Hydrophobically modified starch

Abstract

A hydrophobically modified starch having the following structure (I): wherein R1 is a C3 to C19 branched or linear alkyl or alkenyl group, R2 is H or an alkyl group having 1 to 10 carbon atoms, R3 is H, CH3 or COOH, R4 is H or CH3, n is 2 or 3, and M is H, an alkali metal, an alkaline earth metal or ammonium; and wherein Starch represents a starch fraction. (I)

Description

TECHNICAL FIELD

[0001] The present disclosure relates generally to hydrophobically modified starches. The present disclosure more specifically relates to hydrophobically modified amphoteric starches formed using alkenyl succinic anhydride. BACKGROUND

[0002] Oil-in-water (O / W) dispersions are widely used in emulsions, creams, and moisturizers to provide moisturizing, emollient, and other benefits to the skin. However, these dispersions can suffer from long-term stability issues that can lead to changes in texture and appearance over time, thereby incurring consumer dissatisfaction.

[0003] The following are some common issues with long-term stability of oil-in-water dispersions. Creaming occurs when oil droplets rise to the top of the dispersion, causing the surface to form a cream or thick layer. This is often caused by a difference in density between the oil and water phases and can be exacerbated by temperature changes, agitation, or aging. Phase separation occurs when the oil and water phases separate, resulting in a clear layer of oil floating on top of the water layer. This can occur due to various factors, including insufficient emulsification, temperature changes, and aging. Flocculation occurs when oil droplets in the dispersion aggregate to form larger clusters that can settle or float to the top of the product. This can be caused by a variety of factors, including changes in pH, ionic strength, and the presence of certain ingredients. Coalescence occurs when oil droplets in the dispersion fuse together, resulting in larger oil droplets that can settle or float to the top of the product.

[0004] These stability issues can lead to a variety of problems, including changes in product texture, appearance, and performance, as well as shortened shelf life and consumer dissatisfaction. Addressing these issues requires careful formulation design and ingredient selection, as well as appropriate manufacturing and storage conditions to ensure long-term stability.

[0005] Traditionally, synthetic materials, including small molecules, have been commonly used as emulsifiers. However, certain small molecule emulsifiers can cause skin irritation and negatively interact with the cosmetic functional materials in the formulation. In addition, certain small molecule emulsifiers can also fail to provide the desired long-term emulsion stability.

[0006] Hydrophobically modified cross-linked acrylate polymers, such as Carbopol and Pemulen, have been used to stabilize emulsions to overcome van der Waals forces and gravity. Van der Waals forces lead to flocculation and coalescence, while gravity leads to the upward or downward movement of the dispersed phase in the emulsion. However, known solutions to these issues include synthetic, non-natural polymers.

[0007] Therefore, there remains an opportunity for improvement. Moreover, the desired features and characteristics of the present disclosure will become apparent from the ensuing detailed description of the disclosure and the appended claims, taken in conjunction with the background of the disclosure and the accompanying drawings. SUMMARY

[0008] This disclosure provides a hydrophobically modified starch having the following structure: ; Where R 1 It is C3 to C 19 Branched or straight-chain alkyl or alkenyl groups, R 2 It is H or an alkyl group having 1 to 10 carbon atoms, R 3 It is H, CH3 or COOH, R 4 It is H or CH3, n is 2 or 3, and M is H, alkali metal, alkaline earth metal or ammonium; and Starch represents the starch moiety. Attached Figure Description

[0009] This disclosure will be described in conjunction with the following figures, wherein: Figure 1A This is a schematic diagram illustrating the differences between emulsion flocculation, aggregation, and flotation; and Figure 1B This is a graph showing the relationship between the system energy and the distance between droplets in an oil-in-water emulsion, illustrating the first and second energy barriers for aggregation, as well as the energy valley for flocculation. Detailed Implementation

[0010] The following specific embodiments are exemplary in nature and are not intended to limit the present compounds or compositions. Furthermore, there is no intention to be bound by any theories presented in the foregoing background or the following specific embodiments.

[0011] Embodiments of this disclosure generally relate to hydrophobically modified starch compounds, emulsions and compositions comprising such compounds, and methods for forming the same. For the sake of brevity, conventional techniques associated with the preparation of starch compounds, emulsions, and such compositions may not be described in detail herein. Furthermore, the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process with additional steps or functions not described in detail herein. Specifically, the various steps in the manufacture of emulsions and related compositions are well known; therefore, for the sake of brevity, many conventional steps will be described only briefly or will be omitted entirely without providing well-known process details.

[0012] In this disclosure, the term "about" can be described in various embodiments as a value ±0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%. Furthermore, it should be understood that, in consideration of various non-limiting embodiments, all numerical values ​​provided herein, other than actual embodiments, are approximate values, wherein endpoints or specific values ​​should be understood as "about" or "approximate" to said values. It is also understood that all isomers and chiral options of each compound described herein are expressly considered for use in various non-limiting embodiments.

[0013] Throughout the present disclosure, the term“active” percent refers to the percentage amount of active or actual compound or molecule present, for example, as compared to the total weight of a dilute solution of the compound and solvent. Certain compounds, for example solvents, are not described in relation to active percent because it is well known that their active percent is approximately 100% active. It will be understood by those skilled in the art that any one or more of the values described herein can alternatively be described as an active percent.

[0014] In various embodiments, the term“free of’ describes embodiments containing less than about 5, 4, 3, 2, 1, 0.5, or 0.1 wt% (or wt% active) of the relevant compound or element using an appropriate weight basis as understood by those skilled in the art. In other embodiments, the term“free of’ describes embodiments in which the relevant compound or element is zero percent by weight.

[0015] The term“consisting essentially of’ can describe various non-limiting embodiments that are free of one or more optional compounds described herein and / or free of one or more polymers, surfactants, additives, solvents, and the like.

[0016] It will be understood that the subscript of a polymer is generally described as an average because the synthesis of a polymer will generally result in a distribution of individual molecules.

[0017] The emulsions, polymers, and compositions disclosed herein can suitably comprise, consist of, or consist essentially of the component, element, and process delineations described herein. The embodiments exemplarily disclosed herein can be suitably practiced in the absence of any element not specifically disclosed herein.

[0018] In various embodiments, the term“modified” as applied to starch refers to a starch molecule in which one or more of its hydroxyl groups have been reacted. In other embodiments, the term“hydrophobically modified” describes a starch molecule that has been substituted with one or more aliphatic or aromatic, saturated or unsaturated, straight chain, branched, or cyclic C8-C 30 hydrocarbyl chain. Generally, the“weight” of any starch or cellulose material is reported on a dry weight basis. In various embodiments, the term“stability” or“long-term stability” can describe the stability of an emulsion over a period of at least 28 days, measured using a TURBISCAN® LAB stability analyzer at both 22 °C and 45 °C, as described in more detail below. Hydrophobically modified starch

[0019] The present disclosure provides a hydrophobically modified amphoteric starch, which can alternatively be described as a hydrophobically modified amphoteric starch.

[0020] In one embodiment, the hydrophobically modified starch has the following structure: ; wherein R 1 is a C3to C 19 branched or straight chain alkyl or alkenyl group, R 2 is H or an alkyl group having 1 to 10 carbon atoms, R 3 is H, CH3, or COOH, R 4 is H or CH3, and n is 2 or 3; and M is selected from H, an alkali metal, an alkaline earth metal, or ammonium.

[0021] In another embodiment, the hydrophobically modified starch has the following structure:

[0022] wherein R 1 is a C3to C 19 branched or straight chain alkyl or alkenyl group, R 2 is H or an alkyl group having 1 to 10 carbon atoms, R 3 is H, CH3, or COOH, R 4 is H or CH3, and n is 2 or 3. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values described above and numerical values falling within the ranges described above, are expressly contemplated for use herein. In other embodiments, both of the above structures can be present.

[0023] In various embodiments, R 1 is a branched or straight chain alkyl or alkenyl group having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 carbon atoms. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values described above and numerical values falling within the ranges described above, are expressly contemplated for use herein.

[0024] In other embodiments, R 2 is H or an alkyl group having 1 to 10 carbon atoms, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values described above and numerical values falling within the ranges described above, are expressly contemplated for use herein.

[0025] In other embodiments, R 3 is H, CH3, or COOH.

[0026] In other embodiments, R 4 is H or CH3.

[0027] In other embodiments, n is 2 or 3 or a value therebetween.

[0028] Further, the term "starch" represents a starch moiety. Alternatively, the term can be described as representing a starch or modified starch moiety, wherein a hydrogen atom of a hydroxyl group of a deoxyglucose unit of the starch or modified starch moiety is replaced. The term can alternatively refer to O-Starch or Starch-O as shown below: or

[0029] In various embodiments, the starch can be hydrophobically modified with an alkenyl succinic anhydride, which can be branched or unbranched. For example, the anhydride can alternatively be described as octenyl succinic anhydride (OSA). In the art, alternative structures of OSA are provided such that the double bond shown above can alternatively be located elsewhere. In various non-limiting embodiments, all versions of alkenyl succinic anhydride and OSA that are recognized in the art are expressly contemplated for use herein.

