Treated compositions comprising delivery particles made from chitosan treated with a redox initiator

Abstract

A processing composition comprising a processing aid and a population of core / shell delivery particles, wherein the shell is made at least in part of chitosan that has been treated with a redox initiator. Related methods of making and using such compositions.

Description

[Technical Field]

[0001] The present disclosure relates to a processing composition comprising a processing aid and a population of core / shell delivery particles, wherein the shell is made, at least in part, of chitosan that has been treated with a redox initiator. The disclosure also relates to related methods of making and using such compositions. [Background technology]

[0002] Delivery particles, particularly core / shell delivery particles, are a convenient way to deliver benefit agents in treatment compositions such as laundry products. For environmental reasons, it may be desirable to use delivery particles with walls made from naturally occurring and / or biodegradable materials.

[0003] Delivery particles having a shell made at least in part from chitosan-based materials are known. However, such particles may not deliver the desired level of performance and / or product. Furthermore, chitosan can be a difficult material to handle due to its tendency to build viscosity. Summary of the Invention [Problem to be solved by the invention]

[0004] There is a need for improved treatment compositions including delivery particles made from chitosan-based materials, as well as related methods. [Means for solving the problem]

[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 a persulfate or a peroxide.

[0006] For example, the present disclosure relates to a processing composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, and the shell comprising a polymeric material that is the reaction product of a modified chitosan and a crosslinker, the modified chitosan being formed by treating the chitosan with a redox initiator, the redox initiator being selected from the group consisting of persulfates, peroxides, and combinations thereof.

[0007] The present disclosure also relates to a method of making a processing composition according to the present disclosure, comprising providing a base composition, the base composition including a processing aid, and combining a population of delivery particles with the base composition.

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

[0009] The drawings herein are illustrative in nature and are not intended to be restrictive. [Figure 1] 1 shows a digital image of a delivery particle. [Figure 2] Various images are shown regarding the intensity of each peak measured by EDX method. [Figure 3] 1 shows a graph of the EDX spectrum of a given sample. [Figure 4] 1 illustrates the charge differential of particles made in accordance with the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure relates to a treatment composition comprising a delivery particle having a shell made at least in part from a chitosan-based material. More specifically, the shell comprises chitosan that has been treated with a redox initiator, such as a persulfate or peroxide. The chitosan may be further treated with an acid. The resulting modified chitosan is then reacted with a crosslinker to form the shell of the delivery particle.

[0011] The resulting particles exhibit benefits in one or more vectors. For example, the delivery particles may be characterized by improved product stability (e.g., in fabric care products), which may be indicated by reduced agglomeration in the slurry or product. The delivery particles may also have improved processability, leakage profile, performance, and / or biodegradability, for example, compared to comparable particles that do not contain redox initiator-treated chitosan.

[0012] Typically, chitosan is a difficult material to use in solution because it can be difficult to dissolve and / or tends to build up viscosity. Without being bound by theory, it is believed that the redox initiator at least partially depolymerizes chitosan. This results in a chitosan solution characterized by reduced viscosity, which is easier to process and may contribute to improved particle shell formation.

[0013] In addition, it may be beneficial to treat chitosan with acid. Acidic conditions tend to help solubilize chitosan in water. Surprisingly, acid treatment has also been found to reduce the viscosity of the aqueous phase while increasing the molecular weight of chitosan. The use of a redox initiator before, during, or after acid treatment can further reduce the viscosity and molecular weight of chitosan.

[0014] It has been found that treating chitosan as described herein results in effective (and product-compatible) delivery particles that also exhibit a promising biodegradation profile. Without being bound by theory, it is believed that chitosan treated with a redox initiator may be characterized by a relatively low molecular weight and, therefore, may degrade more readily during the biodegradation process.

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

[0016] As used herein, the articles "a" and "an," when used in the claims, are understood to mean one or more of what is claimed or described. As used herein, the terms "include," "includes," and "including" are meant to be open-ended. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0017] The terms "substantially free of" or "substantially free from" may be used herein. This means that the indicated material is in minimal amounts and has not been intentionally added to the composition to form part of the composition, or preferably is not present at analytically detectable concentrations. It refers to compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material, if present at all, may be present at a concentration of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0018] As used herein, "consumer product" means a baby care, beauty care, fabric and home care, family care, feminine care, or health care product or device that is intended for use or consumption in the form in which it is sold and not for subsequent commercial manufacture or modification. Such products include diapers, bibs, wipes; products for treating human hair and / or related methods of treatment, including bleaching, coloring, dyeing, conditioning, shampooing, and styling; deodorants and antiperspirants; personal cleansing; skin care, including the application of creams, lotions, and other topically applied products intended for consumer use; and shaving products, products and / or related methods for treating fabrics, hard surfaces, and any other surface in the fabric or home care field (including air care, auto care, dishwashing, fabric conditioning (including softening)). products and / or methods related to toilet paper, tissue, paper handkerchiefs, and / or paper towels; tampons, feminine napkins; adult incontinence products; oral care products and / or methods including toothpaste, tooth gels, mouth rinses, denture adhesives, tooth whitening agents; non-prescription health care including cough and cold treatments; pest control products, and water purification.

[0019] As used herein, the phrase "fabric care composition" includes compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric deodorizing compositions, laundry pre-cleaning agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions can be used as laundry pre-treatment agents, laundry post-treatment agents, or can be added during the rinse or wash cycle of laundry operations.

[0020] As used herein, "delivery particles," "particles," "encapsulations," "microcapsules," and "capsules" are used interchangeably unless otherwise indicated. As used herein, these terms typically refer to core / shell delivery particles.

