Modified particle

Abstract

A modified particle includes at least one hydroxyl group or residue thereof and a modifier disposed about the core and including a citrate ester and / or a esterification product of the citrate ester and at least part of the core.

Description

PCT Patent ApplicationAtty Docket No.: 364.1790PCMODIFIED PARTICLECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 778,863, filed March 27, 2025, the entirety of which is expressly incorporated herein by reference.TECHNICAL FIELD

[0002] The present disclosure generally relates to a modified particle. More specifically, this disclosure relates to a modified particle that includes at least one hydroxyl group or residue thereof and a modifier disposed about the core and including a citrate ester and / or an esterification product of the citrate ester and at least part of the core.BACKGROUND

[0003] In modern personal care product development, consumer demand for natural, sustainable, and high-performance ingredients continues to grow. One key challenge in formulating products such as lotions, creams, and ointments is balancing oil-phase components that contribute to skin feel, stability, and efficacy while minimizing undesirable sensory attributes such as greasiness, tackiness, and excessive gloss.

[0004] Traditional starches and oil-absorbing powders such as aluminum-based compounds, talc, or modified polysaccharides have been used to improve formulation aesthetics by reducing excess shine and improving spreadability. However, these ingredients can pose sustainability concerns, regulatory restrictions, or formulation drawbacks such as instability across a broad pH range. Accordingly, there remains an opportunity for improvement.

[0005] Furthermore, other desirable features and characteristics of the present disclosure will become apparent from the subsequent detailed description of the disclosure and the appended claims, taken in conjunction with the accompanying drawings and this background of the disclosure.BRIEF SUMMARY

[0006] This disclosure provides a modified particle that includes at least one hydroxyl group or residue thereof and a modifier disposed about the core and including a citrate ester and / or a esterification product of the citrate ester and at least part of the core.PCT Patent ApplicationAtty Docket No.: 364.1790PCDETAILED DESCRIPTION

[0007] The following detailed description is merely exemplary in nature and is not intended to limit the current composition. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.

[0008] Embodiments of the present disclosure are generally directed to modified particles, compositions including the same, and methods for forming the same. For the sake of brevity, conventional techniques related to making related polymers and such compositions may not be described in detail herein. Moreover, the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process having additional steps or functionality not described in detail herein. In particular, various steps in the manufacture of polymers and associated compositions are well-known and so, in the interest of brevity, many conventional steps will only be described briefly herein or will be omitted entirely without providing the well-known process details.

[0009] In this disclosure, the terminology “about” can describe values ± 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%, in various embodiments. Moreover, it is contemplated that, in various nonlimiting embodiments, it is to be appreciated that all numerical values as provided herein, save for the actual examples, are approximate values with endpoints or particular values intended to be read as “about” or “approximately” the value as recited. It is also contemplated that all isomers and chiral options for each compound described herein are hereby expressly contemplated for use herein in various non-limiting embodiments.

[0010] Throughout this disclosure, the terminology percent "actives" is well recognized in the art and means the percent amount of active or actual compound or molecule present as compared to, for example, a total weight of a diluted solution of a solvent and such a compound. Some compounds, such as a solvent, are not described relative to a percent actives because it is well known to be approximately 100% actives. Any one or more of the values described herein may be alternatively described as percent actives as would be understood by the skilled person.

[0011] In various embodiments, the terminology “free of’ describes embodiments that include less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent (or weight percent actives) of the compound or element at issue using an appropriate weight basis as would be understood by one of skill in the art. In other embodiments, the terminology “free of’ describes embodiments that have zero weight percent of the compound or element at issue.PCT Patent ApplicationAtty Docket No.: 364.1790PC

[0012] The terminology “consists essentially of’ may 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, etc.

[0013] It is to be understood that the subscripts of polymers are typically described as average values because the synthesis of polymers typically produces a distribution of various individual molecules.

[0014] The polymers and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process delineations described herein. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.

[0015] This disclosure provides a modified particle that includes at least one hydroxyl group or residue thereof and a modifier disposed about the core and including a citrate ester and / or a esterification product of the citrate ester and at least part of the core.

[0016] In various embodiments, the modified particle enhances product aesthetics by reducing greasiness and tackiness as well as controlling the gloss caused by oil-phase components in lotions, creams and ointments, enabling the reduction of oil or grease in personal care products, while being biodegradable and bio-derived. In some embodiments, such modified particles are obtained through a treatment with citrate esters, in particular citrate esters that are or include citrate monoesters such as a monoglyceride monocitrate compounds.

[0017] Absorbing excess oil-phase components is desirable to ensure a smoother, dry-touch finish, preventing the heavy or sticky feel associated with rich formulations. Modulating surface reflectance can create a more desirable matte or soft-focus effect, preventing excessive glossiness without compromising hydration. In various embodiments, the modified particle improves one of more of these attributes.

[0018] Unlike conventional powders that may feel dry or chalky, there is a need to design a product that has lightweight texture without sacrificing emolliency. Such a product typically has excellent pH stability to ensure compatibility across a wide range of personal care formulations thereby minimizing a risk of ingredient degradation, phase separation, or texture alteration over time. Additionally, biodegradability and aluminum-free compositions align with modern sustainability trends and regulatory expectations, ensuring that products meet clean beauty standards while delivering high-performance oil control. Moreover, sourcing from renewable, bio-based materialsPCT Patent ApplicationAtty Docket No.: 364.1790PCensures that the product contributes to a circular, eco-conscious beauty industry. Unlike synthetic oil-absorbers or modified starches derived from petrochemical processing, this naturally derived alternative provides formulators with a high-performance yet environmentally responsible solution. In various embodiments, the modified particle improves one of more of these attributes.Modified Particle

[0019] The modified particle includes the core that includes at least one hydroxyl group or residue thereof. For example, the core itself may have one or more than one hydroxyl group. Any compound in the art having one or more than one hydroxyl group may be used herein. In one embodiment, the core is chosen from starch, modified starch, pectin, agar, carrageenan, inulin, hyaluronic acid, chitosan, dextran, xanthan gum, heparin, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, alginate, beta-glucan, guar gum, locust bean gum, pullulan, glactomannan, and combinations thereof. In another embodiment, the core is chosen from polysaccharides, oligosaccharides, polyvinyl alcohol, polyols, hydroxyalkyl celluloses, hydrogels, dendrimers with hydroxyl terminal groups, polyethylene glycols, carbohydrate-based nanoparticles, protein-based particles, hydroxyapatite-based particles, hydroxyl terminated polyesters, polyesteramides, hydroxyl terminated polyurethanes, and combinations thereof, so long as the core comprises the at least one hydroxyl group. In another embodiment, the core is a polysaccharide. In a further embodiment, the core is a starch.

