SKIN CARE FORMULA

Description

[0001] The present invention relates to an oil / polymer blend, a skin care formulation and a cosmetic method.

[0002] Consumers increasingly desire skin care formulations that provide long wear properties, such that the formulation might be applied once and last through the work day and beyond without the need for refreshing or touching up. Given todays active lifestyles, it is no simple task to provide such long wear skin care formulations.

[0003] An approach to providing such cosmetic formulations is disclosed by Konik et al. in U.S. Patent No. 6,060,072. In U.S. Patent No. 6,060,072, Konik et al. disclose water proof or water resistant cosmetic compositions which comprise a styrene-ethylene-propylene copolymer in an amount of 5 to 10 %, a combination of a PVP / eicosene copolymer and tricontanyl PVP copolymer in an amount of 0.1 to 50 %, a C 8-9 isoparaffin, a C 9-12 aliphatic hydrocarbon, or a combination thereof, in an amount of 50 to 85%.

[0004] In U.S. Patent Application Publication No. US 2001 / 0021387, Krammer et al. disclose water-soluble, organosilylated cellulose ethers. The organosilylated cellulose ethers exhibit thickening action in aqueous solution and are suitable as thickeners in paints, adhesives, and cosmetics.

[0005] Notwithstanding, there remains a need for new skin care formulations that provide effective wear resistance with color retention.

[0006] The present invention provides an oil / polymer blend comprising: (a) 75 to 99.9 wt%, based on the weight of the oil / polymer blend, of an oil, wherein the oil is a cosmetically acceptable oil, selected from the group consisting of linear or branched C 8-30 alkanes, C 8-30 alkyl esters, C 8-30 carboxylic acid esters, C 8-30 linear or branched alcohols, silicone fluids, and mixtures thereof; (b) 0.1 to 25 wt%, based on the weight of the oil / polymer blend, of a thickening polymer, wherein the thickening polymer is a silylated cellulose polymer, comprising a cellulose polymer functionalized with -Si(R 1< ) 3 groups; wherein each R 1< is independently selected from the group consisting of a hydrogen, a C 1-8 alkyl group, a C 1-8 haloalkyl group, an aryl group, a C 1-8 alkylaryl group and a C 1-8 haloalkylaryl group; wherein the unfunctionalized cellulose polymer has a weight average molecular weight of 50,000 to 1,500,000 Daltons as measured by gel permeation chromatography (GPC).

[0007] The present invention also provides a skin care formulation, comprising: a cosmetically acceptable carrier; a color ingredient, wherein the color ingredient is selected from the group consisting of inorganic pigments, organic pigments, dyes, aqueous pigment dispersions and mixtures thereof; and an oil / polymer blend of the present invention.

[0008] The present invention also provides a cosmetic method, comprising: providing a skin care formulation of the present invention, and applying the skin care formulation to skin.DETAILED DESCRIPTION

[0009] We have now surprisingly found the unique oil / polymer blend, as described herein, when formulated into skin care formulations provide effective thickening (preferably, ≥ 500 Pa·s at 0.01 sec -1< (more preferably, ≥ 5,000 Pa·s at 0.01 sec -1< )); effective shear thinning (preferably, ≤ 10 Pa·s at 100 sec -1< (more preferably, ≤ 0.5 Pa·s at 100 sec -1< )); and good rub off resistance, which properties benefit an array of skin care compositions including foundation, lip stick, lip gloss, mascara, hair oils, sunscreen oil and antiperspirant / deodorant formulations.

[0010] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.

[0011] As used herein, unless otherwise indicated, the terms "weight average molecular weight" and "M w " are used interchangeably to refer to the weight average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and conventional standards, such as polystyrene standards. GPC techniques are discussed in detail in Modern Size Exclusion Liquid Chromatography: Practice of Gel Permeation and Gel Filtration Chromatography, Second Edition, Striegel, et al., John Wiley & Sons, 2009. Weight average molecular weights are reported herein in units of Daltons.

[0012] The term "cosmetically acceptable" as used herein and in the appended refers to ingredients typically used in personal care compositions, and is intended to underscore that materials that are toxic when present in the amounts typically found in personal care compositions are not contemplated as part of the present invention.