[0021] As used herein, "shell" and "wall" are used interchangeably with respect to delivery particles unless otherwise indicated.

[0022] Unless otherwise noted, all ingredient or composition concentrations are in terms of the active portion of that ingredient or composition and are exclusive of impurities, e.g., residual solvents or by-products, that may be present in commercial sources of such ingredient or composition.

[0023] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All measurements herein are made at 20°C and atmospheric pressure unless otherwise stated.

[0024] In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless specifically stated otherwise.

[0025] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0026] Treatment Composition The present disclosure relates to treatment compositions (or simply "compositions" as used herein). The compositions of the present disclosure may include a population of delivery particles and a treatment aid, each of which is described in more detail below. The treatment compositions may be useful in the methods of treating surfaces, such as fabrics, described herein.

[0027] The treatment composition is preferably a consumer product composition. The consumer product composition of the present disclosure can be useful in baby care, beauty care, fabric care, home care, family care, feminine care, and / or health care applications. The consumer product composition can be useful for treating surfaces such as fabric, hair, or skin. The consumer product composition can be intended to be used or consumed in the form in which it is sold. The consumer product composition of the present disclosure is typically not intended for subsequent commercial manufacture or modification.

[0028] The consumer product composition may preferably be a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition (such as a shampoo or conditioner), a body cleansing composition, or a mixture thereof, preferably a fabric care composition.

[0029] The consumer product composition may be a fabric care composition such as a laundry detergent composition (including a heavy-duty liquid cleaning detergent or unit dose article), a fabric conditioning composition (including a liquid fabric softening and / or enhancing composition), a laundry additive, a fabric pretreatment composition (including a spray, pourable liquid, or spray), a fabric refresher composition (including a spray), or a mixture thereof. The treatment composition is preferably a fabric conditioning composition, even more preferably a liquid fabric conditioning composition. The consumer product composition may preferably be a laundry detergent composition, because the delivery particles described herein have been found to have improved compatibility in such product matrices (e.g., in products containing anionic surfactants).

[0030] The composition may be a beauty care composition, such as a hair treatment product (including shampoo and / or conditioner), a skin care product (including a cream, lotion, or other topically applied product for consumer use), a shaving care product (including a shaving lotion, foam, or pre- or post-shave treatment), a personal cleansing product (including a liquid body wash, liquid hand soap, and / or bar soap), a deodorant and / or antiperspirant, or mixtures thereof.

[0031] The compositions may be home care compositions such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other consumer or institutional cleaning.

[0032] The treatment composition may be in the form of a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, pastilles or beads, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven sheet, or mixtures thereof.

[0033] The treatment composition may be in the form of a liquid. The liquid composition may comprise from about 50% to about 97%, preferably from about 60% to about 96%, more preferably from about 70% to about 95%, and even from about 80% to about 95% water by weight of the fabric treatment composition. The liquid composition may be a liquid fabric conditioner. The liquid may be packaged in a pourable bottle. The liquid may be packaged in an aerosol can or other spray bottle. Suitable containers are described in more detail below.

[0034] The treatment composition may be in the form of a solid. The composition may be in the form of beads or pastilles, which may be pastilles from a liquid melt. The composition may be an extruded product. The treatment composition may be in the form of a powder or granules.

[0035] The composition may be in the form of a unit-dose article such as a tablet, pouch, sheet, or fiber article. Such pouches typically include a water-soluble film, e.g., a polyvinyl alcohol water-soluble film, that at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition may be enclosed in a single-compartment pouch or a multi-compartment pouch. A multi-compartment pouch may have at least two, at least three, or at least four compartments. A multi-compartment pouch may include compartments arranged side-by-side and / or stacked. The composition contained in the pouch or its compartments may be liquid, solid (e.g., powder), or a combination thereof. The pouch composition may have a relatively low amount of water, e.g., less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% by weight of the detergent composition.

[0036] The treatment composition may be in the form of a spray, for example, dispensed via an aerosol container having a trigger sprayer and / or a valve.

[0037] The treatment composition is applied for 20 seconds. -1and 21°C, 1 to 1500 centipoise (1 to 1500 mPa * s), 100-1000 centipoise (100-1000 mPa * s), or 200 to 500 centipoise (200 to 500 mPa * s).

[0038] The treatment compositions of the present disclosure may be characterized by a pH of about 2 to about 12, or about 2 to about 8.5, or about 2 to about 7, or about 2 to about 5. The treatment compositions of the present disclosure, preferably in aqueous liquid form, may have a pH of about 2 to about 4, preferably about 2 to about 3.7, and more preferably about 2 to about 3.5. Such pH levels are believed to promote the stability of the quaternary ammonium ester compound, if present. Meanwhile, detergent compositions are typically characterized by a pH of about 7 to about 12, preferably about 7.5 to about 11. The pH of the composition is measured by dissolving / dispersing the composition in deionized water to form a 10% concentration solution at about 20°C.

[0039] Additional components and / or properties of the composition are discussed in more detail below.

[0040] Delivery particle population The treatment composition of the present disclosure comprises a population of delivery particles. The delivery particles comprise a core and a shell surrounding the core. The core may comprise a benefit agent and, optionally, a partitioning modifier. The core can be liquid or solid at room temperature, preferably liquid.

[0041] 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 delivery particles. The composition may comprise a sufficient amount of total delivery particles to provide the composition with from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 2%, by weight of the composition, of encapsulated benefit agent, preferably perfume ingredient. As discussed herein, the amount or weight percent of delivery particles refers to the combined wall material and core material.