[0020] The core may be granular, in a powder form, in a paste form, etc. The terminology “core” may refer to a molecule itself, e.g. a starch molecule, or a collection of molecules, e.g. a starch granule. The core, or each molecule making up the core, may have one, two, three, four, five, etc. hydroxyl groups. Typically, the hydroxyl groups are available for reaction via an esterification reaction, e.g. as described in greater detail below. The core may have some molecules that have the hydroxyl group and other molecules that has a residue of the hydroxyl group because it has already reacted. However, reaction of the hydroxyl groups is not required and may not occur.

[0021] If the core particle is a granule, such as a starch granule, the size may be chosen by the skilled person. Starch granules exhibit a wide range of particle sizes depending on their botanical source. The granule size is typically measured in micrometers (pm) and varies from sub-micron (<1 pm) to over 100 pm. In various embodiments, the granule may be described as follows: Rice (2- 8 pm); Wheat (2 - 35 pm; bimodal: small -2-10 pm, large -15-35 pm); Com (Maize; 2 - 30 pm); Potato (15 - 100 pm); Tapioca (Cassava; 5 - 35 pm); Oat (3 - 10 pm); Barley (2 - 10PCT Patent ApplicationAtty Docket No.: 364.1790PCpm (small) and 20 - 40 pm (large). Several analytical techniques are commonly used to determine granule size, such as Optical Microscopy (Brightfield & Polarized Light), Scanning Electron Microscopy (SEM), Laser Diffraction Particle Size Analysis (LDPSA), Dynamic Light Scattering (DLS), Coulter Counters (Electrical Sensing Zone Method), and Atomic Force Microscopy (AFM). Smaller granules (<10 pm) can provide better surface coverage and oil absorption, reducing greasiness in formulations. Large granules (e.g., potato starch) swell more significantly upon hydration, which can impact viscosity and texture. Fine starch particles may be preferred for applications requiring smooth textures, while larger granules contribute to structural integrity.

[0022] In various embodiments, the core may have a DvlO, Dv50, Dv90, Dv99, DnlO, Dn50, Dn90, and / or Dn99 particle size each independently as described below, e.g. each independently of from about 1 to about 200, about 1 to about 175, about 1 to about 150, about 1 to about 125, about 1 to about 100, about 1 to about 75, about 1 to about 50, about 1 to about 25, about 1 to about 10, about 1 to about 5, about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50, pm as determined using one or more methods such as ASTM D5861 (2025), ISO 13320 (2025) or the like. It is also contemplated that one or more of the DvlO, Dv50, Dv90, Dv99, DnlO, Dn50, Dn90, and / or Dn99 particle size measurements may fall outside of the aforementioned ranges. Alternatively, a DvlO, Dv50, Dv90, Dv99, DnlO, Dn50, Dn90, and / or Dn99 particle size may be any described above. Moreover, the particle size may be determined using any apparatus known in the art, e.g. a Malvern Mastersizer such as the Mastersizer 3000. Relative to software version, type of light scattering model applied, real and imaginary part of complex refractory index if Mie theory is applied, refractive index, sampling procedure, amount and power of ultrasound, etc. can each be chosen by one of skill in the art if not set forth in the aforementioned standard procedures. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, both between and including each of the above, are hereby expressly contemplated for use herein.

[0023] It is also contemplated that any one or more of the aforementioned measurements may apply to the modified particle as a whole and not simply the core. For example, the modified particle may have a particle size that is larger than the size of the core particle alone, e.g. by 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 76, 80, 85, 90, 95, or even 100, percent. In various non-limiting embodiments, all values and ranges of values, both whole andPCT Patent ApplicationAtty Docket No.: 364.1790PCfractional, both between and including each of the above, are hereby expressly contemplated for use herein.Modifier

[0024] The modified particle also includes the modifier disposed about the core. The modifier may be disposed about or around an entirety of the core, e.g. entirely encapsulating or covering the core, such as in an embodiment wherein the core is a starch granule. Alternatively, the modifier may be disposed around or about less than an entirety of the core, e.g. about or around about 0.1 to 99.9% of the core. In various embodiments, the modifier is disposed about or around about 1 to 99, about 5 to 95, about 10 to 90, about 15 to 85, about 20 to 80, about 25 to 75, about 30 to 70, about 35 to 65, about 40 to 60, about 45 to 55, or about 50, percent of the core. In various nonlimiting embodiments, all values and ranges of values, both whole and fractional, both between and including each of the above, are hereby expressly contemplated for use herein.

[0025] If the core is simply a molecule or a collection of molecules (e.g. and not a granule), the modifier may be disposed adjacent to the core and still be considered disposed “about” the core, e.g. through hydrogen bonding or any other non-covalent type of bonding. In other embodiments, if the core is simply a molecule or a collection of molecules (e.g. again and not a granule), the modifier may alternatively be bonded through one or more covalent bonds to the core and still be considered to be disposed “about” the core. The modifier may be disposed on, and in direct contact with, the core. Alternatively, the modifier may be disposed on, and separated from, the core, e.g. with a layer in-between, such as any additive described herein. The modifier may form an outermost layer of an encapsulated, or partially encapsulated, core or particle. The terminology outermost layer describes that the modifier would face the environment (or outside) on one side. The other side would typically face the core, e.g. the interior of the core. The terminology outermost layer means that such a layer would not be disposed between two other layers. However, it is contemplated that the modifier may be an inner layer of a larger encapsulated particle with an outermost layer disposed on one side of the modifier and another layer, or simply the core, disposed on the other side of the modifier. In this embodiment, such layers would be formed by any component described herein.

[0026] The modifier can be, include, consist essentially of, or consist of, a citrate ester and / or a esterification product of the citrate ester and at least part of the core. In various embodiments, the terminology “consist essentially of’ describes a modifier that is free of esters that are not citratePCT Patent ApplicationAtty Docket No.: 364.1790PCesters and / or any other compound that may react with the core, as would be understood by the skilled person.

[0027] The citrate ester itself is not particularly limited and may be any known in the art. In one embodiment, the citrate ester is a condensation product of citric acid and a fatty alcohol. The fatty alcohol may be any having from about 5 to about 22 carbon atoms, e.g. about 6 to about 20, about 8 to about 18, about 10 to about 16, or about 12 to about 14, carbon atoms. In various non-limiting embodiments, the alcohol may have one, two, or three -OH groups. In other non-limiting embodiments, all values and ranges of values, both between and including each of the above, are hereby expressly contemplated for use herein.

[0028] In various embodiments, the citrate ester is a condensation product of citric acid and a glyceride. The glyceride is also not particularly limited. In various embodiments, the glyceride has from about 5 to about 22 carbon atoms. The glyceride may be any having from about 5 to about 22 carbon atoms, e.g. about 6 to about 20, about 8 to about 18, about 10 to about 16, or about 12 to about 14, carbon atoms. In various non-limiting embodiments, all values and ranges of values, both between and including each of the above, are hereby expressly contemplated for use herein.