[0013] The term "aesthetic characteristics" as used herein and in the appended claims in reference to an acidic aqueous cleansing formulation refers to visual and tactile sensory properties (e.g., smoothness, tack, lubricity, texture, color, clarity, turbidity, uniformity). The oil / polymer blend of the present invention, comprises 75 to 99.9 wt% (preferably, 80 to 99.7 wt%; more preferably, 85 to 99.6 wt%; most preferably, 90 to 99.5 wt%), based on weight of the oil / polymer blend, of an oil, wherein the oil is a cosmetically acceptable oil selected from the group consisting of linear or branched C 8-30 alkanes (preferably, C 14-22 mineral oil, isododecane, C 11 / C 13 linear alkane blends (e.g., Cetiol Ultimate), hemisqualane; more preferably, isododecane, C 11 / C 13 linear alkane blends (e.g., Cetiol Ultimate), most preferably, isododecane); C 8-30 alkyl esters (preferably, 2-methylundecanoate, C 12 alkyl benzoate, ethyl decanoate, ethyl dodecanoate, pentaerythrityl tetraethylhexanoate, octyldodecyl neopentanoate, tricaprylin, ethylhexyl isononanoate, methylheptyl isostearate, dicaprylyl maleate, ethylhexyl hydroxystearate); C 8-30 carboxylic acid esters (preferably, oleic acid, decanoic acid, octanoic acid, linoleic acid, palmitic acid, stearic acid, lauric acid, myristic acid, ricinoleic acid); C 8-30 linear or branched alcohols (preferably, 2-butyl-1-octanol, cetyl alcohol (aka 1-hexadecanol), stearyl alcohol, dodecanol (aka lauryl alcohol), octanol (aka capryl alcohol), 1-nonanol, 1-decanol (aka capric alcohol), 1-undecanol, 1-tridecanol, myristyl alcohol (aka 1-tetradecanol), 1-pentadecanol, cis-9-hexadecen-1-ol, heptadecyl alcohol, oleyl alcohol (aka 1-octadecenol), 1-nonadecanol, 1-eicosanol, 1-heneicosanol, behenyl alcohol (aka 1-docosanol), cis-13-docosen-1-ol, 1-tetracosanol, ceryl alcohol (aka 1-hexacosanol), 1-heptacosanol, montanyl alcohol, 1-nonacosanol, myricyl alcohol); silicone fluids (preferably, caprylyl methicone, methylhexyl trisiloxane, phenyl trimethicone, cyclosiloxanes (e.g., cyclopentasiloxane, cyclohexasiloxane), polydimethylsiloxane (e.g., 5 cSt 200 fluid)); and mixtures thereof. Preferably, the oil / polymer blend of the present invention, comprises 75 to 99.9 wt% (preferably, 80 to 99.7 wt%; more preferably, 85 to 99.6 wt%; most preferably, 90 to 99.5 wt%), based on weight of the oil / polymer blend, of an oil, wherein the oil is a cosmetically acceptable oil selected from the group consisting of C 14-22 mineral oil, isododecane, C 11 / C 13 linear alkane blend, hemisqualane, 2-methylundecanoate, C 12 alkyl benzoate, ethyl decanoate, ethyl dodecanoate, pentaerythrityl tetraethylhexanoate, octyldodecyl neopentanoate, tricaprylin, ethylhexyl isononanoate, methylheptyl isostearate, dicaprylyl maleate, ethylhexyl hydroxystearate, oleic acid, decanoic acid, octanoic acid, linoleic acid, palmitic acid, stearic acid, lauric acid, myristic acid, ricinoleic acid, 2-butyl-1-octanol, cetyl alcohol, stearyl alcohol, dodecanol, octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-tridecanol, myristyl alcohol, 1-pentadecanol, cis-9-hexadecen-1-ol, heptadecyl alcohol, oleyl alcohol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, behenyl alcohol, cis-13-docosen-1-ol, 1-tetracosanol, ceryl alcohol, 1-heptacosanol, montanyl alcohol, 1-nonacosanol, myricyl alcohol, caprylyl methicone, methylhexyl trisiloxane, phenyl trimethicone, cyclopentasiloxane, cyclohexasiloxane, polydimethylsiloxane and mixtures thereof. Most preferably, the oil / polymer blend of the present invention, comprises 75 to 99.9 wt% (preferably, 80 to 99.7 wt%; more preferably, 85 to 99.6 wt%; most preferably, 90 to 99.5 wt%), based on weight of the oil / polymer blend, of an oil, wherein the oil is a cosmetically acceptable oil selected from the group consisting of isododecane, caprylyl methicone and mixtures thereof.

[0014] The oil / polymer blend of the present invention, comprises 0.1 to 25 wt% (preferably, 1 to 20 wt%; more preferably, 2 to 15 wt%; most preferably, 2.5 to 7.5 wt%), based on weight of the oil / polymer blend, of the thickening polymer; wherein the thickening polymer is a silylated cellulose polymer; wherein the silylated cellulose polymer comprises a cellulose polymer functionalized with -Si(R 1< ) 3 groups; wherein the unfunctionalized cellulose polymer has a weight average molecular weight of 50,000 to 1,500,000 Daltons (preferably, 50,000 to 1,250,000 Daltons; more preferably, 80,000 to 1,150,000 Daltons; most preferably, 100,000 to 1,100,000 Daltons) as measured by gel permeation chromatography (GPC); wherein each R 1< is independently selected from the group consisting of a hydrogen, a C 1-8 alkyl group, a C 1-8 haloalkyl group, an aryl group, a C 1-8 alkylaryl group and a C 1-8 haloalkylaryl group. Preferably, the oil / polymer blend of the present invention, comprises 0.1 to 25 wt% (preferably, 1 to 20 wt%; more preferably, 2 to 15 wt%; most preferably, 2.5 to 7.5 wt%), based on weight of the oil / polymer blend, of a thickening polymer, wherein the thickening polymer is a silylated cellulose polymer; wherein the silylated cellulose polymer comprises a cellulose polymer functionalized with -Si(R 1< ) 3 groups; wherein the unfunctionalized cellulose polymer has a weight average molecular weight of 50,000 to 1,500,000 Daltons (preferably, 50,000 to 1,250,000 Daltons; more preferably, 80,000 to 1,150,000 Daltons; most preferably, 100,000 to 1,100,000 Daltons) as measured by gel permeation chromatography (GPC); wherein each R 1< is independently selected from the group consisting of a hydrogen and a C 1-8 alkyl group. More preferably, the oil / polymer blend of the present invention, comprises 0.1 to 25 wt% (preferably, 1 to 20 wt%; more preferably, 2 to 15 wt%; most preferably, 2.5 to 7.5 wt%), based on weight of the oil / polymer blend, of a thickening polymer, wherein the thickening polymer is a silylated cellulose polymer; wherein the silylated cellulose polymer comprises a cellulose polymer functionalized with -Si(R 1< ) 3 groups; wherein the unfunctionalized cellulose polymer has a weight average molecular weight of 50,000 to 1,500,000 Daltons (preferably, 50,000 to 1,250,000 Daltons; more preferably, 80,000 to 1,150,000 Daltons; most preferably, 100,000 to 1,100,000 Daltons) as measured by gel permeation chromatography (GPC); wherein each R 1< is independently selected from the group consisting of a C 1-4 alkyl group. Still more preferably, the oil / polymer blend of the present invention, comprises 0.1 to 25 wt% (preferably, 1 to 20 wt%; more preferably, 2 to 15 wt%; most preferably, 2.5 to 7.5 wt%), based on weight of the oil / polymer blend, of a thickening polymer, wherein the thickening polymer is a silylated cellulose polymer; wherein the silylated cellulose polymer comprises a cellulose polymer functionalized with -Si(R 1< ) 3 groups; wherein the unfunctionalized cellulose polymer has a weight average molecular weight of 50,000 to 1,500,000 Daltons (preferably, 50,000 to 1,250,000 Daltons; more preferably, 80,000 to 1,150,000 Daltons; most preferably, 100,000 to 1,100,000 Daltons) as measured by gel permeation chromatography (GPC); wherein each R 1< is independently selected from the group consisting of a C 1-2 alkyl group. Most preferably, the oil / polymer blend of the present invention, comprises 0.1 to 25 wt% (preferably, 1 to 20 wt%; more preferably, 2 to 15 wt%; most preferably, 2.5 to 7.5 wt%), based on weight of the oil / polymer blend, of a thickening polymer, wherein the thickening polymer is a silylated cellulose polymer; wherein the silylated cellulose polymer comprises a cellulose polymer functionalized with -Si(R 1< ) 3 groups; wherein the unfunctionalized cellulose polymer has a weight average molecular weight of 50,000 to 1,500,000 Daltons (preferably, 50,000 to 1,250,000 Daltons; more preferably, 80,000 to 1,150,000 Daltons; most preferably, 100,000 to 1,100,000 Daltons) as measured by gel permeation chromatography (GPC); wherein each R 1< is a methyl group.