[0030] The starch can be made amphoteric by any reaction known in the art. For example, the starch can be made amphoteric by reaction with 2-chloroethylaminodipropionic acid (EDPA). The reaction between the starch and the EPA is typically carried out by an etherification reaction, in which the chloroethyl group of the EPA reacts with a hydroxyl group of the starch to form an ether linkage.

[0031] The amphoteric starch can be further hydrophobically modified by reaction with an alkenyl succinic anhydride (ASA), thereby introducing a hydrophobic group to the surface of the starch. The reaction between the starch and the ASA is typically carried out by an esterification reaction, in which the anhydride group of the ASA reacts with a hydroxyl group of the starch to form an ester linkage. The reaction can be catalyzed by an acid, such as sulfuric acid or hydrochloric acid, or an enzyme, such as a lipase or protease. During the reaction, the ASA molecule is hydrolyzed to form an acid, which acts as a catalyst for the esterification reaction. The reaction can also be catalyzed by a base. In a typical base-catalyzed reaction, the particulate starch is treated with the ASA in an aqueous slurry having a pH of 7 to 11, more preferably a pH of about 7.5 to 9. The hydrophobic alkyl or alkenyl group on the ASA molecule is thereby attached to the starch, which makes the modified starch more hydrophobic and less water-soluble than the unmodified starch. The degree of modification or the number of alkyl or alkenyl groups attached to the starch molecule can be controlled by varying the reaction conditions, such as the amount of ASA used, the reaction time, and the temperature. In one embodiment, the starch is reacted with octenyl succinic anhydride (OSA). In another embodiment, the starch is reacted with dodecenyl succinic anhydride (DDSA).

[0032] In alternative embodiments, the hydrophobically modified starch can be modified with one or more aliphatic or aromatic, saturated or unsaturated, straight chain, branched, or cyclic C8-C 30hydrophobic groups containing 8 to 30 carbon atoms. In another embodiment, the hydrophobic substituents used can include C8-C 30 In another embodiment, C8-C 22 alkyl, alkenyl, aralkyl, or alkaryl groups, and mixtures thereof. In one embodiment, the hydrophobic substituents are C8-C 22 , for example C8-C 12 alkenyl chains, such as octenyl (unsaturated C8) and linear or branched dodecenyl (unsaturated C 12 ) groups. In one embodiment, the hydrophobic groups are derived from natural sources, including but not limited to, tall oil, tallow, soy, coconut oil, and palm oil. The hydrophobic modifier can be attached to the starch substrate by ether linkages, ester linkages, or urethane linkages. Ester linkages are preferred.

[0033] In one embodiment, the hydrophobically modified amphoteric starch is present, wherein R 1 is a C5 linear alkyl, R 2 is H, n is 2, R 3 is H, and R 4 is H. This can be described as an OSA modified amphoteric starch or an octenyl succinic anhydride modified amphoteric starch.

[0034] In another embodiment, the hydrophobically modified amphoteric starch is present, wherein R 1 is a C9 linear alkyl, R 2 is H, n is 2, R 3 is H, and R 4 is H. In another embodiment, the hydrophobically modified amphoteric starch is present, wherein R 1 is a C9 branched alkyl, R 2 is H, n is 2, R 3 is H, and R 4 is H. These can be described as a DDSA modified amphoteric starch or a dodecenyl succinic anhydride modified amphoteric starch, as DDSA can be linear or branched.

[0035] The starch can be derived from a variety of sources, including plants, animals, and microorganisms. In various embodiments, the starch is derived from corn, wheat, rice, or a combination thereof. In other embodiments, the starch is derived from potato, cassava, manioc, or a combination thereof. In other embodiments, the starch is derived from peas, beans (such as soybeans), lentils, or a combination thereof. In other embodiments, the starch is derived from bone marrow and / or animal tissue. In other embodiments, the starch is derived from a fermentation process of microorganisms. Any combination of the above can be used.

[0036] The starch of the present disclosure can be any type. Starch is a complex carbohydrate composed of two types of glucose polymers: amylose and amylopectin. Amylose is a straight-chain polymer of glucose units linked by a-1,4-glucosidic bonds. This imparts a helical structure to amylose, which is stabilized by intermolecular hydrogen bonds. The degree of polymerization of amylose can vary by source, but is typically from a few hundred to a few thousand glucose units. Amylopectin is a branched polymer of glucose units linked by a-1,4-glucosidic bonds and a-1,6-glucosidic bonds. This branching imparts a highly branched structure to amylopectin, with clusters of glucose units linked by a-1,6-glucosidic bonds. The degree of branching of amylopectin can vary by source, but is typically one branching point per 20 to 30 glucose units. Both amylose and amylopectin are composed of glucose monomers linked by glycosidic bonds. A glycosidic bond is formed when a hydroxyl group of a first glucose unit condenses with a hydroxyl group of a second glucose unit, forming an oxygen bridge between the two units. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly considered to be used in this disclosure.

[0037] While not intending to be bound by any particular theory, it is believed that due to the amphoteric nature of the starch, it can act as a polymeric surfactant in the emulsion, with the hydrophobic functional group providing an anchoring point at the oil-water interface (on the oil phase side and the water phase side of the interface), and the modified starch, due to the charge and hydrophilicity of the hydroxyl functional group and the high hydrodynamic volume (especially amylopectin), acting as an energy barrier, as shown in Figure 1B It is believed that the advantage of a polymeric surfactant material compared to a small molecule surfactant is that it provides a higher energy barrier at even longer inter-droplet distances, resulting in a lower probability of oil droplet coalescence.

[0038] In various embodiments, the starch is gelatinized. The term "gelatinized starch" includes "pregelatinized starch," "pre-gelatinized slurry starch," and "cold water swelling starch." The term "gelatinized" starch refers to swollen starch granules that have lost their birefringent cross under polarized light. Gelatinized modified starches are soluble in cold water without the need for cooking. In this context, "soluble" does not necessarily mean that a true molecular solution is formed, but also that a colloidal dispersion is obtained. In one embodiment, the hydrophobically modified starch is fully gelatinized.

[0039] In various embodiments, the hydrophobically modified starch can be formed by a method comprising reacting a starch with an aminopolycarboxylic acid reagent to form a first intermediate, and reacting the first intermediate with an alkenyl succinic anhydride to form the hydrophobically modified starch. In one embodiment, the starch is potato starch. Alternatively, the starch can be any starch described herein.

[0040] In various embodiments, the aminopolycarboxylic acid agent is 2-chloroethylaminodipropionic acid. In alternative embodiments, the aminopolycarboxylic acid agent can be selected from 2-chloro-l-methylethylaminodipropionic acid and 2-chloro-l,l-dimethylethylaminodipropionic acid (and the corresponding bromo agents), 2-bromoethylaminodipropionic acid, 3-chloropropylaminodipropionic acid, 3-bromopropylaminodipropionic acid, 2-chloroethyl, N-methyl aminosuccinic acid, and combinations thereof. In various non-limiting embodiments, the option of using these aminopolycarboxylic acid agents, and the corresponding hydrophobically modified starches of the structures formed using such agents, are expressly contemplated, even though the structures of the hydrophobically modified starches formed using such agents are different from the structures described above. Those skilled in the art understand what the corresponding structures of such hydrophobically modified starches are if formed using the aminopolycarboxylic acid agents described above. Oil-in-water emulsion

[0041] The present disclosure also provides an oil-in-water (O / W) emulsion having long-term stability, which will be described in more detail below.

[0042] More specifically, the emulsion includes (I) an oil phase in an amount of about 5 to about 60 wt.% active based on the total weight of the emulsion, wherein the oil phase is present in the emulsion in the form of droplets, which can have a Dv50 of about 0.2 to about 50 microns. The emulsion also includes (II) an aqueous phase in an amount of about 30 to about 94.5 wt.% active based on the total weight of the emulsion. The emulsion further provides (III) a polymer component in an amount of about 0.5 to about 10 wt.% active based on the total weight of the emulsion. The polymer component itself includes (A) a hydrophobically modified starch described above in an amount of about 15 to about 45 wt.% active based on the total weight of the polymer component. The hydrophobically modified starch comprises a hydrophobically modified amphipathic starch.

[0043] The polymer component also includes (B) a non-starch polysaccharide in an amount of about 0 to about 40 wt.% active based on the total weight of the polymer component. The polymer component further includes (C) a crosslinked starch in an amount of about 20 to about 75 wt.% active based on the total weight of the polymer component. The emulsion exhibits stability of at least 4 weeks at room temperature. Each of these will be described in detail below.

