1. Field of the Invention
This invention relates to color cosmetic compositions, and, more particularly, to compatible gel and emulsion color compositions which include a crosslinked, linear poly(vinyl amide-polymerizable carboxylic acid) copolymer as rheology modifier (thickener) and film-former in such compositions.
2. Description of the Prior Art
J. Shih, in U.S. Pat. No. 5,015,708, described a process for making terpolymers of vinyl pyrrolidone, acrylic acid and lauryl methacrylate monomers by precipitation polymerization in an aliphatic hydrocarbon solvent.
Frenz, V. in WO 02/32975, Apr. 25, 2002, described absorbent materials made by grafting acrylic acid monomer onto polyvinyl pyrrolidone polymer in water in the presence of a crosslinking agent. The resultant crosslinked graft copolymer matrix contained 79.9-99.9% of acrylic acid.
However, most rheology modifiers, e.g. crosslinked acrylic acid, are incompatible with iron oxides present in color cosmetic compositions and do not provide film-forming properties for the compositions. Rheology modifiers known to be useful in conjunction with iron oxides, e.g., xanthan gum and cellulosics such as HPMC and HPC, tend to provide an unpleasant, unacceptable slimy feel.
We have discovered improved color cosmetic compositions which include a color ingredient e.g. an iron oxide, a copolymer which is a compatible rheology modifier and film-former, and which provide an aesthetically pleasing application and end feel.
In another embodiment of this invention, there is provided a gel and emulsion color cosmetic formulations in which a crosslinked, linear poly(vinyl amide-polymerizable carboxylic acid) copolymer is present as thickener and film-former and is compatible with iron oxides in such formulations.
A specific object of this invention is to use a crosslinked, linear copolymer of poly(vinyl pyrrolidone-acrylic acid) as rheology modifier and film-former in color cosmetic compositions containing iron oxides in compatible formulations such as gel and oil-in-water emulsions, e.g. gel eyelid enhancers, oil-in-water emulsion eyeliner, and oil-in-water emulsion foundation products.
What is described herein is the use of a rheology modifier/personal care resin which is a crosslinked, linear poly(vinyl amide/polymerizable carboxylic acid) copolymer in color cosmetic compositions. The color cosmetic composition includes a color ingredient, e.g. iron oxide, and a compatible crosslinked, linear copolymer of poly(vinylamide-polymerizable carboxylic acid) as rheology modifier and film-former, e.g. in compositions which are gels or emulsions, e.g. oil-in-water or water-in-oil emulsions.
Representative color cosmetic composition include an eyelid enhancer, an eyeliner and foundation compositions.
Suitably the color cosmetic composition of the invention includes about 0.1-20 wt. % of the defined copolymer, preferably 0.2 to 10 wt. %.
Preferably, the copolymer is a crosslinked, linear poly(vinyl pyrrolidone-acrylic acid) copolymer, most preferably comprising about 10-90 wt. % of vinyl pyrrolidone and about 10-90 wt. % of acrylic acid.
Suitable vinyl amides include vinyl pyrrolidone, vinyl caprolactam, N-vinyl formamide, N-vinylacetamide, N-vinyl-N-methylacetamide and mixtures thereof, preferably vinyl pyrrolidone.
Suitable polymerizable carboxylic acids include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid and mixtures thereof, preferably acrylic acid.
Suitable crosslinkers have at least two free radical polymerizable groups in the molecule, e.g. pentaerythritol triallylether, pentaerythritol triacrylate, pentaerythritol tetraacrylate or methylene bisacrylamide.
The composition of the rheology modifier/personal care resin of the present invention includes a vinyl amide, in an amount of by weight, 1-99% of the composition, a polymerizable carboxylic acid in an amount of 1-99% of the composition, and a crosslinker in an amount of 0.2-3%, based on total weight of monomers.
Preferably, the vinyl amide monomer is present in an amount of 25-80%, the polymerizable carboxylic acid in an amount of 20-80%, and the crosslinker 0.4-2%, based on total weight of monomers.
Optionally, the rheology modifier/personal care resin may include one or more additional monomers, e.g. lauryl(meth)acrylate, stearyl(meth)acrylate, alkyl(meth)acrylamide or alkyl(meth)acrylate. The alkyl group can be C1 to C30 or polyethylene oxide.
The rheology modifier/personal care resin is made by precipitation polymerizing, by wt., 5-50%, preferably 10-25%, of a mixture of a vinyl amide, a polymerizable carboxylic acid and a crosslinker, in the presence of 50-95%, preferably 75-90%, of a non-polar, removable organic solvent, and 0.1-5%, preferably 0.5-2%, of a free radical initiator, based on total weight of monomers.