[0015] Preferably, the oil / polymer blend of the present invention, comprises 0.1 to 25 wt% (preferably, 1 to 20 wt%; more preferably, 2 to 15 wt%; most preferably, 2.5 to 7.5 wt%), based on weight of the oil / polymer blend, of a thickening polymer, wherein the thickening polymer is a silylated cellulose polymer of formula I wherein n is an average of 308 to 9,252 (preferably, 308 to 6,167; more preferably, 3083 to 4,317); wherein each R 2< is independently selected from the group consisting of a hydrogen, a C 1-8 alkyl group and a -Si(R 1< ) 3 group (preferably, a hydrogen, a C 1-4 alkyl group and a -Si(R 1< ) 3 group; more preferably, a hydrogen, a C 1-2 alkyl group and a -Si(R 1< ) 3 group; most preferably, a hydrogen and a -Si(R 1< ) 3 group); wherein each R 1< is independently selected from the group consisting of a hydrogen, a C 1-8 alkyl group, a C 1-8 haloalkyl group, an aryl group, a C 1-8 alkylaryl group and a C 1-8 haloalkylaryl group (preferably, a hydrogen and a C 1-8 alkyl group; more preferably, a C 1-4 alkyl group; still more preferably, a C 1-2 alkyl group; most preferably, a methyl group).

[0016] Preferably, the thickening polymer is a silylated cellulose polymer; wherein the silylated cellulose polymer comprises a cellulose polymer functionalized with -Si(R 1< ) 3 groups having a degree of substitution, DS, of the -Si(R 1< ) 3 groups of 1.4 to 3.0 (preferably, 1.5 to 3.0; more preferably, 2.0 to 3.0; most preferably, 2.25 to 3.0) determined by Attenuated Total Reflection - Fourier Transform Infrared (ATR-FTIR) Spectroscopy.

[0017] The skin care formulation of the present invention comprises: a cosmetically acceptable carrier (preferably, 30 to 92 wt% (more preferably, 35 to 92 wt%; most preferably, 40 to 80 wt%), based on weight of the skin care formulation, of the cosmetically acceptable carrier); a color ingredient (preferably, 0.01 to 25 wt% (more preferably, 0.1 to 20 wt%; most preferably, 1 to 10 wt%), based on weight of the skin care formulation, of the color ingredient); and an oil / polymer blend of the present invention (preferably, 5 to 69.9 wt% (more preferably, 7 to 50 wt%; most preferably, 15 to 30 wt%), based on weight of the skin care formulation, of the oil / polymer blend). Preferably, the skin care formulation of the present invention, comprises 30 to 92 wt% (preferably, 35 to 92 wt%; more preferably, 40 to 80 wt%), based on weight of the skin care formulation, of a cosmetically acceptable carrier. More preferably, the skin care formulation of the present invention, comprises 30 to 92 wt% (preferably, 35 to 92 wt%; more preferably, 40 to 80 wt%), based on weight of the skin care formulation, of a cosmetically acceptable carrier; wherein the color ingredient and the oil / polymer blend are dispersed in the cosmetically acceptable carrier. Still more preferably, the skin care formulation of the present invention, comprises 30 to 92 wt% (preferably, 35 to 92 wt%; more preferably, 40 to 80 wt%), based on weight of the skin care formulation, of a cosmetically acceptable carrier; wherein the color ingredient and the oil / polymer blend are dispersed in the cosmetically acceptable carrier. Most preferably, the skin care formulation of the present invention, comprises 30 to 92 wt% (preferably, 35 to 92 wt%; more preferably, 40 to 80 wt%), based on weight of the skin care formulation, of a cosmetically acceptable carrier; wherein the color ingredient and the oil / polymer blend are dispersed in the cosmetically acceptable carrier.

