MXPA98007317A - Compositions containing copolymers as a thickening agent - Google Patents

Abstract

The present invention is directed to compositions, particularly cosmetic compositions, in which the oil is thickened using at least one copolymer which has a hydrophobic funtionality sufficient to provide at least partial solubility and optionally stability in oil and a hydrophilic functionality sufficient to provide thickening of the oil. Use of such copolymers as thickening agents are advantageous in that they are soluble and stable in the oil phase. Further, sufficient thickening may be accomplished using very low amounts of these copolymers without the use of additional polymeric thickeners.

Description

OUE COMPOSITIONS CONTAIN COPOLYMERS AS A THICKENING AGENT DESCRIPTION OF THE INVENTION The present invention relates to compositions in which the oil is thickened using copolymers which have sufficient hydrophobic functionality to provide at least partial solubility and optionally oil stability and functionality. enough hydrophilic to provide oil thickening. Numerous cosmetic compositions use 'oils as a main component. The oils possess highly desirable cosmetic characteristics, such as cleaning, makeup removal and emolliency. Unfortunately, its use is inconvenient in the fluid form and its application is unpleasant and difficult. These disadvantages are reduced by using the oil in the form of a thick composition, such as a cream or a gel or in the form of an emulsion, particularly of the water-in-oil type. The preparation of such water-in-oil emulsions requires thickening of the continuous oily phase of the emulsion. The thickening of the oily phase is also necessary to prepare such cosmetic gels, particularly anhydrous gels. The formulation in the form of an anhydrous gel is useful, especially if the substances present in the composition are sensitive to moisture and / or oxygen.

