AND NATURAL DETERGENT ALCOHOLS

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority of U. S. Provisional Patent Application No. 62/662,377 filed April 25, 2018, the entire content which is incorporated by reference herein.

BACKGROUND

[0001] This disclosure relates to specific combinations of a dialkyl carbonate and a paraffin for use in personal care products including cosmetics, and in particular to dialkyl carbonates manufactured from urea and alcohol.

[0002] Silicone compounds are a family of synthetic oils that are frequently used in formulations for personal care products. For example, silicones can to impart a light and smooth feeling on the skin in cosmetic formulations, and can be used in hair products to provide conditioning, shine, or strengthening. However, silicones can have ecological disadvantages. Research has been directed to preparing substitutes for silicone without losing the desired benefits.

[0003] There accordingly remains a need in the art for a silicone substitute that can provide similar end-use properties. It would be a further advantage if the silicone substitute could be prepared using convenient raw materials.

BRIEF DESCRIPTION

[0004] In an aspect, a nonaqueous, silicone-free personal care composition comprises 2 to 90%, preferably 10 to 70%, more preferably 10 to 50% by weight of a dialkyl carbonate, based on the total weight of the composition; and 2 to 95%, preferably 10 to 90%, more preferably 50 to 90% by weight of a C _8-4 o paraffin compound, based on the total weight of the composition, wherein the dialkyl carbonate is a bis(Ci_ ₃₆ alkyl)carbonate, preferably a bis(Ci_ ₂ 4 alkyl)carbonate, more preferably a bis(Ci_i ₂ alkyl)carbonate, even more preferably a bis(Ci_ ₈ alkyl)carbonate that is manufactured by reacting urea and a Ci_ ₃₆ alcohol, preferably a Ci_ ₂ 4 alcohol, more preferably aC _l-l2 alcohol, even more preferably aC _l-8 alcohol.

[0005] In another aspect, a personal care formulation comprises the nonaqueous, silicone-free personal care composition.

[0006] In still another aspect, a method for the manufacture of a personal care

formulation comprises combining the personal care composition with a solvent, a surfactant, a fatty acid or ester thereof, a viscosity modifier, an antioxidant, a fragrance, an essential oil, a humectant, a moisturizing agent, a colorant, or a combination thereof, to provide the personal care formulation.

[0007] In yet another aspect, a method for using a personal care product comprises contacting skin or hair with the personal care composition or the personal care formulation.

[0008] In an aspect, a kit comprises the personal care composition or the personal care formulation; and an applicator.

[0009] The above described and other features are exemplified by the following figures and detailed description.

DETAILED DESCRIPTION

[0010] This disclosure relates to a nonaqueous, silicone-free personal care composition. The composition can be used in silicone-free formulations and personal care products. The nonaqueous, silicone-free personal care composition comprises a dialkyl carbonate derived from an alcohol and urea, together with a paraffin compound. Thus, the dialkyl carbonate, and by extension the nonaqueous, silicone-free personal care composition, can be prepared using convenient, cost efficient raw materials.

[0011] The nonaqueous, silicone-free personal care composition can include 2 to 90%, preferably 10 to 70%, more preferably 10 to 50% by weight of a dialkyl carbonate, based on the total weight of the composition; and 2 to 95%, preferably 10 to 90%, more preferably 50 to 90% by weight of a C _8-4 o paraffin compound, based on the total weight of the composition. The dialkyl carbonate can be a bis(Ci_ ₃₆ alkyl)carbonate, preferably a bis(Ci_ ₂₄ alkyl)carbonate, more preferably a bis(Ci_i ₂ alkyl)carbonate, even more preferably a bis(Ci_ ₈ alkyl)carbonate. The bis(Ci_36 alkyl)carbonate is manufactured by reacting urea and a C _l-36 alcohol, preferably a C _l-24 alcohol, more preferably a C _l-l2 alcohol, even more preferably a C _l-8 alcohol.

[0012] The dialkyl carbonate can be a compound of formula (1):

wherein each R 1 and R 2 is the same or different substituted or unsubstituted C _l-36 alkyl group, preferably a Ci_ ₂₄ alkyl group, more preferably a C _l-l2 alkyl group, even more preferably a Ci_ ₈ alkyl group. Alternatively, R and R together form a substituted or unsubstituted heterocyclic ring having 3 to 6 carbon atoms. For example, R and R together can form a five-membered, six-membered, or seven-membered heterocyclic ring that includes both oxygen atoms.

[0013] For example, the dialkyl carbonate can be a compound of formula (2) or formula

wherein each R’ R ⁴ , and R ⁵ is the same or different, and is a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a Ci_ ₃₂ alkyl group, a C2-32 alkenyl group, a Ci_ ₃ 2 hydroxyalkyl group, a Ci-32 alkoxy group, a C _2-3 2 hydroxyalkyloxyalkyl group, a C _3-3 2 alkoxycarbonyl group, a C _6-i 2 aryl group, or a C ₇ _i ₃ arylalkylene group; W is a single bond or a C1-2 alkylene; and m and n are each independently 0 to 33, or 0 to 26, or 0 to 20, or 0 to 10, or 0 to 5. For example, each R _, R ⁴ , and R ⁵ can be the same or different, and can be a hydrogen atom, a C _l-l2 alkyl group, a C _l-l2 hydroxyalkyl group, a C _l-l2 alkoxy group, a C2-12 hydroxyalkyloxyalkyl group, a C _3-l2 alkoxycarbonyl group, a C _6-i 2 aryl group, or a C _7-l3 arylalkylene group, and m and n each can be independently 1 to 24. In some aspects, W is a single bond.

[0014] Exemplary dialkyl carbonates can include at least one compound of formulas (4) to (9)

[0015] Paraffin compounds are saturated aliphatic hydrocarbons and include compounds that are more commonly known as paraffin, hard paraffin, hydrocarbon wax, paraffin wax, poly(alkylene) wax, synthetic paraffin wax, petroleum wax, or the like. The paraffin compound can be linear or branched, and is a C _8- 4o alkane, preferably a C _8-36 alkane, more preferably a C ₈ _2 ₄ alkane. The paraffin compound can be a single compound or a mixture of different compounds and/or isomeric compounds. Two or more different paraffin compounds can also be used. The paraffin compound can be a mixture of alkanes that includes 1 to 50 weight percent (wt%), preferably 5 to 30 wt%, more preferably 10 to 20 wt% of one or more branched alkanes, based on the total weight of the mixture of alkanes. The paraffin compound can be substantially free of unsaturated alkanes, substantially free of cyclic alkanes, or both. The paraffin compound can be a liquid or a solid, as measured at 20°C and ambient pressure. Preferably, the paraffin compound is a solid at 20°C and ambient pressure. Paraffin compounds can be a solid at 20°C and include less than 6 wt%, less than 3 wt%, or less than 1 wt% of a liquid phase, based on the total weight of the paraffin compound. In an aspect, the parraffin compound can be paraffin wax, synthetic wax, polyethylene wax, or a combination thereof.

[0016] The bis(Ci_36 alkyl)carbonate can be manufactured by reacting urea and a C _l-36 alcohol. Exemplary Ci_ ₃₆ alcohols include a Ci_ ₃₆ alkyl monohydroxy compound, a Ci_ ₂₄ alkyl monohydroxy compound, a C _l-l2 alkyl monohydroxy compound, or a Ci_ ₈ alkyl monohydroxy compound; a C _2-36 alkyl dihydroxy compound, preferably a C _2-36 alkyl l,2-diol or a C _3-36 alkyl l,3-diol; or a C _3-36 alkyl trihydroxy compound, preferably a C _3-36 alkyl l,2,x-triol or a C _3-36 alkyl l,3,x- triol wherein x is 4 to 36; or a combination thereof. The alcohol can be a mixture of Ci_ ₃₆ alcohols, for example cetostearyl alcohol. The alkyl group of the foregoing Ci_ ₃₆ alkyl monohydroxy compound, C _2-36 alkyl dihydroxy compound, or C _3-36 alkyl trihydroxy compound can be substituted or unsubstituted. Examples of the C _l-36 alkyl monohydroxy compound include, but are not limited to, methanol, ethanol, 1 -propanol, 2-propanol, 1 -butanol, 2-butanol, amyl alcohol, l-hexanol, 2-hexanol, 3-hexanol, l-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-phenylpropanol, 3-phenylpropanol, and the like. Examples of the C _2-36 alkyl dihydroxy compound include, but are not limited to, ethylene glycol; 1,2- propylene glycol; 1, 3-propylene glycol; 2, 2-dimethyl- 1, 3-propane diol; 2-ethyl, 2-methyl, 1, 3-propane diol; 1, 3-pentane diol; or the like. Examples of the C _3-36 alkyl trihydroxy compound include, but are not limited to, 1,2,3- propanetriol; l,2,6-hexanetriol; l,2,l0-decanetriol; or the like.

