Treatment composition with modified chitosan-based delivery particles

Abstract

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

Description

Technical Field

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

[0002] Delivery particles, particularly core / shell delivery particles, are a convenient way to deliver beneficial agents in treatment compositions such as laundry products. For environmental reasons, it may be desirable to use delivery particles having walls made of natural source materials and / or biodegradable materials. In addition, it is preferred that such delivery particles exhibit effective encapsulation, good product compatibility, and good deposition and performance under target use conditions.

[0003] Chitosan is a polysaccharide known for use in the shells of delivery particles, but chitosan 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. In addition, when dissolved, chitosan can form viscous solutions that are difficult to handle or process. Additionally, due to its cationic charge, chitosan can interact with anionic materials and surfaces, which can lead to aggregation or other physical instabilities, particularly in certain product matrices such as liquid laundry detergents.

[0004] Accordingly, there is a need for improved treatment compositions comprising delivery particles that are at least partially derived from natural materials and / or biodegradable materials and that exhibit good product compatibility and / or performance. Summary of the Invention

[0005] The present disclosure relates to treatment compositions comprising chitosan-based core / shell delivery particles, wherein the chitosan used to prepare the shell is characterized by a specific molecular weight.

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

[0007] The present disclosure also relates to a method of preparing a treatment composition, the method comprising the steps of: providing a base composition, wherein the base composition comprises a treatment aid; and combining a population of delivery particles with the base composition, wherein the delivery particles are as described herein.

[0008] The present disclosure also relates to a method of treating a surface, the method comprising the step of: contacting the surface (preferably a fabric) with a treatment composition as described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The figures herein are illustrative in nature but are not intended to be limiting.

[0010] Figure 1 is a ζ-potential plot showing delivery particles prepared according to the present invention. DETAILED DESCRIPTION

[0011] The present disclosure relates to a treatment composition comprising delivery particles having a shell made at least in part of a chitosan-based material. Specifically, the delivery particles comprise a shell that comprises a reaction product of a modified chitosan and an electrophile that can act as a crosslinking agent. The modified chitosan can alter the resulting surface charge of the delivery particles, which in turn can advantageously affect product compatibility and / or performance.

[0012] The modified chitosan can be prepared by reacting a chitosan polymer with a modifying compound that can form a C-N covalent bond with an amine group of the chitosan, particularly a primary or secondary amine. The modifying compound can be selected from an epoxide compound, an aldehyde compound, or an α,β-unsaturated compound. The epoxide compound, aldehyde compound, or α,β-unsaturated compound can be anionic, cationic, or nonionic. The modifying compound can contain an acidic group, a hydroxyl group, or a quaternary ammonium group.

[0013] Without being bound by theory, it is believed that modifying the chitosan results in a modified surface charge of the delivery particles compared to particles made of unmodified chitosan. Accordingly, the final surface charge of the delivery particles can be modified and tailored by the selection of the modifying compound and / or the timing of its addition to, for example, an aqueous phase or an emulsion. Specifically, the surface charge can be modified when the modifying compound is selected to have a cationic group or anionic group.

[0014] Additionally or alternatively, modification of the chitosan can alter the solubility of the chitosan, which can, for example, promote improved particle formation and / or processability by reducing viscosity.

[0015] The chitosan, delivery particles, treatment composition, and related methods of the present disclosure are discussed in more detail below.

[0016] As used herein, the articles "a" and "an" when used in the claims are understood to mean one or more of the things claimed or described. As used herein, the terms "comprising," "including," and "containing" are intended to be non-limiting. The compositions of the present disclosure can comprise the components of the present disclosure, consist essentially of, or consist of the components of the present disclosure.

[0017] The term "substantially free of" can be used herein. This means that the indicated material is present in very small amounts, not intentionally added as part of the composition to form the composition, or preferably the indicated material is not present at levels detectable by analysis. This means compositions that include those in which the indicated material is present only as an impurity in one of the other materials intentionally added. If present at all, the indicated material can be present at levels less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0018] As used herein, "consumer product" means baby care products, beauty care products, fabric and home care products, household care products, feminine care products, and / or health care products or devices intended to be used or consumed in a sold form and not intended for subsequent commercial manufacture or modification. Such products include, but are not limited to, diapers, bibs, wipes; products and / or methods related to the treatment of human hair, which treatment includes bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; skin care, including the application of creams, lotions, and other topically applied products for consumer use; and shaving products, products and / or methods related to the treatment of fabrics, hard surfaces, and any other surfaces in the fabric and home care areas, including: air care, automotive care, dishwashing, fabric conditioning (including softening), laundry detergency, laundry washing and rinse additives and / or care, hard surface cleaning and / or treatment, and other cleaning for consumer or business use; products and / or methods related to toilet paper, facial tissue, paper handkerchiefs, and / or paper towels; tampons, feminine sanitary napkins; adult incontinence products; products and / or methods related to oral care, including toothpaste, teething gels, teeth cleaning, denture adhesives, teeth whitening; over-the-counter health care products, including cough and cold medicines; pest control products; and water purification.

[0019] As used herein, the phrase "fabric care composition" includes compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry detergent compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-wash compositions, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents incorporated in or on a porous substrate or nonwoven sheet, and other suitable forms that would be apparent to one of ordinary skill 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 cycle or wash cycle of a laundry operation.

[0020] For ease of reference in this specification and the claims, the term "monomer" as used herein with respect to the structural material of the wall polymer forming the delivery particles is to be understood as monomers, but also includes oligomers and / or prepolymers formed from the particular monomers.

[0021] As used herein, the term "water-soluble material" means a material that has a solubility of at least 0.5 wt% in water at 60 °C.

[0022] As used herein, the term "oil-soluble" means a material that has a solubility of at least 0.1 wt% in the core of interest at 50 °C.

[0023] As used herein, the term "oil-dispersible" means a material that can be dispersed in the core of interest at 50 °C at least 0.1 wt% without visible agglomerates.

[0024] As used herein, unless otherwise specified, "delivery particles", "particles", "enclosures", "microcapsules", and "capsules" are used interchangeably. As used herein, these terms generally refer to core / shell delivery particles.

[0025] Unless otherwise specified, all component or composition levels are with respect to the active portion of that component or composition and do not include impurities that may be present in commercially available sources of such components or compositions, such as residual solvents or by-products.

[0026] Unless otherwise specified, all temperatures herein are in degrees Celsius (°C). Unless otherwise specified, all measurements herein are made at 20 °C and atmospheric pressure.

[0027] In all embodiments of the present disclosure, unless otherwise specifically stated, all percentages are by weight of the total composition. Unless otherwise specifically stated, all ratios are weight ratios.

[0028] It should be understood that every upper numerical limit given throughout this specification includes every lower numerical limit, as if such lower numerical limits were expressly written herein. Every lower numerical limit given throughout this specification will include every upper numerical limit, as if such upper numerical limits 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.

[0029] Treatment composition

[0030] The present disclosure relates to treating compositions (or simply referred to as "compositions" as used herein). The compositions of the present disclosure may comprise a population of delivery particles and a processing aid, each of which is described in more detail below. The treating composition can be used in the methods of treating surfaces (such as fabrics) described herein.

[0031] The treating composition is preferably a consumer product composition. The consumer product compositions of the present disclosure can be used in baby care products, beauty care products, fabric care products, home care products, household care products, feminine care products, and / or health care applications. The consumer product composition can be used to treat surfaces such as fabrics, hair, or skin. The consumer product composition is intended to be used or consumed in its sold form. The consumer product compositions of the present disclosure are generally not intended for subsequent commercial manufacturing or modification.

[0032] The consumer product composition can 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, preferably a fabric care composition.

[0033] The consumer product composition can be a fabric care composition, such as a laundry detergent composition (including heavy-duty liquid detergents or unit-dose products), a fabric conditioning composition (including liquid fabric softening and / or enhancing compositions), a laundry additive, a fabric pretreatment composition (including sprays, pourable liquids, or sprays), a fabric freshener composition (including sprays), or a mixture thereof. The treating composition is preferably a fabric conditioning composition, and even more preferably a liquid fabric conditioning composition.

[0034] The composition can be a beauty care composition, such as a hair treatment product (including shampoos and / or conditioners), a skin care product (including creams, lotions, or other topically applied products for consumer use), a shaving care product (including shaving lotions, foams, or pre- or post-shave treatments), a personal cleansing product (including liquid bath products, liquid hand soaps, and / or bar soaps), a deodorant and / or antiperspirant, or a mixture thereof.

[0035] The composition can be a home care composition, such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other cleaning for consumer or institutional use.

[0036] The treatment composition can be in the form of a liquid composition, a particulate composition, an aqueous colloid, a single-compartment sachet, a multi-compartment sachet, a soluble sheet, a lozenge or bead, a fibrous article, a tablet, a bar, a strip, a wafer, a foam / mousse, a nonwoven sheet, or a mixture thereof.

[0037] The treatment composition can be in liquid form. The liquid composition can preferably contain about 50% to about 97%, preferably about 60% to about 96%, more preferably about 70% to about 95%, or even about 80% to about 95% water by weight of the fabric treatment composition. The liquid composition can be a liquid fabric conditioner. The liquid can be packaged in a pourable bottle. The liquid can be packaged in an aerosol can or other spray bottle. Suitable containers are described in more detail below.

[0038] The treatment composition can be in solid form. The composition can be in the form of beads or lozenges, which can be made from a liquid melt. The composition can be an extruded product. The treatment composition can be in the form of a powder or granule.

[0039] The composition can be in the form of a combined dose product such as a tablet, sachet, sheet, or fibrous article. Such sachets typically include a water-soluble film, such as a polyvinyl alcohol water-soluble film, which at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition can be encapsulated in a single-compartment sachet or a multi-compartment sachet. The multi-compartment sachet can have at least two, at least three, or at least four compartments. The multi-compartment sachet can include compartments that are side-by-side and / or stacked. The composition contained in the sachet or its compartments can be liquid, solid (such as a powder), or a combination thereof. The sachet composition can have a relatively small amount of water, for example less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% water by weight of the detergent composition.

[0040] The treatment composition can be in spray form and can be dispensed from a bottle, for example, via a trigger sprayer and / or an aerosol container with a valve.

[0041] The treatment composition can have a viscosity at 20 s -1 and 21 °C of from 1 centipoise to 1500 centipoise (1 mPa·s to 1500 mPa·s), from 100 centipoise to 1000 centipoise (100 mPa·s to 1000 mPa·s), or from 200 centipoise to 500 centipoise (200 mPa·s to 500 mPa·s).

[0042] The treatment composition of the present disclosure may be characterized by a pH of from about 2 to about 12, or from about 2 to about 8.5, or from about 2 to about 7, or from about 2 to about 5. The treatment composition of the present disclosure may have a pH of from about 2 to about 4, preferably from about 2 to about 3.7, more preferably from about 2 to about 3.5, and is preferably in the form of an aqueous liquid. It is believed that such pH levels are beneficial for the stability of the quaternary ammonium ester compound, if present. On the other hand, the detergent composition is typically characterized by a pH of from about 7 to about 12, preferably from about 7.5 to about 11. The pH of the composition is determined by dissolving / dispersing the composition in deionized water at about 20 °C to form a 10% strength solution.

[0043] The additional components and / or features of the composition are discussed in more detail below.

[0044] Delivery particle population

[0045] 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 beneficial agent and optionally a dispensing modifier. The core may be liquid or solid at room temperature, preferably liquid.

[0046] 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% by weight of the composition of the delivery particles. The composition may comprise a sufficient amount of the delivery particles to provide from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 2% by weight of the composition of the encapsulated beneficial agent, which may preferably be a fragrance ingredient. When discussing the amount or weight percentage of the delivery particles herein, it means the sum of the wall material and the core material.

[0047] The population of delivery particles according to the present disclosure may be characterized by a volume weighted median particle size of from about 1 micron to about 100 microns, preferably from about 10 microns to about 100 microns, preferably from about 15 microns to about 50 microns, more preferably from about 20 microns to about 40 microns, and even more preferably from about 25 microns to about 35 microns. For certain compositions, it may be preferred that the population of delivery particles is characterized by a volume weighted median particle size of from about 1 micron to about 50 microns, preferably from about 5 microns to about 20 microns, more preferably from about 10 microns to about 15 microns. Different particle sizes can be obtained by controlling the droplet size during the emulsification process.