The thickening of the oils has been carried out by incorporation of silicas, bentonites, or metal salts of fatty acids such as aluminum salts, or esterified derivatives of sugars such as dextrin palmitate. Such thickening has also been carried out by incorporation of a wax in the oily phase. However, creams thickened with waxes have a sense or texture which is generally considered undesirable. U.S. Patent No. 5,318,995 assigned to L'Oreal describes the thickening of a water-in-oil emulsion with certain copolymers containing a slight amount of ionic or ionizable groups. These copolymers are mainly of the formula: Where M is O or -N (R3) -; R is H or -CH3; R2 is a hydrocarbon chain of C4_22; R3 is H or a C1-22 hydrocarbon chain • European Patent 550 745 assigned to L'Oreal describes the thickening of the oily phase of a cosmetic composition using a combination of a first copolymer containing units derived from a lipophilic monomer and a hydrophilic monomer containing carboxylic or sulfonic acid groups which include copolymers such as those described in U.S. Patent No. 5,318,995 and a second copolymer containing units derived from a lipophilic monomer and a hydrophilic monomer containing a amine, amide, alcohol or an ether group. Both copolymers are necessary to thicken the cosmetic composition. Surprisingly, it has now been discovered that the oily phase of a composition can be thickened by incorporating as the only polymeric thickener at least one copolymer which has sufficient hydrophobic functionality to provide at least partial solubility and optionally oil stability and a hydrophilic functionality enough to provide thickening to the oil. The present invention relates to compositions, particularly cosmetic compositions, in which the oil is thickened using at least one copolymer which has sufficient hydrophobic functionality to provide at least partial solubility and optionally oil stability and sufficient hydrophilic functionality to provide oil thickening. It is further related to the process of preparing such compositions. It is an object of the present invention to provide a composition in which the oil is thickened using at least one copolymer which has sufficient hydrophobic functionality to provide at least partial solubility and optionally oil stability and sufficient hydrophilic functionality to provide thickening to oil. Another object of the present invention is to provide a composition particularly in the form of a cream, or an emulsion, more particularly a water-in-oil emulsion, in which the oil is thickened using at least one copolymer which has sufficient hydrophobic functionality to provide at least partial solubility and optionally oil stability and functionality * enough hydrophilic to provide oil thickening. Yet another object of the present invention is to provide a composition, particularly in the form of a cream, a gel or an emulsion, more particularly a water-in-oil emulsion, in which the oil is thickened using at least one acrylate copolymer or methacrylate A further object of the present invention is to provide a method for oil thickening using at least one copolymer which has sufficient hydrophobic functionality to provide at least solubility and optionally oil stability and sufficient hydrophilic functionality to provide oil thickening . These and other objects of the present invention will become apparent to one skilled in the art from the following detailed description and subsequent examples. The present invention is directed to compositions, particularly cosmetic compositions, in which the oil is thickened using at least one copolymer which has sufficient hydrophobic functionality to provide at least partial solubility and optionally oil stability and sufficient hydrophilic functionality to provide oil thickening. The use of such copolymers as thickening agents is advantageous in that they are soluble and stable in the oil phase. Additionally, sufficient thickening can be carried out using very low amounts of these copolymers without the use of additional polymeric thickeners. Hydrophobic functionality is necessary to provide at least partial solubility and preferably stability in the oil. The hydrophobic functionality can be provided by any hydrophobic constituent conventionally used in the art including C? 0-C22 acrylates or methacrylates. acrylamides or methacrylamides of C? 0-C22 / vinyl ethers or C10-C22 esters. siloxanes or alpha-olefins of C10-C22; fluorinated aliphatic side chains of at least 6 carbons; and alkylstyrene side chains wherein the alkyl is from 1 to 24 carbon atoms. Of particular use in the present invention are the C 2 -C 22 acrylates or methacrylates and styrenes, more particularly C 8-22 acrylates or methacrylates. The hydrophobic functionality generally comprises from about 80% to about 98%, more particularly from about 85% to about 97% by weight of the copolymer. The hydrophilic functionality is necessary to thicken the oil and can be provided by the α, β-ethylenically unsaturated C 3 -C 6 monoacid, unsaturated C 4 -C 6 diacid carboxylic acid, and / or a monoester or monoamide of such a diacid carboxylic acid. The unsaturated carboxylic monoacids include acrylic acid, methacrylic acid, and crotonic acid. The unsaturated carboxylic diacids include maleic acid and itaconic acid. The monoesters and monoamides are derived from alcohols or amines containing from 1 to 22 carbon atoms, respectively. Of particular use in the present invention are acrylic acid or methacrylic acid. Copolymers which have an acidity of from about 0.1 to about 4.0 meq / g, particularly from about 0.4 to about 2.0 meq / g, are of use in this application. Copolymers with a molecular weight greater than 50,000, particularly in the range of approximately 50,000-200,000 daltons also have use in this application. Any of the copolymers described above, or a mixture of at least two, can be used in the present invention. Those copolymers of alkyl acrylate or methacrylate and acrylic acid or methacrylic acid are particularly useful in the present invention, more particularly docosyl acrylate (C22) / styrene / acrylic acid and stearyl acrylate / methacrylic acid. In the compositions, the amount of the thickening copolymer, as defined above, is present in an amount sufficient to thicken the composition to the desired thickness. In general, it is present in an amount of from about 0.1% to about 12%, particularly from about 0.5 to about 10% by weight of the oil. If the composition is a pure composition, the thickening copolymer is in an amount of from about 2 to about 8% by weight of the oil in particular. Pure composition is proposed, as used herein, to mean a composition which is essentially free of water. If the composition is an emulsion composition, the thickening copolymer is present in an amount of from about 0.5 to about 3.% by weight of the oil in particular. The composition can be thickened to the desired viscosity which is dependent on the functional properties of the composition. To thicken the oil phase, the copolymer is generally heated above its melting point in the oil to allow it to solubilize more easily. Agitation is often provided to further facilitate solubilization. The oily phase is constituted by any oil or mixtures of oils conventionally employed in formulations and known in the art. The oils include, but are not limited to: Hydrocarbons, including mineral oils, such as paraffin oils, petrolatum oils, hydrogenated polyisobutylene, such as that commercially available from NIPPON OIL under the brand name PARLEAM branched hydrocarbons, such as as those commercially available under the name ISOPAR; Triglycerides, especially vegetable oils, such as sunflower seed oil, sesame seed oil, rapeseed oil, sweet almond oil, calofilum oil, palm oil, avocado oil, jojoba oil, castor oil, or grain germ oils, such as wheat germ oil; Various oily esters derived from a large chain acid and / or alcohol, such as purcelin oil, butyl myristate or cetyl, isopropyl, butyl or ethyl-2-hexyl palmitate, isopropyl, butyloctyl, hexadecyl or isocetyl stearate, oleate of decyl, hexyl laurate, propylene glycol dicaprylate, diisopropyl adipate, and mixtures of C12-C5 benzoic esters commercially available under the trademark FINSOLV TN from WITCO; Animal oils, such as perhydrosqualene; Silicone oils, such as dimethyl polysiloxanes, phenyldimethicones, cyclomethicones and alkyldimethicones; Large chain alcohols, such as oleyl, linoleyl, linolenyl, and isostearyl or octyl dodecanol alcohols; Esters derived from lanolic acid, such as isopropyl or isocetyl lanolate; and Acetylglycerides, the octanoates and decanoates of alcohols, or of polyalcohols (especially glycol or glycerol) and the ricinoleates of alcohols or polyalcohols, for example, cetyl ricinoleate. In general, the copolymers herein are soluble in oils with the exception of certain silicone oils used alone. When the copolymer is not sufficiently soluble in oil, it may be possible to obtain the desired viscosity as described above using an organic cosolvent which is compatible with cosmetological use. Representative cosolvents include, but are not limited to, ethanol, propanol, isopropanol, glycerol, and propylene glycol. The co-solvent is usually added directly to the oil and, in the case of an emulsion, before mixing with the aqueous phase of the emulsion. Generally, the amount of the cosolvent is not greater than 30 volume percent relative to the volume of the oil. The copolymers present can be used to thicken the oil in a composition in any form, including without limitation water-in-oil emulsions, oil-in-water emulsions, anhydrous compositions and gelled oils. The present copolymers can be used to thicken compositions containing a water-in-oil type emulsion. When the copolymers present in this type of system are used, a conventional emulsifying agent or surfactant can be added to provide a stable emulsion. An emulsifying agent known in the art and compatible with the cosmetological use in the present invention may be employed. Such agents include, but are not limited to, glycerol isoterate such as IMITOR 780K (commercially available from Dynamit Nobel) and polyglycerol ethers having the formula: C12H2S-CH (C10H2)) - CH2O - [- C2H3O (CH2OH) -] - nH, Where n = to an integer from 2 to 15 and it is described for example in French Patent Application 07.00 878 (2,593,509). The amount of the emulsifying agent in the art is known, but is generally in the range of up to about 15% by weight of the composition.