[0044] As known in the art, an oil-in-water (O / W) emulsion is a mixture or dispersion in which small droplets of oil are suspended within a continuous phase (e.g., aqueous or water phase). In an O / W emulsion, the oil droplets are typically dispersed in the continuous phase with a reduction in the interfacial tension between the oil and the continuous phase, which allows them to mix and form a stable dispersion. Most commonly, the continuous phase of the emulsion of the present invention is an aqueous phase (water phase), and is as described below. However, the aqueous phase is not necessarily entirely water, and can or can not include one or more components described below. The emulsion can be formed using any method known in the art.

[0045] In personal care products, O / W emulsions are often used as a means to deliver oil-based active ingredients or moisturizers to the skin in an easy-to-apply and non-greasy form. The aqueous phase of an O / W emulsion serves as a carrier for the oil phase, helping to distribute the oil-based ingredients evenly throughout the product and ensuring their effective delivery to the skin.

[0046] In various embodiments, the emulsion exists at room temperature. For some oils with freezing points below about 100°C, the emulsion can also be a formulation in which the oil is first dispersed in water, but upon cooling to room temperature, the oil can solidify to some extent. Typically, the aqueous phase forms the continuous phase and the oil is not soluble in the aqueous phase. In one embodiment, the solubility in the aqueous phase is about 0.1 wt%, typically about 0.05 wt%, or lower.

[0047] In various embodiments, the emulsion is defined as a plurality of oil droplets substantially uniformly distributed or dispersed in a liquid medium. Typically, the emulsion exists in this form at room temperature. For some oils with freezing points below about 100°C, the emulsion can also be a formulation in which the oil is first dispersed in water, but upon cooling to room temperature, the oil can solidify to some extent. The liquid medium forms the continuous phase and the oil is not soluble in the liquid medium. In one embodiment, the solubility in the liquid medium is about 0.1 wt%, typically about 0.05 wt%, or lower. Some non-limiting examples of suitable liquid media include water, ethanol, methanol, isopropanol, glycerin, propylene glycol, or acetone, or mixtures thereof. In one embodiment of the present disclosure, the liquid medium is a mixture of water and one or more of ethanol, methanol, isopropanol, glycerin, glycols such as propylene glycol, or acetone. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly contemplated for use herein. Long-term stability

[0048] The oil-in-water emulsion exhibits long-term stability. The term "long-term stability" means, for example, that the emulsion can exhibit stability of at least 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 weeks or more (or any value or range of values therebetween) at any temperature from about 5 to about 45 °C (e.g., room temperature) as measured using a TURBISCAN® LAB stability analyzer. For example, emulsion "stability" can be quantitatively measured using a TURBISCAN® LAB stability analyzer, which is used to take an initial backscattering signal of an emulsion sample. The sample can be stored at any temperature from about 0 to about 45 °C or 50 °C (or any value or range of values therebetween, e.g., room temperature) and then scanned periodically over a period of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 weeks or more. In various embodiments, the emulsion can be stable for at least any of the above-mentioned number of weeks when stored at room temperature as measured using a TURBISCAN® LAB stability analyzer. In other embodiments, the emulsion can be stable for at least any of the above-mentioned number of weeks when stored at 45 °C as measured using a TURBISCAN® LAB stability analyzer. In various non-limiting embodiments, all numerical values and numerical ranges, including the above-mentioned numerical values and numerical ranges therebetween, are expressly contemplated for use herein.

[0049] To determine stability, the emulsion can be added to a glass vial provided by Formulaction. The vials are approximately 1 inch in diameter and approximately 2 inches in height. The emulsion sample is added to the vial, ensuring that there are no air bubbles or cavities in the liquid. The fill height is approximately 1 and 5 / 8 inches or 42 mm. After filling, the TurbiScan sample can be conditioned for one day under the desired aging conditions, and then an initial scan is performed. The TurbiScan readings are typically taken when the sample has cooled to approximately 22 °C.

[0050] The backscattering signal measured over time can be compared to the signal of the initial sample. More specifically, if the maximum difference of the subsequent backscattering signal relative to the initial signal is greater than 20%, the number of days to reach a 20% difference in backscattering signal can be recorded as a measure of stability or "Turbiscan® time". The longer this time, the more stable the emulsion. This technique is able to detect potential instability of the sample well before such instability is visually observed. The software accompanying the TurbiScan is used for data analysis, including not only backscattering intensity, but also changes in oil droplet size over time. Oil phase

[0051] Generally, the emulsion comprises an oil phase dispersed in water or a water-based medium (as an aqueous phase). In various embodiments, the oil phase is or comprises a cosmetically acceptable oil, which can provide a consumer with a skin feel, protection, repair, UV protection, occlusivity, slipperiness, moisturization, or free radical scavenging ability. The cosmetically acceptable oil can be selected from hydrocarbon-based oils and natural oils. Non-limiting examples of cosmetically acceptable oils are: palm oil, mineral oil, petrolatum, petroleum jelly, silicone, dimethicone, jojoba oil, castor oil, squalene, avocado oil, almond oil, coconut oil, cocoa butter, grape seed oil, lanolin, peanut oil, sesame oil, jojoba oil, olive oil, silicone oil, sunflower oil, safflower oil, shea butter, and wheat germ oil. Other oils include: argan oil, sweet almond oil, avocado oil, rosehip oil, tea tree oil, and lavender oil. In one embodiment, the cosmetically acceptable oil can be an aerosol propellant.

[0052] The oil phase can be present in the emulsion in any amount selected by one of skill in the art. In various embodiments, the oil phase is present in the emulsion in an amount of at least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by weight. In other embodiments, the oil phase is present in the emulsion in an amount of less than about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by weight. In yet other embodiments, the oil phase is present in the emulsion in an amount of about 5 to about 60, about 10 to about 55, about 15 to about 50, about 20 to about 45, about 25 to about 40, about 10 to about 40, or about 30 to about 35% by weight. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly considered available for use herein.

[0053] In various embodiments, the oil phase is present in the form of droplets. The size of the droplets is not particularly limited. In various embodiments, the average droplet size of the droplets is about 0.2 microns to about 100 microns, about 0.2 to about 50 microns, about 0.5 microns to about 35 microns, about 1 to about 30 microns, about 1 to about 25 microns, or about 5 to about 30 microns. In other embodiments, the droplet size is about 10 to about 25 microns or about 15 to about 20 microns. In other embodiments, the average droplet size of the oil droplets in the emulsion is about 0.2 microns to about 100 microns. In another embodiment, the average droplet size of the oil droplets is about 0.5 microns to about 35 microns. In other embodiments, the lower limit of the average droplet size can be 0.2 microns, 0.5 microns, and 1 micron, respectively, and the upper limit can be 100 microns, 35 microns, and 25 microns, respectively, and the range of embodiments can be a combination of these lower and upper limits. For example, the average droplet size can be measured by any light scattering technique known to one of skill in the art and / or described herein. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly incorporated herein.

[0054] The droplet size can be further defined as Dn10, Dn50, Dn90, Dv10, Dv50, or Dv90. Alternatively, the droplet size can be further defined as any one of Dn1-100 or Dv1-100, as understood in the art. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly incorporated herein.

[0055] In various embodiments, the droplet size can be determined with a particle size analyser (e.g. Malvern MS2000, 3000, 3000E, etc.). However, any droplet size analyser can be used. The volume distribution can be easily converted by the particle size analyser into many other types of distribution, such as surface area, length or number distribution. Thus, the volume and number distribution of the droplets can be determined by laser granulometry in the form of equivalent spheres. The volume distribution provides information on the volume of the particles within each droplet size sub-range. In the volume distribution, the contribution of each particle is related to the volume of that particle, so the relative contribution of each particle will be proportional to the cube of its size [i.e. (droplet size)3]. Thus, larger sized particles are not proportionally represented in the volume distribution (and vice versa; smaller particles are under-represented in the volume distribution). However, the number distribution provides information on the number of particles within each droplet size sub-range. That is, in the number distribution, each particle is given equal weight, regardless of its size; i.e. the relative contribution of each particle in the distribution is equal. Thus, the number distribution provides information on the relative number of particles (percentage of the total number) within each droplet size sub-range, whereas the volume distribution provides information on the relative volume of particles (percentage of the total volume) within each droplet size sub-range. Throughout, the term “droplet” can be replaced by “particle” where appropriate, as understood by the skilled person.

[0056] Thus, the Dv10 value means that 10% of the sample volume is below this droplet size, whereas the Dn10 value corresponds to the largest droplet size for which 10% of the total number of particles in the sample. Thus, these parameters relate to different physical characteristics of any given particulate material, and have very different values. Similar considerations apply to the other claimed parameters (e.g. D50, D90, etc.).