[0048] The characteristics of the delivery particles can lie in a core-to-shell ratio of up to 99:1, or even 99.5:0.5, based on weight. The shell can be present at a level of about 1% to about 25%, preferably about 1% to about 20%, preferably about 1% to 15%, more preferably about 5% to about 15%, even more preferably about 10% to about 15%, even more preferably about 10% to about 12% by weight of the delivery particles. The shell can be present at a content of at least 1%, preferably at least 3%, more preferably at least 5% by weight of the delivery particles. The shell can be present at a level of up to about 25%, preferably up to about 20%, more preferably up to about 15%, more preferably up to about 12% by weight of the delivery particles.

[0049] Delivery particles prepared with chitosan generally exhibit a positive ζ potential. Such capsules have improved deposition efficiency on surfaces (such as certain fabrics, like cotton) and / or improved compatibility in product formulations. At higher pH values, the particles can be made non-ionic or anionic. The delivery particles can have a surface charge due to charged domains or charged side groups from the compositions and methods of the present invention. When the modifying compound has a cationic group or anionic group, the regulation of the surface charge of the shell can be effectively achieved. By the selection of the modifying compound and pH, the delivery particles can even be made non-ionic or anionic.

[0050] The delivery particles can be cationic in nature, preferably cationic at a pH of 4.5. The characteristics of the delivery particles can lie in a ζ potential of at least 15 millivolts (mV) at a pH of 4.5. The delivery particles can be made to have a ζ potential of at least 15 millivolts (mV) at a pH of 4.5, or even a ζ potential of at least 40 mV at a pH of 4.5, or even a ζ potential of at least 60 mV at a pH of 4.5.

[0051] The characteristics of the delivery particles can lie in a ζ potential of 200 mV or less, preferably 150 mV or less, more preferably 100 mV or less at a pH of 4.5. Figure 1 The ζ potentials of various delivery particles (including particles according to the present disclosure) at various pH values are shown.

[0052] The delivery particles of the present disclosure include a shell surrounding a core. (As used herein, "shell" and "wall" can be used interchangeably with respect to delivery particles, unless otherwise indicated.) The shell contains a polymeric material. The polymeric material is a reaction product of chitosan (usually modified chitosan) and an electrophile.

[0053] Chitosan can include anionically modified chitosan, cationically modified chitosan, or a combination thereof. Modifying chitosan in an anionic and / or cationic manner changes the characteristics of the shell of the delivery particles, such as by changing the surface charge and / or ζ potential, which affects the deposition efficiency and / or formulation compatibility of the particles.

[0054] The modified chitosan in the shell of the delivery particles for the present disclosure can be prepared from chitosan, which can 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 electrophile.

[0055] The modified chitosan can comprise a reaction product of chitosan and a modifying compound. Chitosan generally has a free amine moiety (e.g., -NH2). The modified chitosan according to the present disclosure can be produced by combining chitosan with a modifying compound that can form a C-N covalent bond with the amine moiety of chitosan. The modifying compound generally comprises an epoxide, an aldehyde, or an α,β-unsaturated compound.

[0056] The modifying compound can comprise a cationic group, an anionic group, a non-ionic group, or a mixture thereof. The modifying compound can preferably comprise a cationic group, an anionic group, or a mixture thereof. The modifying compound can preferably comprise an anionic group, which can reduce the surface charge of the resulting particles.

[0057] The modifying compound can comprise an acidic group, a hydroxyl group, a quaternary ammonium group, or a mixture thereof, preferably an acidic group.

[0058] The modifying compound comprises an α,β-unsaturated compound, preferably wherein the α,β-unsaturated compound is an α,β-unsaturated carbonyl compound.

[0059] The modifying compound can be an α,β-unsaturated compound, preferably 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 selected from the group consisting of: acrylic acid, acrylate, acrylate ester, 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-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, (3-acrylamidopropyl)trimethylammonium salt, acrylamide, acrylamide salt, 3-sulfopropyl acrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, quaternized vinylimidazole, diallyldialkylammonium salt, vinylamine, vinyl ketone, vinyl sulfone, vinyl phosphonate, acrylonitrile, and combinations thereof.

[0060] The modified compound may comprise a material selected from the group consisting of glycidyltrimethylammonium salts, 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, alginaldehyde, acrylic acid, acrylate salts, maleic acid, vinylsulfonic 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, N,N-dialkylaminoalkyl acrylamides, (3-acrylamidopropyl)trimethylammonium salts, 3-sulfopropyl acrylate salts, 2-acrylamide-2-methyl-1-propanesulfonic acid and its salts, quaternized vinylimidazoles, diallyldialkylammonium salts, vinylamines, and combinations thereof.

[0061] Prior to modification, chitosan typically contains free amine (e.g., -NH2) moieties, which can react with the modifying compound. Thus, it may be useful to select an appropriate amount of the modifying compound in order to run the reaction effectively and / or tune the resulting surface charge of the delivery particles. For example, it may be advantageous to select the amount of material such that the molar ratio of the modifying compound to the free amine moieties of chitosan is from 0.1% to 100%, 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%.

[0062] The modified chitosan according to the present disclosure is soluble at pH values above 6.0, even above 8.0, and even further above 10.0. The increased solubility can facilitate improved particle formation and / or improved processing, e.g., by providing a solution with a specific viscosity.

[0063] 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. It can be added to the aqueous phase or the emulsion. The water-soluble or dispersible modifying compound can be added to the aqueous phase or the emulsion at room temperature or an elevated temperature. The modifying compound can be added during emulsification (such as after milling), or after emulsification at an elevated temperature. The modifying compound, i.e., an epoxide, aldehyde, or α,β-unsaturated compound, reacts with the free amine moieties of chitosan.

[0064] The modified chitosan of the present disclosure enables the formation of a reactive polymeric shell having a high proportion of modified chitosan moieties in the polymer. Such a high weight percentage proportion of modified chitosan in the modified chitosan delivery particles enables an improved capsule system that was not achievable with previous interfacial encapsulation methods. The methods and compositions of the present disclosure differ from coagulation-based ionic methods in that the polymeric materials of the present disclosure are covalently crosslinked.

[0065] Chitosan can be characterized by a weight average molecular weight of from about 100 kDa to about 600 kDa. Preferably, chitosan is characterized by a weight average molecular weight (Mw) of from about 100 kDa to about 500 kDa, 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. Methods for determining the molecular weight and related parameters of chitosan are provided in the Test Methods section below and use gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) techniques. Selecting chitosan with a preferred weight average molecular weight can result in capsules with suitable shell formation and / or desired processability.

[0066] Chitosan can be characterized by a degree of deacetylation of at least 50%, preferably from about 50% to about 99%, more preferably from about 75% to about 90%, and even more preferably from about 80% to about 85%. The degree of deacetylation affects the solubility of chitosan, which in turn affects its reactivity or behavior during the formation of the particle shell. For example, too low a degree of deacetylation (e.g., below 50%) can result in relatively insoluble and relatively unreactive chitosan. A relatively high degree of deacetylation can result in very soluble chitosan, leading to relatively little chitosan traveling to the oil / water interface during shell formation.

[0067] Chitosan can preferably be acid-treated chitosan. For example, chitosan (which may be referred to as raw chitosan or parent chitosan before acid treatment) can preferably be acid-treated at a temperature of from about 25°C to about 99°C, preferably from about 75°C to about 95°C, at a pH of 6.5 or lower for at least one hour, preferably from about one hour to about three hours. The acid can be selected from strong acids (such as hydrochloric acid), organic acids (such as formic acid or acetic acid), or mixtures thereof. Chitosan can preferably be acid-treated at a pH of from 2 to 6.5, preferably from 3 to 6, or even from 4 to 6.

[0068] As described 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 can comprise a polyurea resin, where the polyurea resin comprises the reaction product of a polyisocyanate and chitosan.

[0069] The polyisocyanate materials useful in the present disclosure are to be understood as isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. "Polyisocyanate" is intended to denote a material or compound containing two or more isocyanate moieties. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended to be covered by the term "polyisocyanate" herein. The polyisocyanates useful in the present disclosure include isocyanate monomers, oligomers or prepolymers having at least two isocyanate groups, or their dimers or trimers. Preferred crosslinking can be achieved using polyisocyanates having at least three functional groups.

[0070] Aromatic polyisocyanates may be preferred; however, aliphatic polyisocyanates and their blends can 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 crosslinking agent may comprise a mixture of aromatic polyisocyanates and aliphatic polyisocyanates.

[0071] Polyisocyanates, when aromatic, may be but are not limited to methylene diphenyl diisocyanate, toluene diisocyanate, tetramethylxylene diisocyanate, polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name RC), trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name L75), naphthalene-1,5-diisocyanate, benzene diisocyanate, or trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name D-110N).

[0072] Aliphatic polyisocyanates may include the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate, the trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or the biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name N 100).

[0073] Derivatives of polyisocyanates may include oligomers or polymers of isocyanate monomers. As a non-limiting example, polyisocyanates may preferably include oligomers or polymers of diphenylmethane diisocyanate (MDI), such as MR-Light.

[0074] The polyisocyanate can preferably be selected from the group consisting of: polyisocyanurates of toluene diisocyanate; trimethylolpropane adducts of toluene diisocyanate; trimethylolpropane adducts of phthalic diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethyldimethylaniline diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; their derivatives (such as their prepolymers, oligomers and / or polymers); and combinations thereof.

[0075] The electrophile need not be limited to polyisocyanates. The electrophile can include monomers, oligomers and prepolymers having an electrophilic moiety, and such electrophilic moieties can include any one of formyl, keto, carboxyl, isocyanate, carboxylate, acyl halide, amide carboxylic anhydride, alkyl halide, epoxide, sulfonyl halide, chlorophosphate, β-unsaturated carbonyl, α,β-unsaturated nitrile, trifluoromethanesulfonate, p-toluenesulfonate and α,β-unsaturated methanesulfonyl groups.

[0076] Suitable polyfunctional electrophiles can include glutaraldehyde, succinaldehyde, glyoxal; glyoxal trimer, paraformaldehyde, bis(dimethyl)acetal, bis(diethyl)acetal, polymerized dialdehydes (such as oxidized starch), low molecular weight bifunctional aldehydes, 1,3-propanedial, 1,4-butanedial, 1,5-pentanedial or 1,6-hexane.

[0077] Additional co-crosslinking agents such as polyfunctional amines and / or polyamines such as diethylenetriamine (DETA), polyethyleneimine, polyvinylamine or mixtures thereof can also be used to strengthen the particle shell. Acrylates can also be used as additional co-crosslinking agents, for example for strengthening the shell.

[0078] Polymeric materials can be formed in a reaction where 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 the desired ratio of the biopolymer to the electrophile can provide the desired ductility benefit as well as improved biodegradability. It may be preferred that at least 21 wt% of the shell consists of a portion derived from chitosan, preferably derived from modified chitosan and / or acid-treated chitosan. The weight percentage of chitosan in the shell can be from about 21% to about 95% of the shell. Based on weight, the ratio of chitosan in the aqueous phase to the electrophile (preferably polyisocyanate) in the oil phase can be 21:79 to 90:10, or even 1:2 to 9:1, or even 1:1 to 7:1. The shell can contain chitosan in an amount of 21 wt% or even higher, preferably from about 21 wt% to about 90 wt%, or even 21 wt% to 85 wt%, or even 21 wt% to 75 wt%, or 21 wt% to 55 wt% of the total shell of chitosan. The chitosan in this paragraph is preferably modified according to the present disclosure and / or is acid-treated chitosan.

[0079] A population of delivery particles is prepared by or can be obtained using a method comprising the steps of: forming an aqueous phase by dissolving or dispersing chitosan in an aqueous acidic medium at a pH of 6.5 or lower and a temperature of at least 25 °C, the chitosan having a free amine moiety; forming an oil phase comprising combining at least one beneficial 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 the 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 the 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, the modifying compound reacting with the free amine moiety 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 at the interface of the droplets and the aqueous phase, the shell surrounding the core.

[0080] A population of delivery particles is prepared by a method comprising the following steps or can be obtained using a method comprising the following steps: dissolving or dispersing chitosan in an aqueous phase, the chitosan having an amine moiety; combining the aqueous phase and 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 greater; mixing the aqueous phase for a period of time to form modified chitosan, wherein the modifying compound is covalently bonded via a C-N bond to the amine moiety of the chitosan, and wherein the modified chitosan remains dissolved in the aqueous phase; providing an oil phase, comprising dissolving at least one beneficial agent comprising an oil and at least one electrophile, preferably at least one polyisocyanate, optionally together 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 beneficial 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 and the aqueous phase, the shell surrounding the core.

