Patent Application
20100074859
Moisturizing formulations for skin care typically contain hydrophobic materials such as petrolatum or other oils or waxes which include liquids, solid or semi-solid at room temperature, in the form of oil-in-water emulsions. The hydrophobic materials are typically introduced into the aqueous medium by adding under shear stress a hot oil phase containing, e.g., petrolatum, into a hot aqueous phase in the presence of emulsifiers to allow for homogenous dispersion of the petrolatum into the surfactant system. Simply incorporating melted petrolatum or similar material into a cold base is not feasible as the melted petrolatum solidifies upon contact with the base material. The need for hot processing, however, renders the manufacturing relatively expensive and difficult. Moreover, the emulsifiers can interfere with the desired deposition of the hydrophobic agents on the skin.
A skin care composition comprising an acrylate polymer; a yield value increaser; and a surfactant. The composition has a yield value of at least about 4.
Methods of depositing a hydrophobic material on an epidermal surface comprise: (a) applying to the epidermal surface the skin care composition; and (b) removing the composition from the epidermal surface, wherein at least a portion of the hydrophobic material remains deposited on the surface.
Methods of incorporating a hydrophobic material into a skin care composition, comprise (a) forming a base comprising mixing an acrylate polymer and a surfactant; (b) forming a hydrophobic material premix comprising mixing a hydrophobic material and a yield value increasing polymer; and (c) combining the hydrophobic material premix with the base, wherein the method is carried out at a temperature of no greater than 50° C.
FIG. 3—(a) G′/G″, (b) Yield Stress and (c) Viscosity; as a function of wt % of CARBOPOL™ Aqua SF1 acrylates copolymer for two different surfactant formulations: (1) 31.37 wt % SPES; 10.00 wt % CAPB and (2) 36.86% SPES; 5.36 wt % CAPB. Total active ingredients (AI) in both formulas is 11.0 wt % surfactants.
a and b illustrate a comparison of viscosity (4a) and structural parameter values (4b) for the following formulations: a) 36.86% SPES, 5.36% CAPB, 7% CARBOPOL™ Aqua SF1 polymer; b) 36.86% SPES, 5.36% CAPB, 7% CARBOPOL™ Aqua SF1 polymer, 0.25% NaCl; and c) 31.37% SPES, 10.0% CAPB, 7% CARBOPOL™ Aqua SF1 polymer.
) 35.28% SPES, 5.36% CAPB, 8.5% CARBOPOL™ Aqua SF1 polymer; (
) 29.8% SPES, 10% CAPB, 5.5% CARBOPOL™ Aqua SF1 polymer; (∘) 29.8% SPES. 10% CAPB, 7% CARBOPOL™ Aqua SF1 polymer.
a and 7b illustrate aging profiles of a composition containing surfactants/acrylates copolymer/guar quat and 4% sunflower oil (SFO) at 48.9° C. (120° F.) aging profile.
a illustrates yield stress as a function of % wt Cesmetic™ DP4 guar hydroxypropyl trimonium chloride with 4% sunflower oil (SFO). ) versus another composition (29.8% SPES, 10% CAPB, and 7% CARBOPOL™ Aqua SF1 polymer) with 4% sunflower oil (SFO) (□).
a and 11b illustrate the effect on G′ and G″ dPa (dyne/cm2) versus strain for compositions with and without sunflower oil (SFO).
As used throughout, ranges are used as a shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. All references cited herein are incorporated herein by reference. If there is any conflict in a definition of a term between a reference and this specification, the definition in this specification shall control.
As used throughout, amounts of materials are based on supplied amounts, which includes the active amount of material and the amount of any carrier for the material.
Described herein are skin care compositions that may be prepared by cold processes and include at least an acrylate polymer, a yield value increaser, and a surfactant. In one embodiment. the composition has a yield value of at least about 4.
The skin care composition may be a substantially non-emulsified composition. The term “substantially non-emulsified” as used herein means a composition other than a conventional emulsion, or a composition which is not an O/W type emulsion or a W/O type emulsion. In other words, when two solutions are mixed one phase is not dispersed in the other phase in the form of micelles that are completely stabilized by an emulsifying agent.
