Treatment compositions with modified chitosan-based delivery particles

Abstract

A processing composition comprising a processing aid and a population of core / shell delivery particles, wherein the shell is made of a polymeric material that is the reaction product of a modified chitosan and at least one electrophile, the modified chitosan being the reaction product of chitosan and a modifying compound, the modifying compound being an epoxide, an aldehyde, or an α,β-unsaturated compound. Related methods of making and using such compositions.

Description

[Technical Field]

[0001] The present disclosure relates to processing compositions comprising a processing aid and a population of core / shell delivery particles, wherein the shell is made of a polymeric material that is the reaction product of a modified chitosan and at least one electrophile, the modified chitosan being the reaction product of chitosan and a modifying compound, the modifying compound being an epoxide, an aldehyde, or an α,β-unsaturated compound. The present disclosure also relates to related methods of making and using such compositions. [Background technology]

[0002] Delivery particles, especially core / shell delivery particles, are a convenient way to deliver benefit agents into treatment compositions such as laundry products.For environmental reasons, it may be desirable to use delivery particles with walls made from naturally occurring materials and / or biodegradable materials.Furthermore, it is preferable that such delivery particles exhibit efficient encapsulation, good product compatibility, and good deposition and performance under intended use conditions.

[0003] Chitosan is a polysaccharide known for use in the shell of delivery particles, but it presents certain challenges. For example, chitosan is generally insoluble in water above pH 7 and tends to be cationic in aqueous mixtures below about pH 6.5. Furthermore, when dissolved, chitosan can form viscous solutions that are difficult to handle or process. Furthermore, due to its cationic charge, chitosan can interact with anionic substances and surfaces, which can lead to aggregation or other physical instability, especially in certain product matrices such as liquid laundry detergents. Summary of the Invention [Problem to be solved by the invention]

[0004] Thus, there is a need for improved treatment compositions comprising delivery particles derived at least in part from natural and / or biodegradable materials that exhibit good product compatibility and / or performance. [Means for solving the problem]

[0005] The present disclosure relates to processing compositions comprising chitosan-based core / shell delivery particles, where the chitosan used to make the shell is characterized by a particular molecular weight.

[0006] For example, the present disclosure relates to a processing composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, the shell comprising a polymeric material that is the reaction product of a modified chitosan and an electrophile, the modified chitosan comprising the reaction product of chitosan and a modifying compound, the modifying compound comprising an epoxide, an aldehyde, or an α,β-unsaturated compound.

[0007] The present disclosure also relates to a method of making a treatment composition, the method comprising the steps of providing a base composition including a treatment aid and combining a population of delivery particles with the base composition, the delivery particles being as described herein.

[0008] The present disclosure also relates to a method of treating a surface, the method comprising contacting the surface, preferably a fabric, with the treatment composition described herein. [Brief explanation of the drawings]

[0009] The drawings herein are illustrative in nature and are not intended to be limiting. [Figure 1] 1 is a zeta potential graph showing delivery particles prepared in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure relates to a treatment composition comprising delivery particles having a shell made at least in part from a chitosan-based material. In particular, the delivery particles include a shell comprising the reaction product of a modified chitosan and an electrophile that can act as a crosslinker. The modified chitosan can alter the resulting surface charge of the delivery particles, which in turn can favorably affect product compatibility and / or performance.

[0011] Modified chitosan can be prepared by reacting chitosan polymer with a modifying compound capable of forming a C-N covalent bond with the amine groups of chitosan, particularly primary or secondary amines. The modifying compound can be selected from epoxide compounds, aldehyde compounds, or α,β-unsaturated compounds. The epoxide, aldehyde compounds, or α,β-unsaturated compounds can be anionic, cationic, or nonionic. The modifying compound can contain an acidic group, a hydroxyl group, or a quaternary ammonium group.

[0012] Without being bound by theory, it is believed that modifying chitosan modifies the surface charge of the delivery particles compared to particles made from unmodified chitosan. Thus, the final surface charge of the delivery particles can be modified and adjusted by the selection of the modifying compound and / or the timing of its addition to, for example, the aqueous phase or emulsion. In particular, the surface charge can be modified when the modifying compound is selected to have a cationic or anionic group.

[0013] Additionally or alternatively, modification of chitosan can alter the solubility of chitosan, which may facilitate improved particle formation and / or processability, for example by reducing viscosity.

[0014] The chitosans, delivery particles, processing compositions, and related methods of the present disclosure are described in more detail below.

[0015] As used herein, the articles "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described. As used herein, the terms "include," "includes," and "including" are meant to be open-ended. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0016] The term "substantially free of" or "substantially free from" may also be used herein. This means that the indicated material is in minimal amounts and has not been intentionally added to the composition to form part of the composition, or preferably is not present at analytically detectable concentrations. It includes compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material, if present at all, may be present at a concentration of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0017] As used herein, "consumer product" means a baby care, beauty care, fabric and home care, family care, feminine care, or health care product or device intended for use or consumption in the form in which it is sold and not intended for subsequent commercial manufacture or modification. Such products include diapers, bibs, wipes; products for and / or methods relating to the treatment of human hair, including bleaching, coloring, dyeing, conditioning, shampooing, and styling; deodorants and antiperspirants; personal cleansing; skin care, including the application of creams, lotions, and other topically applied products intended for consumer use; and shaving products, products for and / or methods relating to the treatment of fabrics, hard surfaces, and any other surface in the fabric or home care field (including air care, auto care, dishwashing, fabric conditioning (including softening)). products and / or methods related to toilet paper, tissue, paper handkerchiefs, and / or paper towels; tampons, feminine napkins; adult incontinence products; oral care products and / or methods, including toothpaste, tooth gels, mouth rinses, denture adhesives, tooth whitening agents; non-prescription health care, including cough and cold treatments; pest control products; and water purification.

[0018] As used herein, the phrase "fabric care composition" includes compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric deodorizing compositions, laundry pre-cleaning agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions can be used as laundry pre-treatment agents, laundry post-treatment agents, or can be added during the rinse or wash cycle of laundry operations.

[0019] For ease of reference in this specification and claims, the term "monomer" or "monomers" as used herein with respect to the structural materials that form the wall polymer of the delivery particles should be understood to refer to monomers, but also to include oligomers and / or prepolymers formed from the particular monomer.

[0020] As used herein, the term "water-soluble material" means a material that has a solubility of at least 0.5% by weight in water at 60°C.

[0021] As used herein, the term "oil-soluble" means a material that has a solubility of at least 0.1% by weight in the target core at 50°C.

[0022] As used herein, the term "oil-dispersible" means a material that can be dispersed in a target core at least 0.1% by weight at 50°C without visible agglomerates.

[0023] As used herein, "delivery particles," "particles," "encapsulations," "microcapsules," and "capsules" are used interchangeably unless otherwise indicated. As used herein, these terms typically refer to core / shell delivery particles.

[0024] Unless otherwise noted, all ingredient or composition concentrations are in terms of the active portion of that ingredient or composition and are exclusive of impurities, e.g., residual solvents or by-products, that may be present in commercial sources of such ingredient or composition.

[0025] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All measurements herein are made at 20°C and atmospheric pressure unless otherwise stated.

[0026] In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless specifically stated otherwise.

[0027] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0028] Treatment Composition The present disclosure relates to treatment compositions (or simply "compositions" as used herein). The compositions of the present disclosure may include a population of delivery particles and a treatment aid, each of which is described in more detail below. The treatment compositions may be useful in the methods of treating surfaces, such as fabrics, described herein.

[0029] The treatment composition is preferably a consumer product composition.The consumer product composition of the present disclosure can be useful in baby care, beauty care, fabric care, home care, family care, feminine care, and / or health care applications.The consumer product composition can be useful for treating surfaces such as fabric, hair, or skin.The consumer product composition can be intended to be used or consumed in the manner in which it is sold.The consumer product composition of the present disclosure may typically not be intended for subsequent commercial manufacture or modification.

[0030] The consumer product composition may preferably be a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition (such as a shampoo or conditioner), a body cleansing composition, or a mixture thereof, and may preferably be a fabric care composition.

[0031] The consumer product composition may be a fabric care composition such as a laundry detergent composition (including a heavy-duty liquid cleaning detergent or unit dose article), a fabric conditioning composition (including a liquid fabric softening and / or enhancing composition), a laundry additive, a fabric pre-treatment composition (including a spray, pourable liquid, or spray), a fabric refresher composition (including a spray), or a mixture thereof. The treatment composition is preferably a fabric conditioning composition, and even more preferably a fabric conditioning liquid composition.

[0032] The composition may be a beauty care composition, such as a hair treatment product (including shampoo and / or conditioner), a skin care product (including a cream, lotion, or other topically applied product for consumer use), a shaving care product (including a shaving lotion, foam, or pre- or post-shave treatment), a personal cleansing product (including a liquid body wash, liquid hand soap, and / or bar soap), a deodorant and / or antiperspirant, or mixtures thereof.

[0033] The compositions may be home care compositions such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other consumer or institutional cleaning.

[0034] The treatment composition may be in the form of a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, pastilles or beads, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven sheet, or mixtures thereof.

[0035] The treatment composition may be in the form of a liquid. The liquid composition may comprise from about 50% to about 97%, preferably from about 60% to about 96%, more preferably from about 70% to about 95%, and even from about 80% to about 95% water by weight of the fabric treatment composition. The liquid composition may be a liquid fabric conditioner. The liquid may be packaged in a pourable bottle. The liquid may be packaged in an aerosol can or other spray bottle. Suitable containers are described in more detail below.

[0036] The treatment composition may be in solid form. The composition may be in the form of beads or tablets, which may be tableted from a liquid melt. The composition may be an extruded product. The treatment composition may be in the form of a powder or granules.

[0037] The composition may be in the form of a unit-dose article such as a tablet, pouch, sheet, or fiber article. Such pouches typically include a water-soluble film, e.g., a polyvinyl alcohol water-soluble film, that at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition may be enclosed in a single-compartment pouch or a multi-compartment pouch. A multi-compartment pouch may have at least two, at least three, or at least four compartments. A multi-compartment pouch may include compartments arranged side-by-side and / or stacked. The composition contained in the pouch or its compartments may be liquid, solid (e.g., powder), or a combination thereof. The pouch composition may have a relatively low amount of water, e.g., less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% by weight of the detergent composition.

[0038] The treatment composition may be in the form of a spray, for example, dispensed via an aerosol container having a trigger sprayer and / or a valve.

[0039] The treatment composition is applied for 20 seconds. -1 and 21°C, 1 to 1500 centipoise (1 to 1500 mPa * s), 100-1000 centipoise (100-1000 mPa * s), or 200 to 500 centipoise (200 to 500 mPa * s).

[0040] The treatment compositions of the present disclosure may be characterized by a pH of about 2 to about 12, or about 2 to about 8.5, or about 2 to about 7, or about 2 to about 5. The treatment compositions of the present disclosure, preferably in the form of an aqueous liquid, may have a pH of about 2 to about 4, preferably about 2 to about 3.7, and more preferably about 2 to about 3.5. It is believed that such pH levels promote the stability of the quaternary ammonium ester compound, if present. On the other hand, detergent compositions are typically characterized by a pH of about 7 to about 12, preferably about 7.5 to about 11. The pH of the composition is measured by dissolving / dispersing the composition in deionized water to form a 10% concentration solution at about 20°C.

[0041] Additional components and / or properties of the composition are discussed in more detail below.

[0042] Delivery particle population The treatment composition of the present disclosure comprises a population of delivery particles. The delivery particles comprise a core and a shell surrounding the core. The core may comprise a benefit agent and, optionally, a partitioning modifier. The core can be liquid or solid at room temperature, preferably liquid.

[0043] The treatment composition may comprise from about 0.05% to about 20%, or from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.2% to about 2% delivery particles by weight of the composition. The composition may comprise a sufficient amount of delivery particles to provide the composition with from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 2% encapsulated benefit agent, preferably perfume ingredient, based on the weight of the composition. As discussed herein, the amount or weight percent of delivery particles refers to the combined wall material and core material.

[0044] A population of delivery particles according to the present disclosure can be characterized by a volume-weighted median particle size of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 25 to about 35 microns. For certain compositions, it may be preferred that the population of delivery particles be characterized by a volume-weighted median particle size of about 1 to about 50 microns, preferably about 5 to about 20 microns, and more preferably about 10 to about 15 microns. Different particle sizes can be obtained by controlling droplet size during emulsification.

[0045] The delivery particles can be characterized by a core-to-shell ratio of up to 99:1, or even 99.5:0.5, by weight. The shell may be present in a concentration of about 1% to about 25%, preferably about 1% to about 20%, preferably about 1% to about 15%, more preferably about 5% to about 15%, even more preferably about 10% to about 15%, and even more preferably about 10% to about 12% by weight of the liquid premix composition. The shell may be present in a concentration of at least 1%, preferably at least 3%, and more preferably at least 5% by weight of the delivery particle. The shell may be present in a concentration of up to about 25%, preferably up to about 20%, more preferably up to about 15%, and even more preferably up to about 12% by weight of the delivery particle.