[0081] After modifying the chitosan with the modifying compound, if desired, the pH of the aqueous phase comprising the modified chitosan solution can be adjusted to above 6.5, or even above 7, or even above 9.

[0082] The molar ratio of the modifying compound to the free amine moiety of the chitosan can preferably be from 0.1% to 100%, preferably 10% to 100%, more preferably 25% to 90%.

[0083] The method for preparing the delivery particles can comprise forming an aqueous phase by dissolving or dispersing chitosan and the modifying compound in an aqueous acidic medium at a pH of 6.5 or lower and a temperature of at least 25 °C.

[0084] The modifying compound, preferably a water-soluble or water-dispersible modifying compound, can be added to the aqueous phase and / or the emulsion at room temperature or an elevated temperature, preferably to the aqueous phase. The modifying compound can be added during emulsification (such as after milling) or after emulsification at an elevated temperature. As described in more detail above, the modifying compound contains a cationic group, an anionic group or a non-ionic group, typically selected from one or more acidic groups or quaternary ammonium functional groups. The modifying compound, namely an epoxide, an aldehyde or an α,β-unsaturated compound, reacts with the free amine moiety of the chitosan. The modifying compound is covalently bonded via a C-N bond to the primary or secondary amine moiety of the chitosan and helps to keep the modified chitosan dissolved in the aqueous phase even at high pH.

[0085] The pH of the emulsion can 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 to 10 or higher. The emulsion can be heated to at least 40 °C for a time sufficient to form a shell at the interface of the droplets and the aqueous phase such that the shell surrounds the core. The delivery particles formed according to the methods of the present disclosure, particularly when the modifying compound has a cationic or anionic group, result in the shell of the delivery particles having a surface charge. Such surface-charged delivery particles can have a ζ potential of 200 mV or less, preferably 150 mV or less at pH 4.5.

[0086] The emulsion can 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 of the droplets and the aqueous phase. The shell is a polymeric material that is a reaction product of an electrophile (e.g., polyisocyanate) and modified chitosan, and the shell surrounds droplets of the oil phase containing the beneficial agent. The target droplet size can be from 0.1 micron to 100 microns, or even from 0.5 micron to 50 microns.

[0087] To dissolve or disperse chitosan, chitosan can be processed by acid treatment at a pH less than 6.5 (such as a pH of 3 to pH 6) and a temperature of at least 25 °C, or even at least 60 °C, or even at least 80 °C. Depending on the pH and temperature, the time of acid treatment can be brief, but more typically will be at least one hour, or even at least 24 hours. Chitosan can 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%. Advantageously, chitosan has a weight average molecular weight of 600 kilodaltons (kDa) or less.

[0088] Chitosan can be modified by reacting it with a modifying compound containing an epoxide, an aldehyde, or an α,β-unsaturated compound. The resulting shell can be considered a reaction product of a polyurea as well as a polyisocyanate (e.g., containing any of an isocyanate monomer, oligomer, or prepolymer) and modified chitosan.

[0089] The population of delivery particles can be in the form of an aqueous slurry, or alternatively can be sprayed onto a substrate, or alternatively spray dried, thereby producing a polyurea-chitosan shell with additional chitosan deposited on the surface of the formed delivery particles. If not decanted, unreacted chitosan in the aqueous slurry can form additional chitosan deposited on the surface of the formed microcapsules.

[0090] A redox initiator (preferably comprising a persulfate or a peroxide) can be added to the aqueous phase and / or the emulsion. A redox initiator which may comprise a persulfate or a peroxide can be added to the acid-treated chitosan. In the in-situ variant, after combining the oil phase and the aqueous phase under high-shear stirring, the redox initiator can be added to the emulsion. The redox initiator advantageously depolymerizes the hydrolyzed chitosan or the modified chitosan, reducing the viscosity and thus facilitating the polymer formation of the shell during the capsule formation process. Although the redox initiator (peroxide or persulfate) can be introduced simultaneously with or even before the modifying compound, it is preferably completed the modification of chitosan with an epoxide, an aldehyde or an α,β-unsaturated compound before adding the redox initiator. The redox initiator is optionally 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 a peroxide, can be present at a level of about 0.1 wt% to about 99 wt% based on chitosan.

[0091] For clarity, there can be several variants of this method. By adding the modifying compound to the chitosan in the aqueous phase, the acidified chitosan solution can be treated with the modifying compound. Additionally or alternatively, the modifying compound can be added to the emulsion. Similarly and independently, an optional redox initiator can be added to the acidified chitosan solution (e.g., the aqueous phase) or to the emulsion in the emulsification step after adding the oil phase. The redox initiator can be added sequentially before, simultaneously with, or after the modification step, wherein the modifying compound comprises an epoxide, an aldehyde or an α,β-unsaturated compound.

[0092] When tested according to test method OECD 301B, the shell can degrade by at least 50% after 20 days (or less). When tested according to test method OECD 301B, the shell can degrade at least 60% of its mass after 60 days (or less). When tested according to test method OECD 301B, the shell can preferably degrade at least 60% of its mass after 60 days (or less). The shell can degrade 30% to 100%, preferably 40% to 100%, 50% to 100%, 60% to 100% or 60% to 95% after 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, more preferably 14 days.

[0093] The delivery particles of the present disclosure include a core. The core contains a beneficial agent. The core optionally contains a partitioning modifier.

[0094] The core of the granule is surrounded by a shell. When the shell ruptures, the beneficial agent in the core is released. Additionally or alternatively, the beneficial agent in the core may diffuse out of the granule and / or the beneficial agent may be extruded. Suitable beneficial agents located in the core may include beneficial agents that provide beneficial effects to surfaces such as fabrics or hair.

[0095] The core may contain from about 5% to about 100% by weight of the core of the beneficial agent, which may preferably comprise a fragrance. The core may contain from about 45% to about 95%, preferably from about 50% to about 80%, more preferably from about 50% to about 70% by weight of the core of the beneficial agent, which may preferably comprise a fragrance.

[0096] The beneficial agent may comprise an aldehyde-containing beneficial agent, a ketone-containing beneficial agent, or a combination thereof. Such beneficial agents (e.g., aldehyde / ketone-containing fragrance raw materials) are known to provide preferred beneficial effects such as a fresh beneficial effect. The beneficial agent may comprise at least about 20%, preferably at least about 25%, more preferably at least about 40%, even more preferably at least about 50% by weight of the beneficial agent of an aldehyde-containing beneficial agent, a ketone-containing beneficial agent, or a combination thereof.

[0097] The beneficial agent may be a hydrophobic beneficial agent. Such agents are compatible with the oil phase commonly found in the delivery granules of the present disclosure.

[0098] The beneficial agent is selected to provide a beneficial effect under the preferred use of the treatment composition. The beneficial agent in the core may be selected from the group consisting of: fragrance materials, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin coolants, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleaching granules, silica granules, malodor attenuators, odor control materials, chelating agents, antistatic agents, softeners, insect and moth repellents, colorants, bases, disinfecting sheets and morphology control agents, smoothers, wrinkle control agents, hygiene treatment agents, disinfectants, microbial control agents, mildew control agents, mold control agents, antiviral agents, desiccants, soil release agents, detergents, fabric fresheners and freshness extenders, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color restoration / recovery agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, anti-wear agents, fabric integrity agents, anti-pilling agents, defoamers, ultraviolet protection agents, photo-fading inhibitors, anti-allergenic agents, enzymes, water repellents, fabric comfort agents, anti-shrink agents, anti-stretch agents, stretch recovery agents, skin care agents, synthetic or natural active substances, antibacterial active substances, antiperspirant active substances, cationic polymers, dyes, and mixtures thereof.

[0099] The beneficial agent in the core preferably includes an aroma material (or simply "aroma"), which may contain one or more perfume raw materials. The aroma is particularly suitable for encapsulation in the delivery particles described in the present invention, because the aroma-containing particles can provide a refreshing beneficial effect across multiple contact points.

[0100] As used herein, the term "perfume raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mol, and it can be used alone or in combination with other perfume raw materials to impart an odor, fragrance, essence or scent. Typical PRMs particularly include alcohols, ketones, aldehydes, esters, ethers, nitrites and olefins, such as terpenes. A list of common PRMs can be found in various references, such as "Perfume and Flavor Chemicals", Volumes I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology", Miller, P.M. and Lamparsky, D., Blackie Academic and Professional (1994).

[0101] PRMs can be characterized by their boiling point (B.P.) measured at normal pressure (760 mmHg), and their octanol / water partition coefficient (P), which can be described by logP and is determined according to the test method below. Based on these properties, PRMs can be classified as first quadrant, second quadrant, third quadrant or fourth quadrant perfumes, as described in more detail in U.S. Patent 6,869,923. Suitable first quadrant, second quadrant, third quadrant and fourth quadrant perfume raw materials are disclosed herein.

[0102] Perfume raw materials having a boiling point B.P. of less than about 250 °C and a logP of less than about 3 are called first quadrant perfume raw materials. First quadrant perfume raw materials are preferably limited to less than 30% of the aroma material.

[0103] The aroma may include perfume raw materials having a logP of about 2.5 to about 4. It should be understood that other perfume raw materials may also be present in the aroma.

[0104] The core of the delivery particles disclosed herein may contain a partitioning modifier, which can promote a more robust shell formation. The partitioning modifier can be combined with the perfume oil material of the core before incorporating the wall-forming monomer. The partitioning modifier can be present in the core at a level of 0% to 95%, preferably about 5% to about 55%, preferably about 10% to about 50%, more preferably about 20% to about 50%, even more preferably about 25% to about 50% by weight of the core.

[0105] The dispensing modifier may comprise a material selected from the group consisting of vegetable oils, modified vegetable oils, monoesters, diesters and triesters of C4-C 24 fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The dispensing modifier may preferably comprise isopropyl myristate or even consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably comprise castor oil and / or soybean oil. U.S. Patent Application Publication 20110268802, which is incorporated herein by reference, describes other dispensing modifiers that may be used in the delivery particles described herein.

[0106] In cases where the beneficial agent itself is not sufficient to serve as the oil phase or solvent, particularly during the process of forming the shell of the delivery particles for the wall-forming material, the oil phase may comprise a suitable carrier and / or solvent. In this sense, the oil is optional because the beneficial agent itself can sometimes be an oil. These carriers or solvents are typically oils, preferably having a boiling point greater than about 80 °C and low volatility and being non-flammable. Although not limited thereto, they preferably comprise one or more esters, preferably esters and / or triglycerides having a chain length of at most 18 carbon atoms or even at most 42 carbon atoms, such as esters of C6 to C12 fatty acids with glycerol.

[0107] Optionally, the aqueous phase may comprise an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (such as alkyl sulfates, alkyl ether sulfates, and / or alkylbenzene sulfonates), nonionic surfactants (such as alkoxylated alcohols, preferably containing ethoxy), polyvinyl alcohol, and / or polyvinylpyrrolidone. It is possible in the present application that dissolved chitosan can provide emulsification benefits. The emulsifier, if employed, is typically from about 0.1 wt% to 40 wt%, preferably 0.2 wt% to about 15 wt%, more typically 0.5 wt% to 10 wt% based on the total weight of the aqueous phase.

[0108] The population of delivery particles may be provided in the form of a slurry, preferably an aqueous slurry. The slurry may comprise one or more processing aids, which may include water, aggregation-inhibiting substances such as divalent salts, or particulate suspension polymers such as xanthan gum, guar gum, cellulose (preferably microfibrillated cellulose), and / or carboxymethyl cellulose. When the delivery particles are characterized by a cationic nature (e.g., when the shell is at least partially derived from chitosan), non-anionic structuring agents, preferably nonionic structuring agents, may be preferred, for example to avoid harmful charge interactions that can lead to undesirable aggregation.

[0109] The slurry may comprise one or more carriers selected from the group consisting of: polar solvents including, but not limited to, water, ethylene glycol, propylene glycol, polyethylene glycol, glycerol; non-polar solvents including, but not limited to, mineral oil, perfume raw materials, silicone oil, hydrocarbon paraffin oil; and mixtures thereof. An aqueous slurry may be preferred. The slurry may comprise unencapsulated (“free”) perfume raw materials that differ in properties and / or amount from those encapsulated in the core of the delivery particles.

