Cleansing compositions containing nanoemulions of oligomers

Abstract

A nanoemulsion composition comprises an internal oil phase, comprising 10 to 80% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight of greater than or equal to 2000; and an external aqueous phase, comprising: water; and 1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion. A cleansing composition comprises a nanoemulsion comprising: an internal oil phase, comprising: 40 to 75% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight of greater than or equal to 2000; and an external aqueous phase, comprising: water; and 1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion.

Description

[0001] CLEANSING COMPOSITIONS CONTAINING NANOEMULIONS OF OLIGOMERS

[0002] Field of the invention

[0003] Disclosed herein are stable isotropic cleansing compositions, for example, personal cleansing compositions comprising nanoemulsions of plant-based oligomers. The plant-based oligomers comprise estolide esters having a molecular weight of greater than or equal to 2000.

[0004] Background of the invention

[0005] Nanoemulsions are becoming increasingly popular for use in personal care compositions. They are stable and have a high surface area in view of their unit volume.

[0006] Nanoemulsions can also carry actives in their water and oil phases and are desirable since they enhance penetration of actives through the skin as well as topical benefits delivered to consumers that employ end use compositions formulated with the same. Nanoemulsions not only result in better active penetration, but they also improve the therapeutic impact and overall sensory benefits appreciated by consumers when compared to compositions formulated without them.

[0007] It is therefore of increasing interest to develop nanoemulsions that can be incorporated into a consumer product and result in excellent benefits to consumers after topical application.

[0008] Oily benefit agents are increasingly needed in personal cleansing liquids to be deposited onto the skin or hair to provide a conditioning effect. Nano oil droplets of synthetic silicone polymers have been present in 2-in-1 shampoos and conditioners since the 1980s to provide a conditioning effect in hair. Additionally, nano droplets of triglyceride oils have been incorporated into liquid crystalline or lamellar (hereinafter "lamellar") cleansing compositions to condition the skin. However, to incorporate sustainable plant-based oils, such as soybean oil, in the nano droplet format into an isotropic micellar (hereinafter "isotropic") bodywash or shampoo has been a challenge, as the nano oil tends to significantly reduce the viscosity of the isotropic cleanser, leading to phase separation. In EP Patent No. EP 2 981 245 B1 , it is disclosed that a soy oligomer with a number average molecular weight of 1500 or above can be made into nano droplets of 100 nanometers to 1 micrometer via a pre-emulsified emulsion, which is then incorporated into an isotropic shampoo. The viscosity can be maintained to the desired range. Such a soy oligomer is synthesized by metathesis of unsaturated polyol esters, such as soybean oil. Accordingly, it is continually desired to produce cleansing products containing nanoemulsions to provide a conditioning effect to skin or hair without losing viscosity.

[0009] Summary of the invention

[0010] Disclosed in various aspects are nanoemulsion compositions, cleansing compositions, and methods of making thereof.

[0011] A nanoemulsion composition comprises an internal oil phase, comprising 10 to 80% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight of greater than or equal to 2000; and an external aqueous phase, comprising: water; and 1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion.

[0012] A cleansing composition comprises a nanoemulsion comprising: an internal oil phase, comprising: 10 to 80% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight of greater than or equal to 2000; and an external aqueous phase, comprising: water; and 1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion.

[0013] These and other features and characteristics are more particularly described below.

[0014] Detailed description of the invention

[0015] Disclosed herein is a nanoemulsion and a cleansing composition made therefrom. The nanoemulsion comprises an internal oil phase comprising 40 to 75% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight (Mn) of greater than or equal to 2000; and an external aqueous phase, comprising: water; and 1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion.

[0016] Plant-based as described herein generally refers to being based on plants and made from plants other than the traditional sources. Stated another way, plant-based refers to materials that are currently plant-based and not petroleum based currently or millions of years ago.

[0017] NANOEMULSION

[0018] It was unexpectedly discovered that a new class of oligomers, polyestolide esters, which can be synthesized by polymerization of unsaturated fatty acid or hydroxy fatty acid and capped with saturated carboxylic acid on one end and branched alcohol on the other end, could be made into nanoemulsions with cleansing surfactants, resulting in a volume average diameter (D[4,3]) of 100 nanometers to 500 nanometers after homogenization. For example, the volume average diameter of the droplets can be 125 to 400 nanometers. Isotropic liquid cleansers can be made comprising such nanoemulsions. The isotropic liquid cleansers, either for skin or hair, can remain stable with a viscosity change of less than or equal to 35%, for example, less than or equal to 30%, even after being stored at 50°C for two weeks, provided that the number average molecular weight of the polyestolide ester is greater than or equal to 2000. It was unexpectedly discovered that a viscosity of isotropic cleansing compositions containing the nanoemulsions described herein changed by less than or equal to 35%, for example, less than or equal to 30% after a two-week time period stored at 50°C measured using a Discovery HR-2 Rheometer using sand blasted plates having a 1000 micron gap, at 25°C and 30 second intervals and a shear rate of 4 s’1.

[0019] The nanoemulsion composition comprises an internal oil phase, comprising 10 to 80% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight of greater than or equal to 2000, preferably 40 to 75% by weight, more preferably, 50 to 65% by weight; and an external aqueous phase, comprising: water; and 1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, ora combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion.

[0020] Polyestolide esters can generally be synthesized by the following description. A backbone of the estolide ester can be formed from a carboxylic acid capping agent, an alcohol capping agent, a monomer, or a combination thereof. In an embodiment, the backbone of the estolide ester is formed from a carboxylic acid capping agent, an alcohol capping agent, a monomer, or a combination thereof. The monomer forming the backbone of the estolide ester can comprise unsaturated fatty acid, unsaturated hydroxy fatty acid, saturated hydroxy fatty acid, or a combination thereof. In an embodiment, the monomer forming the backbone of the estolide ester is unsaturated fatty acid, unsaturated hydroxy fatty acid, saturated hydroxy fatty acid, or a combination thereof. The monomer forming the backbone of the estolide ester can comprise oleic acid, hydroxy stearic acid, ricinoleic acid, or a combination thereof. In an embodiment, the monomer is oleic acid, hydroxy stearic acid, ricinoleic acid, or a combination thereof.

[0021] Oleic acid contains a double bond (-CH=CH-) and a carboxylic acid (-COOH). The double bond on the backbone of one oleic acid molecule reacts with the carboxylic acid group on a second oleic acid to form a secondary ester linkage, which is defined as an estolide structure. The newly formed dimer still contains an unreacted carboxylic acid (-COOH) from the first oleic acid and a double bond (-CH=CH-) from the second oleic acid and would continue to react with another oleic acid to form a polyestolide. When the desired size is reached, a capping agent, such as a saturated carboxylic acid (with a chain length of 2 to 24 carbons), would react with the unreacted double bond on one end of the polymer, and another capping agent, such as a branched alcohol (with a chain length of 6 to 18 carbons), would react to esterify the free carboxylic acid group on the other end of the polyestolide, thereby resulting in polyestolide esters. For example, the carboxylic acid capping agent can comprise a C2 to C18 carboxylic acid. Preferably, the carboxylic acid capping agent can comprise acetic acid, lauric acid, myristic acid, coconut fatty acid, or a combination thereof. In an embodiment, the carboxylic acid capping agent is a C2 to C18 carboxylic acid. In an embodiment, the carboxylic acid capping agent is acetic acid, lauric acid, myristic acid, coconut fatty acid, or a combination thereof. The alcohol capping agent can comprise 2-ethylhexyl alcohol, 2-octanol, or a combination thereof. In an embodiment, the alcohol capping agent is 2-ethyhexyl alcohol, 2- octanol, or a combination thereof. The monomer forming the backbone of the estolide polymer can comprise saturated or unsaturated hydroxy fatty acid, such as 12-hydroxy stearic acid, which contains a hydroxy group (-OH) on the 12thcarbon of its alkyl backbone and a carboxylic acid (-COOH). Different from oleic acid, the estolide linkage in the polyestolide is formed via esterification of a hydroxy group (-OH) on one molecule and a carboxylic acid (-COOH) on another. The same capping agents, as in the case of oleic acid, can be used to cap both ends of the polyestolide, thereby resulting in polyestolide esters. BIOESTOLIDE™ 30, 250, and 1300 series from Biosynthetic Technologies, utilize saturated hydroxy stearic acid, while BIOESTOLIDE™ 250-100 and 1300-100 utilize the unsaturated hydroxy fatty acid, ricinoleic acid, and thus form the unsaturated polyestolide esters. In this embodiment, the capping agent saturated carboxylic acid is acetic acid and the alcohol capping agent is 2-ethylhexyl alcohol or 2-octanol in both cases.

[0022] As previously mentioned herein, the nanoemulsion composition comprises an internal oil phase and an external aqueous phase.

[0023] The internal oil phase comprises 10 to 80% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight (Mn) of greater than or equal to 2000, for example, 40 to 75% by weight, for example, 50 to 65% by weight.

[0024] An optional ingredient which may be used in the internal oil phase is an oil phase stabilizer. For example, small amounts (e.g., 0.0002 to 2%, preferably 0.0005 to 1.5%, more preferably, 0.0005- 1 % by weight of the nanoemulsion) of antioxidant may be used. For example, exemplary antioxidants can be butylated hydroxytoluene (BHT), tocopherol (vitamin E), ascorbic acid (vitamin C), or a combination thereof.

[0025] It is within the scope of the present end use compositions and nanoemulsions within the internal oil phase to optionally include, oil soluble benefit actives like hydroxy stearic acid (e.g., 10- hydroxystearic acid, 12-hydroxystearic acid, etc.) (including an ester thereof), vitamins A, D, E, or K (and their oil soluble derivatives), vitamin E acetate, sunscreens like octocrylene, octisalate (ethylhexyl salicylate), homosalate (3,3,5-trimethylcyclohexyl salicylate), ethylhexylmethoxycinnamate, 2-ethylhexyl-2-hydroxybenzoate, drometriazole trisiloxane, bisethyl hexyloxyphenol methoxyphenol triazine, 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propanoic acid, 3,3,5-trimethyl cyclohexyl 2-hydroxybenzoate, 2-ethylhexyl-2-hydroxybenzoate, or a combination thereof. The external aqueous phase comprises water and a surfactant.

[0026] NANOEMULSION AND CLEANSING COMPOSITION

[0027] The surfactant can preferably comprise an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof. The anionic surfactant can comprise 70% or greater of all surfactant(s) present in the external aqueous phase of the nanoemulsion. The surfactant can be present in an amount of 1.0 to 20% by weight of the total nanoemulsion composition, for example, 1.6 to 15% by weight of the total nanoemulsion composition. For example, the surfactant can be present in an amount of 2.0 to 15% by weight, for example, 4.0 to 14% by weight, for example, 5.0 to 13% by weight, for example, 6.0 to 12% by weight, for example, 7.5 to 10% by weight surfactant of the total nanoemulsion composition, including any and all ranges and values subsumed therein.