[0046] Delivery particles prepared using chitosan typically exhibit a positive zeta potential. Such capsules have improved adhesion efficiency on surfaces (e.g., certain fabrics such as cotton) and / or improved compatibility in product formulations. At higher pH, the particles can be made nonionic or anionic. The delivery particles can have a surface charge due to charged domains or charged pendant groups from the compositions and methods of the present invention. Adjusting the shell surface charge can be effectively achieved when the modifying compound has cationic or anionic groups. The delivery particles can even be made nonionic or anionic by selecting the modifying compound and pH.

[0047] The delivery particles may be cationic in nature, preferably cationic at pH 4.5. The delivery particles may be characterized by a zeta potential of at least 15 millivolts (mV) at a pH of 4.5. The delivery particles may be configured to have a zeta potential of at least 15 millivolts (mV) at a pH of 4.5, or even at least 40 mV at a pH of 4.5, or even at least 60 mV at a pH of 4.5.

[0048] The delivery particles may be characterized by a zeta potential of 200 mV or less, preferably 150 mV or less, and more preferably 100 mV or less at pH 4.5. Figure 1 shows the zeta potential of various delivery particles at various pHs, including particles according to the present disclosure.

[0049] The delivery particles of the present disclosure include a shell surrounding a core. (As used herein, "shell" and "wall" are used interchangeably with respect to delivery particles unless otherwise indicated.) The shell comprises a polymeric material that is the reaction product of chitosan, typically modified chitosan, with an electrophile.

[0050] The chitosan may comprise anionically modified chitosan, cationically modified chitosan, or a combination thereof. Anionic and / or cationic modification of chitosan can alter the surface charge and / or zeta potential, which can affect, for example, the deposition efficiency and / or formulation compatibility of the particles, thereby altering the shell characteristics of the delivery particles.

[0051] The modified chitosan used in the shell of the delivery particles of the present disclosure can be prepared from chitosan, which may be acid-treated chitosan modified with a modifying compound. The chitosan can be dissolved or dispersed in water. The modified chitosan is a nucleophilic substance and is used as a crosslinking agent to form the shell of the core-shell microcapsules by crosslinking with an electrophilic substance.

[0052] Modified chitosans may include the reaction product of chitosan and a modifying compound. Chitosans typically have free amine moieties (e.g., -NH). Modified chitosans according to the present disclosure may result from combining chitosan with a modifying compound capable of forming a C-N covalent bond with the amine moiety of chitosan. The modifying compound typically includes an epoxide, an aldehyde, or an α,β-unsaturated compound.

[0053] The modifying compound may comprise a cationic group, an anionic group, a non-ionic group, or a mixture thereof. The modifying compound may preferably comprise a cationic group, an anionic group, or a mixture thereof. The modifying compound may preferably comprise an anionic group, which can reduce the surface charge of the resulting particles.

[0054] The modifying compound may contain acidic groups, hydroxyl groups, quaternary ammonium groups, or mixtures thereof, preferably acidic groups.

[0055] The modifying compound includes an α,β-unsaturated compound, and preferably the α,β-unsaturated compound is an α,β-unsaturated carbonyl compound.

[0056] The modifying compound may be an α,β-unsaturated compound, and may preferably be selected from the group consisting of acrylate, alkyl acrylate, α,β-unsaturated ester, acrylic acid, acrylamide, vinyl ketone, vinyl sulfone, vinyl phosphonate, acrylonitrile, or a combination thereof. More preferably, the α,β-unsaturated compound is acrylic acid, acrylate, acrylate, alkyl acrylate, α,β-unsaturated ester, maleic acid, vinyl sulfonic acid, 2-carboxyethyl acrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylamide, (2-(acryloyloxy)ethyl)trimethylammonium salt, (3-(methacryloylamino)propyl)trimethylammonium salt, N,N-acrylic acid The alkylaminoalkyl group is selected from the group consisting of dialkylaminoalkyl, N,N-dialkylaminoalkylacrylamide, (3-acrylamidopropyl)trimethylammonium salt, acrylamide, acrylamide salt, 3-sulfopropyl acrylate salt, 2-acrylamido-2-methyl-1-propanesulfonic acid and salts thereof, quaternized vinylimidazole, diallyldialkylammonium salt, vinylamine, vinyl ketone, vinyl sulfone, vinyl phosphonate, acrylonitrile, and combinations thereof.

[0057] The modifying compounds were glycidyl trimethylammonium salt, glycidyl isopropyl ether, glycidyl methacrylate, furfuryl glycidyl ether, glycidol, 1,4-butanediol diglycidyl ether, 2-ethylhexyl glycidyl ether, (3-glycidyloxypropyl)trimethoxysilane, poly(ethylene glycol) diglycidyl ether, trimethylolpropane triglycidyl ether, glutaraldehyde, alginic aldehyde, acrylic acid, acrylates, maleic acid, vinyl sulfonic acid, 2-carboxyethyl acrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylate, 2- The compound may comprise a material selected from the group consisting of (2-oxo-1-imidazolidinyl)ethyl methacrylamide, (2-(acryloyloxy)ethyl)trimethylammonium salt, (3-(methacryloylamino)propyl)trimethylammonium salt, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, (3-acrylamidopropyl)trimethylammonium salt, 3-sulfopropyl acrylate salt, 2-acrylamido-2-methyl-1-propanesulfonic acid and salts thereof, quaternized vinylimidazole, diallyldialkylammonium salt, vinylamine, and combinations thereof.

[0058] Prior to modification, chitosan typically contains free amine (e.g., —NH) moieties that can react with a modifying compound. Therefore, it may be useful to select an appropriate amount of modifying compound to efficiently carry out the reaction and / or to adjust the resulting surface charge of the delivery particle. For example, it may be advantageous to select the amount of material such that the molar ratio of modifying compound to free amine moieties of chitosan is 0.1% to 100%, preferably 10% to 100%, more preferably 10% to 90%, even more preferably 25% to 90%, and even more preferably 25% to 75%.

[0059] Modified chitosan according to the present disclosure may be soluble at a pH greater than 6.0, even greater than 8.0, and even greater than 10.0. Increased solubility may facilitate improved particle formation and / or improved processing, for example, by providing a solution with reduced viscosity.

[0060] Advantageously, the surface charge of the crosslinked chitosan capsules can be modified before, during, or after the formation of the capsule shell. This can be achieved by timing the addition of the modifying compound. The addition can be to the aqueous phase or emulsion. The water-soluble or water-dispersible modifying compound can be added to the aqueous phase or emulsion at room temperature or at an elevated temperature. The modifying compound can be added during emulsification, such as after milling, or can be added thereafter at an elevated temperature. The modifying compound, i.e., an epoxide, aldehyde, or α,β-unsaturated compound, is reacted with the free amine moieties of chitosan.

[0061] The modified chitosan of the present disclosure allows for the formation of a reactive polymer shell with a high proportion of modified chitosan moieties in the polymer. Such a high weight percent proportion of modified chitosan in the modified chitosan delivery particles allows for improved capsule systems not previously achieved with interfacial encapsulation processes. The methods and compositions of the present disclosure differ from ionic methods based on coacervation because the polymeric materials of the present disclosure are covalently crosslinked.

[0062] The chitosan may be characterized by a weight-average molecular weight of about 100 kDa to about 600 kDa. Preferably, the chitosan is characterized by a weight-average molecular weight (Mw) of about 100 kDa to about 500 kDa, preferably about 100 kDa to about 400 kDa, more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa. The method used to determine the molecular weight and related parameters of chitosan is provided in the Test Methods section below and uses gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) technology. Selecting a chitosan with a preferred weight-average molecular weight can result in capsules with suitable shell formation and / or desirable processability.

[0063] The chitosan may be characterized by a degree of deacetylation of at least about 50%, preferably about 50% to about 99%, more preferably about 75% to about 90%, and even more preferably about 80% to about 85%. The degree of deacetylation can affect the solubility of the chitosan, which can affect its reactivity or behavior in the process of forming the particle shell. For example, a degree of deacetylation that is too low (e.g., less than 50%) can result in a chitosan that is relatively insoluble and relatively unreactive. A relatively high degree of deacetylation can result in a chitosan that is very soluble, with relatively little chitosan migrating to the oil / water interface during shell formation.

[0064] Chitosan may preferably be acid-treated chitosan. For example, chitosan (before acid treatment, which may be called raw chitosan or parent chitosan) may be treated with an acid, preferably at a pH of 6.5 or less, for at least 1 hour, preferably about 1 hour to about 3 hours, at a temperature of about 25°C to about 99°C, preferably about 75°C to about 95°C. The acid may be selected from strong acids (such as hydrochloric acid), organic acids (such as formic acid or acetic acid), or mixtures thereof. Chitosan may be acid-treated preferably at a pH of 2 to 6.5, preferably 3 to 6, or even 4 to 6.

[0065] As noted above, the shell is a polymeric material that is the reaction product of chitosan and an electrophile. Preferably, the electrophile comprises a polyisocyanate. Thus, the shell of the delivery particle may comprise a polyurea resin, which comprises the reaction product of a polyisocyanate and chitosan.

[0066] For purposes of this specification, polyisocyanate materials useful in the present disclosure should be understood as isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. "Polyisocyanate" is intended to refer to materials or compounds containing two or more isocyanate moieties. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended to be encompassed by the term "polyisocyanate" herein. Polyisocyanates useful in the present disclosure include isocyanate monomers, oligomers, or prepolymers, or dimers or trimers thereof, having at least two isocyanate groups. Preferred crosslinking can be achieved using polyisocyanates with a functionality of at least three.

[0067] Aromatic polyisocyanates may be preferred. However, aliphatic polyisocyanates and their blends may also be useful. Aliphatic polyisocyanates are understood to be polyisocyanates that do not contain any aromatic moieties. Aromatic polyisocyanates are understood to be polyisocyanates that contain at least one aromatic moiety. The crosslinker may also comprise a mixture of aromatic and aliphatic polyisocyanates.

[0068] If the polyisocyanate is aromatic, it can be, but is not limited to, methylene diphenyl isocyanate, toluene diisocyanate, tetramethylxylidene diisocyanate, polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® RC), trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® L75), naphthalene-1,5-diisocyanate, phenylene diisocyanate, or trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name Takenate® D-110N).

[0069] Aliphatic polyisocyanates may include trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N100).

[0070] Derivatives of polyisocyanates may include oligomers or polymers of isocyanate monomers. As a non-limiting example, the polyisocyanate may preferably include oligomers or polymers of diphenylmethane diisocyanate (MDI), such as Mondur® MR-Light.

[0071] The polyisocyanate may preferably include polyisocyanurate of toluene diisocyanate; trimethylolpropane adduct of toluene diisocyanate; trimethylolpropane adduct of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethylxylidene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (e.g., prepolymers, oligomers, and / or polymers thereof); and combinations thereof.

[0072] The electrophile need not be limited to polyisocyanates. The electrophile can include monomers, oligomers, and prepolymers having an electrophilic moiety, which can include any of formyl, keto, carboxyl, isocyanate, carboxylic acid ester, acyl halide, amidocarboxylic acid anhydride, alkyl halide, epoxide, sulfonyl halide, chlorophosphate, β-unsaturated carbonyl, α,β-unsaturated nitrile, trifluoromethanesulfonate, p-toluenesulfonate, and α,β-unsaturated methanesulfonyl groups.

[0073] Suitable polyfunctional electrophiles can include glutaric dialdehyde, succinic dialdehyde, glyoxal; glyoxyl trimer, paraformaldehyde, bis(dimethyl)acetal, bis(diethyl)acetal, polymeric dialdehydes such as oxidized starch, small molecular weight difunctional aldehydes, 1,3-propanedialdehyde, 1,4-butanedialdehyde, 1,5-pentanedialdehyde, or 1,6-hexane.

[0074] The particle shell may also be reinforced using additional co-crosslinking agents such as polyfunctional amines and / or polyamines, e.g., diethylene triamine (DETA), polyethyleneimine, polyvinylamine, or mixtures thereof. Acrylates can also be used as additional co-crosslinking agents, e.g., to reinforce the shell.

[0075] The polymeric material may be formed in a reaction in which the weight ratio of chitosan present in the reaction to the electrophile present in the reaction is from about 1:10 to about 1:0.1. It is believed that selecting a desired ratio of biopolymer to electrophile can provide the desired ductility benefits and improved biodegradability. It may be preferred that at least 21% by weight of the shell be comprised of moieties derived from chitosan, preferably modified and / or acid-treated chitosan. The chitosan weight percentage of the shell may be from about 21% to about 95% of the shell. The ratio of chitosan in the aqueous phase compared to the electrophile, preferably polyisocyanate, in the oil phase may be from 21:79 to 90:10, or even from 1:2 to 9:1, or even from 1:1 to 7:1, by weight. The shell may comprise chitosan at a concentration of 21% or more by weight of the total shell being chitosan, preferably from about 21% to about 90%, or even from 21% to 85%, or even from 21% to 75%, or even from 21% to 55% by weight. The chitosan in this paragraph is preferably chitosan modified according to the present disclosure and / or acid-treated chitosan.