[0017] For example, the C _l-36 alcohol can be 1, 2-propanediol, 1, 3-propanediol, 1,2,3- propanetriol, l,2-butanediol, l,2,3-butanetriol, l,2-hexanediol, l,3-hexanediol, 2,4-hexanediol, l,2,6-hexanetriol, l,2-octanediol, l,2-decanediol, l,2,l0-decanetriol, capric alcohol, caprylic alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, myricyl alcohol, geddyl alcohol, cetostearyl alcohol, isostearyl alcohol, or a combination thereof. In an aspect, the Ci_ ₃₆ alcohol is 2- ethylhexyl alcohol, capric alcohol, caprylic alcohol, lauryl alcohol, cetostearyl alcohol, stearyl alcohol, l,2,3-propanetriol, or a combination thereof.

[0018] The nonaqueous, silicone-free personal care composition can be substantially free of silicone and substantially free of water. As used herein, "substantially free of silicone" means the composition has less than 5 weight percent (wt%), or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt% of a silicone material, based on the total weight of the composition. As used herein, "substantially free of water" means the composition has less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt% of water. [0019] The nonaqueous, silicone-free personal care composition can further include an effective amount of a propellant. For example, the propellant can be a hydrocarbon propellant that includes one or more hydrocarbons or halogenated derivatives thereof, such as a C _l-7 alkane, Ci haloalkane, C _2-4 ether, C _2-4 haloether, or the like. Exemplary volatile hydrocarbons include, but are not limited to, propane, isopentane, n-pentane isobutane, n-butane, chloromethane, chloroethane, 2,2-dichloro-l,l,l-trifluoroethane, trichlorofluoromethane, 1, l,2-trichloro- 1,2,2, - trifluoroethane, dimethyl ether, bis(difluoromethyl) ether, perfluorodimethyl ether, or a combination thereof. In other aspects, the propellant can be an aerosol propellant such as a compressed gas, soluble gas, liquefied gas, or a combination thereof. Exemplary aerosol propellants include, but are not limited to, nitrous oxide, carbon dioxide, nitrogen, helium, ambient air, or the like. The propellant can be included in the composition in any effective amount, for example 0.1 to 10 wt%, preferably 0.5 to 8 wt%, more preferably 1 to 5 wt%, based on the total weight of the composition.

[0020] The personal care composition can have a melting point of from 20 to 90°C, or 30 to 90°C, preferably 30 to 80°C, or 40 to 80°C, more preferably 40 to 70°C, or 50 to 70°C, as determined according to ASTM D87.

[0021] The personal care composition can have a congealing point of from 40 to l00°C, or 45 to l00°C, or 50 to l00°C, preferably 50 to 90°C, or 55 to 85°C, more preferably 60 to 80°C, as determined according to ASTM D938.

[0022] The personal care composition can have a needle pen penetration at 25 °C of from 0.2 to 4 mm, preferably 0.2 to 3 mm, more preferably 0.2 to 2.5 mm, or 0.4 to 2.5 mm, or 0.8 to 2.5 mm, or 1 to 2.5 mm, as determined according to ASTM D1321.

[0023] The personal care composition can have a drop melting point of from 60 to l20°C, or 70 to l20°C, preferably 70 to 1 l0°C, or 80 to 1 l0°C, more preferably 80 to l00°C, as determined according to ASTM D3954.

[0024] In an aspect, the personal care product have one or more of a melting point of from 20 to 90°C, a congealing point of from 40 to l00°C, a needle pen penetration at 25°C of from 0.2 to 4 mm, and a drop melting point of from 60 to l20°C.

[0025] The dialkyl carbonates such as the bis(Ci_ ₃₆ alkyl)carbonate can be prepared via urea alcoholysis, for example by reacting urea and an alcohol. As illustrated in Scheme 1, carbamate (III) can be produced in- situ via a first reaction of urea (I) and a first equivalent of alcohol ROH (II), and the carbamate (III) reacts with a second equivalent of alcohol ROH (II) to yield a dialkyl carbonate (V). In both steps, ammonia (IV) is produced. Alternatively, the reaction can be performed sequentially, for example by using a lower temperature to form the carbamate (III) and a higher temperature to form the dialkyl carbonate (V). The ammonia (IV) that is produced from each reaction step can be separated and reacted with carbon monoxide to regenerate urea (I), thus providing a method to recycle the urea starting material. In Scheme 1, R is a Ci-36 alkyl.

111 II V ^IV Scheme 1

[0026] Preparing the bis(Ci_ ₃₆ alkyl)carbonate using this method can provide a convenient route to manufacture dialkyl carbonates from aliphatic alcohols. Moreover, the dialkyl carbonates can be obtained without the need for phosgene or requiring a multi-step process such as oxidative carbonylation followed by transesterification. Because urea can be synthesized from ammonia and carbon dioxide, combining the reactions of urea synthesis and urea alcoholysis can provide for the preparation of bis(Ci_ ₃₆ alkyl)carbonate with a net input of only the aliphatic alcohol. In an aspect, the method for the manufacture of the personal care composition does not include the use of phosgene.

[0027] The ammonia gas formed as byproduct in the reaction of urea and the alcohol can be preferably removed from the reaction system. The process for the removal of byproduct ammonia gas is not particularly limited and the removal can be effected by attaching a fractionation column to the reactor to separate ammonia from other high-boiling components, or adding a deammoniation agent that can react with ammonia to remove it, for example hydrogenated molecular sieves.

[0028] The reaction of the alcohol and urea can be done in the presence of a catalyst. Exemplary catalysts can include Ti, Al, Zn, Pb, Sn, Ca, Mg, Zr, Rb, Cs, Na, K, ammonium, or a combination thereof. For example, the catalyst can be a titanium tetra(Ci_ ₆ alkoxide), an aluminum tri(Ci_ ₆ alkoxide), a zirconium tetra(Ci_ ₆ alkoxide), a di(Ci- ₆ alkyl)tin oxide, a di(Ci- ₆ alkyl)tin di(Ci_ ₃ alkoxide), a tri(C _{6 i} 2 aryl)tin halide, or a combination thereof. Other examples of catalysts include, but are not limited to, sodium hydroxide, potassium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, zinc oxide, zinc nitrate, zinc chloride, zinc acetate, zinc hydroxide, zinc carbonate, lead oxide, lead acetate, lead nitrate, calcium oxide, magnesium oxide, zirconium oxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ditetramethylammonium carbonate, ditetraethvlammonium carbonate, or a combination thereof. [0029] The amount of catalyst can be from 0.005 to 10 mole percent (mol%), preferably 0.1 to 5 mol%, more preferably 0.5 to 3 mol%, based on the number of moles of urea.

