Oxidatively stable emollient composition

Abstract

The present disclosure relates to an emollient composition and a method for making the same. The emollient composition comprises a mixture of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. The method includes the steps of: (a) providing cocoa butter and a C1-C6 alkyl alcohol; (b) mixing the cocoa butter and the C1-C6 alkyl alcohol in the presence of an esterification catalyst at an esterification temperature to obtain an ester mixture; and (c) hydrogenating the ester mixture with hydrogen gas in the presence of a hydrogenation catalyst to obtain the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. Personal care products comprising the emollient composition are also disclosed herein.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 268,642, filed February 28, 2022, which is incorporated by reference herein in its entirety.

[0002] The present invention relates to an emollient composition, its method of preparation, and its use in personal care products. [Background technology]

[0003] Emollients are personal care products commonly used to relieve dry skin by keeping the skin moist. Emollients can be a wide variety of ingredients ranging from synthetically derived compounds (e.g., mineral oil) to natural ingredients (e.g., vegetable oils).

[0004] Mineral oil, a by-product of petroleum refining, has long been used as a main ingredient in emollient formulations due to its low volatility and smooth texture. Like other moisturizers, mineral oil helps to lock in moisture and smooth dry and rough skin. However, because mineral oils do not easily absorb and penetrate the skin, they remain on the skin surface, where they can clog pores and cause other skin problems.

[0005] There have been many efforts in the personal care and cosmetics industry to develop bio-based and natural alternatives to mineral and vegetable oils, and they have emerged as one of the most popular alternatives. An important advantage of vegetable oils is their natural source. They are generally not harmful to the environment and more closely mimic the lipid composition of skin and hair, making them easily absorbed. They promote the protection of the skin against excessive loss of water and nutrients, without interfering with the skin's natural functions, and help moisturize and structure the underlying tissues.

[0006] Despite these desirable properties, natural vegetable oils have some inherent limitations: Oxidation of vegetable oils, along with the breakdown of antioxidants, can cause products to acquire undesirable properties or even lose their effectiveness after a relatively short shelf life.

[0007] Cocoa butter is fat derived from cocoa beans. It is widely accepted and recognized as an essential ingredient for producing chocolate and confectionery. Due to its pleasant fatty acid profile and good odor on skin, cocoa butter has emerged as one of the most promising and healthy ingredients in cosmetics and personal care products.

[0008] As the demand for natural-based ingredients useful in personal care and cosmetic applications increases, it would be advantageous to have new natural-based materials with improved properties that more closely mimic the texture, appearance, stability, and properties of traditional materials for making personal care and cosmetic products. It is also desirable for such new materials to be more oxidatively stable. Summary of the Invention

[0009] The present disclosure provides an emollient composition comprising a mixture of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. Personal care formulations comprising the emollient composition are also described herein. The present disclosure further provides a method for producing a composition comprising hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. The method includes the steps of: (a) providing cocoa butter and C1-C6 ethyl alcohol; (b) hydrogenating the cocoa butter with hydrogen gas in the presence of a hydrogenation catalyst to obtain hydrogenated cocoa butter; and (c) combining the hydrogenated cocoa butter with the C1-C6 alkyl alcohol in the presence of an esterification catalyst at an esterification temperature to obtain the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Explanations of abbreviations and terms used in this disclosure are provided to aid in understanding and practicing the invention.

[0011] Throughout this specification, values ​​expressed in range format should be interpreted flexibly to include not only the numerical values ​​explicitly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within the range as if each numerical value and subrange were explicitly recited. For example, the range "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also the individual values ​​(e.g., 1%, 2%, 3% and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the range recited. The statement "about X to Y" has the same meaning as "about X to about Y" unless otherwise indicated. Similarly, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise indicated.

[0012] All percentages of composition or formulation components referred to herein are disclosed as weight percent (wt%) unless otherwise specified.

[0013] Unless otherwise stated, all parameter ranges disclosed are inclusive of the endpoints and all values ​​therebetween.

[0014] When used in the specification and claims, the terms "comprise" and "comprising" and variations thereof mean that the specified features, steps or integers are included. The terms are not to be interpreted as excluding the presence of other features, steps or components.

[0015] As used herein, the singular forms "a", "an" and "the" and similar referents in the context of describing elements (particularly in the context of the claims that follow) include plural referents unless the context clearly dictates otherwise. For example, reference to "a substituent" encompasses two or more substituents in addition to a single substituent, and so forth. Unless otherwise indicated herein or clearly contradicted by the context, it is understood that any term in the singular form may include its plural counterpart, and vice versa.

[0016] As used herein, the term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. The statement "at least one of A and B" has the same meaning as "A, B, or A and B."

[0017] As used herein, the terms "for example," "for instance," "such as," or "including" are meant to introduce examples that further clarify a more general subject matter. Unless otherwise specified, these examples are provided only as an aid to understanding the applications illustrated in this disclosure and are not meant to be limiting in any way.