[0057] Any Dv or Dn parameter of the droplets is not an absolute characteristic of the droplets themselves, but a construct based on mathematical approximations of the laser diffraction data (“equivalent spheres”). The value of each of these parameters can be influenced to a large extent by the conditions used to measure them. Typically, the standard operating procedure for measuring the droplets is a procedure pre-programmed by the droplet size analyser itself. These parameters can be selected in accordance with the international standard ISO 13320-1. In various embodiments, any one or more of these parameters can be the parameter pre-programmed by the instrument itself.

[0058] In other implementations, various droplet size measurement techniques can be used. The most common method is dynamic light scattering (DLS), also known as photon correlation spectroscopy (PCS). It is frequently used in colloid science, nanotechnology, and biophysics. DLS is based on the Brownian motion of particles suspended in a liquid medium. The intensity fluctuations detected by the photodetector in DLS are analyzed using autocorrelation techniques. Autocorrelation measures the correlation between intensity fluctuations at different time intervals, calculated by analyzing the rate of scattered light intensity fluctuations. The autocorrelation function provides information about the rate of particle motion (Brownian motion) in the sample. From this information, the particle diffusion coefficient can be determined. Furthermore, the droplet size distribution can be calculated using the Stokes-Einstein equation (which correlates the diffusion coefficient with the droplet size). Static multiple light scattering (SMLS), also known as static light scattering (SLS), is another technique for measuring droplet size. Unlike dynamic light scattering (DLS), which analyzes scattered light intensity fluctuations caused by Brownian motion, SMLS relies on measuring the intensity of scattered light at a fixed angle. SMLS operates in the Fraunhofer scattering region, where the scattering angle is sufficiently large that the scattering pattern can be approximated by a simple scattering equation known as the Fraunhofer equation, which correlates the intensity of scattered light with the droplet size and concentration. Based on backscattering intensity measurements, the average equivalent particle diameter can be calculated using the following formula:

[0059] in: I BS Backscattered light intensity; g Asymmetric factor; Q e Extinction efficiency factor; Volume fraction; D : average equivalent particle diameter; and Alpha and Beta: Coefficients related to the geometry of the optical set-up in the instrument (angles, beam size, glass cell, etc.) and embedded in the instrument software based on the instrument settings. In various embodiments, the TurbiScan Lab and its software provided by Formulaction (address: 3-5 Rue Paule Raymondis) is used to assess the stability of the emulsion over time, in particular the measurement of the emulsion droplet size is performed according to ISO TS 21357:2022 “Nanotechnologies - Estimation of the mean size of nanoobjects in liquid dispersions by static multiplicative light scattering (SMLS)”. Detailed information can also be found in Mengual, O., Meunier, G., Cayre, I., Puech, K., and Snabre, P. (1999). “TURBISCAN MA 2000: multiple light scattering measurement for concentrated emulsion and suspension instability analysis”, Talanta, 50(2), 445-456, which is expressly incorporated by reference herein for various non-limiting embodiments.

[0060] In various embodiments, the detailed experimental procedure is as follows: 1) The prepared emulsion containing all the key ingredients is added to the TurbiScan vial provided by the instrument company. Special care must be taken when adding the sample not to leave any cavities or air bubbles. In addition, the emulsion should not leave any stains on the glass surface of the upper part of the vial where the sample is not placed. Over time, these stains can drip into the sample body, thus interfering with the integrity of the original emulsion conditions.

[0061] 2) Once prepared, the sample should be aged at the desired aging temperature for at least 12 hours before the initial scan. For samples aged at 45°C, they should be completely cooled to 22°C before scanning.

[0062] 3) After the initial scan, the sample is returned to the target temperature conditions, i.e. 22°C or 45°C. Periodically, the sample is removed from the aging conditions, for the 45°C aged samples, readjusted to 22°C, and then scanned again by the TurbiScan, adding a new trace to the original file for comparison with the original scan trace.

[0063] 4) Due to the opacity of the emulsion, backscattered traces are used to monitor the stability properties of the emulsion system. In addition to the change in oil droplet size over time, possible creaming or aging progression is also closely monitored. Typically, the criterion is that if any point of the backscattered trace shows a relative change of no more than 20% relative to the original backscattered trace over a specified duration of time (e.g., about 4 weeks), the sample will be considered stable for 4 weeks under the specified aging conditions. Otherwise, the sample will be considered unstable over the specified duration.

[0064] In various embodiments, the (I) oil phase includes an additive selected from glycerol monostearate, a fatty alcohol, and combinations thereof. The fatty alcohol is not particularly limited and can be any fatty alcohol known in the art. For example, the fatty alcohol can be linear or branched and contain from about 6 to about 20, from about 8 to about 18, from about 10 to about 16, or from about 12 to about 14 carbon atoms. The fatty alcohol can be alkoxylated (e.g., ethoxylated) or non-alkoxylated. If alkoxylated, the number of moles of alkylene oxide (e.g., ethylene oxide) used is not limited, for example, it can be from about 0.5 to about 20, from about 0.5 to about 10, from about 1 to about 10, from about 1 to about 5, from about 5 to about 10, and the like. In various non-limiting embodiments, all numerical values and numerical ranges, including the above-mentioned numerical values and numerical values therebetween, are expressly considered for use herein. In other embodiments, the oil phase, and optionally the entire emulsion, can be free of fatty acids and / or surfactants. Aqueous Phase

[0065] The aqueous phase can be or include water. For example, the aqueous phase can be about 100% water, or can include water and one or more co-solvents. Some non-limiting examples of suitable co-solvents are ethanol, methanol, isopropanol, glycerol, propylene glycol, or acetone, or mixtures thereof. In one embodiment, the aqueous phase is a mixture of water and one or more of ethanol, methanol, isopropanol, glycerol, glycols (such as propylene glycol), or acetone. The particular weight percentages of water and the one or more co-solvents can independently be any value between 0.5 and 99.5 as selected by one of skill in the art. Typically, the aqueous phase is present in an amount of from about 30 to about 94.5, from about 35 to about 90, from about 40 to about 85, from about 45 to about 80, from about 50 to about 75, from about 55 to about 70, or from about 60 to about 65 weight % active based on the total weight of the emulsion. Water is 100% active as known in the art. In various non-limiting embodiments, all numerical values and numerical ranges, including the above-mentioned numerical values and numerical values therebetween, are expressly considered for use herein. Polymer Component

[0066] The emulsion further provides (III) a polymer component, which is present in an amount of about 0.5 to about 10% by weight of active ingredient, based on the total weight of the emulsion. In various embodiments, the polymer component is present in amounts of about 1 to about 9.5, about 1.5 to about 9, about 2 to about 8.5, about 2.5 to about 8, about 3 to about 7.5, about 3.5 to about 7, about 4 to about 6.5, about 4.5 to about 6, or about 5 to about 5.5% by weight of active ingredient, based on the total weight of the emulsion. In other embodiments, the polymer component is present in amounts of about 1 to about 7, about 1.5 to about 6.5, about 2 to about 6, about 2.5 to about 5.5, about 3 to about 5, about 3.5 to about 4.5, or about 4 to about 4.5% by weight of active ingredient, based on the total weight of the emulsion. In various non-limiting embodiments, all numerical values ​​and ranges, including the values ​​above and values ​​between the values ​​above, are expressly intended to be used herein.

[0067] The (III) polymer component may be present in the (I) oil phase, in the (II) aqueous phase, simultaneously in the (I) oil phase and the (II) aqueous phase, or between the (I) oil phase and the (II) aqueous phase. (A) Hydrophobically modified starch

[0068] The polymer component itself includes the hydrophobically modified starch (A) described above, in an amount of about 15 to about 45% by weight of active ingredient based on the total weight of the polymer component. In various embodiments, the hydrophobically modified starch is present in an amount of about 20 to about 40, about 20 to about 35, about 25 to about 35, or about 30 to about 35% by weight of active ingredient based on the total weight of the polymer component. In various non-limiting embodiments, all numerical values ​​and ranges, including the values ​​described above and values ​​between the values ​​described above, are expressly intended to be used herein. (B) Non-starch polysaccharides

[0069] The polymer component also includes (B) a non-starch polysaccharide in an amount of from about 0 to about 40 wt. % active based on the total weight of the polymer component. In various embodiments, the amount is from about 0 to about 35, from about 0 to about 30, from about 0 to about 25, from about 0 to about 20, from about 0 to about 15, from about 0 to about 10, from about 0 to about 5, from about 5 to about 30, from about 5 to about 25, from about 5 to about 20, from about 5 to about 15, from about 5 to about 10, from about 10 to about 30, from about 10 to about 25, from about 10 to about 20, from about 10 to about 15, from 15 to about 30, or from about 20 to about 25 wt. % active based on the total weight of the polymer component. In other embodiments, the (B) non-starch polysaccharide is present in an amount of from about 5 to about 40, from about 10 to about 35, from about 20 to about 35, or from about 20 to about 30 wt. % active based on the total weight of the polymer component. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values noted above and numerical values falling within the ranges noted above, are expressly contemplated for use herein.