[0030] The reaction of the alcohol and urea can be performed in a solvent, for example diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, l,3-dimethoxy propane, l,2-dimethoxy propane, n-butyl ether, l,4-dioxane, 2,3- pentanedione, 2,4-pentainedione, l,3-dimethoxybenzene, l,4-dimethoxybenzene, 3-methyl tetrahydrofuran, 2,5-dimethoxy tetrahydrofuran, 6,7-dimethoxy-l-tetralone, 2,3-dimethoxy toluene, 2,3-dimethoxy toluene, 2,6-dimethoxy toluene, 3,3'-dimethoxy biphenyl, 4,4'- dimethoxy biphenyl, 2-methoxyethyl acetate, 2-methoxyethyl acetoacetate, 2-methoxyfuran, 2- [2-(2-methoxyethoxy)ethoxy]-l,3-dioxolane, l-methoxy-2-propanol, l,2-dimethoxy propane, 2- methoxytetrahydropyran, 5-methoxy-l-tetralone, 7-methoxy-2-tetralone, or the like, or a combination thereof.

[0031] The reaction of the alcohol and urea can be performed at an alcohol to urea molar ratio of from 0.5:1 to 20:1, preferably from 1:1 to 10:1, more preferably from 1:1 to 5:1, even more preferably from 1:1 to 2:1.

[0032] The reaction of the alcohol and urea can be performed at 130 to 250°C, or 150 to 220°C, or 170 to 200°C. The reaction temperature can be for 0.5 to 20 hours, or 2 to 15 hours, or 5 to 12 hours.

[0033] Also provided is a personal care formulation that includes the nonaqueous, silicone-free personal care composition as described herein. For example, the formulation can be used as a cosmetic, a moisturizer, a sunscreen, a cleanser, a shampoo, a conditioner, a hair dye, an anti-perspirant, or a pharmaceutical.

[0034] The personal care formulation can further include an adjunct ingredient that can modify the physical, chemical, cosmetic, or aesthetic characteristics of the formulation or serve as“active” components when deposited on the skin or hair, for example. The personal care formulation can also include adjunct ingredients, non-limiting examples of which include surfactants, emulsifiers, viscosity modifiers such as bulking agents, thickening agents, fillers, gellants, or suspending agents, carriers, solvents, pH modifiers, buffering agents, active agents including pharmaceutical, therapeutic, and cosmetic agents, vitamins, vitamin derivatives (e.g., tocopherol acetate, retinoic acid, retinol, retinoids, retinyl palmitate, panthenol, or the like), enzymes, enzyme stabilizers, abrasives, emollients, humectants, skin exfoliating agents, anti abrasion agents, skin bleaching agents (or lightening agents) (e.g., hydroquinone, kojic acid, ascorbic acid, magnesium ascorbyl phosphate, and ascorbyl glucosamine), skin-conditioning agents, moisturizing agents, skin soothing and/or healing agents such as panthenol and derivatives (e.g., ethyl panthenol), skin sensates, absorbents, essential oils, astringents (e.g., clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate), anti-acne agents (e.g., resorcinol, sulfur, salicylic acid, erythromycin, zinc, etc.), skin treating agents such as agents for preventing, retarding, arresting, or reversing skin wrinkles (e.g., alpha- hydroxy acids such as lactic acid and glycolic acid and beta-hydroxy acids such as salicylic acid), anti-caking agents, antifoaming agents, antimicrobial agents (e.g., iodopropyl

butylcarbamate), sunscreens, cosmetic biocides, germicides, binders, biological additives, chemical additives, denaturants, drug astringents, external analgesics, oil components such as fats, oils, and fatty acids or esters thereof, waxes, polymers or copolymers, film formers or materials for aiding the film-forming properties and substantivity of the composition (e.g., copolymer of eicosene and vinyl pyrrolidone), fragrances, deodorants, antiper spirants, nutrients, opacifying agents, chelating agents, preservatives, reducing agents, sequestrants, aloe vera, pantothenic acid and its derivatives (e.g., allantoin, bisabolol and dipotassium glycyrrhizinate), hydrocolloids, zeolites, colorants such as pigments or dyes, or a combination thereof. Still other adjuvant ingredients include hydrotopes, suds boosters, suds suppressors (antifoams), dispersants, silvercare, anti-tarnish and/or anti-corrosion agents, inorganic salts, alkalinity sources, dye transfer inhibiting agents, and fabric softeners. An adjunct ingredient can also be described as more than one type of ingredient. In an aspect, the adjunct ingredient can be, but is not limited to, a solvent, a surfactant, a fatty acid or ester thereof, a viscosity modifier, an antioxidant, a fragrance, an essential oil, a humectant, a moisturizing agent, a colorant, or a combination thereof.

[0035] The formulation can include a solvent, for example, an organic solvent such as 2- butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethanol, isopropanol, n-propanol, n-butanol, 1, 2-propanediol, 1 ,3- propanediol, glycerol, l-methoxy-2-propanol, l-ethoxy-2-propanediol, l,4-butanediol, 1,2- hexanediol, benzyl alcohol, phenoxyethanol, 2-phenylethyl alcohol, ethylene diglycol, methoxybutanol, n-butylene glycol, or a combination thereof. The formulation can include preferably from 2 to 20 wt% by weight and in particular from 5 to 15 wt% of a solvent, based on the total weight of the formulation. The formulation can further include polyethylene glycol (PEG) having a relative molecular mass of between 200 g/mol and 2,000 g/mol, in amounts from 2 to 17 wt%, based on the total weight of the formulation.

[0036] The solvent can also include a non-aqueous solvent, for example, an isosorbide derivative such as dimethyl isosorbide, propylene gycol (PG), hexylene glycol, glycerin, diethylene glycol monoethyl ether, glycofurol, tetrahydrofurfuryl alcohol, pyrrolidone, N-methyl pyrrolidone, ethyl proxitol, dimethylacetamide, benzyl alcohol, dimethylsulfoxide (DMSO), ethoxydiglycol (transcutol), butylene glycol, glycerol, or a combination thereof. In another aspect, the solvent can include a hydrophobic solvent or carrier such as an ester oil. Specific non-limiting examples of the ester oils include isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, octyldodecyl myristate, di-isopropyl adipate, isocetyl myristate, di isopropyl sebacate, or the like.

[0037] Emulsifiers that can be used include glyceryl stearate, polysorbate 60, PEG- 6/PEG- 32/glycol stearate mixture, fatty esters such as isopropyl myristate, decyl oleate, 2- ethylhexyl palmitate, PEG-7 glyceryl cocoate, and glyceryl linoleate, di- and triglycerides such as lecithin, caprylic/capric triglyceride, propoxylated fatty ethers such as PPG-2 butyl ether, PPG-4 butyl ether, PPG- 5 butyl ether, PPG- 9 butyl ether, PPG- 12 butyl ether, PPG- 14 butyl ether, PPG- 15 butyl ether, PPG- 16 butyl ether, PPG- 17 butyl ether, PPG- 18 butyl ether, PPG-20 butyl ether, PPG-22 butyl ether, PPG-24 butyl ether, PPG-26 butyl ether, PPG-30 butyl ether, PPG-33 butyl ether, PPG-40 butyl ether, PPG-52 butyl ether, PPG-53 butyl ether, PPG- 10 cetyl ether, PPG-28 cetyl ether, PPG-30 cetyl ether, PPG-50 cetyl ether, PPG-30 isocetyl ether, PPG-4 lauryl ether, PPG-7 lauryl ether, PPG-2 methyl ether, PPG-3 methyl ether, PPG-3 myristyl ether, PPG-4 myristyl ether, PPG- 10 oleyl ether, PPG-20 oleyl ether, PPG-23 oleyl ether, PPG-30 oleyl ether, PPG-37 oleyl ether, PPG-50 oleyl ether, PPG-l 1 stearyl ether, or the like.

[0038] Humectants can include glycerin, alkylene polyols and their derivatives, including propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1, 3-butylene glycol, 1,2,6- hexanetriol, ethoxylated glycerol, propoxylated glycerol, sodium hyaluronate, or the like.

[0039] Skin freshening and soothing agents include menthol, aloe, allantoin, lanolin, collagen and hyaluronic acid, fluorosurfactants, or silicones (e.g. dimethicone, dimethiconol, dimethicone copolyol, stearyl dimethicone, cetyl dimethicone copolyol, phenyl dimethicone, cyclomethicone, etc.), or the like. The formulation does not comprise silicone.