[0018] Preferably, the skin care formulation of the present invention, comprises 30 to 92 wt% (preferably, 35 to 92 wt%; more preferably, 40 to 80 wt%), based on weight of the skin care formulation, of a cosmetically acceptable carrier; wherein the cosmetically acceptable carrier is selected to be capable of evaporating upon application of the skin care formulation to mammalian skin (preferably, human skin).

[0019] Preferably, the skin care formulation of the present invention, comprises 30 to 92 wt% (preferably, 35 to 92 wt%; more preferably, 40 to 80 wt%), based on weight of the skin care formulation, of a cosmetically acceptable carrier; wherein the cosmetically acceptable is selected from the group consisting of water (e.g., deionized, distilled water); short chain alcohols (e.g., C 1-4 straight or branched chain alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol); glycols (e.g., ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, ethoxydiglycol); cyclosiloxanes (e.g., cyclopentasiloxane, cyclohexasiloxane); glycerin; isododecane; isohexadecane; acetone; methyl acetate; butyl cellosolve and mixtures thereof. More preferably, the skin care formulation of the present invention, comprises 30 to 92 wt% (preferably, 35 to 92 wt%; more preferably, 40 to 80 wt%), based on weight of the skin care formulation, of a cosmetically acceptable carrier; wherein the cosmetically acceptable carrier includes at least one of water and isododecane (preferably, at least one of deionized water, distilled water and isododecane; more preferably, at lease one of deionized water and isododecane).

[0020] The skin care formulation of the present invention comprises a color ingredient; wherein the color ingredient is selected from the group consisting of inorganic pigments, organic pigments, dyes, aqueous pigment dispersions and mixtures thereof. Preferably, the skin care formulation of the present invention comprises a color ingredient; wherein the color ingredient is selected from the group consisting of Ext. D&C Yellow No. 2, Ext. D & C Violet No. 2, FD&C Red No. 4, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, FD&C Green No. 3, FD&C Blue No. 1, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, D&C Violet No. 2, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 34, D&C Red No. 33, D&C Red No. 36, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Blue No. 4, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Brown No. 1, Aluminum powder, Annatto, Bismuth citrate, Bismuth Oxychloride, Bronze powder, Caramel, Carmine, β-Carotene, Chromium hydroxide green, Chromium oxide green, Copper chlorophyllin, Copper powder, Dihydroxyacetone, Ferric Ammonium ferrocyanide, Ferric ferrocyanide, Guanine, Iron oxide, Manganese Violet, Mica, Silver, Titanium Dioxide, Ultramarine, Zinc Oxide and mixtures thereof. More preferably, the skin care formulation of the present invention comprises a color ingredient; wherein the color ingredient includes at least one iron oxide and titanium dioxide. Most preferably, preferably, the skin care formulation of the present invention comprises a color ingredient; wherein the color ingredient includes a mixture of iron oxides and titanium dioxide.

[0021] Preferably, the skin care formulation of the present invention, optionally, further comprises an optional additive. More preferably, the skin care formulation of the present invention, further comprises an optional additive, wherein the optional additive is selected from the group consisting of suncare actives, film formers, emollients, preservatives, antioxidants, fragrances, humectants, rheology modifiers, aesthetic modifiers, vitamins, skin protectants, oils, emulsifiers, surfactants, pearlizers, consistency factors, thickeners, super fatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, fillers, light management powders and particles, and mixtures thereof.

[0022] Preferably, the skin care formulation of the present invention, further comprises a suncare active. More preferably, the skin care formulation of the present invention further comprises a suncare active; wherein the suncare active is a UV radiation absorbing agent. Still more preferably, the skin care formulation of the present invention, further comprises a suncare active, wherein the suncare active is a UV radiation absorbing agent selected from the group consisting of physical blockers (e.g., red petrolatum, titanium dioxide, zinc oxide) and chemical absorbers (e.g., 1-(4-methoxyphenol)-3-(4-tert-butylphenyl)propane-1,3-dione (INCI: Butyl Methoxydibenzoylmethane); 2-hydroxy-4-methoxybenzophenone (INCI: Benzophenone-3); dioxybenzone; sulisobenzone; menthyl anthranilate; para-aminobenzoic acid; amyl paradimethylaminobenzoic acid; octyl para-dimethylaminobenzoate; ethyl 4-bis (hydroxypropyl) para-aminobenzoate; polyethylene glycol (PEG-25) para-aminobenzoate; ethyl 4-bis (hydroxypropyl) aminobenzoate; diethanolamine para-methyoxycinnamate; 2-ethoxyethyl para-methoxycinnamate; ethylhexyl para-methoxycinnamate; octyl para-methoxycinnamate; isoamyl para-methoxycinnamate; 2-ethylhexyl-2-cyano-3,3-diphenyl-acrylate; 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI: octocrylene); 2-ethylhexyl-2-hydroxybenzoate (INCI: Ethylhexyl Salicylate); homomenthyl salicylate; glyceryl aminobenzoate; triethanolamine salicylate; digalloyl trioleate; lawsone with dihydroxyacetone; 2-phenylbenzimidazole-5-sulfonic acid; 4-methylbenzylidine camphor; avobenzone; triazines; benzotriazoles; vinyl group-containing amides; cinnamic acid amides; sulfonated benzimidazoles); 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI: Homosalate). Yet more preferably, the skin care formulation of the present invention, further comprises of a suncare active, wherein the suncare active is a UV radiation absorbing agent comprises a mixture of UV radiation absorbing agents. Most preferably, the skin care formulation of the present invention, comprises a suncare active, wherein the suncare active is a UV radiation absorbing agent is a mixture of UV absorbing agents including at least one of titanium dioxide; 1-(4-methoxyphenol)-3-(4-tert-butylphenyl)propane-1,3-dione; 2-ethylhexyl-2-hydroxybenzoate; 2-ethyhexyl-2-cyano-3,3-diphenyl-2-propenoate; 2-hydroxy-4-methoxybenzophenone and 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate.