[0029] In other embodiments, the glyceride is chosen from mono- and di- glycerides, distilled monoglycerides, acetylated monoglycerides, glyceryl monooleate, glyceryl dioleate, MCT oil, caprylic / capric glycerides, glyceryl stearate; glyceryl cocoate; glyceryl behenate, and combinations thereof.

[0030] In other embodiments, the glyceride is chosen from the polyols, cyclodextrins, polyglycerol esters of fatty acids, and combinations thereof.

[0031] In other embodiments, the citrate ester is a monocitrate ester. However, di-citrate esters can also be used. Alternatively, the citrate ester is, includes, consists essentially of, or consists of, a citrate having the following formula (I) and a glyceride citrate having the following formula (II) or (III), and compounds of the types (IV), or (V):PCT Patent ApplicationAtty Docket No.: 364.1790PCPCT Patent ApplicationAtty Docket No.: 364.1790PCThe citrate ester of formula (II) represents a mono-citrate ester of a monoglyceride, whereas structure (III) represents a citrate ester of a diglyceride. Other potential structures are represented in the adducts (IV) and more generically (V).

[0032] In the above:in formula (I) the citrate has a single R group;each R and R’ in formulas (I), (II), (III), (IV), and (V) is independently an alkyl, aryl or arylalkyl group that is linear, branched, or cycloaliphatic, saturated or unsaturated, and includes 5 or more carbon atoms;X is a dialkylenyloxy group, a substituted dialkylenyloxy group, a diaminoalkylenyl group, an aminoalkyloxy group, and oxy or amino-terminated radical, and oxy or amino-terminated oligomers such as from esters of polyglycerol, sucrose esters of fatty acids or combinations thereof; andY is a linker to R, or multiples of it, which may be an alkyl, aryl or arylalkyl group that is linear, branched, or cycloaliphatic, saturated or unsaturated, and includes 5 or more carbon atoms. The linker Y can include polyols, such as in alkyl glycosides, cyclodextrins, and the like.

[0033] In various embodiments, the terminology “consist essentially of’ describes the citrate ester that is free of other esters that are not citrate esters and / or any other compound that may react with the core, as would be understood by the skilled person. All isomers are herein expressly contemplated for use herein in various non-limiting embodiments.

[0034] More specifically, in formula (I) the citrate ester typically has a single R group which may be an alkyl, aryl or arylalkyl group that is linear, branched, or cycloaliphatic, saturated or unsaturated, and includes 5 or more carbon atoms. However, it is contemplated the citrate ester could have two R groups. In various embodiments, the R group has 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 atoms, or any range thereof. For example, in such embodiments, the citrate may be further described as having the following formulae:PCT Patent ApplicationAtty Docket No.: 364.1790PC

[0035] Relative to formula (II) and (III), R and R’ may independently be any described above. All isomers are herein expressly contemplated for use herein in various non-limiting embodiments.

[0036] In various embodiments, X may be a dialkylenyloxy group, a substituted dialkylenyloxy group, a diaminoalkylenyl group, an aminoalkyloxy group, and oxy or amino-terminated radical, oxy or amino-terminated oligomers, or combinations thereof. In other embodiments, X is derived from oxy 1,2 ethanediyl, poly(oxy 1,2 ethanediyl), oxy 1,3-propanediyl, poly(l,3-propanediyl), oxy methyl 1,2 ethanediyl, poly(oxy methyl 1,2 ethanediyl), or combinations thereof. X may also be derived from a diol or a diamine, such as from 1,2- and 1,3-propanediol, butanediol, cyclohexanedimethanol, an aromatic diol like resorcinol, isosorbide and its isomers, a polyol like pentaerythritol, a nature-based diol like a dextrin, and an hydroxyamine like ethanolamine. X may be any of the above groups or residues of such groups. In any of the above, the alkyl groups may be any known in the art. In various embodiments, the alkyl groups have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. All isomers are herein expressly contemplated for use herein in various nonlimiting embodiments.

[0037] In various embodiments, Y may be a sugar-base linker, as derived from an alkyl glycoside, a dextrin, a cyclodextin, an alkoxylated fatty compound, such as an alkyl propoxylate, an alkoxylated fatty acid, a silanol, or combinations thereof.

[0038] The compound of formulae (I)-(V) may be or include isomers because monocitrate components can derive from an esterification at the central or peripheral carboxylic acid unit. Commercial and produced citrate esters may also include multiple esters of citric acid, as well as unreacted citric acid and hydrophobe reagent.

[0039] In addition, many isomers exist for the compound of formula (II) as both the glyceride alkyl group (R) and the citrate ester can occur on either the primary or secondary hydroxyl groups of a glyceryl linker. Similarly, diglycerides can also form esters with citric acid, and that di-citrate esters, for example, can form from the condensation of two molecules of citric acid onto aPCT Patent ApplicationAtty Docket No.: 364.1790PCmonoglyceride. While not shown, the use of a diol such as hexanediol could be used to form dimers containing two citrate groups, which can be useful for crosslinking reactions.

[0040] Iln addition, materials known as citrems can be used. These compounds are citric acid esters of mono- and diglycerides, obtained from esterification of monoglycerides of fatty acids and citric acid. As such, these compounds might be represented by formula (II) and (III) as one of their components. These compounds can be partially or totally neutralized. These compounds can be obtained from esterification of monoglycerides of fatty acids with citric acid.

[0041] It is possible to use products similar to the compounds of formula (II) and (III) wherein a polyol linker might not be glycerol, though derived from a bio-based source. Diols such as 1,3-propanediol and isosorbide are examples. Sugars also bear multiple hydroxyl groups, and thus can form the base for both citrate esters and hydrophobes. Similarly, compounds such as polyglycidol carry several hydroxyl groups that are esterifiable with both citric acid and hydrophobic reagents. Such hydrophobes could be present as esters or as ethers, such as with alkyl glycosides and alkyl poly glycosides. Other natural or naturally derived polyols like sorbitol could also be used.