[0110] The slurry may comprise a deposition aid, which may include polymers selected from the group comprising: polysaccharides such as chitosan, cationically modified starch and / or cationically modified guar gum; polysiloxanes; poly(diallyldimethylammonium halide); copolymers of poly(diallyldimethylammonium chloride) and polyvinylpyrrolidone; compositions comprising polyethylene glycol and polyvinylpyrrolidone; acrylamide; imidazole; imidazoline halide; polyvinylamine; copolymers of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; polyglycerolether siloxane crosslinked polymer; copolymers of polyacrylic acid, polyacrylate, polyvinylamine and polyvinyl alcohol oligomers with amines, in one aspect, diethylenetriamine, ethylenediamine, bis(3-aminopropyl)piperazine, N,N-bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine and mixtures thereof; polyethyleneimine, derivatized polyethyleneimine, 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 on the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile or combinations thereof; preformed coacervates of anionic surfactants in combination with cationic polymers; polyamines, and mixtures thereof.

[0111] At least one population of delivery particles may be included in an agglomerate and then combined with a different population of delivery particles and at least one adjuvant material. The agglomerate may comprise materials selected from the following: silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride and substrates such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0112] Suitable apparatuses for use in the methods disclosed herein can include continuous stirred tank reactors, homogenizers, turbine agitators, recycle pumps, paddle mixers, plowshare shear mixers, ribbon blenders, vertical axis granulators, and tumble mixers (both of which can be in batch process configurations and continuous process configurations when available), spray dryers, and extruders. Such apparatuses can be purchased from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., U.S.A.), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., U.S.A.), Arde Barinco (New Jersey, U.S.A.).

[0113] Auxiliary component

[0114] In addition to delivering particles, the treatment compositions of the present disclosure can also include one or more adjuvant materials. The adjuvant materials can provide beneficial effects in the intended end use of the composition, or they can be processing aids and / or stabilizing aids.

[0115] Suitable adjuvant materials can 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, clays and soil removal / antiredeposition agents, optical brighteners, antifoaming agents, silicones, hueing agents, aesthetic dyes, additional fragrances and fragrance delivery systems, structure elasticizers, carriers, hydrotropes, processing aids, antiagglomerants, coatings, formaldehyde scavengers, and / or pigments. Preferably, the adjuvant materials include additional fabric conditioners, dyes, pH control agents, solvents, rheology modifiers, structurants, cationic polymers, surfactants, fragrances, additional fragrance delivery systems, chelating agents, antioxidants, preservatives, or mixtures thereof.

[0116] Depending on the desired form, formulation, and / or end use, the compositions of the present disclosure may not contain one or more of the following adjuvant materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / antiredeposition agents, optical brighteners, defoamers, dyes, additional fragrances and fragrance delivery systems, structurants, fabric softeners, carriers, hydrotropes, processing aids, structurants, anti-caking agents, coatings, formaldehyde scavengers, and / or pigments.

[0117] The exact nature of these additional components and their levels of incorporation will depend on the physical form of the composition and the nature of the operations for which it is used. However, when one or more adjuvants are present, such one or more adjuvants may be present as detailed below. The following is a non-limiting list of suitable additional adjuvants.

[0118] A. Surfactant

[0119] The compositions of the present disclosure may contain surfactants. For example, surfactants can be used to provide cleaning benefits. The composition may contain a surfactant system, which may contain one or more surfactants.

[0120] The compositions of the present disclosure may contain 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 the surfactant system. Liquid compositions may contain from about 5% to about 40% by weight of the composition of the surfactant system. Compact formulations, including compact liquids, gels, and / or compositions suitable for unit dosage forms, may contain from about 25% to about 70% or from about 30% to about 50% by weight of the composition of the surfactant system.

[0121] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include linear alkylbenzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, nonionic surfactants such as ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactant may be at least partially derived from natural sources, such as natural raw material alcohols.

[0122] Suitable anionic surfactants can include any conventional anionic surfactant. This can include sulfate detergency surfactants (such as alkoxylated and / or non-alkoxylated alkyl sulfate materials) and / or sulfonate detergency surfactants (such as alkylbenzene sulfonates). The anionic surfactant can be linear, branched, or a combination thereof. Preferred surfactants include linear alkylbenzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactant can be present in acid form, salt form, or a mixture thereof. The anionic surfactant can be partially or fully neutralized with, for example, an alkali metal (such as sodium) or an amine (such as monoethanolamine). Due to the presence of the cationic ester quaternary compound material, it may be desirable to limit the amount of the anionic surfactant to avoid undesirable interactions of the materials; for example, the composition can contain less than 5%, preferably less than 3%, more preferably less than 1%, and even more preferably less than 0.1% of the anionic surfactant by weight of the composition.

[0123] The surfactant system can include nonionic surfactants. 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 (such as alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(alkoxylated) alcohol surfactants, and mixtures thereof. The alkoxylate units can be ethyleneoxy units, propyleneoxy units, or a mixture thereof. The nonionic surfactant can be linear, branched (such as mid-chain branched), or a combination thereof. Specific nonionic surfactants can include alcohols having an average of about 12 to about 16 carbon atoms and an average of about 3 to about 9 ethoxy groups, such as C12-C14EO7 nonionic surfactant.

[0124] Suitable zwitterionic surfactants can include any conventional zwitterionic surfactant, such as betaines, including alkyl dimethyl betaines and coconut dimethylamidopropyl betaines, C8 to C 18 (e.g., C 12 to C 18 ) amine oxides (e.g., C 12-14 dimethylamine oxide), and / or sulfobetaines and hydroxybetaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonates, wherein the alkyl group can be C8 to C 18 or C 10 to C 14The zwitterionic surfactant may include amine oxides.

[0125] Depending on the formulation and / or intended end use, the composition may be substantially free of certain surfactants. For example, liquid fabric enhancer compositions, such as fabric softeners, may be substantially free of anionic surfactants because such surfactants can interact unfavorably with cationic components.

[0126] B. Conditioning active substance

[0127] The compositions of the present disclosure may contain conditioning actives. Compositions containing conditioning actives may provide softness, wrinkle resistance, antistatic, conditioning, anti-stretch, color and / or appearance benefits.

[0128] The conditioning actives may be present at a level of from about 1% to about 99% by weight of the composition. The composition may contain from about 1%, or about 2%, or about 3% to about 99%, or up to about 75%, or up to about 50%, or up to about 40%, or up to about 35%, or up to about 30%, or up to about 25%, or up to about 20%, or up to about 15%, or up to about 10% by weight of the composition of the conditioning actives. The composition may contain from about 5% to about 30% by weight of the conditioning actives.

[0129] Conditioning actives suitable for the compositions of the present disclosure may include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty 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, wherein one or more adjuvant components comprise a quaternary ammonium ester material; such materials are particularly suitable for fabric enhancing / conditioning / softening compositions.

[0130] The composition may contain a quaternary ammonium ester compound, a silicone, or a combination thereof, preferably a combination. The total amount of the combination of the quaternary ammonium ester compound and the silicone may be from about 5% to about 70%, or about 6% to about 50%, or about 7% to about 40%, or about 10% to about 30%, or about 15% to about 25% by weight of the composition. The composition may contain the quaternary ammonium ester compound and the silicone in a weight ratio of from 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.

[0131] The composition may contain a mixture of different types of conditioning actives. The compositions of the present disclosure may contain certain conditioning actives but 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 quaternary ammonium ester compounds but be substantially free of silicones. The composition may contain silicones but be substantially free of quaternary ammonium ester compounds.

[0132] C. Deposition aid

[0133] The compositions of the present disclosure may include deposition aids. As described above, due to the synergistic beneficial effects from the ester quaternary ammonium compound materials and the delivery particles of the present disclosure, relatively little (or even no) deposition aid may be required to provide similar or even improved performance; alternatively, deposition aids may be used in the compositions of the present disclosure to further enhance performance.

[0134] Deposition aids may facilitate the deposition of delivery particles, conditioning actives, fragrances, or combinations thereof, thereby improving the performance benefits of the composition and / or allowing for more efficient formulation of such beneficial agents. The composition may include from 0.0001% to 3%, preferably from 0.0005% to 2%, more preferably from 0.001% to 1%, or about 0.01% to about 0.5%, or about 0.05% to about 0.3% by weight of the composition of the deposition aid. The deposition aid may be a cationic polymer or an amphoteric polymer, preferably a cationic polymer.

[0135] Generally speaking, cationic polymers and their manufacturing methods are known in the literature. Suitable cationic polymers may include quaternary ammonium polymers known as "polyquaternium" polymers, as designated by the International Nomenclature for Cosmetic Ingredients, such as polyquaternium-6 (poly(diallyldimethylammonium chloride)), polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), polyquaternium-10 (quaternized hydroxyethyl cellulose), polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride), etc.

[0136] The deposition aid may be selected from polyvinylformamide, partially hydroxylated polyvinylformamide, polyvinylamine, polyethyleneimine, ethoxylated polyethyleneimine, polyvinyl alcohol, polyacrylate, and combinations thereof. The cationic polymer may include cationic acrylate.

[0137] The deposition aid may be added simultaneously with the delivery particles (simultaneously with, for example, the encapsulated beneficial agent) or added directly / independently to the consumer product composition. As measured by size exclusion chromatography relative to a polyethylene oxide standard using refractive index (RI) detection, 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. The weight average molecular weight of the cationic polymer may be from 5,000 daltons to 37,500 daltons.

[0138] D. Rheology modifier / structurant

[0139] The compositions of the present disclosure may comprise rheological modifiers and / or structurants. Rheological modifiers can be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structurants can be used to promote phase stability and / or to suspend or inhibit aggregation of particles in a liquid composition, such as the delivery particles described herein.

[0140] Suitable rheological modifiers and / or structurants can include non-polymeric crystalline hydroxy-functionalized structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulose fibers (e.g., microfibrillated cellulose, which can be derived from bacterial, fungal, or plant sources, including wood), diacylamino gelling agents, or combinations thereof.

[0141] Polymeric structuring agents can be of natural or synthetic origin. Natural origin polymeric structurants can include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives can include: pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structurants can include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated polyurethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers can include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates can include copolymers of unsaturated mono- or di-carboxylic acids with C1-C 30 alkyl esters of (meth)acrylic acid. Such copolymers are available from Noveon 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), can be used as structurants. Another suitable structurant is sold under the trade name Rheovis CDE and is available from BASF.

[0142] E. Other auxiliaries

[0143] The treatment compositions of the present disclosure may comprise other adjuvants suitable for inclusion in a product and / or suitable for end use. For example, the treatment compositions can comprise neat fragrances, fragrance delivery technologies (such as pre-fragrances and / or encapsulates having non-polyisocyanate / chitosan wall materials), cationic surfactants, cationic polymers, solvents, antifoaming agents, or combinations thereof.

[0144] Method for preparing treatment composition

[0145] The present disclosure also relates to methods for preparing treatment compositions, such as those treatment compositions and / or consumer product compositions described herein.

[0146] The method may comprise the following steps: providing a base composition, wherein the base composition comprises a processing aid; and combining a population of delivery particles with the base composition. The population of delivery particles may preferably be provided in the form of an aqueous slurry. The base composition is in the form of a liquid composition.

[0147] When the delivery particles are in one or more forms (including slurry form, pure particle form, and / or spray-dried particle form), preferably in slurry form, the delivery particles may be combined with one or more adjuvant components. The delivery particles may be combined with such adjuvants by methods including mixing and / or spraying.

[0148] The treatment composition of the present disclosure may be formulated into any suitable form and prepared by any method selected by the formulator. The one or more adjuvant components and the delivery particles may be combined in a batch process, in a recycle loop process, and / or by an in-line mixing method. Suitable equipment for use in the methods disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recycle pumps, paddle mixers, high-shear mixers, static mixers, plow shear mixers, ribbon blenders, vertical-axis granulators, and tumbling mixers (both of which may be in intermittent process configurations and continuous process configurations (when available)), spray dryers, and extruders.

[0149] The treatment composition may be placed in a container to form a consumer product as described herein. The container may be a bottle, preferably a plastic bottle. The treatment composition may be placed in an aerosol or other spray container according to known methods.

[0150] Treatment method

[0151] The present disclosure also relates to a method of treating a surface (preferably a fabric). Generally speaking, the method comprises the step of contacting the surface (preferably a fabric) with a treatment composition according to the present disclosure, wherein the treatment composition comprises a population of delivery particles as described herein.

[0152] Additionally or alternatively, the method may comprise the step of contacting the surface (preferably a fabric) with a population of delivery particles as described herein. The population of delivery particles may be included in a treatment composition according to the present disclosure, preferably a fabric care composition.