[0018] As used herein, the term "about" can allow for a degree of variation within a value or range, for example, within 10%, within 5%, or within 1% of the specified value or within the limits of a specified range, plus or minus, and includes the exact specified value or range.

[0019] As used herein, the term "substantially" refers to a majority or majority portion, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.

[0020] In the methods described herein, unless a temporal or operational order is explicitly recited, acts may be performed in any order without departing from the principles of the present disclosure. Moreover, certain acts may be performed in parallel unless express "claim" language recites them separately. For example, a claimed act of doing X and a claimed act of doing Y may be performed simultaneously in a single operation, with the resulting process falling within the literal scope of the claimed process.

[0021] Representative features are presented in the following description, which may be used alone or in any combination with one or more features disclosed elsewhere in the description and / or drawings herein.

[0022] As used herein, the term "fatty acid" may refer to a molecule that includes a hydrocarbon chain and a terminal carboxylic acid group. As used herein, the carboxylic acid group of a fatty acid may be modified or esterified (e.g., COOR, where R refers to, for example, a carbon atom), such as occurs when the fatty acid is incorporated into a glyceride or another molecule. Alternatively, the carboxylic acid group may be in the form of a free fatty acid or a salt (i.e., COO" or COOH). The "tail" or hydrocarbon chain of a fatty acid may also be referred to as a fatty acid chain, a fatty acid side chain, or a fatty chain. The hydrocarbon chain of a fatty acid is typically a saturated or unsaturated aliphatic group. A fatty acid with N carbon atoms typically has a fatty acid side chain with N-1 carbons.

[0023] The term "acylglyceride" as used herein refers to a molecule having at least one glycerol moiety with at least one fatty acid residue linked via an ester bond. For example, acylglyceride can include monoacylglyceride, diacylglyceride, triacylglyceride. The group of acylglycerides can be further narrowed down by additional descriptive terms and modified to explicitly exclude or include certain subsets of acylglycerides. For example, the phrases mono- and di-acylglyceride refer to MAG (monoacylglyceride) and DAG (diacylglyceride), while the phrase non-MAG / non-DAG acylglyceride refers to the group of acylglycerides excluding MAG and DAG.

[0024] A "fatty acid residue" is a fatty acid in its acyl or esterified form.

[0025] The concentration of a particular type of fatty acid may be provided herein as a percentage of the total fatty acid content of the oil. Unless otherwise specified, such percentage is a weight percentage based on total fatty acids, including empirically calculated free and esterified fatty acids.

[0026] A "saturated" fatty acid is one that does not contain any carbon-carbon double bonds in the hydrocarbon chain. For example, stearic acid (C18:0) is a saturated fatty acid with a chain of 18 carbons with no carbon-carbon double bonds. An "unsaturated" fatty acid contains one or more carbon-carbon double bonds. For example, oleic acid (C18:1) is an unsaturated fatty acid with a chain of 18 carbons with one carbon-carbon double bond. A "polyunsaturated" fatty acid contains one or more such carbon-carbon double bonds, while a "monounsaturated" fatty acid contains only one carbon-carbon double bond. The carbon-carbon double bonds may be in one of two configurations, designated cis and trans. Naturally occurring unsaturated fatty acids are generally in the "cis" form.

[0027] Non-limiting examples of fatty acids include C14, C16 (e.g., C16:0, C16:1), C18 (e.g., C18:0, C18:1, C18:2, C18:3, C18:4), C20 (e.g., C20:0, C20:1, C20:2, C20:3, C20:4, C20:5), C22 (e.g., C22:0, C22:1, C22:2, C22:3, C22:4, C22:5, C22:6), and C24 (e.g., C24:0, C24:1, C24:2, C24:3, C24:4, C24:5, C24:6, C24:7) fatty acids. For example, the fatty acids can be myristic acid (14:0), palmitic acid (16:0), stearic or isostearic acid (18:0), oleic acid (18:1), linoleic acid (18:2), alpha-linolenic acid (18:3).

[0028] As used herein, the term "C14-C24 fatty acid" refers to a fatty acid containing 14 to 24 carbons. The C14-C24 fatty acid can be straight chain or branched chain. In some embodiments, the C14-C24 fatty acid is a C16 or C18 fatty acid.

[0029] The C14 to C24 fatty acid may be a mixture of C14 to C24 fatty acids.

[0030] As used herein, the term "C1-C6 alkyl ester or alkyl ester" refers to a fatty acid containing 14 to 24 carbons esterified with a C1-C6 alkyl group. For example, the term "ethyl ester" refers to a fatty acid containing 14 to 24 carbons esterified with an ethyl group. The C1-C6 alkyl group can be straight or branched chain. In one aspect, the C1-C6 alkyl has a straight chain. In one aspect, the C1-C6 alkyl is an ethyl group.

