Treatment composition with delivery particles made of chitosan treated with redox initiator

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 chitosan treated with a redox initiator. 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 at least partially made of chitosan treated with a redox initiator. The present disclosure also relates to related methods for 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 materials from natural sources and / or biodegradable materials.

[0003] Delivery particles having a shell at least partially made of a chitosan-based material are known. However, such particles may not deliver the desired level of performance and / or product compatibility. In addition, due to the viscosity-building tendency of chitosan, it may be a challenging material.

[0004] There is a need for improved treatment compositions comprising delivery particles made of chitosan-based materials, and related methods. Summary of the Invention

[0005] The present disclosure relates to a treatment composition comprising chitosan-based core / shell delivery particles, wherein the chitosan used to make the shell is treated with a redox initiator such as persulfate or peroxide.

[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, wherein the shell comprises a polymeric material that is a reaction product of a modified chitosan and a crosslinking agent, wherein the modified chitosan is formed by treating chitosan with a redox initiator, and wherein the redox initiator is selected from the group consisting of persulfates, peroxides, and combinations thereof.

[0007] The present disclosure also relates to a method of making a treatment composition according to the present disclosure, which includes the steps of: providing a base composition, wherein the base composition comprises the treatment aid; and combining the population of delivery particles with the base composition.

[0008] The present disclosure also relates to a method of treating a surface, which method includes the steps of: contacting the surface, preferably a fabric, with a treatment composition according to the present disclosure. Description of the Drawings

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

[0010] Figure 1 Shows a digital image of the delivery particles.

[0011] Figure 2 Shows various images associated with the intensity of each peak measured by the EDX method.

[0012] Figure 3 Shows the EDX spectrogram of a given sample.

[0013] Figure 4 Depicts the charge difference of the particles made according to the present disclosure. Detailed Description

[0014] The present disclosure relates to a treatment composition comprising delivery particles having a shell made at least in part of a chitosan-based material. More specifically, the shell comprises chitosan that has been treated with a redox initiator such as persulfate or peroxide. The chitosan can be further treated with an acid. The resulting modified chitosan is then reacted with a crosslinking agent to form the shell of the delivery particles.

[0015] The resulting particles show benefits in one or more vectors. For example, the delivery particles can be characterized by improved product stability (e.g., in fabric care products), which can be indicated by a reduction in aggregation in the slurry or product. Compared to comparative particles that do not contain, for example, chitosan treated with a redox initiator, the delivery particles can also improve processability, leakage characteristics, performance, and / or biodegradability.

[0016] Generally, chitosan is a material that is challenging to use in solution because it can be difficult to dissolve and / or tends to gradually increase in viscosity. Without wishing to be bound by theory, it is believed that the redox initiator at least partially depolymerizes chitosan. This can produce a chitosan solution characterized by a reduced viscosity, which is easier to process and can contribute to improved particle shell formation.

[0017] In addition, treating chitosan with an acid can also be beneficial. Acidic conditions tend to facilitate the dissolution of chitosan in water. It has also been surprisingly found that acid treatment increases the molecular weight of chitosan but reduces the viscosity of the aqueous phase. The redox initiator used before, during, or after the acid treatment can further reduce the viscosity of chitosan and reduce its molecular weight.

[0018] It has been found that processing chitosan as described herein produces effective (and product-compatible) delivery particles that also exhibit promising biodegradability profiles. Without being bound by theory, it is believed that redox initiator-treated chitosan may be characterized by a relatively low molecular weight and, thus, the chitosan may be more readily broken down during the biodegradation process.

[0019] The chitosan processing, delivery particles, processing compositions, and related methods of the present disclosure will be discussed in more detail below.

[0020] 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 may comprise, consist essentially of, or consist of the components of the present disclosure.

[0021] The term "substantially free of" may be used herein. This means that the indicated material is present in very small amounts, not intentionally added to form part of the composition, or preferably the indicated material is not present at levels detectable by analysis. This means including compositions 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 may 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.

[0022] 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 treating 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 treating 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 soil removal, 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.

[0023] As used herein, the phrase "fabric care composition" includes compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-wash compositions, laundry pre-treatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, 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-treatments, laundry post-treatments, or can be added during the rinse cycle or wash cycle of a laundry operation.

[0024] As used herein, unless otherwise indicated, the terms "delivery particle", "particle", "encapsulate", "microcapsule", and "capsule" are used interchangeably. As used herein, these terms generally refer to core / shell delivery particles.

[0025] As used herein, the terms "shell" and "wall" are used interchangeably with respect to delivery particles, unless otherwise specified.

[0026] Unless otherwise indicated, all component or composition levels are based on the active portion of that component or composition and do not include impurities, such as residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

[0027] Unless otherwise indicated, all temperatures herein are in degrees Celsius (°C). Unless otherwise indicated, all measurements herein are made at 20 °C and atmospheric pressure.

[0028] 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.

[0029] 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 falling within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0030] Treatment composition

[0031] The present disclosure relates to treatment 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 treatment aid, each described in more detail below. The treatment composition may be used in the methods of treating surfaces (such as fabrics) described herein.

[0032] The treatment 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 manufacture or modification.

[0033] 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.

[0034] 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 treatment composition is preferably a fabric conditioning composition, even more preferably a liquid fabric conditioning composition. The consumer product composition can preferably be a laundry detergent composition because the delivery particles described herein have improved compatibility in such product matrices (e.g., in products containing anionic surfactants).

[0035] The composition can be a beauty care composition, such as a hair treatment product (including shampoo and / or conditioner), 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 agents, liquid hand soaps, and / or bar soaps), a deodorant and / or antiperspirant, or a mixture thereof.

[0036] 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.

[0037] The treatment composition may 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 flake, a foam / mousse, a non-woven sheet, or a mixture thereof.

[0038] The treatment composition may be in liquid form. The liquid composition may preferably comprise from about 50% to about 97%, preferably from about 60% to about 96%, more preferably from about 70% to about 95%, or even from about 80% to about 95% water, by weight of the fabric treatment composition. The liquid composition may be a liquid fabric conditioner. The liquid may be packaged in a pourable bottle. The liquid may be packaged in an aerosol can or other spray bottle. Suitable containers are described in more detail below.

[0039] The treatment composition may be in solid form. The composition may be in the form of beads or lozenges, which may be made from a liquid melt. The composition may be an extruded product. The treatment composition may be in the form of a powder or granule.

[0040] The composition may be in the form of a combined dose article 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 may be encapsulated in a single-compartment sachet or a multi-compartment sachet. The multi-compartment sachet may have at least two, at least three, or at least four compartments. The multi-compartment sachet may include compartments that are side-by-side and / or stacked. The composition contained in the sachet or its compartments may be liquid, solid (such as a powder), or a combination thereof. The sachet composition may 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.

[0041] The treatment composition may be in the form of a spray and may be dispensed from a bottle, for example, via a trigger sprayer and / or an aerosol container having a valve.

[0042] The treatment composition may have a viscosity at 20s -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).

[0043] 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 (when present). On the other hand, detergent compositions are 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.

[0044] Additional components and / or features of the composition are discussed in more detail below.

[0045] Delivery particle population

[0046] 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.

[0047] 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.

[0048] 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, preferably, 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.

[0049] 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 level 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 at most about 25%, preferably at most about 20%, preferably at most about 15%, more preferably at most about 12% by weight of the delivery particles.

[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. Delivery particles prepared with chitosan generally exhibit a positive ζ potential. Such capsules have improved deposition efficiency on fabrics. At higher pH values, the particles can be made non-ionic or anionic.

[0051] The delivery particles of the present disclosure comprise a shell surrounding a core. (As used herein, "shell" and "wall" can be used interchangeably with respect to the delivery particles, unless otherwise specified.) The shell comprises a polymeric material. The polymeric material is a reaction product of a modified chitosan and a cross-linking agent.

[0052] The modified chitosan is formed by treating chitosan with a redox initiator. The redox initiator can be selected from the group consisting of persulfates, peroxides, and combinations thereof. The redox initiator can preferably be a persulfate. The redox initiator can preferably be a peroxide.

[0053] The treatment of chitosan with a redox initiator is generally carried out in an aqueous phase, preferably an acidic aqueous phase, and then an emulsion is formed that leads to the formation of the delivery particles. That is, a second redox initiator can be added to the emulsion to further improve the properties and / or product compatibility.

[0054] As mentioned above, it is believed that the redox initiator causes at least partial depolymerization of chitosan and reduces its weight-average molecular weight. It has been found that such modified chitosan shows a reduced viscosity in the aqueous phase, improved product compatibility (e.g., less aggregation / agglomeration in certain fabric care products), good properties, and / or improved biodegradability.

[0055] Suitable redox initiators may include ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof. The redox initiator may preferably be selected from sodium persulfate, hydrogen peroxide, or mixtures thereof. The redox initiator may preferably be sodium persulfate.

[0056] In the reaction for forming the modified chitosan, the redox initiator and chitosan may be present in a weight ratio of from about 90:10 to about 0.01:99.99, preferably from about 50:50 to about 1:99, more preferably from about 30:70 to about 3:97.

[0057] The shell of the delivery particle may contain sulfur atoms, which may be generated, for example, by the interaction between a sulfur-containing redox initiator (such as a persulfate compound) and chitosan. For example, when persulfate is used, the sulfate groups are thought to be ionically bonded to the amino groups of chitosan. The sulfur atoms may be present in the shell at a level of from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, even more preferably from about 0.1% to about 1% by weight of the shell. The presence and amount of sulfur atoms can be determined by energy dispersive X-ray microanalysis according to the EDX method provided in the Test Methods section below.

[0058] It is also believed that treating chitosan under acidic conditions is beneficial. Acidic conditions can improve the solubility of chitosan, making it more available for reaction with redox initiators. It is also believed that acidic conditions can affect the molecular weight and / or structure of chitosan, thereby improving the particles and / or properties.

[0059] For example, the modified chitosan can be formed under acidic conditions at a temperature of at least 25°C, preferably at a pH of 6.5 or lower, preferably less than 6.5, even more preferably at a pH of from about 3 to about 6, more preferably from about 4 to about 6, more preferably from about 5 to about 6, even more preferably from 5.2 to about 6. The acidic conditions may preferably be at a pH of 6.5 or less, preferably less than 6.5, even more preferably at a pH of from 3 to 6.2, or even at a pH of from 5 to 6.2.

[0060] Chitosan (which may be referred to as raw chitosan or parent chitosan before acid treatment and / or redox initiator treatment) can be treated with an acid 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, or for the period of time required to obtain a chitosan solution of acid-treated chitosan having a viscosity of no greater than about 1500 cps, or even no greater than 500 cps.