[0153] The method may comprise the step of contacting a fabric (such as a garment) with a treatment composition. The treatment composition comprises a population of delivery particles. The contacting step results in the deposition of one or more of the delivery particles on the surface of the fabric. The delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, preferably an aromatic material comprising one or more fragrance raw materials. The shell comprises a polymeric material that is, for example, a reaction product of chitosan of a specific molecular weight and a crosslinking agent. Suitable treatment compositions and delivery particles are described in more detail above.

[0154] The contacting step can occur during a manual laundry process, such as in a laundry tub when handling fabric by hand, or during an automatic laundry process, such as in an automatic washing machine. The contacting step can occur during the wash cycle of an automatic washing machine; in this case, the treatment composition can be a laundry detergent or a laundry wash additive. The contacting step can preferably occur during the rinse cycle of an automatic washing machine; in this case, the treatment composition can be a fabric enhancer, preferably a liquid fabric enhancer. The contacting step can even occur during the drying step of a laundry process, such as in an automatic dryer; in this case, the treatment composition can be in the form of a non-woven dryer sheet or a dryer bar. The contacting step can occur due to the direct application of the treatment composition to the fabric, such as in a pretreatment operation or in a "refreshing" step (e.g., for fabric that has been used or worn since the last wash); in this case, the treatment composition can be in the form of a liquid, a stick, or a spray, preferably a spray. Contacting the target fabric relatively late in the laundry process, such as during the rinse cycle, improves the likelihood or efficiency of deposition onto the fabric because the target fabric is less likely to be flushed down the drain.

[0155] The contacting step can be carried out in the presence of water. The treatment composition can be diluted with water to form a treatment liquid. The treatment composition can be diluted from about 100-fold to about 1500-fold, preferably 300-fold to about 1000-fold.

[0156] The liquid containing the disclosed composition can have a pH of from about 3 to about 11.5. Such compositions are typically used at a concentration of from about 500 ppm to about 15,000 ppm in solution when diluted. When the washing solvent is water, the water temperature is typically in the range of from about 5 °C to about 90 °C, and the ratio of water to fabric can typically be from about 1:1 to about 30:1.

[0157] Dilution can occur in the drum of an automatic washing machine. The treatment composition can be placed in the dispenser drawer of an automatic washing machine. During the treatment process, the treatment composition can be dispensed from the dispenser drawer into the drum.

[0158] As described above, the method can further include a step of drying the fabric that has one or more delivery particles on the surface of the fabric. The drying step can include a passive drying process, such as on a clothesline or a drying rack. The drying step can include an automatic drying process, such as in an automatic dryer.

[0159] Combination

[0160] Specifically contemplated combinations of the present disclosure are described herein in the following lettered paragraphs. These combinations are illustrative in nature and not restrictive.

[0161] A. A treatment composition, the treatment composition comprising a treatment aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, wherein the shell comprises a polymeric material which is a reaction product of a modified chitosan and at least one electrophile, wherein the modified chitosan comprises a reaction product of chitosan and a modifying compound, and wherein the modifying compound comprises an epoxide, an aldehyde or an α,β-unsaturated compound.

[0162] B. The treatment composition according to paragraph A, wherein the modifying compound comprises a cationic group, an anionic group, a non-ionic group or a mixture thereof.

[0163] C. The treatment composition according to any one of paragraphs A or B, wherein the modifying compound comprises a cationic group, an anionic group or a mixture thereof, more preferably comprises an anionic group.

[0164] D. The treatment composition according to any one of paragraphs A to C, wherein the modifying compound comprises an acidic group, a hydroxyl group, a quaternary ammonium group or a mixture thereof, preferably an acidic group.

[0165] E. The treatment composition according to any one of paragraphs A to D, wherein the modifying compound comprises an α,β-unsaturated compound, preferably wherein the α,β-unsaturated compound is an α,β-unsaturated carbonyl compound.

[0166] F. The treatment composition according to any one of paragraphs A to E, wherein 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 ketones, vinyl sulfones, vinyl phosphonates, acrylonitrile or combinations thereof, preferably wherein the α,β-unsaturated compound is selected from the group consisting of: acrylic acid, acrylate salts, acrylates, alkyl acrylates, α,β-unsaturated esters, maleic acid, vinylsulfonic 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, N,N-dialkylaminoalkyl acrylamides, (3-acrylamidopropyl)trimethylammonium salts, acrylamide, acrylamide salts, 3-sulfopropyl acrylate salts, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, quaternized vinylimidazoles, diallyldialkylammonium salts, vinylamines, vinyl ketones, vinyl sulfones, vinyl phosphonates, acrylonitrile and combinations thereof.

[0167] G. A treatment composition according to any one of paragraphs A to F, wherein the modified compound comprises a material selected from the group consisting of glycidyltrimethylammonium salts, 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, alginaldehyde, acrylic acid, acrylate salts, maleic acid, vinylsulfonic 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, N,N-dialkylaminoalkyl acrylamides, (3-acrylamidopropyl)trimethylammonium salts, 3-sulfopropyl acrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, quaternized vinylimidazoles, diallyldialkylammonium salts, vinylamines, and combinations thereof.

[0168] H. A treatment composition according to any one of paragraphs A to G, wherein the chitosan comprises a free amine moiety, and wherein the molar ratio of the modified compound to the free amine moiety of the chitosan is from 0.1% to 100%, 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%.

[0169] I. A treatment composition according to any one of paragraphs A to H, wherein the shell comprises at least 18%, preferably at least 21% by weight of the shell of the modified chitosan.

[0170] J. A treatment composition according to any one of paragraphs A to 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, even more preferably from about 100 kDa to about 200 kDa.

[0171] K. A treatment composition comprising a treatment aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, and wherein the shell comprises a polymeric material which is a reaction product of at least one modified chitosan and at least one electrophile, wherein the population of delivery particles can be obtained by a method comprising the steps of: forming an aqueous phase by dissolving or dispersing chitosan in an aqueous acidic medium at a pH of 6.5 or lower and a temperature of at least 25 °C, the chitosan having a free amine moiety; forming an oil phase comprising combining at least one beneficial 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 the aqueous phase under high shear agitation, thereby forming droplets of the oil phase dispersed in the aqueous phase; adding a modifying compound to the aqueous phase and / or the emulsion, preferably at least to the aqueous phase, the modifying compound comprising one or more of an epoxide, an aldehyde or an α,β-unsaturated compound, the modifying compound reacting with the free amine moiety 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 and the aqueous phase, the shell surrounding the core.

[0172] L. A treatment composition comprising a treatment aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, and wherein the shell comprises a polymeric material which is a reaction product of at least one modified chitosan and at least one electrophile, the modified chitosan comprising a reaction product of chitosan and a modifying compound, wherein the modifying compound comprises an epoxide, an aldehyde or an α,β-unsaturated compound covalently bonded to the chitosan, wherein the population of delivery particles can be obtained by a method comprising the steps of: dissolving or dispersing chitosan into an aqueous phase, the chitosan having an amine moiety; combining the aqueous phase and the modifying compound; optionally adjusting the pH of the aqueous phase to a pH of 3.0 or higher, preferably a pH of 3.0 to a pH of 6; optionally adjusting the temperature of the aqueous phase to 25 °C or greater; mixing the aqueous phase for a period of time to form a modified chitosan, wherein the modifying compound is covalently bonded to the amine moiety of the chitosan via a C-N bond, and wherein the modified chitosan remains dissolved in the aqueous phase; providing an oil phase comprising dissolving at least one beneficial agent comprising an oil and at least one electrophile, preferably at least one polyisocyanate, 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 beneficial 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 and the aqueous phase, the shell surrounding the core.

[0173] M. The treatment composition according to any one of paragraphs A to L, wherein the method capable of obtaining the population of delivery particles further comprises the step of adding a redox initiator to the aqueous phase or the emulsion, wherein the redox initiator comprises persulfate, peroxide, or a combination thereof.

[0174] N. The treatment composition according to any one of paragraphs A to M, wherein the modified compound comprises cationic groups and / or anionic groups.

[0175] O. The treatment composition according to any one of paragraphs A to N, wherein the delivery particles comprise from about 1% to about 25% of the shell by weight of the delivery particles.

[0176] P. The treatment composition according to any one of paragraphs A to O, wherein when tested according to test method OECD 301B, the shell degrades by at least 50%, preferably at least 60%, after 60 days.

[0177] Q. The treatment composition according to any one of paragraphs A to P, wherein the delivery particles are characterized by a ζ potential of 150 mV or less at pH 4.5.

[0178] R. The treatment composition according to any one of paragraphs A to R, wherein the electrophile comprises a polyisocyanate, preferably a polyisocyanate selected from the group consisting of: 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; tetramethyldimethylaniline diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (such as their prepolymers, oligomers, and / or polymers); and combinations thereof.

[0179] S. The treatment composition according to any one of paragraphs A to R, wherein the beneficial agent is an aromatic material.

[0180] T. The treatment composition according to any one of paragraphs A to S, wherein the core further comprises a dispensing modifier, which is optionally present in the core at a level of from about 5% to about 55%, preferably from about 10% to about 50%, more preferably from about 25% to about 50% by weight of the core, and preferably the dispensing modifier is selected from the group consisting of: vegetable oil, modified vegetable oil, C4-C 24Mono-esters, di-esters and tri-esters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate.

[0181] U. The treatment composition according to any one of paragraphs A to T, wherein the delivery particles are characterized by a volume-weighted median particle size of from about 1 micron to about 100 microns, preferably from about 10 microns to about 100 microns, preferably from about 15 microns to about 50 microns, more preferably from about 20 microns to about 40 microns, and even more preferably from about 25 microns to about 35 microns.

[0182] V. The treatment composition according to any one of paragraphs A to U, wherein the treatment 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, clays and soil removal / antiredeposition agents, optical brighteners, defoamers, silicones, colorants, aesthetic dyes, perfume bases, additional perfume delivery systems, structuring elastomers, carriers, hydrotropes, processing aids, antiagglomerants, coatings, formaldehyde scavengers, pigments, and mixtures thereof.

[0183] W. The treatment composition according to any one of paragraphs A to V, wherein the treatment aid comprises an anionic surfactant, a cationic conditioner, or a mixture thereof.

[0184] X. The treatment composition according to any one of paragraphs A to W, wherein the treatment composition is a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition, a body cleansing composition, or a mixture thereof, preferably a fabric care composition, and more preferably a fabric care composition in the form of a laundry detergent composition, a fabric conditioner composition, a laundry additive, a fabric pretreatment composition, a fabric freshener composition, or a mixture thereof.

[0185] Y. The treatment composition according to any one of paragraphs A to X, wherein the treatment composition is in the form of a liquid composition, a particulate composition, an aqueous colloid, a single-compartment sachet, a multi-compartment sachet, a soluble sheet, a lozenge or a bead, a fibrous article, a tablet, a bar, a strip, a flake, a foam / mousse, a nonwoven sheet, or a mixture thereof, preferably in the form of a single-compartment sachet, a multi-compartment sachet, a lozenge or a bead, or a mixture thereof.

[0186] Z. A treatment composition according to any one of paragraphs A to Y, wherein the treatment composition comprises 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 treatment composition.

[0187] AA. A method for preparing a treatment composition according to any one of paragraphs A to Z, the method comprising the steps of: providing a base composition, wherein the base composition comprises a treatment aid; and combining a population of delivery particles with the base composition.

[0188] BB. The method according to paragraph AA, wherein the population of delivery particles is provided in the form of an aqueous slurry.

[0189] CC. The method according to paragraph BB, wherein the aqueous slurry comprises 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.

[0190] DD. The method according to any one of paragraphs AA to CC, wherein the base composition is in the form of a liquid composition.

[0191] EE. A method for treating a surface, the method comprising the step of: contacting the surface with a treatment composition according to any one of paragraphs A to Z.

[0192] Testing method

[0193] It should be understood that the test methods disclosed in the test methods section of this application should be used to determine the corresponding parameter values of the subject matter claimed by the applicant as claimed and described herein.

[0194] Determination of polymer molecular weight and related parameters

[0195] The method described below with gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) is used to find the molecular weight distribution measurements and related values of the polymers described herein.

[0196] Gel permeation chromatography (GPC) with multi-angle light scattering (MALS) and refractive index (RI) detection (GPC-MALS / RI) allows the measurement of the absolute molecular weight of polymers without the need for column calibration methods or standards. The GPC system allows the separation of molecules according to their molecular size. MALS and RI allow the obtaining of information on the number average (Mn) and weight average (Mw) molecular weights.