By “cold process” it is meant that at least the step of incorporating the hydrophobic material into the final composition may be carried out at ambient temperature, for example, about 10° C. to about 50° C. or about 15° C. to about 30° C., up to about 45° C., up to about 40° C., up to about 35° C., or up to about 30° C.
It has surprisingly been discovered that the structure of formulations containing an acrylate copolymer can be kept the same or increased by (1) using an amount of a salt of guar hydroxypropyl trimonium or (2) using a modified surfactant system by selecting the ratio of zwitterionic surfactant to anionic surfactant, for example, higher cocamidopropyl betaine (CAPB) and lower sodium laureth sulfate with an average of 2 moles of ethylene oxide groups (SPES) in order to lower the amount of CARBOPOL™ Aqua SF1 polymer necessary to obtain a structured system. Thus, the inventors have found a method of enhancing the performance of the CARBOPOL™ Aqua SF1 polymer by modifying the zwitterionic surfactant to anionic surfactant ratio (CAPB:SPES ratio) in the formulation.
The composition includes an acrylate homopolymer or copolymer (hereinafter collectively referred to as “polymer”). The acrylate polymer may be any known or to be developed in the art and may include swellable acrylate co-polymer, e.g., such as CARBOPOL™ Aqua SF-1 (from Noveon, Cleveland, Ohio, United States of America). Suitable polymers (including homopolymers or co-polymers of the listed components) may include those of 2-hydroxyethyl acrylate, hydroxypropyl acrylate, polymers of acrylic acid and its esters, polymers of methacrylic acid and its esters, acrylnitriles, ethylacrylate, methacrylate, polyalkenyl ethers of sucrose, polyalkenyl ethers of polyalcohols, trimethylpropone tri(meth)acrylate, glycidal methacrylate, and N-methylolacryamide. Other polymers that may be suitable are described in U.S. Pat. No. 6,635,702, the contents of which are incorporated herein by reference. Mixtures of polymers (co- and homo-) may also be used, if desired.
The selected polymer(s) may be present in the composition in any amount. In certain embodiments, they are present in an amount of about 1% to about 30% by weight of the total skin care composition, with amounts of about 3% to about 12%, and about 5% to 12% of the total weight of the skin care composition also being suitable.
The composition of the invention can include a yield-increasing polymer that is different from the acrylate polymer. By “yield value increaser” it is meant a component, for example, a salt of guar hydroxypropyl trimonium or a modified surfactant system, when added to an acrylate polymer, the yield value increased by about at least 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 40% or more (yield values measured as described herein).
The yield value increaser may be a cationic polymer. It may be, for example, a cationic gum. The cationic polymer may be a modified guar gum or other gum, such as a salt of guar hydroxypropyl trimonium, hydroxypropyl guar and/or C18 to C12 alkyl hydroxypropyl guar. The salt of guar hydroxypropyl trimonium may be, e.g., any containing a suitable anion, such as guar hydroxypropyl trimonium chloride.
The yield value increaser may also be a modified surfactant system. It may be, for example, a surfactant system having a selected ratio of anionic surfactant to cationic surfactant. In one embodiment, the modified surfactant system includes a higher CAPB (i.e., the zwitterionic surfactant) and lower SPES (i.e., the anionic surfactant) content. In certain embodiments, the ratio of zwitterionic surfactant to anionic surfactant is greater than about 0.2, about 0.25, about 0.3, about 0.4, about 0.5, about 1, about 1.5, about 2, about 5, or about 10.
The cationic polymer may be present in the composition in any amount. In one embodiment, it is present in an amount of up to about 20% by weight. Alternatively, amounts may be up to about 10% by weight, about 0.1% to about 5% by weight and about 7% to about 12% by weight.