[0042] The modifier may be or include the citrate ester and / or the esterification product of the citrate ester and at least part of the core. For example, if the citrate ester reacts with one or more of the at least one hydroxyl group of the core (e.g. via an esterification reaction), a covalent bond may be formed. In such an embodiment, the core may no longer include the at least one hydroxyl group (or may include less than its original number of hydroxyl groups) and include a residue of the hydroxyl group in place of the hydroxyl group itself due to the (esterification) reaction with the citrate ester. Such a reaction may proceed as follows:Citrate Ester + OH-R — > New Ester + Water

[0043] In one embodiment, the modifier includes the citrate ester without the esterification product. In such an embodiment, there typically is no covalent bond between the modifier and the core. In another embodiment, the modifier includes the esterification product. In this embodiment, there typically is a covalent bond between the modifier and the core. It is also contemplated that a mixture of cores having a covalent bond and those not having a covalent bond may be present.Personal Care Composition

[0044] This disclosure also provides a personal care composition that includes the modified particle of this disclosure. The personal care composition is not particularly limited and can be an emulsion, an aqueous system, a solvent system, as well as anhydrous and powdered system. InPCT Patent ApplicationAtty Docket No.: 364.1790PCvarious embodiments, the person care composition is a lotion, cream, ointment, shampoo and / or conditioner, body, skin or hair spray, facial, body or hair powder, eye shadow, blush, lip gloss, lip stick, lip balm, deodorant, etc. In other embodiments, the personal care composition may be chosen from moisturizing lotion, anti-aging cream, sunscreen lotion, cleansing gel, exfoliating scrub, hydrating serum, whitening cream, toning mist, antibacterial hand wash, deodorant stick, shaving cream, aftershave balm, lip balm, bb cream, cc cream, hair conditioner, hair mask, shampoo, dry shampoo, scalp serum, body butter, body oil, body wash, facial mask (sheet / clay / peel-off), eye cream, foot cream, hand cream, makeup remover, micellar water, nail treatment serum, cuticle oil, beard oil, stretch mark cream, cellulite treatment gel, anti-dandruff shampoo, tinted moisturizer, facial essence, skin brightening toner, pore minimizing serum, night repair cream, SPF lip balm, anti-acne spot treatment, soothing aloe gel, tanning lotion, self-tanning mousse, makeup primer, setting spray, hair styling gel, hair serum, or combinations thereof.

[0045] An emulsion such as an oil-in-water emulsion or water-in-oil emulsions, aqueous system, or solvent system, which may be used in or as the personal care composition, may include from about 0.1% to about 25% by weight of the modified particle of this disclosure based on a total weight of any of the above. In other embodiments, this amount is from about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.4 to about 0.5, about 1 to about 10, about 2 to about 8, about 3 to about 7, about 4 to about 6, about 4 to about 5, about 1 to about 25, about 5 to about 25, about 5 to about 20, about 5 to about 15, about 5 to about 10, about 10 to about 25, about 10 to about 20, about 10 to about 15, about 15 to about 25, about 15 to about 20, or about 20 to about 25, by weight of the modified particle of this disclosure based on a total weight of any of the above. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, both between and including each of the above, are hereby expressly contemplated for use herein.

[0046] An anhydrous system, which alternatively may be used in or as the personal care composition, may include from about 0.1% to about 50% by weight of the modified particle of this disclosure based on a total weight of the anhydrous system. In other embodiments, this amount is from about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.4 to about 0.5, about 1 to about 10, about 2 to about 8, about 3 to about 7, about 4 to about 6, about 4 to about 5, about 5 to about 25, about 5 to about 20, about 5 to about 15, about 5 to about 10, about 10 to about 25, about 10 to about 20, about 10 to about 15, about 15 to aboutPCT Patent ApplicationAtty Docket No.: 364.1790PC25, about 15 to about 20, about 20 to about 25, about 1 to about 50, about 5 to about 45, about 10 to about 40, about 15 to about 35, about 20 to about 30, or about 25 to about 30, percent by weight of the modified particle of this disclosure based on a total weight of the anhydrous system. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, both between and including each of the above, are hereby expressly contemplated for use herein.

[0047] A powdered system, which also be may used in or as the personal care composition, may include from 0.5% to about 99.5% by weight of the modified particle, based on a total weight of the powdered system. In other embodiments, this amount is from about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.4 to about 0.5, about 1 to about 10, about 2 to about 8, about 3 to about 7, about 4 to about 6, about 4 to about 5, about 5 to about 25, about 5 to about 20, about 5 to about 15, about 5 to about 10, about 10 to about 25, about 10 to about 20, about 10 to about 15, about 15 to about 25, about 15 to about 20, about 20 to about 25, about 1 to about 50, about 5 to about 45, about 10 to about 40, about 15 to about 35, about 20 to about 30, or about 25 to about 30, about 1 to about 99, about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50, % by weight of the modified particle, based on a total weight of the powdered system. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, both between and including each of the above, are hereby expressly contemplated for use herein.