[0061] The modified chitosan can be an acid-treated modified chitosan. For example, chitosan can be treated with an acid. The acid can include a weak acid. The acid preferably includes a mixture of acids, more preferably a mixture of a first acid and a second acid, where the first acid is a strong acid and where the second acid is a weak acid. Preferably, the first acid and the second acid are present in an equivalent concentration ratio of from about 20:80 to about 80:20, preferably from about 35:65 to about 65:35. The first acid can have a first pKa of less than 1, and the second acid can have a first pKa of 5.5 or less. Preferably, the second acid has a first pKa of from 1 to 5.5.

[0062] The first acid can comprise, consist essentially of, or consist of a strong acid selected from the group consisting of hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, and mixtures thereof, preferably hydrochloric acid. The second acid can comprise, consist essentially of, or consist of a weak acid selected from the group consisting of formic acid, acetic acid, ascorbic acid, glutamic acid, lactic acid, maleic acid, malic acid, succinic acid, citric acid, acrylic acid, oxalic acid, tartaric acid, and mixtures thereof, preferably formic acid, acetic acid, and mixtures thereof.

[0063] Before treating chitosan with a redox initiator, it can be treated with an acid. However, for at least some of the treatment methods, it may be convenient to treat chitosan with a redox initiator and an acid simultaneously. For example, chitosan can be dissolved or dispersed in an acidic aqueous phase, and a redox initiator can be added after dissolution / dispersion. Alternatively, the acid and the redox initiator can be provided to the aqueous phase (in any suitable order), and then chitosan can be added and dissolved / dispersed.

[0064] It is believed that selecting chitosan and / or modified chitosan having a specific molecular weight can help improve processability, properties, and / or biodegradability. Chitosan that is relatively too large can result in a highly viscous solution that is difficult to handle. Chitosan that is relatively too small can result in poor shell formation, which may be due to an increased solubility of chitosan, resulting in chitosan being less likely to migrate to the water / oil interface during shell formation.

[0065] The characteristics of chitosan before treatment with a redox initiator and / or an acid, preferably before treatment with a redox initiator at least, can be 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.

[0066] The characteristics of the modified chitosan after treatment with a redox initiator and / or an acid, preferably at least after treatment with a redox initiator, may lie in a weight average molecular weight of from about 1 kDa to about 600 kDa, preferably from about 5 kDa to about 300 kDa, more preferably from about 10 kDa to about 200 kDa, more preferably from about 15 kDa to about 150 kDa, even more preferably from about 20 kDa to about 100 kDa. The characteristics of the modified chitosan may lie in a weight average molecular weight of from about 1 kDa to about 600 kDa, preferably from about 5 kDa to about 300 kDa, more preferably from about 30 kDa to about 100 kDa.

[0067] Chitosan may 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%, 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%) results in relatively insoluble and relatively unreactive chitosan. A relatively high degree of deacetylation can result in very soluble chitosan, thus resulting in relatively little chitosan traveling to the oil / water interface during shell formation.

[0068] Chitosan may be further modified with a charged moiety. For example, chitosan before or after treatment with a redox initiator may 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 particle, e.g., by changing the surface charge and / or zeta potential, which affects the deposition efficiency of the particle and / or the formulation compatibility. For example, the modified chitosan may be further modified with a modifying compound, where the modifying compound includes an epoxide, an aldehyde, an α,β-unsaturated compound, or a combination thereof.

[0069] As mentioned above, the shell is a polymeric material that is a reaction product of chitosan and a crosslinker. Preferably, the crosslinker comprises a polyisocyanate. Thus, the shell of the delivery particle may comprise a polyurea resin, where the polyurea resin comprises the reaction product of a polyisocyanate and chitosan.

[0070] The polyisocyanate materials useful in the present disclosure are to be understood, for the purposes of the present disclosure, 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 encompassed 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.

[0071] 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 to be understood as polyisocyanates containing at least one aromatic moiety. The crosslinking agent can comprise a mixture of aromatic and aliphatic polyisocyanates.

[0072] Polyisocyanates, when aromatic, can be but are not limited to methylene diphenyl diisocyanate, toluene diisocyanate, tetramethylxylidene diisocyanate, the polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name RC), the trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name L75), naphthalene-1,5-diisocyanate, phenylene diisocyanate, or the trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name D-110N).

[0073] Aliphatic polyisocyanates can 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).

[0074] Derivatives of polyisocyanates can include oligomers or polymers of isocyanate monomers. As a non-limiting example, the polyisocyanate can preferably contain oligomers or polymers of diphenylmethane diisocyanate (MDI), such as MR-Light.

[0075] The polyisocyanate can preferably be selected from the group consisting of: polyisocyanurates of tolylene diisocyanate; trimethylolpropane adducts of tolylene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; tolylene diisocyanate; tetramethylxylylene 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.

[0076] 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 to strengthen the shell.

[0077] The polymeric material can be formed in a reaction in which the weight ratio of chitosan present in the reaction to the crosslinking agent present in the reaction is from about 1:10 to about 1:0.1. It is believed that selecting the desired ratio of biopolymer to crosslinking agent can provide the desired ductility benefits as well as improved biodegradability. Preferably, at least 21% by weight of the shell consists of a portion derived from chitosan, preferably derived from 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 crosslinking agent (preferably isocyanate) in the oil phase can be from 21:79 to 90:10, or even from 1:2 to 9:1, or even from 1:1 to 7:1. The polymeric material can be formed in a reaction in which the weight ratio of chitosan or its derivatives (which can include acid-treated chitosan) present in the reaction to the crosslinking agent present in the reaction is from about 1:10 to about 10:1, preferably from about 1:5 to about 5:1, preferably from about 1:4 to about 5:1, more preferably from about 1:1 to about 5:1, more preferably from about 3:1 to about 5:1. The shell can contain chitosan at a level of 21% by weight or even higher, preferably from about 21% to about 90% by weight, or even from 21% to 85% by weight, or even from 21% to 75% by weight, or 21% to 55% by weight of the total shell. The chitosan in this paragraph is preferably the modified chitosan as described herein.

[0078] The delivery particles can be obtained by or even made by a method comprising the following steps: forming an aqueous phase by treating chitosan with a redox initiator in the presence of water at a pH of 6.5 or lower and at a temperature of at least 25 °C, preferably for at least one hour and / or for a time until the aqueous phase is characterized by a viscosity of less than 1500 cp, preferably less than 500 cp, to form modified chitosan, preferably wherein the aqueous phase further comprises a mixture of a first acid and a second acid; forming an oil phase, the forming step comprising dissolving at least one beneficial agent and at least one crosslinking agent, preferably a polyisocyanate, optionally with an added oil, preferably a partitioning modifier; forming an emulsion by mixing the oil phase, preferably under high-shear agitation, into an excess of the aqueous phase so as to form droplets of the oil phase dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to be within the range of pH 2 to pH 6; optionally, providing a second redox initiator to the emulsion, wherein the second redox initiator is the same as or different from the redox initiator added to the aqueous phase; curing the emulsion at a temperature of at least 40 °C for a time sufficient to form a shell at the interface between the droplets and the aqueous phase, the shell comprising the reaction product of the crosslinking agent and the modified chitosan, and the shell surrounding a core comprising the droplets of the oil phase.

[0079] As described above, a redox initiator can be added to the aqueous phase and optionally to the emulsion. When a redox initiator is added to both phases, the redox initiator provided to the aqueous phase can be considered the first redox initiator, and the redox initiator provided to the emulsion can be considered the second redox initiator. When the second redox initiator is added to the emulsion, the second redox initiator can be the same as or different from the (first) redox initiator added to the aqueous phase. For ease of processing, it can be preferred that the first and second redox initiators are the same. For performance reasons, it can be preferred that the first and second redox initiators are different; for example, it is believed that beneficial results can be obtained by adding a persulfate to the aqueous phase and subsequently adding a peroxide to the emulsion. The relative amounts of the first and second redox initiators can be different. Note that although the present invention uses "first" and "second" redox initiators to describe the redox initiators added at the aqueous phase and / or emulsion phases, respectively, it should be understood that more than one redox initiator can be added at any suitable stage, or even more than one redox initiator can be added in batches at any stage.

[0080] Although the present disclosure generally relates to the modification of chitosan with a redox initiator in an aqueous phase (usually further in the presence of an acid), it is also contemplated that the chitosan can be modified with a redox initiator at a later stage during the particle formation process. For example, it is contemplated that the redox initiator can be added to the emulsion, and possibly or even preferably only to the emulsion (e.g., not providing the redox initiator to the aqueous phase).

[0081] Chitosan can be added to water in a jacketed reactor and at a pH adjusted to 2 or even 3 to 6.5 using an acid such as concentrated HCl and / or a weak acid such as formic acid or acetic acid. The redox initiator can be added to the aqueous phase simultaneously. The chitosan in the mixture can be heat-treated by heating to an elevated temperature such as 85°C within 60 minutes, and then it can be maintained at that temperature for 1 minute to 1440 minutes or longer. Then the aqueous phase can be cooled to 25°C. Optionally, deacetylation can also be further promoted or enhanced by an enzyme to depolymerize or deacetylate the chitosan. The oil phase can be prepared by dissolving an isocyanate such as a trimer of xylylene diisocyanate (XDI) or a polymer of methylene diphenyl diisocyanate (MDI) in oil at 25°C. A diluent such as isopropyl myristate can be used to adjust the hydrophobicity of the oil phase. Then the oil phase can be added to the aqueous phase and ground at high speed to obtain the target size. Then the emulsion can be cured in one or more heating steps, such as heating to 40°C within 30 minutes and maintaining at 40°C for 60 minutes. The time and temperature are approximate. The temperature and time are selected to be sufficient to form and cure a shell at the interface of the droplets of the oil phase and the water continuous phase. For example, the emulsion can be heated to 85°C within 60 minutes, and then maintained at 85°C for 360 minutes to cure the particles. Then the slurry can be cooled to room temperature.

[0082] 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% in 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, more preferably 14 days.

[0083] The delivery particles of the present disclosure include a core. The core contains a beneficial agent. The core optionally contains a partitioning modifier.

[0084] 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 can diffuse out of the granule, and / or it can be extruded. Suitable beneficial agents located in the core can include beneficial agents that provide beneficial effects to surfaces such as fabrics or hair.

[0085] The core can contain from about 5% to about 100% by weight of the core of the beneficial agent, which can preferably contain a fragrance. The core can 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 can preferably contain a fragrance.

[0086] The beneficial agent can include 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 can contain 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 the aldehyde-containing beneficial agent, the ketone-containing beneficial agent, or a combination thereof.

[0087] The beneficial agent can be a hydrophobic beneficial agent. Such agents are compatible with the oil phase commonly found in preparing the delivery granules of the present disclosure.

[0088] The beneficial agent is selected to provide a benefit under the preferred use of the treatment composition. The beneficial agent in the core can 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 drapes and morphology control agents, smoothers, wrinkle control agents, hygiene treatment agents, disinfectants, microbial control agents, mold control agents, mildew 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 recovery / restoration 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-allergy agents, enzymes, water repellents, fabric comfort agents, anti-shrinkage agents, anti-stretching agents, stretch recovery agents, skin care agents, synthetic or natural active substances, antibacterial active substances, antiperspirant active substances, cationic polymers, dyes, and mixtures thereof.