[0040] Emollients include ester emollients such as alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms, for example, isoarachidyl neopentanoate, isononyl isonanonoate, oleyl myristate, oleyl stearate, and oleyl oleate; ether-esters such as fatty acid esters of ethoxylated fatty alcohols; polyhydric alcohol esters such as ethylene glycol mono- and di- fatty acid esters, diethylene glycol mono- and di- fatty acid esters, polyethylene glycol mono- and di fatty acid esters, propylene glycol mono- and di- fatty acid esters, polypropylene glycol 2000 monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol

monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty esters, ethoxylated glyceryl monostearate, 1, 3-butylene glycol monostearate, 1, 3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxy-ethylene sorbitan fatty acid esters; wax esters such as beeswax, spermaceti, myristyl myristate, stearyl stearate, and arachidyl behenate; and sterol esters such as cholesterol fatty acid esters. Other exemplary emollients include isopropyl myristate, isopropyl palmitate, isopropyl isostearate, diisopropyl adipate, diisopropyl dimerate, maleated soybean oil, octyl palmitate, cetyl lactate, cetyl ricinoleate, tocopheryl acetate, cetyl acetate, tocopheryl linoleate, wheat germ glycerides, arachidyl propionate, myristyl lactate, decyl oleate, propylene glycol ricinoleate, isopropyl lanolate, pentaerythrityl tetrastearate, neopentylglycol dicaprylate/dicaprate, isononyl isononanoate, isotridecyl isononanoate, myristyl myristate, octyl dodecanol, octyl

hydroxystearate, or the like.

[0041] Preservatives can include an antimicrobial agent, an anti-bacterial agent, an anti fungal agent, or a combination thereof. Preservatives herein include, but are not limited to, benzethonium chloride, benzisothiazolinone, benzoic acid, benzyl alcohol, 2-Bromo-2- nitropropane-l ,3-diol, butylparaben, caprylyl glycol, chlorhexidine digluconate, DMDM hydantoin, diazolidinyl urea, dehydroacetic acid, ethylparaben, iodopropynyl butylcarbamate, methylchloroisothiazolinone, methylisothiazolinone, methyldibromo glutaronitrile,

methylparaben, pentylene glycol, phenethyl alcohol, phenoxyethanol, propylparaben, polyaminopropyl biguanide, quatemium-l5, salicylic acid, sodium benzoate, sodium

methylparaben, sodium dehydroacetate, thymol, triclosan, or a combination thereof.

[0042] The formulation can include a polymer or copolymer. Examples include polyvinyl pyrrolidone (PVP); polyethyleneglycol dimethylether (DM-PEG);

vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate; a polystyrenesulphonate (PSS); polyvinyl pyridine-N-oxide (PVNO); polyvinylpyrrolidone/vinylimidazole (PVP- VI);

polyvinylpyrrolidone/poly(meth)acrylic acid (PVP-AA); polyvinylpyrrolidone/vinylacetate (PVP-VA); poly (meth) acrylate or poly(meth)acrylicmalate; or a combination thereof.

Exemplary cationic polymers include cationic cellulose derivatives such as quatemized hydroxyethyl cellulose, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quatemized vinyl pyrrolidone/vinyl imidazole polymers, condensation products of polyglycols and amines, quatemized collagen polypeptides, quatemized wheat polypeptides,

polyethyleneimine, cationic silicone polymers such as amodimethicone, copolymers of adipic acid and dimethylamino-hydroxypropyl diethylenetriamine, copolymers of acrylic acid and dimethyl diallyl ammonium chloride, polyaminopolyamides, cationic chitin derivatives such as quatemized chitosan, condensation products of dihaloalkyls, such as dibromobutane, with bis- dialkylamines, for example bis-dimethylamino- 1,3 -propane, cationic guar gum such as quatemized ammonium salt polymers, or the like. The formulation can include 0.005 to 5.0 wt% of the polymer or copolymer, preferably 0.10 to 4.0 wt%, more preferably from 0.1% to 3.0 wt%, based on total weight of the formulation.

[0043] Surfactants can also be included in the formulation. Total concentration of the surfactant can be 0.1 to 50 wt%, preferably 1 to 20 wt%, more preferably 1 to 5 wt% by weight of the formulation. The surfactant can be anionic, nonionic, cationic, amphoteric, or a combination thereof.

[0044] Anionic surfactants can include soap, alkyl ether sulfate and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, C ₈ -20 acyl isethionates, acyl glutamates, C ₈ -20 alkyl ether phosphates, or a combination thereof.

[0045] Nonionic surfactants can be those with a C 10-20 fatty alcohol or acid hydrophobe condensed with 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; C2-10 alkyl phenols condensed with 2 to 20 moles of alkylene oxide; mono- and di- fatty acid esters of ethylene glycol; fatty acid monoglyceride; sorbitan, mono- and di- C ₈ -C2o fatty acids; block copolymers (ethylene oxide/propylene oxide); and polyoxyethylene sorbitan, or a combination thereof. Alkyl polyglycosides and saccharide fatty amides (e.g. methyl gluconamides) can be used as nonionic surfactants.

[0046] Cationic surfactants include quaternary ammonium compounds such as ammonium halides, imidazolium compounds such as Quaternium-27 and Quaternium-83, or the like. The cationic surfactants can be included in an amount of 0.05 to 10 wt %, based on the weight of the formulation.

[0047] Amphoteric/zwitterionic surfactants can be, for example, betaine surfactants. Examples of betaine surfactants include the high alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha- carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxy-ethyl) carboxy methyl betaine, stearyl bis-(2-hydroxy-propyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl) alpha-carboxyethyl betaine, or the like. Other betaines are the sulfobetaines which may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxy-ethyl) sulfopropyl betaine and the like; amido betaines and

amidosulfobetaines, wherein a RCONH(CH ₂ ) _x radical is attached to the nitrogen atoms of the betaine are also useful. A preferred betaine is cocamidopropyl betaine. Other amphoteric surfactants include N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N- alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N- alkylsarcosines, 2-alkylaminopropionic acids, N-alkyl-N,N-dimethylammonium glycinates, N- acylaminopropyl-N,N-dimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3- hydroxyethylimidazolines, alkylaminoacetic acids, or the like.

[0048] The formulation can include an oil component. Exemplary oil components include, for example, esters of linear C ₆ -22 fatty acids with linear or branched C ₆ -22 fatty alcohols or esters of branched C _6-i 3 carboxylic acids with linear or branched C ₆ -22 fatty alcohols such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Other examples are esters of linear C ₆ -22 fatty acids with branched alcohols, more particularly 2-ethyl hexanol, esters of Cis-38 alkylhydroxycarboxylic acids with linear or branched C ₆ -22 fatty alcohols, triglycerides based on C _6-i o fatty acids, liquid mono-, di- and triglyceride mixtures based on C _6-i8 fatty acids, esters of C ₆ -22 fatty alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of C2-12 dicarboxylic acids with linear or branched alcohols containing 1 to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -22 fatty alcohol carbonates such as, for example, dicaprylyl carbonate, esters of benzoic acid with linear and/or branched C ₆ -22 alcohols, linear or branched, symmetrical or nonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group such as, for example, dicaprylyl ether, ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicon methicone types, etc.) and/or aliphatic or naphthenic hydrocarbons, for example squalane or dialkyl cyclohexanes.

