- (hydroxyphenylbenzotriazole) compounds, the sunscreen polymers and silicones, or mixtures thereof. Also exemplary of the sunscreens which may be formulated into the compositions of this invention are physical blockers such as cerium oxides, chromium oxides, cobalt oxides, iron oxides, red petrolatum, silicone-treated titanium dioxide, titanium dioxide, zinc oxide, and/or zirconium oxide, or mixtures thereof.

[0091] Examples of suitable sunscreens include, but are not limited to: aminobenzoic acid, amyldimethyl PABA, cinoxate, diethanolamine p-methoxycinnamate, digalloyl trioleate, dioxybenzone, 2-ethoxyethyl p- methoxycinnamate, ethyl 4-bis(hydroxypropyl)aminobenzoate, 2-ethylhexyl-2- cyano-3,3-diphenylacrylate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl salicylate, glyceryl aminobenzoate, homomenthyl salicylate, homosalate, 3- imidazol-4-ylacrylic acid and ethyl ester, methyl anthranilate, octyldimethyl PABA, 2-phenylbenzimidazole-5-sulfonic acid and salts, red petrolatum, sulisobenzone, titanium dioxide, triethanolamine salicylate, N, N, ΛMrimethyl- 4-(2-oxobom-3-ylidene methyl)anillinium methyl sulfate, and mixtures thereof.

[0092] The composition of the present invention may be in the form of a liquid, semi solid such as a gel, or a solid. The cosmetic compositions may be used to make up the lips such as lip glosses or lipsticks, or to make up eyelids such as eyeshadows, or to make up eye lashes such as mascaras.

[0093] The composition of the present invention may be anhydrous or non anhydrous, in the form of an aqueous emulsion, such as oil in water (O/W), water in oil (VWO), or a multiple emulsion (W/O/W, O/W/O,...), or non aqueous emulsion, in which case the water is replaced with a material compatible with water, such as a diol, alcohol, glycol, polyhydric alcohol and derivatives thereof. By anhydrous, it is meant that the composition contains no added water (other than the water that may be provided by other components of the composition such as a latex or the like).

[0094] The present invention is further described in terms of the following non-limiting examples. Unless otherwise indicated, all parts and percentages are on a weight-by-weight percentage basis.

[0095] Lipstick compositions: Inventive examples 1-3

[0096] Example 4

[0097] Four non-transfer lipsticks were prepared as Compositions A-D below. Of these compositions, only Composition B contained polar metallocene wax. Compositions C and D contained both silicone resin (T resin) and Regalite. Composition A contained only silicone resin (T resin). The ingredients of compositions A-D are set forth below.

[0098] Wear properties of all four compositions were determined. It was determined that composition B containing both polar metallocene wax and silicone resin possessed the best wear characteristics, the best transfer-resistance characteristics, and the best feel (non-sticky) characteristics of all the compositions. The data reflecting these improved properties of composition B are set forth below.

Claims

What is claimed is:

1. A method of making up a keratinous substrate involving applying onto the keratinous substrate a composition comprising:

(a) a polar modified wax;

(b) an alkyl silsesquioxane resin;

(c) a low melting point polyolefin wax

(d) a liquid fatty phase; and

(e) optionally, a colorant.

2 . The method according to claim 1 , wherein the polar modified wax is present in an amount ranging from about 0.1 % to about 30% by weight, based on the weight of the composition.

3 . The method according to claim 1 , wherein the polar modified wax is present in an amount ranging from about 1% to about 15% by weight, based on the weight of the composition.

4 . The method according to claim 1 , wherein the alkyl silsesquioxane resin is present in an amount ranging from about 3% to about 50% by weight, based on the weight of the composition.

5 . The method according to claim 1 , wherein the alkyl silsesquioxane resin is present in an amount ranging from about 5% to about 30% by weight, based on the weight of the composition.

6 . The method according to claim 1 , wherein the liquid fatty phase is present in an amount of from greater than 0% to about 80% by weight, based on the weight of the composition.

7 . The method according to claim 1 , wherein the low melting point polyolefin wax is present in an amount ranging from about 1 % to about 20% by weight, based on the weight of the composition.

8 . The method according to claim 1 , wherein the low melting point polyolefin wax is present in an amount ranging from about 5% to about 15% by weight, based on the weight of the composition.

9 . A cosmetic composition comprising:

(a) a polar modified wax;

(b) a film forming agent;

(c) a low melting point polyolefin wax

(d) a liquid fatty phase; and

(e) optionally, a colorant.

10 . The composition according to claim 9, wherein the polar modified wax is present in an amount ranging from about 0.5% to about 20% by weight, based on the weight of the composition.

11 . The composition according to claim 9, wherein the polar modified wax is present in an amount ranging from about 1 % to about 15% by weight, based on the weight of the composition.

12 . The composition according to claim 9, wherein the film forming agent is an alkyl silsesquioxane resin, and the alkyl silsesquioxane resin is present in an amount ranging from about 3% to about 50% by weight, based on the weight of the composition.

13 . The composition according to claim 9, wherein the film forming agent is an alkyl silsesquioxane resin, and the alkyl silsesquioxane resin is present in an amount ranging from about 5% to about 30% by weight, based on the weight of the composition.

14 . The composition according to claim 9, wherein the low melting point wax is present in an amount ranging from about 1% to about 20% by weight, based on the weight of the composition.

15 . The composition according to claim 9, wherein the low melting point wax is present in an amount ranging from about 5% to about 15% by weight, based on the weight of the composition.

16. The composition according to claim 9, wherein the polar modified wax is selected from the group consisting of a wax consisting essentially of polypropylene and maleic anhydride units, a wax consisting essentially of C26-C28 alpha olefin and maleic acid anhydride units, and mixtures thereof.

17. The composition according to claim 9, wherein the polar modified wax is a wax consisting essentially of polypropylene and maleic anhydride units.

18. The composition according to claim 9, wherein the polar modified wax is a wax consisting essentially of C26-C28 alpha olefin and maleic acid anhydride

units.