[0089] The beneficial agent in the core preferably includes a fragrance material (or simply "fragrance"), which can include one or more fragrance raw materials. Fragrances are particularly suitable for encapsulation in the delivery granules described in the present invention because fragrance-containing granules can provide a fresh beneficial effect across multiple contact points.

[0090] 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 which can be used alone or in combination with other perfume raw materials to impart an odor, aroma, essence or fragrance. Typical PRMs include, inter alia, 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).

[0091] 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 as logP and is determined according to the test methods below. Based on these properties, PRMs can be classified as first quadrant, second quadrant, third quadrant or fourth quadrant perfumes, as detailed in U.S. Patent 6,869,923. Suitable first quadrant, second quadrant, third quadrant and fourth quadrant perfume raw materials are disclosed therein.

[0092] Perfume raw materials having a boiling point B.P. below about 250 °C and a logP less than about 3 are referred to as first quadrant perfume raw materials. First quadrant perfume raw materials are preferably limited to less than 30% of the fragrance material.

[0093] The fragrance can include perfume raw materials having a logP of about 2.5 to about 4. It should be understood that other perfume raw materials can also be present in the fragrance.

[0094] The core of the delivery particles of the present disclosure can contain a partitioning modifier that can promote more robust shell formation. The partitioning modifier can be combined with the perfume oil material of the core before incorporation of 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.

[0095] The partitioning modifier can contain a material selected from the group consisting of vegetable oils, modified vegetable oils, monoesters, diesters and triesters of C4-C 24 monoesters, diesters and triesters of fatty acids, isopropyl myristate, lauryl benzophenone,

[0096] Lauryl laurate, methyl docosanoate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning 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 partitioning modifiers that may be used in the delivery particles described herein.

[0097] In cases where the beneficial agent itself is not sufficient to serve as the oil phase or solvent (especially 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 generally oils, preferably having a boiling point greater than about 80 °C, low volatility, and being non-flammable. Although not limited thereto, they preferably comprise one or more esters, preferably esters having a chain length of at most 18 carbon atoms or even at most 42 carbon atoms and / or triglycerides, such as esters of C6 to C12 fatty acids with glycerol.

[0098] 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 alkyl benzene sulfonates), non-ionic surfactants (such as alkoxylated alcohols, preferably containing ethoxy groups), polyvinyl alcohol, and / or polyvinyl pyrrolidone. It is possible in the present application that dissolved chitosan can provide emulsification benefits. The emulsifier (if employed) is typically 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.

[0099] The population of delivery particles may be provided as a slurry, preferably an aqueous slurry. The slurry may comprise one or more processing aids, which may include water, aggregation-inhibiting materials (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 non-ionic structuring agents, are preferred, for example to avoid harmful charge interactions that can lead to undesirable aggregation.

[0100] 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, fragrance raw materials, silicone oil, hydrocarbon paraffin oil; and mixtures thereof. An aqueous slurry may be preferred. The slurry may comprise unencapsulated ( "free") fragrance raw materials that differ in properties and / or amount from those encapsulated in the core of the delivery particles.

[0101] 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; polyglycerether silicone crosslinked polymers; copolymers of polyacrylic acid, polyacrylate, polyvinylamine and polyvinyl alcohol oligomers of 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 having 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.

[0102] 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 group consisting of silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride and binders such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0103] Suitable apparatuses for use in the methods disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plowshare shear mixers, ribbon blenders, vertical axis granulators, and tumbling mixers (both of which may be in batch process configurations and continuous process configurations (when available)), spray dryers, and extruders. Such apparatuses may 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.).

[0104] Auxiliary ingredient

[0105] In addition to delivering the particles, the therapeutic compositions of the present disclosure may further comprise one or more adjuvant materials. The adjuvant materials may provide beneficial effects in the intended end use of the composition, or they may be processing aids and / or stabilizing aids.

[0106] Suitable adjuvant materials may include: surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / anti-redeposition agents, optical brighteners, defoamers, silicones, colorants, aesthetic dyes, additional fragrances and fragrance delivery systems, structure elasticizers, carriers, hydrotropes, processing aids, anti-caking agents, 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.

[0107] Depending on the desired form, formulation, and / or end use, the compositions of the present disclosure may not include one or more of the following adjunct materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / antiredeposition agents, optical brighteners, defoamers, dyes, additional fragrances and fragrance delivery systems, structurants, fabric softeners, carriers, hydrotropes, processing aids, structuring agents, anti-caking agents, coatings, formaldehyde scavengers, and / or pigments.

[0108] 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 to be used. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below. The following is a non-limiting list of suitable additional adjuncts.

[0109] A. Surfactant

[0110] The compositions of the present disclosure may include surfactants. For example, surfactants can be used to provide cleaning benefits. The composition may include a surfactant system, which may include one or more surfactants.

[0111] The compositions of the present disclosure may include 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 include 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 include from about 25% to about 70% or from about 30% to about 50% by weight of the composition of the surfactant system.

[0112] 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 surfactants may be at least partially derived from natural sources, such as natural raw material alcohols.

[0113] 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 straight-chain, branched-chain, 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.

[0114] 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 straight-chain, branched-chain (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 a C12-C14 EO7 nonionic surfactant.

[0115] Suitable zwitterionic surfactants can include any conventional zwitterionic surfactant, such as betaines, including alkyl dimethyl betaines and coconut oil 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, where the alkyl group can be C8 to C 18 or C 10 to C 14Zwitterionic surfactants may include amine oxides.

[0116] 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.

[0117] Treatment compositions may contain anionic surfactants because it has been found that the delivery particles of the present disclosure are surprisingly compatible in such products. For example, a consumer product composition may preferably be a laundry detergent composition (e.g., a heavy-duty liquid or soluble unit-dose product) containing an anionic surfactant; such compositions typically also contain additional surfactants (such as nonionic surfactants) and / or other ingredients.

[0118] b. Conditioning active substance

[0119] The compositions of the present disclosure may contain conditioning actives. Compositions containing conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color and / or appearance benefits.

[0120] 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 active. The composition may contain from about 5% to about 30% by weight of the conditioning active.

[0121] 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 the one or more adjuvant components comprise a quaternary ammonium ester material; such materials are particularly useful in fabric enhancing / conditioning / softening compositions.

[0122] The composition may comprise 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 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 comprise the quaternary ammonium ester compound and the silicone in a weight ratio of about 1:10 to about 10:1, or about 1:5 to about 5:1, or about 1:3 to about 1:3, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.

[0123] The composition may comprise a mixture of different types of conditioning actives. The compositions of the present disclosure may comprise 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 comprise a quaternary ammonium ester compound, but be substantially free of silicones. The composition may comprise a silicone, but be substantially free of quaternary ammonium ester compounds.

[0124] C. Deposition aid

[0125] The compositions of the present disclosure may comprise a deposition aid. As described above, due to the synergistic beneficial effects from the ester quaternary compound material 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, a deposition aid may be used in the compositions of the present disclosure to further enhance performance.

[0126] The deposition aid may facilitate the deposition of the delivery particles, conditioning actives, fragrance, or a combination thereof, thereby improving the performance benefits of the composition and / or allowing for more efficient formulation of such beneficial agents. The composition may comprise 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.

[0127] Generally speaking, cationic polymers and their methods of manufacture are known in the literature. Suitable cationic polymers may include quaternary ammonium polymers referred to 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.

[0128] The deposition aids may be selected from the group consisting of: polyvinylformamide, partially hydroxylated polyvinylformamide, polyvinylamine, polyethyleneimine, ethoxylated polyethyleneimine, polyvinyl alcohol, polyacrylate, and combinations thereof. The cationic polymer may include cationic acrylate.

[0129] The deposition aids may be added simultaneously with the delivery particles (simultaneously with, for example, an encapsulated benefit 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.

[0130] d. Rheology modifier / structurant

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

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

[0133] The polymeric structuring agents may be of natural or synthetic origin. Natural origin polymeric structurants may include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives may include: pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structurants may include: polycarboxylate, polyacrylate, hydrophobically modified ethoxylated polyurethane, hydrophobically modified nonionic polyol, and mixtures thereof. Polycarboxylate polymers may include polyacrylate, polymethacrylate, or mixtures thereof. Polyacrylate may include unsaturated mono- or di-carboxylic acids and C1-C 30Copolymers of alkyl esters. 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.

[0134] E. Other auxiliaries

[0135] The treatment compositions of the present disclosure may comprise other auxiliaries suitable for inclusion in products and / or suitable for end use. For example, the treatment compositions may comprise pure fragrances, fragrance delivery technologies (such as pre-fragrances and / or encapsulates having non-polyisocyanate / chitosan wall materials), cationic surfactants, cationic polymers, solvents, defoamers, or combinations thereof.

[0136] Method for preparing a treatment composition

[0137] The present disclosure further relates to methods for making treatment compositions, such as those treatment compositions and / or consumer product compositions described herein.

[0138] The method may comprise the steps of: providing a base composition, wherein the base composition comprises treatment aids; and combining a population of delivery particles with the base composition. The population of delivery particles may preferably be provided as an aqueous slurry. The base composition is in the form of a liquid composition.

[0139] 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 can be combined with one or more auxiliary components. The delivery particles can be combined with such auxiliaries by methods including mixing and / or spraying.

[0140] The treatment compositions of the present disclosure can be formulated into any suitable form and prepared by any method chosen by the formulator. The one or more auxiliary components and delivery particles can 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 can 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 tumble mixers (both of which can be in batch process configurations and continuous process configurations (when available)), spray dryers, and extruders.

[0141] The treatment composition can be placed in a container to form a consumer product as described herein. The container can be a bottle, preferably a plastic bottle. The treatment composition can be placed in an aerosol or other spray container according to known methods.

[0142] Treatment method

[0143] The present disclosure also relates to a method of treating a surface, preferably a fabric. Generally speaking, the method includes the step of contacting the surface, preferably the fabric, with a treatment composition according to the present disclosure, wherein the treatment composition comprises a population of delivery particles as described herein.

[0144] Additionally or alternatively, the method can include the step of contacting the surface, preferably the fabric, with a population of delivery particles as described herein. The population of delivery particles can be included in a treatment composition according to the present disclosure, preferably a fabric care composition.

[0145] The method can include the step of contacting a fabric (such as a piece of clothing) with the 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 include a core and a shell surrounding the core, wherein the core comprises a beneficial agent, which is preferably an aromatic material comprising one or more fragrance ingredients. 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.