[0048] The personal care composition may additionally include or be free of additional non-biodegradable polymers such as: from Nouryon, AMPHOMER® and AMPHOMER® LV-71 polymers (octylacrylamide / acrylates / butylaminoethyl methacrylate com polymer), AMPHOMER® HC® polymer (acrylates / octylacrylamide copolymer), BALANCE® 0 / 55 and BALANCE CR® polymers (acrylates copolymer), BALANCE® 47 polymer (octylacrylamide / butylaminoethyl methacrylate copolymer), RESYN® 28-2930 polymer (VA / crotonates / vinyl neodecanoate copolymer), RESYN® 28-1310 polymer (VA / Crotonates copolymer), FLEXAN® polymers (sodium polystyrene sulfonate), DynamX polymer (polyurethane- 14 (and) AMP- Acrylates copolymer), RESYN XP® polymer (acrylates / octylacrylamide copolymer), STRUCTURE 2001 (acrylates / steareth-20 itaconate copolymer) and STRUCTURE® 3001 (acrylates / ceteth-20 itaconate copolymer); from ISP, OMNIREZ-2000® (PVM / MA half ethyl ester copolymer), GANEX P-904® (butylated PVP),PCT Patent ApplicationAtty Docket No.: 364.1790PCGANEX V-216® (PVP / hexadecene copolymer), GANEX® V-220 (PVP / eicosene copolymer), GANEX® WP-660 (tricontanyl PVP), GANTREZ® A425 (butyl ester of PVM / MA copolymer), GANTREZ® AN- 119 PVM / MA copolymer, GANTREZ ES 225® (ethyl ester of PVM / MA copolymer), GANTREZ ES425 (butyl ester of PVM / MA copolymer), GAFFIX VC-713® (vinyl caprolactam / PVP / dimethylaminoethyl methacrylate copolymer), GAFQUAT755® (polyquaternium-11), GAFQUAT HS-100® (poly-quaternium-28), AQUAFLEX XL-306 (Polyimide-1), AQUAFLEX SF-40® (PVP / Vinylcaprolactam / DMAPA Acrylates Copolymer), AQUAFLEX FX-64® (Isobutylene / Ethylmaleimide / Hydroxyethylmaleimide Copolymer), ALLIANZ LT-120® (Acrylates / Cl-2 Succinates / Hydroxy acrylates Copolymer), STYLEZE CC-10® (PVP / DMAPA Acrylates Copolymer), STYLEZE 2000® (VP / Acrylates / Lauryl Methacrylate Copolymer), STYLEZE W-20® (Poly quatemium-55), Copolymer Series (PVP / Dimethylamino ethylmethacrylate Copolymer), ADVANTAGE S® and ADVANTAGE LCA® (VinylcaprolactamNP / Dimethylaminoethyl Methacrylate Copolymer), ADVANTAGE PLUS (VA / Butyl Maleate / Isobornyl Acrylate Copolymer), Antaron ECo (Ethylcellulose); from BASF, ULTRAHOLD STRONG (acrylic acid / ethyl acrylate / t-butyl acrylamide), LUVIMER 100P® (t-butyl acrylate / ethyl acrylate / methacrylic acid), LUVIMER 36D (ethyl acrylate / t-butyl acrylate / methacrylic acid), LUVIQUAT HM-552® (polyquaternium-16), LUVIQUAT HOLD® (polyquaternium-16), LUVISKOL K30 (PVP)LUVISKOL K90® (PVP), LUVISKOL VA 64® (PVP / VA copolymer), LUVISKOL VA73W® (PVPNA copolymer), LUVISKOL VA®, LUVISET PUR® (Polyurethane- 1), LUVISET® Clear (VP / MethacrylamideNinyl Imidazole Copolymer), LUVIFLEX SOFT® (Acrylates Copolymer), ULTRA HOLD 8® (Acrylates / Acrylamide Copolymer), LUVISKOL® Plus (Polyvinylcaprolactam), LUVIFLEX® Silk (PEG / PPG-25 / 25 Dimethicone / Acrylates Copolymer); from Amerchol, AMERHOLD® DR-25 (acrylic acid / meth acrylic acid / acrylates / methacrylates); from Rohm & Haas, ACUDYNE 258® (acrylic acid / methacrylic acid / acrylates / methacrylates / hydroxy ester acrylates; from Mitsubishi and distributed by Clariant, DIAFORMER Z-301®, DIA FORMER Z-SM®, and DIAFORMER Z-400® (methacryloyl ethyl betaine / acrylates copolymer), ACUDYNE 180® (Acrylates / Hydroxyesters Acrylates Copolymer), ACU DYNE SCP (Ethylenecarboxyamide / AMPSA / Methacrylates Copolymer), and the ACULYN® rheological modifiers; from ONDEO Nalco, FIXOMER A-30® and FIXOMER N-28 ® (INCI names: methacrylic acid / sodium acrylamidomethyl propane sulfonate copolymer); from Noveon,PCT Patent ApplicationAtty Docket No.: 364.1790PCFIXATE G-100® (AMP-Acrylates / Allyl Meth acrylate Copolymer), FIXATE PLUS® (Polyacrylates-X), CARBOPOL® Ultrez 10 (Carbomer), CARBOPOL Ultrez 20® (Acrylates / C 10-30 Alkyl Acrylates Copolymer), AVALLTRE AC® series (Acrylates Copolymer), AVALURE UR® series (Polyurethane-2, Polyurethane-4, PPG- 17 / IPDI / DMPA Copolymer); polyethylene glycol; water-soluble acrylics; water-soluble polyesters; polyacryl amides; polyamines; polyquaternary amines; styrene maleic anhydride (SMA)resin; polyethylene amine; from Covestro, Baycusan® C 2000 (Polyurethane solution in ethanol (INCI- Polyurethane - 64)), Baycusan® eco E 1000 (water-based polyurethane), Baycusan® C 1010 (water-based polyurethane), Baycusan® C 1008 (water-based polyurethane), Baycusan® C 1001 (water-based polyurethane); from Inolex, Inolex Lexfilm Sun (INCI- Polyester-7 (and) Neopentyl Glycol Diheptanoate), Inolex Lexfilm Sun Natural MB (INCI- Capryloyl Glycerin / Sebacic Acid Copolymer), Inolex WetFilm MB (INCI- Trimethylpentanediol / Adipic Acid / Glycerin Crosspolymer), Inolex Lexfilm Spray (INCI- Polyester- 10 (and) Propylene Glycol Dibenzoate) and Inolex Lexorez 100 MB (INCI- Adipic Acid / Diglycol Crosspolymer). Other conventional polymers that are polar solvent soluble or that can be made soluble through neutralization with an appropriate base can also be used. In one embodiment, the personal care composition additionally includes or is free of a starch ester polyglucose polymer.

[0049] The personal care composition may include or be free of one or more performance enhancers. Non-limiting examples of these performance enhancers include: absorbents, abrasives, anticaking agents, antifoaming agents, antioxidants, binders, biological additives, buffering agents, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formers, fragrance components, humectants, opacifying agents, pH adjusters, plasticizers, reducing agents, skin bleaching agents, skin-conditioning agents, skin protectants, solvents, foam boosters, hydrotropes, solubilizing agents, suspending agents, SPF boosters, waterproofing agents, and viscosity modifiers. In one embodiment, the personal care composition optionally further includes a neutralizing agent. Suitable neutralizing agents include both inorganic and organic compounds. Non-limiting examples of inorganic neutralizing agents include sodium or potassium hydroxide. Non-limiting examples of organic neutralizing agents include amines or alkanolamines. Primary, secondary, and tertiary amines or alkanolamines may be used, such as mono-, di-, and tri- long chain fatty amines containing a C4 to C24 hydrocarbon chain, ethoxylates and propoxylates longPCT Patent ApplicationAtty Docket No.: 364.1790PCchain (C4 to C24) fatty amines and mixtures thereof. In one embodiment, the neutralizing agent is chosen from 2-amino-2-methyl-propanol, 2-amino-2-methyl-l, 3-propanediol aminomethylpropanol, di- methyl stearamine, triethanolamine and combinations thereof.

[0050] The personal care composition may further include or be free of one or more cosmetic additives. Non limiting examples of cosmetic additives are absorbents, abrasives, anticaking agents, antifoaming agents, antioxidants, binders, biological additives, buffering agents, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formers, fragrance components, humectants, opacifying agents, pH adjusters, plasticizers, reducing agents, skin bleaching agents, skin-conditioning agents (emollient, humectants, miscellaneous, and occlusive), skin protectants, solvents, foam boosters, hydrotropes, solubilizing agents, suspending agents (nonsurfactant), SPF boosters, waterproofing agents, viscosity increasing agents (aqueous and nonaqueous), and combinations thereof.Physical Properties

[0051] The inclusion of the modified particle in the personal care composition may affect one or more physical properties of the personal care composition. For example, the modified particle may or may not affect one or more of Friction Coefficient; Angle of Repose; Cohesiveness of powders; Water Repellency; and Demand Adsorbency of a composition.Friction Coefficient (COF)

[0052] The friction coefficient of a composition reflects how a powder behaves when rubbed against skin or other surfaces. A lower COF generally indicates a silkier, smoother feel and easier application. This can be important in foundations, body powders, or baby powders where tactile sensory attributes are critical. Powders with an optimized COF help ensure even layering without caking or dragging, enhancing user experience and efficacy. High COF may lead to agglomeration or inconsistent dispersion in emulsions or creams, affecting final product performance. The modified particle of this disclosure may improve any one or more of the above physical properties and performance of a personal care composition.