[0028] The surfactant in the external aqueous phase or additional surfactant present when the end use composition is a cleansing composition can be selected from an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof. The surfactant can contain Cs-Cis alkyl groups, for example, Ci2-Ci6 alkyl groups, for example, C10-C14 alkyl groups, or mixtures thereof. For example, the surfactant can contain C10 alkyl groups, Ci2alkyl groups, C14 alkyl groups, or any combination thereof. A cleansing composition comprising the nanoemulsion can comprise 20 to 95% by weight of the anionic surfactant, based on a total amount of surfactant in the overall cleansing composition. Any of the surfactants disclosed herein can be present in either the nanoemulsion (in the external aqueous phase) or in an end use cleansing composition. The surfactant or surfactants used in the nanoemulsion are different from the surfactants in the cleansing composition. Stated another way, the surfactant or surfactants used in cleansing composition are in addition to those used in the nanoemulsion.

[0029] The anionic surfactant used can include aliphatic sulfonates, such as a primary alkane (e.g., Cs- C22) sulfonate, primary alkane (e.g., Cs-C22) disulfonate, Cs-C22alkene sulfonate, Cs-C22hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate. The anionic surfactant may also be an alkyl sulfate (e.g., Ci2-Cis alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates). Among the alkyl ether sulfates are those having the formula:

[0030] RO(CH2CH2O)nSO3M wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of at least 1 .0, preferably less than 5, and most preferably 1 to 4, and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium.

[0031] The anionic surfactant may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., Ce- C22 sulfosuccinates); alkyl and acyl taurates (often methyl taurates), alkyl and acyl sarcosinates, sulfoacetates, C8-C22 alkyl phosphates and phosphonates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates, sulphoacetates, alkyl glucosides and acyl isethionates, and the like.

[0032] Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:

[0033] R1OC(O)CH2CH(SO3M)CO2M; and amide-MEA sulfosuccinates of the formula:

[0034] R1CONHCH2CH2OC(O)CH2CH(SO3M)CO2M wherein R1ranges from C8-C22 alkyl.

[0035] Sarcosinates are generally indicated by the formula:

[0036] R2CON(CH3)CH2CC>2M, wherein R2ranges from C8-C20 alkyl.

[0037] Taurates are generally identified by formula:

[0038] R3CONR4CH2CH2SO3M wherein R3is a C8-C20 alkyl, R4is a C1-C4 alkyl.

[0039] M is a solubilizing cation as previously described.

[0040] The anionic surfactant can contain Cs-Cis acyl isethionates. These esters are prepared by a reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.

[0041] The acyl isethionate may be an alkoxylated isethionate such as is described in llardi et al., U.S. Pat. No. 5,393,466, entitled "Fatty Acid Esters of Polyalkoxylated Isethonic Acid; issued Feb. 28, 1995; hereby incorporated by reference. This compound has the general formula:

[0042] R5C— (0)0— C(X)H— C(Y)H— (OCH2— CH2)m— SO3M wherein R5is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are each independently hydrogen or an alkyl group having 1 to 4 carbons and M is a solubilizing cation as previously described.

[0043] In an aspect, the anionic surfactant used is 2-acrylamido-2-methylpropane sulfonic acid, ammonium lauryl sulfate, ammonium perfluorononanoate, potassium lauryl sulfate, sodium alkyl sulfate, sodium dodecyl sulfate, sodium laurate, sodium laureth sulfate, sodium lauroyl sarcosinate, sodium stearate, sodium sulfosuccinate esters, sodium lauroyl isethionate, or a combination thereof. Such anionic surfactants are commercially available from suppliers like Galaxy Surfactants, Clariant, Sino Lion, Stepan Company, and Innospec.

[0044] Amphoteric surfactants (which depending on pH can be zwitterionic) include sodium acyl amphoacetates, sodium acyl amphopropionates, disodium acyl amphodiacetates and disodium acyl amphodipropionates where the acyl (i.e., alkanoyl group) can comprise a C7-C18 alkyl portion. Illustrative examples of amphoteric surfactants include sodium lauroamphoacetate, sodium cocoamphoacetate, or a combination thereof.

[0045] As to the zwitterionic surfactants employed, such surfactants include at least one acid group. Such an acid group may be a carboxylic or a sulphonic acid group. They often include quaternary nitrogen, and therefore, can be quaternary amino acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms and generally comply with an overall structural formula:

[0046] R6— [— 0(0)— NH(CH2)q— ]r— N+(R7)(R8)-A— B where R6is alkyl or alkenyl of 7 to 18 carbon atoms; R7and R8are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms; q is 2 to 4; r is 0 to 1 ; A is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl, and B is — CO2 — or — SO3 — .

[0047] Desirable zwitterionic surfactants include simple betaines of formula:

[0048] R6— N+(R7)(R8)-CH2CO2‘ and amido betaines of formula:

[0049] R6— CONH(CH2)t— N+(R7)(R8)-CH2CO2- where t is 2 or 3.

[0050] In both formulae R6, R7and R8are as defined previously. R6may, in particular, be a mixture of Ci2and C14 alkyl groups derived from coconut oil so that at least half, preferably at least three quarters of the groups R6have 10 to 14 carbon atoms. R7and R8are preferably methyl.

[0051] A further possibility is that the zwitterionic surfactant is a sulphobetaine of formula:

[0052] R6— N+(R7)(R8)-(CH2)3SO3' or

[0053] R6— CONH(CH2)U— N+(R7)(R8)-(CH2)3SO3- where u is 2 or 3, or variants of these in which — (CH2)3SO3‘ is replaced by — CH2C(OH)(H)CH2SO3-.

[0054] In these formulae, R6, R7and R8are as previously defined.

[0055] Illustrative examples of the zwitterionic surfactants desirable for use include betaines such as lauryl betaine, betaine citrate, cocodimethyl carboxymethyl betaine, cocoamidopropyl betaine, coco alkyldimethyl betaine, and laurylamidopropyl betaine. An additional zwitterionic surfactant suitable for use includes cocoamidopropyl sultaine, for example, cocamidopropyl hydroxysultaine. Preferred zwitterionic surfactants include lauryl betaine, betaine citrate, sodium hydroxymethylglycinate, (carboxymethyl) dimethyl-3-[(1 -oxododecyl) amino] propylammonium hydroxide, coco alkyldimethyl betaine, (carboxymethyl) dimethyloleylammonium hydroxide, cocoamidopropyl betaine, (carboxymethyl) dimethyloleylammonium hydroxide, cocoamidopropyl betaine, (carboxylatomethyl) dimethyl(octadecyl)ammonium, cocamidopropyl hydroxysultaine, or a combination thereof. Such surfactants are made commercially available from suppliers like Stepan Company, Solvay, Evonik and the like and it is within the scope of the nanoemulsions disclosed herein to employ mixtures of the aforementioned surfactants.

[0056] In an embodiment, the zwitterionic surfactant comprises cocobetaine, cocamidopropyl betaine, lauroampoacetate, hydroxysultaine, or a combination thereof. The hydroxysultaine includes lauryl hydroxysultaine.

[0057] The zwitterionic surfactant can comprise less than or equal to 30% by weight of all surfactant present in the external aqueous phase of the nanoemulsion, for examples, less than or equal to 20% by weight, for example, less than or equal to 10% by weight of all surfactant present in the external aqueous phase of the nanoemulsion.

[0058] Nonionic surfactants may optionally be used in the external aqueous phase of the nanoemulsion. When used, nonionic surfactants are typically used at levels as low as 0.5, 1 , 1.5 or 2% by weight and at levels as high as 6, 8, 10 or 12% by weight of the total nanoemulsion composition, including any and all ranges and values subsumed therein. The nonionic surfactants which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic surfactant compounds are alkyl (C6-C22) phenols, ethylene oxide condensates, the condensation products of aliphatic (Cs-Cis) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other nonionic surfactants include long chain tertiary amine oxides, long chain tertiary phosphine oxides, dialkyl sulphoxides, and the like.

[0059] In an aspect, nonionic surfactants can include fatty acid / alcohol ethoxylates having the following structures a) HOCH2(CH2)s(CH2CH2O)cH or b) HOOC(CH2)v(CH2CH2O)d H; where s and v are each independently an integer up to 18; and c and d are each independently an integer from 1 or greater. In an aspect, s and v can be each independently 6 to 18; and c and d can be each independently 1 to 30. Other options for nonionic surfactants include those having the formula HOOC(CH2)i — CH=CH — (CH2)k(CH2CH2O)zH, where i and k are each independently 5 to 15; and z is 5 to 50. In another aspect, i and k are each independently 6 to 12; and z is 15 to 35.

[0060] The nonionic surfactant can also include a sugar amide, such as a polysaccharide amide. Specifically, the surfactant can be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al., entitled "Compositions Comprising Nonionic Glycolipid Surfactants” issued Feb. 14, 1995; which is hereby incorporated by reference or it may be one of the sugar amides described in U.S. Pat. No. 5,009,814 to Kelkenberg, titled "Use of N-Poly Hydroxyalkyl Fatty Acid Amides as Thickening Agents for Liquid Aqueous Surfactant Systems" issued Apr. 23, 1991 ; hereby incorporated into the subject application by reference.

[0061] Illustrative examples of nonionic surfactants that can optionally be used in the cleansing compositions disclosed herein include, but are not limited to, polyglycoside, cetyl alcohol, decyl glucoside, lauryl glucoside, octaethylene glycol monododecyl ether, n-octyl beta-d- thioglucopyranoside, octyl glucoside, oleyl alcohol, polysorbate, sorbitan, stearyl alcohol, or a combination thereof.

[0062] In an aspect, cationic surfactants may optionally be used in the nanoemulsion of the present application.

[0063] One class of cationic surfactants includes heterocyclic ammonium salts such as cetyl or stearyl pyridinium chloride, alkyl amidoethyl pyrrylinodium methyl sulfate, and lapyrium chloride.

[0064] Tetra alkyl ammonium salts are another useful class of cationic surfactants for use. Examples include cetyl or stearyl trimethyl ammonium chloride or bromide; hydrogenated palm or tallow trimethylammonium halides; behenyl trimethyl ammonium halides or methyl sulfates; decyl isononyl dimethyl ammonium halides; ditallow (or distearyl) dimethyl ammonium halides, and behenyl dimethyl ammonium chloride.