[0042] A population of delivery particles according to the present disclosure may be characterized by a volume-weighted median particle size of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 25 to about 35 microns. For certain compositions, it may be preferred that the population of delivery particles be characterized by a volume-weighted median particle size of about 1 to about 50 microns, preferably about 5 to about 20 microns, and more preferably about 10 to about 15 microns. Different particle sizes can be obtained by controlling droplet size during emulsification.

[0043] The delivery particles may be characterized by a core to shell ratio of up to 99:1, or even 99.5:0.5, by weight. The shell may be present in a concentration of about 1% to about 25% by weight of the delivery particle, preferably about 1% to about 20% by weight, preferably about 1% to about 15% by weight, more preferably about 5% to about 15% by weight, even more preferably about 10% to about 15% by weight, and even more preferably about 10% to about 12% by weight. The shell may be present in a concentration of at least 1% by weight of the delivery particle, preferably at least 3% by weight, and more preferably at least 5% by weight. The shell may be present in a concentration of up to about 25% by weight of the delivery particle, preferably up to about 20% by weight, preferably up to about 15% by weight, and more preferably up to about 12% by weight.

[0044] The delivery particles can be cationic in nature, preferably cationic at a pH of 4.5. The delivery particles can be characterized by a zeta potential of at least 15 millivolts (mV) at a pH of 4.5. The delivery particles can be configured to have a zeta potential of at least 15 millivolts (mV) at a pH of 4.5, or at least 40 mV at a pH of 4.5, or at least 60 mV at a pH of 4.5. Delivery particles prepared using chitosan typically exhibit a positive zeta potential. Such capsules have improved adhesion efficiency to fabrics. At higher pHs, the particles can be nonionic or anionic.

[0045] The delivery particles of the present disclosure comprise a shell surrounding a core. (As used herein, "shell" and "wall" are used interchangeably with respect to the delivery particles unless otherwise indicated.) The shell comprises a polymeric material. The polymeric material is the reaction product of modified chitosan and a crosslinker.

[0046] The modified chitosan is formed by treating chitosan with a redox initiator. The redox initiator may be selected from the group consisting of persulfates, peroxides, and combinations thereof. The redox initiator may preferably be a persulfate. The redox initiator may preferably be a peroxide.

[0047] Treatment of chitosan with a redox initiator is typically carried out in an aqueous phase, preferably an acidic aqueous phase, prior to forming an emulsion that results in the formation of delivery particles, although a second redox initiator can be added to the emulsion to further improve performance and / or product compatibility.

[0048] As discussed above, redox initiators are believed to at least partially depolymerize chitosan, reducing its weight average molecular weight. Chitosans modified in this manner have been found to exhibit reduced viscosity in aqueous phases, improved product compatibility (e.g., reduced flocculation / agglomeration in certain fabric care products), better performance, and / or improved biodegradability.

[0049] 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.

[0050] In the reaction to form the modified chitosan, the redox initiator and chitosan may be present in a weight ratio of about 90:10 to about 0.01:99.99, preferably about 50:50 to about 1:99, and more preferably about 30:70 to about 3:97.

[0051] The shell of the delivery particle may contain sulfur atoms, which may result, for example, from the interaction between a sulfur-containing redox initiator (e.g., a persulfate compound) and chitosan. For example, when a persulfate is used, the sulfate groups are believed to ionically bond with the amino groups of chitosan. The sulfur atoms may be present in the shell at a concentration of about 0.1% to about 20% by weight of the shell, more preferably about 0.1% to about 10% by weight, and even more preferably about 0.1% to about 1% by weight. 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.

[0052] It is believed that treating chitosan under acidic conditions can also be beneficial. Acidic conditions may improve the solubility of chitosan, making it more available for reaction with redox initiators. Acidic conditions may also affect the molecular weight and / or structure of chitosan, resulting in improved particle size and / or performance.

[0053] For example, the modified chitosan may be formed under acidic conditions at a temperature of at least 25°C, preferably at a pH of 6.5 or less, preferably less than 6.5, even more preferably 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 be at a pH of preferably 6.5 or less, preferably less than 6.5, even more preferably from a pH of 3 to 6.2, or even from a pH of 5 to 6.2.

[0054] Chitosan (which may be referred to as raw chitosan or parent chitosan before acid treatment and / or redox initiator treatment) may be treated with acid, preferably at a pH of 6.5 or less, at a temperature of about 25°C to about 99°C, preferably about 75°C to about 95°C, for at least 1 hour, preferably about 1 hour to about 3 hours, or for as long as required to obtain a chitosan solution viscosity of the acid-treated chitosan of about 1500 cps or less, or even 500 cps or less.

[0055] The modified chitosan may be an acid-treated modified chitosan. For example, chitosan may be treated with an acid. The acid may 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 the second acid is a weak acid. Preferably, the first acid and the second acid are present in a normality ratio of about 20:80 to about 80:20, preferably about 35:65 to about 65:35. The first acid may have a first pKa of less than 1, and the second acid may have a first pKa of 5.5 or less. Preferably, the second acid has a first pKa of 1 to 5.5.

[0056] The first acid may 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 may 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.

[0057] Chitosan may be treated with an acid before being treated with a redox initiator. However, it may be advantageous to treat chitosan with a redox initiator and an acid simultaneously during at least part of the treatment process. For example, chitosan may be dissolved or dispersed in an acidic aqueous phase, and the redox initiator may be added after dissolution / dispersion. Alternatively, the acid and redox initiator may be provided in the aqueous phase (in any suitable order), and then chitosan is added and dissolved / dispersed.