[0146] The contacting step can be carried out during a manual laundry process, for example, in a sink when handling the fabric by hand, or during an automatic laundry process, for example, in an automatic washing machine. The contacting step can be carried out during the wash cycle of an automatic washing machine; in such cases, the treatment composition can be a laundry detergent or a laundry washing additive. The contacting step can preferably be carried out during the rinse cycle of an automatic washing machine; in such cases, the treatment composition can be a fabric enhancer, preferably a liquid fabric enhancer. The contacting step can even be carried out during the drying step of a laundry process, for example, in an automatic dryer; in such cases, the treatment composition can be in the form of a non-woven dryer sheet or a dryer bar. The contacting step can occur as a result of the treatment composition being directly applied to the fabric, for example, in a pre-treatment operation or in a "refreshing" step (e.g., for a fabric that has been used or worn since the last wash); in such cases, the treatment composition can be in the form of a liquid, a bar, or a spray, preferably a spray. Contacting the target fabric relatively late in the laundry process (e.g., during the rinse cycle) increases the likelihood or efficiency of deposition onto the fabric because they are less likely to be washed down the drain.

[0147] 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 about 100-fold to about 1500-fold, preferably 300-fold to about 1000-fold.

[0148] The liquid containing the disclosed composition can have a pH of about 3 to about 11.5. Such compositions are typically used at a concentration of about 500 ppm to about 15,000 ppm in solution when diluted. When the washing solvent is water, the water temperature is generally in the range of about 5°C to about 90°C, and the ratio of water to fabric can generally be about 1:1 to about 30:1.

[0149] Dilution can be carried out in the drum of an automatic washing machine. The treatment composition can be placed in the dispensing drawer of the automatic washing machine. During the treatment process, the treatment composition can be dispensed from the dispensing drawer into the drum.

[0150] As described above, the method can further include a step of drying the fabric having one or more delivery particles on its surface. The drying step can include a passive drying process, such as on a clothesline or drying rack. The drying step can include an automatic drying process, such as in an automatic dryer.

[0151] Combination

[0152] Specifically contemplated combinations of the present disclosure are described herein in the following lettered paragraphs. These combinations are illustrative in nature and not restrictive.

[0153] A. 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 contains a beneficial agent, wherein the shell contains a polymeric material which is a reaction product of a modified chitosan and a crosslinking agent, wherein the modified chitosan is formed by treating chitosan with a redox initiator, and wherein the redox initiator is selected from the group consisting of persulfates, peroxides, and combinations thereof.

[0154] B. The treatment composition according to paragraph A, wherein the redox initiator is selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof, preferably sodium persulfate, hydrogen peroxide, and mixtures thereof, more preferably sodium persulfate.

[0155] C. The treatment composition according to any one of paragraphs A or B, wherein the redox initiator and the chitosan are present in a weight ratio of about 90:10 to about 0.01:99.99, preferably about 50:50 to about 1:99, more preferably about 30:70 to about 3:97.

[0156] D. A treating composition according to any one of paragraphs A to C, wherein the shell of the delivery particle comprises sulfur atoms, preferably wherein the sulfur atoms are present in the shell at a level of from about 0.1% to about 20%, more preferably from about 0.1% to 10%, even more preferably from about 0.1% to 1% by weight of the shell.

[0157] E. A treating composition according to any one of paragraphs A to D, wherein the modified chitosan is formed under acidic conditions at a temperature of at least 25°C, preferably at a pH of 6.5 or lower, preferably less than 6.5, even more preferably at a pH of from about 3 to about 6, even more preferably at a pH of from about 4 to about 6, preferably from about 5 to about 6, more preferably from 5.2 to 6; alternatively, preferably at a pH of 6.5 or lower, preferably less than 6.5, even more preferably at a pH of from 3 to 6.2, or even at a pH of from 5 to 6.2.

[0158] F. A treating composition according to any one of paragraphs A to E, wherein the modified chitosan is an acid-treated modified chitosan, wherein the chitosan has been further treated with an acid, preferably a mixture of acids, more preferably a mixture of a first acid and a second acid, wherein the first acid is a strong acid and wherein the second acid is a weak acid, preferably wherein the first acid and the second acid are present in an equivalent concentration ratio of from about 20:80 to about 80:20, preferably from about 35:65 to about 65:35.

[0159] G. A treating composition according to any one of paragraphs A to F, wherein at least one of the following is true: (a) the chitosan before treatment with the redox initiator and / or acid is characterized by a weight average molecular weight of from about 100 kDa to about 600 kDa, preferably from about 100 kDa to about

[0160] 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;

[0161] and / or (b) the modified chitosan is characterized by a weight average molecular weight of from about 1 kDa to about 600 kDa, preferably from about

[0162] 5 kDa to about 300 kDa, more preferably from about 10 kDa to about 200 kDa, more preferably from about

[0163] 15 kDa to about 150 kDa, even more preferably from about 20 kDa to about 100 kDa.

[0164] H. A treatment composition according to any one of paragraphs A to G, wherein the crosslinking agent 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;

[0165] tetramethylbenzene dimethylene 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.

[0166] I. A treatment composition according to any one of paragraphs A to H, wherein the reaction product is formed in a reaction in which the weight ratio of the chitosan present in the reaction to the crosslinking agent present in the reaction is from about 1:10 to about 1:0.1.

[0167] J. A treatment composition according to any one of paragraphs A to I, wherein the shell is present in the delivery particles at a level of about 15 wt% or less, based on the weight of the delivery particles.

[0168] K. A treatment composition according to any one of paragraphs A to J, wherein the beneficial agent is an aromatic material, preferably an aromatic material comprising a perfume raw material characterized by a logP of about 2.5 to about 4.5.

[0169] L. A treatment composition according to any one of paragraphs A to K, wherein the core further comprises a partitioning modifier, optionally present in the core at a level of about 5% to about 55%, preferably about 10% to about 50%, more preferably about 25% to about 50% by weight of the core, preferably a partitioning modifier selected from the group consisting of: vegetable oil, modified vegetable oil, mono-esters, di-esters and tri-esters of C4-C 24 fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate and mixtures thereof, more preferably isopropyl myristate.

[0170] M. A treatment composition according to any one of paragraphs A to L, 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, even more preferably from about 25 microns to about 35 microns.

[0171] N. A treatment composition according to any one of paragraphs A to M, wherein the delivery particles can be obtained from a method comprising the steps of: forming an aqueous phase by treating the chitosan with the redox initiator in the presence of water at a pH of 6.5 or lower and at a temperature of at least 25 °C, preferably for at least one hour and / or for a time until the aqueous phase is characterized by a viscosity of less than 1500 cp, preferably less than 500 cp, to form the modified chitosan, preferably wherein the aqueous phase further comprises a mixture of the first acid and the second acid; forming an oil phase, the forming step comprising dissolving at least one beneficial agent and at least one crosslinking agent, preferably a polyisocyanate, optionally with an added oil, preferably a partitioning modifier; forming an emulsion by mixing the oil phase, preferably under high shear agitation, into an excess of the aqueous phase so as to form droplets of the oil phase dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to be in the range of pH 2 to pH 6;

[0172] Optionally, a second redox initiator is provided to the emulsion, wherein the second redox initiator is the same as or different from the redox initiator added to the aqueous phase; curing the emulsion at a temperature of at least 40 °C for a time sufficient to form a shell at the interface between the droplets and the aqueous phase, the shell comprising the reaction product of the crosslinking agent and the modified chitosan, and the shell surrounding the core of the droplets comprising the oil phase.

[0173] O. A treatment composition according to any one of paragraphs A to O, wherein the delivery particles are cationic, preferably wherein the delivery particles are characterized by a ζ potential of at least 15 mV at a pH of 4.5.

[0174] P. A treatment composition according to any one of paragraphs A to O, wherein the modified chitosan is further modified with a modifying compound, wherein the modifying compound comprises an epoxide, an aldehyde, an α,β-unsaturated compound, or a combination thereof.

[0175] Q. A treatment composition according to any one of paragraphs A to P, wherein when tested according to test method OECD 301B, the shell of the delivery particles degrades by at least 60% in 60 days.

[0176] R. A treatment composition according to any one of paragraphs A to Q, 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 / anti-redeposition agents, optical brighteners, defoamers, silicones, colorants, aesthetic dyes, perfume, additional perfume delivery systems, structuring elastifiers, carriers, hydrotropes, processing aids, anti-caking agents, coatings, formaldehyde scavengers, pigments, and mixtures thereof.

[0177] S. A treatment composition according to any one of paragraphs A to R, wherein the treatment aid comprises an anionic surfactant, a cationic conditioner, or a mixture thereof.

[0178] T. A treatment composition according to any one of paragraphs A to S, 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, 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.

[0179] U. A treatment composition according to any one of paragraphs A to T, wherein the treatment composition is in the form of a liquid composition, a granular composition, an aqueous colloid, a single-compartment sachet, a multi-compartment sachet, a soluble sheet, a tablet, a bead, a fibrous article, a tablet, a bar, a strip, a wafer, a foam / mousse, a non-woven sheet, or a mixture thereof, preferably in the form of a liquid composition.

[0180] V. A treatment composition according to any one of paragraphs A to U, wherein the treatment composition comprises from about 50% to about 99% water, preferably from about 60% to about 98%, more preferably from about 80% to about 96% water, by weight of the treatment composition.

[0181] W. A method of making a treatment composition according to any one of paragraphs A to V, the method comprising the steps of: providing a base composition, wherein the base composition comprises a treatment aid; and combining the population of delivery particles with the base composition.

[0182] X. A method of treating a surface, the method comprising the step of: contacting the surface, preferably a fabric, with a treatment composition according to any one of paragraphs A to V.

[0183] Test method

[0184] It should be understood that the test methods disclosed in the test method section of the present application should be used to determine the corresponding parameter values of the claimed subject matter of the applicant as claimed and described herein.

[0185] Determination of polymer molecular weight and related parameters

[0186] The method described below for 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.

[0187] 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 molecules to be separated according to their molecular size. MALS and RI allow the obtaining of information on the number-average (Mn) and weight-average (Mw) molecular weights.

[0188] 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 0.1 M sodium nitrate solution 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).

[0189] Typically, a sample is 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.

[0190] 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) were determined using the dn / dc value (differential change of refractive index with concentration, 0.15) by the Astra detector software.

[0191] Viscosity

[0192] The viscosity of the liquid finished product was 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. -1 The high-shear viscosity at 20 s -1 and the low-shear viscosity at 0.05 s -1 were obtained from a log shear rate sweep from 0.01 s -1 to 25 s

[0193] Test method for determining logP

[0194] The logarithm of the octanol / water partition coefficient (logP) was calculated for each material tested (e.g., each PRM in the flavor mixture). The logP of individual materials (e.g., PRM) was 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.