[0065] Still other types of cationic surfactants that may be used are the various ethoxylated quaternary amines and ester quats. Examples include PEG-5 stearyl ammonium lactate (e.g., Genamin KSL manufactured by Clariant), PEG-2 coco ammonium chloride, PEG-15 hydrogenated tallow ammonium chloride, PEG 15 stearyl ammonium chloride, dipalmitoyl ethyl methyl ammonium chloride, dipalmitoyl hydroxyethyl methyl sulfate, and stearyl amidopropyl dimethylamine lactate. Still other useful cationic surfactants include quaternized hydrolysates of silk, wheat, and keratin proteins, and it is within the scope of the cleansing composition to use mixtures of the aforementioned cationic surfactants.

[0066] If used, cationic surfactants will make up no more than 1 .0% by weight of the total weight of the nanoemulsion. When present, cationic surfactants typically make up from 0.01 to 0.7%, and more typically, from 0.1 to 0.5% by weight of the total weight of the nanoemulsion, including any and all ranges subsumed therein.

[0067] In an embodiment, the anionic surfactant can comprise alkyl sulfate, alkyl ether sulfate, alkyl sulfosuccinate, alkyl taurate, acyl taurate, alkyl sarcosinate, acyl sarcosinate, sulfoacetate, Cs- C22 alkyl phosphate, C8-C22 alkyl phosphonate, alkyl phosphate ester, alkoxyl alkyl phosphate ester, acyl lactate, C8-C22 monoalkyl succinate and C8-C22 monoalkyl maleate, sulphoacetate, alkyl glucoside, acyl isethionate, or a combination thereof.

[0068] In an embodiment, the anionic surfactant can comprise 2-acrylamido-2-methylpropane sulfonic acid, ammonium lauryl sulfate, ammonium perfluorononanoate, potassium lauryl sulfate, sodium alkyl sulfate, sodium dodecyl sulfate, sodium laurate, sodium laureth sulfate, sodium lauroyl sarcosinate, sodium stearate, sodium sulfosuccinate esters, sodium cocoyl glycinate, sodium lauroyl glutamate, sodium cocoyl glutamate, sodium lauroyl isethionate, sodium cocoyl isethionate, sodium methyl lauroyl taurate, sodium methyl cocoyl taurate, sodium pareth sulfate, alpha olefin sulfonate (AOS), or a combination thereof.

[0069] In an embodiment, the anionic surfactant can comprise sodium acyl isethionate, sodium acyl methyl isethionate, sodium methyl cocoyl taurate, sodium trideceth sulphate, sodium lauryl ether sulfate-3EO, acylglutamate, acylglycinate, lauroyl sarcosinate, acyl sarcosinate or mixtures thereof. Optional amphoteric surfactants suitable for use such include coco betaine, cocamidopropyl betaine, sodium lauroamphoacetate, lauramidopropyl hydroxysultaine, cocamidopropyl hydroxysultaine, or a combination thereof.

[0070] CLEANSING COMPOSITION

[0071] Cleansing compositions comprising the nanoemulsions described herein can additionally include up to 30% by weight skin benefit agents. The term “skin benefit agent” is defined as a substance which softens or improves the elasticity, appearance, and youthfulness of the skin (stratum corneum) by either increasing its water content, adding, or replacing lipids and other skin nutrients, or both, and keeps it soft by retarding the decrease of its water content. Included among the desirable skin benefit agents are emollients, including, for example, hydrophobic emollients, hydrophilic emollients, or blends thereof. Preferred benefit agents include moisturizers, emollients, sunscreens, and anti-aging compounds.

[0072] Desirably the optional skin benefit agents used in the cleansing composition disclosed herein include niacinamide (vitamin B3), tocopherol (Vitamin E), aloe vera, alpha-hydroxy acids and esters, beta-hydroxy acids and esters, hydroxyethyl urea, polyhydroxy acids and esters, creatine, hydroquinone, t-butyl hydroquinone, mulberry, hyaluronic acid and salts thereof (including, but not limited to, Na+ and K+ salts of the same), extract, liquorice extract, resorcinol derivatives, or a combination thereof. For example, the skin benefit agent can be sodium hyaluronate. Such benefit agents, including sodium hyaluronate can be present in an amount of 0.0001 to 10%, for example, 0.001 to 6.5%, for example, 0.01 to 3.5%, and for example, 0.01% by weight, based on total weight of the cleansing composition including any and all ranges and values subsumed therein.

[0073] Further optional water-soluble skin benefit agents include acids, such as amino acids like arginine, valine or histidine, or a combination thereof. Other vitamins can be used such as vitamin B2, picolinamide, panthenol (vitamin B5), vitamin Be, vitamin C, a combination thereof or the like. Derivatives (generally meaning something that has developed or been obtained from something else), and especially, water soluble derivatives of such vitamins can also be employed. For instance, vitamin C derivatives such as ascorbyl tetraisopalmitate, magnesium ascorbyl phosphate and ascorbyl glycoside may be used alone or in combination with each other. Niacinamide derivatives such as nicotinamide adenine dinucleotide (NADH) and nicotinamide adenine dinucleotide phosphate (NADPH) may be used alone or in combination with each other. Other skin benefit agents that can be used include 4-ethyl resorcinol, extracts like sage, aloe vera, green tea, sugar cane, citrus, grapeseed, thyme, chamomile, yarrow, cucumber, liquorice, rosemary extract, or a combination thereof. Electrolytes such as sodium chloride (NaCI), potassium chloride (KOI), magnesium chloride (MgCh), or a combination thereof can also be used. The total amount of optional water-soluble benefit agents (including mixtures) when present in the composition disclosed herein can be 0.0001 to 10%, preferably, 0.001 to 6.5%, and most preferably, 0.01 to 3.5% by weight, based on total weight of the cleansing composition, including any and all ranges and values subsumed therein. It is also within the scope of the cleansing composition to optionally include oil soluble benefit agents. Illustrative examples of the types of oil soluble benefit agents that can optionally be used in the cleansing composition disclosed herein include components like stearic acid, vitamins like vitamin A, D, E and K (and their oil soluble derivatives).

[0074] Other optional oil soluble benefit agents for use include resorcinols and resorcinol derivatives like 4-hexyl resorcinol, 4-phenylethyl resorcinol, 4-cyclopentyl resorcinol, 4-cyclohexyl resorcinol 4- isopropyl resorcinol or a combination thereof. Also, 5-substituted resorcinols like 4-cyclohexyl-5- methylbenzene-1 ,3-diol, 4-isopropyl-5-methylbenzene-1 ,3-diol, combination thereof or the like may be used. The 5-substituted resorcinols and their synthesis are described in commonly assigned U.S. Patent No. 10,470,986 B2, which is incorporated by reference herein in its entirety.

[0075] Even other desirable oil soluble actives include omega-3 fatty acids, omega-6 fatty acids, climbazole, farnesol, ursolic acid, myristic acid, geranyl geraniol, oleyl betaine, cocoyl hydroxyethyl imidazoline, hexanoyl sphingosine, 12-hydroxystearic acid, petroselinic acid, conjugated linoleic acid, terpineol, thymol, or a combination thereof.

[0076] In an embodiment, the oil soluble benefit active can be a retinoic acid precursor represented by the formula: where each R is independently a hydrogen or a C1-6 alkyl group and X is any of the structures listed below and further where each R’ is hydrogen or a C1-C3 alkyl and n is an integer from 0 to 16 (preferably, 1 to 5).

[0077] The optional oil soluble benefit agent can be a retinoic acid precursor. The retinoic acid precursor can be retinol, retinal, retinyl propionate, retinyl palmitate, retinyl acetate, or a combination thereof. Retinyl propionate, retinyl palmitate, or a combination thereof can be typically preferred.

[0078] Still another retinoic acid precursor is hydroxyanasatil retinoate made commercially available under the name RETEXTRA® as supplied by Molecular Design International. The same may be used in a mixture with the oil soluble actives described herein.

[0079] When used, the oil soluble benefit agent can be present in an amount of 0.001 to 12% by weight, preferably, 0.01 to 8% by weight, more preferably, 0.1 to 6% by weight of the cleansing composition, including any and all ranges and values subsumed therein.

[0080] In still another embodiment, a peroxisome proliferator-activated receptor ligand (“PPAR”) may be included in the wash composition. The PPAR used is preferably a lipid PPAR a (alpha) activator such as a C10-18 saturated fatty acid which is branched or derivatized (i.e., functionalized) with groups like hydroxy groups. The PPAR used can also include a C10-20 monounsaturated fatty acid and C10-22 polyunsaturated fatty acids. Corresponding alcohols, triglycerides and phospholipids of any of the noted PPAR acids can also be used in the cleansing compositions disclosed herein. These include petroselinic acid, 12-hydroxystearic acid, stearic acid, cis-parinaric acid, trans-7- octadecenoic acid, cis 5,8,11 ,14,17 eicosapentanoic acid, cis-4,7, 10, 13, 16, 19 docosahexenoic acid, columbinic acid, linolenelaidic acid, ricinolaidic acid, stearidonic acid, 2-hydroxystearic acid, 10- hydroxy stearic acid, alpha-linolenic acid, arachidonic acid, cis-11 ,14-eicosadienoic acid, conjugated linoleic acid (c9,t11) or (t10,c12), conjugated linoleic acid (50:50 mix of c9, t11 and t10 d 2), coriander acid, linolelaidic acid, monopetroselinic acid, ricinoleic acid, stearolic acid or mixtures thereof.

[0081] Additional PPAR alpha activator includes cis-11 , 14, 17 eicosatrienoic acid, cis-5 eicosenoic acid, cis-8,11 ,14 eicosatrienoic acid, hexadecatrienoic acid, palmitoleic acid, petroselaidic acid, trans farnesol, cis 13, 16 docosadienoic acid, cis-vaccenic acid, cis-11 eicosenoic acid, cis-13,16,19 docosatrienoic acid, cis-13-octadecenoic acid, cis-15-octadecanoic acid, cis-7, 10, 13, 16 docosatetraenoic acid, elaidic acid, gamma-linolenic acid, geranic acid, geranyl geranoic acid, linoleic acid, oleic acid, petroselinyl alcohol, phytanic acid, pinolenic acid, tridecyl salicylic acid or a mixture thereof.

[0082] A further suitable category of PPAR alpha activator includes plant extracts, such as biochanin A (red clover phytoestrogen), chromolaena odorata extract, pomegranate saponifiable hydrolysable extract, buglossoides (stearidonic plant extract), and zanthalene (extract from Sichuan peppercorn). Such PPARs are further described in U.S. Patent No. 6,423,325, the disclosure of which is incorporated herein by reference.