[0058] It is believed that selecting chitosan and / or modified chitosan with a specific molecular weight can contribute to improved processability, performance, and / or biodegradability. If the chitosan is rather large, a highly viscous solution that is difficult to process may result. If the chitosan is rather small, it is believed that poor shell formation may occur, possibly due to increased solubility of the chitosan, resulting in chitosan that is less likely to migrate to the water / oil interface during shell formation.

[0059] The chitosan may be characterized by a weight average molecular weight of about 100 kDa to about 600 kDa, preferably about 100 kDa to about 500 kDa, more preferably about 100 kDa to about 400 kDa, more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa, prior to treatment with a redox initiator and / or acid, preferably at least prior to treatment with a redox initiator.

[0060] The modified chitosan may be characterized by a weight average molecular weight of about 1 kDa to about 600 kDa, preferably about 5 kDa to about 300 kDa, more preferably about 10 kDa to about 200 kDa, more preferably about 15 kDa to about 150 kDa, and even more preferably about 20 kDa to about 100 kDa, after treatment with a redox initiator and / or an acid, preferably at least after treatment with a redox initiator. The modified chitosan may be characterized by a weight average molecular weight of about 1 kDa to about 600 kDa, preferably about 5 kDa to about 300 kDa, and more preferably about 30 kDa to about 100 kDa.

[0061] The chitosan may be characterized by a degree of deacetylation of at least 50%, preferably about 50% to about 99%, more preferably about 75% to about 90%, and even more preferably about 80% to about 85%. The degree of deacetylation may affect the solubility of the chitosan, which in turn may affect its reactivity or behavior in the process of forming the particle shell. For example, a degree of deacetylation that is too low (e.g., less than 50%) may result in a chitosan that is relatively insoluble and relatively unreactive. A relatively high degree of deacetylation may result in a chitosan that is very soluble, with relatively little chitosan migrating to the oil / water interface during shell formation.

[0062] 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 can change the shell characteristics of the delivery particle, for example, by changing the surface charge and / or zeta potential, which can affect the particle's adhesion efficiency and / or formulation compatibility. For example, modified chitosan may be further modified with a modifying compound, including an epoxide, an aldehyde, an α,β-unsaturated compound, or a combination thereof.

[0063] As noted above, the shell is a polymeric material that is the reaction product of chitosan and a cross-linking agent. Preferably, the cross-linking agent comprises a polyisocyanate. Thus, the shell of the delivery particle may comprise a polyurea resin, which comprises the reaction product of a polyisocyanate and chitosan.

[0064] Polyisocyanate materials useful in the present disclosure are understood for purposes of this specification as isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. "Polyisocyanate" is intended to mean 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. Polyisocyanates useful in the present disclosure include isocyanate monomers, oligomers, or prepolymers, or dimers or trimers thereof having at least two isocyanate groups. Preferred crosslinking can be achieved using polyisocyanates having a functionality of at least three.

[0065] Aromatic polyisocyanates may be preferred; however, aliphatic polyisocyanates and blends thereof may also be useful. Aliphatic polyisocyanates are understood to be polyisocyanates that do not contain any aromatic moieties. Aromatic polyisocyanates are understood to be polyisocyanates that contain at least one aromatic moiety. The crosslinker may comprise a mixture of aromatic and aliphatic polyisocyanates.

[0066] If the polyisocyanate is aromatic, it can be, but is not limited to, methylene diphenyl isocyanate, toluene diisocyanate, tetramethylxylidene diisocyanate, polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® RC), trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® L75), naphthalene-1,5-diisocyanate, and phenylene diisocyanate, or trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name Takenate® D-110N).

[0067] Aliphatic polyisocyanates may include trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N 100).

[0068] Derivatives of polyisocyanates may include oligomers or polymers of isocyanate monomers. As a non-limiting example, the polyisocyanate may preferably include oligomers or polymers of diphenylmethane diisocyanate (MDI), such as Mondur® MR-Light.

[0069] The polyisocyanate may preferably be 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, tetramethylxylidene diisocyanate, naphthalene-1,5-diisocyanate, 1,4-phenylene diisocyanate, 1,3-diisocyanatobenzene, derivatives thereof (such as prepolymers, oligomers, and / or polymers thereof), and combinations thereof.

[0070] The particle shell may also be reinforced using additional co-crosslinkers such as polyfunctional amines and / or polyamines, such as diethylene triamine (DETA), polyethyleneimine, polyvinylamine, or mixtures thereof. Acrylates may also be used as additional co-crosslinkers, for example, to reinforce the shell.

[0071] The polymeric material may be formed during the reaction in a weight ratio of chitosan present in the reaction to crosslinker present in the reaction of about 1:10 to about 1:0.1. It is believed that selecting a desired ratio of biopolymer to crosslinker can provide desired ductility benefits and improved biodegradability. It may be preferred that at least 21% by weight of the shell be comprised of moieties derived from chitosan, preferably acid-treated chitosan. The chitosan as a weight percentage of the shell may be about 21% to about 95% of the shell. The ratio of chitosan in the aqueous phase compared to the crosslinker, preferably an isocyanate, in the oil phase may be 21:79 to 90:10, or even 1:2 to 9:1, or even 1:1 to 7:1, by weight. The polymeric material may be formed during the reaction in which the weight ratio of chitosan or its derivative (which may include acid-treated chitosan) present in the reaction to crosslinker present in the reaction is about 1:10 to about 10:1, preferably about 1:5 to about 5:1, preferably about 1:4 to about 5:1, more preferably about 1:1 to about 5:1, more preferably about 3:1 to about 5:1. The shell may contain chitosan at a concentration of 21% by weight or more of the total shell, preferably about 21% to about 90% by weight, or even 21% to 85% by weight, or even 21% to 75% by weight, or even 21% to 55% by weight. The chitosan in this paragraph is preferably a modified chitosan as described herein.