[0031] As used herein, the term "hydrogenated C1-C6 alkyl ester or hydrogenated alkyl ester" refers to a fatty acid C1-C6 alkyl ester that is partially, substantially, or fully hydrogenated. For example, the term "hydrogenated ethyl ester" refers to a fatty acid containing 14 to 24 carbons that is esterified with an ethyl group and is partially, substantially, or fully hydrogenated.

[0032] The fatty acid composition of an oil can be determined by methods known in the art. The American Oil Chemists' Society (AOCS) maintains analytical methods for a wide variety of tests performed on vegetable oils. Hydrolysis of oil constituents to produce free fatty acids, conversion of the free fatty acids to methyl esters, and analysis by gas-liquid chromatography (GLC) is a generally accepted standard method for determining the fatty acid composition of an oil sample. AOCS Procedure Ce 1-62 describes the procedure used.

[0033] The term "iodine value" (commonly abbreviated IV), as used herein, is the mass in grams of iodine consumed by 100 grams of a chemical. The iodine value is often used to determine the amount of unsaturation in fats, oils and waxes. In fatty acids, unsaturation occurs primarily as double bonds, which are highly reactive towards halogens, in this case iodine. Thus, the higher the iodine value, the more unsaturation is present in the sample. The iodine value of a material can be determined by the standard well-known Wijs method (AOCSCd1-25). Cd1-25).

[0034] The term "esterification or esterified" means that an ester bond is formed, including: 1) a dehydration reaction between an alcohol and an acid; 2) transesterification, which is the reaction of an alcohol with an ester to form a new ester; or 3) transesterification, which is the rearrangement of fatty acids within a triacylglycerol structure.

[0035] As used herein, "cocoa butter" refers to triacylglycerides (triglycerides or triacylglycerols) derived from a mixture of fatty acids derived from the seeds of the cocoa plant. Non-limiting examples of fatty acids in cocoa butter include C14 (e.g., C14:0), C16 (e.g., C16:0, C16:1), C18 (e.g., C18:0, C18:1, C18:2, C18:3), C20 (e.g., C20:0, C20:1), C22 (e.g., C22:0), and C24 (e.g., C24:0) fatty acids. In one embodiment, the cocoa butter has a fatty acid profile including, but not limited to, myristic acid (C14:0), palmitic acid (C16:0), palmitoleic acid (C16:1), stearic acid (C18:0), oleic acid (C18:1), linoleic acid (C18:2), alpha-linolenic acid (C18:3), arachidic acid (C20:0), paulic acid (C20:1), behenic acid (C22:0), and lignoceric acid (C24:0).

[0036] As used herein, "cocoa butter fatty acid C1-C6 ethyl esters" or "cocoa butter C1-C6 ethyl esters" refers to cocoa butter fatty acids containing 14 to 24 carbons (C14-C24 fatty acids) esterified with a C1-C6 ethyl group. As used herein, "hydrogenated cocoa butter fatty acid C1-C6 alkyl esters" or "hydrogenated cocoa butter C1-C6 alkyl esters" refers to cocoa butter fatty acid C1-C6 alkyl esters or cocoa butter C1-C6 alkyl esters that are partially, substantially, or fully hydrogenated.

[0037] As used herein, "cocoa butter fatty acid ethyl esters" or "cocoa butter ethyl esters (CBEEs)" refers to cocoa butter fatty acids containing 14 to 24 carbons (C14-C24 fatty acids) esterified with an ethyl group. As used herein, "hydrogenated cocoa butter fatty acid ethyl esters" or "hydrogenated cocoa butter ethyl esters (HCBEEs)" refers to cocoa butter fatty acid ethyl esters or cocoa butter ethyl esters that have been partially, substantially, or fully hydrogenated.

[0038] The term "emollient" as used herein refers to a composition or product that softens, smoothes, and moisturizes the skin by building and / or replenishing the skin barrier, repairing and filling skin cracks, and relieving roughness and redness caused by dry skin and other conditions (e.g., eczema, psoriasis). Thus, it prevents moisture loss from the skin, relieves dry skin, protects the skin, and keeps the skin healthy. Emollients may include synthetic compounds (e.g., mineral oil) and / or natural compounds (e.g., vegetable oils). Emollients may be, but are not limited to, lotions, creams, and ointments, depending on the water-to-oil ratio.

[0039] In one aspect, the emollient is a vegetable oil and / or vegetable fat such as cocoa butter. In another aspect, the emollient comprises an ester derived from cocoa butter fatty acids, including but not limited to cocoa butter fatty acid ethyl esters. In another aspect, the emollient comprises a hydrogenated ester derived from cocoa butter fatty acids, including but not limited to hydrogenated cocoa butter fatty acid C1-C6 alkyl esters, such as hydrogenated cocoa butter fatty acid ethyl esters.