[0023] Preferably, the skin care formulation of the present invention has a pH of 4 to 9. More preferably, the skin care formulation of the present invention has a pH of 4.5 to 8.5. Still more preferably, the skin care formulation of the present invention has a pH of 5.0 to 8.0. Most preferably, the skin care formulation of the present invention has a pH of 5.5 to 7.5.

[0024] Preferably, the skin care formulation of the present invention is provided a product form selected from the group consisting of a cream, an aqueous solution, an emulsion (e.g., water-in-oil emulsion, oil-in-water emulsion), an oil, an ointment, a paste, a gel, a lotion, a milk, a foam, a stick and a suspension.

[0025] The skin care formulation of the present invention are useful for enhancing the appearance of skin through application to the skin. Preferably, the skin care formulation of the present invention applies easily to the skin, leaving a clear vivid color that remains in place at least through the work day and preferably thereafter.

[0026] Some embodiments of the present invention will now be described in detail in the following Examples. Examples S1-S25: Synthesis of Thickening Polymer

[0027] To a two liter three-neck flask equipped with a nitrogen inlet and a temperature controller was weighed the type and amount of cellulose noted in TABLE 1. Then N,N-dimethylacetamide (DMAc) solvent was added to the flask in the amount noted in TABLE 1. The flask contents were then placed under an atmosphere of nitrogen. Then hexamethyldisilazane (HMDS) was added to the flask contents all at once in the amount noted in TABLE 1. The flask contents were then slowly heated while stirring to the set temperature, T 1 , noted in TABLE 1 and stirred for time, t 1< , in hours noted in TABLE 1. The heat source was then removed and the flask contents were left to cool. Then xylene (Xyl) was added to the flask contents in the amount noted in TABLE 1 and the flask contents were then heated to set temperature, T 2 , noted in TABLE 1 and stirred for time, t 2< , in hours noted in TABLE 1. The product solution was then transferred to a separatory funnel and subjected to non-solvent precipitation by dropwise addition into two liters of vigorously stirring methanol. The product was precipitated in the form of a thread or flakes. The product was isolated by filtration, and the product was dried in a vacuum oven at 50 °C overnight. The product was then suspended in 500 mL of methanol and left overnight, then refiltered and dried in vacuum oven at 50 °C overnight. TABLE 1 Example Cellu lose DMAc (g) HMDS(g) T 1 (°C) t 1< (hr) Xyl (g) T 2 (°C) t 2< (hr) Type (g) S1A15.230040.01403.04001404.0S2B15.233050.01402.03201404.0S3B15.240050.01402.06001404.0S4A15.030050.01305.03001406.0S5C15.133049.91307.54001255.0S6D15.033149.81307.54001255.0S7E15.033050.01305.04001406.0S8C15.2333149.91353.54001355.0S9D15.1332150.11353.54001355.0S10F15.532949.71355.04001203.0S11G15.432950.01355.04001203.0S12C2.0395.961304.00----S13H15.233750.11356.04001353.5S14G15.231549.71354.04001303.0S15G15.230850.21354.04001303.0S16G15.231598.7804.03001305.5S17G15.330899.0804.03201305.5S18F15.131250.01305.04001058.0S19G15.232450.21305.04001058.0S20E15.231849.91304.03301305.0S21C15.032849.61304.03301305.0S22G15.232919.91304.03301202.0S23G15.232630.01304.03301202.0S24A15.232749.91304.03301304.0S25A15.237849.91304.03301304.0 A< Avicel PH-101 (51 µm) microcrystalline cellulose having weight average molecular weight of 60,000 Daltons available from Sigma-Aldrich B< Crystal PL HD eucalyptus pulp having weight average molecular weight of 400,000 Daltons available from Bahi Specialty Cellulose C< Biofloc 92 MV wood pulp having weight average molecular weight of 600,000 Daltons available from Tartas (Rayonier) D< Biofloc XV wood pulp having weight average molecular weight of 900,000 Daltons available from Tartas (Rayonier) E< PCS-2400 cotton linters having weight average molecular weight of 1,000,000 Daltons available from Gaomi F< E4 wood pulp having weight average molecular weight of 100,000 Daltons available from GP Cellulose G< E60-HB wood pulp having weight average molecular weight of 125,000 Daltons available from GP Cellulose H< Biofloc 94 MV wood pulp having weight average molecular weight of 600,000 Daltons available from Tartas (Rayonier) DS Determination