[0197] 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, Agilent Technology, Santa Clara, CA, USA) and a column set operating at 40 °C (e.g., 2 Tosoh TSKgel G6000WP 7.8 x 300 mm 13 um pore size, guard column A0022 6 mm x 40 mm PW xl-cp, King of Prussia, PA). The mobile phase is an aqueous solution of 0.1 M sodium nitrate 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. Using a multi-angle light scattering (18-Angle MALS) detector controlled by Wyatt software v8.0 and a differential refractive index (RI) detector (Wyatt Technology, Santa Barbara, California, USA).

[0198] Typically, samples are prepared by dissolving the chitosan material at approximately 1 mg / ml in the mobile phase and hydrating the solution by mixing overnight at room temperature. Before GPC analysis, the sample is filtered through a 0.8 μm Versapor membrane filter (PALL, Life Sciences, NY, USA) into an LC autosampler vial using a 3 ml syringe.

[0199] 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) are determined using the dn / dc value (differential change of refractive index with concentration, 0.15) by the Astra detector software.

[0200] Viscosity

[0201] The viscosity of the liquid finished product is measured using an AR 550 rheometer / viscometer from TA Instruments (New Castle, DE, USA), with parallel steel plates having a diameter of 40 mm and a gap size of 500 μm. The high-shear viscosity at 20 s -1 and the low-shear viscosity at 0.05 s -1 are obtained from a logarithmic shear rate sweep from 0.01 s -1 to 25 s -1 over a 3-minute period at 21 °C.

[0202] Testing method for determining logP

[0203] Calculate the logarithm (logP) of the octanol / water partition coefficient for each material tested (e.g., each PRM in the spice blend). The logP of the individual material (e.g., PRM) is calculated using the Consensus logP Computational Model version 14.02 (Linux) purchased from Advanced Chemistry Development Inc. (ACD / Labs) (Toronto, Canada) to provide a dimensionless logP value. The Consensus logP Computational Model of ACD / Labs is part of the ACD / Labs model suite.

[0204] Volume-weighted particle size and size distribution

[0205] Determine the volume-weighted particle size distribution by single particle optical sensing (SPOS) (also known as optical particle counting (OPC)) using an AccuSizer 780AD instrument and the accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, U.S.A.) or equivalent. The instrument is configured with the following conditions and selections: flow rate = 1 ml / sec; lower size threshold = 0.50 μm; sensor model = LE400-05 or equivalent; automatic dilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 ml; maximum coincidence = 9200. Start the measurement by flushing the sensor with water until the background count is less than 100 to bring it to a cold state. Introduce the sample in suspension of the delivery capsule and adjust the density of the capsule with DI water by automatic dilution as needed to obtain a capsule count of at least 9200 / ml. Analyze the suspension over a 60-second period. Plot and record the resulting volume-weighted PSD data and determine the values of the volume-weighted particle size required (e.g., median / 50th percentile, 5th percentile, and / or 90th percentile).

[0206] Procedure for determining % degradation

[0207] To determine % degradation, use the procedure described in the "OECD Guideline for Testing of Chemicals" 301B CO2 Evolution (Modified Sturm Test) adopted on July 17, 1992. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0208] Fabric treatment method

[0209] Use a Miele washing machine to process fabrics. For each treatment, the washing machine loads 3 kg of fabrics, which include 1100 g of knitted cotton fabrics and 1100 g of polyester cotton fabrics (50 / 50). Additionally, 18 thick terrycloth cotton tracers are added, and these tracers together weigh approximately 780 g.

[0210] Before the test treatment, the load is pre-treated twice, each time using a 95°C short cotton cycle with 79 g of unperfumed IEC A basic detergent (purchased from WFK Testgewebe GmbH), followed by two additional 95°C washes without detergent.

[0211] For the test treatment, wash the load using a 40°C short cotton cycle, a 1200 rpm spin speed, and 79 g of IEC A basic detergent, which is added to a suitable dispenser at the start of the wash cycle. Add a 35 g dose of the test fabric treatment composition (i.e., LFE according to the example) to the appropriate dispenser. At the end of the treatment cycle, remove the thick terrycloth tracers from the washing machine and hang them to dry overnight.

[0212] The next day, analyze the dried thick terrycloth tracers by the rapid headspace GC / MS (gas chromatography - mass spectrometry) method as described below. For comparison purposes, all treatments are washed on the same day and analyzed on the same day, which is reported as "one - wash test."

[0213] Method for determining headspace concentration above treated dry fabric

[0214] Analyze the cotton tracers by the rapid headspace GC / MS (gas chromatography - mass spectrometry) method. Transfer a 4X4 cm aliquot of the thick terrycloth cotton tracers to a 25 mL headspace vial. Equilibrate the fabric sample at 65°C for 10 minutes. Sample the headspace above the fabric for 5 minutes via the SPME (50 / 30μm DVB / Carboxen / PDMS) method. Subsequently, thermally desorb the SPME fiber immediately into the GC. Analyze the analytes by rapid GC / MS in full - scan mode. Calculate the total HS response and the perfume headspace composition above the test legs using ion extraction of specific masses with PRM.

[0215] Procedure for determining the amount of free oil ("QFO")

[0216] This method measures the amount of oil in the aqueous phase (i.e., the amount of free oil or "QFO") and uses 1 mg / ml dibutyl phthalate (DBP) / hexane as the internal standard solution.

[0217] Weigh slightly more than 250 mg of DBP into a small beaker and transfer it to a 250 ml volume. Rinse the beaker thoroughly. Fill it to 250 ml with hexane.

[0218] Sample preparation: Weigh approximately 1.5 g to 2 g (40 drops) of the capsule slurry into a 20 ml scintillation vial, add 10 ml of the ISTD solution, and cap tightly. Shake vigorously several times within 30 minutes, pipette the solution into an autosampler vial and analyze by GC.

[0219] Additional details. Instrument: HP5890 GC connected to HP Chem Station Software; Column: 5 m × 0.32 mm inner diameter, with 1 μm DB-1 liquid phase; 1 minute at 50 °C, then heat to 320 °C at a rate of 15 °C / minute; Syringe: 275 °C; Detector: 325 °C; Inject 2 μl.

[0220] Calculation: Add the total peak area minus the area of DBP for both the sample and the calibration.

[0221] Calculate the mg of free core oil:

[0222]

[0223] Calculate the % of free core oil:

[0224]

[0225] Procedure for determining beneficial agent leakage

[0226] Obtain two 1 g samples of the beneficial agent particle composition. Add 1 g (Sample 1) of the particle composition to 99 g of the product matrix in which the particles will be used. Age the product matrix containing the particles (Sample 1) in a sealed glass wide-mouth bottle at 35 °C for 2 weeks. Age the other 1 g sample (Sample 2) similarly.

[0227] After 2 weeks, recover the particles of the particle composition from the product matrix (Sample 1) and from the particle composition (Sample 2) using filtration. Treat each particle sample with a solvent that will extract all of the beneficial agent from each sample particle. Inject the solvent containing the beneficial agent from each sample into a gas chromatograph, and integrate the peak areas to determine the total amount of beneficial agent extracted from each sample.

[0228] Determine the beneficial agent leakage percentage by calculating the difference between the value obtained for the total amount of beneficial agent extracted from Sample 2 minus the value obtained for the total amount of beneficial agent extracted from Sample 1, expressed as a percentage of the total amount of beneficial agent extracted from Sample 2, as represented by the following formula:

[0229]

[0230] Procedure for qualitatively measuring the compatibility of delivery particles in a laundry wash matrix

[0231] The compatibility of the delivery particles in the laundry matrix is measured by visually inspecting the mixture of the delivery particles and the laundry matrix in a glass wide-mouth bottle. The slurry containing the delivery particles is homogenized by stirring with an overhead mixer for at least one minute. Then, the homogenized slurry is added to the laundry matrix (such as a heavy-duty laundry matrix) at a ratio of 1:40 (such as 1 g of slurry in 40 g of matrix) under mixing. The above mixture is mixed with an overhead mixer at 350 rpm for at least 15 minutes. Mixing is stopped, and the mixture is allowed to stand for 5 minutes before examination. The mixture is visually inspected with the naked eye and under an optical microscope to detect any aggregates in the mixture. If any aggregates are observed with the naked eye or aggregates larger than 100 microns are observed under the optical microscope, it is determined that the delivery particles are incompatible in the laundry matrix.

[0232] Examples

[0233] The examples provided below are essentially intended to be illustrative and not restrictive.

[0234] In the following examples, the 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, wherein chitosan is modified in the aqueous phase. Examples 7-21 disclose the synthesis of delivery particles according to the present disclosure, wherein chitosan is modified in the emulsion phase.

[0235] Table 1 .

[0236]

[0237]

[0238] Comparative Example 1. Polyurea capsules with (unmodified) chitosan

[0239] A chitosan stock solution is prepared by dispersing 39.60 g of chitosan Chitoclear into 840.4 g of deionized water while mixing in a jacketed reactor. Then, the pH of the chitosan dispersion is adjusted to 3.87 using 17.90 g of concentrated HCl under stirring. Then, the temperature of the chitosan solution is raised to 85 °C within 60 minutes and subsequently maintained at 85 °C for 2 hours to hydrolyze ChitoClear. Then, the temperature is lowered to 25 °C within 90 minutes after the hydrolysis step. The pH of the acid-treated chitosan solution is 3.97.

[0240] The aqueous phase was prepared by mixing 426.30 g of the above chitosan stock solution and 6.70 g of 5% PVA540 solution in a jacketed reactor. The oil phase was prepared by mixing 146.63 g of fragrance, 36.66 g of isopropyl myristate, and 4.00 g of Takenate D-110N at room temperature. The oil phase was added to the aqueous phase under high-shear grinding to obtain an emulsion with a desired particle size. The emulsion was heated to 40 °C within 30 minutes and then held at 40 °C for 60 minutes. Then the emulsion was heated to 85 °C within 60 minutes and held at this temperature for 6 hours while mixing. The formed capsules had a median particle size of 8.05 microns. The formed capsules had a one-week leakage of 20.78%. The prepared slurry showed aggregation in a heavy-duty liquid laundry detergent matrix.

[0241] Example 1. Pre-modification with [2-(acryloyloxy)ethyl]trimethylammonium chloride

[0242] A modified chitosan solution was prepared by dispersing 40.92 g of chitosan powder in 792.00 water at 70 °C. The pH of the above mixture was adjusted to 4.91 using 9.79 g of glacial acetic acid. Then 46.36 g of 80% [2-(acryloyloxy)ethyl]trimethylammonium chloride solution was added to the above 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 obtained modified chitosan solution was 4.05.

[0243] The aqueous phase was prepared by weighing 255.8 g of [2-(acryloyloxy)ethyl]trimethylammonium chloride-modified chitosan solution in a jacketed reactor at 25 °C.

[0244] The oil phase was prepared by mixing 87.98 g of fragrance, 2.40 g of Takenate D110, and 22.00 g of isopropyl myristate in a beaker at 25 °C.

[0245] The oil phase was added to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature.

[0246] Then the emulsion was heated to 40 °C within 30 minutes and then held at 40 °C for 60 minutes. Then the emulsion was heated to 85 °C within 60 minutes and held for 6 hours to cure the wall. Then the emulsion was cooled to 25 °C within 90 minutes. The obtained capsules had a median particle size of 12.27 microns. The QFO and one-week leakage of the capsule slurry were 7.69% and 68.59% respectively. The prepared slurry did not show aggregation in a heavy-duty liquid laundry detergent matrix.

[0247] Example 2. Pre-modification with [2-(acryloyloxy)ethyl]trimethylammonium chloride and pH adjustment

[0248] Example 2 was prepared according to the procedure of Example 1, except that the pH of the aqueous phase was adjusted to 6.8 using a sodium hydroxide solution. After the pH adjustment, the aqueous phase remained clear. The obtained capsules had a median particle size of 36.44 microns. The QFO and 1-week leakage of the capsule slurry were 0.11% and 0.99%, respectively. The prepared slurry did not show aggregation in the heavy-duty liquid laundry detergent matrix.

[0249] Example 3. Pre-modification with [2-(acryloyloxy)ethyl]trimethylammonium chloride and pH adjustment and a second crosslinking agent (pentaerythritol triacrylate) Example 4. Pre-modification with CD9055 (acidic acrylate oligomer)

[0250] A modified chitosan solution was prepared according to the procedure in Example 1. The modified chitosan solution had a pH of 4.10. The aqueous phase consisted of the modified chitosan solution, and the pH was adjusted to 9.35 using a sodium hydroxide solution.