[0070] Starches and starch derivatives are known to impart desirable tactile qualities to personal care formulations. Traditionally, starches used in such formulations can be used at concentrations of about 3% or more, otherwise the starches can undergo a phenomenon known as aging and precipitate out of the formulation, which is undesirable. However, in one embodiment, wherein the (III) polymer component is present in an amount of from about 3.5 to about 10 wt. % active based on the total weight of the emulsion, then the (B) non-starch polysaccharide is optional, absent, or present in an amount of less than about 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, or 0.01 wt. % active based on the total weight of the polymer component. In another embodiment, wherein the (III) polymer component is present in an amount of from about 0.5 to less than about 3.5 wt. % active based on the total weight of the emulsion, and the (B) non-starch polysaccharide is present in an amount greater than zero wt. %. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values noted above and numerical values falling within the ranges noted above, are expressly contemplated for use herein.

[0071] As known in the art, polysaccharides can form helical, linear fibrous, or branched structures. The conformation of polysaccharides can be simply classified into two general types - ordered and disordered - which are determined by the regularity of the molecular structure. In aqueous solution, most non-starch polysaccharides with heterogeneous structure exhibit disordered conformation, including random coil, rigid, and globular conformations. High performance size exclusion chromatography (HPSEC) can be used to investigate the conformational properties of polysaccharides in aqueous solution. In combination with refractive index (RI) light scattering detectors (LALS and RALS) and an online viscometer, the relationship of Mw with intrinsic viscosity [η] can be obtained, as well as Rg, Rh, and Rg / Rh (p), where Rgis the radius of gyration and Rhis the hydrodynamic radius. Rgis a mathematically defined size that describes the distribution of mass centers in a molecule, while Rhis a phenomenological property of the molecule.

[0072] In various embodiments, the (B) non-starch polysaccharide has a coil size (Rh) of at least 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, or 1600 nanometers. Alternatively, the coil size can be from about 400 to about 1600, about 450 to about 1550, about 500 to about 1500, about 550 to about 1450, about 600 to about 1400, about 650 to about 1350, about 700 to about 1300, about 750 to about 1250, about 800 to about 1200, about 850 to about 1150, about 900 to about 1100, about 950 to about 1050, or about 950 to about 1000 nanometers. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values noted above and numerical values falling within the ranges noted above, are expressly contemplated for use. The hydrodynamic volume of non-starch polysaccharides is most commonly measured using dynamic light scattering. The principle behind using dynamic light scattering (DLS) to measure the hydrodynamic volume of a polymer involves measuring the Brownian motion of the polymer molecules in solution. In some non-limiting embodiments, the significance of the coil size of a non-starch polysaccharide is illustrated as shown in FIG. 1. When oil droplets and non-starch polysaccharides are co-dispersed in a water system, their interaction is exactly opposite, the latter is compatible with water and forms a homogeneous solution. The former is not compatible with water, leading to the most famous Oswald ripening phenomenon. At the microscopic level, when two oil droplets approach each other due to van der Waals forces, when the inter-droplet distance becomes slightly smaller than the average hydrodynamic volume size of the non-starch polysaccharide, the polymer coil will be pushed away from this inter-droplet region, resulting in a concentration of the non-starch polysaccharide that is practically zero. This de-mixing process creates an energy barrier when two oil droplets approach each other, commonly referred to as the depletion mechanism, which is thermodynamically unfavorable for the two oil droplets to coalesce with each other, which is shown on the right side of the graph of energy versus inter-droplet distance (FIG. 1). Figure 1B When oil droplets and non-starch polysaccharides are co-dispersed in a water system, their interaction is exactly opposite, the latter is compatible with water and forms a homogeneous solution. The former is not compatible with water, leading to the most famous Oswald ripening phenomenon. At the microscopic level, when two oil droplets approach each other due to van der Waals forces, when the inter-droplet distance becomes slightly smaller than the average hydrodynamic volume size of the non-starch polysaccharide, the polymer coil will be pushed away from this inter-droplet region, resulting in a concentration of the non-starch polysaccharide that is practically zero. This de-mixing process creates an energy barrier when two oil droplets approach each other, commonly referred to as the depletion mechanism, which is thermodynamically unfavorable for the two oil droplets to coalesce with each other, which is shown on the right side of the graph of energy versus inter-droplet distance (FIG. 1). Figure 1B). From simple geometric considerations, it is not difficult to surmise that the larger the hydrodynamic volume of the non-starch polysaccharide, the further apart the distance between the oil droplets at which the energy barrier occurs, thus reducing the probability of coalescence.

[0073] The non-starch polysaccharide is not particularly limited and can be any non-starch polysaccharide known in the art. In one embodiment, the non-starch polysaccharide is xanthan gum. In another embodiment, the (B) non-starch polysaccharide is selected from the group consisting of xanthan gum, non-ionic cellulose, ionic cellulose, and combinations thereof. In other embodiments, the (B) non-starch polysaccharide is selected from the group consisting of cellulose ethers, such as methyl ethyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, and combinations thereof. In other embodiments, it is contemplated that the cellulose can also be ionic.

[0074] In various embodiments, the non-starch polysaccharide is a cellulose ether. Cellulose is a polysaccharide composed of 1,4-anhydroglucose units. The cellulose molecules in natural cellulose are not soluble in water. In order to make cellulose soluble, it is typically modified into a cellulose derivative, such as hydroxyethyl cellulose (HEC), ethyl hydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), hydroxybutyl methyl cellulose (HBMC), hydroxypropyl methyl cellulose (HPMC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobically modified ethyl hydroxyethyl cellulose (HMEHEC). Carboxymethyl cellulose can also be used.

[0075] To make modified cellulose, the cellulose is typically subjected to an alkalization step, then reacted with ethylene oxide and chloroethane to make EHEC, and with chloromethane to make MEHEC. Each anhydroglucose unit of cellulose has three hydroxyl groups available for reaction. The number of reacted hydroxyl groups in each anhydroglucose unit is expressed as the degree of substitution (DS), which ranges from 0 to 3. The molar substitution of ethylene oxide (MSEO) is the average total number of ethylene oxide groups per anhydroglucose unit.

[0076] The cellulose ether can be derived from any source of cellulose, including but not limited to, hardwood pulp, softwood pulp, cotton sources (including cotton linters), bacterial cellulose, and regenerated cellulose.

[0077] In one embodiment, the cellulose ether is a non-ionic cellulose ether. In another embodiment, the cellulose ether is a hydroxy(Ci-C4)alkyl cellulose. Examples of non-ionic cellulose ethers are methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, methylhydroxyethyl cellulose, ethylhydroxyethyl cellulose, methylethylhydroxyethyl cellulose, propylhydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropylethyl cellulose, hydroxypropylpropyl cellulose, hydroxypropylhydroxyethyl cellulose, methylhydroxypropylhydroxyethyl cellulose, hydroxypropyl cellulose, and mixtures thereof. In one embodiment, the cellulose ether can be selected from the group consisting of methyl cellulose, ethyl cellulose, ethylhydroxyethyl cellulose, methylhydroxyethyl cellulose, methylethylhydroxyethyl cellulose, hydroxypropylmethyl cellulose, and mixtures thereof.

[0078] In one embodiment, the cellulose ether is methylethylhydroxyethyl cellulose, referred to herein as "MEHEC". In one embodiment, the cellulose ether is ethylhydroxyethyl cellulose, referred to herein as "EHEC". Non-ionic cellulose ethers can be particularly useful for applications requiring good salt tolerance.

[0079] In one embodiment, the cellulose ether is an anionic cellulose ether, particularly in formulations that do not require high salt tolerant compound capabilities. Examples of anionic cellulose ethers are carboxymethyl cellulose, hydroxyethyl carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose, sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, and mixtures thereof.

[0080] The cellulose ethers can be prepared according to conventional methods known to those of ordinary skill in the art. For example, alkali cellulose (activated cellulose) can be prepared by first mercerizing cellulose with base, then reacting with base cellulose in one or more steps at temperatures of about 50 to about 120 °C with an appropriate amount of one or more etherifying agents selected from the group consisting of oxirane, propylene oxide, butylene oxide, chloromethane, chloroethane, monochloroacetic acid (MCA), and MCA salts, in the presence of an organic reaction medium such as chloroethane, acetone, alkyl blocked mono- or poly(ethylene glycol), isopropyl alcohol, t-butyl alcohol, ethers such as methyl t-butyl ether, methyl sec-butyl ether, dimethoxyethane, or mixtures thereof.

[0081] The cellulose ethers can include one or more substituents on the cellulose chain.

[0082] In one embodiment, the cellulose ether is substituted with hydroxyalkyl groups (e.g., oxirane, referred to as MSEO). In various embodiments, the MSEO is at least 1.0, at least 1.5, at least 2.0, or at least 2.4. In various non-limiting embodiments, all numerical values and numerical ranges, including the values noted above and values therebetween, are expressly contemplated for use herein.