[0028] The degree of substitution, DS, of -Si(CH 3 ) 3 in the thickening polymers prepared according to Examples S1-S25 was determined using well known techniques based on Attenuated Total Reflection - Fourier Transform Infrared Spectroscopy analyzing spectra peak areas calculated with MATLAB using the spectral parameters provided in TABLE 2 with the DS values determined as reported in TABLE 3. TABLE 2 Species Integration (cm -1< ) Baseline (cm -1< ) Start End Start End -Si(CH 3 ) 3 1277122012781219-OH3685303336973040 TABLE 3 Example IR Peak Area DS Si (wt%) OH (wt%) Si(CH 3 ) 3 CO OH S2 1.289.920.2642.5820.82.04S3 1.4712.00.6862.2019.24.26S4 1.4413.31.591.6116.28.49S5 0.9637.350.4262.2319.44.07S6 1.6212.80.7142.2319.44.06S7 0.5974.950.3512.0518.65.19S8 0.9387.240.2822.4320.22.89S9 0.7606.510.3822.1519.04.54S10 1.088.490.2482.5420.62.26S11 1.037.670.01942.9622.10.20S12 1.137.84-0.03373.0022.20S13 0.8118.811.511.2213.712.1S14 1.6312.60.2372.6921.21.47S15 2.1215.3-0.1513.0022.20S16 1.349.58-0.006813.0022.20S17 0.6234.470.05352.8121.60.88S18 0.9336.840.1022.7621.41.11S19 1.087.820.2152.6020.81.97S20 1.339.27-0.06483.0022.20S21 0.4913.48-0.002823.0022.20S22 0.2052.090.1651.8417.56.70S23 1.118.440.2482.5520.72.20S24 0.72810.52.920.729.4718.1S25 2.0215.1-0.2183.0022.20 Comparative Example C1 and Examples 1-4: Skin Care Formulations

[0029] The skin care formulations of Comparative Example C1 and Examples 1-4 were prepared having the formulation noted in TABLE 4. The Phase B ingredients were mixed in a separate container. The Phase C ingredients were combined in a separate container with mixing until uniform. The Phase A and D ingredients were combined in a separate beaker and mixed until uniform. The mixed Phase C ingredients were then added to the combined Phase A and D ingredients with shear at 450 rpm until homogeneous. Then the mixed Phase B ingredients were then slowly added to the combined Phase A, C and D ingredients with shear at 700 rpm. The combined formulation was then mixed for an additional 5 minutes with shear at 2,000 rpm to provide the product skin care formulation. TABLE 4 Phase Ingredient INCI name Example C1 1 2 3 4 (wt%) (wt%) (wt%) (wt%) (wt%) ALauryl PEG-10 Tris(trimethylsiloxy)silyethyl Dimeticone 1< 66666ACaprylyl methicone 2< 44444AIsododecane 3< 15.7518181818BDeionized water5353535353BSodium chloride11111BPhenoxyethanol (and) Ethylhexylglycerin 4< 11111BGlycerin55555DIron Oxide (CI 77499), dimethicone 5< 0.070.070.070.070.07CIron Oxide (CI 77491), dimethicone 6< 0.250.250.250.250.25CIron Oxide (CI 77492), dimethicone 7< 1.091.091.091.091.09CTitanium Dioxide (and) dimethicone 8< 5.815.815.815.815.81CCaprylyl Methicone 2< 3.283.283.283.283.28DIsododecane (and) Acrylates / Polytimethylsiloxymethacrylate Copolymer 9< 3.75--------DExample S16 --1.5------DExample S17 ----1.5----DExample S20 ------1.5--DExample S21 --------1.5 1< Available from The Dow Chemical Company under tradename DOWSIL ™< ES-5300. 2< Available from The Dow Chemical Company under tradename DOWSIL ™< FZ-3196. 3< Available from The Innovation Company under tradename Creasil ID CG. 4< Available from Schulke Inc. under tradename Euxyl PE 9010. 5< Available from Miyoshi America under tradename SAT-B-335198. 6< Available from Miyoshi America under tradename SAT-Y-338075. 7< Available from Miyoshi America under tradename SAT-R-338073. 8< Available from Miyoshi America under tradename SAT-TRI-77891. 9< Available from The Dow Chemical Company under tradename DOWSIL ™< FA4002 ID. Thickening and shear thinning

[0030] The viscosity of the skin care formulations of Comparative Example C1 and Examples 1-4 was determined using a TA Instruments DHR-3 rheometer at 25 °C, equipped with a stainless steel 60 mm, 0.5° cone and plate sensor, a gap set at 17 microns and a shear rate of 6.31 s -1< . Shear sweep method was used with shear rate ranges from 0.01 s -1< to 100 s -1< . Viscosities measured at low shear (0.1 s -1< ) and high shear (100 s -1< ) are reported in TABLE 5.

[0031] The shear thinning efficiency of the thickeners was assessed by fitting the viscosity data to the power-law fluid equation η = K ⋅ γ n − 1 wherein η is the viscosity, γ is the shear rate, K is the flow consistency index and n is the flow behavior index. For a shear thinning fluid, n < 1. Smaller n values indicate a higher degree of shear thinning. The calculated shear thinning efficiencies for the thickeners is reported in TABLE 5.