[0195] Volume-weighted particle size and size distribution

[0196] The volume-weighted particle size distribution is determined 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; auto dilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 ml; maximum coincidence = 9200. The measurement is started by flushing the sensor with water until the background count is less than 100 to bring it to a cold state. The sample in suspension in the delivery capsule is introduced and the density of the capsule is adjusted with deionized water by auto dilution as needed to obtain a capsule count of at least 9200 per ml. The suspension is analyzed over a 60-second period. The resulting volume-weighted PSD data is plotted and recorded, and the values of the volume-weighted particle sizes required (e.g., median / 50th percentile, 5th percentile, and / or 90th percentile) are determined.

[0197] Procedure for determining % degradation

[0198] To determine % degradation, the procedure described in the "OECD Guideline for Testing of Chemicals" 301B CO2 Evolution (Modified Sturm Test), adopted on July 17, 1992, is used. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0199] Fabric treatment method

[0200] A Miele washing machine is used to process the fabric. For each treatment, the washing machine is loaded with 3 kg of fabric, which consists of 1100 g of knitted cotton fabric and 1100 g of polyester cotton fabric (50 / 50). Additionally, 18 thick terrycloth cotton tracers are added, with a total weight of approximately 780 g.

[0201] 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.

[0202] For test processing, a short cotton cycle at 40 °C, a spin speed of 1200 rpm, and a 79 g IEC A base detergent were used to wash the load, which was added to a suitable dispenser at the start of the wash cycle. A 35 g dose of the test fabric treatment composition (i.e., the LFE according to the examples) was added to a suitable dispenser. At the end of the treatment cycle, the terry cloth towel tracer was removed from the washing machine and air-dried overnight.

[0203] The next day, the dried terry cloth towel tracer was analyzed by the rapid headspace GC / MS (gas chromatography mass spectrometry) method described below. All treatments washed and analyzed on the same day for comparison purposes were reported as "one-wash tests".

[0204] Method for determining the headspace concentration above a treated dry fabric

[0205] The cotton tracer was analyzed by the rapid headspace GC / MS (gas chromatography mass spectrometry) method. A 4X4 cm aliquot of the terry cloth towel cotton tracer was transferred to a 25 mL headspace vial. The fabric sample was equilibrated at 65 °C for 10 minutes. The headspace above the fabric was sampled for 5 minutes via the SPME (50 / 30 μm DVB / Carboxen / PDMS) method. Subsequently, the SPME fiber was instantaneously thermally desorbed into the GC. The analytes were analyzed by rapid GC / MS in full scan mode. The total HS response and the fragrance headspace composition above the test legs were calculated using ion extraction of specific masses with PRM.

[0206] EDX method

[0207] Energy-dispersive X-ray (EDX) microanalysis is an X-ray technique used to identify the elemental composition of materials. The technique can be qualitative or quantitative and can even provide the spatial distribution of elements by mapping, as elemental concentrations can be collected from points, along lines, or as images.

[0208] The instrument used in the methods described herein is a scanning electron microscope (SEM) ZEISS 300 equipped with a Bruker Quantax 400 EDX detector.

[0209] To analyze the delivery particles in the premix or slurry, 2 μl of the slurry solution was deposited on an SEM stub (sample holder) that had been thoroughly cleaned previously with acetone and alcohol in sequence.

[0210] To analyze the delivery particles in the product composition, the particles can be extracted according to the "Extracting Delivery Particles from the Finished Product" method provided below.

[0211] The EDX detector was used according to the manufacturer's instructions to collect the required data using the guidance for qualitative and quantitative analysis given below.

[0212] The data generated by EDX analysis includes the spectra reported in the figure, where the x-axis relates to the reported X-ray energy (keV) and the y-axis relates to the signal intensity. The figure is characterized by different peaks, each peak corresponding to the characteristic energy of the detected element, which then enables the determination of the chemical composition of the analyzed sample.

[0213] A. Qualitative analysis

[0214] For a given sample, elemental mapping is achieved at a resolution of 600×400 pixels for 3 minutes to identify the surface arrangement of the detected elements, thereby obtaining an area of 140um×95um (corresponding to a magnification of 800X).

[0215] The chemical information generated by the EDX technique can be visualized in several ways, including elemental mapping. For a specific region of interest (ROI), a digital image can be obtained, where the intensity at each location (pixel) is proportional to the intensity of each peak. Figure 1 A digital image of a specific ROI when using a delivery particle slurry sample is shown; a number of delivery particles 100 are shown. Figure 2 Various images (initially in color) associated with the intensity of each peak are shown. Typically, the images are in color, and the brighter colors are associated with larger peak intensities. In Figure 2 , the first image 110 shows a representative sample of the delivery particles 100. The second image 111 shows an image representative of the carbon present. The third image 112 shows an image representative of the oxygen present. The fourth image 113 shows an image representative of the nitrogen present. The fifth image 114 shows an image representative of the sulfur present. The sixth image 115 shows an image representative of the chlorine present.

[0216] B. Quantitative analysis

[0217] The EDX technique can be used to detect the presence of elements and their concentrations. The MDL (minimum detection limit) of this analytical technique is approximately 0.1 wt% for quantitative elements; if the mass concentration is below the MDL, the element is not quantified.

[0218] For quantitative analysis, an EDX spectrum is obtained in an area of 50μm×40μm for 3 minutes. The output is a spectrum where the peaks are identified as corresponding to the detected elements; a table showing the mass percentage and atomic distribution percentage (stoichiometry) is also generated. Figure 3 A spectrogram of a given sample is shown.

[0219] Extraction of delivery particles from the finished product

[0220] Unless otherwise specified herein, the preferred method for separating delivery particles from the finished product is based on the fact that the density of most such delivery particles is different from that of water. The finished product is mixed with water to dilute and / or release the delivery particles. The diluted product suspension is centrifuged to accelerate the separation of the delivery particles. Such delivery particles tend to float or sink in the diluted solution / dispersion of the finished product. Using a pipette or spatula, the top and bottom layers of the suspension are removed, and additional dilution and centrifugation cycles are performed to separate and enrich the delivery particles. The delivery particles are observed using an optical microscope equipped with a crossed-polarized filter or differential interference contrast (DIC) at a total magnification of 100x and 400x. Microscopic observation provides an initial indication of the presence, size, quality, and aggregation of the delivery particles.

[0221] To extract delivery particles from a liquid fabric enhancer, the finished product undergoes the following procedures:

[0222] 1. Place three aliquots of approximately 20 ml of the liquid fabric enhancer into three separate 50 ml centrifuge tubes, and dilute each aliquot 1:1 with deionized water (e.g., 20 ml of fabric enhancer + 20 ml of deionized water). Mix each aliquot well and centrifuge each aliquot at approximately 10,000 x g for 30 minutes.

[0223] 2. After centrifugation according to step 1, discard the bottom water layer (about 10 ml) in each 50 ml centrifuge tube, and then add 10 ml of deionized water to each 50 ml centrifuge tube.

[0224] 3. For each aliquot, repeat the process of centrifugation, removing the bottom water layer, and then adding 10 ml of deionized water to each 50 ml centrifuge tube two more times.

[0225] 4. Remove the top layer with a spatula or pipette, and

[0226] 5. Transfer the top layer to a 1.8 ml centrifuge tube and centrifuge at approximately 20,000 x g for 5 minutes.

[0227] 6. Remove the top layer with a spatula and transfer it to a new 1.8 ml centrifuge tube, add deionized water until the tube is full, and then centrifuge at approximately 20,000 x g for 5 minutes.

[0228] 7. Remove the bottom layer with a fine pipette, add deionized water until the tube is full, and centrifuge at approximately 20,000 x g for 5 minutes.

[0229] 8. Repeat step 7 five more times (for a total of six times).

[0230] If both the top and bottom layers with enriched delivery particles appear in step 1 above, immediately proceed to step 3 (i.e., skip step 2), and continue with steps 4 through 8. Once those steps have been completed, additionally use a spatula or / and a pipette to remove the bottom layer from the 50 ml centrifuge tube of step 1. Transfer the bottom layer to a 1.8 ml centrifuge tube and centrifuge at approximately 20,000 x g for 5 minutes. Remove the bottom layer from the new tube and add deionized water until the tube is completely full, then centrifuge at approximately 20,000 x g for 5 minutes. Remove the top layer (water), and add deionized water again until the tube is full. Repeat this 5 more times (6 times in total). Recombine the enriched delivery particles with the separated top and bottom layers.

[0231] If the fabric softener has a white color, or it is difficult to distinguish the layer enriched with delivery particles, add 4 drops of dye (such as Liquitint Blue JH 5% premix from Milliken & Company (Spartanburg, South Carolina, USA)) to the centrifuge tube of step 1 and separate as described above.

[0232] For extracting delivery particles from solid finished products that are easily dispersible in water, mix 1 L of deionized water with 20 g of the finished product (e.g., detergent foam, film, gel, and granule; or water-soluble polymer; soap flakes and bars; and other water-soluble matrices such as salts, sugars, clays, and starches). When extracting delivery particles from finished products that are not easily dispersible in water such as wax, dryer sheets, dryer bars, and greasy materials, it may be necessary to add detergent, stir and / or gently heat the product, and dilute to release the delivery particles from the matrix. The use of organic solvents or drying the delivery particles should be avoided during the extraction step as these actions can damage the delivery particles during this stage.

[0233] To extract delivery particles from liquid finished products that are not fabric softeners or fabric enhancers (e.g., liquid laundry detergents, liquid dishwashing detergents, liquid hand soaps, lotions, shampoos, conditioners, and hair dyes), mix 20 ml of the finished product with 20 ml of deionized water. If needed, NaCl (e.g., 1 g to 4 g of NaCl) can be added to the diluted suspension to increase the density of the solution and facilitate the floating of the delivery particles to the top layer. If the product has a white color that makes it difficult to distinguish the layer of delivery particles formed during centrifugation, a water-soluble dye can be added to the diluent to provide visual contrast.

[0234] Subjecting the water and product mixture to successive centrifugation cycles involves removing the top and bottom layers, resuspending those layers in fresh diluent, and then further centrifuging, separating, and resuspending. Each centrifugation cycle occurs in a tube with a volume of 1.5 ml to 50 ml, using a centrifugal force of up to 20,000 x g for a period of 5 minutes to 30 minutes. Typically, at least six centrifugation cycles are required to extract and clean sufficient delivery particles for testing. For example, the initial centrifugation cycle can be performed in a 50 ml tube, spinning at 10,000 x g for 30 minutes, and then followed by five additional centrifugation cycles, where the material from the top and bottom layers is separately resuspended in fresh diluent in 1.8 ml tubes, and each cycle spins at 20,000 x g for 5 minutes.

[0235] If delivery particles are microscopically observed in both the top and bottom layers, the delivery particles from these two layers are recombined after the final centrifugation step to form a single sample containing all of the delivery particles extracted from the product. The extracted delivery particles should be analyzed as soon as possible, but they can be stored in the form of a suspension in deionized water for up to 14 days before analysis.

[0236] Those skilled in the art will recognize that various other protocols can be designed for extracting and separating delivery particles from the finished product, and will recognize that such methods need to be confirmed by comparing the resulting measurements taken before and after adding the delivery particles to the finished product and extracting the delivery particles from the finished product.