[0083] In other embodiments, the cellulose ether is methyl and / or ethyl substituted, wherein the sum of the DS ethyl and the DS methyl is at least 0.1, at least 0.2, at least 0.4, at least 0.6, or at least 0.8. In various non-limiting embodiments, all numerical values and numerical ranges, including the above-noted numerical values and numerical ranges, are expressly incorporated herein.

[0084] In one method of making alkyl-substituted cellulose ethers, the cellulose is mercerized in one or more steps with an aqueous base in a total amount of about 0.8 to about 1.8 moles of base per mole of sugar units; then the mercerized cellulose is reacted with ethylene oxide in a total amount of about 2.6 to about 5.5 moles per mole of sugar units. The reaction product is then reacted with chloroethane in a total amount of about 0.2 to about 1.5 moles per mole of sugar units to make EHEC, or with chloroethane and chloromethane in a total amount of about 0.2 to about 1.5 moles per mole of sugar units to make MEHEC. These components are added to the mercerized cellulose in one or more steps and the reaction is carried out in the presence of an organic reaction medium at a temperature of about 50 to about 120 °C. In one embodiment, the weight ratio between the reaction medium and the cellulose is about 1:1 to about 10:1, and in another embodiment about 4:3 to about 3:1. In various non-limiting embodiments, all numerical values and numerical ranges, including the above-noted numerical values and numerical ranges, are expressly incorporated herein.

[0085] In one embodiment, chloromethane or chloroethane can be used both as an etherifying agent and as a reaction medium, in which case the required amount of chloromethane or chloroethane is already present in the reaction mixture without further addition of chloromethane or chloroethane. The degree of alkylation can be adjusted by the source of the cellulose, the amount of base used, the reaction temperature, and the reaction time. If desired, a portion of the base can be added at a later stage of the reaction to further activate the cellulose. The total degree of substitution of the methyl and ethyl groups can be controlled by the amount of base used in the mercerization process, as the equivalent amount of NaOH is consumed and forms sodium chloride. However, due to side reactions, the yield of alkyl substitution is about 40% to about 60%. U.S. Patent No. 7,319,146, the entire contents of which are incorporated herein by reference for various non-limiting embodiments, provides a general description of the process used to make cellulose ether polymers. In various non-limiting embodiments, all numerical values and numerical ranges, including the above-noted numerical values and numerical ranges, are expressly incorporated herein.

[0086] One method of making a cellulose ether suitable for use herein is disclosed in U.S. Publication No. 2009 / 0326217, the entire contents of which are incorporated herein by reference for various non-limiting embodiments, wherein the cellulose ether is generally made in the presence of an ether-based solvent.

[0087] While not intending to be bound by any particular theory, it is believed that (B) the non-starch polysaccharide plays multiple roles. For example, the non-starch polysaccharide can inhibit the aging of the starch. It is well known that two starch molecules form a double helix due to intermolecular hydrogen bonding and the specific conformation of the starch molecule. The same is true for cellulose molecules, although the intermolecular hydrogen bonding is the same, the ordered structure of cellulose will be very different in nature due to conformational differences. However, the same conformation of two adjacent polysaccharide molecules allows them to form intermolecular hydrogen bonds, which will further develop into ordered structures. If two polysaccharide molecules with different conformations are close to each other, intermolecular hydrogen bonds will still be formed, but the possibility of forming large area ordered structures is low. The non-polysaccharide can enhance the thickening effect of the continuous phase of the emulsion. Non-starch polysaccharides with larger hydrodynamic volume can effectively thicken the system by strong hydrophilicity, high molecular weight, and relatively high glass transition temperature. (C) Crosslinked Starch

[0088] The polymer component further includes (C) a crosslinked starch in an amount of from about 3 to about 75 wt% active based on the total weight of the polymer component. In various embodiments, the amount is from about 5 to about 75, about 10 to about 75, about 15 to about 75, about 20 to about 75, about 25 to about 70, about 30 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50 wt% active based on the total weight of the polymer component. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values described above and numerical values between the numerical values described above, are expressly incorporated herein for use.

[0089] The crosslinked starch can be any crosslinked starch known in the art or described herein, including crosslinked versions of the starches described above.

[0090] In various embodiments, the starch can be isolated from any plant starch source, including, for example, corn, wheat, rice, sorghum, pea, potato, cassava (manihot), sweet potato, and sago. In various embodiments, the starch comprises greater than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt% amylopectin. In one embodiment, the starch comprises greater than about 90 wt% amylopectin. In another embodiment, the starch comprises greater than 95 wt% amylopectin. In yet another embodiment, the starch comprises greater than 97 wt% amylopectin. Such high amylopectin starches are traditionally referred to in the art as waxy starches, and there are a variety of commercially available waxy starch varieties. In one embodiment, the waxy starch is derived from corn, rice, potato, or cassava. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values described above and numerical values between the numerical values described above, are expressly incorporated herein for use.

[0091] In various embodiments, the starch has a high molecular weight, which is defined as the molecular weight of the naturally occurring starch that has not been intentionally degraded to a lower molecular weight. That is, while some degradation can occur during the isolation of the starch and during the chemical processing and drying of the starch, high molecular weight starch is that which has been maintained as much as possible in its natural molecular weight. In another embodiment, the starch can be partially degraded in a controlled manner by means known in the art, including but not limited to acid catalyzed hydrolysis, enzyme catalyzed hydrolysis, and oxidative degradation. In the case where the starch is intentionally partially degraded, the water flowability (WF) of the degraded starch will be less than 70, typically less than 60, or most commonly less than 45. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly contemplated for use herein.

[0092] Cross-linking of the starch chains can be achieved by a suitable cross-linking agent, such as a difunctional compound. For example, cross-linking can be achieved by reaction of the starch with epichlorohydrin. In one embodiment, the cross-linking method is phosphorylation, in which the starch is reacted with phosphorus oxychloride, phosphorus pentoxide, and / or sodium tripolyphosphate, such that two starch chains are cross-linked through anionic P-0 groups. The anionic nature of the cross-linking sites contributes to the emulsion stabilizing effect of the starch. In further embodiments, the cross-linking method uses a C4-C18 alkane or alkene dicarboxylic acid or a C4-C8 alkane dicarboxylic acid or adipic acid. The alkane or alkene dicarboxylic acid links two starch chains through an ester linkage. It can be in linear or branched form. In further embodiments, the cross-linked starch is obtained, for example, by reaction of the starch with a mixed anhydride of a dicarboxylic acid and acetic acid. The starch can be cross-linked with about 15 ppm to about 400 ppm of the cross-linking agent, typically about 50 to about 300 ppm in another embodiment, and more commonly about 100 ppm to about 200 ppm in yet another embodiment. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly contemplated for use herein.

[0093] In a further aspect, the crosslinked starch is further modified by the addition of a C2-C5 hydroxyalkyl moiety. While not wishing to be bound by theory, it is believed that the presence of a hydroxyl group attached to the starch backbone through an alkyl group having 2 to 5 carbon atoms results in a starch having a suitable hydrophilic-lipophilic balance. The position of the hydroxyl group in the alkyl group is not critical and can be in the alpha to omega position. The degree of substitution is the average number of OH groups per anhydroglucose unit of the starch molecule that are substituted. In one embodiment, the degree of substitution of the hydroxyalkylated is about 0.08 to 0.3, and in another embodiment, the degree of substitution of the hydroxyalkylated is about 0.15 to 0.25. Hydroxyalkylation of native starches can be achieved by reacting the native starch with an alkylene oxide having the appropriate number of carbon atoms. In one embodiment, hydroxyethylated and / or hydroxypropylated starches obtained by reaction of starch with ethylene oxide or propylene oxide are used. The starch can also include more than one hydroxyl group per alkyl group. In one embodiment, the starch is crosslinked hydroxypropyl distarch phosphate or crosslinked acetylated distarch adipate. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly considered to be used in this disclosure.

[0094] The crosslinked starch can be hydrophobically modified or unmodified. For example, the crosslinked starch can be substituted with one or more aliphatic or aromatic, saturated or unsaturated, straight chain, branched, or cyclic C8-C 30 alkyl chains, particularly substituted with hydrophobic groups containing 8 to 30 carbon atoms. In another embodiment, the hydrophobic substituents used can include C8-C 30 , typically C8-C 22 alkyl, alkenyl, aralkyl, or alkaryl groups, and mixtures thereof. In one embodiment, the hydrophobic substituents are C8-C 22 , typically C8-C 12 alkenyl chains, such as octenyl (unsaturated C8) and straight chain or branched dodecenyl (unsaturated C 12 ) groups. In one embodiment, the hydrophobic groups are derived from natural sources, including but not limited to tall oil, tallow, soybean, coconut oil, and palm oil. In one embodiment, the hydrophobic substituents according to the present disclosure are octenyl or dodecenyl. The hydrophobic modifying agents can be attached to the starch substrate through ether linkages, ester linkages, or urethane linkages. Ester linkages are preferred. Exemplary modifying agents include, but are not limited to, octenyl succinic anhydride and dodecenyl anhydride. The crosslinked starch can also be modified using any of the methods or compounds described in the present disclosure.