[0076] The population of delivery particles is made or obtainable by a process comprising the steps of: forming an aqueous phase by dissolving or dispersing chitosan having free amine moieties in an aqueous acidic medium at a pH of 6.5 or less and a temperature of at least 25°C; forming an oil phase comprising combining at least one benefit agent, and at least one electrophile, preferably at least one polyisocyanate, optionally with an added oil; forming an emulsion by mixing the oil phase into an excess of an aqueous phase under high shear agitation, thereby forming droplets of the oil phase dispersed in the aqueous phase; adding to the aqueous phase and / or emulsion, preferably at least to the aqueous phase, a modifying compound comprising one or more of an epoxide, an aldehyde, or an α,β-unsaturated compound, which modifying compound reacts with the free amine moieties of the chitosan; optionally adjusting the pH of the emulsion to a pH of 4 or greater; and heating the emulsion to at least 40°C for a time sufficient to form a shell surrounding the core at the interface of the droplets with the aqueous phase.

[0077] The population of delivery particles can be prepared by dissolving or dispersing chitosan in an aqueous phase, the chitosan having an amine moiety; combining the aqueous phase with a modifying compound; optionally adjusting the pH of the aqueous phase to pH 3.0 or higher, preferably pH 3.0 to pH 6; optionally adjusting the temperature of the aqueous phase to 25°C or higher; mixing the aqueous phase for a period of time, thereby forming a modified chitosan, the modifying compound being covalently bonded to the amine moiety of the chitosan via a C-N bond, wherein the modified chitosan remains dissolved in the aqueous phase; and mixing the aqueous phase with at least one oil containing chitosan. The emulsion may be made or obtainable by a process comprising the steps of: providing an oil phase comprising a benefit agent and at least one electrophile, preferably at least one polyisocyanate, dissolved therein, optionally with a second oil; forming an emulsion by mixing the oil phase into an aqueous phase under high shear agitation, thereby forming droplets of the oil phase and benefit agent dispersed in the aqueous phase; and heating the emulsion to at least 40°C for a time sufficient to form a shell at the interface of the droplets with the aqueous phase, the shell surrounding the core.

[0078] After the chitosan has been modified with the modifying compound, the pH of the aqueous phase containing the modified chitosan solution can be adjusted to above 6.5, or even above 7, or even above 9, as needed.

[0079] The molar ratio of the modifying compound to the free amine moieties of chitosan may be preferably 0.1% to 100%, preferably 10% to 100%, more preferably 25% to 90%.

[0080] The process for making the delivery particles can include dissolving or dispersing chitosan and modified compounds in an aqueous acidic medium at a pH of 6.5 or less and a temperature of at least 25°C to form an aqueous phase.

[0081] The modifying compound, preferably a water-soluble or water-dispersible modifying compound, can be added to the aqueous phase and / or emulsion, preferably the aqueous phase, at room temperature or elevated temperature. The modifying compound can be added during emulsification, such as after milling, or can be added subsequently at elevated temperature. As described in more detail above, the modifying compound typically contains one or more cationic, anionic, or nonionic groups selected from acidic or quaternary ammonium functional groups. The modifying compound, i.e., an epoxide, aldehyde, or α,β-unsaturated compound, is reacted with the free amine moieties of chitosan. The modifying compound covalently bonds to the primary or secondary amine moieties of chitosan via a C-N bond, helping to maintain the modified chitosan dissolved in the aqueous phase even at high pH.

[0082] The pH of the emulsion may optionally be adjusted to a pH of 4 or greater, or even a pH of 6, or even 8, or even an alkalinity of 8-10 or greater. The emulsion may be heated to at least 40°C for a time sufficient to form a shell at the interface between the droplets and the aqueous phase, such that the shell surrounds the core. Delivery particles formed according to the methods of the present disclosure result in the shell of the delivery particle having a surface charge, particularly when the modifying compound has cationic or anionic groups. Such surface-charged delivery particles may have a zeta potential of 200 mV or less, preferably 150 mV or less, at pH 4.5.

[0083] The emulsion may be cured by heating to at least 40°C, or even at least 60°C, for a time sufficient to form a shell at the interface between the droplets and the aqueous phase. The shell is a polymeric material comprising the reaction product of an electrophile (e.g., polyisocyanate) and modified chitosan, and the shell surrounds the droplets of oil phase containing the benefit agent. The target droplet size may be 0.1 to 100 microns, or even 0.5 to 50 microns.

[0084] To dissolve or disperse the chitosan, it can be processed by acid treatment at a pH of less than 6.5, for example, pH 3 to pH 6, and a temperature of at least 25°C, or even at least 60°C, or even at least 80°C. The time of acid treatment can be short, depending on the pH and temperature, but more typically is at least 1 hour, or even at least 24 hours. The chitosan may be deacetylated to at least 50%, or even at least 75%, or even at least 80%, or even at least 85%, or even at least 92%. Desirably, the chitosan has a weight average molecular weight of 600 kilodaltons (kDa) or less.

[0085] Chitosan can be modified by reacting it with modifying compounds including epoxides, aldehydes, or α,β-unsaturated compounds. The shell formed can be considered the reaction product of the modified chitosan with a polyurea and a polyisocyanate (e.g., including either an isocyanate monomer, oligomer, or prepolymer).

[0086] The population of delivery particles may be in the form of an aqueous slurry, or alternatively may be sprayed onto a substrate, or alternatively may be spray dried, resulting in a polyurea-chitosan shell with additional chitosan deposited on the surface of the formed delivery particles. Unreacted chitosan in the aqueous slurry, if not decanted, can form additional chitosan deposited on the surface of the formed microcapsules.

[0087] A redox initiator, preferably comprising a persulfate or peroxide, may be added to the aqueous phase and / or emulsion. The redox initiator, which may comprise a persulfate or peroxide, can be added to the acid-treated chitosan. As an in-situ alternative, the redox initiator can be added to the emulsion after combining the oil and aqueous phases under high shear stirring. The redox initiator advantageously depolymerizes the hydrolyzed or modified chitosan to reduce viscosity and facilitate shell polymer formation in the capsule formation process. The modification of chitosan with an epoxide, aldehyde, or α,β-unsaturated compound is preferably accomplished before the addition of the redox initiator, although the redox initiator (peroxide or persulfate) can be introduced simultaneously with or even before the modifying compound. The redox initiator can be selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof. The redox initiator, preferably a persulfate or peroxide, may be present in a concentration of from about 0.1% to about 99% by weight of the chitosan.

[0088] For clarity, there are several process variations possible. The acidified chitosan solution can be treated with a modifying compound by adding the modifying compound to the chitosan in the aqueous phase. Additionally or alternatively, the modifying compound can be added to the emulsion. Similarly, and independently, an optional redox initiator can be added to the chitosan in the acidified solution (e.g., aqueous phase) or to the emulsion in the emulsification step after the addition of the oil phase. The redox initiator can be added before, simultaneously with, or subsequently to the modification step with a modifying compound containing an epoxide, aldehyde, or α,β-unsaturated compound.

[0089] The shell may degrade by at least 50% after 20 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by 30-100%, preferably 40-100%, 50-100%, 60-100%, or 60-95% in 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, or more preferably 14 days.

[0090] The delivery particles of the present disclosure comprise a core. The core comprises a benefit agent. The core also optionally comprises a partitioning modifier.

[0091] The core of the particle is surrounded by a shell. When the shell ruptures, the benefit agent in the core is released. Additionally or alternatively, the benefit agent in the core may diffuse and / or be squeezed out of the particle. Suitable benefit agents disposed within the core may include benefit agents that provide a benefit to a surface such as fabric or hair.

[0092] The core may comprise from about 5% to about 100% benefit agent, preferably a fragrance, by weight of the core. The core may comprise from about 45% to about 95%, preferably from about 50% to about 80%, more preferably from about 50% to about 70% benefit agent, preferably a fragrance, by weight of the core.

[0093] The benefit agent may comprise an aldehyde-containing benefit agent, a ketone-containing benefit agent, or a combination thereof. Such benefit agents, such as aldehyde- or ketone-containing perfume ingredients, are known to provide desirable benefits, such as freshness benefits. The benefit agent may comprise at least about 20%, preferably at least about 25%, more preferably at least about 40%, and even more preferably at least about 50% by weight of the benefit agent of the aldehyde-containing benefit agent, ketone-containing benefit agent, or a combination thereof.

[0094] The benefit agent may be a hydrophobic benefit agent, which is compatible with the oil phase typically used in making the delivery particles of the present disclosure.

[0095] The benefit agents are selected to provide a benefit under the preferred use of the treatment composition. The benefit agents in the core may be fragrance materials, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin cooling agents, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleach particles, silicon dioxide particles, malodor reducing agents, odor control materials, chelating agents, antistatic agents, softening agents, insect and moth repellents, colorants, thickeners, drape and foam modifying agents, smoothing agents, wrinkle control agents, sanitizing agents, disinfectants, bacterial inhibitors, mold inhibitors, mildew inhibitors, antiviral agents, drying agents, stain resistant agents, soil release agents, fabric The active ingredient may be selected from the group consisting of refreshing and fresh-wash maintaining agents, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color restoration / revitalization agents, anti-fade agents, whiteness enhancers, anti-abrasion agents, abrasion resistant agents, fabric integration agents, anti-abrasion agents, anti-pilling agents, foam suppressors, defoamers, UV protection agents, fade inhibitors, anti-allergy agents, enzymes, waterproofing agents, fabric comfort agents, shrink resistance agents, stretch resistance agents, stretch recovery agents, skin care agents, synthetic or natural actives, antibacterial actives, antiperspirant actives, cationic polymers, dyes, and mixtures thereof.

[0096] The benefit agent within the core may preferably comprise a fragrance material (or simply "fragrance"), which may include perfume ingredients. Fragrances are particularly suitable for encapsulation in the delivery particles described herein, as fragrance-containing particles can provide fresh wash benefits across multiple touch points.

[0097] As used herein, the term "perfume raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mole and useful for imparting odors, fragrances, essences, or scents, either alone or in combination with other perfume raw materials. Typical PRMs include, among others, alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes such as terpenes. Lists of common PRMs can be found in various reference sources, such as, for example, "Perfume and Flavor Chemicals," Vol. I and Vol. II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology," Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0098] PRMs may be characterized by their boiling point (BP), measured at atmospheric pressure (760 mmHg), and their octanol / water partition coefficient (P), which may be described in terms of logP, determined according to the following test method. Based on these characteristics, PRMs may be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV perfumes, as described in more detail in U.S. Pat. No. 6,869,923. Suitable Quadrant I, II, III, and IV perfume raw materials are disclosed in U.S. Pat. No. 6,869,923.

[0099] Perfume raw materials having a boiling point BP below about 250° C. and a logP below about 3 are known as Quadrant I perfume raw materials. Quadrant I perfume raw materials are preferably limited to less than 30% of the fragrance materials.

[0100] The fragrance may include perfume raw materials having a logP of from about 2.5 to about 4. It is understood that other perfume raw materials may also be present in the fragrance.

[0101] The core of the delivery particles of the present disclosure may include a partitioning modifier, which may promote more robust shell formation. The partitioning modifier may be combined with the perfume oil material of the core prior to incorporation of the wall-forming monomer. The partitioning modifier may be present in the core at a concentration of from 0% to about 95% by weight of the core, preferably from about 5% to about 55% by weight, preferably from about 10% to about 50% by weight, more preferably from about 20% to about 50% by weight, and more preferably from about 25% to about 50% by weight.

[0102] Partition adjusters include vegetable oils, modified vegetable oils, and C4-C 24 The partitioning modifier may include a material selected from the group consisting of monoesters, diesters, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning modifier may preferably include isopropyl myristate, or may even consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably include castor oil and / or soybean oil. U.S. Patent Application Publication No. 20110268802, incorporated herein by reference, describes other partitioning modifiers that may be useful in the delivery particles described herein.

[0103] In cases where the benefit agent itself is not sufficient to function as an oil phase or solvent for the wall-forming material, particularly during the process of forming the shell of the delivery particle, the oil phase can comprise a suitable carrier and / or solvent. In this sense, oil is optional, since the benefit agent itself can sometimes be oil. These carriers or solvents are generally oils, preferably with a boiling point above about 80°C, low volatility, and non-flammable. Although not limited thereto, they preferably comprise one or more esters, preferably with a chain length of up to 18 carbon atoms or even up to 42 carbon atoms, and / or triglycerides, such as esters of C6-C12 fatty acids with glycerol.

[0104] Optionally, the aqueous phase may contain an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (e.g., alkyl sulfates, alkyl ether sulfates, and / or alkylbenzene sulfonates), nonionic surfactants (e.g., alkoxylated alcohols, preferably alkoxylated alcohols containing ethoxy groups), polyvinyl alcohol, and / or polyvinylpyrrolidone. Solubilized chitosan can provide emulsification benefits in this application. When used, the emulsifier is typically present in an amount of about 0.1 to 40 wt %, preferably 0.2 to about 15 wt %, more typically 0.5 to 10 wt %, based on the total weight of the aqueous phase.