[0040] The term "personal care formulation or personal care product" means and includes any cosmetic, hygiene, toiletry, skin care and topical care products, including, but not limited to, leave-on products (i.e., products that are left on the keratin substrate after application), rinse-off products (i.e., products that are washed or rinsed off from the keratin substrate during or within minutes of application), shampoos; hair curling and straightening products; hairstyle maintenance and hair conditioning products; lotions and creams for the nails, hands, feet, face, scalp and / or body; hair dyes; face and body make-up; nail care products; astringents; deodorants; antiperspirants; anti-acne medications; anti-aging; depilatories; colognes and fragrances; skin protection creams and lotions (such as sunscreens); skin and body cleansers; skin conditioners; skin toners; skin firming compositions; skin tanning and whitening compositions; liquid soaps; bar soaps; bath products; and shaving products.

[0041] The texture of such personal care formulations or personal care products may be, but is not limited to, liquids, gels, sprays, emulsions (such as lotions and creams), shampoos, pomades, foams, tablets, sticks (such as lip care products), make-up, among others, any of which may be applied to the skin or hair and are typically designed to remain in contact therewith until removed, such as by rinsing with water or washing with shampoo or soap. Other forms may be gels, which may be soft, hard or squeezable. Sprays may be non-pressurized aerosols delivered from hand-pumped finger-actuated sprayers, or pressurized aerosols such as mousses, sprays or foam-forming formulations where chemical or gaseous propellants are used.

[0042] The topical formulations including the emollient compositions disclosed herein may be creams used in skin care applications.

[0043] The formulations prepared using the compositions disclosed herein generally have a white or pale white color that is considered aesthetically pleasing. In some cases, the formulations of the present invention may be further processed to produce a colored final product. In such cases, the white color is beneficial because it allows additional pigments to stand out without affecting the final color.

[0044] Furthermore, the formulation prepared using the composition disclosed herein has acceptable oil content and good spreadability, and does not leave a greasy residual feeling on skin.This texture feels comfortable to touch and apply.Furthermore, the consistency is such that good product pick-up can be achieved.Good product pick-up means that the user's fingers can collect enough product (i.e., not too much, not too little).

[0045] The compositions of the present disclosure are particularly useful in sunscreen applications. Sunscreens contain ingredients intended to block ultraviolet light from reaching the skin. The UV blockers or sunscreens can be physical or chemical salts, such as ZnO, or TiO2, or chemicals (maximum approved levels are given), such as avobenzone (3%), homosalate (15%), butyl methoxydibenzoylmethane (5%), octocrylene (10%), titanium dioxide (25%), ethylhexyl salicylate (5%), ethylhexyl methoxycinnamate (10%), bis-ethylhexyloxyphenol methoxyphenyl triazine (10%). The compositions of the present disclosure can be used with any type of UV blocker or sunscreen known in the art, or a mixture of UV blockers or sunscreens.

[0046] "Mettler Drop Point" (MDP) is the temperature at which a solid fat becomes a flowing fluid. MDP can be determined, for example, using ASTM standard D127-19.

[0047] Emollient Composition The emollient compositions described herein comprise a mixture of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. In one aspect, the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters are hydrogenated cocoa butter fatty acid ethyl esters or hydrogenated cocoa butter ethyl esters (HCBEE). In one aspect, the HCBEE has a fatty acid ethyl ester profile as shown in Table 1.

[0048] [Table 1]

[0049] In one embodiment, the HCBEE comprises from about 15% to about 30%, from about 20% to about 30%, or from about 24% to about 28% palmitic acid ethyl ester.

[0050] In one embodiment, the HCBEE comprises about 65% to about 80%, about 70% to about 80%, or about 70% to about 75% ethyl stearate.

[0051] In one embodiment, the HCBEE contains about 15% to about 30% ethyl palmitate and about 65% to about 80% ethyl stearate.In one embodiment, the HCBEE contains about 24% to about 28% ethyl palmitate and about 70% to about 75% ethyl stearate.

[0052] In one embodiment, the emollient composition comprises greater than 50%, greater than 75%, greater than 90%, greater than 95%, or greater than 99% hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. In another embodiment, the content of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters in the emollient composition ranges from about 50% to about 99%, about 75% to about 99%, about 90% to about 99%, about 95% to about 99%, about 95% to about 99%, about 95% to about 99.3%, about 95% to about 99.5%, or about 99.3% to about 99.5%. In another embodiment, the content of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters in the emollient composition is about 99.3% or about 99.5%.

[0053] In one aspect, the emollient composition may be blended with other emollients, such as natural emollients, synthetic emollients, and / or petroleum-based emollients.

[0054] In one embodiment, the emollient composition comprises greater than 50%, greater than 75%, greater than 90%, greater than 95%, or greater than 99% HCBEE. In another embodiment, the content of HCBEE in the emollient composition ranges from about 50% to about 99%, about 75% to about 99%, about 90% to about 99%, about 95% to about 99%, about 95% to about 99%, about 95% to about 99.3%, or about 95% to about 99.5%. In another embodiment, the content of HCBEE in the emollient composition is about 99.3% or about 99.5.