[0049] Animal or vegetable fats and oils can be used, and include triglycerides, almond oil, avocado oil, borage oil, castor oil, cocoa butter, palm oil, turtle oil, cod-liver oil, whale oil, beef tallow, butter fat, shea butter, shorea butter, or the like. The fatty acid triglycerides or triglyceride mixtures which occur in soy oil, peanut oil, olive oil, sunflower oil, macadamia nut oil, Moringa oil, apricot kernel oil, Marula oil, coconut oil, hardened castor oil, or a combination thereof. Soy oil includes a mixture of triglycerides which is composed of the components palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid. Peanut oil is composed of the components palmitic acid, stearic acid, behenic acid, lignoceric acid, oleic acid, and linoleic acid which are present in a form esterified with glycerol. Olive oil includes fatty acid triglycerides such as myristic acid, palmitic acid, oleic acid, and linoleic acid. Sunflower oil includes trifatty acid glycerides based on palmitic acid, stearic acid, oleic acid, and linoleic acid. The trifatty acid glycerides of macadamia nut oil include linoleic acid, palmitic acid, arachidic acid, and stearic acid that forms ester bonds with glycerol. Moringa oil includes fatty acid triglycerides obtained by esterification of glycerol with myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, and linoleic acid. Apricot kernel oil includes oleic acid and linoleic acid. The triglycerides of coconut oil include dodecanoic acid, tetradecanoic acid, oleic acid, palmitic acid, decanoic acid, octanoic acid, and stearic acid. Marula oil includes fatty acid triglycerides of glycerol and palmitic acid, stearic acid, oleic acid, and linoleic acid.

[0050] Exemplary hydrotropes that can be used include toluenesulfonate,

xylenesulfonate, cumenesulfonate, or a combination thereof.

[0051] Exemplary waxes can include candelilla wax, carnauba wax, Japan wax, espartograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, soy, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), tallow, uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffin waxes, microwaxes, or the like. Chemically modified waxes (hard waxes) can include montan ester waxes, sasol waxes, hydrogenated jojoba waxes, and synthetic waxes such as polyalkylene waxes, polyol ether-ester waxes, chlorinated naphtalenes, Fisher Tropsch derived waxes, polyethylene glycol waxes, or the like.

[0052] Glycerophospholipids (lecithin), including phospholipids such as mono- and diesters of phosphoric acid with glycerol, sphingosines, sphingolipids, or the like, are also useful.

[0053] Moisturizers can include allantoin, petrolatum, urea, lactic acid, sodium PCV, glycerin, shea butter, caprylic/capric/stearic triglyceride, candelilla wax, propylene glycol, lanolin, hydrogenated oils, squalene, sodium hyaluronate, lysine PCA, or the like.

[0054] Colorants can include dyes and pigments. Exemplary dyes include cochineal red A, patent blue V, indigotin, chlorophyllin, quinoline yellow, titanium dioxide, indanthrene blue RS, madder lake, or the like. Luminol can be present as a luminescent dye.

[0055] Antioxidants can include ascorbic acid and its salts, ascorbyl esters of fatty acids, ascorbic acid derivatives (e.g., magnesium ascorbyl phosphate, sodium ascorbyl phosphate, ascorbyl sorbate), tocopherol , tocopherol sorbate, tocopherol acetate, other esters of tocopherol, butylated hydroxy benzoic acids and their salts, 6-hydroxy-2,5,7,8-tetramethylchroman-2- carboxylic acid, gallic acid and its alkyl esters, propyl gallate, uric acid and its salts and alkyl esters, sorbic acid and its salts, lipoic acid, amines (e.g., N,N-diethylhydroxylamine, amino- guanidine), sulfhydryl compounds (e.g., glutathione), di hydroxy fumaric acid and its salts, lysine pidolate, arginine pilolate, nordihydroguaiaretic acid, bioflavonoids, curcumin, lysine, methionine, proline, superoxide dismutase, silymarin, tea extracts, grape skin/seed extracts, melanin, rosemary extract, or a combination thereof. The antioxidants can further include a radical or anion scavenger such as salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, or the like. A modulating agent can also be a preservative or an antioxidant or an ionization agent. The modulating agent can include a flavonoid such as benzquercin, diosmin, ethoxazorutoside, flavodate, sodium hesperidin, leucocianido, monoxerutin, oxerutin, quercetin, rutoside, or rosmarinic acid. Ionization agents may for example act to protect or reduce sensitivity of active agents. Non-limiting examples of positive ionization agents are benzyl conium chloride, and cetyl pyridium chloride. Non-limiting examples of negative ionization agents are sodium lauryl sulphate, sodium lauryl lactylate, and phospholipids.

[0056] Bleaches can yield hydrogen peroxide in water, and include, for example, sodium perborate tetrahydrate, sodium perborate monohydrate, peroxycarbonate, citrate perhydrates, and salts of peracids, such as perbenzoates, peroxyphthalates, or diperoxydodecanedioic acid.

Bleaches and bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. A photoactivated bleaching agent such as sulfonated zinc and/or aluminum phthalocyanine can be used. In another aspect, the bleaching compounds can be catalyzed by means of a manganese compound or a cobalt compound. The bleaches can be included in amounts of from 0.025 to 25 wt%, based on the total weight of the formulation.

[0057] Viscosity modifiers can include thickeners and gelling agents. The viscosity modifier(s) can be included in an amount of 0.0001 to 5 wt%, preferably 0.001 to 2 wt%, more preferably 0.01 to 0.5 wt%, by weight of the formulation. Non limiting examples include cellulose derivatives and modified cellulose polymers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, nitro cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder,

polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, Arabia gum, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch (rice, com, potato, wheat), algae colloids (algae extract), microbiological polymers such as dextran, succinoglucan, pulleran, starch-based polymers such as

carboxymethyl starch, methylhydroxypropyl starch, alginic acid-based polymers such as sodium alginate, alginic acid propylene glycol esters, (meth)acrylate polymers such as sodium poly(meth)acrylate, polyethyl(meth)acrylate, poly(meth)acrylamide, polyethyleneimine, and inorganic water soluble material such as bentonite, aluminum magnesium silicate, laponite, hectonite, and anhydrous silicic acid. Other exemplary viscosity modifiers are polymeric compounds such as polyvinylpyrrolidone, urethanes, and the salts of polymeric

polycarboxylates, examples including homopolymeric or copolymeric poly(meth)acrylates, and, in particular, copolymers of (meth)acrylic acid with maleic acid. The molecular mass of the homopolymers can be 1,000 and 100,000 grams per mole (g/mol), the copolymers can be 2,000 and 200,000 g/mol, based on the free acid. Also suitable are water-soluble poly(meth)acrylates that are crosslinked, for example, with 1 wt% of a polyallyl ether of sucrose. Examples include the polymers having a thickening action which are obtainable under the name CARBOPOL® 934, 940, 941, 950, 951, 980, and 981. The formulation can further comprise from 5 to 20 wt% of partially esterified copolymers, for example as obtained by copolymerizing (a) at least one C ₄ - 28 olefin or mixtures of at least one C4_ ₂₈ olefin with up to 20 mol% of Ci_ ₂₈ alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic anhydrides having from 4 to 8 carbon atoms in a molar ratio of 1:1, and then partially esterifying the copolymers with reaction products such as Ci-i3 alcohols, C _8-22 fatty acids, C _l-l2 alkylphenols, secondary C _2-3 o amines, or a combination thereof, with at least one C _2-4 alkylene oxide or tetrahydrofuran, and hydrolyzing the anhydride groups of the copolymers to carboxyl groups, the partial esterification of the copolymers being conducted to an extent such that from 5 to 50% of the carboxyl groups of the copolymers are esterified. The partially esterified copolymers then either can be present in the form of the free acid or, preferably, in partly or fully neutralized form. The formulation can include partially esterified copolymers in amounts of from 5 to 15 wt%, and in particular 8 to 12 wt%, based on the total weight of the formulation.

[0058] Non limiting examples of viscosity modifiers also include inorganic salts.

Examples of inorganic salts include magnesium nitrate, trimagnesium phosphate, calcium chloride, sodium carbonate, sodium chloride, sodium aluminum sulfate, disodium phosphate, sodium polymetaphosphate, sodium magnesium succinate, sodium sulfate, sodium

tripolyphosphate, aluminum sulfate, aluminum chloride, aluminum chlorohydrate, aluminum- zirconium trichlorohydrate, aluminum- zirconium trichlorohydrate glycine complex, zinc sulfate, ammonium chloride, ammonium phosphate, ammonium sulfate, calcium acetate, calcium nitrate, calcium phosphate, calcium sulfate, ferric sulfate, magnesium chloride, magnesium sulfate, alkyl ether sulfate, mixtures thereof, or the like. Viscosity regulators include salts of long-chain fatty acids, examples being sodium, potassium, aluminum, magnesium, and titanium stearates, or the sodium or potassium salts of behenic acid.