[0251] An emulsion was prepared according to Example 1 and then heated to 70 °C. Then, the second crosslinking agent (pentaerythritol triacrylate) was added to the emulsion at 70 °C. The emulsion was then heated to 90 °C within 60 minutes and maintained for another 8 hours, and then cooled to 25 °C to complete the curing process. The obtained capsules had a median particle size of 23.63 microns. The QFO and 1-week leakage of the capsule slurry were 0.35% and 6.19%, respectively. The prepared slurry did not show aggregation in the heavy-duty liquid laundry detergent matrix.

[0252] Example 5. Pre-modification with CD9055 (acidic acrylate oligomer) and pH adjustment

[0253] A modified chitosan solution was prepared by dispersing 42.11 g of chitosan powder in 840.00 g of water at 70 °C. Then, 42.11 g of CD9055 (acidic acrylate oligomer) was added to the above chitosan mixture and mixed at 70 °C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the obtained modified chitosan solution was 4.08.

[0254] The aqueous phase was prepared by weighing 328.00 g of the CD9055-modified chitosan solution in a jacketed reactor at 25 °C.

[0255] The oil phase was prepared by mixing 112.82 g of fragrance, 3.08 g of Takenate D110, and 28.21 g of isopropyl myristate in a beaker at 25 °C.

[0256] The oil phase was added to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature.

[0257] The emulsion was then heated to 40 °C within 30 minutes and subsequently held at 40 °C for 60 minutes. The emulsion was then heated to 85 °C within 60 minutes and held for 6 hours to cure the wall. The emulsion was then cooled to 25 °C within 90 minutes. The obtained capsules had a median particle size of 37.74 microns. The QFO and 1-week leakage of the capsule slurry were 0.83% and 41.46%, respectively.

[0258] Example 6. Pre-modification with CD9055 (acidic acrylate oligomer) and a second modification compound (pentaerythritol triacrylate)

[0259] The aqueous phase was prepared by weighing 255.78 g of the CD9055-modified chitosan solution from Example 4 in a jacketed reactor at 25 °C. The pH of the aqueous phase was then adjusted to 8.23 using sodium hydroxide. After pH adjustment, the aqueous phase remained clear.

[0260] The oil phase was prepared by mixing 87.98 g of fragrance, 2.40 g of Takenate D110, and 22.00 g of isopropyl myristate in a beaker at 25 °C.

[0261] The oil phase was added to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature.

[0262] The emulsion was then heated to 40 °C within 30 minutes and subsequently held at 40 °C for 60 minutes. The emulsion was then heated to 85 °C within 60 minutes and held for 6 hours to cure the wall. The emulsion was then cooled to 25 °C within 90 minutes. The obtained capsules had a median particle size of 25.72 microns. The QFO and 1-week leakage of the capsule slurry were 0.28% and 6.95%, respectively. The prepared slurry did not show aggregation in a heavy-duty liquid laundry detergent matrix.

[0263] Example 7. Pre-modification with CD9055 (acidic acrylate oligomer) and a second modification compound Example 8. In-situ modification of crosslinked chitosan capsules with CD9055 (acidic acrylate oligomer)

[0264] The modified chitosan solution was prepared by dispersing 42.11 g of chitosan in 840 g of water at 70 °C. The pH of the above mixture was adjusted to 4.86 using 11.26 g of glacial acetic acid. Then 35.85 g of CD9055 was added to the above chitosan solution and mixed at 70 °C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the obtained modified chitosan solution was 3.90.

[0265] The aqueous phase was prepared by adding 266.70 g of the CD9055-modified chitosan solution in a jacketed reactor.

[0266] The oil phase was prepared by mixing 99.71 g of fragrance, 2.72 g of Takenate D110, and 24.93 g of isopropyl myristate in a beaker at 25 °C.

[0267] The oil phase was added to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature.

[0268] Then the obtained emulsion was heated to 70 °C, and then the second cross-linking agent (pentaerythritol triacrylate) was added to the emulsion at 70 °C. Then the emulsion was heated to 90 °C within 60 minutes and held for another 8 hours, and then cooled to 25 °C to complete the curing process. The obtained capsules had a median particle size of 27.52 μm. The QFO and 1-week leakage of the capsule slurry were 0.10% and 34.40% respectively.

[0269] Example 9. In-situ modification of crosslinked chitosan capsules with [2-(acryloyloxy)ethyl]trimethylammonium chloride

[0270] A modified chitosan solution was prepared by dispersing 42.11 g of chitosan powder in 840.00 g of water at 70 °C. Then 42.11 g of CD9055 (acidic acrylate oligomer) was added to the above chitosan mixture and mixed at 70 °C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the obtained modified chitosan solution was 4.08.

[0271] The aqueous phase was prepared by weighing 255.78 g of the CD9055-modified chitosan solution in a jacketed reactor at 25 °C.

[0272] The oil phase was prepared by mixing 87.98 g of fragrance, 2.40 g of Takenate D110 and 22.00 g of isopropyl myristate in a beaker at 25 °C.

[0273] The oil phase was added to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature. The pH of the emulsion was adjusted to 9.07 using a sodium hydroxide solution at 40 °C.

[0274] Then the emulsion was heated to 40 °C within 30 minutes and the pH of the emulsion was adjusted to 9.07 using a sodium hydroxide solution. Then the emulsion was held at 40 °C for 60 minutes, and subsequently the emulsion was heated to 85 °C within 60 minutes and held for 6 hours to cure the wall. Then the emulsion was cooled to 25 °C within 90 minutes. The obtained capsules had a median particle size of 25.95 μm. The QFO and 1-week leakage of the capsule slurry were 0.66% and 24.91% respectively. The prepared slurry did not show aggregation in a heavy-duty liquid laundry detergent matrix.

[0275] Example 10. In-situ modification of crosslinked chitosan capsules with 25 mol% acrylic acid

[0276] A chitosan solution was prepared as in Comparative Example 1, but the pH of the chitosan solution was 5.23.

[0277] The aqueous phase was prepared by adding 308.70 g of the above chitosan solution in a jacketed reactor at 25 °C.

[0278] The oil phase was prepared by mixing 102.64 g of a fragrance, 2.80 g of Takenate D110, and 25.66 g of isopropyl myristate in a beaker at 25°C.

[0279] The oil phase was added to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature.

[0280] The obtained emulsion was then heated to 70°C, and then the modifying compound (10.71 g of CD9055) was added to the emulsion at 70°C. The emulsion was then heated to 90°C within 60 minutes and held for an additional 8 hours, and then cooled to 25°C to complete the curing process. The obtained capsules had a median particle size of 30.22 microns. The QFO and 1-week leakage of the capsule slurry were 0.49% and 48.08%, respectively.

[0281] Example 11. In-situ modification of crosslinked chitosan capsules with 100 mol% acrylic acid Example 12. In-situ modification of crosslinked chitosan capsules by adding 100 mol% acrylic acid at 25 °C

[0282] A chitosan solution was prepared as in Comparative Example 1, but the pH of the chitosan solution was 5.23.

[0283] The aqueous phase was prepared by adding 308.70 g of the above chitosan solution to a jacketed reactor at 25°C.

[0284] The oil phase was prepared by mixing 102.64 g of a fragrance, 2.80 g of Takenate D110, and 25.66 g of isopropyl myristate in a beaker at 25°C.

[0285] The oil phase was added to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature.

[0286] The obtained emulsion was then heated to 70°C, and then the modifying compound (17.92 g of 80% [2-(acryloyloxy)ethyl]trimethylammonium chloride solution) was added to the emulsion at 70°C. The emulsion was then heated to 90°C within 60 minutes and held for an additional 8 hours, and then cooled to 25°C to complete the curing process. The obtained capsules had a median particle size of 27.84 microns. The QFO and 1-week leakage of the capsule slurry were 0.29% and 4.62%, respectively. The prepared slurry did not show aggregation in a heavy-duty liquid laundry detergent matrix.

[0287] Example 13. In-situ modification of crosslinked chitosan capsules with 25 mol% acrylic acid and 5 mol% SR268

[0288] The chitosan stock solution was prepared by dispersing 155.7 g of chitosan Chitoclear into 3304 g of deionized water while mixing in a jacketed reactor. Then, the pH of the chitosan dispersion was adjusted to 5.23 using 69.84 g of concentrated HCl (31%) under stirring. Then, the temperature of the chitosan solution was raised to 65 °C within 30 minutes, then to 85 °C within 30 minutes, then to 95 °C within 30 minutes, and then maintained at 95 °C for 2 hours to hydrolyze ChitoClear. Then, the temperature was lowered to 25 °C within 90 minutes after the hydrolysis step. The pH of the hydrolyzed chitosan solution was 5.31.

[0289] The aqueous phase was prepared by mixing 433.6 g of the above chitosan stock solution in a jacketed reactor at 25 °C. The oil phase was prepared by mixing 128.9 g of fragrance, 32.2 g of isopropyl myristate, and 4.88 g of Takenate D-110N at room temperature. The oil phase was added to the aqueous phase under high-shear grinding to obtain an emulsion with a desired particle size. The emulsion was heated to 60 °C within 45 minutes, and then to 95 °C within 60 minutes. Once at 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) was added to the slurry, and then maintained at 95 °C for 360 minutes. Then, the temperature was lowered to 25 °C within 90 minutes. The formed capsules had a median particle size of 30.42 microns.

[0290] Example 14. In-situ modification with 25 mol% potassium 3-sulfopropyl acrylate

[0291] The cross-linked chitosan capsule slurry was prepared in the same manner as in Example 10, except that a solution of 8.29 g of acrylic acid (TCI Chemical #A0141), 8.29 g of RO water, and 20.31 g of 21.5% NaOH (prepared in an ice bath) was added at once at 95 °C instead 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. The formed capsules had a median particle size of 31.25 microns.

[0292] Example 15. In-situ modification of crosslinked chitosan capsules by adding 50 mol% glycidyltrimethylammonium chloride at 25 °C

[0293] Except that once an emulsion with the desired particle size is obtained at 25°C, 8.29 g of acrylic acid (TCI Chemical #A0141), 8.29 g of RO water, and 20.31 g of a solution of 21.5% NaOH (prepared in an ice bath) are added, instead of adding 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of a solution of 21.5% NaOH at 95°C, the crosslinked chitosan capsule slurry is prepared in the same manner as in Example 10. The formed capsules have a median particle size of 31.68 microns.

[0294] Example 16. In-situ modification of crosslinked chitosan capsules by adding 25 mol% glycidyltrimethylammonium chloride at 95 °C

[0295] Except that after adding 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of a solution of 21.5% NaOH at 95°C all at once, 1.74 g of tetraethylene glycol diacrylate (Sartomer #SR268) is also immediately added, the crosslinked chitosan capsule slurry is prepared in the same manner as in Example 10. The formed capsules have a median particle size of 30.83 microns.

[0296] Example 17. In-situ modification of crosslinked chitosan capsules by adding 25 mol% glycidyltrimethylammonium chloride at 25 °C

[0297] Except that 6.69 g of potassium 3-sulfopropyl acrylate (Sigma-Aldrich #251631) is added all at once at 95°C, instead of 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of a solution of 21.5% NaOH, the crosslinked chitosan capsule slurry is prepared in the same manner as in Example 10. The formed capsules have a median particle size of 30.83 microns.

[0298] Example 18. In-situ modification of crosslinked chitosan delivery particles with 25 mol% CD9055 neutralized with respect to chitosan, 13.5 mol% SR268 and 10 wt% KPS

[0299] Except that once an emulsion with the desired particle size is obtained at 25°C, 10.92 g of 80% glycidyltrimethylammonium chloride (TCI Chemical #G0476) is added, instead of 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of a solution of 21.5% NaOH at 95°C, the crosslinked chitosan capsule slurry is prepared in the same manner as in Example 10. The formed capsules have a median particle size of 32.98 microns.

[0300] Example 19. Modification of crosslinked chitosan delivery particles with 50 mol% acrylic acid and KPS ​

[0301] A crosslinked chitosan capsule slurry was prepared in the same manner as in Example 10, except that 5.46 g of 80% glycidyltrimethylammonium chloride (TCI Chemical #G0476) was added once at 95°C instead of 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of a 21.5% NaOH solution. The capsules formed had a median particle size of 30.84 microns.

[0302] ​ ​

[0303] A crosslinked chitosan capsule slurry was prepared in the same manner as in Example 10, except that once an emulsion with the desired particle size was obtained at 25°C, 5.46 g of 80% glycidyltrimethylammonium chloride (TCI Chemical #G0476) was added instead of adding 2.07 g of acrylic acid (TCI Chemical #A0141), 2.07 g of RO water, and 5.08 g of a 21.5% NaOH solution at 95°C. The capsules formed had a median particle size of 29.61 microns.