[0055] In one embodiment, the Mettler dropping point of the hydrogenated cocoa butter fatty acid C1-C6 alkyl ester is in the range of about 33°C to about 37°C, about 33°C to about 36°C, about 33°C to about 35°C, or about 33°C to about 34°C.

[0056] In one embodiment, the Mettler dropping point of the HCBEE is in the range of about 33°C to about 37°C, about 33°C to about 36°C, about 33°C to about 35°C, or about 33°C to about 34°C.

[0057] In one aspect, the HCBEE produced by the methods described herein has a rich texture with a solid appearance and off-white color. Moreover, HCBEE can easily dissolve on the skin, leaving a light film on the skin surface and providing a cushioning effect. These properties make HCBEE a good candidate for applications such as personal care products and cosmetics. For example, HCBEE can be added to lotions, creams, or skin care products at a loading level of 1-10%. In another example, HCBEE can be added to anhydrous balms or sticks at a loading level of 1-20%. In yet another example, HCBEE can be added to hair care products at a loading level of 1-5%.

[0058] In one embodiment, the HCBEE has a viscosity, as determined by a Brookfield viscometer, of about 46,600 MPa.s.

[0059] Personal Care Formulations The personal care formulations described herein include an emollient composition, the emollient composition comprising a mixture of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. In one embodiment, the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters are hydrogenated cocoa butter fatty acid ethyl esters (HCBEEs). In another embodiment, the HCBEEs have a fatty acid ethyl ester profile as shown in Table 1.

[0060] In one embodiment, the personal care formulations described herein can contain any useful amount of the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters of the present disclosure. In one embodiment, the content of the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters in the personal care formulation ranges from 1% to 100%, 10% to 50%, 15% to 45%, 20% to 40%, 22% to 38%, or 25% to 35% by weight. In one embodiment, the content of the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters in the personal care formulation is 30% by weight.

[0061] In one embodiment, the personal care formulations described herein can contain any useful amount of the HCBEE of the present disclosure. In one embodiment, the content of HCBEE in the personal care formulation ranges from 1% to 100%, 10% to 50%, 15% to 45%, 20% to 40%, 22% to 38%, or 25% to 35% by weight. In one embodiment, the content of HCBEE in the personal care formulation is 30% by weight.

[0062] Method for producing hydrogenated cocoa butter fatty acid C1-C6 alkyl ester The process for producing hydrogenated cocoa butter fatty acid C1-C6 alkyl esters described herein comprises a step of hydrogenating cocoa butter and an esterification step in which the hydrogenated cocoa butter is mixed with a C1-C6 alkyl alcohol to obtain HCBEE. In one embodiment described in the examples below, the hydrogenation step is carried out before the esterification step.

[0063] In one aspect, the esterification step can be carried out before the hydrogenation step. In this particular embodiment, the method for producing hydrogenated cocoa butter fatty acid C1-C6 alkyl esters comprises the steps of: (a) providing cocoa butter and a C1-C6 alkyl alcohol; (b) hydrogenating the cocoa butter with hydrogen gas in the presence of a hydrogenation catalyst to obtain hydrogenated cocoa butter; and (c) combining the hydrogenated cocoa butter with the C1-C6 alkyl alcohol in the presence of an esterification catalyst at an esterification temperature to obtain hydrogenated cocoa butter fatty acid C1-C6 alkyl esters.

[0064] The esterification of triglyceride vegetable oils is well known in the art, for example in the preparation of biodiesel. Typically, the oil is mixed with an excess of alcohol and heated to high temperature in the presence of a catalyst. The catalyst is typically, but not necessarily, a metal salt of the corresponding alcohol. The choice of reaction temperature is related to the alcohol used, and one skilled in the art will choose a temperature that balances the reaction rate with the production of undesirable by-products. In one embodiment, the esterification temperature is about 70° C., the alcohol is ethanol, and the esterification catalyst is sodium ethoxide.

[0065] Hydrogenation of triglyceride vegetable oils and esterified fatty acids is also well known in the art. Typically, the oil (or in this case, cocoa butter fatty acid C1-C6 alkyl esters) is exposed to hydrogen gas and heated in the presence of a catalyst. Many catalysts can be used, but nickel-based catalysts are commonly used. The hydrogenation proceeds until a desired endpoint is reached. The iodine value (IV) of the oil can be monitored to understand the amount of unsaturated double bonds remaining in the product. It is well understood in the art that it is often difficult, expensive, or impractical to completely eliminate all double bonds in the oil being hydrogenated. At the end of hydrogenation, the catalyst can be removed by simple filtration to obtain the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. In one embodiment, the hydrogenation catalyst is nickel (Pricat 9910, Johnson Matthey Process Technologies).