[0072] The delivery particles are prepared by the following steps: forming an aqueous phase, which comprises treating chitosan with a redox initiator in the presence of water at a pH of 6.5 or less and at least 25°C, preferably for at least 1 hour, and / or until the aqueous phase is characterized by a viscosity of less than 1500 cp, preferably a viscosity of less than 500 cp, to form a modified chitosan, preferably wherein the aqueous phase further comprises a mixture of a first acid and a second acid; forming an oil phase, which comprises dissolving together at least one benefit agent and at least one crosslinking agent, preferably a polyisocyanate, optionally with an additive oil, preferably a partitioning control agent; forming an emulsion, which comprises dissolving the oil phase in excess of the aqueous phase; The emulsion may be obtainable or may even be made from a process comprising the steps of: forming an emulsion, preferably by mixing under high shear agitation, to form droplets of an oil phase dispersed in an aqueous phase, and optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6; optionally providing a second redox initiator to the emulsion, where the second redox initiator is the same as or different from the redox initiator added to the aqueous phase; and 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, where the shell comprises a reaction product of a crosslinker and a modified chitosan, and where the shell surrounds a core comprising the oil phase droplets.

[0073] As described above, the redox initiator can be added to the aqueous phase and, optionally, to the emulsion. When the redox initiator is added to both phases, the redox initiator provided to the aqueous phase may be considered the first redox initiator, and the redox initiator provided to the emulsion may be considered the second redox initiator. When the second redox initiator is provided to the emulsion, the second redox initiator may be the same or different from the (first) redox initiator added to the aqueous phase. For convenience of processing, it may be preferable for the first redox initiator and the second redox initiator to be the same. For performance reasons, it may be preferable for the first redox initiator and the second redox initiator to be different; for example, it is believed that beneficial results can be achieved by adding a persulfate to the aqueous phase and then adding a peroxide to the emulsion. The relative amounts of the first redox initiator and the second redox initiator may be different. Although "first" and "second" redox initiators are used herein to describe redox initiators added in the aqueous phase and / or emulsion phase, respectively, it is understood that two or more redox initiators may be added at any suitable stage, or even added incrementally at any stage.

[0074] While the present disclosure is generally directed to modifying chitosan with a redox initiator in the aqueous phase (typically also in the presence of an acid), it is also contemplated that chitosan may be modified with a redox initiator later in the particle formation process. For example, it is contemplated that a redox initiator may be added to the emulsion, optionally, or even preferably, only to the emulsion (e.g., no redox initiator is provided in the aqueous phase).

[0075] Chitosan may be added to water in a jacketed reactor at a pH of 2 or even 3 to 6.5, adjusted using concentrated HCl and / or a weak acid, such as formic acid or acetic acid. A redox initiator may be added simultaneously to the aqueous phase. The chitosan in this mixture may be acid-treated by heating to an elevated temperature, such as 85°C, for 60 minutes and then held at this temperature for 1 to 1440 minutes, or longer. The aqueous phase may then be cooled to 25°C. Optionally, deacetylation may be further promoted or enhanced by an enzyme that depolymerizes or deacetylates chitosan. The oil phase may be prepared by dissolving an isocyanate, such as a trimer of xylylene diisocyanate (XDI) or a polymer of methylene diphenyl isocyanate (MDI), in oil at 25°C. A diluent, such as isopropyl myristate, may be used to adjust the hydrophilicity of the oil phase. The oil phase may then be added to the water phase and milled at high speed to obtain a target size.The emulsion may then be hardened in one or more heating steps, such as heating to 40°C in 30 minutes and holding at 40°C for 60 minutes.The time and temperature are approximate.The temperature and time are selected to be sufficient to form and harden a shell at the interface between the oil phase droplets and the water continuous phase.For example, the emulsion may be heated to 85°C in 60 minutes and then held at 85°C for 360 minutes to harden the particles.The slurry may then be cooled to room temperature.

[0076] The shell may degrade by at least 50% after 20 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by 30-100%, preferably 40-100%, 50-100%, 60-100%, or 60-95% in 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, or more preferably 14 days.

[0077] The delivery particles of the present disclosure comprise a core. The core comprises a benefit agent. The core optionally comprises a partitioning modifier.

[0078] The core of the particle is surrounded by a shell. When the shell ruptures, the benefit agent in the core is released. Additionally or alternatively, the benefit agent in the core may diffuse from the particle and / or be squeezed. Suitable benefit agents disposed within the core may include benefit agents that provide a benefit to a surface such as fabric or hair.

[0079] The core may comprise from about 5% to about 100% benefit agent, preferably a fragrance, by weight of the core.The core may comprise from about 45% to about 95%, preferably from about 50% to about 80%, more preferably from about 50% to about 70% benefit agent, preferably a fragrance, by weight of the core.

[0080] The benefit agent may comprise an aldehyde-containing benefit agent, a ketone-containing benefit agent, or a combination thereof. Such benefit agents, such as aldehyde- or ketone-containing perfume ingredients, are known to provide desirable benefits, such as freshness benefits. The benefit agent may comprise at least about 20%, preferably at least about 25%, more preferably at least about 40%, and even more preferably at least about 50% by weight of the benefit agent of the aldehyde-containing benefit agent, ketone-containing benefit agent, or a combination thereof.