The copolymers present can also be used to thicken compositions of the pure type, that is, those compositions which do not contain a substantial amount of water. Such pure compositions include, for example, creams and gels. The compositions of the present invention may additionally contain a rheology control agent to improve the properties of the thickened oil composition if deemed necessary or desirable. This is generally applied in the case in which the composition obtained is pfuy viscous and tends to be glossy or is less viscous but not sufficiently malleable and very fluid. These rheology control agents are known in the art and are generally non-ionic amphiphilic agents having an EHL value between about 12 and about 40. They are preferably used in the presence of water or a water-soluble alcohol. The rheological control agents include: esters of fatty acids and polyoxyethylene sorbitan, esters of fatty acids and polyoxyethylene glycerol; the polyoxyethylene or polyoxypropylene alkyl ethers; polyoxyethylene or polyoxypropylene alkyl phenyl ethers; and polyoxyethylene Guerbet alcohols. When the compositions of the present invention are cosmetic compositions, they may optionally contain additives conventionally used in the cosmetic industry, including but not limited to active ingredients, perfumes, preservatives, and sunscreen agents. These additives and their use in cosmetic compositions are well known in the art and can be added by known techniques before, during or after oil thickening. Several active lipophilic substances which are beneficial to the skin, such as tocopherol and its esters, the fatty esters of ascorbic acid, 18-β-glycyrrhetinic acid, ceramides, filter substances that absorb ultraviolet light, antioxidants, etc., can also be optionally incorporated in the oils. Cosmetic compositions are proposed, as used herein, to include all cosmetic compositions based on oil, including, but not limited to, products for the care and hydration of the face and / or body, including hands, lotions pre-tanning, sunscreens, sun tan lotions, after-tanning lotions, make-up removers, lipstick, masks, bases, scented gels or oils, hair treatment oils, deodorants, bath oils, and cleansers. Cosmetic compositions containing the thickened oil or water-in-oil emulsion have a pleasing appearance with light texture. They are not significantly oily to the touch. Additionally, they penetrate the skin well and, after application, leave a uniform, fresh sensation.

The following examples are presented to further illustrate and explain the present invention and should not be taken as limiting in any respect. Ex amps Example 1 A solution of five percent solids of the copolymer in mineral oil (Drakeol 7 light mineral oil from Penreco, Karns City PA) is prepared and neutralized with 2-amino-2-methyl-1-propanol (AMP) ( commercially available from Angus Chemical Co.) according to its acidity content. The mixture is heated to 60 ° C with constant stirring to allow the copolymer to solubilize. The solution is allowed to cool to room temperature overnight. The above experiment is carried out individually using each of the copolymers listed in Table 1. Table 1 Sample 124-93 is docosyl acrylate / styrene / acrylic acid in a ratio of 72/24/4 by weight.