[0066] In one embodiment, the method may include additional steps to purify and / or modify the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters. For example, the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters may be desolventized under reduced pressure with nitrogen gas to remove volatile substances such as solvents and ethanol. The desolventized hydrogenated cocoa butter fatty acid C1-C6 alkyl esters may be decanted with nitrogen gas, bleached with a bleaching agent, and deodorized with a deodorizing agent or process. These procedures are also well known in the art of vegetable oil refining and are referred to as "refining". These steps can be easily modified or altered depending on the impurities to be removed.

[0067] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. As used herein, each of the following terms has the meaning associated with it as defined below.

[0068] The present invention will be described in more detail by reference to the following experimental examples. These examples are provided for illustrative purposes only and are not intended to be limiting unless otherwise specified. Therefore, the present invention should not be construed as being limited to the following examples in any way, but rather as embracing any and all variations that become evident as a result of the teachings provided herein. EXAMPLES

[0069] Example 1 - Method for producing HCBEE Table 2 shows the ingredients for producing HCBEE using the methods described herein.

[0070] [Table 2]

[0071] The process begins with the hydrogenation step. Cocoa butter was first melted and the molten cocoa butter was heated to 135° C. under a flow of hydrogen gas in the presence of a heterogeneous nickel catalyst (Pricat 9910, Johnson Matthey Process Technologies). The iodine value (IV) was monitored throughout the reaction and hydrogenation was determined to be complete when the IV was less than 1. An absorbent (Select 450, Oil-Dri Fluids Purification) was then added to remove the catalyst from the hydrogenated cocoa butter by filtration.

[0072] To produce the ethyl esters (i.e., HCBEE), an excess of 40%-50% ethanol and 1.4 wt. % of 21% sodium ethoxide catalyst in ethanol (based on the total weight of cocoa butter and ethanol) was mixed with the molten hydrogenated cocoa butter with stirring at 70°C for 120 minutes, or until esterification was complete as evidenced by the ethyl esters produced, as determined by high performance liquid chromatography (HPLC) analysis.

[0073] The HCBEE was desolvated under nitrogen flow and reduced pressure until the volatiles present in the HCBEE were less than 0.5% as measured by a volatile analyzer (scale oven). The ethanol removed from the HCBEE was recovered. The desolvated HCBEE was decanted with nitrogen gas at 70°C to remove glycerol produced during esterification. An additional glycerol wash was used to further remove glycerol from the ethyl ester phase. The decanted HCBEE was bleached with adsorbents (Sorbsil 92, PQ Corporation; and Perform 6000, Oil-Dri Fluids Purification) at 95°C under stirring. The bleached HCBEE was deodorized with water at 160-165°C. Finally, the deodorized HCBEE was cooled to 70°C and tocopherol (70% tocopherol in vegetable oil base, BASF Covi-Ox T70 EU (non-GM version)) was added to the cooled product.

[0074] Example 2 - Oxidation Stability of CBEE The Oxidative Stability Index (OSI) measures the relative oxidative stability of fatty materials. A sample of HCBEE was heated to 110°C under a constant airflow. As the oxidative degradation of the material began, the volatile short chain fractions broke down and became entrapped in the airflow. The short chain fractions were then trapped in distilled water and detected by a conductivity probe to give the OSI reading.

[0075] Table 3 below shows the OSI for HCBEE and other fatty substances. OSI values ​​below 20 hours are generally considered unstable.

[0076] [Table 3]

[0077] As can be seen, HCBEE has a significantly higher OSI than other fatty acid esters and silicones, which are traditional ingredients for making personal care products. The excellent oxidative stability makes HCBEE a good candidate as an ingredient in personal care products.

[0078] Example 3 - Skin Care Formulation Table 4 shows skin care formulations in which HCBEE is one of the ingredients.

[0079] [Table 4]

[0080] The skin care formulation has a pH adjusted to 5.0-5.5 and the appearance of a viscous white cream. It is stable at room temperature and at 45°C for 2 months.

[0081] Example 4 - Skin Care Formulation Table 5 shows skin care formulations in which HCBEE is one of the ingredients.

[0082] [Table 5]

[0083] To prepare the skin care formulation, deionized water, tetrasodium glutamate diacetate, glycerin, propanediol, and sclerotium gum were mixed in a first vessel at room temperature with uniform mixing stirring (2000-3000 rpm).The mixture in the first vessel was then heated to 75-80°C to obtain a Phase A mixture.

[0084] In a second vessel, HCBEE, Jojoba Esters (Diene Esters), Helianthus Annuus (Sunflower) Seed Oil, Tocopheryl Acetate, Jojoba Oil / Macadamia Seed Oil Esters (and) Squalene, (and) Phytosteryl Macadamiate, (and) Phytosterols, Jojoba Esters (Saturated Esters), Polyglycerol-3 Stearate, Sodium Stearoyl Lactylate, Glyceryl Stearate SE, and Cetearyl Alcohol were mixed and heated to 75-80°C to obtain a Phase B mixture.

[0085] The Phase B mixture was mixed with the Phase A mixture under uniform mixing agitation (3,000-6,000 rpm) at 75-80°C to obtain a Phase A / B blend. The Phase A / B blend was further mixed under propeller agitation (300-450 rpm) and cooled to 50-55°C.