[0083] In a preferred embodiment, the PPAR selected is 12-hydroxystearic acid, stearic acid, or a mixture thereof. When used, the PPAR may make up from 0.01 to 1.2%, or from 0.03 to 0.8%, or from 0.04 to 0.5%, or from 0.04 to 0.4% by weight of thecleansing composition, based on the overall weight of the cleansing composition, including any and all ranges and values subsumed therein.

[0084] In another embodiment, the cleansing composition comprises a skin prolipid rejuvenating mix comprising a C14-16 fatty acid (preferably palmitic acid), glycerol, and PPAR such as 12- hydroxystearic acid, petroselinic acid, conjugated linoleic acid, stearic acid or a mixture thereof. When used, the weight percent of the skin prolipid rejuvenating mix, collectively, in the wash compositions is 0.1 to 12%, or 0.1 to 10%, or 0.5 to 6.5%, or 0.6 to 2.5%, based on the overall weight of the cleansing composition, including any and all ranges and values subsumed therein.

[0085] In still another embodiment of the invention, the cleansing composition can comprise at least one of S-adenosyl-L-methionine, a 1 -alkyl nicotinamide having structure X, and a methionine having structure XI: wherein Rcis a C1-4 alkyl, preferably, methyl (N-methyl nicotinamide) and X is a negative counter ion, preferably, CI-, Rdis methyl, ethyl, propyl, hydroxymethyl, 2-hydroxyethyl, preferably, methyl and Reis H, methyl, ethyl, isopropyl, preferably, H (N-acetyl methionine). Such components are described in International Publication No. W02021 / 008824A1 , the disclosure of which is incorporated herein by reference. When used, 0.0001 to 10% or 0.001 to 8%, and most preferably, 0.01 to 5% or 0.01 to 3% or 0.01 to 2% or 0.01 to 1% by weight of each of such ingredients are used. In even another embodiment, the lamellar wash composition may comprise acetyl cysteine at 0.001 to 1.8% by weight, based on the overall cleansing composition, including any and all ranges and values subsumed therein.

[0086] Even other oil soluble benefit agents that can be used include omega-3 fatty acids, omega-6 fatty acids, climbazole, magnolol, honokiol, farnesol, ursolic acid, myristic acid, geranyl geraniol, oleyl betaine, cocoyl hydroxyethyl imidazoline, hexanoyl sphingosine, 10-hydroxystearic acid (10HSA), 12-hydroxystearic acid (12HSA), petroselinic acid, conjugated linoleic acid, stearic acid, palmitic acid, lauric acid, terpineol, thymol essential components, the dissolution auxiliary selected from limonene, pinene, camphene, cymene, citronellol, citronellal, geraniol, nerol, linalool, rhodinol, borneol, isoborneol, menthone, camphor, safrole, isosafrole, eugenol, isoeugenol, tea tree oil, eucalyptus oil, peppermint oil, neem oil, lemon grass oil, orange oil, bergamot oil, or a combination thereof.

[0087] When an optional (i.e. , 0.0 to 1.5% by weight) oil soluble benefit agent is used in the cleansing composition, it typically is present in an amount of 0.001 to 1 .5% by weight of the overall cleansing composition including any and all values and ranges subsumed therein, and for example, 0.05 to 1.2% by weight, for example, 0.2 to 0.75% by weight of the total weight of the cleansing composition including any and all values and ranges subsumed therein.

[0088] Other useful skin benefit agents include the following:

[0089] (a) silicone oils and modifications thereof such as linear and cyclic polydimethylsiloxanes; amino, alkyl, alkylaryl, and aryl silicone oils;

[0090] (b) fats and oils including natural fats and oils such as jojoba, soybean, sunflower, rice bran, avocado, almond, olive, sesame, persic, castor, coconut, and mink oils; cacao fat; beef tallow and lard; hardened oils obtained by hydrogenating the aforementioned oils; and synthetic mono, di and triglycerides such as myristic acid glyceride and 2-ethylhexanoic acid glyceride;

[0091] (c) waxes such as carnauba, spermaceti, beeswax, lanolin, and derivatives thereof;

[0092] (d) hydrophobic and hydrophilic plant extracts; (e) hydrocarbons such as liquid paraffin, petrolatum, microcrystalline wax, ceresin, squalene, pristan and mineral oil;

[0093] (f) higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PLIFA);

[0094] (g) higher alcohols such as lauryl, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol;

[0095] (h) esters such as cetyl octanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol monolaurate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate;

[0096] (i) essential oils and extracts thereof such as mentha, jasmine, camphor, white cedar, bitter orange peel, ryu, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, peppermint, rose, sage, sesame, ginger, basil, juniper, lemon grass, rosemary, rosewood, avocado, grape, grapeseed, myrrh, cucumber, watercress, calendula, elder flower, geranium, linden blossom, amaranth, seaweed, ginko, ginseng, carrot, guarana, tea tree, jojoba, comfrey, oatmeal, cocoa, neroli, vanilla, green tea, penny royal, aloe vera, menthol, cineole, eugenol, citral, Citronelle, borneol, linalool, geraniol, evening primrose, camphor, thymol, spirantol, penene, limonene, and terpenoid oils;

[0097] (j) polyhydric alcohols, for example, glycerine, sorbitol, propylene glycol, and the like; and polyols such as the polyethylene glycols, examples of which are: POLYOX™ WSR-205 PEG 14M, POLYOX™ WSR-N-60K PEG 45M, or POLYOX™ WSR-N-750, and PEG 7M;

[0098] (k) lipids such as cholesterol, ceramides, sucrose esters and pseudo-ceramides as described in European Patent Specification No. 556,957;

[0099] (l) vitamins, minerals, and skin nutrients such as milk, vitamins A, E, and K; vitamin alkyl esters, including vitamin C alkyl esters; magnesium, calcium, copper, zinc and other metallic components; (m) sunscreens such as octyl methoxyl cinnamate (Parsol MCX) and butyl methoxy benzoylmethane (Parsol 1789);

[0100] (n) phospholipids; and

[0101] (o) anti-aging compounds such as alpha-hydroxy acids and beta-hydroxy acids.

[0102] Preferred skin benefit agents include fatty acids, hydrocarbons, polyhydric alcohols, polyols, and mixtures thereof, with emollients that include at least one C12 to C18 fatty acid, petrolatum, glycerol, glycerin, sorbitol, and / or propylene glycol being of particular interest in one or more embodiments. The agents may be added at an appropriate step during the process of making the cleansing compositions. Some benefit agents may be introduced as macro domains.

[0103] The cleansing composition can further comprise a humectant. The humectant can be present in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 0.75 to 8% by total weight of the cleansing composition, including any and all ranges and values subsumed therein. The humectant can be employed to assist in moisturization effects of the cleansing composition. Humectants are generally known as moisturizers that attract water from the air or deeper in the skin. Stated another way, humectants draw water into the skin, hair, or nails. The humectants can generally be polyhydric alcohol type materials. Typical polyhydric alcohols include glycerol (i.e., glycerine or glycerin), propylene glycol, dipropylene glycol, polypropylene glycol (e.g., PPG-9), polyethylene glycol, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1 ,3- butylene glycol, isoprene glycol, 1 ,2,6-hexanetriol, ethoxylated glycerol, propoxylated glycerol, or a combination thereof. Most preferred is glycerin, propylene glycol, dipropylene glycol, or a combination thereof. In an embodiment, the humectant can be propylene glycol, butylene glycol, dipropylene glycol, glycerin, triethylene glycol, erythritol, capryl glycol, hyaluronic acid, polypropylene glycol-7 proypyl heptyl ether, or a combination thereof. In an embodiment, the humectant is glycerin and can be present in an amount of 0.1 to 1.0% by weight of the overall cleansing composition, preferably 0.25 to 0.75% by weight of the overall cleansing composition, more preferably, 0.4 to 0.7% by weight of the overall cleansing composition, including any and all ranges and values subsumed therein.

[0104] Other optional ingredients like antioxidants, fragrances, perfumes, polymers, chelating agents, colorants, deodorants, dyes, enzymes, foam boosters, germicides, anti-microbials, lathering agents, pearlescers, skin conditioners, stabilizers, or superfatting agents, may be added in suitable amounts in the process of making the cleansing compositions.

[0105] Additional optional ingredients which may be present in the cleansing compositions are, for example: fragrances; sequestering and chelating agents such as tetrasodium ethylenediaminetetraacetate (EDTA), ethane hydroxyl diphosphonate (EHDP), sodium phytate, tetra sodium glutamate diacetate and / or sodium gluconate, and etidronic acid, aka 1- hydroxyethylidene diphosphonic acid (HEDP); coloring agents; opacifiers, and pearlizers such as zinc stearate, magnesium stearate, titanium dioxide (TiCh), ethylene glycol monostearate (EGMS), ethylene glycol distearate (EGDS) or Lytron 621 (Styrene / Acrylate copolymer), and the like; pH adjusters; antioxidants, for example, butylated hydroxytoluene (BHT) and the like; stabilizers; suds boosters, such as for example, coconut acyl mono- or diethanol amides; ionizing salts, such as, for example, sodium chloride and sodium sulfate, and other ingredients such as are conventionally used in cleansing compositions. The total amount of such additional optional ingredients is typically from 0 to 10% by weight, more particularly from 0.1 to 5% by weight, based on the total weight of the cleansing composition, including any and all ranges and values subsumed therein.

[0106] The cleansing compositions disclosed herein can be used to deliver antimicrobial benefits. Antimicrobial agents that can be included to deliver these benefits include oligodynamic metals or compounds thereof. Preferred metals are silver, copper, zinc, gold, or aluminum. Silver is particularly preferred. In the ionic form it may exist as a salt or any compound in any applicable oxidation state. Preferred silver compounds are silver oxide, silver nitrate, silver acetate, silver sulfate, silver benzoate, silver salicylate, silver carbonate, silver citrate, silver phosphate, or a combination thereof, with silver oxide, silver sulfate and silver citrate being of particular interest in one or more embodiments. In at least one aspect, the silver compound is silver oxide. Oligodynamic metal or a compound thereof can be included in an amount of 0.0001 to 2%, preferably 0.001 to 1 % by weight of the cleansing composition, including any and all ranges and values subsumed therein. Alternately, an essential oil antimicrobial active may be included in the cleansing composition. Essential oil actives which can be included are terpineol, thymol, carvacol, (E)-2(prop-1-enyl) phenol, 2-propylphenol, 4-pentylphenol, 4-sec-butylphenol, 2-benzyl phenol, eugenol, or a combination thereof. Furthermore, preferred essential oil actives are terpineol, thymol, carvacrol, thymol, or a combination thereof, with the most preferred being terpineol or thymol, or a combination thereof. When present, essential oil actives can be included in an amount of 0.001 to 1 %, preferably 0.01 to 0.5% by weight of the composition, including any and all ranges and values subsumed therein.