Sample 124-130 is docosyl acrylate / styrene / acrylic acid in a ratio of 68/27/5 by weight. Sample 124-194 is stearyl acrylate / methacrylic acid in a ratio of 92.5 / 7.5 by weight. Sample 124-195 is stearyl acrylate / methacrylic acid in a ratio of 90/10 by weight. All copolymers are available from Landec Corporation, Menlo Park, California, E.U.A. A control is prepared in which no copolymer is added. The solubility and appearance of the resulting compositions are examined visually. The viscosity of the compositions is obtained using a Brookfield viscometer with Helipath rods. The procedure recommended by Brookfield Engineering Laboratories, Inc. is used (Stoughton, MA). The rod is fixed in such a way that the cross piece is covered by approximately 1/4 inch of the test material. The TC rod is used for the more viscous compositions but does not provide reading for the less viscous compositions. The TE rod is used for the less viscous compositions, but does not provide a reading for the more viscous compositions. The TA rod is used for at least the viscous compositions. The results are listed in Table II.

Table II Each of the copolymers results in a stable formulation. Example 2 Ingredient Quantity (% by weight) Sample 124-194 2.50 Parsol 1789 1.25 Isopropyl myristate 20.00 Mineral oil # 7 76.25 Sample 124-194 is stearyl acrylate / methacrylic acid in a ratio of 92.5 / 7.5 by weight available from Landec Corporation, Menlo Park, California, USA Parsol 1789 is a butylmethoxydibenzoylmethane commercially available from Givaudan-Roure in Clifton NJ. Drakeol Mineral Oil # 7 is commercially available from Penreco, Karns City PA. All the ingredients are combined and heated to 80 ° C. The composition is mixed until uniform and cooled to room temperature. The viscosity of the resulting compositions is determined using the same procedure as in Example 1 using the TB rod and 10 rpm.

Example 3 Ingredient Experimental amount Quantity of (% by weight) control (% in pe.soJ Phase A Dow Corning 344 5.0 5.0 Abil EM 90 2.0 2.0 Mineral Oil # 7 8.5 8.5 Octyl stearate 9.0 9.0 Sample 124-194 1.0 0.0 Phase B deionized H20 73.80 74.80 NaCl 0.50 0.50 Phase C Liquapar 0.20 0.20 Sample 124-194 is stearyl acrylate / methacrylic acid in a ratio of 92.5 / 7.5 by weight available from Landec Corporation, Menlo Park, Calif., E.U.A. Dow Corning 344 is a silicone oil and is commercially available from Dow Corning, Midland MI. Abil EM 90 is a silicone oil and is commercially available from Goldschmidt Hopewell VA Liquapar is isopropylparaben (e) isobutylparaben (y) Butylparaben (conservative) and is commercially available from Sutton Labs. Chatham NJ. Procedure: Phase A is combined in a large container and heated to 80 ° C. Phase B is combined in a separate vessel. Slowly, with gentle agitation, Phase B is added to Phase A. Agitation is increased as soon as the emulsion forms and thickens until uniform mixing is maintained. When the emulsion is uniform and at a temperature of 40 to 35 ° C, Phase C is added and mixed thoroughly. The viscosity of the resulting compositions is determined using the same procedure as in Example 1 using the TB rod and 10 rpm.

Example 4 Ingredient Experimental amount Quantity of (% by weight) control (% by weight) Phase A Mineral Oil # 7 17.00 17.00 Dioctyl adipate 2.00 2.00 Estol 1526 3.00 3.00 Miritol 318 5.00 5.00 Arlacel pl35 1.00 1.00 Sample 124-194 1.00 0.00 Phase B H20 deionized 69.80 70.80 Magnesium sulphate 1.00 i. oo (anhydrous) Phase C Liquapar 0.20 1.00 Sample 124-194 is stearyl acrylate / methacrylic acid in a ratio of 92.5 / 7.5 by weight available from Landec Corporation, Menlo Park, California, E.U.A. Estol 1526 is propylene glycol dicaprylate / dicaprate and is commercially available from Unichema, Chicago IL. Miritol 318 is caprylic / capric triglyceride commercially available from Henkel, Hoboken NJ. Arlacel pl35 is PEG-30 dipolyhydroxystearate and is commercially available from ICI Surfactants, Wilmington DE. Liquapar is isopropylparaben (e) isobutylparaben (y) butylparaben (conservative) and is commercially available from Sutton Labs. Chatham NJ. Procedure: Phase A is combined in a large container and heated to 80 ° C. Phase B is combined and heated to 40 ° C. Phase B is slowly added to Phase A with gentle agitation and mixed thoroughly. The mixture is cooled to 40 to 35 ° C and Phase C is added until it is uniform. The viscosity of the resulting compositions is determined using the same procedure as in Example 1 using the TB rod and 10 rpm.