[0304] ​ ​

[0305] A chitosan stock solution was prepared by dispersing 155.7 g of chitosan Chitoclear into 3304 g of deionized water while mixing in a jacketed reactor. 1.56 g of potassium persulfate (KPS) was added. Then the pH of the chitosan dispersion was adjusted to 5.84 using 57.29 g of concentrated HCl with stirring. Then the temperature of the chitosan solution was raised to 65°C within 30 minutes, then to 85°C within 30 minutes, then to 95°C within 30 minutes, and then held at 95°C for 2 hours to hydrolyze chitosan ChitoClear. Then the temperature was lowered to 25°C within 90 minutes after the hydrolysis step. The pH of the acid-treated chitosan solution was 5.85.

[0306] The aqueous phase was prepared by mixing 390.0 g of the above chitosan stock solution in a jacketed reactor at 25 °C. The oil phase was prepared by mixing 115.9 g of fragrance, 29.0 g of isopropyl myristate, and 4.40 g of Takenate D-110N at room temperature. The oil phase was added to the aqueous phase under high-shear milling to obtain an emulsion with a desired particle size. The emulsion was heated to 60 °C in 45 minutes and then to 95 °C in 60 minutes. Once 95 °C was reached, a solution of 4.52 g of CD9055, 4.52 g of RO water, and 4.97 g of 21.5% NaOH (prepared in an ice bath) was added to the slurry within 1 minute, then 4.20 g of SR268 was added within 1 minute, then held at 95 °C for 180 minutes, then 1.90 g of potassium persulfate was added within 1 minute, and subsequently held at 95 °C for 180 minutes. Then the temperature was lowered to 25 °C in 90 minutes. The capsules formed had a median particle size of 28.44 microns. The slurry prepared did not show aggregation in a heavy-duty liquid laundry detergent matrix.

[0307] ​

[0308] The chitosan stock solution was prepared by dispersing 155.7 g of chitosan Chitoclear into 3304 g of deionized water while mixing in a jacketed reactor. 1.56 g of potassium persulfate was added. Then the pH of the chitosan dispersion was adjusted to 5.84 using 57.24 g of concentrated HCl with stirring. Then the temperature of the chitosan solution was raised to 65 °C in 30 minutes, then to 85 °C in 30 minutes, then to 95 °C in 30 minutes, and then held at 95 °C for 2 hours to hydrolyze ChitoClear. Then the temperature was lowered to 25 °C in 90 minutes after the hydrolysis step. The pH of the acid-treated chitosan solution was 5.83.

[0309] The aqueous phase was prepared by mixing 433.6 g of the above chitosan stock solution in a jacketed reactor at 25 °C. The oil phase was prepared by mixing 129.0 g of fragrance, 32.0 g of isopropyl myristate, and 4.88 g of Takenate D-110N at room temperature. The oil phase was added to the aqueous phase under high-shear milling to obtain an emulsion with a desired particle size. The emulsion was heated to 60 °C in 45 minutes and then to 95 °C in 60 minutes. Thirty 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) was added to the slurry within 1 minute, and subsequently held at 95 °C for 360 minutes. Then the temperature was lowered to 25 °C in 90 minutes. The capsules formed had a median particle size of 27.86 microns. The slurry prepared did not show aggregation in a heavy-duty liquid laundry detergent matrix.

[0310] Example 20. In-situ modification of cross-linked chitosan delivery particles using CD9055 neutralized to 50 mol% based on chitosan, 5.5 mol% of SR268, and 10% by mass of KPS

[0311] The chitosan stock solution was prepared by dispersing 155.7 g of chitosan Chitoclear into 3304 g of deionized water while mixing in a jacketed reactor. 1.56 g of potassium persulfate was added. Then the pH of the chitosan dispersion was adjusted to 5.84 using 57.37 g of concentrated HCl under stirring. Then the temperature of the chitosan solution was raised to 65 °C within 30 minutes, then to 85 °C within 30 minutes, then to 95 °C within 30 minutes, and then held at 95 °C for 2 hours to hydrolyze ChitoClear. Then the temperature was lowered to 25 °C within 90 minutes after the hydrolysis step. The pH of the acid-treated chitosan solution was 5.82.

[0312] The aqueous phase was prepared by mixing 432.5 g of the above chitosan stock solution in a jacketed reactor at 25 °C. The oil phase was prepared by mixing 110.0 g of fragrance, 27.3 g of isopropyl myristate, and 4.15 g of Takenate D-110N at room temperature. The oil phase was added to the aqueous phase under high-shear milling to obtain an emulsion with a desired particle size. The emulsion was heated to 60 °C within 45 minutes, and then to 95 °C within 60 minutes. Once 95 °C was reached, a solution of 9.29 g of CD9055, 9.29 g of RO water, and 10.22 g of 21.5% NaOH (prepared in an ice bath) was added to the slurry within 1 minute, then 1.95 g of SR268 was added within 1 minute, then held at 95 °C for 180 minutes, then 1.96 g of potassium persulfate was added within 1 minute, and subsequently held at 95 °C for 180 minutes. Then the temperature was lowered to 25 °C within 90 minutes. The formed capsules had a median particle size of 30.26 microns.

[0313] Example 21. Modification of cross-linked chitosan delivery particles using CD9055, SR268, and KPS

[0314] The modified chitosan solution was prepared by dispersing 42.11 g of chitosan powder in 840.00 g of water at 70 °C. Then the pH of the chitosan solution was adjusted to 4.85 using 11.06 g of glacial acetic acid. Then 35.82 g of CD9055 (acidic acrylate oligomer) was added to the above chitosan mixture and mixed at 70 °C for 12 hours to obtain a CD9055-modified chitosan solution. The pH of the obtained modified chitosan solution was 3.86.

[0315] Place 266.7 g of the above-mentioned modified chitosan solution in a jacketed reactor at 25 °C, and then adjust the pH of the chitosan solution to 9.27 with 18.84 g of 21.5% sodium hydroxide solution at room temperature. Then add a potassium persulfate solution containing 2.06 g of potassium persulfate and 50 g of water to the chitosan solution to form an aqueous phase.

[0316] Prepare an oil phase by mixing 99.71 g of fragrance, 2.72 g of Takenate D110 and 24.93 g of isopropyl myristate in a beaker at 25 °C.

[0317] Add the oil phase to the aqueous phase under high shear for a period of time to obtain an emulsion at room temperature.

[0318] Heat the emulsion to 70 °C, and then add 13 g of SR268 to the emulsion. Then heat the emulsion to 90 °C in 60 minutes and hold for 8 hours to cure the wall. Then cool the emulsion to 25 °C in 90 minutes. The obtained encapsulated product in the form of an aqueous slurry has a median particle size of 43.94 microns. The QFO and 1-week leakage of the capsule slurry are 0.13% and 3.27% respectively. The prepared slurry does not show aggregation in a heavy-duty liquid laundry detergent matrix.

[0319] The dimensions and values disclosed herein should not be construed as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to represent the recited value and a range functionally equivalent to that value. For example, a dimension disclosed as "40 mm" is intended to represent "about 40 mm".

[0320] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of its filing date, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, or that it alone or in any combination with any one or more other references anticipates, suggests, or discloses any such invention. Further, when any meaning or definition of a term in this invention conflicts with the same term's meaning or definition in a document incorporated by reference, the meaning or definition assigned to the term in this invention shall govern.

[0321] Although specific embodiments of the invention have been illustrated and described, it will be apparent 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. Accordingly, it is intended that all such changes and modifications that fall within the scope of the invention be covered by the appended claims.

Claims

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

2. The treatment composition according to claim 1, wherein the modifying compound comprises a cationic group, an anionic group, a nonionic group, or a mixture thereof.

3. The treatment composition according to any one of claims 1 or 2, wherein the modifying compound comprises a cationic group, an anionic group, or a mixture thereof, more preferably comprising an anionic group.

4. The treatment composition according to any one of the preceding claims, wherein the modifying compound comprises an acidic group, a hydroxy group, a quaternary ammonium group, or a mixture thereof, preferably an acidic group.

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

6. The treatment composition according to any one of the preceding claims, wherein 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 ketones, vinyl sulfones, vinyl phosphonates, acrylonitrile, or combinations thereof, preferably wherein the α,β-unsaturated compound is selected from the group consisting of: acrylic acid, acrylate salts, acrylates, alkyl acrylates, α,β-unsaturated esters, maleic acid, vinylsulfonic 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, N,N-dialkylaminoalkyl acrylamides, (3-acrylamidopropyl)trimethylammonium salts, acrylamide, acrylamide salts, 3-sulfopropyl acrylate salts, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, quaternized vinylimidazoles, diallyldialkylammonium salts, vinylamine, vinyl ketones, vinyl sulfones, vinyl phosphonates, acrylonitrile, and combinations thereof.

7. The treatment composition according to any one of the preceding claims, wherein the modifying compound comprises a material selected from the group consisting of glycidyltrimethylammonium salts, 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, algal aldehyde, acrylic acid, acrylate salts, maleic acid, vinylsulfonic 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, N,N-dialkylaminoalkyl acrylamides, (3-acrylamidopropyl)trimethylammonium salts, 3-sulfopropyl acrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, quaternized vinylimidazole, diallyldialkylammonium salts, vinylamine, and combinations thereof.

8. The treatment composition according to any one of the preceding claims, wherein the chitosan comprises a free amine moiety, and wherein the molar ratio of the modifying compound to the free amine moiety of the chitosan is from 0.1% to 100%, preferably from 10% to 100%, more preferably from 10% to 90%, even more preferably from 25% to 90%, and even more preferably from 25% to 75%.

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

10. The treatment composition according to any one of the preceding claims, 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.

11. A treatment composition comprising a treatment aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, wherein the shell comprises a polymeric material which is a reaction product of at least one modified chitosan and at least one electrophile, wherein the population of delivery particles can be obtained by a method comprising the steps of: forming an aqueous phase by dissolving or dispersing chitosan in an aqueous acidic medium at a pH of 6.5 or lower and a temperature of at least 25 °C, the chitosan having a free amine moiety; forming an oil phase by combining at least one beneficial agent and at least one electrophile, preferably at least one polyisocyanate, optionally with added oil; An emulsion is formed by mixing the oil phase into an excess of the water phase under high-shear agitation, thereby forming droplets of the oil phase dispersed in the water phase; A modifying compound is added to the water phase and / or the emulsion, preferably at least to the water phase, The modifying compound comprises one or more of an epoxide, an aldehyde or an α,β-unsaturated compound, The modifying compound reacts with the free amine moiety of the chitosan; Optionally, the pH of the emulsion is adjusted to a pH of 4 or greater; The emulsion is heated to at least 40 °C for a time sufficient to form a shell at the interface of the droplets and the water phase, the shell surrounding the core.

12. A treatment composition comprising a treatment aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, wherein the shell comprises a polymeric material which is a 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, wherein the modifying compound comprises an epoxide, an aldehyde or an α,β-unsaturated compound covalently bonded to the chitosan, wherein the population of delivery particles can be obtained by a method comprising the steps of: Dissolving or dispersing chitosan into an aqueous phase, the chitosan having an amine moiety; Combining the aqueous phase and the modifying compound; Optionally, the pH of the aqueous phase is adjusted to a pH of 3.0 or higher, preferably pH 3.0 to pH 6; Optionally, the temperature of the aqueous phase is adjusted to 25 °C or higher; The aqueous phase is mixed for a period of time to form modified chitosan, wherein the modifying compound is covalently bonded to the amine moiety of the chitosan via a C-N bond, wherein the modified chitosan remains dissolved in the aqueous phase; Providing an oil phase, including dissolving at least one beneficial agent comprising an oil and at least one electrophile, preferably at least one polyisocyanate, optionally together with a second oil; An emulsion is formed by mixing the oil phase into the aqueous phase under high-shear agitation, thereby forming droplets of the oil phase and the beneficial agent dispersed in the aqueous phase; The emulsion is heated to at least 40 °C for a time sufficient to form the shell at the interface of the droplets and the water phase, the shell surrounding the core.

13. The treatment composition according to any one of the preceding claims, wherein the method by which the population of delivery particles can be obtained further comprises the step of adding a redox initiator to the aqueous phase or the emulsion, wherein the redox initiator comprises a persulfate, a peroxide or a combination thereof.

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

15. The treatment composition according to any one of the preceding claims, wherein the delivery particles comprise from about 1% to about 25% of the shell by weight of the delivery particles.

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