[0105] The population of delivery particles can be provided as a slurry, preferably an aqueous slurry. The slurry can include one or more processing aids, which can include water, an agglomeration inhibitor material such as a divalent salt, or a particle suspending polymer such as xanthan gum, guar gum, cellulose (preferably microfibrillated cellulose), and / or carboxymethyl cellulose. When the delivery particles are cationic in nature (e.g., when the shell is at least partially derived from chitosan), a non-anionic structuring agent, preferably a non-ionic structuring agent, can be preferred, for example, to avoid adverse charge interactions that can result in undesirable agglomeration.

[0106] The slurry may include one or more carriers selected from the group consisting of polar solvents, including but not limited to water, ethylene glycol, propylene glycol, polyethylene glycol, and glycerol; non-polar solvents, including but not limited to mineral oil, perfume raw materials, silicone oil, and hydrocarbon paraffin oil; and mixtures thereof. Aqueous slurries may be preferred. The slurry may include non-encapsulated ("free") perfume raw materials of different identity and / or amount than those encapsulated in the core of the delivery particle.

[0107] The slurry may also include a deposition aid which may comprise a polymer selected from the group including: polysaccharides, such as chitosan, cationically modified starch, and / or cationically modified guar; polysiloxanes; polydiallyldimethylammonium halides; copolymers of polydiallyldimethylammonium chloride and polyvinylpyrrolidone; compositions comprising polyethylene glycol and polyvinylpyrrolidone; acrylamides; imidazoles; imidazolinium halides; polyvinylamines; copolymers of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; polyglycerol ether silicone crosspolymers; polyacrylic acid, polyacrylates, polyvinylamines and amines, and in one embodiment diethylenetriamine. copolymers of N,N-bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine, and mixtures thereof with polyvinyl alcohol oligomers; polyethyleneimine, derivatized polyethyleneimine, and in one aspect, ethoxylated polyethyleneimine; polymeric compounds comprising at least two moieties selected from the group consisting of carboxylic acid moieties, amine moieties, hydroxyl moieties, and nitrile moieties in a backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile, or combinations thereof; preformed coacervates of anionic surfactants combined with cationic polymers; polyamines, and mixtures thereof.

[0108] At least one population of delivery particles may be contained in an agglomerate, which may then be combined with a separate group of delivery particles and at least one auxiliary material. The agglomerate may comprise a material selected from the group consisting of silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride, and a binder, such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0109] Suitable equipment for use in the processes disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, where available, continuous process configurations), spray dryers, and extruders. Such equipment is available from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., USA), and Arde Barinco (New Jersey, USA).

[0110] Supplementary ingredients In addition to the delivery particles, the treatment compositions of the present disclosure may also include one or more auxiliary materials that may provide a benefit in the intended end use of the composition or may be processing and / or stabilizing aids.

[0111] Suitable adjunct materials may include surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, additional perfumes and perfume delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-agglomerating agents, coating agents, formaldehyde scavengers, and / or pigments. Preferably, the adjunct materials include additional fabric conditioning agents, dyes, pH control agents, solvents, rheology modifiers, structurants, cationic polymers, surfactants, perfumes, additional perfume delivery systems, chelating agents, antioxidants, preservatives, or mixtures thereof.

[0112] Depending on the intended form, formulation, and / or end use, the compositions of the present disclosure may be free of one or more of the following adjunct materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural elastomers, fabric softeners, carriers, hydrotropes, processing aids, structurants, anti-agglomerating agents, coatings, formaldehyde scavengers, and / or pigments.

[0113] The exact nature of these additional components and the concentration at which they are incorporated depend on the physical form of the composition and the nature of the work to be used. However, if one or more adjuvants are present, such one or more adjuvants can be present as detailed below. The following is a non-limiting list of suitable additional adjuvants:

[0114] A. Surfactants The composition of the present disclosure may include a surfactant. The surfactant may be useful, for example, to provide cleaning benefits. The composition may include a surfactant system, which may contain one or more surfactants.

[0115] Compositions of the present disclosure may comprise from about 0.1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50% by weight of the composition of a surfactant system. Liquid compositions may comprise from about 5% to about 40% by weight of the composition of a surfactant system. Compositions suitable for dense formulations, e.g., dense, liquid, gel, and / or unit dose forms, may comprise from about 25% to about 70%, or from about 30% to about 50% by weight of the composition of a surfactant system.

[0116] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include nonionic surfactants such as linear alkyl benzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactant may be derived, at least in part, from natural sources, such as natural feedstock alcohols.

[0117] Suitable anionic surfactants may include any conventional anionic surfactant. This may include, for example, sulfate detersive surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid-based detersive surfactants, such as alkyl benzene sulfonates. The anionic surfactant may be linear, branched, or a combination thereof. Preferred surfactants include linear alkyl benzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkyl benzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactant may be present in acid form, salt form, or a mixture thereof. The anionic surfactant may be partially or totally neutralized, for example, with an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine). Due to the presence of cationic ester quat materials, it may be desirable to limit the amount of anionic surfactant to avoid undesirable interactions of materials. For example, the composition may contain less than 5% by weight of the composition, preferably less than 3% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight of anionic surfactant.

[0118] The surfactant system may include a nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(oxyalkylated) alcohol surfactants, and mixtures thereof. The alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof. The nonionic surfactant may be linear, branched (e.g., mid-chain branched), or a combination thereof. Specific nonionic surfactants may include alcohols having an average of about 12 to about 16 carbons and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactants.

[0119] Suitable zwitterionic surfactants include betaines, C8-C9 alkyl dimethyl betaines, including alkyl dimethyl betaines and cocodimethylamidopropyl betaine. 18 (For example, C 12 ~C 18 ) amine oxides (e.g., C 12 ~ 14 dimethylamine oxide), and / or N-alkyl-N,N-dimethylamino-1-propanesulfonate (wherein the alkyl group is C8 to C 18 or C 10 ~C 14 The zwitterionic surfactant may include any conventional zwitterionic surfactant, such as sulfo and hydroxybetaines, such as (which may be

[0120] Depending on the formulation and / or intended end use, the composition may be substantially free of certain surfactants. For example, a liquid fabric strengthening composition, such as a fabric softener, may be substantially free of anionic surfactants, as such surfactants may negatively interact with cationic components.

[0121] B. Conditioning Actives The compositions of the present disclosure may include conditioning actives. Compositions containing conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color, and / or appearance benefits.

[0122] The conditioning active may be present at a level of about 1% to about 99% by weight of the composition. The composition may comprise from about 1%, or about 2%, or about 3%, to about 99%, or about 75%, or about 50%, or about 40%, or about 35%, or about 30%, or about 25%, or about 20%, or about 15%, or about 10% conditioning active by weight of the composition. The composition may comprise from about 5% to about 30% conditioning active by weight of the composition.

[0123] Suitable conditioning active materials for the composition of the present disclosure can include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty acid esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof.Preferably, the treatment composition is a fabric care composition in which one or more adjunct ingredients comprise quaternary ammonium ester materials.Such materials are particularly useful in fabric enhancing / conditioning / softening compositions.

[0124] The composition may contain a quaternary ammonium ester compound, a silicone, or a combination of these, preferably a single combination. The total amount of the quaternary ammonium ester compound and the silicone may be about 5% to about 70% by weight of the composition, or about 6% to about 50% by weight, or about 7% to about 40% by weight, or about 10% to about 30% by weight, or about 15% to about 25% by weight. The composition may contain the quaternary ammonium ester compound and the silicone in a weight ratio of about 1:10 to about 10:1, or about 1:5 to about 5:1, or about 1:3 to about 1:3, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.

[0125] The composition may contain a mixture of different types of conditioning actives. The composition of the present disclosure may contain a specific conditioning active but may be substantially free of other conditioning actives. For example, the composition may be free of quaternary ammonium ester compounds, silicones, or both. The composition may contain a quaternary ammonium ester compound but may be substantially free of silicones. The composition may contain silicones but may be substantially free of quaternary ammonium ester compounds.

[0126] C. Adhesion aid The composition of the present disclosure may also include a deposition aid. As mentioned above, due to the synergistic effect of the ester quaternary material and the delivery particles of the present disclosure, less (or even no) deposition aid may be required to provide comparable or even improved performance. Alternatively, a deposition aid may be used in the composition of the present disclosure to further enhance performance.

[0127] The deposition aid may promote deposition of the delivery particles, conditioning actives, fragrance, or combinations thereof, which may improve the performance benefits of the composition and / or allow for more efficient incorporation of such benefit agents. The composition may comprise from 0.0001% to 3%, preferably from 0.0005% to 2%, more preferably from 0.001% to 1%, or from about 0.01% to about 0.5%, or from about 0.05% to about 0.3%, by weight of the composition, of the deposition aid. The deposition aid may be a cationic or amphoteric polymer, preferably a cationic polymer.

[0128] Cationic polymers in general and methods for their preparation are well known in the literature. Suitable cationic polymers include quaternary ammonium polymers known as "polyquaternium" polymers as designated in the International System of Nomenclature for Cosmetic Ingredients, such as Polyquaternium-6 (poly(diallyldimethylammonium chloride)), Polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), Polyquaternium-10 (quaternized hydroxyethylcellulose), and Polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride).

[0129] The deposition aid may be selected from the group consisting of polyvinyl formamide, partially hydroxylated polyvinyl formamide, polyvinyl amine, polyethylene imine, ethoxylated polyethylene imine, polyvinyl alcohol, polyacrylate, and combinations thereof. The cationic polymer may include a cationic acrylate.

[0130] The deposition aid can be added simultaneously with the delivery particles (e.g., simultaneously with the encapsulated benefit agent) or directly / independently into the fabric treatment composition. The weight average molecular weight of the polymer may be from 500 Daltons to 5,000,000 Daltons, or from 1,000 Daltons to 2,000,000 Daltons, or from 2,500 Daltons to 1,500,000 Daltons, as measured by size exclusion chromatography against polyethylene oxide standards using refractive index (RI) detection. The weight average molecular weight of the cationic polymer may be from 5,000 Daltons to 37,500 Daltons.

[0131] D. Rheology Modifiers / Structuring Agents The compositions of the present disclosure may include a rheology modifier and / or a structuring agent. Rheology modifiers may be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structuring agents may be used to promote phase stability and / or to suspend or inhibit aggregation of particles in the liquid composition, such as the delivery particles described herein.

[0132] Suitable rheology modifiers and / or structurants may include non-polymeric crystalline hydroxyl-functional structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulosic fibers (e.g., microfibrillated cellulose, which may be derived from bacterial, fungal, or plant sources, including wood), diamide gelling agents, or combinations thereof.

[0133] The polymeric structurant may be of natural or synthetic origin. Naturally derived polymeric structurants may include hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives may include pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structurants may include polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers may include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates are polymers of unsaturated mono- or dicarbonates and C1-C (meth)acrylic acid. 30 The structuring agent may include copolymers with alkyl esters. Such copolymers are available from Noveon Inc. under the trade name Carbopol Aqua 30. Crosslinked polymers, such as crosslinked polyacrylates, and / or polymers and / or copolymers, such as those further comprising nonionic monomers, such as acrylamide or methacrylamide monomers, may be useful as structuring agents. Another suitable structuring agent is sold under the trade name Rheovis CDE, available from BASF.

[0134] E. Other adjuvants The treatment compositions of the present disclosure may include other adjuvants suitable for inclusion in a product and / or end use. For example, the treatment compositions may include pure perfume, perfume delivery technology (such as secondary perfumes and / or encapsulates having non-polyisocyanate / chitosan wall materials), cationic surfactants, cationic polymers, solvents, suds suppressors, or combinations thereof.

[0135] Method for producing the treatment composition The present disclosure further relates to methods for making treatment compositions, such as the treatment compositions and / or consumer product compositions described herein.

[0136] The method can include providing a base composition including a processing aid and combining a population of delivery particles with the base composition. The population of delivery particles can be preferably provided as an aqueous slurry. The base composition is in liquid form.

[0137] The delivery particles may be combined with one or more auxiliary ingredients when the delivery particles are in one or more forms including a slurry form, a neat particle form, and / or a spray-dried particle form, preferably a slurry form. The delivery particles may be combined with such auxiliary ingredients by methods including mixing and / or spraying.

[0138] The processing composition of the present disclosure can be formulated into any suitable form and can be prepared by any process selected by the formulator.One or more auxiliary ingredients and delivery particles can be combined in a batch process, a circulation loop process, and / or an in-line mixing process.Suitable equipment for use in the methods disclosed herein can include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, high shear mixers, static mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, if available, in continuous process configurations), spray dryers, and extruders.

[0139] As described herein, the treatment composition may be packaged in a container to form a consumer product. The container may be a bottle, preferably a plastic bottle. The treatment composition may be packaged in an aerosol or other spray container according to known methods.

[0140] Processing method The present disclosure also relates to a method of treating a surface, preferably a fabric, generally comprising contacting the surface, preferably a fabric, with a treatment composition according to the present disclosure, comprising a population of delivery particles as described herein.