[0081] The benefit agent may be a hydrophobic benefit agent, which is compatible with the oil phase typically used in making the delivery particles of the present disclosure.

[0082] The benefit agents are selected to provide benefits under the preferred use of the treatment composition. The benefit agents in the core may be fragrances, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin cooling agents, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleach particles, silicon dioxide particles, malodor reducing agents, odor control substances, chelating agents, antistatic agents, softening agents, insect and moth repellents, colorants, thickeners, drape and foam inhibitors, smoothing agents, wrinkle inhibitors, sanitizing agents, disinfectants, bacterial inhibitors, mold inhibitors, mildew inhibitors, antiviral agents, drying agents, stain resistant agents, soil release agents, fabric The active ingredient may be selected from the group consisting of fabric refreshing and deodorizing maintenance agents, chlorine bleach odor suppressants, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color restoration / revitalization agents, anti-fade agents, whiteness enhancers, anti-abrasion agents, abrasion resistant agents, fabric integration agents, anti-abrasion agents, anti-pilling agents, foam suppressors, defoamers, UV protection agents, anti-fading agents, anti-allergy agents, enzymes, waterproofing agents, fabric comfort agents, shrink resistance agents, stretch resistance agents, stretch recovery agents, skin care agents, synthetic or natural actives, antibacterial actives, antiperspirant actives, cationic polymers, dyes, and mixtures thereof.

[0083] The benefit agent in the core preferably comprises a fragrance material (or simply "fragrance"), which may include one or more perfume ingredients. Fragrances are particularly suitable for encapsulation in the delivery particles described herein, as fragrance-containing particles can provide freshness benefits across multiple touch points.

[0084] As used herein, the term "perfume raw material" (or "perfume raw material, PRM") refers to a compound having a molecular weight of at least about 100 g / mole and useful for imparting an odor, fragrance, essence, or scent, either alone or in combination with other perfume raw materials. Typical PRMs include alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes, such as terpenes, among others. Lists of common PRMs can be found in various reference sources, such as, for example, "Perfume and Flavor Chemicals," Volumes I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology," Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0085] PRMs may be characterized by their boiling point (BP) measured at atmospheric pressure (760 mmHg) and octanol / water partition coefficient (P), which may be described in terms of logP, determined according to the following test method. Based on these characteristics, PRMs can be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV fragrances, as described in more detail in U.S. Patent No. 6,869,923. Suitable Quadrant I, II, III, and IV fragrance raw materials are disclosed in that U.S. patent.

[0086] Perfume raw materials that have a boiling point BP of less than about 250° C. and a logP of less than about 3 are known as Quadrant I perfume raw materials. Quadrant I perfume raw materials are preferably limited to less than 30% of the fragrance materials.

[0087] The fragrance may include a perfume raw material having a logP of from about 2.5 to about 4. It is understood that other perfume raw materials may also be present in the fragrance.

[0088] The core of the delivery particles of the present disclosure may include a partitioning modifier, which may promote more robust shell formation. The partitioning modifier may be combined with the perfume oil material of the core prior to incorporation of the wall-forming monomer. The partitioning modifier may be present in the core at a concentration of 0% to 95% by weight of the core, preferably about 5% to about 55% by weight, preferably about 10% to about 50% by weight, more preferably about 20% to about 50% by weight, and even more preferably about 25% to about 50% by weight.

[0089] Partition adjusters include vegetable oils, modified vegetable oils, and C4-C 24 The partitioning modifier may include a substance selected from the group consisting of monoesters, diesters, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning modifier may preferably include, or even consist of, isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably include castor oil and / or soybean oil. U.S. Patent Application Publication No. 20110268802, incorporated herein by reference, describes other partitioning modifiers that may be useful in the delivery particles described herein.

[0090] If the benefit agent itself is not sufficient to function as an oil phase or solvent, especially during the process of forming the shell of the delivery particle of the wall-forming material, the oil phase can comprise a suitable carrier and / or solvent. In this sense, the oil is optional, since the benefit agent itself can sometimes be oil. These carriers or solvents are generally oils, preferably with a boiling point above about 80°C, low volatility, and non-flammable. Without being limited thereto, they preferably comprise one or more esters, preferably with a chain length of up to 18 carbon atoms or even up to 42 carbon atoms, and / or triglycerides, such as esters of C6-C12 fatty acids with glycerol.

[0091] Optionally, the aqueous phase may contain an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (such as alkyl sulfates, alkyl ether sulfates, and / or alkylbenzene sulfonates), nonionic surfactants (preferably alkoxylated alcohols containing ethoxy groups), polyvinyl alcohol, and / or polyvinylpyrrolidone. Solubilized chitosan may provide emulsification benefits in this application. When used, the emulsifier is typically present in an amount of about 0.1 to 40% by weight, preferably 0.2 to about 15% by weight, and more typically 0.5 to 10% by weight, based on the total weight of the aqueous phase.

[0092] The population of delivery particles may be provided as a slurry, preferably an aqueous slurry. The slurry may include one or more processing aids, which may include water, an anti-agglomerating material such as a divalent salt, or a particle-suspending polymer such as xanthan gum, guar gum, cellulose (preferably microfibrillated cellulose), and / or carboxymethylcellulose. When the delivery particles are characterized by cationic nature (e.g., when the shell is at least partially derived from chitosan), a non-anionic structuring agent, preferably a non-ionic structuring agent, may be preferred, for example, to avoid adverse charge interactions that may result in undesirable aggregation.