[0032] As shown in TABLE 5, data for all of the thickeners fitted well to the power-law fluid equation, with the coefficient of determination, r 2< , value being close to 1. The flow behavior index (n) for the inventive thickeners was much lower than the commercial material (DOWSIL ™< FA4002 ID Silicone Acrylate), indicating a much higher degree of sheer thinning which is highly favorable in personal care formulations for better sprayability and spreadability of the formulation. The inventive polymer also lead to a much higher increase in formulation viscosity than the commercial material (DOWSIL ™< FA4002 ID Silicone Acrylate), indicating a much higher thickening efficiency for the inventive polymer. TABLE 5 Skin Care Formulation Thickener Viscosity (Pa·s) Fitted power law equation Flow behavior index, n 0.01 sec -1< 100 sec -1< C1 Commercial material 1< 3.990.4η=1.125·γ -0.256< 0.744r 2< = 0.9671 Example S16 7952.5η=36.351·γ -0 064< 0.360r 2< = 0.99472 Example S17 1,3332.8η=45.241·γ -0.683< 0.317r 2< = 0.99013 Example S20 3,2763.9η=79.197·γ -0 736< 0.264r 2< = 0.99214 Example S21 2,5202.6η=57.845·γ -0.767< 0.233r 2< = 0.993 1< DOWSIL ™< FA4002 ID Silicon Isododecane (and) Acrylates / Polytrimethylsiloxymethacrylate Copolymer available from The Dow Chemical Company Comparative Example C2-C3 and Examples 5-9: Skin Care Formulations

[0033] The skin care formulations of Comparative Examples C2-C3 and Examples 5-9 were prepared having the formulation noted in TABLE 6. The Phase B ingredients were mixed in a separate container. The Phase C ingredients were combined in a separate container with mixing until uniform. The Phase A and D ingredients were combined in a separate beaker and mixed until uniform. The mixed Phase C ingredients were then added to the combined Phase A and D ingredients with shear at 450 rpm until homogeneous. Then the mixed Phase B ingredients were then slowly added to the combined Phase A, C and D ingredients with shear at 700 rpm. The combined formulation was then mixed for an additional 5 minutes with shear at 2,000 rpm to provide the product skin care formulation. TABLE 6 Phase Ingredient INCI name Example (wt %) C2 C3 5 6 7 8 9 ALauryl PEG-10 Tris(trimethylsiloxy)silyethyl Dimeticone 1< 6666666ACaprylyl methicone 2< 3.6333333AIsododecane 3< 1211.11212121212BDeionized water60.960.960.960.960.960.960.9BSodium chloride1111111BPhenoxyethanol (and) Ethylhexylglycerin 4< 1111111BGlycerin5555555DIron Oxide (CI 77499), dimethicone 5< 0.070.070.070.070.070.070.07CIron Oxide (CI 77491), dimethicone 6< 0.250.250.250.250.250.250.25CIron Oxide (CI 77492), dimethicone 7< 1.091.091.091.091.091.091.09CTitanium Dioxide (and) dimethicone 8< 5.815.815.815.815.815.815.81CCaprylyl Methicone 2< 3.283.283.283.283.283.283.28DIsododecane (and) Acrylates / Polytimethylsiloxymethacryla te Copolymer 9< --1.5----------DExample S8 ----0.6--------DExample S14 ------0.6------DExample S15 --------0.6---DExample S16 ----------0.6--DExample S17 ------------0.6 1< Available from The Dow Chemical Company under tradename DOWSIL ™< ES-5300. 2< Available from The Dow Chemical Company under tradename DOWSIL ™< FZ-3196. 3< Available from The Innovation Company under tradename Creasil ID CG. 4< Available from Schulke Inc. under tradename Euxyl PE 9010. 5< Available from Miyoshi America under tradename SAT-B-335198. 6< Available from Miyoshi America under tradename SAT-Y-338075. 7< Available from Miyoshi America under tradename SAT-R-338073. 8< Available from Miyoshi America under tradename SAT-TRI-77891. 9< Available from The Dow Chemical Company under tradename DOWSIL ™< FA4002 ID. Wear Resistance

[0034] The skin care formulations prepared according to Comparative Examples C2-C3 and Examples 5-9 were each coated on a white vinyl chart (available from Leneta) using a doctor blade film applicator with the gap set at 6 mils (0.1524 mm) and allowed to dry at 22 °C for at least 48 hours. The color reading of each sample was then measured by colorimeter (Ocean Optics). The wear resistance of the deposited film of skin care formulations was characterized by the change (ΔE) before and after abrasion with a pre-cut bath towel (55 mm x 45 mm). The bath towel was fixed to a moving robotic part that moves back and forth periodically at a constant speed. The film was abraded by the bath towel by 3 and 6 wear cycles under a pressure of approximately 600 Pa, each wear cycle lasts 6 seconds. Readings were taken from ten point on each deposited film. The average of the readings from each sample is provided in TABLE 7. Lower ΔE indicates less color change after rub-off and higher wear resistance. The ΔE of the inventive polymers were lower than the commercial material, which is highly favorable for skin care formulations to enable long lasting performance. TABLE 7 Skin care formulation Wear Cycles 3 6 ΔE ΔE Comp. Example C2 10.5112.03Comp. Example C3 7.8611.44Example 5 5.707.85Example 6 4.967.40Example 7 8.0710.93Example 8 5.608.62Example 9 7.158.47 Comparative Examples C4-C13 and Examples 10-28: Viscosity