The skin care composition may also include a hydrophobic material, which may be a non-silicone hydrophobic material. Such material may be liquid, solid or semi-solid at room temperature and may function to confer a skin benefit when applied topically, e.g., skin moisturization. Exemplary hydrophobic materials include: mineral oils, synthetic oils, vegetable oils, semi-solid hydrocarbons, petrolatum, long chain alkanes and alkenes, isodedecane, isohexadecane, hydrogenated polydecene, polydecene, and hydrocarbons found in beeswax (for example, C21-37 hydrocarbons), esters of fatty acids (including hydrogenated forms or derivatives thereof) and long straight chain alcohols, triacontanol hexadecanoate, hexacosanol hexacosanoate, and myricyl palmitate, fatty acid triglycerides, animal fats, lanolin, hydrogenated or partially hydrogenated vegetable oils, hydrogenated or partially hydrogenated sunflower oil, safflower oil, soybean oil, rapeseed oil, grape seed oil, corn oil, olive oil, sweet almond oil, coconut oil, palm kernel oil, soybean oil, and/or derivatives thereof, castoryl maleate, hydrophobic vegetable extracts, rhea butter, cocoa butter, and derivatives and fractions thereof: hydrophobic UV absorbers, for example cinnamates, octinoxate, benzophenes and benzophenone, oxybenzone, salicylates, octisalate, anthranilates, and p-aminobenzoic acid esters, water-insoluble vitamins, including water-insoluble vitamin derivatives, vitamin A, vitamin D2, vitamin D3, vitamin E, vitamin E acetate, and water-insoluble pharmaceuticals for topical application, antibiotic agents, antifungal agents, antibacterial agents, analgesic agents, anti-inflammatory agents, an organic sunscreen, an agent coated with organic material, a synthetic oil, a hydrophobically coated particle, a liquid organic material containing a hydrophobic material, an insect repellent, a semi-solid hydrocarbon. The hydrophobic material can be present as a homogenous dispersion.
The hydrophobic material may be present in any amount. In one embodiment, it is present in an amount of about 0.2% to about 20% by weight of the total skin care composition or about 4% to about 10% by total weight of the skin care composition.
The hydrophobic material may be present in the skin care composition in a non-conventional-emulsion form; it may be present or substantially present as a suspended non-emulsified droplet or dispersion. Accordingly, the skin care composition itself may be referred to as a substantially emulsifier free composition. In certain embodiments, at least about 80%, about 85%, about 90%, about 95%, and about 98% of the hydrophobic material is present as non-emulsified droplets or dispersions. The droplets or dispersions may be homogenous or they may be mixtures or emulsifications of other hydrophobic or hydrophilic materials.
In certain embodiments, the droplets/dispersions have an average diameter of about 0.01 to about 100 microns, about 0.1 to about 10 microns, or about 1 micron to about 50 microns.
The composition has a yield value of at least about 4. In some embodiments, the compositions may have a yield value of about 5 to about 10 or about 4 to about 25. Yield values are measured using a Brookfield Yield Rheometer YR-1 at ambient temperature (25° C.), using the spindle # 72.
The composition may also include a surfactant or mixture of surfactants. The base composition may contain a surfactant. As mentioned above, one embodiment of the invention provides a selected ratio of zwitterionic surfactant to anionic surfactant. However, any surfactant suitable for a skin cleansing product may be incorporated. In addition to the selected ratio of zwitterionic surfactant to anionic surfactant, the compositions may also optionally include one or more additional surfactants.
Suitable surfactants may include a surfactant or mixture of surfactants having a combined HLB value which is at least about one HLB unit higher than the HLB required for desired emulsion of the hydrophobic material used in the skin care composition. In certain embodiments, the HLB is at least about two HLB units higher than the HLB required for desired emulsion. The HLB of the surfactant/surfactant may be, for example, at least about 10, at least about 12, or at least about 14.
Surfactants may include amphoteric, sulfate, zwitterionic, sulfonate, anionic surfactants, such as, for example, lauryl sulfates, lauryl ether sulfates, sodium lauryl sulfate, sodium laureth sulfate, sodium methyl-2 sulfolaurate, disodium 2-sulfolaurate, sodium lauryl sulfoacetate, disodium laureth sulfosuccinate, amphoteric acetates, sodium laurylamphoacetate, betaine derivatives, cocoamidopropyl betaine (CAP-Betaine), alkyl amines, alkyl imidazolines, cetylpyridinium chloride, PEG-50 stearamine, and dimethyl palmitamine.