[0093] The slurry may include one or more carriers selected from the group consisting of polar solvents, including but not limited to water, ethylene glycol, propylene glycol, polyethylene glycol, glycerol; and non-polar solvents, including but not limited to mineral oil, perfume raw materials, silicone oil, hydrocarbon paraffin oil, and mixtures thereof. Aqueous slurries may be preferred. The slurry may also include unencapsulated ("free") perfume raw materials that differ in identity and / or amount from those encapsulated in the core of the delivery particle.

[0094] The slurry may comprise a polysaccharide such as chitosan, cationically modified starch, and / or cationically modified guar; polysiloxane; polydiallyldimethylammonium halide; copolymer of polydiallyldimethylammonium chloride and polyvinylpyrrolidone; composition comprising polyethylene glycol and polyvinylpyrrolidone; acrylamide; imidazole; imidazolinium halide; polyvinylamine; copolymer of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; polyglycerol ether silicone crosspolymer; polyacrylic acid, polyacrylate, polyvinylamine and amines, in one embodiment diethylenetriamine, ethylenediamine, bis(3-aminopropyl)piperazine, N,N-bis(2 ... copolymers of tris-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine, and mixtures thereof with polyvinyl alcohol oligomers; polyethyleneimine, derivatized polyethyleneimine, and in one embodiment, ethoxylated polyethyleneimine; polymeric compounds comprising at least two moieties selected from the group consisting of carboxylic acid moieties, amine moieties, hydroxyl moieties, and nitrile moieties in the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile, or combinations thereof; preformed coacervates of anionic surfactants combined with cationic polymers; polyamines, and mixtures thereof.

[0095] At least one group of delivery particles may be contained in an agglomerate, which may then be combined with a separate population of delivery particles and at least one auxiliary material. The agglomerate may be comprised of a material selected from the group consisting of silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride, and a binder such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0096] Suitable equipment for use in the processes disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, where available, continuous process configurations), spray dryers, and extruders. Such equipment is available from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., USA), and Arde Barinco (New Jersey, USA).

[0097] Supplementary ingredients In addition to the delivery particles, the treatment compositions of the present disclosure may also include one or more auxiliary materials that may provide a benefit in the intended end use of the composition or may be processing and / or stabilizing aids.

[0098] Suitable adjunct materials may include surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, additional perfumes and perfume delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-agglomerating agents, coating agents, formaldehyde scavengers, and / or pigments. Preferably, the adjunct materials include additional fabric conditioning agents, dyes, pH control agents, solvents, rheology modifiers, structurants, cationic polymers, surfactants, perfumes, additional perfume delivery systems, chelating agents, antioxidants, preservatives, or mixtures thereof.

[0099] Depending on the intended form, formulation, and / or end use, the compositions of the present disclosure may be free of one or more of the following adjunct materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural elastomers, fabric softeners, carriers, hydrotropes, processing aids, structurants, anti-agglomerating agents, coatings, formaldehyde scavengers, and / or pigments.

[0100] The exact nature of these additional components and the concentration at which they are incorporated depend on the physical form of the composition and the nature of the work to be used. However, if one or more adjuvants are present, such one or more adjuvants can be present as detailed below. The following is a non-limiting list of suitable additional adjuvants:

[0101] A. Surfactants The composition of the present disclosure may include a surfactant. The surfactant may be useful, for example, to provide cleaning benefits. The composition may include a surfactant system, which may contain one or more surfactants.

[0102] Compositions of the present disclosure may comprise from about 0.1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50% by weight of the composition of a surfactant system. Liquid compositions may comprise from about 5% to about 40% by weight of the composition of a surfactant system. Compositions suitable for dense formulations, e.g., dense, liquid, gel, and / or unit dose forms, may comprise from about 25% to about 70%, or from about 30% to about 50% by weight of the composition of a surfactant system.

[0103] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include nonionic surfactants such as linear alkylbenzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactant may be derived, at least in part, from natural sources, such as natural feedstock alcohols.

[0104] Suitable anionic surfactants may include any conventional anionic surfactant. This may include, for example, sulfate detersive surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid-based detersive surfactants, such as alkyl benzene sulfonates. The anionic surfactants may be linear, branched, or a combination thereof. Preferred surfactants include linear alkyl benzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkyl benzene sulfonate (MLAS), methyl ester sulfonate (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylate (AEC). The anionic surfactant may be present in acid form, salt form, or a mixture thereof. The anionic surfactant may be partially or totally neutralized, for example, with an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine). Due to the presence of cationic ester quat materials, it may be desirable to limit the amount of anionic surfactant to avoid undesirable interactions of materials. For example, the composition may contain less than 5%, preferably less than 3%, more preferably less than 1%, and even more preferably less than 0.1% anionic surfactant by weight of the composition.

[0105] The surfactant system may include a nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(oxyalkylated) alcohol surfactants, and mixtures thereof. The alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof. The nonionic surfactant may be linear, branched (e.g., mid-chain branched), or a combination thereof. Specific nonionic surfactants may include alcohols having an average of about 12 to about 16 carbons and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactants.

[0106] Suitable zwitterionic surfactants include betaines, C8-C9 alkyl dimethyl betaines, including alkyl dimethyl betaines and cocodimethylamidopropyl betaine. 18 (For example, C 12 ~C 18 ) amine oxides (e.g., C 12 ~ 14 dimethylamine oxide), and / or N-alkyl-N,N-dimethylamino-1-propanesulfonate (wherein the alkyl group is C8 to C 18 or C 10 ~C 14 The zwitterionic surfactant may include any conventional zwitterionic surfactant, such as sulfo and hydroxybetaines, such as (which may be

[0107] Depending on the formulation and / or intended end use, the composition may be substantially free of certain surfactants. For example, a liquid fabric strengthening composition, such as a fabric softener, may be substantially free of anionic surfactants, as such surfactants may negatively interact with cationic components.