[0059] Fragrances can include extracts and essences which can comprise complex mixtures of natural ingredients, such as orange oil, lemon oil, rose extract, rose hip, lavender, musk, patchouli, balsamic essence, anise, basil, bergemont, camphor, cardamom, carrot, canola, catnip, cedarwood, citronella, clove, cypress, eucalyptus, frankincense, garlic, geranium oil bourbon, ginger, grapefruit, hyssop, jasmine, jojova, lavender, lavandin, lemon, lime, linalool, lyral, mandarin, marjoram, myrrh, neroli, nutmeg, orange, peppermint, petitgrain, rosemary, sage, sandelice, spearmint, star anise, tangerine, thyme vanilla, verbena and white clover, sandalwood oil, pine oil, Peru balsam, Olibanum resinoid, styrax, labdanum resin, cassia oil, benzoin resin, coriander, lavandinor, or the like. Non-limiting examples of fragrance ingredients include: benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, 7-acetyl-l,2,3,4,5,6,7,8-octahydro-l,l,6,7-tetramethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl l,6,l0-trimethyl-2,5,9- cyclododecatrien-l-yl ketone; 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-l,l- dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-l,l,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-l,l,2,6-tetramethyl indane; 1- dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene- l-carboxaldehyde; 7 -hydroxy- 3,7- dimethyl octanal; lO-undecen-l-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl

tricyclodecane; condensation products of hydroxycitronellal and methyl anthranilate,

condensation products of hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and indol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2-(para-iso- propylphenylj-propionaldehyde; coumarin; decalactone gamma; cyclopentadecanolide; 16- hydroxy-9-hexadecenoic acid lactone; 1,3, 4,6,7, 8-hexahydro4, 6, 6,7,8, 8-hexamethylcyclopenta- gamma-2-benzo-pyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6, 6,9a- tetramethyl-naphtho[2,l]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)-2-buten-l-ol; caryophyllene alcohol;

tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate; and para- (tert-butyl) cyclohexyl acetate; hexyl cinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)- propionaldehyde; 7-acetyl-l,2,3,4,5,6,7,8-octahydro-l,l,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para- iso-propylphenyl)-propionaldehyde; l,3,4,6,7,8-hexahydro-4,6,6,7,8, 8-hexamethyl-cyclopenta- gamma-2-benzopyrane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2, 1 bjfuran; anisalde-hyde; coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenyl acetate; phenylethyl alcohol; phenylacetic acid; geranyl acetate; benzyl acetate; rose oxide; irotyl; floramat; tricyclodecenyl propionate, or a combination thereof. [0060] Enzymes include proteases, lipases, amylases, cellulases, cutinases, or a combination thereof. The compositions can comprise further enzyme stabilizers. For example, from 0.5 to 1 wt% of sodium formate can be used. In an aspect, proteases stabilized with soluble calcium salts, with a calcium content of preferably 1.2% by weight, based on the weight of the enzyme, can be used. Enzyme stabilizers include boric acid, boron oxide, borax, and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), of metaboric acid (HB0 ₂ ), and of pyroboric acid (tetraboric acid, H ₂ B ₄ O ₇ ).

[0061] The formulation can further include a chelating agent. Exemplary chelating agents include amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents, or a combination thereof. For example, the chelating agent can be acetyl trihexyl citrate, aminotrimethylene phosphonic acid, beta-alanine diacetic acid, bismuth citrate, calcium disodium ethylenediamine tetraacetic acid (edta), citric acid, cyclohexanediamine tetraacetic acid, diammonium citrate, dibutyl oxalate, diethyl oxalate, diisobutyl oxalate, diisopropyl oxalate, dilithium oxalate, dimethyl oxalate, dipotassium edta, dipotassium oxalate, dipropyl oxalate, disodium edta, disodium edta-copper, disodium pyrophosphate, edta, etidronic acid, hedta, methyl cyclodextrin, oxalic acid, pentapotassium, triphosphate, pentasodium aminotrimethylene phosphonate, pentasodium pentetate, pentasodium triphosphate, pentetic acid, phytic acid, potassium citrate, sodium citrate, sodium dihydroxyethylglycinate, sodium gluceptate, sodium gluconate, sodium hexametaphosphate, sodium metaphosphate, sodium metasilicate, sodium oxalate, sodium trimetaphosphate, triethanolamine-edta (tea-edta), tetrahydroxypropyl ethylenediamine, tetrapotassium etidronate, tetrapotassium pyrophosphate, tetrasodium edta, tetrasodium etidronate, tetrasodium pyrophosphate, tripotassium edta, trisodium edta, trisodium hydroxyethyl ethylenediamine triacetic acid (hedta), trisodium nitrilotriacetate (nta), trisodium phosphate, malic acid, fumaric acid, maltol, succimer, penicillamine, dimercaprol, and desferrioxamine melate, N-hydroxyethylethylene diamine triacetate, nitrilotriacetate, ethylene diamine tetrapropionate, triethylene tetraamine hexacetate, diethylene triamine pentaacetate, ethanol diglycine, or alkali metal, ammonium, and substituted ammonium salts thereof; dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene; a biodegradable chelator such as ethylenediamine disuccinate or methyl glycine diacetic acid salts, or a combination thereof.

[0062] Foam inhibitors include soaps of natural or synthetic origin containing a high proportion of C _{l 8} -24 fatty acids, organopolysiloxanes and their mixtures with microfine silica, and their mixtures with silanized silica or bistearylethylenediamide, or a combination thereof.

[0063] Antiperspirants include aluminum chlorohydrate, aluminum chlorohydrex polyethylene glycol, aluminum chlorohydrex propylene glycol, aluminum dichlorohydrate, aluminum dichlorohydrex polyethylene glycol, aluminum dichlorohydrex propylene glycol, aluminum sesquichlorohydrate, aluminum sesquichlorohydrex polyethylene glycol, aluminum sesquichlorohydrex propylene glycol, aluminum zirconium octachlorohydrate, aluminum zirconium octachlorohydrex gly, aluminum zirconium pentachlorohydrate, aluminum zirconium pentachlorohydrex gly, aluminum zirconium tetrachlorohydrate, aluminum zirconium

tetrachlorohydrex gly, aluminum zirconium trichlorohydrate, aluminum zirconium

trichlorohydrex gly, or the like, or a combination thereof.

[0064] Sunscreens include materials useful to block ultraviolet light. Examples include the derivatives of PABA, cinnamate, and salicylate. For example, avobenzophenone, octyl methoxycinnamate, and oxybenzone can be used.

[0065] Buffering agents can include pH modifiers such as acetic acid, adipic acid, calcium hydroxide, citric acid, glycine, hydrochloric acid, lactic acid, magnesium

aluminometasilicates, phosphoric acid, sodium carbonate, sodium citrate, sodium hydroxide, sorbic acid, succinic acid, tartaric acid, and derivatives, salts, or a combination thereof.