[0141] Additionally or alternatively, the method may comprise contacting a surface, preferably a fabric, with a population of delivery particles described herein, which may be contained in a treatment composition, preferably a fabric care composition, according to the present disclosure.

[0142] The method can include contacting a fabric, such as a garment, with a treatment composition. The treatment composition includes a population of delivery particles. The contacting step results in one or more of the delivery particles being deposited on the surface of the fabric. The delivery particles include a core and a shell surrounding the core, the core including a benefit agent, preferably a fragrance material including one or more perfume ingredients. The shell includes a polymeric material, for example, a reaction product of chitosan of a specific molecular weight and a crosslinker. Suitable treatment compositions and delivery particles are described in more detail above.

[0143] The contacting step may occur during a manual laundry process, e.g., in a basin when fabrics are treated by hand, or during an automatic laundry process, e.g., in an automatic washing machine. The contacting step may occur during the wash cycle of an automatic washing machine. In such cases, the treatment composition may be a laundry detergent or a laundry additive. The contacting step may preferably occur during the rinse cycle of an automatic washing machine. In such cases, the treatment composition may be a fabric enhancer, preferably a liquid fabric enhancer. The contacting step may also occur during the drying step of the laundry process, e.g., in an automatic dryer. In such cases, the treatment composition may be in the form of a nonwoven dryer sheet or a dryer bar. The contacting step may occur as a result of the treatment composition being applied directly to the fabric, e.g., in a pre-treatment operation or a "refreshing" step (e.g., in the case of fabrics that have been used or worn since the last wash). In such cases, the treatment composition may be in the form of a liquid, stick, or spray, preferably a spray. Contacting the target fabric relatively late in the laundry process, e.g., during the rinse cycle, improves the likelihood or efficiency of deposition on the fabric, as the fabric is less likely to be washed down the drain.

[0144] The contacting step may occur in the presence of water. The treatment composition can be diluted with water to form a treatment solution. The treatment composition can be diluted from about 100 to about 1500 times, preferably from 300 to about 1000 times.

[0145] Liquids containing the disclosed compositions may have a pH of about 3 to about 11.5. When diluted, such compositions are typically used at concentrations of about 500 ppm to about 15,000 ppm in solution. When the cleaning solvent is water, the water temperature typically ranges from about 5°C to about 90°C, and the water-to-fabric ratio may typically be about 1:1 to about 30:1.

[0146] The dilution may occur in the drum of an automatic washing machine. The treatment composition may be placed in a dispensing drawer of the automatic washing machine. The treatment composition may be dispensed from the dispensing drawer into the drum during the treatment process.

[0147] As alluded to above, the method may further comprise drying the fabric having one or more delivery particles on the surface of the fabric. The drying step may comprise a passive drying process, such as on a clothesline or drying rack. The drying step may comprise an automatic drying process, such as an automatic dryer.

[0148] combination Specifically contemplated combinations of the present disclosure are set forth herein in the following alphabetized sections, which are intended to be exemplary in nature and not limiting. A. A treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, and the shell comprising a polymeric material that is the reaction product of a modified chitosan and at least one electrophile, the modified chitosan comprising the reaction product of chitosan and a modifying compound, the modifying compound comprising an epoxide, an aldehyde, or an α,β-unsaturated compound. B. The treatment composition of paragraph A, wherein the modifying compound comprises a cationic group, an anionic group, a nonionic group, or a mixture thereof. C. The treatment composition of paragraph A or B, wherein the modifying compound comprises a cationic group, an anionic group, or a mixture thereof, more preferably an anionic group. D. The treatment composition of any one of paragraphs A-C, wherein the modifying compound comprises an acidic group, a hydroxyl group, a quaternary ammonium group, or a mixture thereof, preferably an acidic group. E. The treating composition of any one of paragraphs AD, wherein the modifying compound comprises an α,β-unsaturated compound, preferably the α,β-unsaturated compound is an α,β-unsaturated carbonyl compound. F. The modifying compound comprises an α,β-unsaturated compound, wherein the α,β-unsaturated compound is selected from the group consisting of acrylates, alkyl acrylates, α,β-unsaturated esters, acrylic acid, acrylamide, vinyl ketone, vinyl sulfone, vinyl phosphonate, acrylonitrile, or combinations thereof, and preferably the α,β-unsaturated compound is selected from the group consisting of acrylic acid, acrylates, acrylates, alkyl acrylates, α,β-unsaturated esters, maleic acid, vinyl sulfonic acid, 2-carboxyethyl acrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylamide, (2-(acryloyloxy)ethyl)thiazolinone, 2-(2-acryloyloxy)ethyl ... 2-Acrylamido-2-methyl-1-propanesulfonic acid and salts thereof, quaternized vinylimidazole, diallyldialkylammonium salt, vinylamine, vinyl ketone, vinyl sulfone, vinyl phosphonate, acrylonitrile, and combinations thereof. G. Modified compounds include glycidyl trimethylammonium salt, glycidyl isopropyl ether, glycidyl methacrylate, furfuryl glycidyl ether, glycidol, 1,4-butanediol diglycidyl ether, 2-ethylhexyl glycidyl ether, (3-glycidyloxypropyl)trimethoxysilane, poly(ethylene glycol) diglycidyl ether, trimethylolpropane triglycidyl ether, glutaraldehyde, alginic aldehyde, acrylic acid, acrylates, maleic acid, vinyl sulfonic acid, 2-carboxyethyl acrylate, 2-(2-oxo-1-imidazolidinyl)ethyl meth ... 10. The treatment composition of any one of paragraphs A through F, comprising a material selected from the group consisting of (2-(acryloyloxy)ethyl)methacrylamide, (2-(acryloyloxy)ethyl)trimethylammonium salts, (3-(methacryloylamino)propyl)trimethylammonium salts, N,N-dialkylaminoalkyl acrylates, N,N-dialkylaminoalkylacrylamides, (3-acrylamidopropyl)trimethylammonium salts, 3-sulfopropyl acrylate salts, 2-acrylamido-2-methyl-1-propanesulfonic acid and salts thereof, quaternized vinylimidazole, diallyldialkylammonium salts, vinylamine, and combinations thereof. H. A treatment composition according to any one of paragraphs A to G, wherein the chitosan contains free amine moieties and the molar ratio of the modifying compound to the free amine moieties of the chitosan is 0.1% to 100%, preferably 10% to 100%, more preferably 10% to 90%, even more preferably 25% to 90%, and even more preferably 25% to 75%. I. The treatment composition of any one of paragraphs AH, wherein the shell comprises at least 18%, preferably at least 21%, by weight of the shell, of modified chitosan. J. The treatment composition of any one of paragraphs A-I, wherein the modified chitosan is characterized by a weight average molecular weight of from about 100 kDa to about 600 kDa, preferably from about 100 kDa to about 500 kDa, more preferably from about 100 kDa to about 400 kDa, more preferably from about 100 kDa to about 300 kDa, and even more preferably from about 100 kDa to about 200 kDa. K. A treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, and the shell comprising a polymeric material that is the reaction product of at least one modified chitosan and at least one electrophile, the population of delivery particles being prepared by forming an aqueous phase by dissolving or dispersing chitosan in an aqueous acidic medium at a pH of 6.5 or less and at a temperature of at least 25°C, the chitosan having free amine moieties; forming an oil phase comprising combining at least one benefit agent and at least one electrophile, preferably at least one polyisocyanate, optionally with an added oil; and dissolving the oil phase under high shear agitation. into an excess of an aqueous phase to form an emulsion, thereby forming droplets of the oil phase dispersed in the aqueous phase; adding to the aqueous phase and / or emulsion, preferably at least to the aqueous phase, a modifying compound, the modifying compound comprising one or more of an epoxide, an aldehyde, or an α,β-unsaturated compound, which reacts with the free amine moieties of the chitosan; optionally adjusting the pH of the emulsion to a pH of 4 or higher; and heating the emulsion to at least 40°C for a time sufficient to form a shell surrounding the core at the interface of the droplets with the aqueous phase, the shell surrounding the core. L. A treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, the shell comprising a polymeric material that is the reaction product of at least one modified chitosan and at least one electrophile, the modified chitosan comprising the reaction product of chitosan and a modifying compound, the modifying compound comprising an epoxide, an aldehyde, or an α,β-unsaturated compound covalently bonded to the chitosan, the population of delivery particles comprising the steps of: dissolving or dispersing chitosan in an aqueous phase, the chitosan having an amine moiety; combining the aqueous phase with the modifying compound; optionally adjusting the pH of the aqueous phase to pH 3.0 or greater, preferably pH 3.0 to pH 6; optionally adjusting the temperature of the aqueous phase to 25° C. or greater; and mixing the aqueous phase for a period of time. providing an oil phase comprising at least one benefit agent comprising an oil and at least one electrophile, preferably at least one polyisocyanate, dissolved optionally with a second oil; forming an emulsion by mixing the oil phase into the aqueous phase under high shear agitation, thereby forming droplets of the oil phase and benefit agent dispersed in the aqueous phase; and heating the emulsion to at least 40°C for a time sufficient to form a shell at the interface of the droplets with the aqueous phase, the shell surrounding the core. M. The treatment composition of any one of paragraphs A-L, wherein the method for obtaining a population of delivery particles further comprises adding a redox initiator to the aqueous phase or emulsion, wherein the redox initiator comprises a persulfate, a peroxide, or a combination thereof. N. The treatment composition of any one of paragraphs AM, wherein the modifying compound comprises a cationic group and / or an anionic group. O. The treatment composition of any one of paragraphs A-N, wherein the delivery particle comprises from about 1% to about 25% shell by weight of the delivery particle. P. The treatment composition of any one of paragraphs A-O, wherein the shell degrades by at least 50%, preferably at least 60%, after 60 days when tested according to test method OECD 301B. Q. The treatment composition of any one of paragraphs A-P, wherein the delivery particles are characterized by a zeta potential of 150 mV or less at pH 4.5. R. The treatment composition of any one of paragraphs A-R, wherein the electrophile comprises a polyisocyanate, preferably a polyisocyanate selected from the group consisting of polyisocyanurates of toluene diisocyanate; trimethylolpropane adducts of toluene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethylxylidene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (e.g., prepolymers, oligomers, and / or polymers thereof); and combinations thereof. S. The treatment composition of any one of paragraphs A-R, wherein the benefit agent is a fragrance material. T. The core may optionally contain a partitioning modifier, preferably a vegetable oil, modified vegetable oil, C4-C6, optionally present in the core at a concentration of about 5% to about 55% by weight of the core, preferably about 10% to about 50% by weight, more preferably about 25% to about 50% by weight. 24 The treating composition of any one of paragraphs A-S, further comprising a partitioning modifier selected from the group consisting of mono-, di-, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate. U. The treatment composition of any one of paragraphs A-T, wherein the delivery particles are characterized by a volume-weighted median particle size of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 25 to about 35 microns. V. The treatment composition of any one of paragraphs A-U, wherein the processing aid is selected from the group consisting of surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic metal complexes, polymeric dispersants, mud and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, undiluted perfume, additional perfume delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-agglomerating agents, coatings, formaldehyde scavengers, pigments, and mixtures thereof. W. The treatment composition of any one of paragraphs AV, wherein the treatment adjunct comprises an anionic surfactant, a cationic conditioning agent, or a mixture thereof. X. The treatment composition of any one of paragraphs A-W, wherein the treatment composition is a fabric care composition, a hard surface cleaning composition, a dish care composition, a hair care composition, a body cleansing composition, or a mixture thereof, preferably a fabric care composition, more preferably a fabric care composition that is a laundry detergent composition, a fabric conditioning composition, a laundry additive, a fabric pre-treatment composition, a fabric refresher composition, or a mixture thereof. Y. The treatment composition of any one of paragraphs A-X, wherein the treatment composition is in the form of a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, a tablet or bead, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven, or a mixture thereof, preferably a liquid composition, preferably a single-compartment pouch, a multi-compartment pouch, a tablet or bead, or a mixture thereof. Z. The treatment composition of any one of paragraphs A-Y, wherein the treatment composition comprises less than about 25% water by weight of the treatment composition, preferably less than about 20% water, more preferably less than about 15% water, even more preferably less than about 12% water, even more preferably less than about 10% water, and even more preferably less than about 5% water. AA. A method for producing a base composition described in any one of paragraphs A-Z, the method comprising the steps of providing a base composition including a processing aid and combining a population of delivery particles with the base composition. BB. The method of paragraph AA, wherein the population of delivery particles is provided as an aqueous slurry. CC. The method of paragraph BB, wherein the aqueous slurry contains less than about 25% water, preferably less than about 20% water, more preferably less than about 15% water, even more preferably less than about 12% water, even more preferably less than about 10% water, and even more preferably less than about 5% water, by weight of the aqueous slurry. DD. The method of any one of paragraphs AA-CC, wherein the base composition is in the form of a liquid composition. EE. A method of treating a surface, the method comprising contacting the surface, preferably a fabric, with a treatment composition of any one of paragraphs A-Z.