Claims (15)

1. CLAIMS 1. A composition characterized in that it comprises an oil and a polymeric thickener consisting essentially of at least one copolymer which has sufficient hydrophobic functionality to provide at least partial solubility in oil and a hydrophilic functionality present in an amount effective to provide oil thickening, hydrophilic functionality that is provided by a constituent selected from the group consisting of α, β-ethylenically unsaturated C 3 -C 6 monoacid, unsaturated C 4 -C 6 diacid carboxylic acid, monoesters or monoamides of such diacid carboxylic acid.
2. 2. The composition according to claim 1, characterized in that the hydrophobic functionality is provided by a constituent selected from the group consisting of C10-C22 acrylate, C? O-C22 methacrylate. C? 0-C22 acrylamide C? 0-C22 methacrylamide, C? 0-C22 vinyl ether, C? 0-C22 vinylester siloxane, C10-C22 alpha olefin; fluorinated aliphatic side chain of at least 6 carbons; styrene and styrene substituted C1-C24 alkyl.
3. 3. The composition according to claim 2, characterized in that the hydrophobic functionality is provided by a constituent selected from the group consisting of C12-C22 acrylate. C12-C22 methacrylate styrene and styrene substituted C? -C24 alkyl.
4. 4. The composition according to claim 1, characterized in that the hydrophilic functionality is provided by a constituent selected from the group consisting of acrylic acid and methacrylic acid.
5. The composition according to claim 1, characterized in that the copolymer is selected from the group consisting of docosyl acrylate / styrene / acrylic acid and stearyl acrylate / methacrylic acid.
6. 6. The compliance composition * with claim 1, characterized in that the copolymer is present in an amount in the range of about 0.1 to about 12% by weight of the oil.
7. The composition according to claim 1, characterized in that the composition is pure and the copolymer is present in an amount from about 2 to about 8% by weight of the oil.
8. The composition according to claim 1, characterized in that the composition is a water-in-oil emulsion and the copolymer is present in an amount from about 0.5 to about 3.5% by weight of the oil.
9. 9. The composition according to claim 1, characterized in that the composition is a cosmetic composition.
10. 10. A process for thickening an oil characterized in that it comprises adding to the oil a polymeric thickener consisting essentially of at least one copolymer which has sufficient hydrophobic functionality to provide at least partial solubility in oil and a hydrophilic functionality present in an effective amount for providing oil thickening, hydrophilic functionality that is provided by a constituent selected from the group consisting of α, β-ethylenically unsaturated C3-Ce carboxylic acid, C4-Ce unsaturated carboxylic acid diacid, monoesters or monoamides of such diacid carboxylic acid.
11. 11. The process in accordance with the claim 10, characterized in that the hydrophobic functionality is provided by a constituent selected from the group consisting of C? 0-C22 acrylate, C? 0-C22 methacrylate. C10-C22 acrylamide. C10-C22 methacrylamide, C?-C22 vinyl ether / C ?0-C22 siloxane vinylester, C ?0-C22 α-olefin; fluorinated aliphatic side chain of at least 6 carbons; styrene and styrene substituted alkyl of Cx-C24- 12. The process in accordance with the claim 11, characterized in that the hydrophobic functionality is provided by a constituent selected from the group consisting of C12-C22 acrylate, C12-C22 methacrylate, styrene and styrene-substituted alkyl of C? -24-24. The process according to claim 10, characterized in that the hydrophilic functionality is provided by a constituent selected from the group consisting of acrylic acid and methacrylic acid. 14. The process in accordance with the claim 10, characterized in that the copolymer is selected from the group consisting of docosyl acrylate / styrene / acrylic acid and stearyl acrylate / methacrylic acid. 15. The process according to claim 10, characterized in that the copolymer is present in an amount in the range of about 0.1 to about 12% by weight of the oil.