[0107] Even other ingredients which may be used include octopirox (piroctone), zinc pyrithione, chloroxylenol, triclosan, cetylpyridinium chloride, as well as silver compounds including silver oxide, nitrate, sulfate, phosphate, carbonate, acetate, benzoate, a combination thereof or the like. If used, these other components typically make up from 0.001 to 1.6% by weight of the overall cleansing composition including any and all values and ranges subsumed therein, and preferably, from 0.01 to 1.2% by weight of the overall cleansing composition including any and all values and ranges subsumed therein.

[0108] Preservatives can be used in the cleansing composition disclosed herein. When used, illustrative preservatives for use include sodium benzoate, iodopropynyl butyl carbamate (IPBC), caprylyl glycol (1 ,2-octane diol), phenoxyethanol, hydroxyacetophenone, ethylhexylglycerine, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate, propanediol, dimethyldimethyl (DMDM) hydantoin, alkyl esters of para-hydroxybenzoic acid, organic acids and salts thereof, hydroxyacetophenone, climbazole, propionate salts, a variety of quaternary ammonium compounds, benzyl alcohol, or a combination thereof. Other preservatives suitable for use include sodium dehydroacetate, chlorophenesin, and decylene glycol. GALGUARD® Lipo G (capryloyl glycine), commercially available from TRI-K is an amino acid based antimicrobial booster technology that can assist in preservation of the cleansing composition disclosed herein. Preservatives can be employed in amounts of 0.01% to 2.0% by weight of the total weight of cleansing composition, including any and all values and ranges and values subsumed therein.

[0109] Fragrances, fixatives, opacifiers (like titanium dioxide or glycol distearate), and chelating agents can optionally be included in the cleansing composition. Possible chelating agents include, but are not limited to, ethylyene diaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene diamine disuccinic acid (EDDS), pentasodium diethylenetriaminepentaacetate, trisodium N-(hydroxyethyl)-ethylenediaminetracetate, an acid form of EDTA, sodium thiocynate, trisodium salt of methylglycinediacetic acid, tetrasodium glutamate diacetate and phytic acid, preferably wherein the chelating agent can be ethylene diaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene diamine disuccinic acid (EDDS), or a combination thereof. Each of these substances may be present in an amount of about 0.03 to about 3% by weight of the overall cleansing composition including all values and ranges subsumed therein, preferably, about 0.1 to about 2.6% by weight, weight of the overall cleansing composition, including all values and ranges subsumed therein.

[0110] The cleansing compositions can additionally comprise a viscosity adjusting agent. The viscosity adjusting agent can be a salt. The salt can comprise sodium chloride, potassium chloride, or a combination thereof. In an embodiment, the viscosity is a salt and the salt is sodium chloride, potassium chloride, or a combination thereof. The salt can be present in an amount of less than or equal to 1 % of the overall cleansing composition.

[0111] In an embodiment, the cleansing composition comprises 0.2 to 8% by weight of the oil droplets, for example, 0.3 to 7% by weight of the oil droplets, for example, 0.4 to 6% by weight of the oil droplets, based on the overall cleansing composition, including any and all ranges and values subsumed therein.

[0112] When a nanoemulsion is not the end use composition, the consumer will be instructed to mix the nanoemulsion and end use composition (leave-on or wash off) in his or her hands until a homogeneous mixture is made. Upon obtaining a homogeneous mixture, product may then be topically applied. In a most preferred embodiment and when a nanoemulsion and end use composition are mixed, 2 to 50% by weight, and preferably, 5 to 35% by weight, and most preferably, 10 to 25% by weight nanoemulsion is used based on total weight of nanoemulsion and end use composition, including any and all ranges and values subsumed therein.

[0113] Since water is present, traditional preservatives found in topical consumer products may be used. The preservatives typically make up from 0.01 to 3% by weight of the total weight of the nanoemulsion or cleansing composition, for example, 0.01 to 2.0% by weight of the total weight of the nanoemulsion or cleansing composition, including any and all ranges and values subsumed therein. Preservatives can desirably be incorporated into the nanoemulsion or cleansing composition to protect against the growth of potentially harmful microorganisms. Cosmetic chemists are familiar with appropriate preservatives and routinely choose them to satisfy the preservative challenge test and to provide product stability.

[0114] Inorganic salt is an optional but often desired ingredient to aid in composition thickening. Salts that may be used include NaCI, KCI, MgCh, CaCh, combinations thereof, or the like. Typically, the inorganic salt makes up 0 to 10% by weight, and preferably, 0.001 to 12% by weight, more preferably, from 0.05 to 4.5% by weight, and even more preferably, 0.09 to 2% by weight of the concentrated cleansing composition, including any and all ranges and values subsumed therein.

[0115] Polymeric viscosity aids are an optional but often desired ingredient in the cleansing composition. Preferred polymers are those generally classified as high molecular weight ethoxylated fatty acid esters. Illustrative examples include PEG 120 methyl glucose dioleate, PEG 18 glyceryloleate / cocoate, PEG 150 pentaerythritol tetrastearate, or combinations thereof, or the like. One polymeric viscosity aid is PEG 150 pentaerythritol tetrastearate which is sold under the VERSATHIX™ name by Croda. When used, such aids make up from 0.001 to 0.8%, and preferably, from 0.001 to 0.5%, and most preferably, from 0.001 to 0.3% by weight of the cleansing composition, including any and all ranges and values subsumed therein.

[0116] Adjusters to modify / buffer the pH may be used. Such pH adjusters include triethylamine, sodium hydroxide (NaOH), potassium hydroxide (KOH), sulfuric acid (H2SO4), hydrogen chloride (HCI), CeHsO? (i.e. , citric acid), C3H6O3 (i.e. , lactic acid), or a combination thereof. The pH adjusters are added at amounts to yield the desired final pH. The pH adjusters can include various alphahydroxy acids or a combination thereof. For example, the pH adjusters can comprise the alphahydroxy acids of citric acid, glycolic acid, lactic acid, malic acid, tartaric acid, or a combination thereof. The pH values can be assessed with commercial instrumentation such as a pH meter made commercially available from Thermo Scientific®. The pH adjusters can be present in an amount of 0.1 to 1 .0% by weight of the cleansing composition, including any and all ranges and values subsumed therein, for example, 0.1 to 0.75% by weight of the cleansing composition, including any and all ranges and values subsumed therein.

[0117] The pH of the composition is assessed by using conventional instrumentation such as a pH meter made commercially available from Thermo Scientific®. A pH of the cleansing composition can be 3 to 9, preferably, 4 to 8, more preferably, 5 to 7.

[0118] The cleansing compositions disclosed herein typically contain water in an amount of 20 to 95% by weight, more particularly 50 to 93% by weight, more specially, 60 to 90% by weight, based on the total weight of the cleansing composition, including any and all ranges and values subsumed therein. Such water contents are representative of a relatively broad range of formulations, including both concentrated and non-concentrates products, with formulations having water contents of 20 to less than 50% by weight of water being typical of concentrated products. When making the cleansing compositions disclosed herein, the desired ingredients can be mixed with conventional apparatus under moderate shear and atmospheric conditions, with a temperature of 30 to 85°C whereby shear continues until a homogeneous product is recovered. As previously noted, occlusive having a droplet size of less than 1 micrometer is preferably provided as an ingredient as an emulsion with submicron droplets (i.e. , nanoemulsion).

[0119] NANOEMULSION

[0120] Neutralizer desirable for use to neutralize fatty acid in the present nanoemulsion is limited to the extent that the same may be used in a topical composition and is able to neutralize up to 100% by weight of the fatty acid within the nanoemulsion. Preferred neutralizers include sodium hydroxide (NaOH), potassium hydroxide (KOH), triethanolamine, or a combination thereof. It is within the scope of the present nanoemulsions to add, with or in lieu of fatty acid and neutralizer, fatty acid soap, and fatty acid soap with additional neutralizer.

[0121] As to the amount of neutralizer employed to make the nanoemulsions, the same is adjusted so that 10 to 100%, and preferably, 20 to 85%, and most preferably, 35 to 65% by weight of all fatty acid within the nanoemulsion is neutralized. To the extent neutralization of the fatty acid exceeds 70%, it is especially preferred that less than 55%, and most preferably, less than 50% by weight of the total neutralizer used is NaOH when the fatty acid used is saturated, linear, and Ci6 or greater.

[0122] In another preferred embodiment, if fatty acid neutralization is to exceed 70% with NaOH as the neutralizer, it is preferred that more than 45%, and preferably, more than 50% by weight of the fatty acid used to make the nanoemulsion is branched and saturated, and / or linear and unsaturated.

[0123] Optionally, additional anionic and amphoteric surfactants can be used when preparing the nanoemulsion. When present, the nanoemulsion comprises less than 6% by weight, and preferably, 0.001 to 4% by weight of the additional surfactants.

[0124] In a preferred embodiment a water miscible liquid is not used in the aqueous phase. Preferably, water makes up at least 25%, by weight, of the external aqueous phase, preferably at least 50%, even more preferably at least 75% of the external aqueous phase, by weight of the external aqueous phase. In a preferred embodiment, the external aqueous phase comprises water and a water miscible liquid. Preferably, the water miscible liquid makes up 5 to 75% by weight of the aqueous phase.

[0125] In another preferred embodiment, the external aqueous phase comprises water and a surfactant, where the surfactant comprises 1.5 to 15% by weight of the total weight of the nanoemulsion.

[0126] As to the external aqueous phase (water; water and water miscible liquid mixed therewith; water and surfactant; water, surfactant, and water miscible liquid mixed therewith), the same typically makes up 20 to 55% by weight, and preferably, from 25 to 45% by weight, and most preferably, from 30 to 40% by weight of the total weight of the nanoemulsion.

[0127] Preferred water miscible liquids include those classified as humectants like glycerol, sorbitol, hydroxypropyl sorbitol, hexyleneglycol, 1 ,3-butylene glycol, 1 ,2,6-hexanetriol, ethoxylated glycerine, propoxylated glycerine, or a combination thereof.

[0128] For example, the water miscible liquid used can be glycerol. Typically, the water miscible liquid to water weight ratio is from 1 :3 to 3: 1 , and preferably, 1 :2.5 to 2.5: 1 , and most preferably, 1.5:1 to 1 :1.5, including all ratios subsumed therein.