[0149] Test Method It will be understood that the test methods disclosed in the Test Methods section of this application should be used to determine the values ​​of each of the parameters of the inventive subject matter claimed and described herein.

[0150] Determination of polymer molecular weight and related parameters The following method, which describes gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI), is used to obtain molecular weight distribution measurements and related values ​​for the polymers described herein.

[0151] Gel Permeation Chromatography (GPC) with Multi-Angle Light Scattering (MALS) and Refractive Index (RI) detection (GPC-MALS / RI) allows the measurement of the absolute average molecular weight of a polymer without the need for column calibration or standards. GPC systems allow the separation of molecules as a function of their molecular size. MALS and RI can provide information on number-average (Mn) and weight-average (Mw) molecular weight.

[0152] The Mw distribution of water-soluble polymers such as chitosan is typically measured using a liquid chromatography system (e.g., an Agilent 1260 Infinity Pump System with OpenLab Chemstation software, available from Agilent Technologies, Santa Clara, CA, USA) and a column set (e.g., two TSKgel G6000WP 7.8 x 300 mm 13 μm pore size columns, guard column A0022 6 mm x 40 mm PW xl-cp columns, available from Tosoh, King of Prussia, PA) operated at 40°C. The mobile phase is 0.1 M sodium nitrate in water containing 0.02% sodium azide and 0.2% acetic acid. The mobile phase solvent is pumped isocratically at a flow rate of 1 mL / min. A multi-angle light scattering (18-angle MALS) detector DAWN® and a differential refractive index (RI) detector (Wyatt Technology, Santa Barbara, CA, USA) controlled by Wyatt Astra® software v.8.0 can be used.

[0153] Samples are typically prepared by dissolving chitosan material in the mobile phase at approximately 1 mg / mL, mixing the solution, and allowing it to hydrate overnight at room temperature. Prior to GPC analysis, samples are filtered through 0.8 μm Versapor filters (PALL Life Sciences, NY, USA) using a 3 mL syringe into LC autosampler vials.

[0154] The dn / dc value (differential change in refractive index with concentration, 0.15) is used to determine the number average molecular weight (Mn), weight average molecular weight (Mw), Z-average molecular weight (Mz), molecular weight at the peak maximum (Mp), and polydispersity (Mw / Mn) by the Astra detector software.

[0155] viscosity Measure the viscosity of the liquid final product using an AR550 rheometer / viscometer from TA instruments (New Castle, Delaware, USA) using parallel steel plates with a diameter of 40 mm and a gap size of 500 μm. -1 High shear viscosity at 0.05 seconds -1 The low shear viscosity at 21°C for 3 minutes is 0.01 s -1 ~25 seconds -1 is obtained from a logarithmic shear rate sweep.

[0156] Test Method for Determining logP For each material tested (e.g., each PRM in a fragrance mixture), the logarithm of the octanol / water partition coefficient (logP) is calculated. The logP values ​​of individual materials (e.g., PRMs) are calculated using the Consensus logP Computational Model, version 14.02 (Linux), available from Advanced Chemistry Development Inc. (ACD / Lab) (Toronto, Canada), which yields unitless logP values. The ACD / Labs Consensus logP Computational Model is part of the ACD / Labs model suite.

[0157] Volume-weighted particle size and size distribution Volume-weighted particle size distributions were determined by single-particle optical sensing (SPOS), also known as optical particle counting (OPC), using an AccuSizer 780 AD instrument and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent. The instrument was configured with the following conditions and options: flow rate = 1 mL / s, minor threshold = 0.50 μm, sensor model number = LE400-05 or equivalent, autodilution = on, collection time: 60 seconds, number of channels = 512, reservoir fluid volume = 50 mL, and maximum coincidence count = 9200. Measurements were initiated by cold-conditioning the sensor by flushing with water until the background count was less than 100. A sample of delivery capsules in suspension is introduced, and the capsule density is adjusted, if necessary, via automated dilution with deionized water to achieve a capsule count of at least 9200 per mL. The suspension is analyzed for 60 seconds. The resulting volume-weighted PSD data is plotted and recorded, and desired volume-weighted particle size values ​​(e.g., median / 50th percentile, 5th percentile, and / or 90th percentile) are determined.

[0158] Procedure for determining decomposition % To determine % degradation, the procedure described in the "OECD Guideline for Testing of Chemicals" 301B CO2 Evolution (Modified Sturm Test), adopted on July 17, 1992, is used. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0159] Fabric treatment methods The fabrics were treated using a Miele washing machine. For each treatment, 3 kg of fabric was loaded into the washing machine, including 1100 g of knitted cotton fabric and 1100 g of polyester-cotton (50 / 50) fabric. Additionally, 18 terry towel cotton tracers were added, totaling approximately 780 g.

[0160] Prior to the test treatment, the load is preconditioned twice with 79 g of unscented IEC A-based detergent (ex WFK, Testgewebe GmbH), each time using a short cotton cycle at 95°C, followed by two additional 95°C washes without detergent.

[0161] For the test treatment, the load is washed using a short cotton cycle at 40°C, a spin speed of 1200 rpm, and 79 g of IEC A-based detergent, which is added to the appropriate dispenser at the beginning of the wash cycle. A 35 g dose of the test fabric treatment composition (i.e., the LFE according to the example) is added to the appropriate dispenser. At the end of the treatment cycle, the terry towel tracer is removed from the washing machine and line dried overnight.

[0162] The next day, the dried terry towel tracer is analyzed by a rapid headspace GC / MS (gas chromatography mass spectrometry) technique as described below. For comparison, all treatments are washed on the same day, and all treatments analyzed on the same day are reported as a "single wash test."

[0163] Method for determining headspace concentrations above treated fabrics The cotton tracer was analyzed by fast headspace GC / MS (gas chromatography mass spectrometry) technique. A 4 x 4 cm aliquot of terry towel tracer was transferred to a 25 mL headspace vial. The fabric sample was equilibrated at 65°C for 10 minutes. The headspace above the fabric was sampled by SPME (50 / 30 μm DVB / Carboxen / PDMS) technique for 5 minutes. The SPME fibers were then thermally desorbed online into the GC. The analytes were analyzed in full scan mode by fast GC / MS. Ion extraction of specific masses from the PRM was used to calculate the total HS reaction and perfume headspace composition above the tested leg.

[0164] Procedure for determination of quantity of free oil ("QFO") This method measures the amount of oil in the aqueous phase (quantity of free oil, "QFO") and uses 1 mg / mL dibutyl phthalate (DBP) / hexane as an internal standard solution.

[0165] Weigh slightly more than 250 mg of DBP into a small beaker and transfer to a 250 mL volume. Rinse the beaker thoroughly. Fill to 250 mL with hexane.

[0166] Sample preparation: Weigh approximately 1.5-2 grams (40 drops) of capsule slurry into a 20 mL scintillation vial, add 10 mL of ISTD solution, and cap tightly. Shake vigorously several times over a 30-minute period. Pipette the solution into an autosampler vial and analyze by GC.

[0167] Additional Details: Equipment used: HP5890 GC connected to HP Chem Station Software; Column: 5 m x 0.32 mm id (using a 1 μm DB-1 liquid phase); Temperature: 50°C for 1 minute, then heated to 320°C at 15°C / min; Injector: 275°C; Detector: 325°C; 2 μL injection.

[0168] Calculation: Add the total peak area minus the area of ​​DBP for both the sample and the calibration.

[0169] Calculate mg of free core oil.

[0170]

number

[0171] Calculate the % free core oil.

[0172]

number

[0173] Beneficial Agent Leakage Determination Procedure Two 1 gram samples of benefit agent particle composition are obtained. 1 gram of the particle composition (Sample 1) is added to 99 grams of the product matrix in which the particles will be used. The particle-containing product matrix (Sample 1) is aged in a sealed glass jar at 35°C for 2 weeks. Another 1 gram sample (Sample 2) is aged in the same manner.

[0174] After two weeks, filtration is used to recover the particles of the particulate composition from the product matrix (Sample 1) and the particulate composition (Sample 2). Each particle sample is treated with a solvent that extracts all of the benefit agent from the particles in each sample. The benefit agent-containing solvent from each sample is injected into a gas chromatograph and the peak areas are integrated to determine the total amount of benefit agent extracted from each sample.

[0175] The percentage of benefit agent leakage is determined by calculating the difference between the value obtained for the total amount of benefit agent extracted from Sample 2 minus the value from Sample 1 and expressed as a percentage of the total amount of benefit agent extracted from Sample 2, represented by the following equation:

[0176]

number

[0177] A method for qualitatively determining the compatibility of delivery particles in laundry matrices. The compatibility of the delivery particles in the laundry matrix is ​​measured by visually inspecting the mixture of delivery particles and laundry matrix in a glass bottle. The slurry containing the delivery particles is homogenized by stirring for at least 1 minute using an overhead mixer. Then, the homogenized slurry is added to the laundry matrix, such as a heavy-duty laundry matrix, at a ratio of 1:40, for example, 1 g of slurry in 40 g of matrix, while mixing. The mixture is mixed at 350 rpm using an overhead mixer for at least 15 minutes. Mixing is stopped, and the mixture is allowed to stand for 5 minutes before testing. The mixture is visually inspected with the naked eye and under an optical microscope to detect any agglomerates in the mixture. If agglomerates are observed with the naked eye or under an optical microscope that are larger than 100 microns, the delivery particles are determined to be incompatible in the laundry matrix. [Example]

[0178] The examples provided below are intended to be illustrative in nature and not limiting.

[0179] In the following examples, abbreviations correspond to the materials listed in Table 1. Comparative Example 1 discloses the synthesis of comparative delivery particles. Examples 1-7 disclose the synthesis of delivery particles according to the present disclosure in which chitosan is modified in the aqueous phase. Examples 7-21 disclose the synthesis of delivery particles according to the present disclosure in which chitosan is modified in the emulsion stage.

[0180] [Table 1]

[0181] Comparative Example 1. Polyurea capsules with (unmodified) chitosan A chitosan stock solution is prepared by dispersing 39.60 g of chitosan ChitoClear in 840.4 g of deionized water while mixing in a jacketed reactor. The pH of the chitosan dispersion solution is then adjusted to 3.87 using 17.90 g of concentrated HCl under stirring. The temperature of the chitosan solution is then increased to 85°C over 60 minutes and then held at 85°C for 2 hours to hydrolyze the ChitoClear. After the 90-minute hydrolysis step, the temperature is then reduced to 25°C. The pH of the acid-treated chitosan solution is 3.97.

[0182] In a jacketed reactor, an aqueous phase is prepared by mixing 426.30 g of the chitosan stock solution with 6.70 g of a 5% PVA540 solution. An oil phase is prepared by mixing 146.63 g of fragrance and 36.66 g of isopropyl myristate with 4.00 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion of the desired particle size. The emulsion is heated to 40°C in 30 minutes and held at 40°C for 60 minutes. The emulsion is then heated to 85°C in 60 minutes and held at this temperature for 6 hours with mixing. The formed capsules have a median particle size of 8.05 microns. The formed capsules had a leakage rate of 20.78% over one week. The prepared slurry exhibits cohesion in a heavy-duty liquid laundry matrix.

[0183] Example 1. Pre-modification with [2-(acryloyloxy)ethyl]trimethylammonium chloride A modified chitosan solution was prepared by dispersing 40.92 g of chitosan powder in 792.00 g of water at 70°C. The pH of the mixture was adjusted to 4.91 using 9.79 g of glacial acetic acid. 46.36 g of 80% [2-(acryloyloxy)ethyl]trimethylammonium chloride solution was then added to the chitosan solution and mixed at 70°C for 12 hours to obtain a [2-(acryloyloxy)ethyl]trimethylammonium chloride-modified chitosan solution. The pH of the resulting modified chitosan solution was 4.05.

[0184] The aqueous phase is prepared by weighing 255.8 g of the [2-(acryloyloxy)ethyl]trimethylammonium chloride modified chitosan solution into a jacketed reactor at 25°C.

[0185] The oil phase is prepared by mixing 87.98 g of perfume, 2.40 g of Takenate D110, and 22.00 g of isopropyl myristate in a beaker at 25°C.

[0186] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion.

[0187] The emulsion is then heated to 40°C in 30 minutes and held at 40°C for 60 minutes. The emulsion is then heated to 85°C in 60 minutes and held for 6 hours to harden the walls. The emulsion is then cooled to 25°C in 90 minutes. The resulting capsules have a median particle size of 12.27 microns. The QFO and 1-week leakage of the capsule slurry are 7.69% and 68.59%, respectively. The prepared slurry did not exhibit agglomeration in a heavy-duty liquid laundry matrix.

[0188] Example 2. Pre-modification with [2-(acryloyloxy)ethyl]trimethylammonium chloride and pH adjustment Example 2 is prepared according to the procedure of Example 1, except that the pH of the aqueous phase is adjusted to 6.8 using sodium hydroxide solution. The aqueous phase remains clear after the pH adjustment. The resulting capsules have a median particle size of 36.44 microns. The QFO and 1-week leakage of the capsule slurry are 0.11% and 0.99%, respectively. The prepared slurry does not exhibit clumping in a heavy-duty liquid laundry matrix.