[0066] Non-limiting examples of active agents also include an anti-infective, an antibiotic, an antibacterial, an antifungal, an antiviral, an antiparasitic, a steroidal anti inflammatory, a nonsteroidal anti-inflammatory, an immunosuppressive, an immunomodulator, an immunoregulator, a hormonal agent, a steroid, a vasoactive agent, a vasoconstrictor, a vasodilator, vitamins A, B, C, D, E, F, K, or derivatives thereof including retinoid and alpha- tocopheryl polyethylene glycol succinate, a wound healing agent, a burn healing agent, a disinfectant, an anesthetic, an antiallergic agent, an alpha-hydroxy acid, lactic acid, glycolic acid, a beta-hydroxy acid, a protein, a peptide, a neuropeptide, an allergen, an immunogenic substance, a haptene, an oxidizing agent, an antioxidant, a dicarboxylic acid, azelaic acid, sebacic acid, adipic acid, fumaric acid, an insecticide, an antiproliferative agent, an anticancer agent, a photodynamic therapy agent, an anti- wrinkle agent, a radical scavenger, a metal oxide (e.g., titanium dioxide, zinc oxide, zirconium oxide, iron oxide), silicone oxide, talc, an anti-acne agent, a skin whitening agent, a self-tanning agent, an anti-cellulite agent, a skin protective agent, a masking agent, an anti-wart agent, a refatting agent, a lubricating agent, or a

combination thereof. The concentration of the active agent can be adapted to exert a desired effect when applied to the skin or hair.

[0067] The formulations can be prepared as emulsions or dispersions which contain water and oil phases. For example, cosmetic formulation can be in the form of a water in oil (w/o) or oil in water (o/w) emulsion with oils/fats/waxes, emulsifiers, water, and the other auxiliaries and additives. The quantities in which the particular additives are used can be determined by the intended application. [0068] Also provided is a method for using a personal care product. The method includes contacting the skin or hair with the personal care composition or the personal care formulation. The composition or formulation can be used as or in personal care products for treating or cleansing a portion of the human body. Personal care products include various products suitable for application to the skin, hair, or genital region of the body, such as shampoos, hand, face, and/or body washes, bath additives, gels, lotions, creams, and the like.

[0069] The quantity of personal care product, for example 1 to 100 mL, can be applied to a site from a container or applicator and, if necessary, spread over and/or rubbed into the site by hand, finger(s), or device. The product can be formulated for use as a treatment for a specific area, e.g., hands, face, arms, or hair. The personal care product can be prepared in any form suitable for application to the site of interest, including a lotion, cream, gel, or the like.

[0070] Also provided herein is a cosmetic kit comprising the personal care composition or personal care formulation, and a device such as an applicator. The cosmetic kit can alternatively include a container. The product can be packaged in any container to suit its viscosity and intended use by the consumer. For example, a lotion or cream can be packaged in a bottle, or a propellant-driven aerosol device or a container fitted with a pump for finger operation. When the composition or formulation is a cream, it can be stored as a personal care product in a non-deformable bottle or squeeze container, such as a tube or a lidded jar. The disclosure also provides a closed container comprising a personal care product as herein defined.

[0071] The personal care product can also be a cleaning product that is not intended for use on the skin or hair. In an aspect, the composition or formulation can be used as or in cleaning products for cleaning non-porous surfaces. For example, the composition or formulation can be used in automotive detergents, textile scouring agents, metal surface- treatment agents, metal degreasing agents, detergents for metallic parts, detergents for electronic parts, leather detergents, depitching agents, detergents for linen supplies (laundry detergents), kitchen detergents, fingertip detergents, dry-cleaning additives, or the like.

[0072] The formulations can have a viscosity from 1 to 100,000 milliPascal· second (mPa- s), or 1 to 10,000 mPa- s, or 1 to 1,000 mPa- s, or 1 to 100 mPa-s, or 1 to 50 mPa-s, or 1 to 25 mPa- s (22°C/Brookfield RVT viscometer/spindle 5/4 rpm).

[0073] This disclosure is further illustrated by the following examples, which are non limiting.

EXAMPLES

[0074] For the examples below, the physical properties were determined as follows: Melting point was determined according to ASTM D87. Drop melting point was determined according to ASTM D3954. Congealing point was determined according to ASTM D938. Needle pen penetration was determined at 25°C according to ASTM D1321.

[0075] In Examples 1 to 3, personal care compositions were prepared by combining 10 to 50 wt% of a wax and 50 to 90 wt% of distearyl carbonate (obtained from the alcoholysis of urea; SABIC). Examples 1 and 2 can further include 0 to 10 wt% of a propellant (either carbon dioxide or nitrogen). A container including Example 3 can further include a mechanical propellant.

[0076] In Examples 4 to 6, personal care compositions were prepared by combining 10 to 50 wt% of a wax and 50 to 90 wt% of di-cetostearyl carbonate (di(C _l4-l6 alkyl) carbonates obtained from the alcoholysis of urea; SABIC). Examples 4 and 5 and further include 0 to 10 wt% of a propellant (either carbon dioxide or nitrogen). A container including Example 6 can further include a mechanical propellant.

[0077] Table 1 shows the melting point, drop melting point, congealing point, and needle pen penetration of the personal care compositions of Examples 1 to 6.

Table 1.

[0078] As shown in Table 1, personal care compositions can be prepared having a variety of properties such as melting, drop melting point, congealing point in conjunction with desirable needle penetration. Moreover, these desirable properties for personal care products can be obtained without the use of silicone and without water.

[0079] This disclosure further encompasses the following aspects that are not intended to be limiting.

[0080] Aspect 1. A nonaqueous, silicone-free personal care composition, the

composition comprising: 2 to 90%, preferably 10 to 70%, more preferably 10 to 50% by weight of a dialkyl carbonate, based on the total weight of the composition; and 2 to 95%, preferably 10 to 90%, more preferably 50 to 90% by weight of a C _8-4 o paraffin compound, based on the total weight of the composition, wherein the dialkyl carbonate is a bis(Ci_ ₃₆ alkyl)carbonate, preferably a bis(Ci_ ₂₄ alkyl)carbonate, more preferably a bis(Ci_i ₂ alkyl)carbonate, even more preferably a bis(Ci_ ₈ alkyl)carbonate that is manufactured by reacting urea and a Ci_ ₃₆ alcohol, preferably a Ci_ ₂₄ alcohol, more preferably aCi_i ₂ alcohol, even more preferably aCi_ ₈ alcohol. [0081] Aspect 2. The nonaqueous, silicone-free personal care composition of claim 1, wherein the dialkyl carbonate is a compound of formula (1) wherein each R 1 and R 2 is the same or different substituted or unsubstituted C _l-36 alkyl group, preferably a C _l-24 alkyl group, more preferably a C _l-l2 alkyl group, even more preferably a C _l-8 alkyl group; or R and R together form a substituted or unsubstituted heterocyclic ring having 3 to 6 carbon atoms.

[0082] Aspect 3. The nonaqueous, silicone-free personal care composition of Aspect 1 or 2, wherein the dialkyl carbonate is a compound of formulas (2) or (3), wherein, each R ³ , R ⁴ , and R ⁵ is the same or different, and is a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a Ci-32 alkyl group, a C2-32 alkenyl group, a Ci_32 hydroxyalkyl group, a Ci_32 alkoxy group, a C2-32 hydroxyalkyloxyalkyl group, a C3_32 alkoxycarbonyl group, a C ₆ - 12 aryl group, or a C7-13 arylalkylene group, W is a single bond or a C1-2 alkylene, and m and n are each

independently 0 to 32.

[0083] Aspect 4. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 3, wherein the dialkyl carbonate is at least one compound of the formulas (4) to (9).

[0084] Aspect 5. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 4, wherein the paraffin compound is a linear or branched C _8- 4o alkane, preferably a C ₈ _3 ₆ alkane, more preferably a C ₈ _2 ₄ alkane.

[0085] Aspect 6. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 6, wherein the C1-36 alcohol is a C1-36 alkyl monohydroxy compound; a C2- 36 alkyl dihydroxy compound, preferably a C2-36 alkyl l,2-diol or a C3_3 ₆ alkyl l,3-diol; or a C3_3 ₆ alkyl trihydroxy compound, preferably a C3_3 ₆ alkyl l,2,x-triol or a C3_3 ₆ alkyl l,3,x- triol wherein x is 4 to 36.

[0086] Aspect 7. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 6, wherein the Ci_3 ₆ alcohol is 1, 2-propanediol, 1, 3-propanediol, 1,2,3- propanetriol, l,2-butanediol, l,2,3-butanetriol, l,2-hexanediol, l,3-hexanediol, 2,4-hexanediol, l,2,6-hexanetriol, l,2-octanediol, l,2-decanediol, l,2,l0-decanetriol, capric alcohol, caprylic alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, myricyl alcohol, geddyl alcohol, cetostearyl alcohol, isostearyl alcohol, or a combination thereof.