The rheology modifier copolymer resin of the invention, suitably is present in the color cosmetic composition in an amount of 0.1-20% by wt., preferably 0.2-10%, and most preferably 0.3-5%, of the composition.
The color ingredient can be dispersed by conventional mixing techniques preferably in the water phase after the rheology modifier has been dispersed in the water phase. Suitable color ingredients include pigments, such as iron oxides, titanium dioxides, organic pigments, the Lakes, ultramarines, and the like. Suitable iron oxides include red iron oxides, yellow iron oxides, black iron oxides and known iron oxides.
Preferred cosmetic colorants (approved for use in the United States) include Ext. D & C Yellow No. 2, D & C Red No. 36, FD & C Red No. 4, D & C Orange No.4, D & C Red No.31, D & C Red No.6, D & C Red No.7, D & C Red No.34, FD & C Yellow No.6, FD & C Red No.40, D & C Red No.33, FD & C Yellow No.5, D & C Brown No. 1, D & C Red No. 17, FD & C Green No. 3, D & C Blue No.4, FD & C Blue No.1, D & C Yellow No.8, D & C Yellow No.7, D & C Orange No.5, D & C Red No.22, D & C Red No.21, D & C Red No. 28, D & C Red No. 27, D & C Orange No. 11, D & C Orange No. 10, D & C Yellow No.11, D & C Yellow No. 10, D & C Green No. 8, D & C Violet No. 2, Ext. D & C Violet No.2, D & C Green No.6, D & C Green No.5, D & C Red No. 30, Annatto, Beta-Carotene, Guanine, Carmine, Henna, Chlorphyllin-Copper, Complex Aluminum Powder, Ultramarines, Mica, Bismuth Oxychloride, Chromium Oxide Greens, Chromium Hydroxide, Green, Bronze Powder, Copper Powder, Iron Oxides, Ferric Ferrocyanide, Ferric Ammonium, Ferrocyanide, Manganese Violet, Silver, Titanium Dioxide, Zinc Oxide, Bismuth Citrate, Caramel, Dihydroxyacetone, Disodium EDTA-Copper, Gualazulene, LeadAcetate, and Pyrophyllite.
Typically color cosmetic compositions of the invention which include the invention resin have an advantageously high viscosity of about 30,000 to 100,000 cps, preferably 40,000 to 80,000 cps, at a pH of about 5 to 9.
The crosslinked linear copolymer used herein is sold by International Specialty Products as Ultrathix™ P-100.
The scope of the invention is illustrated by the following Table.
The process of making the rheology modifier/color cosmetic resin of the present invention is suitably carried out in a non-polar solvent, e.g. heptane, benzene, isopropyl acetate or cyclohexane, which can be removed easily after the polymerization, in the presence of a free radical initiator, at a polymerization temperature of 40°-150° C., preferably 55°-100° C., at monomer feeding times in 2 feeding lines of 0-10 hrs, preferably 3-5 hrs. The reactants are monomers and crosslinker. The product is a crosslinked, linear copolymer of a vinyl amide, e.g. vinyl pyrrolidone, and a polymerizable carboxylic acid, e.g. acrylic acid, which is crosslinked with a suitable crosslinking agent e.g. pentaerythritol triallyl ether in the form of a powder.
Aqueous solutions of the resin of the invention also have the advantageous property of a high yield stress, generally 10 to 100,000, and preferably 100 to 10,000, in dynes/cm2.
The process of making the crosslinked linear copolymer of the invention is shown in Examples 1-15 which follow.
Into a 1-liter, four-necked glass kettle, equipped with two feeding pumps, an anchor agitator, a thermocouple and a condenser, 500 g of heptane as solvent was charged and agitated at 200 rpm while being purged with nitrogen throughout the process. The solvent then was heated to 65° C. with an oil bath and held there for 30 minutes. Feeding Solution I was prepared by mixing 50 g of N-vinylpyrrolidone (VP) and 1.0 g of pentaerythritol triallylether (PETE). Feeding Solution II was prepared by weighing 50 g of acrylic acid (AA) into a bottle. 200 microliter of Luperox® 11M75 as initiator was charged into the kettle. Then Feeding Solutions I and II were simultaneously pumped into the kettle over a period of 4 hours at a constant feeding rate. The resulting solution then was held at 65° C. for 1 hour and the reaction temperature was raised to 90° C. Then an additional 100 microliter of Luperox® 11M75 was added every two hours for 4 times and the reactor was held at 90° C. for two additional hours after the last dose of Luperox® 11M75 was charged. The contents then were cooled and discharged. The solvent was removed at an oven temperature of 100° C. The resultant resin powder was further dried in a vacuum oven at 100° C. The product was a crosslinked, linear copolymer of VP and AA crosslinked with PETE in a wt. ratio of 50/50/1.