[0053] The friction coefficient can be measured using any method known in the art. The friction coefficient is typically measured using a tribometer or skin friction teste which measures dynamic and static friction between a powder (usually applied on a substrate) and a probe or skin simulant. Typical substrates include silicone, glass, or artificial skin. These instruments outputPCT Patent ApplicationAtty Docket No.: 364.1790PCCOF values as a function of applied force, velocity, and area. Trained human evaluators can subjectively rank tactile properties (silkiness, drag, glide) which can be correlated with COF. These values are not quantitative but useful for consumer-centered validation. Typically, COF can be determined used ASTM DI 894 (for general friction testing).Angle of Repose

[0054] The angle of repose is a measurement of how easily a powder flows, e.g. the steepest angle at which powder remains stable without sliding. A lower angle of repose indicates better flow. In manufacturing, this means easier handling, more consistent dosing, and less clogging in filling equipment. In pressed powders or compacts, poor flowability can lead to uneven packing or visual inconsistencies. In dry shampoos or aerosolized skincare, powders need excellent flow to avoid clogging and ensure even delivery. The modified particle of this disclosure may improve any one or more of the above physical properties and performance of a personal care composition.

[0055] The angle of repose can be measured using any method known in the art. In one embodiment, the angle of repose is measured using a Fixed Funnel Method wherein powder is allowed to fall through a funnel onto a flat surface, forming a conical heap. The height (h) and radius (r) of the pile are measured and the following formula is used:tan(0) = - > 0 = tan1tanx( / i / r)r

[0056] Alternatively, automated powder flow testers can be used such as a Hosokawa Micron Powder Tester or GranuDrum which may allow more consistent, automated angle of repose testing. In various embodiments, an angle < 30° is indicative of excellent flow while an angle of about 45° is indicative of poor flow.Cohesiveness of Powders

[0057] Cohesiveness relates to how strongly powder particles stick to each other. High cohesiveness can cause clumping, poor blending, or patchiness on skin. Low to moderate cohesiveness allows powders to blend seamlessly. In dry shampoo or other airborne delivery systems, low cohesiveness supports better dispersion and prevents clogging. In pressed powder formulations, a certain degree of cohesiveness is needed to ensure mechanical strength without crumbling. The modified particle of this disclosure may improve any one or more of the above physical properties and performance of a personal care composition.PCT Patent ApplicationAtty Docket No.: 364.1790PC

[0058] Cohesiveness of powders may be determined using any method known in the art. In one embodiment, tapped density / Hausner ratio can be used wherein bulk and tapped density are measured. The Hausner ratio is calculated as the tapped density divided by the bulk density. A high ratio, e.g. of greater than 1.25, typically indicated greater cohesiveness than lower ratios. Alternatively, Carr’s Index may be used, e.g. calculated as shown below:Carr Index - ( Tnppcc D.u.hv B.dk jwherein higher values indicate greater cohesiveness. Still further, shear cell testing may be used. As is known in the art, Jenike Shear Cell or Ring Shear Testing measures powder strength under shear stress. These methods quantify flow function and cohesiveness directly. Typically, cohesiveness can be determined using USP <1174> or ISO 4324 for powder flow properties. Water Repellency

[0059] Water repellency is a measure of a powder's hydrophobicity, i.e., its ability to resist water. Water repellency can be related to sweat and water resistance of various products such as foundations, sunscreens, or deodorant powders, as it keeps the product from breaking down with moisture. Water repellency may also affect stability in emulsions wherein powders that are too hydrophilic may destabilize oil-in-water emulsions or absorb water, changing texture and consistency. Water repellency may also contribute to sensory feel wherein hydrophobic powders often contribute to a dry, velvety skin feel — desirable in oil control or mattifying products. The modified particle of this disclosure may improve any one or more of the above physical properties and performance of a personal care composition.

[0060] Water repellency may be measured by any method known in the art. For example, water repellency may be measured using a contact angle measurement wherein a droplet of water is placed on a compressed powder disc or powder-coated slide and the contact angle is measured. A value of about 90° is indicative of hydrophobicity while a value of less than about 90° is indicative of increasing hydrophilicity. Wash-off and water float tests may also be used wherein a powder is sprinkled on water and observed if it floats (hydrophobic) or sinks (hydrophilic). This can be semi-quantified by timing or percentage remaining on surface. In addition, a gravimetric absorption test may be used wherein a known amount of water is placed on powder and absorbance is measured over time.PCT Patent ApplicationAtty Docket No.: 364.1790PCDemand Adsorbency (or Oil / Water Adsorption Capacity)

[0061] Demand absorbency is a measure of how much liquid (typically oil or water) a powder can absorb. High adsorbency can be important in products like mattifying powders, acne-control formulations, or dry shampoos which would be indicative of absorbing sebum or oils effectively. A powder with high demand adsorbency may "steal" too much oil or water from the formula, requiring adjustments in binder / emollient levels. High adsorbency can enhance a dry, clean afterfeel but may compromise glide or softness if not balanced correctly. The modified particle of this disclosure may improve any one or more of the above physical properties and performance of a personal care composition.

[0062] Demand adsorbency can be measured using any method known in the art. In one embodiment, demand adsorbency is measured using an Oil Absorption Value (OAV) wherein a known amount of powder is mixed with oil until a stiff paste forms. The OAV is calculated as the mL of oil used divided by 100g of the powder. ASTM D281 is a standard method that can be used to determine OAV. In addition, Water Absorption Capacity can be used which is similar to the above using water instead of oil. This can also be measured using centrifuge separation wherein powder is mixed with water, centrifuged, the supernatant quantified. In addition, Isothermal Adsorption Testing (Dynamic Vapor Sorption) can be used which measures how much water vapor or oil vapor a powder can adsorb under controlled humidity.

[0063] In various embodiments, friction coefficient is measured using one or more of the following: ASTM D6128 - Standard Test Method for Shear Testing of Bulk Solids Using the Jenike Shear Cell; ISO 11697 - Determination of the angle of internal friction of bulk solids using a shear tester (e.g., Jenike); ASTM D6773 - Shear Testing of Bulk Solids Using the Schulze Ring Shear Tester; and / or DIN 22113-3 - Bulk materials testing: Measurement of wall friction.

[0064] In other embodiments, angle of repose is measured using one or more of the following: ASTM C1444 - Standard Test Method for Determining the Angle of Repose of Free-Flowing Mold Powders; ISO 4324 - Determination of the static angle of repose of loose materials; and / or USP <1174> - Powder Flow - includes method for determining angle of repose.

[0065] In other embodiment, Cohesiveness of Powders is measured using one or more of the following: ASTM D6393 - Standard Test Method for Bulk Solids Using the Jenike Shear Cell; USP <1174> - Powder Flow - methods include compressibility, angle of repose, and flow ratePCT Patent ApplicationAtty Docket No.: 364.1790PCthrough an orifice; ISO 4333 - Bulk materials: Determination of flow properties using a ring shear tester; and / or Carr’s Index and Hausner Ratio, see e.g. USP <616>.