[0237] Procedure for measuring the compatibility of delivery particles in a laundry wash matrix

[0238] The compatibility of the delivery particles in a laundry wash matrix is measured by the percentage of aggregates formed in the laundry detergent matrix. 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 wash matrix (such as a single unit dose (SUD) matrix) at a ratio of 1:40 (such as 1 g of slurry in 40 g of matrix) under mixing. The mixture is mixed with an overhead mixer at 350 rpm for at least 15 minutes. Then, after mixing, the mixture of the delivery particles and the laundry wash matrix is poured through a 425 μm sieve. The particle aggregates on the sieve are washed with a large amount of deionized (DI) water until no visible laundry wash matrix is observed. The original filtrate and the water wash filtrate are collected and then passed through a 212 μm sieve to collect any particle aggregates on the 212 μm sieve. Then, the particle aggregates are washed with a large amount of deionized water until no visible matrix is observed. The particle aggregates from the 212 μm and 425 μm sieves are combined and washed again with deionized water to rinse away any remaining matrix. Then, the particle aggregates are collected and dried to a constant weight in a CEM oven to determine the weight of the particle aggregates in the laundry wash matrix. The aggregation percentage is calculated as follows:

[0239]

[0240] Examples

[0241] The examples provided below are essentially intended to be illustrative and not restrictive.

[0242] In the following examples, the abbreviations correspond to the materials listed in Table 1.

[0243] Table 1.

[0244]

[0245] Comparative Example 1

[0246] Comparative Example 1 is the same as Example 13 in Published US20210252469 A1. The aqueous phase was prepared by dispersing 20.66 g of ChitoClear into 439.00 g of water while mixing in a jacketed reactor. Then, the pH of the aqueous phase was adjusted to 4.9 using concentrated HCl with stirring. Then, the temperature of the aqueous phase was raised to 85 °C within 60 minutes and then held at 85 °C for a period of time to hydrolyze ChitoClear. Then, the temperature of the aqueous phase was lowered to 25 °C within 90 minutes after the hydrolysis step. The oil phase was prepared by mixing 159.38 g of spice oil, 23.91 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. The emulsion was heated to 40 °C within 30 minutes and held for 60 minutes. Then, the pH of the emulsion was adjusted to 2.97 using hydrochloric acid. Then, the emulsion was heated to 85 °C and held at this temperature for 6 hours while mixing. According to OECD 301B, the biodegradability % was 64.26% at 28 days.

[0247] Comparative Example 2.

[0248] Comparative Example 2 is the same as Example 10 in Published US20210252469 A1. The aqueous phase was prepared by dispersing 20.66 g of ChitoClear into 439.00 g of water while mixing in a jacketed reactor. Then, the pH of the aqueous phase was adjusted to 6.0 using concentrated HCl with stirring. Then, the temperature of the aqueous phase was raised to 85 °C within 60 minutes and then held at 85 °C for a period of time to hydrolyze ChitoClear. Then, the temperature of the aqueous phase was lowered to 25 °C within 90 minutes after the hydrolysis step. The oil phase was prepared by mixing 159.38 g of fragrance oil, 23.91 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. The emulsion was heated to 40 °C within 30 minutes and held for 60 minutes. Then, the emulsion was heated to 85 °C and held at that temperature for 6 hours while mixing. An encapsulate was obtained, and according to OECD301B, at 28 days, the degradability % of the encapsulate was 11.07%.

[0249] Various data points related to Comparative Example 1 and Comparative Example 2 are reported in Table 2.

[0250] Table 2.

[0251] Comparative example Aqueous phase pH 1-week leakage rate Degradability % (28 days) 1 4.9 76.18％ 64.26 2 6.0 17.45％ 11.07

[0252] As can be seen in Table 2, the encapsulates obtained at a relatively low pH (4.9) in Comparative Example 1 degraded more extensively in the OECD degradability test. However, these encapsulates had a relatively high leakage rate. The encapsulates prepared at a slightly higher pH (6) performed better in terms of leakage rate but suffered relatively poor performance in the degradability test. Encapsulates with a low leakage rate are needed. Even more desirable are encapsulates that simultaneously have a relatively high degradability. Prior to the present invention, it has been difficult to achieve a balance between low leakage rate and high degradability. Even more difficult to achieve are encapsulates with a low leakage rate, high degradability, and compatibility with a laundry washing matrix.

[0253] Example 1.

[0254] Prepare a chitosan stock solution treated with acid and potassium persulfate as follows. First, prepare a potassium persulfate solution by dissolving 1.55 g of potassium persulfate in 3287.5 g of deionized water at 70 °C. Then disperse 154.89 g of chitosan ChitoClear into the potassium persulfate solution while mixing in a jacketed reactor. Then adjust the pH of the chitosan dispersion to 4.30 using 68.37 g of concentrated HCl with stirring. Then raise the temperature of the chitosan solution to 85 °C within 60 minutes and then hold at 85 °C for a period of time to hydrolyze and depolymerize the chitosan. Then cool the temperature to 25 °C within a 90-minute period after the hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of this chitosan solution is 5.1. Use the formed chitosan stock solution to prepare the capsules in Examples 1, 3, 5, and 7.

[0255] Prepare the aqueous phase by mixing 420.27 g of the above chitosan stock solution in a jacketed reactor. Prepare the oil phase by mixing 128.30 g of a fragrance, 54.99 g of isopropyl myristate, and 4.01 g of Takenate D-110N at room temperature. Add the oil phase to the aqueous phase under high-shear grinding to obtain an emulsion with the desired particle size. Heat the emulsion to 40 °C within 30 minutes and hold for an additional 60 minutes. Then heat the obtained emulsion to 90 °C within 60 minutes and maintain at this temperature for 8 hours while mixing, and then cool to 25 °C within 90 minutes. The formed capsules have a volume-weighted median particle size of 11.71 microns.

[0256] Example 2.

[0257] Prepare a chitosan stock solution treated with acid and potassium persulfate as follows. First, prepare a potassium persulfate solution by dissolving 1.55 g of potassium persulfate (“KPS”) in 3287.97 g of deionized water at 70 °C. Then disperse 154.90 g of chitosan ChitoClear into the potassium persulfate solution while mixing in a jacketed reactor. Then adjust the pH of the chitosan dispersion to 5.10 using 51.72 g of concentrated HCl with stirring. Then raise the temperature of the chitosan solution to 85 °C within 60 minutes and then hold at 85 °C for a period of time to hydrolyze and depolymerize the chitosan. Then cool the temperature to 25 °C within a 90-minute period after the hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of this chitosan solution is 5.93. Use the formed chitosan stock solution to prepare the capsules in Examples 2, 4, 6, and 8.

[0258] The aqueous phase was prepared by mixing 422.15 g of the above chitosan stock solution in a jacketed reactor. The oil phase was prepared by mixing 128.30 g of the fragrance, 54.99 g of isopropyl myristate, and 4.01 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 the desired particle size. The emulsion was heated to 40 °C within 30 minutes and held for an additional 60 minutes. The resulting emulsion was then heated to 90 °C within 60 minutes and maintained at this temperature for 8 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 17.64 microns.

[0259] Various data points related to Example 1 and Example 2 are reported in Table 3.

[0260] Table 3.

[0261]

[0262] As can be seen in Table 3, the encapsulates based on the added persulfate exhibited degradability, but as can be seen in Example 2, with a slight change in pH, the leakage rate was also improved relative to Example 1. In addition, Example 2 exhibited 39.81% degradability within 28 days in addition to improving the leakage rate relative to Example 1. This illustrates that the addition of persulfate enables the achievement of a surprising balance of properties by producing degradable capsules that also have a relatively reduced leakage rate. The desired properties in the encapsulates are one or more of low leakage rate, degradability, or compatibility with a matrix (such as a laundry detergent environment). Example 2 illustrates low leakage rate and degradability. Example 1 illustrates degradability.

[0263] Example 3.

[0264] The aqueous phase was prepared by mixing 420.27 g of the chitosan stock solution from Example 1 in a jacketed reactor. The oil phase was prepared by mixing 146.63 g of the fragrance, 36.66 g of isopropyl myristate, and 5.55 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 the desired particle size. The emulsion was heated to 40 °C within 30 minutes and held for an additional 60 minutes. The resulting emulsion was then heated to 90 °C within 60 minutes and maintained at this temperature for 8 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 13.32 microns.

[0265] Example 4.

[0266] The aqueous phase was prepared by mixing 422.15 g of the chitosan stock solution from Example 2 in a jacketed reactor. The oil phase was prepared by mixing 146.63 g of the fragrance, 36.66 g of isopropyl myristate, and 5.55 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 the desired particle size. The emulsion was heated to 40 °C within 30 minutes and held for an additional 60 minutes. Then the obtained emulsion was heated to 90 °C within 60 minutes and maintained at that temperature for 8 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 14.29 microns.

[0267] Various data points related to Example 3 and Example 4 are reported in Table 4.

[0268] Table 4.

[0269]

[0270] As can be seen in Table 4, the encapsulates based on the added persulfate exhibited one-week leakage rate values of 44.25% and 27.20%, respectively. Even more surprisingly, with the fine-tuning of the pH, the % degradability in these samples increased from 13.14% to 39.97%. The encapsulates according to the present invention consistently show surprising improvements in terms of leakage rate, degradability, or compatibility with the matrix. In a preferred embodiment, an improvement is seen in one category of properties such as leakage rate or degradability. More desirably, an improvement is seen in two categories, such as leakage rate and degradability, such as the leakage rate and degradability shown to be achievable by Example 4 or previously in Example 2. Most desirably, an improvement is seen in all three categories of leakage rate, degradability, and compatibility. For example, an appropriate selection can be made from the examples illustrated in Table 8. The parameters of the present invention surprisingly enable the assembly of encapsulates with high performance in terms of leakage rate, degradability, or matrix compatibility.

[0271] Example 5.

[0272] The aqueous phase was prepared by mixing 420.27 g of the chitosan stock solution from Example 1 in a jacketed reactor. The oil phase was prepared by mixing 146.63 g of the fragrance, 36.66 g of isopropyl myristate, and 2.49 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 the desired particle size. The emulsion was heated to 40 °C within 30 minutes and held for an additional 60 minutes. The resulting emulsion was then heated to 90 °C within 60 minutes and maintained at that temperature for 8 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 18.06 microns.

[0273] Example 6.

[0274] The aqueous phase was prepared by mixing 422.15 g of the chitosan stock solution from Example 2 in a jacketed reactor. The oil phase was prepared by mixing 146.63 g of the fragrance, 36.66 g of isopropyl myristate, and 2.49 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 the desired particle size. The emulsion was heated to 40 °C within 30 minutes and held for an additional 60 minutes. The resulting emulsion was then heated to 90 °C within 60 minutes and maintained at that temperature for 8 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 11.85 microns.