Into a 1-liter, four-necked glass kettle, equipped with an anchor agitator, a thermocouple and a condenser, 500 g of heptane as solvent was charged and agitated at 200 rpm while being purged with nitrogen throughout the process. The solvent then was heated to 65° C. with an oil bath and held there for 30 minutes. Feeding Solution I was prepared by mixing 50 g of N-vinylcaprolactam (VCL) and 1.5 g of pentaerythritol triallylether (PETE). Feeding solution II was prepared by weighing 50 g of acrylic acid (AA) into a bottle. Then 200 microliter of t-butyl peroxypivalate initiator was charged into the kettle. The Feeding Solution I and Feeding Solution II were simultaneously charged into the kettle over 4 hours at a constant feeding rate. The solution was held at 65° C. for 1 hour and the temperature was raised to 90° C. Then an additional 200 microliter of t-butyl peroxypivalate was added every two hours for 4 times and the reactor was held at 90° C. for two additional hours after the last dose of t-butyl peroxypivalate was charged. The contents then were cooled and discharged. The solvent was removed at an oven temperature of 100° C. The resultant resin powder was further dried in a vacuum oven at 100° C. The product was a crosslinked, linear copolymer of VCL and AA crosslinked with PETE in a wt. ratio of 50/50/1.5.
Into a 1-liter, four-necked glass kettle, equipped with two feeding pumps, an anchor agitator, a thermocouple and a condenser, 500 g of heptane as solvent was charged and agitated at 200 rpm while being purged with nitrogen throughout the process. The solvent then was heated to 65° C. with an oil bath and held there for 30 minutes. Feeding Solution I was prepared by mixing 60 g of N-vinylpyrrolidone (VP), 15 g of stearyl methacrylate (SM) and 1.0 g of pentaerythritol triallylether (PETE). Feeding Solution II was prepared by weighing 25 g of acrylic acid (AA) into a bottle. 200 microliter of Luperox® 11M75 as initiator was charged into the kettle. Then Feeding Solutions I and II were simultaneously pumped into the kettle over a period of 4 hours at a constant feeding rate. The resulting solution then was held at 65° C. for 1 hour and the reaction temperature was raised to 90° C. Then an additional 100 microliter of Luperox® 11M75 was added every two hours for 4 times and the reactor was held at 90° C. for two additional hours after the last dose of Luperox® 11M75 was charged. The contents then were cooled and discharged. The solvent was removed at an oven temperature of 100° C. The resultant resin powder was further dried in a vacuum oven at 100° C. The product was a crosslinked, linear terpolymer of VP, M and SM crosslinked with PETE in a wt. ratio of 600125/15/1.
Into a 1-liter, four-necked glass kettle, equipped with two feeding pumps, an anchor agitator, a thermocouple and a condenser, 600 g of heptane as solvent is charged and agitated at 300 rpm while being purged with nitrogen throughout the process. The solvent then is heated to 70° C. with an oil bath and held there for 30 minutes. Feeding Solution I is prepared by mixing 50 g of N-vinylpyrrolidone (VP) and 1.0 g of pentaerythritol triallylether (PETE). Feeding solution II is prepared by weighing 50 g of methacrylic acid (MAA) into a bottle. Then 300 microliter of t-butyl peroxypivalate initiator is charged into the kettle.
The Feeding Solution I and Feeding Solution II are simultaneously pumped into the kettle over 5 hours at a constant feeding rate. The solution is held at 70° C. for 1 hour and the solution is transferred to stainless high pressure reactor. Then an additional 0.5 g of di-t-butylperoxide is added. The temperature of the reactor is raised to 130° C. and held for 10 hours. The contents then are cooled and discharged. The solvent is removed at an oven temperature of 100° C. The resultant resin powder is further dried in a vacuum oven at 100° C. The product is a crosslinked, linear copolymer of VP and MM crosslinked with PETE in a wt. ratio of 50/50/1.
Examples 16-18 below are illustrative of color cosmetic compositions of the invention which include Ultrathix P-100 as rheology modifier-film former therein.
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This application is related to pending U.S. patent application Ser. No. 10/964,948, filed Oct. 14, 2004, the disclosure of which is hereby incorporated by reference in its entirety.