One or more surfactants may be included in the compositions. In one embodiment, the selected surfactants are sulfate surfactant(s) and amphoteric surfactant(s), which can in one embodiment be present in a weight ratio of about 2:1 to about 4:1 or about 3:1.
The surfactant(s) may be present in the skin care composition in any amount. For example, amounts of about 4% to 20% by weight of the total composition or about 12% to about 18% of the total composition may be present. Alternatively, water may be present in amounts of at least about 90% by weight or at least about 95% by weight of the total composition.
It has been surprisingly found that the addition of small quantities of a viscosity modifier, for example, a salt of guar hydroxypropyl trimonium (e.g., guar hydroxypropyl trimonium chloride (Cesmetic™ DP4/DP2. Rita/Lamberti)), into a surfactant base significantly improves the structural properties of this formulation. Both G′ (the elastic modulus) and G″ (the viscous modulus) significantly increase upon addition of Cesmetic™ DP2 or DP4 guar hydroxypropyl trimonium chloride as illustrated in
In certain illustrative embodiments, the Brookfield viscosity also improved significantly upon adding guar hydroxypropyl trimonium chloride to the structured system so that targeted product viscosity can be achieved without the further addition of salt as illustrated in
In addition, it has been surprisingly found that the structural properties of the surfactant base, for example, CARBOPOL™ Aqua SF1 polymer containing bases, can be greatly improved by increasing the zwitterionic surfactant to anionic surfactant ratio (e.g., ratio of CAP-Betaine to SPES) in the formulation, while maintaining the total surfactant concentration constant.
Rheology data in
Rheology data in
As illustrated in
The addition of guar hydroxypropyl trimonium chloride to a cleanser containing an acrylate polymer, and sunflower oil provided an unexpected increase in yield value. While the viscosity was expected to increase, the synergistic effect of the guar with the polymer increased the yield value of the composition. Additionally, the addition of sunflower oil provides a further increase in yield when combined with the acrylate polymer and the guar.
In order to understand the mechanism of action of this guar material, the rheology of the composition with and without sunflower oil and guar hydroxypropyl trimonium chloride (Cesmetic™ DP4) was compared.
Without being limited by theory, the surprising and unexpected benefits provided by addition of guar hydroxypropyl trimonium chloride to the composition in the presence of sunflower oil illustrated the existence of a synergistic effect between the components of the structured system, guar hydroxypropyl trimonium chloride and sunflower oil.
Water may also be included in the composition. It may be present in an amount, for example, of at least 40% by weight of the total composition. Alternatively, the composition may contain water in an amount of at least about 10%, at least about 20%, at least about 30%, at least about 50%, at least about 60%, or at least about 70%, each by weight of the total composition.
The formulation may optionally further include one or more viscosity modifiers in addition to the acrylate co-polymer, for example a cationic polymer. Any may be used—examples include chitosan, vegetable or marine colloids, and starches. If included, the skin care composition may contain, in one embodiment, about 0.1% to about 2% by weight of the cationic polymer, based on the total weight of the skin care composition. In other embodiments, the amount can be at least about 0.4% or about 0.4% to about 1.5%.
The skin care compositions described herein may also contain any additional additives as are desired. Such additives may include insoluble particles, such as beads, pigments, polyethylene beads, natural particulates, encapsulates, shea butter in gelatin encapsulate, preservatives, chelators, ethylenediaminetetraacetic acid (EDTA), antibacterial agents, 1,3-dimethylol-5,5-dimethyl hydantoin (DMDMH), triclosan, or trichlocarbon, anti-oxidant agents, tocopheryl acetate, perfume, coloring agents, organic sunscreen agents, physical sunscreens, vitamins, creatine or retinoic acid. Other additives may include antimycotic agents, anti-inflammatory agents, menthol, adducts of an oil.