[0275] Various data points related to Example 5 and Example 6 are reported in Table 5.

[0276] Table 5.

[0277]

[0278] Example 5 and Example 6 illustrate the improved degradability in the capsules according to the present invention. As the pH was adjusted to be close to pH 6, in addition to the improvement in degradability, a surprising reduction in the leakage rate was also noted. These examples reinforce the trend observed in the previous examples, namely that the present invention is capable of providing improvements in more than one property category, more specifically in more than one property category in terms of the properties of leakage rate, degradability, and compatibility.

[0279] Example 7.

[0280] The aqueous phase was prepared by mixing 420.27 g of the chitosan stock solution from Example 1 in a jacketed reactor. The oil phase was prepared by mixing 164.96 g of the fragrance, 18.33 g of isopropyl myristate, and 4.01 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 the desired particle size. The emulsion was heated to 40 °C within 30 minutes and held for an additional 60 minutes. The resulting emulsion was then heated to 90 °C within 60 minutes and maintained at that temperature for 8 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 20.54 microns.

[0281] Example 8.

[0282] The aqueous phase was prepared by mixing 422.15 g of the chitosan stock solution from Example 2 in a jacketed reactor. The oil phase was prepared by mixing 164.96 g of the fragrance, 18.33 g of isopropyl myristate, and 4.01 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 the desired particle size. The emulsion was heated to 40 °C within 30 minutes and held for an additional 60 minutes. The resulting emulsion was then heated to 90 °C within 60 minutes and maintained at that temperature for 8 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 12.56 microns.

[0283] Various data points related to Example 7 and Example 8 are reported in Table 6.

[0284] Table 6.

[0285]

[0286] Examples 7 and 8 illustrate the improved degradability in the capsules according to the present invention. As the pH was adjusted to be close to pH 6, in addition to the improvement in degradability, a decrease in the leakage rate was also noted. These examples reinforce the trend observed in the previous examples, namely that the present invention is capable of providing improvements in more than one category in terms of the categories of leakage rate, degradability, and compatibility.

[0287] Example 9.

[0288] Prepare a chitosan stock solution treated with acid and potassium persulfate as follows. First, prepare a potassium persulfate solution by dissolving 1.56 g of potassium persulfate in 3303.96 g of deionized water at room temperature. Then disperse 155.68 g of chitosan ChitoClear into the potassium persulfate solution while mixing in a jacketed reactor. Then adjust the pH of the chitosan dispersion to 5.80 using 53.88 g of concentrated HCl with stirring. Then raise the temperature of the chitosan solution to 85 °C within 60 minutes and then hold at 85 °C for a period of time (such as 2 hours) to hydrolyze and depolymerize the chitosan. Then cool the temperature to 25 °C within a 90-minute period after the hydrolysis step to obtain an acid and potassium persulfate-treated chitosan solution. The pH of this chitosan solution is 5.97.

[0289] Prepare an aqueous phase by mixing 2101.81 g of the above chitosan stock solution in a jacketed reactor. Prepare an oil phase by mixing 716.14 g of a fragrance, 179.05 g of isopropyl myristate, and 19.58 g of Takenate D-110N at room temperature. Add the oil phase to the aqueous phase under high-shear milling to obtain an emulsion with a desired particle size. Heat the emulsion to 60 °C within 45 minutes. Then heat the emulsion to 85 °C within 60 minutes and maintain at this temperature for 6 hours while mixing, and then cool to 25 °C within 90 minutes. The formed capsules have a volume-weighted median particle size of 15.69 microns.

[0290] Example 10.

[0291] Prepare a chitosan stock solution treated with acid and potassium persulfate as follows. First, prepare a potassium persulfate solution by dissolving 1.56 g of potassium persulfate in 3303.96 g of deionized water at room temperature. Then disperse 155.68 g of chitosan ChitoClear into the potassium persulfate solution while mixing in a jacketed reactor. Then adjust the pH of the chitosan dispersion to 5.81 using 52.68 g of concentrated HCl with stirring. Then raise the temperature of the chitosan solution to 85 °C within 60 minutes and then hold at 85 °C for a period of time (such as 2 hours) to hydrolyze and depolymerize the chitosan. Then cool the temperature to 25 °C within a 90-minute period after the hydrolysis step to obtain an acid and potassium persulfate-treated chitosan solution. The pH of this chitosan solution is 5.90.

[0292] An aqueous phase was prepared by mixing 2456.58 g of the above chitosan stock solution in a jacketed reactor. An oil phase was prepared by mixing 714.38 g of a fragrance, 178.6 g of isopropyl myristate, and 27.07 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. The emulsion was then heated to 85 °C within 60 minutes and maintained at this temperature for 6 hours while mixing, and then cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 20.54 microns.

[0293] Various data points related to Example 9 and Example 10 are reported in Table 7.

[0294] Table 7.

[0295]

[0296] Examples 9 and 10 illustrate improvements in multiple property categories in terms of improved degradability and leakage rate values (lower is better) for the capsules according to the present invention. As the pH was adjusted to near pH 6, in addition to the improvement in degradability, a surprising decrease in the leakage rate was also observed. These examples illustrate that the present invention is capable of providing improvements in more than one category in terms of the categories of leakage rate, degradability, and compatibility. Compared with Comparative Examples 1 and 2, better performance and degradability were observed in the presence of a redox initiator (KPS).

[0297] Comparative Example 3

[0298] An aqueous phase containing an acid-treated chitosan stock solution was prepared as follows. 96.24 g of chitosan ChitoClear was dispersed in 2044.09 g of deionized water at 25 °C while mixing in a jacketed reactor. The pH of the chitosan dispersion was then adjusted to 5.36 using 42.87 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 and depolymerize the chitosan. The temperature was then lowered to 25 °C within a 90-minute period after the hydrolysis step to obtain an acid-treated chitosan solution. The pH of this chitosan solution was 5.40.

[0299] The oil phase was prepared by mixing 635.63 g of fragrance, 158.92 g of isopropyl myristate, and 24.06 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then heated to 85 °C in 60 minutes, then held at 85 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The formed capsules had a volume-weighted median particle size of 10.06 microns.

[0300] Example 11.

[0301] The aqueous phase containing the acid and potassium persulfate-treated chitosan stock solution was prepared as follows. A potassium persulfate (KPS) solution was prepared by dissolving 0.96 g of potassium persulfate in 2056.32 g of deionized water at 25 °C while mixing in a jacketed reactor. Then 96.43 g of chitosan ChitoClear was added to the KPS solution. Then the pH of the chitosan dispersion was adjusted to 5.91 using 32.96 g of concentrated HCl with stirring. Then the temperature of the chitosan solution was raised to 85 °C in 60 minutes and then held at 85 °C for 2 hours to hydrolyze and depolymerize the chitosan. Then the temperature was lowered to 25 °C over a 90-minute period after the hydrolysis step to obtain the acid and potassium persulfate-treated chitosan solution. The pH of the chitosan solution was 6.04.

[0302] The oil phase was prepared by mixing 636.92 g of fragrance, 159.24 g of isopropyl myristate, and 24.11 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then heated to 85 °C in 60 minutes, then held at 85 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The formed capsules had a volume-weighted median particle size of 33.97 microns.

[0303] Example 12.

[0304] Prepare an acid- and potassium persulfate-treated chitosan stock solution as follows. Disperse 42.08 g of chitosan ChitoClear into 893.0 g of deionized water at 25 °C while mixing in a jacketed reactor. Add 0.42 g of potassium persulfate and dissolve it. Then adjust the pH of the chitosan dispersion to 5.87 using 14.40 g of concentrated HCl with stirring. Then, raise the temperature of the chitosan solution to 65 °C within 30 minutes, then to 85 °C within 30 minutes, then to 95 °C within 30 minutes, and then hold at 95 °C for 2 hours to hydrolyze and depolymerize the chitosan. Then cool the temperature to 25 °C within a 90-minute period after the hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of this chitosan solution is 5.90.

[0305] Prepare the aqueous phase by mixing 433.6 g of the above chitosan stock solution in a jacketed reactor. Prepare the oil phase by mixing 128.86 g of a fragrance, 32.22 g of isopropyl myristate, and 4.88 g of Takenate D-110N at room temperature. Add the oil phase to the aqueous phase under high-shear milling to obtain an emulsion with a desired particle size. Heat the emulsion to 60 °C within 45 minutes, then to 95 °C within 60 minutes, then hold at 95 °C for 4 hours, then add 1.38 g of potassium persulfate and dissolve it, then hold at 95 °C for 2 hours, and then cool to 25 °C within 90 minutes. The capsules formed have a volume-weighted median particle size of 36.25 microns.

[0306] Example 13.

[0307] Prepare an acid- and potassium persulfate-treated chitosan stock solution as follows. Disperse 42.08 g of chitosan ChitoClear into 893.1 g of deionized water at 25 °C while mixing in a jacketed reactor. Add 4.20 g of potassium persulfate and dissolve it. Then adjust the pH of the chitosan dispersion to 5.94 using 14.35 g of concentrated HCl with stirring. Then, raise the temperature of the chitosan solution to 65 °C within 30 minutes, then to 85 °C within 30 minutes, and then hold at 85 °C for 2 hours to hydrolyze and depolymerize the chitosan. Then cool the temperature to 25 °C within a 90-minute period after the hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of this chitosan solution is 5.36.

[0308] The aqueous phase was prepared by mixing 433.6 g of the chitosan stock solution from Example 13 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of the fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 85 °C in 60 minutes, then held at 85 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 50.79 microns.

[0309] Example 14.

[0310] The acid- and potassium persulfate-treated chitosan stock solution was prepared as follows. 42.20 g of chitosan ChitoClear was dispersed in 893.1 g of deionized water at 25 °C while mixing in a jacketed reactor. 0.42 g of potassium persulfate was added and dissolved. Then, the pH of the chitosan dispersion was adjusted to 5.91 using 11.48 g of concentrated HCl and 1.25 g of 90% formic acid 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 and depolymerize the chitosan. Then, the temperature was lowered to 25 °C over a 90-minute period after the hydrolysis step to obtain the acid- and potassium persulfate-treated chitosan solution. The pH of this chitosan solution was 5.99. The capsules in Example 14 and Example 15 were prepared using the chitosan stock solution formed.

[0311] The aqueous phase was prepared by mixing 433.6 g of the chitosan stock solution from Example 14 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of the fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 95 °C in 60 minutes, then held at 95 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 33.48 microns.

[0312] Example 15.

[0313] The aqueous phase was prepared by mixing 433.6 g of the chitosan stock solution from Example 14 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of a fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 95 °C in 60 minutes, then held at 95 °C for 4 hours, then 1.38 g of potassium persulfate was added and dissolved, then held at 95 °C for 2 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 36.25 microns.

[0314] Example 16.