[0129] It is within the scope to include water soluble actives within the aqueous phase of the nanoemulsion. Such water soluble actives are limited only to the extent that they can be used in topical compositions. Illustrative examples of the water soluble actives that can be used include niacinamide, picolinamide, ascorbic acid, salicylic acid, dihydroxyacetone, extracts, like pomegranate extract, vitamins, like Vitamin C, as well as sunscreens such as the salts of benzophenone-4 and phenylbenzimidazole sulfonic acid. Mixtures and water soluble derivatives of the same can also be used. Typically, when used in the nanoemulsion, water soluble active makes up from 0.0 to 6%, and preferably, from 0.001 to 5%, and most preferably, from 0.01 to 4%, based on total weight of the nanoemulsion and including any and all ranges subsumed therein.

[0130] Methods of making the nanoemulsion are also contemplated. When manufacturing the nanoemulsion, ingredients are first mixed (i.e. , oil phase to water phase, or water phase to oil phase or simultaneously) in a conventional mixing vessel equipped with a rotor / stator high shear device to produce a macroemulsion. The high shear mixing device used, which may be in line or within the mixing vessel, is commercially available from suppliers like ESCO-LABOR AG and Silverson®. The macroemulsion produced typically has a volume average droplet diameter size (D[4,3]) of less than 8 micrometers, and preferably, less than 5 micrometers, and most preferably, less than 2 micrometers as measured with an art recognized Malvern Mastersizer. Rotor speed is often 1 ,000 to 8,000 revolutions per minute (rpm), and preferably, 2,000 to 7,500 rpm, and most preferably, 3,000 to 7,000 rpm. The time required to homogeneously mix the ingredients is the time for a theoretical pass minimum, yielding the desired homogeneous macroemulsion.

[0131] Alternatively, the macroemulsion may be made in a continuous mode, by supplying the internal oil phase and external aqueous phase simultaneously into a low pressure homogenizer (e.g., low pressure sonolator), typically operating at 100 to less than 500 pounds per square inch (psi) (0.7 MPa to 3.45 MPa), made commercially available from Sonic Corporation of Connecticut, USA).

[0132] The macroemulsion prepared is then passed through a device, e.g., a high pressure device, i.e., a high pressure homogenizer or a high pressure sonolator to form the desired nanoemulsion. The high pressure homogenizers desirable for use are the art recognized devices that may be operated at 600 to 7000 psi (4.14 to 48.3 MPa), for example, at a pressure of greater than or equal to 1000 pounds per square inch (psi) (6.9 MegaPascals (MPa), for example, 1500 to 5000 psi (10.3 to 34.5 MPa) to form the nanoemulsion, for example, 1500 to 4500 psi (10.3 to 31 MPa), for example, 2000 to 4000 psi (13.8 to 27.6 MPa). Generally, sonolators can operate as pressures of 100 to 5000 psi (0.7 to 34.5 MPa). For pressures above 500 psi 3.4 MPa, the sonolator can be referred to as a high pressure sonolator. Those made commercially available from BEE International, Massachusetts, USA (manufacturer of DeBee series homogenizers) and Sonic Corporation of Connecticut, USA (manufacturer of high pressure sonolators) are desirable for use.

[0133] When formed, the nanoemulsion comprises oil based droplets having a volume average diameter size (D[4,3]) of 100 nanometers (nm) to 750 nm after dilution and homogenization, for example, 100 nm to 500 nm, for example, 125 nm to 400 nm, in terms of volume average diameter, D[4,3], including any and all ranges and values subsumed therein.

[0134] When water miscible liquid is included in the water (external aqueous) phase and fatty acid is included in the oil phase, high pressure homogenization is not required to produce the nanoemulsion of the aforementioned diameter sizes. Therefore, a nanoemulsion of desired diameter is produced after mixing solely with a commercially available rotor / stator device (or low pressure homogenizer) under the conditions described above with respect to the low pressure homogenizer, e.g., typically operating at 100 to less than 500 pounds per square inch (psi) (0.689 MPa to 3.45 MPa).

[0135] In an embodiment, a water miscible liquid makes up from 25 to 75% by weight of the water miscible phase and the nanoemulsion is produced without homogenization that exceeds 500 psi (3.45 MPa).

[0136] In an embodiment, an aqueous phase with water soluble components and an internal oil phase with oil soluble components are each first mixed and prepared prior to mixing all ingredients with a high shear mixing device. If a phase is unclear and / or not homogeneous, it is within the scope to separately heat each phase to a temperature of 30 to 85°C, and preferably, 40 to 80°C, and most preferably, 45 to 75°C until a homogeneous solution or mixture is obtained.

[0137] The pH of the resulting nanoemulsions can typically be 5 to 10, and preferably, 6.5 to 8.5, including any and all ranges and values subsumed therein.

[0138] The nanoemulsions can be used as end use compositions, and therefore, applied topically to hair and / or skin directly by consumers. It is also within the scope of the present nanoemulsions to add the nanoemulsion to a commercially available end use product to boost the efficacy of such end use product.

[0139] Since the nanoemulsions are water continuous, it is preferred that the end use composition used with the nanoemulsion is also water continuous. The nanoemulsions can be used in cleansing compositions, for example, a cleansing composition. The cleansing composition can be a liquid cleansing composition, for example, an isotropic liquid cleansing composition. In an embodiment, the cleansing composition is an isotropic liquid cleansing composition. In an embodiment, the cleansing composition is a facewash, a bodywash, a handwash, or a shampoo.

[0140] Viscosity, unless noted otherwise, was measured with a Discovery HR-2 Rheometer using sand blasted plates with a 1000 micron gap at 25°C and 30 second intervals and a shear rate of 4 s’1. The cleansing compositions disclosed herein had a viscosity change of less than or equal to 30% a two-week time period stored at 50°C measured using a Discovery HR-2 Rheometer using sand blasted plates having a 1000 micron gap, at 25°C and equilibrated for 30 seconds before the viscosity measurement and measured at a shear rate of 4 s’1. Furthermore, the cleansing composition can be stable down to a temperature of 5°C and have a viscosity drift of less than or equal to 30%, preferably, less than or equal to 20%, more preferably, less than or equal to 20% after exposure for 2 weeks 50°C.

[0141] Preservatives for use include hydantoin derivatives and propionate salts. Particularly preferred preservatives include iodopropynyl butyl carbamate, phenoxyethanol, 1 ,2-alkane diols, hydroxyacetophenone, ethylhexylglycerine, hexylene glycol, methyl paraben, propyl paraben, benzyl alcohol, benzoic acid, potassium sorbate, sodium benzoate, iodopropynyl butyl carbamate, caprylyl glycol (CAPG), 1 ,2-octanediol, hydroxyacetophenone, ethylhexylglycerine, hexylene glycol, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate, dimethyl-dimethyl (DMDM) hydantoin, or a combination thereof. Other preservatives include sodium dehydroacetate, chlorophenesin, decylene glycol, or a combination thereof. The preservatives should be selected having regard for the use of the composition and possible incompatibilities between the preservatives and other ingredients in the nanoemulsion or cleansing composition. Preservatives are preferably employed in amounts ranging from 0.01% to 2.0% by weight of the total weight of the end use composition (up to 7% by weight of total cleansing composition), including any and all ranges subsumed therein. Preservatives include sodium benzoate, benzoic acid, potassium sorbate, phenoxy ethanol, CAPB, or a combination thereof.

[0142] Emulsifiers having an HLB of greater than 8 may optionally be used. Illustrative examples include Tween 40, 60, 80, polysorbate 20, or a combination thereof. Typically, emulsifiers for water continuous systems make up from 0.3 to 2.5% by weight of the total weight of the nanoemulsion or cleansing composition.

[0143] Humectants can be employed as additives in the nanoemulsion or cleansing composition to assist in moisturization when such emulsions are topically applied. These are generally polyhydric alcohol type materials. Typical polyhydric alcohols include glycerol (i.e., glycerine or glycerin), propylene glycol, dipropylene glycol, polypropylene glycol (e.g., PPG-9), polyethylene glycol, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1 ,3-butylene glycol, isoprene glycol, 1 ,2,6- hexanetriol, ethoxylated glycerol, propoxylated glycerol, or a combination thereof. Most preferred is glycerin, propylene glycol, dipropylene glycol, or a combination thereof. In an embodiment, the humectant can be propylene glycol, butylene glycol, dipropylene glycol, glycerin, triethylene glycol, erythritol, capryl glycol, hyaluronic acid, or a combination thereof. Often, humectant makes up from 0.0 to 35%, and preferably, 0.001 to 20% by weight, more preferably, 0.5 to 15% by weight (most preferably, 0.75 to 12% by weight) of the total weight of the nanoemulsion, including any and all ranges and values subsumed therein.

[0144] Thickening agents are optionally suitable for use in the cleansing composition. Particularly useful are polysaccharides. Examples include fibers, starches, natural / synthetic gums, and cellulosics. Representative of the starches are chemically modified starches such as sodium hydroxypropyl starch phosphate, and aluminum starch octenylsuccinate. Tapioca starch is often preferred, as is maltodextrin. Suitable gums include xanthan, sclerotium, pectin, karaya, arabic, agar, guar (including Acacia Senegal guar), carrageenan, alginate, or a combination thereof. Suitable cellulosics include hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethylcellulose, sodium carboxy methylcellulose (cellulose gum / carboxymethyl cellulose), and cellulose (e.g., cellulose microfibrils, cellulose nanocrystals or microcrystalline cellulose). Sources of cellulose microfibrils include secondary cell wall materials (e.g., wood pulp, cotton), bacterial cellulose, and primary cell wall materials. Preferably the source of primary cell wall material is selected from parenchymal tissue from fruits, roots, bulbs, tubers, seeds, leaves, and combination thereof; more preferably is selected from citrus fruit, tomato fruit, peach fruit, pumpkin fruit, kiwi fruit, apple fruit, mango fruit, sugar beet, beet root, turnip, parsnip, maize, oat, wheat, peas, and combinations thereof; and even more preferably is selected from citrus fruit, tomato fruit, and combinations thereof. A most preferred source of primary cell wall material is parenchymal tissue from citrus fruit. Citrus fibers, such as those made available by HERBACEL® as AQ Plus can also be used as source for cellulose microfibrils. The cellulose sources can be surface modified by any of the known methods including those described in Colloidal Polymer Science, Kalia et al., “Nanofibrillated cellulose: surface modification and potential applications” (2014), Vol 292, Pages 5-31.