[0066] In other embodiments, Water Repellency (Hydrophobicity) is measured using one or more of the following: ASTM D7334 - Standard Practice for Surface Wettability of Coatings, Substrates and Pigments; ASTM D5084 - Measurement of hydraulic conductivity of saturated soils (used for water repellency of porous solids); ISO 16565 - Contact angle measurement by sessile drop (commonly used to assess hydrophobicity); and / or Modified Molarity Ethanol Drop Test (MEDT).

[0067] In further embodiments, Demand Adsorbency (Powder Liquid Uptake) is measured using one or more of the following: USP <1241> - Water Absorption - general guidelines for excipient functionality; BP Appendix XII C - Water absorption ratio method for tablets / powders; ASTM F716 - Test Method for Absorbent Capacity of materials (e.g., adapted for powders); Modified Washbum Method -used in powder and porous material absorption studies; and / or Powder Rheometer-based methods - (e.g., Freeman Technology’s Liquid Addition Method).

[0068] In various non-limiting embodiments, the modified particle may have none, one, more than one, or any combination thereof, of the properties set forth below wherein all values are approximations and wherein any one or more of the aforementioned methods may be utilized to determine such values:Property Metric Various EmbodimentsWallFrictionFriction < 0.30 0.30 -0.50 > 0.50 0.1 - 1.0 CoefficientCoefficientInterParticle < 0.20 0.20 - 0.50 > 0.50 0.05 - 1.0 FrictionAngle of Degrees< 30° 30° - 45° > 45° 20° - 60° Repose (°)Carr’sCohesiveness < 15% 15 -25% > 25% 5 - 50% Index (%)Hausner< 1.25 1.25 - 1.40 > 1.40 1.00 -2.00 RatioFlowFunction> 10 4- 10 < 4 1 - 20+ Coefficient(ffc)Cohesion 2000 - 5000< 500 Pa 500 - 2000 Pa 0 - 5000+ Pa(Pa) PaPCT Patent ApplicationAtty Docket No.: 364.1790PCWater Contact> 90° 70° - 90° < 70° 0° - 180° Repellency Angle (°)WaterAbsorption < 5% 5 - 15% > 15% 0 - 100%+ (% wt)LiquidDemandUptake > 2 g / g l - 2 g / g 0 - 10+ g / Adsorbency < 1 g / g g (g / g)Absorption< 5 sec 5 - 30 sec > 30 sec 1 - 300+ sec Time (sec)Capillary> 10 mm 5 - 10 mm < 5 mm 0- 50 mmRise (mm)In other non-limiting embodiments, all values and ranges of values, whole and fractional, both between and including each of the above, are also hereby expressly contemplated for use herein.Method

[0069] This disclosure also provides a method of forming the modified particle. In one embodiment, the method includes the step of combining the core particle and the modifier. In such an embodiment, the modifier may or may not covalently bond with the core. In another embodiment, the method includes the step of reacting the citrate ester and the core via an esterification reaction to form a covalent bond between the modifier and the core.EXAMPLESExample 1: Preparation Of A Oleoyl Glycerol Citrate

[0070] 50 g of a technical 1-oleoyl-rac-glycerol (40% monoester) were treated with 59 g of citric acid monohydrate up to 184 °C in a round bottom flask equipped with a Dean-Stark trap. When the evolution of water ceased, the product was cooled to form a very viscous liquid.Example 2: Preparation Of An Oleoyl Glycerol Citrate

[0071] 50 g of a technical 1-oleoyl-rac-glycerol (40% monoester) were treated with 75.8 g of citric acid monohydrate up to 184 °C in a round bottom flask equipped with a Dean-Stark trap. When the evolution of water ceased, the product was cooled to form a very viscous liquid.Example 3: Treatment Of Starch With The Product From Example 1

[0072] 3 g of the product from Example 1 were dissolved into 50 g of ethanol. To the solution were added 30 g of maize starch (Roquette). The slurry was heated up and maintained at 72 °C for 1 h. After cooling it was filtered. Samples were then dried at room temperature, then at 60 °C for 6 h, at 135 °C for 2.5 h, at 165 °C for 2 h, then at 175 °C for 2.5 h.PCT Patent ApplicationAtty Docket No.: 364.1790PC

[0073] A negative water repellency test was obtained for the samples dried at 60, 135, or 165 °C. However, the samples showed good water repellency (very little sedimentation) when dried at 175 °C. The product dried at 175 °C has an oil absorption value of 0.64 ml / g, which is comparable to that of an industry standard (Dry Flo PC from Nouryon)Example 4: Treatment Of Starch With The Product From Example 1 And Solvent Extraction

[0074] 3 g of the product from Example 1 were dissolved into 50 g of ethanol. To the solution were added 30 g of tapioca starch (Ingredion). The slurry was heated up and maintained at 70-80 °C for 1 h. After cooling it was filtered. Samples were then dried at room temperature, then at 60 °C for 6 h, at 135 °C for 2.5 h, at 165 °C for 2 h, then at 175 °C for 2.5 h. The dried samples were then ground using a kitchen chopper. The oil absorption for a sieved material was found to be 0.74 ml / g.

[0075] 2 g of each of these samples were independently suspended in 20 g of acetone to form mixtures which were brought to reflux under stirring conditions for 30 minutes. The mixtures were filtered and the treated starch was dried at room temperature then in a vented 60 °C oven. Despite the extraction, the treated starch maintained its water repellency character, suggesting that a covalent bonding might exist between the starch particle and the citrate esters.Example 5: Treatment Of Starch With The Product From Example 2

[0076] 1.5 g of the product from Example 2 was dissolved into 50 g of isopropanol. To the solution was added 30 g of tapioca starch (Daesang) to form a slurry. The slurry was heated and maintained at 72 °C for 1 h. After cooling, samples were filtered and dried at room temperature, then at 60 °C for 6 h, then at 175 °C for 2 h. The finished modified starch exhibited water repellency behavior.Example 6: Treatment Of Starch With A Commercial Citrem

[0077] A commercial citrem described as “glycerides, C16-18 and C18-unsaturated, mono-and di-, citrates (91052-16-3)” was dissolved in ethanol and mixed with a tapioca starch at 10% by weight. The mixture was brought to 75 °C for 1 h, dried at room temperature then in an oven at 175 °C for 2 h. The resulting material did not exhibit any water repellency.Example 7: Treatment Of Starch With The Product From Example 1 And Complexation

[0078] 1.5 g of the product from Example 1 was dissolved into 50 g of isopropanol. To the solution were added 30 g of tapioca starch (Daesang) to form a slurry. The slurry was heated andPCT Patent ApplicationAtty Docket No.: 364.1790PCmaintained at 72 °C for 1 h. After cooling, samples of the slurry were filtered and dried at room temperature, then at 60 °C for 2 h, and at 175 °C for 2.5 h. This product tested positive in the water repellency test.