[0315] The acid- and potassium persulfate-treated chitosan stock solution was prepared as follows. 42.15 g of chitosan ChitoClear was dispersed in 893.1 g of deionized water at 25 °C with mixing in a jacketed reactor. 0.42 g of potassium persulfate was added and dissolved. Then the pH of the chitosan dispersion was adjusted to 5.92 using 8.66 g of concentrated HCl and 2.52 g of 90% formic acid 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 and depolymerize the chitosan. Then the temperature was lowered to 25 °C over a 90-minute period after the hydrolysis step to obtain the acid- and potassium persulfate-treated chitosan solution. The pH of this chitosan solution was 6.01. The capsules in Examples 16 and 17 were prepared using the chitosan stock solution formed.

[0316] The aqueous phase was prepared by mixing 433.6 g of the chitosan stock solution from Example 16 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of a fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 95 °C in 60 minutes, then held at 95 °C for 4 hours, then 1.38 g of potassium persulfate was added and dissolved, then held at 95 °C for 2 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 31.68 microns.

[0317] Example 17.

[0318] The aqueous phase was prepared by mixing 433.6 g of the chitosan stock solution from Example 16 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of a fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 95 °C in 60 minutes, then held at 95 °C for 4 hours, then 3.90 g of potassium persulfate was added and dissolved, then held at 95 °C for 2 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 31.68 microns.

[0319] Example 18.

[0320] The acid- and potassium persulfate-treated chitosan stock solution was prepared as follows. 156.60 g of chitosan ChitoClear was dispersed in 3321.0 g of deionized water at 25 °C with mixing in a jacketed reactor. 1.57 g of potassium persulfate was added and dissolved. Then the pH of the chitosan dispersion was adjusted to 5.93 using 32.05 g of concentrated HCl and 9.29 g of 90% formic acid with stirring. Then, the temperature of the chitosan solution was raised to 65 °C in 30 minutes, then to 85 °C in 30 minutes, and then held at 85 °C for 2 hours to hydrolyze and depolymerize the chitosan. Then the temperature was lowered to 25 °C over a 90-minute period after the hydrolysis step to obtain the acid- and potassium persulfate-treated chitosan solution. This solution was combined and homogenized with 360 g of the stock solution from Example 19. The pH of this chitosan solution was 5.99. The capsules in Examples 18 and 19 were prepared using the chitosan stock solution formed.

[0321] The aqueous phase was prepared by mixing 433.5 g of the chitosan stock solution from Example 18 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of a fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 85 °C in 60 minutes, then 0.32 g of a 30% hydrogen peroxide (H2O2) solution was added, and then held at 85 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 33.89 microns.

[0322] Example 19.

[0323] The aqueous phase was prepared by mixing 433.5 g of the chitosan stock solution from Example 18 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of the fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 85 °C in 60 minutes, then 0.65 g of 30% hydrogen peroxide solution was added, and then held at 85 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 30.42 microns.

[0324] Example 20.

[0325] The acid and potassium persulfate-treated chitosan stock solution was prepared as follows. 156.55 g of chitosan ChitoClear was dispersed in 3320.0 g of deionized water at 25 °C while mixing in a jacketed reactor. 1.58 g of potassium persulfate was added and dissolved. Then the pH of the chitosan dispersion was adjusted to 5.95 using 32.05 g of concentrated HCl and 9.27 g of 90% formic acid with stirring. Then, the temperature of the chitosan solution was raised to 65 °C in 30 minutes, then to 85 °C in 30 minutes, and then held at 85 °C for 2 hours to hydrolyze and depolymerize the chitosan. Then the temperature was lowered to 25 °C over a 90-minute period after the hydrolysis step to obtain the acid and potassium persulfate-treated chitosan solution. The pH of this chitosan solution was 6.00. The capsules in Examples 20 and 21 were prepared using the chitosan stock solution formed.

[0326] The aqueous phase was prepared by mixing 433.5 g of the chitosan stock solution from Example 20 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of the fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 85 °C in 60 minutes, then 1.30 g of 30% hydrogen peroxide solution was added, and then held at 85 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 25.87 microns.

[0327] Example 21.

[0328] The aqueous phase was prepared by mixing 433.5 g of the chitosan stock solution from Example 20 in a jacketed reactor. The oil phase was prepared by mixing 128.86 g of the fragrance, 32.22 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 the desired particle size. The emulsion was heated to 60 °C in 45 minutes, then to 85 °C in 60 minutes, then 3.25 g of 30% hydrogen peroxide solution was added, and then held at 85 °C for 6 hours, and then cooled to 25 °C in 90 minutes. The capsules formed had a volume-weighted median particle size of 25.87 microns.

[0329] Various data points related to Comparative Example 3 and Examples 11 to 21 are reported in Table 8.

[0330] Table 8.

[0331]

[0332] Examples 11 to 21 illustrate the relative compatibility of the delivery particles according to the present disclosure with product matrices such as laundry detergents (e.g., SUD = soluble unit dose articles). These were compared with Comparative Example 3. Examples 12 and 17, in which a redox initiator was added to the aqueous phase and the emulsion, exhibited surprisingly low leakage rates and matrix compatibility properties. The particles according to the present disclosure also appear to exhibit favorable degradability properties. The table further shows that the aggregate %, can be adjusted or regulated by the amount of redox initiator introduced. High levels of compatibility properties were achieved when the redox initiator was added to the aqueous phase and optionally the emulsion.

[0333] In addition, Figure 4 The charge differences of the delivery particles made according to various treatments such as acid treatment and addition of a redox initiator to the aqueous phase or emulsion are depicted, as described in the indicated examples (i.e., Comparative Example 3 and Examples 13, 14, 17, and 21). As shown in the examples, the steps of the present disclosure enable customization of the ζ potential. For example, the method of the present disclosure enables reduction or moderation of the ζ potential under the pH conditions used, resulting in more controllable delivery particles that are usefully less prone to agglomeration and more compatible with the product matrix in end-use applications.

[0334] The dimensions and values disclosed herein should not be construed as being strictly limited to the exact numerical values recited. Rather, each such dimension is intended to represent the recited value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to represent "about 40 mm".

[0335] 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 its beneficial effects, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. 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 other reference teaches, suggests, or discloses any such invention. Further, when any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this invention shall govern.

[0336] 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 a crosslinking agent, wherein the modified chitosan is formed by treating chitosan with a redox initiator, wherein the redox initiator is selected from the group consisting of persulfates, peroxides, and combinations thereof.

2. The treatment composition according to claim 1, wherein the redox initiator is selected from the group consisting of: ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof, preferably sodium persulfate, hydrogen peroxide, and mixtures thereof, more preferably sodium persulfate.

3. The treatment composition according to any one of claims 1 or 2, wherein the redox initiator and the chitosan are present in a weight ratio of from about 90:10 to about 0.01:99.99, preferably from about 50:50 to about 1:99, more preferably from about 30:70 to about 3:

97.

4. The treatment composition according to any one of the preceding claims, wherein the shell of the delivery particles comprises sulfur atoms, preferably wherein the sulfur atoms are present in the shell at a level of from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, even more preferably from about 0.1% to about 1% by weight of the shell.

5. The treatment composition according to any one of the preceding claims, wherein the modified chitosan is formed under acidic conditions at a temperature of at least 25 °C, preferably at a pH of 6.5 or less, more preferably less than 6.5, even more preferably at a pH of from 3 to 6.2, or even more preferably at a pH of from 5 to 6.

2.

6. The treatment composition according to any one of the preceding claims, wherein the modified chitosan is an acid-treated modified chitosan, wherein the chitosan has been further treated with an acid, preferably a mixture of acids, more preferably a mixture of a first acid and a second acid, wherein the first acid is a strong acid, and wherein the second acid is a weak acid, preferably, wherein the first acid and the second acid are present in an equivalent concentration ratio of from about 20:80 to about 80:20, preferably from about 35:65 to about 65:

35.

7. The treatment composition according to any one of the preceding claims, wherein at least one of the following is true: (a) The chitosan before treatment with the redox initiator and / or acid 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; (b) The modified chitosan is characterized by a weight average molecular weight of from about 1 kDa to about 600 kDa, preferably from about 5 kDa to about 300 kDa, more preferably from about 10 kDa to about 200 kDa, more preferably from about 15 kDa to about 150 kDa, even more preferably from about 20 kDa to about 100 kDa.

8. The treatment composition according to any one of the preceding claims, wherein the crosslinking agent 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; tetramethylxylylene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; their derivatives; and combinations thereof.

9. The treatment composition according to any one of the preceding claims, wherein the reaction product is formed in a reaction in which the weight ratio of the chitosan present in the reaction to the crosslinking agent present in the reaction is from about 1:10 to about 1:0.

1.

10. The treatment composition according to any one of the preceding claims, wherein the shell is present in the delivery particles at a level of about 15 wt% or less, based on the weight of the delivery particles.

11. The treatment composition according to any one of the preceding claims, wherein the beneficial agent is an aromatic material, preferably an aromatic material comprising a fragrance ingredient characterized by a logP of from about 2.5 to about 4.

5.

12. The treatment composition according to any one of the preceding claims, wherein the core further comprises a partitioning modifier, 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%, based on the weight of the core, Preferably select a distribution modifier from the group consisting of: vegetable oil, modified vegetable oil, mono-, di- and triesters of C4-C 24 monoesters, diesters and triesters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate and mixtures thereof, more preferably isopropyl myristate.

13. The treatment composition according to any one of the preceding claims, 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, even more preferably from about 25 microns to about 35 microns.

14. The treatment composition according to any one of the preceding claims, wherein the delivery particles can be obtained by a method comprising the following steps: forming an aqueous phase by treating the chitosan with the redox initiator in the presence of water at a pH of 6.5 or lower and at a temperature of at least 25°C, preferably for at least one hour and / or for a time until the aqueous phase is characterized by a viscosity of less than 1500 cp, preferably less than 500 cp, to form the modified chitosan, Preferably, the aqueous phase further comprises a mixture of the first acid and the second acid; forming an oil phase, the forming step comprising dissolving at least one beneficial agent and at least one crosslinking agent, preferably a polyisocyanate, optionally with an added oil, preferably a partitioning modifier; forming an emulsion by mixing the oil phase, preferably under high shear agitation, into an excess of the aqueous phase such that droplets of the oil phase are dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to be within the range of pH 2 to pH 6; optionally, providing a second redox initiator to the emulsion, wherein the second redox initiator is the same as or different from the redox initiator added to the aqueous phase; curing the emulsion at a temperature of at least 40°C for a time sufficient to form a shell at the interface of the droplets and the aqueous phase, the shell comprising the reaction product of the crosslinking agent and the modified chitosan, and the shell surrounding the core of the droplets comprising the oil phase.

15. The treatment composition according to any one of the preceding claims, wherein the delivery particles are cationic, preferably wherein the delivery particles are characterized by a ζ potential of at least 15 mV at a pH of 4.5.

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