[0035] The viscosity of oils alone, Comparative Examples C4-C13, and thickening oil / polymer blends, Examples 10-28, as noted in TABLE 8 was determined using a TA Instruments DHR-3 rheometer at 25 °C, equipped with a stainless steel 60 mm, 0.5° cone and plate sensor, a gap set at 17 microns and a shear rate of 0.01 s -1< . The viscosities measured are reported in TABLE 8. TABLE 8 Example Oil Thickening Polymer ("TP") Conc. TP in Oil (wt%) Viscosity (mPa·s) C4 XIAMETER ™< PMX-200 Silicone Fluid, 0.65 cSt a< ----4.81 x 10 -1< C5 Cetiol Ultimate b< ----1.20 x 10 0< C6 Isododecane----1.22 x 10 0< C7 2-methylundecenoate----1.89 x 10 0< C8 Octamethylcyclotetrasiloxane----2.24 x 10 0< C9 Hemisqualane c< ----2.42 x 10 0< C10 XIAMETER ™< PMX-200 Silicone Fluid, 5 cSt d< ----4.60 x 10 0< C11 2-butyl-1-octanol e< ----1.91 x 10 2< C12 DOWSIL ™< 4-2737 Fluid f< ----4.47 x 10 1< C13 Sunflower Oil (not claimed)----1.55 x 10 2< 10 XIAMETER ™< PMX-200 Silicone Fluid, 0.65 cSt a< Example S2 2.52.38 x 10 2< 11 Cetiol Ultimate b< Example S2 2.59.49 x 10 2< 12 IsododecaneExample S2 2.53.91 x 10 2< 13 2-methylundecenoateExample S2 2.51.81 x 10 3< 14 OctamethylcyclotetrasiloxaneExample S2 2.53.14 x 10 3< 15 Hemisqualane c< Example S2 2.51.63 x 10 3< 16 XIAMETER ™< MPX-200 Silicone Fluid, 5 cSt d< Example S2 2.54.97 x 10 2< 17 2-butyl-1-octanol e< Example S2 2.5Gel18 DOWSIL ™< 4-2737 Fluid f< Example S2 2.5B19 Sunflower Oil (not claimed)Example S2 2.5B20 Cetiol Ultimate b< Example S2 5.04.73 x 10 4< 21 IsododecaneExample S2 5.04.10 x 10 4< 22 2-methylundecenoateExample S2 5.05.33 x 10 4< 23 Hemisqualane c< Example S2 5.02.25 x 10 4< 24 Cetiol Ultimate b< Example S1 8.04.35 x 10 4< 25 Hemisqualane c< Example S1 8.01.19 x 10 5< 26 IsododecaneExample S1 8.03.30 x 10 4< 27 2-butyl-1-octanol e< Example S1 8.01.52 x 10 5< 28 2-methylundecenoateExample S1 8.08.34 x 10 3< a< available from The Dow Chemical Company b< INCI: Undecane (and) tridecane avaIlable from BASF c< Fully saturated C 15 hydrocarbons (99%) available from Sigma-Aldrich d< available from The Dow Chemical Company e< Isofol 12 available from Sasol f< Linear siloxane fluid available from The Dow Chemical CompanyB - inhomogeneous with suspended chunks

Claims

1. An oil / polymer blend comprising: (a) 75 to 99.9 wt%, based on the weight of the oil / polymer blend, of an oil, wherein the oil is a cosmetically acceptable oil, selected from the group consisting of linear or branched C8-30 alkanes, C8-30 alkyl esters, C8-30 carboxylic acid esters, C8-30 linear or branched alcohols, silicone fluids, and mixtures thereof; (b) 0.1 to 25 wt%, based on the weight of the oil / polymer blend, of a thickening polymer, wherein the thickening polymer is a silylated cellulose polymer, comprising a cellulose polymer functionalized with -Si(R1)3 groups; wherein each R1 is independently selected from the group consisting of a hydrogen, a C1-8 alkyl group, a C1-8 haloalkyl group, an aryl group, a C1-8 alkylaryl group and a C1-8 haloalkylaryl group; wherein the unfunctionalized cellulose polymer has a weight average molecular weight of 50,000 to 1,500,000 Daltons as measured by gel permeation chromatography (GPC).

2. The oil / polymer blend of claim 1, wherein the silylated cellulose polymer is of formula I wherein n is an average of 308 to 9,252; wherein each R2 is independently selected from the group consisting of a hydrogen, a C1-8 alkyl group and a -Si(R1)3 group; wherein each R1 is independently selected from the group consisting of a hydrogen, a C1-8 alkyl group, a C1-8 haloalkyl group, an aryl group, a C1-8 alkylaryl group and a C1-8 haloalkylaryl group.

3. A skin care formulation, comprising: a cosmetically acceptable carrier; a color ingredient, wherein the color ingredient is selected from the group consisting of inorganic pigments, organic pigments, dyes, aqueous pigment dispersions and mixtures thereof; and an oil / polymer blend of claim 1.

4. The skin care formulation of claim 3, wherein the color ingredient is selected from the group consisting of Ext. D&C Yellow No. 2, Ext. D & C Violet No. 2, FD&C Red No. 4, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, FD&C Green No. 3, FD&C Blue No. 1, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, D&C Violet No. 2, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 34, D&C Red No. 33, D&C Red No. 36, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Blue No. 4, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Brown No. 1, Aluminum powder, Annatto, Bismuth citrate, Bismuth Oxychloride, Bronze powder, Caramel, Carmine, β-Carotene, Chromium hydroxide green, Chromium oxide green, Copper chlorophyllin, Copper powder, Dihydroxyacetone, Ferric Ammonium ferrocyanide, Ferric ferrocyanide, Guanine, Iron oxide, Manganese Violet, Mica, Silver, Titanium Dioxide, Ultramarine, Zinc Oxide and mixtures thereof.

5. The skin care formulation of claim 3, wherein the color ingredient includes an iron oxide and titanium dioxide.

6. A cosmetic method, comprising: providing a skin care formulation of claim 3, and applying the skin care formulation to skin.