[0145] Synthetic polymers, in addition to polymeric viscosity aids, are yet another class of effective thickening agents that can optionally be used. This category includes crosslinked polyacrylates such as the Carbomers, polyacrylamides such as SEPIGEL® 305 and taurate copolymers such as SIMULGEL® EG and ARISTOFLEX® AVC, the copolymers being identified by respective INCI nomenclature as sodium acrylate / sodium acryloyldimethyl taurate and acryloyl dimethyltaurate / vinyl pyrrolidone copolymer. Another preferred synthetic polymer suitable for thickening is an acrylate-based polymer made commercially available by Seppic and sold under the name SIMULGEL™ INS100. Calcium carbonate, fumed silica, and magnesium-aluminum- silicate can also be used. Carbomer can also be used as a suspending agent. Carbomer can be present in an amount of 0.1 to 0.5% by weight, based on the total weight of the cleansing composition, for example, 0.2 to 0.4% by weight.

[0146] The amounts of optional thickening agent, when used, may range from 0.001 to 5% by weight of the compositions. Maltodextrin, xanthan gum, and carboxymethyl cellulose are the often preferred optional thickening agents. In an embodiment, the thickening agent can comprise sodium chloride, silica, bentonite, magnesium aluminium silicate, carbomer, cellulose, or a combination thereof.

[0147] The cleansing composition can further comprise a cationic polymer. The cationic polymer can function as a thickening agent, deposition aid and skin conditioner. Cationic polymer such as modified polysaccharides including cationic guar available from Rhone Poulenc under the trade name JAGUAR® C13S, JAGUAR® C14S, JAGUAR® C17, or JAGUAR® C16; cationic modified cellulose such as UCARE™ Polymer JR 30 or JR 40 from Amerchol; N-HANCE® 3000, N- HANCE® 3196, N-HANCE® GPX 215 or N-HANCE® GPX 196 from Hercules; synthetic cationic polymer such as MERQUAT® 100, MERQUAT® 280, MERQUAT® 281 and MERQUAT® 550 sold by Nalco; cationic starches such as STALOK® 100, 200, 300 and 400 sold by Staley Inc.; cationic galactomannans such as GALACTASOL® 800 series by Henkel, Inc.; QUADROSOFT® LM-200; and Polyquaternium-24.

[0148] The cleansing composition can further comprise a stabilizing polymer, a structuring polymer, a starch, a gum, or a combination thereof.

[0149] Particularly preferred thickening agents include an anionic polymer-based thickener, preferably, for example, a polyacrylate based polymer or copolymer, or a combination thereof. Polysaccharides can be used. Examples include fibers, starches, natural / synthetic gums and cellulosics. Representative of the starches are chemically modified starches such as sodium hydroxypropyl starch phosphate and aluminum starch octenylsuccinate. Tapioca starch is often preferred, as is maltodextrin. Suitable gums include xanthan, sclerotium, pectin, karaya, arabic, agar, guar (including Acacia Senegal guar), carrageenan, alginate, and combinations thereof. Suitable cellulosics include hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethylcellulose, sodium carboxy methylcellulose (cellulose gum / carboxymethyl cellulose) and cellulose (e.g., cellulose microfibrils, cellulose nanocrystals or microcrystalline cellulose). Sources of cellulose microfibrils include secondary cell wall materials (e.g. wood pulp, cotton), bacterial cellulose, and primary cell wall materials. Preferably the source of primary cell wall material is selected from parenchymal tissue from fruits, roots, bulbs, tubers, seeds, leaves and combination thereof; more preferably can be selected from citrus fruit, tomato fruit, peach fruit, pumpkin fruit, kiwi fruit, apple fruit, mango fruit, sugar beet, beet root, turnip, parsnip, maize, oat, wheat, peas and combinations thereof; and even more preferably can be selected from citrus fruit, tomato fruit, or a combination thereof. A most preferred source of primary cell wall material can be parenchymal tissue from citrus fruit. Citrus fibers, such as those made available by HERBACEL® as AQ Plus can also be used as source for cellulose microfibrils.

[0150] As mentioned, synthetic polymers are effective thickening agents. This category includes crosslinked polyacrylates such as the Carbomers, polyacrylamides such as SEPIGEL® 305 and taurate copolymers such as SIMULGEL® EG and ARISTOFLEX® AVC, the copolymers being identified by respective INCI nomenclature as sodium acrylate / sodium acryloyldimethyl taurate and acryloyl dimethyltaurate / vinyl pyrrolidone copolymer. Another preferred synthetic polymer suitable for thickening is an acrylate-based polymer made commercially available by Seppic and sold under the name SIMULGEL™ INS100. Calcium carbonate, fumed silica, and magnesium- aluminum-silicate may also be used.

[0151] Sodium hydroxypropyl starch phosphate, aluminum starch octenylsuccinate, tapioca starch, maltodextrin, xanthan gum, agar gum, guar gum, carrageenan gum, alginate gum, hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethylcellulose, sodium carboxy methylcellulose, cellulose, polyethylene glycol (e.g., polyethylene glycol diester stearic acid), or a combination thereof are further examples of thickening agents for use in the present cleansing compositions. Such thickening agents are commercially available from the Dow Chemical Company or the Hallstar Company.

[0152] Other optional ingredients include water soluble / dispersible polymers. These polymers can be cationic, anionic, amphoteric or nonionic types with molecular weights higher than 100,000 Dalton. They are known to increase the viscosity and stability of liquid personal cleansing formulation, to enhance in-use and after-use skin sensory properties, and to enhance lather creaminess and lather stability. When present, the total amount of such polymers commonly ranges from 0.1 to 10% by weight of the personal cleansing formulation, including any and all ranges and values subsumed therein. Examples of water soluble or dispersible polymers include the carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xanthan gum, or a combination thereof; modified and nonmodified starch granules and pregelatinized cold water soluble starch; emulsion polymers such as ACLILYN® 28, ACLIYLN® 22 or CABOPOL® Aqua SF1 ; cationic polymer such as modified polysaccharides including cationic guar available from Rhone Poulenc under the trade name JAGUAR® C13S, JAGUAR® C14S, JAGUAR® C17, or JAGUAR® C16; cationic modified cellulose such as UCARE™ Polymer JR 30 or JR 40 from Amerchol; N-HANCE® 3000, N-HANCE® 3196, N-HANCE® GPX 215 or N-HANCE® GPX 196 from Hercules; synthetic cationic polymer such as MERQUAT® 100, MERQUAT® 280, MERQUAT® 281 and MERQUAT® 550 sold by Nalco; cationic starches such as STALOK® 100, 200, 300 and 400 sold by Staley Inc.; cationic galactomannans such as GALACTASOL® 800 series by Henkel, Inc.; QUADROSOFT® LM-200; and Polyquaternium-24. Also suitable are high molecular weight polyethylene glycols such as POLYOX® WSR-205 (PEG 14M), POLYOX® WSR-N-60K (PEG 45), and POLYOX® WSR-301 (PEG 90M).

[0153] The inventive cleansing composition possesses isotropic micellar phase microstructure. The rheological behavior of all surfactant solutions, including liquid cleansing solutions, is strongly dependent on the microstructure, i.e., the shape and concentration of micelles or other selfassembled structures in solution. When there is sufficient surfactant to form micelles (concentrations above the critical micelle concentration or CMC), for example, spherical, cylindrical (rod-like or discoidal), spherocylindrical, or ellipsoidal micelles may form. As surfactant concentration increases, ordered liquid crystalline phases such as lamellar phase, hexagonal phase, cubic phase or L3 sponge phase may form. The non-isotropic hexagonal phase consists of long cylindrical micelles arranged in a hexagonal lattice. In general, the microstructure of most personal care products consist of either an isotropic dispersion including spherical micelles; and rod micelles; or an ordered liquid crystalline phase such as a lamellar dispersion.

[0154] As noted above, micelles may be spherical or rod-like. Formulations having spherical micelles tend to have a low viscosity and exhibit Newtonian shear behavior (i.e., viscosity stays constant as a function of shear rate; thus, if easy pouring of product is desired, the solution is less viscous. In these systems, the viscosity increases linearly with surfactant concentration. Rod micellar solutions are more viscous because movement of the longer micelles is restricted. At a critical shear rate, the micelles align and the solution becomes shear thinning. Addition of salts increases the size of the rod micelles thereof increasing zero shear viscosity (i.e., viscosity when sitting in bottle) which helps suspend particles but also increases critical shear rate (point at which product becomes shear thinning; higher critical shear rates means that the product is more difficult to pour).

[0155] In an embodiment, the cleansing composition is essentially sulfate free. In an embodiment, the cleansing composition is sulfate free.

[0156] In an embodiment, the cleansing composition is essentially 1 ,4-dioxane free, preferably, the cleansing composition is 1 ,4-dioxane free.

[0157] In an embodiment, the cleansing composition is essentially paraben free and essentially phthalate free, preferably, the cleansing composition is paraben free and phthalate free.

[0158] Substantially free or essentially free as used herein refers to an amount of less than or equal to 100 parts per million in the cleansing composition, for example, less than 50 ppm in the cleansing composition, for example, less than or equal to 25 ppm in the cleansing composition, for example, less than or equal to 10 ppm in the cleansing composition, for example, less than or equal to 5 ppm in the cleansing composition, for example, less than or equal to 4 ppm in the cleansing composition, for example, less than or equal to 2 ppm in the cleansing composition, for example, less than or equal to 1 ppm in the cleansing composition, for example, less than or equal to 0.5 ppm in the cleansing composition.

[0159] A wide variety of packaging may be employed to store and deliver the nanoemulsion. Packaging is often dependent upon the type of personal care end-use. For instance, leave-on skin lotions and creams, shampoos, conditioners and shower gels generally employ plastic containers with an opening at a dispensing end covered by a closure. Typical closures are screwcaps, nonaerosol pumps and flip-top hinged lids. Packaging for antiperspirants, deodorants and depilatories may involve a container with a roll-on ball on a dispensing end. Alternatively, these types of personal care products may be delivered in a composition formulation in a container with a propel / repel mechanism. Metallic cans pressurized by a propellant and having a spray nozzle serve as packaging for antiperspirants, shave creams and other personal care products. Skin, as used herein, is meant to include skin on the arms (including underarms), face, feet, neck, chest, hands, legs, buttocks and scalp (including hair). End use composition (water or oil continuous but preferably water continuous) is a composition for topical application and includes a cream, lotion, balm, serum, gel, mousse, aerosol, deodorant, antiperspirant, shampoo, conditioner, make-up and personal wash, including bars and liquids. Such an end use composition can be the nanoemulsion or nanoemulsion added to an end use composition. Benefit active is an oil soluble component that delivers a benefit to skin after being topically applied. Oil, as used herein, is meant to include a substance that has a melting point below 75°C, including oils which are benefit actives like sunscreens. High pressure, as defined herein, means 500 psi or more, and preferably, over 850 psi. In an embodiment, the end use composition is water continuous as is the nanoemulsion of this invention. In another embodiment, the end use composition is a leave-on skin lotion or cream, or a solid or liquid personal wash composition, for example, an isotropic liquid cleansing composition.