In some embodiment, the skin care compositions described herein may have a viscosity of about 2500 to about 25,000 cps, or about 3500 to about 15,000 cps, as measured using a Brookfield DV-II+ viscometer, with settings at spindle: 5, speed: 20 rpm, time: 60 sec.
It has been found that the skin care compositions described herein provide useful means for delivering dermatologically beneficial compounds to the skin. For example, the skin care composition can be formulated to contain a topically active or protective compound, e.g., a sunscreen compound or vitamin, even when the active or protective compound is highly hydrophobic. The composition may be used to deliver the hydrophobic material and/or an additional, active compound to the skin surface. Specifically, one aspect of the invention includes a method of depositing a hydrophobic material on the epidermal surface. Such method includes applying to an epidermal surface any one of the compositions described herein, and subsequently removing the composition from the epidermal surface, such that at least a portion of the hydrophobic material and/or any additional, active compound(s), remain deposited on the epidermal surface. Removal of the composition can be accomplished by any means, including rinsing (with water or other fluid), wiping, blotting, scraping, evaporating and/or brushing.
The skin care compositions of the invention may be prepared by any process or procedures known or to be developed in the art. An exemplary process may include pre-mixing (e.g., by shear mixing or other means of incorporation) the selected hydrophobic material(s) and the cationic polymer and a surfactant/acrylate copolymer in an aqueous solution to obtain a homogeneous suspension of droplets of hydrophobic material. In one embodiment, a premix of the hydrophobic material, and the cationic polymer is dispersed in the premix. The premix is then added to the surfactant base containing the acrylate polymer. If desired, the pH may be adjusted to obtain the desired viscosity or other properties of the formulation. At least this mixing step may be carried out at cold process temperatures described above. Any other additives may be mixed in subsequently. The method may be adapted or expanded to include preparation of any of the compositions described herein and may further be carried out as a cold process, as defined herein.
A skin care composition that was a body wash is prepared by mixing the first seven ingredients of Table I, below, to form a base (see U.S. Pat. No. 6,635,702). To that base is added a premix composed of hydrogenated polydecene, octinoxate and guar hydroxypropyl trimonium chloride and the remaining ingredients. The resulting composition was substantially emulsifier-free.
A body wash composition containing Vitamin E Acetate is prepared as described above. In this example, however, the premix containing the active hydrophobic material (i.e Vitamin E Acetate) is either composed of sunflower oil and petrolatum or hydrogenated polydecene (Table III). These two compositions were compared against the control (Table II) on deposition performance.
A base composition containing a base structure of 35 wt % of sodium laureth sulfate, 5 wt % of cocoamidopropyl betaine. 8.5 wt % of an acrylate copolymer (CARBOPOL™ Aqua SF-1), and water (remaining content) is produced in accordance with Example 1. With the base composition, test compositions containing guar hydroxypropyl trimonium chloride (CESMETIC™ DP4), in the wt % concentrations of 0.2, 0.4, 0.6, 0.8 and 1.0% are produced. Viscosity is measured using Brookfield DV-II spindle #5, 20 rpm and yield value measured using a Brookfield Yield Rheometer YR-1, spindle 72.
The results demonstrate that the addition of small quantities of a yield-increasing polymer, e.g., guar hydroxypropyl trimonium chloride, into the acrylate copolymer containing composition significantly improves structural properties of this formulation. In addition, the elastic modulus and the viscous modulus increase upon addition of the cationic polymer, as well as the yield stress value, which is a good measure of the suspending capabilities of the system. The effect is maximized when the concentration of the cationic polymer is greater than 0.4 wt %. The Brookfield viscosity improves upon adding the yield-increasing polymer to the system so that targeted product viscosity can be achieved without the further addition of salt.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11683801 | Mar 2007 | US | national |
This application is a continuation-in-part of application Ser. No. 11/683,801, filed on 8 Mar. 2007, which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/823,305 filed 23 Aug. 2006, the contents of each are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US07/76494 | 8/22/2007 | WO | 00 | 1/23/2008 |
| Number | Date | Country | |
|---|---|---|---|
| 60823305 | Aug 2006 | US |