[0086] Phenoxyethanol (and) Ethylhexylglycerin and Citric Acid were added with propeller agitation (150-250 rpm) to the cooled Phase A / B blend at 50-55° C. Mixing was stopped when the temperature of the final mixture reached 45-50° C. to obtain the skin care formulation.

[0087] Example 5 - Skin Care Formulation Table 6 shows skin care formulations in which HCBEE is one of the ingredients.

[0088] [Table 6]

[0089] To prepare the skin care formulation, HCBEE, isononyl isononanoate, jojoba esters (diene esters), tocopherol acetate, polyglyceryl-2 dipolyhydroxystearate, polyglyceryl-3 diisostearate, and isopropyl myristate (and) stearalkonium hectorite (and) propylene carbonate were mixed in a first vessel and heated to 65-70° C. The mixture in the first vessel was then homogenized by uniform mixing stirring (2,000-3,000 rpm) at 65-70° C. to obtain a Phase A mixture.

[0090] The Phase B mixture was added to the Phase A mixture with uniform mixing stirring (2,000-3,000 rpm) at 65-70°C to obtain a Phase A / B blend.

[0091] In a second vessel, deionized water, tetrasodium glutamic acid diacetate, glycerin, sodium chloride, caprylhydroxamic acid (and) glyceryl caprylate (and) glycerin, and citric acid were mixed with propeller agitation (300-450 rpm). The mixture in the second vessel was then heated to 65-70° C. to obtain a Phase A mixture.

[0092] The Phase C mixture was added very slowly to the Phase A / B blend with homogeneous mixing stirring (2000-3000 rpm) at 65-70°C. The homogeneous mixing stirring was increased to a medium speed (3000-6000 rpm) at 65-70°C to obtain the Phase A / B / C blend. The Phase A / B / C blend was cooled to 55-60°C.

[0093] In a third vessel, trihydroxystearin and Helianthus annuus (sunflower) seed oil were mixed at room temperature using propeller agitation (300-450 rpm) until both ingredients were uniformly blended to obtain a Phase D mixture.

[0094] The Phase B mixture was added to the Phase A mixture with uniform mixing stirring (3,000-6,000 rpm) at 55-60°C to obtain a Phase A / B blend. Mixing was stopped when the temperature of the final mixture reached 50-55°C to obtain the skin care formulation.

[0095] The skin care formulations have a Sun Protection Factor (SPF) of about 11.1 (without booster) and about 14.1 (with booster). The SPF was estimated by DSM Sunscreen Optimizer, Broad Spectrum (USA) pass.

[0096] Example 6 - Skin Care Formulation Table 7 shows skin care formulations in which HCBEE is one of the ingredients.

[0097] [Table 7]

[0098] To prepare the skin care formulations, jojoba esters (saturated esters), jojoba esters (mixture of diene, monoene and saturated esters), corn (maize) starch, tocopherol, fragrance, mica (and) titanium dioxide (and) carmine were heated in a water bath to 75-80°C. The heated ingredients were mixed with HCBEE preheated in an oven or water bath at 45-50°C in a rotor-stator mixer (IKA Ultra Turrax T25, S25N-25G workhead) at 6000 rpm for 1 minute until a clear homogenous phase was obtained. The mixture was poured into moulds. The moulded mixture was left at room temperature for 5 minutes and stored in a freezer (-18°C) for 10 minutes or left at room temperature for 30 minutes before being removed from the moulds and packaged to obtain the skin care formulations.

[0099] Example 7 - Skin Care Formulation Table 8 shows skin care formulations in which HCBEE is one of the ingredients.

[0100] [Table 8]

[0101] To prepare the skin care formulations, HCBEE was preheated at 45-50° C. in an oven or water bath until a clear homogenous phase was obtained.

[0102] AQUA (Part B), sodium hyaluronate, and caffeine were mixed with a mixer (IKA Eurostar Digital, dissolver workhead) until a homogenous phase was observed, resulting in a Phase D mixture.

[0103] The water (Part A) and glycerin were mixed with a spatula until a homogenous phase was observed to obtain a Phase A mixture. Additional water (Part A) can be used (e.g., an additional 5% by weight) to compensate for water evaporated due to heat generated in the process.

[0104] The sclerotium gum and starch sodium octenyl succinate were mixed with a spatula until a homogenous phase was observed to obtain a Phase B mixture.

[0105] The Phase B mixture was mixed with the Phase A mixture using a rotor / stator (IKA Ultra Turrax T25, workhead S25N-25G) at 10,000 rpm for 10 minutes to obtain a Phase A / B blend. The Phase A / B blend was heated to 65-75°C in a water bath.

[0106] Mix glyceryl stearate citrate and preheated HCBEE and heat to 65-75°C in a water bath to obtain Phase C mixture.