[0095] In one embodiment, the cross-linked modified starch is gelatinized. The term "gelatinized starch" includes "pregelatinized starch", "pre-gelatinized slurry starch", and "cold water swelling starch". The term "gelatinized" starch refers to swollen starch granules that have lost their birefringent cross under polarized light. Gelatinized modified starches are soluble in cold water without the need for cooking. In this context, "soluble" does not necessarily mean that a true molecular solution is formed, but also that a colloidal dispersion is obtained. In one embodiment, the cross-linked starch is fully gelatinized.

[0096] The cross-linked starch can be gelatinized by cooking in water at a temperature above the gelatinization temperature. Some non-limiting examples of gelatinization are: water bath cooking, steam injection cooking, jet cooking (at a pressure of about 10 to about 150 PSI), and extrusion. The cross-linked starch can be cooked at various temperatures and concentrations. In various embodiments, the cross-linked starch is cooked at a temperature of about 90 °C to about 200 °C. In another embodiment, the cross-linked starch is cooked at a temperature of about 100 °C to about 150 °C. The limits on the concentration of starch in water vary depending on the cooking method due to factors such as viscosity, heat transfer, and solution stability. In one embodiment, the cross-linked starch is cooked at a concentration of about 1 to about 40 weight percent (wt %). In another embodiment, the cross-linked starch is cooked at a concentration of about 2 wt % to about 30 wt %. In yet another embodiment, the concentration is about 3 wt % to about 15 wt %. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges described above, are expressly considered to be used in this disclosure.

[0097] Processes commonly used to produce such gelatinized starches include drum drying, extrusion, and spray drying. Drum drying involves cooking and drying very high viscosity semi-solid starch paste on heated drums. The dried film is peeled off the drum with a metal blade and then ground. This process can be carried out to very high solids content. Extrusion can also be used to cook and dry starch simultaneously. This process uses the physical treatment of the starch / water mixture at high temperature and pressure to gelatinize the starch, and then expand as the water suddenly evaporates upon exiting the nozzle. The use of a gelatinized cross-linked modified starch allows the production of starch at ambient temperature or at temperatures much lower than the production conditions used for known starch-containing compositions. In one embodiment, the gelatinized cross-linked modified starch is typically produced by spray drying.

[0098] In one embodiment, the crosslinked starch has a majority of intact starch granules. Aqueous dispersions of gelatinized crosslinked starch having a substantially intact granular structure have a more uniform, smooth texture than aqueous dispersions of starches that do not have a granular structure, the latter obtained, for example, by drying a starch solution whose dispersion has a slight sandy feel. For gelatinized starches having an intact granular structure, the natural internal structure of hydrogen bonds is disrupted, but the external shape or morphology is preserved. U.S. Patent No. 4,280,851 (the entire contents of which are incorporated herein by reference for various non-limiting embodiments) describes a process for producing a particularly suitable spray-dried gelatinized starch. An apparatus suitable for carrying out the process is described in U.S. Patent No. 4,600,472 (the entire contents of which are also incorporated herein by reference for various non-limiting embodiments). In the process, a granular starch or mixture of modified starches is cooked or gelatinized in an atomized state. The starch to be cooked is atomized through an atomizing opening into a nozzle device to form a relatively finely divided spray material. In addition, a heating medium is injected through an opening in the nozzle device into the spray material in order to heat the starch to the temperature required for gelatinization. A closed chamber surrounds the spray openings for atomization and heating medium and defines a vent opening positioned so that the heated starch spray material can exit the chamber. The arrangement of the device is such that the time elapsed during the passage of the starch spray material through the chamber (i.e., from the atomizing opening to the vent opening) defines the gelatinization time of the starch. The resulting spray-dried gelatinized starch comprises uniformly gelatinized starch granules in the form of dimpled spheres, a majority of which are intact, unbroken, and swollen upon rehydration. Nozzles useful for producing such starches are also described in U.S. Patent No. 4,610,760 (the entire contents of which are incorporated herein by reference for various non-limiting embodiments).

[0099] For the production of suitable gelatinized starches or modified starches, the process of U.S. Patent No. 5,149,799 (the entire contents of which are incorporated herein by reference for various non-limiting embodiments) can also be used. In this process, the starch is uniformly atomized and cooked by single-stage atomization in the presence of an aqueous medium. The atomization stage is carried out in an apparatus having an internal mixing two-fluid spray-drying nozzle and is coupled with a device for drying the cooked atomized starch.

[0100] Spray-dried gelatinized or modified starches with suitable properties can also be produced by a continuous, coupled jet-cooking and spray-drying process. A starch suspension is gelatinized in a jet-cooker with direct steam injection at 138°C to 160°C. The flow of the starch suspension and steam are mixed in a cooking or boiling chamber. The outlet of the latter is connected to a pneumatic spray nozzle or a high-pressure nozzle located in a conventional spray-dryer. The jet-cooked starch is directed to the spray nozzle at elevated temperature and pressure and can be atomized with cold air, hot air or typically with steam. After atomization, the hot jet-cooked starch solution is treated in the same way as conventional spray-dried starch. The drying process is fast enough to prevent the starch molecules from aging during the droplet cooling and drying process. The spray-dried starch is an amorphous material (i.e. essentially non-crystalline) that is readily soluble or colloidally dispersible in water.

[0101] In one embodiment, the crosslinked starch can be provided as a dry powder composition, which is reconstituted in an aqueous medium at the point of use.

[0102] In various embodiments, the crosslinked starches have dermatologically desirable use properties and tactile qualities. They increase the water retention capacity of the skin and help to make the skin smooth and supple.

[0103] In other embodiments, the (C) crosslinked starch is a hydroxypropyl starch phosphate.

[0104] In one embodiment, the (C) crosslinked starch is a hydroxypropyl starch phosphate derived from corn, potato and / or tapioca. In another embodiment, the (C) crosslinked starch is a hydroxypropyl starch phosphate derived from corn.

[0105] While any emulsion is thermodynamically unstable, efforts to improve emulsion stability are directed at addressing the kinetics of this instability process. When the dispersed phase size is small (e.g. on the order of microns), the gravitational forces acting on the oil droplets are largely overshadowed by the more significant intermolecular forces (in essence, interfacial / surface forces). As the surface area to volume ratio gradually decreases (proportional to the ~1stpower of the length dimension of the dispersed phase), gravity begins to become more important as coalescence occurs. This can lead to phenomena such as creaming or settling, depending on the density difference between the dispersed and continuous phases in the emulsion system. One effective way to address the effects of gravity is to thicken the continuous phase, e.g. to lengthen the molecular relaxation time of the molecules dispersed / dissolved in the continuous phase. It is believed that crosslinked starches can significantly increase the molecular weight, and thus the viscosity of the continuous phase, to slow down the creaming / settling process as gravity becomes more important as the dispersed phase size increases, see Figure 1A . Additives

[0106] The emulsions can include one or more additives in one or more of the oil phase, water phase, and / or polymer component, or be free of one or more additives. Such additives can include, but are not limited to, emollients, moisturizers, thickening agents, surfactants, UV inhibitors, styling polymers, pigments, dyes, colorants, alpha-hydroxy acids, aesthetic enhancers (such as starch), perfumes and fragrances, film formers (waterproofing agents), preservatives, antifungals, antimicrobials, and other medicaments, preservatives, and solvents.

[0107] Useful surfactants include nonionic and amphoteric surfactants. Nonionic surfactants that can be used include polyoxyethylenated, polyoxypropylenated, or polyglycerolated alcohols, alkyl phenols, and fatty acids having a linear aliphatic chain containing 8 to 22 carbon atoms, typically containing 2 to 30 moles of ethylene oxide, fatty acid amides, alkoxylated fatty amine, fatty acid esters, glycerides, alkoxylated fatty acid esters, sorbitan esters, alkoxylated sorbitan esters, alkyl phenol alkoxylates, aromatic alkoxylates, and alcohol alkoxylates. Also useful are copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and propylene oxide with fatty alcohols, polyoxyethylenated fatty amides or amines, ethanol amides, fatty acid glycol esters, oxyethylenated or non-oxyethylenated fatty acid sorbitan esters, fatty acid sucrose esters, fatty acid polyethylene glycol esters, phosphoric acid triesters, and fatty acid esters of glucose derivatives. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values and numerical ranges recited above, are expressly considered to be used in this disclosure.