[0189] Example 3. Pre-modification with [2-(acryloyloxy)ethyl]trimethylammonium chloride, pH adjustment, second crosslinker (pentaerythritol triacrylate) A modified chitosan solution is prepared according to the procedure of Example 1. The modified chitosan solution has a pH of 4.10. The aqueous phase consists of the modified chitosan solution with the pH adjusted to 9.35 using sodium hydroxide solution.

[0190] An emulsion was prepared according to Example 1 and then heated to 70°C. The second crosslinker, pentaerythritol triacrylate, was then added to the emulsion at 70°C. The emulsion was then heated to 90°C in 60 minutes and held for an additional 8 hours before being cooled to 25°C to complete the curing process. The resulting capsules have a median particle size of 23.63 microns. The QFO and one-week leakage of the capsule slurry are 0.35% and 6.19%, respectively. The prepared slurry did not exhibit agglomeration in a heavy-duty liquid laundry matrix.

[0191] Example 4. Pre-modification with CD9055 (acidic acrylate oligomer) A modified chitosan solution was prepared by dispersing 42.11 g of chitosan powder in 840.00 g of water at 70°C. 42.11 g of CD9055, an acidic acrylate oligomer, was then added to the chitosan mixture and mixed at 70°C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the resulting modified chitosan solution was 4.08.

[0192] The aqueous phase is prepared by weighing 328.00 g of CD9055 modified chitosan solution into a jacketed reactor at 25°C.

[0193] The oil phase is prepared by mixing 112.82 g of perfume, 3.08 g of Takenate D110, and 28.21 g of isopropyl myristate in a beaker at 25°C.

[0194] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion.

[0195] The emulsion is then heated to 40°C in 30 minutes and held at 40°C for 60 minutes. The emulsion is then heated to 85°C in 60 minutes and held for 6 hours to harden the walls. The emulsion is then cooled to 25°C in 90 minutes. The resulting capsules have a median particle size of 37.74 microns. The QFO and 1-week leakage of the capsule slurry are 0.83% and 41.46%, respectively.

[0196] Example 5. Pre-modification with CD9055 (acidic acrylate oligomer) and pH adjustment An aqueous phase is prepared by weighing 255.78 g of the CD9055 modified chitosan solution from Example 4 into a jacketed reactor at 25° C. The pH of the aqueous phase is then adjusted to 8.23 ​​using sodium hydroxide under stirring. The aqueous phase remains clear after the pH adjustment.

[0197] The oil phase is prepared by mixing 87.98 g of perfume, 2.40 g of Takenate D110, and 22.00 g of isopropyl myristate in a beaker at 25°C.

[0198] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion.

[0199] The emulsion is then heated to 40°C in 30 minutes and held at 40°C for 60 minutes. The emulsion is then heated to 85°C in 60 minutes and held for 6 hours to harden the walls. The emulsion is then cooled to 25°C in 90 minutes. The resulting capsules have a median particle size of 25.72 microns. The QFO and 1-week leakage of the capsule slurry are 0.28% and 6.95%, respectively. The prepared slurry did not exhibit agglomeration in a heavy-duty liquid laundry matrix.

[0200] Example 6. Pre-modification with CD9055 (an acidic acrylate oligomer) and a second modifying compound, pentaerythritol triacrylate A modified chitosan solution was prepared by dispersing 42.11 g of chitosan in 840 g of water at 70°C. The pH of the mixture was adjusted to 4.86 using 11.26 g of glacial acetic acid. 35.85 g of CD9055 was added to the chitosan solution and mixed at 70°C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the resulting modified chitosan solution was 3.90.

[0201] An aqueous phase is prepared by adding 266.70 g of the CD9055 modified chitosan solution into a jacketed reactor.

[0202] The oil phase is prepared by mixing 99.71 g of perfume, 2.72 g of Takenate D110 and 24.93 g of isopropyl myristate in a beaker at 25°C.

[0203] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion.

[0204] The resulting emulsion was then heated to 70°C, after which the second crosslinker, pentaerythritol triacrylate, was added to the emulsion at 70°C. The emulsion was then heated to 90°C in 60 minutes and held for an additional 8 hours before being cooled to 25°C to complete the curing process. The resulting capsules have a median particle size of 27.52 microns. The QFO and 1-week leakage of the capsule slurry are 0.10% and 34.40%, respectively.

[0205] Example 7. Pre-modification with CD9055 (acidic acrylate oligomer) and second modified compound A modified chitosan solution was prepared by dispersing 42.11 g of chitosan powder in 840.00 g of water at 70°C. 42.11 g of CD9055, an acidic acrylate oligomer, was then added to the chitosan mixture and mixed at 70°C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the resulting modified chitosan solution was 4.08.

[0206] The aqueous phase is prepared by weighing 255.78 g of CD9055 modified chitosan solution at 25° C. in a jacketed reactor.

[0207] The oil phase is prepared by mixing 87.98 g of perfume, 2.40 g of Takenate D110, and 22.00 g of isopropyl myristate in a beaker at 25°C.

[0208] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion. The pH of the emulsion is adjusted to 9.07 at 40°C using sodium hydroxide solution.

[0209] The emulsion is then heated to 40°C in 30 minutes, and the pH of the emulsion is adjusted to 9.07 using sodium hydroxide solution. The emulsion is then held at 40°C for 60 minutes, then heated to 85°C in 60 minutes, and held for 6 hours to harden the walls. The emulsion is then cooled to 25°C in 90 minutes. The resulting capsules have a median particle size of 25.95 microns. The QFO and 1-week leakage of the capsule slurry are 0.66% and 24.91%, respectively. The prepared slurry did not exhibit agglomeration in a heavy-duty liquid laundry matrix.

[0210] Example 8. Crosslinked chitosan capsules modified in situ with CD9055 (acidic acrylate oligomer) The chitosan solution is prepared as in Comparative Example 1, except that the pH of the chitosan solution is 5.23.

[0211] In a jacketed reactor at 25°C, an aqueous phase is prepared by adding 308.70 g of the above chitosan solution.

[0212] The oil phase is prepared by mixing 102.64g of perfume, 2.80g of Takenate D110, and 25.66g of isopropyl myristate in a beaker at 25°C.

[0213] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion.

[0214] The resulting emulsion was then heated to 70°C, after which 10.71g of the modified compound, CD9055, was added to the emulsion at 70°C. The emulsion was then heated to 90°C in 60 minutes and held for an additional 8 hours before being cooled to 25°C to complete the hardening process. The resulting capsules have a median particle size of 30.22 microns. The QFO and 1-week leakage of the capsule slurry are 0.49% and 48.08%, respectively.

[0215] Example 9. Cross-linked chitosan capsules modified in situ with [2-(acryloyloxy)ethyl]trimethylammonium chloride A chitosan solution is prepared as in Comparative Example 1, except that the pH of the chitosan solution is 5.23.

[0216] In a jacketed reactor at 25°C, an aqueous phase is prepared by adding 308.70 g of the above chitosan solution.

[0217] The oil phase is prepared by mixing 102.64g of perfume, 2.80g of Takenate D110, and 25.66g of isopropyl myristate in a beaker at 25°C.

[0218] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion.

[0219] The resulting emulsion was then heated to 70°C, after which 17.92g of the modifying compound, an 80% solution of [2-(acryloyloxy)ethyl]trimethylammonium chloride, was added to the emulsion at 70°C. The emulsion was then heated to 90°C in 60 minutes, held for an additional 8 hours, and then cooled to 25°C to complete the curing process. The resulting capsules have a median particle size of 27.84 microns. The QFO and 1-week leakage of the capsule slurry are 0.29% and 4.62%, respectively. The prepared slurry did not exhibit agglomeration in a heavy-duty liquid laundry matrix.

[0220] Example 1: Crosslinked chitosan capsules modified in situ with 0.25 mol% acrylic acid A chitosan stock solution is prepared by dispersing 155.7 g of chitosan ChitoClear in 3304 g of deionized water while mixing in a jacketed reactor. The pH of the chitosan dispersion solution is then adjusted to 5.23 using 69.84 g of concentrated HCl (31%) under stirring. The temperature of the chitosan solution is then increased to 65°C over 30 minutes, then increased to 85°C over 30 minutes, then increased to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze the ChitoClear. After the 90-minute hydrolysis step, the temperature is then reduced to 25°C. The pH of the hydrolyzed chitosan solution is 5.31.

[0221] An aqueous phase is prepared by mixing 433.6 g of the chitosan stock solution in a jacketed reactor at 25°C. An oil phase is prepared by mixing 128.9 g of fragrance and 32.2 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion of the desired particle size. The emulsion is heated to 60°C in 45 minutes, then to 95°C in 60 minutes. After reaching 95°C, a solution of 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of 21.5% NaOH (prepared in an ice bath) is added to the slurry, which is then held at 95°C for 360 minutes. The temperature is then reduced to 25°C in 90 minutes. The capsules formed have a median particle size of 30.42 microns.

[0222] Example 11. Crosslinked chitosan capsules modified in situ with 100 mol% acrylic acid A cross-linked chitosan capsule slurry is prepared identically to Example 10, except that instead of a solution of 2.07 g acrylic acid (TCI Chemical #A0141), 2.07 g RO water, and 5.08 g 21.5% NaOH, a solution of 8.29 g acrylic acid (TCI Chemical #A0141), 8.29 g RO water, and 20.31 g 21.5% NaOH (prepared in an ice bath) is added once at 95° C. The capsules formed have a median particle size of 31.25 microns.

[0223] Example 12. Crosslinked chitosan capsules modified in situ by the addition of 100 mol% acrylic acid at 25°C A cross-linked chitosan capsule slurry is prepared as in Example 10, except that instead of a solution of 2.07 g acrylic acid (TCI Chemical #A0141), 2.07 g RO water, and 5.08 g 21.5% NaOH added at 95° C., a solution of 8.29 g acrylic acid (TCI Chemical #A0141), 8.29 g RO water, and 20.31 g 21.5% NaOH (prepared in an ice bath) is added once an emulsion with the desired particle size is obtained at 25° C. The capsules formed have a median particle size of 31.68 microns.

[0224] Example 13. Crosslinked chitosan capsules modified in situ with 25 mol% acrylic acid and 5 mol% SR268 A cross-linked chitosan capsule slurry is prepared identically to Example 10, except that 1.74 g of tetraethylene glycol diacrylate (Sartomer #SR268) is also added immediately after a single addition of a solution of 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of 21.5% NaOH at 95° C. The capsules formed have a median particle size of 30.83 microns.

[0225] Example 14. Crosslinked chitosan capsules modified in situ with 25 mol% 3-sulfopropyl acrylate potassium salt A cross-linked chitosan capsule slurry is prepared identically to Example 10, except that instead of a solution of 2.07 g acrylic acid (TCI Chemical #A0141), 2.07 g RO water, and 5.08 g 21.5% NaOH, 6.69 g 3-sulfopropyl acrylate potassium salt (Sigma-Aldrich #251631) is added once at 95° C. The capsules formed have a median particle size of 30.83 microns.

[0226] Example 15. Crosslinked chitosan capsules modified in situ by the addition of 50 mol% glycidyltrimethylammonium chloride at 25°C A cross-linked chitosan capsule slurry is prepared as in Example 10, except that instead of 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of 21.5% NaOH solution added at 95° C., 10.92 g of 80% glycidyltrimethylammonium chloride (TCI Chemical #G0476) is added after an emulsion with the desired particle size is obtained at 25° C. The capsules formed have a median particle size of 32.98 microns.

[0227] Example 16. Crosslinked chitosan capsules modified in situ by the addition of 25 mol% glycidyltrimethylammonium chloride at 95°C A cross-linked chitosan capsule slurry is prepared identically to Example 10, except that instead of a solution of 2.07 g acrylic acid (TCI Chemical #A0141), 2.07 g RO water, and 5.08 g 21.5% NaOH, 5.46 g of 80% glycidyltrimethylammonium chloride (TCI Chemical #G0476) is added once at 95° C. The capsules formed have a median particle size of 30.84 microns.

[0228] Example 17. Crosslinked chitosan capsules modified in situ by the addition of 25 mol% glycidyltrimethylammonium chloride at 25°C A cross-linked chitosan capsule slurry is prepared identically to Example 10, except that instead of 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of 21.5% NaOH solution added at 95° C., 5.46 g of 80% glycidyltrimethylammonium chloride (TCI Chemical #G0476) is added after an emulsion with the desired particle size is obtained at 25° C. The capsules formed have a median particle size of 29.61 microns.

[0229] Example 1 Crosslinked Chitosan Delivery Particles Modified in Situ with 8.25 mol% Neutralized CD9055, 13.5 mol% SR268, and 10% KPS by Weight of Chitosan A chitosan stock solution was prepared by dispersing 155.7 g of chitosan ChitoClear in 3304 g of deionized water while mixing in a jacketed reactor. 1.56 g of potassium persulfate (KPS) was added. The pH of the chitosan dispersion solution was then adjusted to 5.84 using 57.29 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, then to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze the chitosan ChitoClear. After the 90-minute hydrolysis step, the temperature was then reduced to 25°C. The pH of the acid-treated chitosan solution was 5.85.