[0087] Aspect 8. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 7, wherein the composition is substantially free of silicone; and the composition is substantially free of water. [0088] Aspect 9. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 8, wherein the bis(Ci_ ₃₆ alkyl)carbonate is manufactured by reacting urea and a C _l-36 alcohol in the presence of a catalyst.

[0089] Aspect 10. The nonaqueous, silicone-free personal care composition of Aspect 9, wherein the catalyst comprises Ti, Al, Zn, Pb, Sn, Ca, Mg, Zr, Rb, Cs, Na, K, ammonium or a combination thereof, preferably a titanium tetra(Ci_ ₆ alkoxide), an aluminum tri(Ci_ ₆ alkoxide), a zirconium tetra(Ci- ₆ alkoxide), a di(Ci- ₆ alkyl)tin oxide, a di(Ci- ₆ alkyl)tin di(Ci_ ₃ alkoxide), a tri(C _{6 i} 2 aryl)tin halide, or a combination thereof.

[0090] Aspect 11. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 10, having one or more of a melting point of from 20 to 90°C, preferably 30 to 80°C, more preferably 40 to 70°C; a congealing point of from 40 to l00°C, preferably 50 to 90°C, more preferably 60 to 80°C, as determined in accordance with ASTM D938; a needle pen penetration at 25°C of from 0.2 to 4 mm, preferably 0.2 to 3 mm, more preferably 0.2 to 2.5 mm, as determined in accordance with ASTM D132; and a drop melting point of from 60 to l20°C, preferably 70 to H0°C, more preferably 80 to l00°C, as determined by ASTM D3954.

[0091] Aspect 12. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 11, wherein the composition comprises: 10 to 70% by weight of a dialkyl carbonate, based on the total weight of the composition; and 10 to 90% by weight of a C _8- 4o paraffin compound, based on the total weight of the composition, wherein the dialkyl carbonate is a bis(Ci_ ₂ 4 alkyl)carbonate that is manufactured by reacting urea and a C _l-2 4 alcohol, and wherein the composition has one or more of a melting point of from 30 to 80°C; a congealing point of from 50 to 90°C, as determined in accordance with ASTM D938; a needle pen penetration at 25°C of from 0.2 to 3 mm, as determined in accordance with ASTM D132; and a drop melting point of from 70 to 1 l0°C, as determined in accordance with ASTM D3954.

[0092] Aspect 13. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 11, wherein the composition comprises: 10 to 50% by weight of a dialkyl carbonate, based on the total weight of the composition; and 50 to 90% by weight of a Cg-40 paraffin compound, based on the total weight of the composition, wherein the dialkyl carbonate is a bis(Ci_ ₂ 4 alkyl)carbonate that is manufactured by reacting urea and a C _l-l8 alcohol, and wherein the composition has one or more of a melting point of from 50 to 60°C; a congealing point of from 60 to 80°C, as determined in accordance with ASTM D938; a needle pen penetration at 25°C of from 0.2 to 2.5 mm, as determined in accordance with ASTM D132; and a drop melting point of from 80 to l00°C, as determined in accordance with ASTM D3954. [0093] Aspect 14. The nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 13, wherein the composition further comprises an effective amount of a propellant.

[0094] Aspect 15. A personal care formulation comprising the nonaqueous, silicone-free personal care composition of any one or more of Aspects 1 to 14.

[0095] Aspect 16. The personal care formulation of Aspect 15, further comprising a solvent, a surfactant, a fatty acid or ester thereof, a viscosity modifier, an antioxidant, a fragrance, an essential oil, a humectant, a moisturizing agent, a colorant, or a combination thereof.

[0096] Aspect 17. The personal care formulation of Aspect 15 or 16, wherein the formulation is a cosmetic, a moisturizer, a sunscreen, a cleanser, a shampoo, a conditioner, a hair dye, an anti-perspirant, or a pharmaceutical.

[0097] Aspect 18. A method for the manufacture of a personal care formulation, the method comprising combining the personal care composition of any one or more of Aspects 1 to 14 with a solvent, a surfactant, a fatty acid or ester thereof, a viscosity modifier, an antioxidant, a fragrance, an essential oil, a humectant, a moisturizing agent, a colorant, or a combination thereof, to provide the personal care formulation.

[0098] Aspect 19. A method for using a personal care product, the method comprising contacting skin or hair with the personal care composition of any one or more of Aspects 1 to 14 or the personal care formulation of any one or more of Aspects 15 to 17.

[0099] Aspect 20. A kit comprising: the personal care composition of any one or more of Aspects 1 to 14 or the personal care formulation of any one or more of Aspect 15 to 17; and an applicator.

[0100] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0101] 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 wt%, or, more specifically,

5 to 20 wt%,” is inclusive of the endpoints and all intermediate values of the ranges of“5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms“first,”“second,” and the like, do not denote any order, quantity, or importance, and are used to distinguish one element from another. The terms“a” and“an” and “the” 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.“Or” means “and/or” unless clearly stated otherwise. Reference throughout the specification to“some aspects,”“an aspect,” and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. As used herein,“a combination thereof’ is an open- ended term that mean one or more of the listed items and can further include additional, unlisted items that are similar.

[0102] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0103] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. 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.

[0104] The term "silicone" encompasses polymeric or oligomeric siloxanes, branched or unbranched, of general formula [-OSiR _2- ] _n wherein R ¹H.

[0105] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash that is not between two letters or symbols is used to indicate a point of attachment for a substituent.

[0106] The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group.“Cycloalkyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon. “Cycloalkylene” means a divalent cyclic alkylene group, -C _n H _2n-x , wherein x is the number of hydrogens replaced by cyclization(s).“Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon. “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., -O-alkyl).“Alkoxycarbonyl” means an alkoxy group that is linked via a carbonyl. “Oxyalkyl” means an alkyl group to which at least one oxygen atom is covalently attached (e.g., via a single bond, forming a hydroxyalkyl or ether group, or double bond, forming a ketone or aldehyde moiety).“Hydroxyalkyloxy alkyl” means a hydroxy-substituted alkyl group that is linked via an oxyalkyl. "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl. “Arylene” means a divalent aryl group.

“Arylalkylene” means an alkylene group substituted with an aryl group. “Halo” or“halogen” means fluoro, chloro, bromo, iodo, or a combination thereof.

[0107] The prefix“hetero” means that the compound or group includes at least one ring member that is a heteroatom wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Heteroaryl” means a monovalent group that includes one or more aromatic rings, having at least one heteroatom ring member.“Hetero arylalkyl” means a heteroaryl group linked via an alkyl moiety. "Heteroaryloxy" means a heteroaryl group is attached to the group it substitutes through an oxygen bridge.“Heterocycloalkyl” means a saturated cyclic group having the indicated number of ring atoms containing from 1 to 3 heteroatoms, with remaining ring atoms being carbon.

[0108] Unless indicated otherwise,“substituted” means that the compound or group is substituted with at least one substituent that can be a C _l-9 alkoxy, a C _l-9 haloalkoxy, a nitro (- N0 ₂ ), a cyano (-CN), a Ci_ ₆ alkyl sulfonyl (-S(=0) ₂ -alkyl), a C _6-i2 aryl sulfonyl (-S(=0) ₂ -aryl), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SC ), a C ₃ _i ₂ cycloalkyl, a C ₂ _i ₂ alkenyl, a Cs_ _l2 cycloalkenyl, a C _6-i2 aryl, a C _7-l3 arylalkylene, a C _4-l2 heterocycloalkyl, and a C _3-l2 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents.

[0109] "Acryl" includes both acrylics and acrylates.“Methacryl” includes both

(meth) acrylics and (meth)acrylates. The prefix“(meth)” includes the both the acryl and methacryl forms.

[0110] 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.