[0079] 12.5 g of the above modified starch were suspended in a combination of 37.5 g of isopropanol and 5 g of a 0.1% solution of calcium chloride in water. This was mixed at room temperature for 6 h then dried for 2 h at 60 °C. This product showed improved spreadability when rubbed onto skin when compared to a non-calcium chloride treated precursor.Example 8: Treatment Of Starch With Glyceryl Stearate Citrate

[0080] A mixture of 85 g water, 22.2 g of sodium sulfate, 1.66 g of glyceryl stearate citrate (from Making Cosmetics) and 22.2 g of barley starch was heated to 63°C and the temperature was maintained for 2 h 15 min. After cooling, the mixture was filtered and the modified starch was washed with 100 g of water. After filtration, samples were dried at 60 °C for 6 h and 130 °C for 2 h. The modified starch showed little translucency in the aqueous phase in a water repellency test. Increasing the treatment at 130 °C by 17 h led to approximately complete water repellency behavior. The modified starch exhibited much better flowability on skin than the native starch.Example 9: Treatment Of Starch With Glyceryl Stearate Citrate

[0081] A mixture of 202 g water, 50 g of sodium sulfate, 1.25 g of glyceryl stearate citrate (from Making Cosmetics) and 50 g of tapioca starch was heated to 63 °C and the temperature was maintained for 2 h 15 min. After cooling, the mixture was filtered and the modified starch was washed with 200 g of water. After filtration, samples were dried at 60 °C for 6 h and 130 °C for 2 h. The modified starch showed very little sediment in the water repellency test.Example 10: Treatment Of Starch With Glyceryl Stearate Citrate

[0082] A mixture of 85 g water, 1.11 g of glyceryl stearate citrate (from Making Cosmetics) and 22.2 g of a high amylose corn starch (Hylon® VII from Ingredion) was heated to 63 °C and the temperature was maintained for 2 h 15 min. After cooling, the mixture was filtered. Samples were then dried at 60 °C for 6 h and 130 °C for 2 h, then ground. The modified starch showed excellent water repellency.Example 11: Preparation Of A Citrate Ester Of Glyceryl Octanoate

[0083] 50 g of octanoic acid, monoester with 1,2,3-propanetriol (Symlite® G8 from Symrise) were treated with 41.85 g of citric acid monohydrate until the evolution of water ceased, to form a citrate ester.PCT Patent ApplicationAtty Docket No.: 364.1790PCExample 12: Treatment Of Starch With Glyceryl Octanoate Citrate

[0084] The product of Example 11 (1.5 g) was dissolved into 50 ml of isopropanol and with 30 g of tapioca starch. The mixture was stirred at 70-75 °C for 1 h, then cooled and filtered. It was then dried at room temperature then in an oven at 175 °C for 2 h, ground and sieved. The resulting material showed a water repellency behavior.

[0085] The results are superior to what would be expected in the art because the modified particles exhibit good water repellency and exhibit a higher demand absorbency, a reduced friction coefficient and have a superior silky smooth and non-greasy sensory feel as compared to an unmodified native starch both independently and within a personal care composition. In addition, the modified particles are bio-based and aluminum-free, which is superior over what is known in the art such as OSA (octenylsuccinate anhydrate) modified starches, while offering similar level of demand absorbency, non-greasy, silky and smooth sensory feelings, as described above.

[0086] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended 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 being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims.

Claims

PCT Patent ApplicationAtty Docket No.: 364.1790PCCLAIMSWhat is claimed is:

1. A modified particle comprising:A. a core comprising at least one hydroxyl group or residue thereof; andB. a modifier disposed about said core and comprising a citrate ester and / or a esterification product of said citrate ester and at least part of said core.

2. The modified particle of claim 1 wherein said citrate ester is a condensation product of citric acid and a fatty alcohol.

3. The modified particle of claim 1 wherein said citrate ester is a condensation product of citric acid and a glyceride.

4. The modified particle of any preceding claim wherein said citrate ester is a monocitrate ester.

5. The modified particle of any preceding claim wherein said core is a polysaccharide.

6. The modified particle of any preceding claim wherein said core is a starch.

7. The modified particle of any preceding claim wherein said glyceride has from about 5 to about 22 carbon atoms.

8. The modified particle of any preceding claim wherein said glyceride is chosen from polyols, mono- and di- glycerides, cyclodextrins, distilled monoglycerides, acetylated monoglycerides, polyglycerol esters of fatty acids, sucrose esters of fatty acids, glyceryl monooleate, glyceryl dioleate, MCT oil, caprylic / capric glycerides, glyceryl stearate; glyceryl cocoate; glyceryl behenate, and combinations thereof.

9. The modified particle of any preceding claim wherein said core is chosen from starch, modified starch, pectin, agar, carrageenan, inulin, hyaluronic acid, chitosan, dextran,PCT Patent ApplicationAtty Docket No.: 364.1790PCxanthan gum, heparin, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, alginate, beta-glucan, guar gum, locust bean gum, pullulan, glactomannan, and combinations thereof.

10. The modified particle of any one of claims 1-8 wherein said core is chosen from polysaccharides, oligosaccharides, polyvinyl alcohol, polyols, hydroxyalkyl celluloses, hydrogels, dendrimers with hydroxyl terminal groups, polyethylene glycols, carbohydrate-based nanoparticles, protein-based particles, hydroxyapatite-based particles, hydroxyl terminated polyesters, polyesteramides, hydroxyl terminated polyurethanes, and combinations thereof, so long as the core comprises the at least one hydroxyl group.

11. The modified particle of any preceding claim wherein said citrate ester comprises a citrate having the following formula (I) and a glyceride citrate having the following formula (II)(I); orwherein in formula (I) the citrate has a single R group;wherein each R in formulas (I) and (II) is independently an alkyl, aryl or arylalkyl group that is linear, branched, or cycloaliphatic, saturated or unsaturated, and comprises 5 or more carbon atoms; andwherein X is a dialkylenyloxy group, a substituted dialkylenyloxy group, a diaminoalkylenyl group, an aminoalkyloxy group, and oxy or amino-terminated radical, and oxy or amino-terminated oligomers, or combinations thereof.PCT Patent ApplicationAtty Docket No.: 364.1790PC12. The modified particle of claim 11 wherein X is derived from oxy 1,2 ethanediyl, poly(oxy 1,2 ethanediyl), oxy 1,3-propanediyl, poly(l,3-propanediyl), oxy methyl 1,2 ethanediyl, poly(oxy methyl 1,2 ethanediyl), or combinations thereof.

13. The modified particle of any preceding claim wherein said modifier comprises said citrate ester without said esterification product.

14. The modified particle of any one of claims 1-12 wherein said modifier comprises said esterification product.

15. A personal care composition comprising:a lotion, cream, ointment, shampoo, and / or conditioner; andthe modified particle of any preceding claim.

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