[0230] The aqueous phase is prepared by mixing 390.0 g of the chitosan stock solution in a jacketed reactor at 25°C. The oil phase is prepared by mixing 115.9 g of fragrance and 29.0 g of isopropyl myristate with 4.40 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion of the desired particle size. The emulsion is heated to 60°C for 45 minutes, then to 95°C for 60 minutes. Once at 95°C, a solution of 4.52g CD9055, 4.52g RO water, and 4.97g 21.5% NaOH (prepared in an ice bath) was added to the slurry over 1 minute, followed by 4.20g SR268 over 1 minute, then held at 95°C for 180 minutes, then 1.90g potassium persulfate over 1 minute, then held at 95°C for 180 minutes. The temperature was then reduced to 25°C over 90 minutes. The formed capsules had a median particle size of 28.44 microns. The prepared slurry did not exhibit agglomeration in a heavy-duty liquid laundry matrix.

[0231] Example 19. Crosslinked Chitosan Delivery Particles Modified with 50 mol% Acrylic Acid and KPS A chitosan stock solution was prepared by dispersing 155.7 g of chitosan ChitoClear in 3304 g of deionized water while mixing in a jacketed reactor. 1.56 g of potassium persulfate was added. The pH of the chitosan dispersion solution was then adjusted to 5.84 using 57.24 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, then to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze the ChitoClear. After the 90-minute hydrolysis step, the temperature was then reduced to 25°C. The pH of the acid-treated chitosan solution was 5.83.

[0232] An aqueous phase is prepared by mixing 433.6 g of the chitosan stock solution in a jacketed reactor at 25°C. An oil phase is prepared by mixing 129.0 g of fragrance and 32.0 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion of the desired particle size. The emulsion is heated to 60°C in 45 minutes, then to 95°C in 60 minutes. 30 minutes after reaching 95°C, a solution of 4.16 g of acrylic acid, 4.16 g of RO water, and 8.04 g of 21.5% NaOH (prepared in an ice bath) is added to the slurry over 1 minute, followed by a 360-minute hold at 95°C. The temperature is then reduced to 25°C in 90 minutes. The capsules formed have a median particle size of 27.86 microns. The prepared slurries did not exhibit clumping in the heavy duty liquid laundry matrix.

[0233] Example 20. Crosslinked chitosan delivery particles modified in situ with 50 mol% neutralized CD9055, 5.5 mol% SR268, and 10% KPS by weight of chitosan A chitosan stock solution was prepared by dispersing 155.7 g of chitosan ChitoClear in 3304 g of deionized water while mixing in a jacketed reactor. 1.56 g of potassium persulfate was added. The pH of the chitosan dispersion solution was then adjusted to 5.84 using 57.37 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, then to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze the ChitoClear. After the 90-minute hydrolysis step, the temperature was then reduced to 25°C. The pH of the acid-treated chitosan solution was 5.82.

[0234] The aqueous phase is prepared by mixing 432.5 g of the chitosan stock solution in a jacketed reactor at 25°C. The oil phase is prepared by mixing 110.0 g of fragrance and 27.3 g of isopropyl myristate with 4.15 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion of the desired particle size. The emulsion is heated to 60°C for 45 minutes, then to 95°C for 60 minutes. Once at 95°C, a solution of 9.29g CD9055, 9.29g RO water, and 10.22g 21.5% NaOH (prepared in an ice bath) was added to the slurry over 1 minute, then 1.95g SR268 was added over 1 minute, then held at 95°C for 180 minutes, then 1.96g potassium persulfate was added over 1 minute, then held at 95°C for 180 minutes. The temperature was then reduced to 25°C in 90 minutes. The formed capsules have a median particle size of 30.26 microns.

[0235] Example 21. Crosslinked chitosan delivery particles modified with CD9055, SR268, and KPS A modified chitosan solution was prepared by dispersing 42.11 g of chitosan powder in 840.00 g of water at 70°C. The pH of the chitosan solution was then adjusted to 4.85 using 11.06 g of glacial acetic acid. 35.82 g of CD9055, an acidic acrylate oligomer, was then added to the chitosan mixture and mixed at 70°C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the resulting modified chitosan solution was 3.86.

[0236] 266.7 g of the above modified chitosan solution was placed in a jacketed reactor at 25° C., and then 18.84 g of 21.5% caustic soda solution was used at room temperature to adjust the pH of the chitosan solution to 9.27. Then, a potassium persulfate solution containing 2.06 g of potassium persulfate and 50 g of water was added to the chitosan solution to form an aqueous phase.

[0237] The oil phase is prepared by mixing 99.71 g of perfume, 2.72 g of Takenate D110 and 24.93 g of isopropyl myristate in a beaker at 25°C.

[0238] The oil phase is added to the water phase under high shear at room temperature over a period of time to obtain an emulsion.

[0239] The emulsion was heated to 70°C, and then 13g of SR268 was added to the emulsion. The emulsion was then heated to 90°C in 60 minutes and held for 8 hours to harden the walls. The emulsion was then cooled to 25°C in 90 minutes. The resulting encapsulates were in the form of a water slurry and had a median particle size of 43.94 microns. The QFO and 1-week leakage of the capsule slurry were 0.13% and 3.27%, respectively. The prepared slurry did not exhibit agglomeration in a heavy-duty liquid laundry matrix.

[0240] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0241] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest, or disclose any such invention, either alone or in combination with any other reference or references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control.

[0242] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A processing composition comprising a processing aid and a population of delivery particles, The delivery particle comprises a core and a shell surrounding the core; the core comprises a benefit agent; the shell comprises a polymeric material that is the reaction product of modified chitosan and at least one electrophile; The modified chitosan comprises a reaction product of chitosan and a modifying compound; The treating composition wherein the modifying compound comprises an epoxide, an aldehyde, or an α,β-unsaturated compound.

2. The treatment composition of claim 1 , wherein the modifying compound comprises a cationic group, an anionic group, a non-ionic group, or a mixture thereof.

3. the modifying compound comprises a cationic group, an anionic group, or a mixture thereof; More preferably, the treatment composition according to claim 1 or 2 comprises an anionic group.

4. The modifying compound may have an acidic group, a hydroxyl group, a quaternary ammonium group, or a mixture thereof; A treatment composition according to any one of claims 1 to 3, which preferably comprises acidic groups.

5. the modified compound comprises an α,β-unsaturated compound; The treatment composition according to any one of claims 1 to 4, wherein the α,β-unsaturated compound is preferably an α,β-unsaturated carbonyl compound.

6. the modified compound comprises an α,β-unsaturated compound; the α,β-unsaturated compound is selected from the group consisting of acrylates, alkyl acrylates, α,β-unsaturated esters, acrylic acid, acrylamides, vinyl ketones, vinyl sulfones, vinyl phosphonates, acrylonitrile, or combinations thereof; Preferably, the α,β-unsaturated compound is acrylic acid, acrylic acid salts, acrylates, alkyl acrylates, α,β-unsaturated esters, maleic acid, vinyl sulfonic acid, 2-carboxyethyl acrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylamide, (2-(acryloyloxy)ethyl)trimethylammonium salts, (3-(methacryloylamino)propyl)trimethylammonium salts, N,N-dialkylaminoalkyl acrylates, 6. The treatment composition of claim 1, wherein the alkyl acrylate is selected from the group consisting of vinyl acrylate, N,N-dialkylaminoalkylacrylamide, (3-acrylamidopropyl)trimethylammonium salt, acrylamide, acrylamide salt, 3-sulfopropyl acrylate salt, 2-acrylamido-2-methyl-1-propanesulfonic acid and salts thereof, quaternized vinylimidazole, diallyldialkylammonium salt, vinylamine, vinyl ketone, vinyl sulfone, vinyl phosphonate, acrylonitrile, and combinations thereof.

7. The modifying compound may be glycidyl trimethylammonium salt, glycidyl isopropyl ether, glycidyl methacrylate, furfuryl glycidyl ether, glycidol, 1,4-butanediol diglycidyl ether, 2-ethylhexyl glycidyl ether, (3-glycidyloxypropyl)trimethoxysilane, poly(ethylene glycol) diglycidyl ether, trimethylolpropane triglycidyl ether, glutaraldehyde, alginic aldehyde, acrylic acid, acrylates, maleic acid, vinyl sulfonic acid, 2-carboxyethyl acrylate, 2-(2-oxo-1-imidazolidinyl)ethyl meth ...

7. The treatment composition of any one of claims 1 to 6, comprising a material selected from the group consisting of (2-(acryloyloxy)ethyl)methacrylamide, (2-(acryloyloxy)ethyl)trimethylammonium salt, (3-(methacryloylamino)propyl)trimethylammonium salt, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, (3-acrylamidopropyl)trimethylammonium salt, 3-sulfopropyl acrylate salt, 2-acrylamido-2-methyl-1-propanesulfonic acid and salts thereof, quaternized vinylimidazole, diallyldialkylammonium salt, vinylamine, and combinations thereof.

8. the chitosan contains free amine moieties; and a molar ratio of the modifying compound to the free amine moieties of the chitosan of 0.1% to 100%; The treatment composition according to any one of claims 1 to 7, preferably from 10% to 100%, more preferably from 10% to 90%, even more preferably from 25% to 90%, even more preferably from 25% to 75%.

9. A treatment composition according to any one of claims 1 to 8, wherein the shell comprises at least 18%, preferably at least 21% by weight of the shell of the modified chitosan.

10. The modified chitosan has a weight average molecular weight of about 100 kDa to about 600 kDa; 10. The treatment composition according to any one of claims 1 to 9, characterized by a weight average molecular weight of preferably from about 100 kDa to about 500 kDa, more preferably from about 100 kDa to about 400 kDa, more preferably from about 100 kDa to about 300 kDa, even more preferably from about 100 kDa to about 200 kDa.

11. A processing composition comprising a processing aid and a population of delivery particles, The delivery particle comprises a core and a shell surrounding the core; the core comprises a benefit agent; the shell comprises a polymeric material that is the reaction product of at least one modified chitosan and at least one electrophile; The population of delivery particles comprises: forming an aqueous phase by dissolving or dispersing chitosan in an aqueous acidic medium at a pH of 6.5 or less and at a temperature of at least 25°C; the chitosan having free amine moieties; forming an oil phase comprising combining at least one benefit agent and at least one electrophile, preferably at least one polyisocyanate, optionally with an additive oil; forming an emulsion by mixing the oil phase into an excess of the aqueous phase under high shear agitation, thereby forming droplets of the oil phase dispersed in the aqueous phase; to the aqueous phase and / or the emulsion, preferably at least to the aqueous phase, adding the modifying compound comprising one or more of an epoxide, an aldehyde, or an α,β-unsaturated compound; reacting the modifying compound with the free amine moieties of the chitosan; Optionally, adjusting the pH of the emulsion to a pH of 4 or greater; heating the emulsion to at least 40°C for a time sufficient to form a shell at the interface of the droplets with the aqueous phase, the shell surrounding the core; A treatment composition obtainable by a method comprising:

12. A processing composition comprising a processing aid and a population of delivery particles, The delivery particle comprises a core and a shell surrounding the core; the core comprises a benefit agent; the shell comprises a polymeric material that is the reaction product of at least one modified chitosan and at least one electrophile; The modified chitosan comprises a reaction product of chitosan and a modifying compound; the modifying compound comprises an epoxide, an aldehyde, or an α,β-unsaturated compound covalently bonded to the chitosan; The population of delivery particles comprises: dissolving or dispersing chitosan in an aqueous phase, said chitosan having an amine moiety; combining the aqueous phase with the modifying compound; Optionally, adjusting the pH of the aqueous phase to pH 3.0 or higher, preferably pH 3.0 to pH 6; Optionally, adjusting the temperature of the aqueous phase to 25°C or higher; mixing the aqueous phase for a period of time, thereby forming a modified chitosan, the modifying compound is covalently attached to the amine moiety of the chitosan via a C-N bond; the modified chitosan remains dissolved in the aqueous phase; providing an oil phase comprising at least one benefit agent comprising an oil and at least one electrophile, preferably at least one polyisocyanate, dissolved optionally with a second oil; forming an emulsion by mixing the oil phase into the aqueous phase under high shear agitation, thereby forming droplets of the oil phase and the benefit agent dispersed in the aqueous phase; heating the emulsion to at least 40°C for a time sufficient to form a shell at the interface of the droplets with the aqueous phase, the shell surrounding the core; A treatment composition obtainable by a method comprising:

13. The method capable of obtaining the population of delivery particles further comprises adding a redox initiator to the aqueous phase or the emulsion; The treatment composition of any one of claims 1 to 12, wherein the redox initiator comprises a persulfate, a peroxide, or a combination thereof.

14. The treatment composition of any one of claims 1 to 13, wherein the modifying compound comprises a cationic group and / or an anionic group.

15. The treatment composition of any one of claims 1 to 14, wherein the delivery particle comprises from about 1% to about 25% of the shell by weight of the delivery particle.

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