[0107] The Phase C mixture was mixed with the heated Phase A / B blend using a rotor / stator (IKA Ultra Turrax T25, workhead S25N-25G) at 10,000 rpm for 2 minutes to obtain a Phase A / B / C blend. The Phase A / B / C blend was cooled to below 40° C. while stirring using an agitator (IKA Eurostar Digital, propeller workhead).

[0108] Parfum and benzyl alcohol (and) salicylic acid (and) glycerin (and) sorbic acid were mixed to obtain Phase E mixture. Phase D mixture and Phase E mixture were added to Phase A / B / C blend while stirring using a stirrer (IKA Eurostar Digital, propeller workhead) until a homogenous phase was obtained. The pH of the resulting skin care formulation was adjusted to 5.0-5.5 by adding sodium hydroxide (35%) while stirring using a stirrer (IKA Eurostar Digital, propeller workhead).

[0109] Example 8 - Hair Care Formulation Table 9 shows hair care formulations in which HCBEE is one of the ingredients.

[0110] [Table 9]

[0111] To prepare the hair care formulation, deionized water, glycerin, sclerotium gum, hydroxypropyl starch phosphate, and sodium starch octenyl succinate and hydroxypropyl starch phosphate were mixed under a Silverson homogenizer at 7000 rpm for 7 minutes to obtain a Phase A mixture.

[0112] Coconut oil and HCBEE were mixed in a separate container and heated to 50° C. with slow mixing until both ingredients were completely melted to obtain Phase B mixture.

[0113] The Phase B mixture was added to the Phase A mixture and mixed for 10 minutes with a scraper mixing at 70 rpm to obtain a Phase A / B blend. The Phase A and Phase B mixtures could also be blended manually with a spatula followed by high shear mixing under a Silverson homogenizer at 5000-7000 rpm to obtain a Phase A / B blend. The Phase A / B blend was further mixed with a propeller mixer at low mixing (approximately 800-1200 rpm) to avoid trapping air bubbles.

[0114] Using a propeller mixer, phenoxyethanol, tocopheryl acetate, and mica were added one by one to the Phase A / B blend. Deionized water was added to make up for the water lost during the process to obtain the hair care formulation.

[0115] The hair care formulation has a pH adjusted to 4.5 to 5.5 and a viscosity of about 14,950 cP.

[0116] In addition to the uses described above, the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters described herein can be used as ingredients in products including, but not limited to, skin care products, sun care products, hair care products (e.g., shampoos, conditioners), makeup products, and the like.

Claims

1. An emollient composition comprising a mixture of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters.

2. 2. The emollient composition of claim 1, wherein the hydrogenated cocoa butter fatty acid C1-C6 alkyl ester is a hydrogenated cocoa butter fatty acid ethyl ester.

3. 10. The emollient composition of claim 1 comprising greater than 90% hydrogenated cocoa butter fatty acid C1-C6 alkyl esters.

4. 2. The emollient composition of claim 1, wherein said hydrogenated cocoa butter fatty acid C1-C6 alkyl esters have a Mettler dropping point in the range of about 33° C. to about 37° C.

5. 13. A personal care formulation comprising the emollient composition of claim 1.

6. 6. The personal care formulation of claim 5, wherein said content of hydrogenated cocoa butter fatty acid C1-C6 alkyl esters is from 20% to 40%.

7. 6. The personal care formulation of claim 5, further comprising one or more of sclerotium gum, glycerin, an emulsifier, a preservative, sodium hydroxide, and citric acid.

8. 6. The personal care formulation of claim 5 further comprising a sunscreen.

9. 6. The personal care formulation of claim 5, further comprising one or more of a fragrance, an active, a preservative, and a colorant.

10. 6. The personal care formulation of claim 5, wherein the personal care formulation is selected from the group consisting of skin protectant creams, lotions, sunscreens, skin or body cleansers, skin conditioners, skin toners, shampoos, hair conditioners, and skin tightening compositions.

11. 1. A method for producing a composition comprising hydrogenated cocoa butter fatty acid C1-C6 alkyl esters, the method comprising: a. providing cocoa butter and a C1-C6 alkyl alcohol; b) hydrogenating the cocoa butter with hydrogen gas in the presence of a hydrogenation catalyst to obtain hydrogenated cocoa butter; c) mixing the hydrogenated cocoa butter with the C1-C6 alkyl alcohol in the presence of an esterification catalyst at an esterification temperature to obtain the hydrogenated cocoa butter fatty acid C1-C6 alkyl ester.

12. 12. The method of claim 11, wherein the hydrogenated cocoa butter fatty acid C1-C6 alkyl esters are hydrogenated cocoa butter fatty acid ethyl esters.

13. 12. The method of claim 11, wherein the C1 to C6 alkyl alcohol is ethanol.

14. 12. The method of claim 11, wherein the hydrogenation temperature ranges from about 135°C to about 170°C.

15. 12. The method of claim 11, wherein the esterification temperature is about 70°C.

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