[0108] In other embodiments, the surfactant is biobased. For example, the surfactant can be selected from the group consisting of phospholipids, lecithin, palmitoyl oligopeptides, glycolipids, glycosphingolipids, sophorolipids, sphingolipids, and combinations thereof.

[0109] The additive can also be or include a fatty alcohol. The fatty alcohol can be or include behenyl alcohol, C 12 -16 alcohol, cetearyl alcohol, cetyl alcohol, cinnamyl alcohol, citronellol, geraniol, linalool, octyldodecanol, PEG-10 rapeseed sterol, phenoxyethanol, retinol, stearyl alcohol, tocopherol, or combinations thereof.

[0110] In various embodiments, one or more components, compounds, methods, or compositions described in U.S. Patent No. 10,100,178, the entirety of which is incorporated by reference herein, can be used for various non-limiting embodiments. Use of the emulsions

[0111] The emulsion can be, or can be used to form, a cosmetic or personal care composition. In one embodiment, the emulsion is a personal care composition. Alternatively, the personal care composition is a skin care composition. In other embodiments, the personal care composition is a hair care or hair styling composition. The emulsion can be, or can be used to form, a hair styling composition selected from the group consisting of gels, mousses, hair oils, and hair waxes.

[0112] In another embodiment, the emulsion can be a personal care composition selected from the group consisting of skin care compositions, skin cleansing compositions, color cosmetics, facial emulsions, cream moisturizers, body washes, body lotions, foot care products (e.g., foot creams), hand creams, lipsticks, lip glosses, lip pencils, eye shadows, gel eye shadows, eye liners, eye liner pencils, mascaras, concealers, foundations, powders, liquid blushes, blushes, deodorants, shaving cream compositions, nail polishes, nail removers, exfoliating agents, exfoliating creams, acne creams, acne scrubs, toothpastes, aftershaves, cream depilatories, emulsion depilatories, wax depilatories, masks made with clay materials, anti-aging products, shampoos, hair care products (e.g., conditioners), hair care creams, styling gels, styling foams, hair mousses, hair sprays, setting lotions, blow-drying lotions, hair dyes and tints, hair bleaching creams, hair straightening compositions, curl activator gels, fragrance boosters, sunscreen products (e.g., sunscreen sticks and sunscreens), soaps, hand washes, hand wash gels, antibacterial hand washes, body scrubs, hand scrubs, bubble baths, bath oils, quick-drying hand washes, baby lotions, diaper rash creams, wet wipes, baby bathes, vitamin creams, and combinations thereof.

[0113] Alternatively, the emulsion can be a cosmetic composition per se. In other embodiments, the emulsion is present in the cosmetic or personal care composition in an amount of from about 1 to about 99.5, from about 5 to about 90, from about 10 to about 85, from about 15 to about 80, from about 20 to about 75, from about 25 to about 70, from about 30 to about 65, from about 35 to about 60, from about 40 to about 55, or from about 45 to about 50 weight percent active based on the total weight of the cosmetic or personal care composition. In various non-limiting embodiments, all numerical values and numerical ranges, including the numerical values noted above and numerical values falling within the ranges noted above, are expressly considered available for use herein.

[0114] Preservatives are commonly used in personal care formulations to provide long term shelf stability, especially microbial shelf life stability. Suitable preservatives include, for example, methyl paraben, propyl paraben, butyl paraben, DMDM hydantoin, imidazolidinyl urea, glutaral, phenoxyethanol, benzalkonium chloride, methylchloroisothiazolinone, benzisothiazolinone, sodium benzoate, chloroacetamide, iodopropynyl butylcarbamate, sodium pyrithione, zinc pyrithione, and other cosmetically acceptable preservatives known to those skilled in the art. Examples

[0115] In one embodiment, the above hydrophobically modified starch is formed using the procedure immediately below:

[0116] To a 1 L jacketed beaker equipped with an overhead mechanical stirrer was added municipal (tap) water. With stirring (~200 rpm), anhydrous sodium sulfate (Na2S04) was added to the beaker. After the Na2S04dissolved, the reaction was warmed to 32 °C (jacket temperature: 32 °C). When the reaction temperature reached 32 °C, 200.08 g of unmodified amphoteric starch was slowly added to the reaction vessel. A fluid slurry / dispersion having a pH of 7.84 was obtained. The pH of the slurry was then adjusted to 8.01 by controlled addition of 0.348 mL (0.44 mmol) of 1.275 N NaOH (Metrohm 718 STAT Titrino, SET mode). To the slurry at this pH was added octenyl succinic anhydride (OSA) over a period of several minutes.

[0117] Using a portable homogenizer (IKA T25 D S1 ULTRA TURRAX), the reaction mixture was homogenized at 10,000 rpm for 2.0 minutes while maintaining the pH at 8.0 by controlled addition of 1.275 N NaOH (Metrohm 718 STAT Titrino, STAT mode). The pH was maintained at 8.0 for the remainder of the reaction.

[0118] After 2.5 hours, the uptake of NaOH had slowed significantly, so the reaction was stopped by controlled addition of 4.72 mL (12.5 mmol) of 2.647 N HC1 to lower the pH to 5.65. The reaction temperature dropped to 27 °C, and the pH was recorded as 5.61. Total base uptake after 2.5 hours of reaction: 23.562 mL (30.04 mmol); theoretical: 22.60 mL (28.82 mmol).

[0119] The starch was recovered by vacuum filtration. The recovered starch was then washed on a filter funnel with 8 x 200 g tap water. The starch was then allowed to air dry.

[0120] Product yield: 213.98 g (before grinding); 211.35 g after grinding into granulated powder using a coffee grinder. Solids content (moisture balance): 85.62%.

[0121] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a multitude of modifications can be made. It should also be understood that the exemplary embodiment is simply intended to illustrate and not to limit the scope, applicability or configuration in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment. It should be understood that various changes can be made in the function and arrangement of elements described in the exemplary embodiment without departing from the scope as set forth in the appended claims.

Claims

1. Hydrophobically modified starch, which has the following structure: ; Where R 1 It is C3 to C 19 Branched or straight-chain alkyl or alkenyl groups, R 2 It is H or an alkyl group having 1 to 10 carbon atoms, R 3 It is H, CH3 or COOH, R 4 It is H or CH3, n is 2 or 3, and M is H, alkali metal, alkaline earth metal or ammonium, and Starch represents the starch moiety.

2. The hydrophobically modified starch according to claim 1, wherein R 1 It is a C5 straight-chain alkyl group, R 2 H is 2, n is 2, R is 2 3 It is H, and R 4 It's H.

3. The hydrophobically modified starch according to claim 1, wherein R 1 It is a C9 straight-chain or branched alkyl group, R 2 H is 2, n is 2, R is 2 3 It is H, and R 4 It's H.

4. The hydrophobically modified starch according to claim 1, wherein R 1 It is a C5 straight-chain alkyl group.

5. The hydrophobically modified starch according to any one of the preceding claims, wherein R 2 It's H.

6. The hydrophobically modified starch according to any one of the preceding claims, wherein n is 2.

7. The hydrophobically modified starch according to any one of the preceding claims, wherein R 3 It's H.

8. The hydrophobically modified starch according to any one of the preceding claims, wherein R 4 It's H.

9. The hydrophobically modified starch according to any one of claims 1 to 8, wherein R 1 It is a C9 straight-chain alkyl group.

10. The hydrophobically modified starch according to any one of claims 1 to 8, wherein R 1 It is a C9 branched alkyl group.

11. A method for forming the hydrophobically modified starch according to any one of the preceding claims, the method comprising the following steps: The starch is reacted with an aminopolycarboxylic acid reagent to form the first intermediate; The first intermediate is reacted with alkenyl succinic anhydride to form the hydrophobic modified starch.

12. The method of claim 11, wherein the starch is potato starch.

13. The method according to claim 11 or 12, wherein the alkenyl succinic anhydride is octenyl succinic anhydride.

14. The method according to claim 11 or 12, wherein the alkenyl succinic anhydride is dodecenyl succinic anhydride.

15. The method according to any one of claims 11-15, wherein the aminopolycarboxylic acid reagent is selected from 2-bromoethylaminodipropionic acid, 3-chloropropylaminodipropionic acid, 3-bromopropylaminodipropionic acid, and combinations thereof.

16. The method according to any one of claims 11-15, wherein the aminopolycarboxylic acid reagent is selected from 2-chloroethylaminodipropionic acid, 2-bromoethylaminodipropionic acid, 3-chloropropylaminodipropionic acid, 3-bromopropylaminodipropionic acid, and combinations thereof.

17. The method according to any one of claims 11-14, wherein the aminopolycarboxylic acid reagent is 2-chloroethylaminodipropionic acid.

18. An emulsion comprising the hydrophobically modified starch according to any one of claims 1-10.

19. A personal care composition comprising the hydrophobically modified starch according to any one of claims 1-10.

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