[0160] Viscosity, as used herein, is taken with a Discovery HR-2 Rheometer using sand blasted plates having a 1000 micron gap and a first shear rate SA of 0.4 s-1for a first viscosity A and a second shear rate SB of 10 s-1for a second viscosity B, both at 25°C and 20 second intervals.

[0161] Except where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and / or use are to be understood as modified by the word “about.” All amounts are by weight of the final composition, unless otherwise specified.

[0162] It should be noted that in specifying any range of concentration or amount, any particular upper concentration can be associated with any particular lower concentration or amount as well as any subranges consumed therein. In that regard, it is noted that all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25% by weight, or, more specifically, 5% by weight to 20% by weight, in inclusive of the endpoints and all intermediate values of the ranges of 5% by weight to 25% by weight, etc.). “Combination is inclusive of blends, mixtures, alloys, reaction products, and the like. Furthermore, the terms “first,” “second,” and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” herein do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term it modifies, thereby including one or more of the term (e.g., the film(s) includes one or more films). Reference throughout the specification to “one embodiment”, “one aspect”, “another embodiment”, “another aspect”, “an embodiment”, “an aspect” and so forth means that a particular element (e.g., feature, structure, and / or characteristic) described in connection with the embodiment or aspect is included in at least one embodiment or aspect described herein and may or may not be present in other embodiments or aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments or aspects.

[0163] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference. While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0164] For the avoidance of doubt the word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of.” In other words, the listed steps, options, or alternatives need not be exhaustive.

[0165] The disclosure of the invention as found herein is to be considered to cover all aspects as found in the claims as being multiply dependent upon each other irrespective of the fact that claims may be found without multiple dependency or redundancy. Unless otherwise specified, numerical ranges expressed in the format "from x to y" are understood to include x and y. In specifying any range of values or amounts, any particular upper value or amount can be associated with any particular lower value or amount. All percentages and ratios contained herein are calculated by weight unless otherwise indicated. The various features of the present invention referred to in individual sections above apply, as appropriate, to other sections mutatis mutandis. Consequently, features specified in one section may be combined with features specified in other sections as appropriate. Any section headings are added for convenience only and are not intended to limit the disclosure in any way. Examples

[0166] The following examples are merely illustrative of the nanoemulsion and cleansing compositions disclosed herein and are not intended to limit the scope hereof.

[0167] Table 1 shows nanoemulsion compositions containing various bioestolides, while Table 2 shows isotropic cleansing compositions made from the bioestolides listed in Table 1. Reference to molecular weight refers to number average molecular weight. The weight percentage value in Table 1 indicates active value unless otherwise noted.

[0168] Table 1 : Examples 1A-1F Nanoemulsions of BioEstolides

[0169] 1from Biosynthetic Technologies, INCI Name: Acetyl Ethylhexyl Polyhydroxystearate, with MW=2680.

[0170] 2from Biosynthetic Technologies, INCI Name: Acetyl IsoOctyl Polyricinoleate, with MW=2680.

[0171] 3from Biosynthetic Technologies, INCI Name: Acetyl Ethylhexyl Polyhydroxystearate, with MW=1426.

[0172] 4from Biosynthetic Technologies, INCI Name: Acetyl IsoOctyl Polyricinoleate, with MW=1426.

[0173] 5from Biosynthetic Technologies, INCI Name: Ethylhexyl Acetoxysterate, with MW=455.

[0174] 6from Innospec, INCI Name: Sodium Lauroyl Isethionate, with 78-82% active and 8-13% free fatty acid, mainly lauric acid.

[0175] 7from Galaxy Surfactants, Ltd, INCI Name: Sodium Methyl Lauroyl Taurate, with 88-91% active and free fatty acid less than 4.5%. Table 2: Examples 2-4 and Comparative Example 5 of isotropic cleansing compositions containing nanoemulsions.

[0176] 1TEXAPON® N 701 S, from BASF

[0177] 2COMPERLAN® CMEA NA, from BASF 3TEGO® Betain F KB 5, Evonik 4CARBOPOL® 980 polymer, Lubrizol 5JAGUAR® C14S, SOLVAY

[0178] The weight percentage value in Table 2 indicates active value unless otherwise noted. The active of the nanoemulsions is the corresponding BioEstolide. The isotropic cleansing compositions, e.g., bodywash, (anionic rich) (Examples 2-4) that contained higher molecular weight (2680) BIOESTOLIDE™ 1300 and BIOESTOLIDE™ 1300-100 nanoemulsions were surprisingly found to be stable with only a 20% viscosity reduction after 2 weeks at 50°C, while the lower molecular weight (1426) BIOESTOLIDE™ 250-100 (Comparative Example 5) yielded a viscosity reduction of greater than 70%.

[0179] Table 3: Examples 6 and 7 and Comparative Examples 8-10 of isotropic cleansing compositions containing nanoemulsions.

[0180] 1from Innospec, INCI name: Sodium Lauroyl Isethionate, with 78-82% active and 8-13% free fatty acid, mainly lauric acid.2from Galaxy, INCI name: Sodium Methyl Lauroyl Taurate, with 32% active.

[0181] 3from Evonik, INCI name: Cocamidopropyl betaine, with 30% active

[0182] 4from JRS, INCI name: Microcrystalline Cellulose (and) Cellulose Gum

[0183] 5from Cargill, INCI name: Hydroxypropyl Distarch Phosphate6from Syensqo, INCI name: Cyamopsis tetragonoloba (guar) gum

[0184] 7from Vertellus LLC, INCI name: Hydroxystearic Acid

[0185] The weight percentage value in Table 2 indicates active value unless otherwise noted. The active of the nanoemulsions is the corresponding BioEstolide. The isotropic cleansing composition, e.g., bodywash, (amphoteric rich) (Examples 6 and 7) containing higher molecular weight (2680) BIOESTOLIDE™ 1300 nanoemulsions were found to be stable with only a 30% viscosity reduction after 2 weeks at 50°C, while the lower molecular weight (1426) BIOESTOLIDE™ 250 and BIOESTOLIDE™ 250-100 yielded a viscosity reduction of greater than or equal to 80%. With a lower molecular weight (455) BIOESTOLIDE™ 30 nanoemulsion (Comparative Example 10 and the same cleanser base, a viscosity of less than 3000 cps at room temperature immediately after being made was observed.

[0186] Table 4: Examples 11-14 of cleansing compositions containing nanoemulsions.

[0187] 1TEXAPON® N 701 S, from BASF

[0188] 2COMPERLAN® CMEA NA, from BASF

[0189] 3TEGO® Betain F KB 5, Evonik

[0190] 4CARBOPOL® 980 polymer, Lubrizol 5JAGUAR® C14S, SOLVAY

[0191] The weight percentage value in Table 4 indicates active value unless otherwise noted. The active of the nanoemulsions is the corresponding BioEstolide. The cleansing compositions, e.g., shampoo, Examples 11-14, that contained higher molecular weight (2680) BIOESTOLIDE™ 1300 and BIOESTOLIDE™ 1300-100 nanoemulsions were surprisingly found to be stable with a less than 30% viscosity reduction after 2 weeks at 50°C. Example 14 even had a less than 6% viscosity reduction after 2 weeks at 50°C

Claims

CLAIMSWhat is claimed is:

1. A nanoemulsion composition, comprising: an internal oil phase, comprising:10 to 80% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight of greater than or equal to 2000; and an external aqueous phase, comprising: water; and1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion.

2. The nanoemulsion of Claim 1, wherein a carboxylic acid capping agent, an alcohol capping agent, a monomer, or a combination thereof form a backbone of the estolide ester.

3. The nanoemulsion of Claim 1 or Claim 2, wherein the monomer forming the backbone of the estolide ester comprises unsaturated fatty acid, unsaturated hydroxy fatty acid, saturated hydroxy fatty acid, or a combination thereof.

4. The nanoemulsion of Claim 3, wherein the backbone of the estolide ester comprises oleic acid, hydroxy stearic acid, ricinoleic acid, or a combination thereof.

5. The nanoemulsion of Claim 2, wherein the carboxylic acid capping agent comprises a C2 to C18 carboxylic acid, preferably wherein the carboxylic acid capping agent comprises acetic acid, lauric acid, myristic acid, coconut fatty acid, or a combination thereof.

6. The nanoemulsion of Claim 2, wherein the alcohol capping agent comprises 2-ethylhexyl alcohol, 2-octanol, or a combination thereof.

7. The nanoemulsion of any of the preceding claims, wherein a volume average diameter of the oil based droplets is 100 to 500 nanometers after dilution and homogenization, preferably wherein the volume average diameter of the droplets is 125 to 400 nanometers.

8. A personal cleansing composition, comprising: a nanoemulsion comprising: an internal oil phase, comprising:10 to 80% by weight of the total nanoemulsion composition of oil droplets comprising a plant-based oligomer comprising an estolide ester comprising a number average molecular weight of greater than or equal to 2000; and an external aqueous phase, comprising: water; and1.6 to 15% by weight of the total nanoemulsion composition of a surfactant comprising an anionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a combination thereof; wherein the anionic surfactant comprises greater than or equal to 70% of all surfactants present in the external aqueous phase of the nanoemulsion.

9. The cleansing composition of Claim 8, wherein the cleansing composition is a liquid cleansing composition, preferably wherein the cleansing composition is a facewash, a bodywash, a handwash, or a shampoo.

10. The cleansing composition of Claim 8 or Claim 9, wherein the cleansing composition is an isotropic cleansing composition.

11. The cleansing composition of any of Claims 8-10, wherein the cleansing composition comprises 0.2 to 8% by weight of the oil droplets.

12. The cleansing composition of any of Claims 8-11 , comprising 20 to 95% by weight of an anionic surfactant, based on a total amount of surfactant in the overall cleansing composition.

13. The cleansing composition of any of Claims 8-12, further comprising a cationic polymer.

14. The cleansing composition of any of Claims 8-13, further comprising a stabilizing polymer, a structuring polymer, a starch, a gum, or a combination thereof.

15. The cleansing composition of Claims 8-14, wherein a viscosity of the cleansing composition changed by less than or equal to 30% after a two-week time period stored at 50°C measured using a Discovery HR-2 Rheometer using sand blasted plates having a 1000 micron gap, at 25°C and 30 second intervals and a shear rate of 4 s’1.

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