[0108] The treatment composition may include an anionic surfactant, as the delivery particles of the present disclosure have surprisingly been found to be compatible with such products. For example, the consumer product composition may be a laundry detergent composition (e.g., a heavy-duty liquid or soluble unit dose article) that preferably includes an anionic surfactant; such compositions typically also include additional surfactants (such as nonionic surfactants) and / or other ingredients.

[0109] B. Conditioning Actives The compositions of the present disclosure may include conditioning actives. Compositions containing conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color, and / or appearance benefits.

[0110] The conditioning active may be present at a concentration of about 1% to about 99% by weight of the composition. The composition may comprise from about 1%, or about 2%, or about 3%, to about 99%, or about 75%, or about 50%, or about 40%, or about 35%, or about 30%, or about 25%, or about 20%, or about 15%, or about 10% by weight of the composition. The composition may comprise from about 5% to about 30% by weight of the composition of the conditioning active.

[0111] Suitable conditioning active materials for the composition of the present disclosure can include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty acid esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof.Preferably, the treatment composition is a fabric care composition in which one or more adjunct ingredients comprise quaternary ammonium ester materials.Such materials are particularly useful in fabric enhancing / conditioning / softening compositions.

[0112] The composition may contain a quaternary ammonium ester compound, a silicone, or a combination of these, preferably a single combination. The total amount of the quaternary ammonium ester compound and the silicone may be about 5% to about 70% by weight of the composition, or about 6% to about 50% by weight, or about 7% to about 40% by weight, or about 10% to about 30% by weight, or about 15% to about 25% by weight. The composition may contain the quaternary ammonium ester compound and the silicone in a weight ratio of about 1:10 to about 10:1, or about 1:5 to about 5:1, or about 1:3 to about 1:3, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.

[0113] The composition may contain a mixture of different types of conditioning actives. The composition of the present disclosure may contain a specific conditioning active but may be substantially free of other conditioning actives. For example, the composition may be free of quaternary ammonium ester compounds, silicones, or both. The composition may contain a quaternary ammonium ester compound but may be substantially free of silicones. The composition may contain silicones but may be substantially free of quaternary ammonium ester compounds.

[0114] C. Adhesion aid The composition of the present disclosure may also include a deposition aid. As mentioned above, due to the synergistic effect of the ester quaternary material and the delivery particles of the present disclosure, less (or even no) deposition aid may be required to provide comparable or even improved performance. Alternatively, a deposition aid may be used in the composition of the present disclosure to further enhance performance.

[0115] The deposition aid may promote deposition of the delivery particles, conditioning actives, fragrance, or combinations thereof, which may improve the performance benefits of the composition and / or allow for more efficient incorporation of such benefit agents. The composition may comprise from 0.0001% to 3%, preferably from 0.0005% to 2%, more preferably from 0.001% to 1%, or from about 0.01% to about 0.5%, or from about 0.05% to about 0.3%, by weight of the composition, of the deposition aid. The deposition aid may be a cationic or amphoteric polymer, preferably a cationic polymer.

[0116] Cationic polymers in general and methods for their preparation are well known in the literature. Suitable cationic polymers include quaternary ammonium polymers known as "polyquaternium" polymers as designated in the International System of Nomenclature for Cosmetic Ingredients, such as Polyquaternium-6 (poly(diallyldimethylammonium chloride)), Polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), Polyquaternium-10 (quaternized hydroxyethylcellulose), and Polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride).

[0117] The deposition aid may be selected from the group consisting of polyvinyl formamide, partially hydroxylated polyvinyl formamide, polyvinyl amine, polyethylene imine, ethoxylated polyethylene imine, polyvinyl alcohol, polyacrylate, and combinations thereof. The cationic polymer may include a cationic acrylate.

[0118] The deposition aid can be added simultaneously with the delivery particles (e.g., simultaneously with the encapsulated benefit agent) or directly / independently into the fabric treatment composition. The weight average molecular weight of the polymer may be from 500 Daltons to 5,000,000 Daltons, or from 1,000 Daltons to 2,000,000 Daltons, or from 2,500 Daltons to 1,500,000 Daltons, as measured by size exclusion chromatography against polyethylene oxide standards using refractive index (RI) detection. The weight average molecular weight of the cationic polymer may be from 5,000 Daltons to 37,500 Daltons.

[0119] D. Rheology Modifiers / Structuring Agents The compositions of the present disclosure may include a rheology modifier and / or a structuring agent. Rheology modifiers may be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structuring agents may be used to promote phase stability and / or to suspend or inhibit aggregation of particles in the liquid composition, such as the delivery particles described herein.

[0120] Suitable rheology modifiers and / or structurants may include non-polymeric crystalline hydroxyl-functional structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulosic fibers (e.g., microfibrillated cellulose, which may be derived from bacterial, fungal, or plant sources, including wood), diamide gelling agents, or combinations thereof.

[0121] The polymeric structurant may be of natural or synthetic origin. Naturally derived polymeric structurants may include hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives may include pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structurants may include polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers may include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates are polymers of unsaturated mono- or dicarbonates and C1-C (meth)acrylic acid. 30 The structuring agent may include copolymers with alkyl esters. Such copolymers are available from Noveon Inc. under the trade name Carbopol Aqua 30. Crosslinked polymers, such as crosslinked polyacrylates, and / or polymers and / or copolymers, such as those further comprising nonionic monomers, such as acrylamide or methacrylamide monomers, may be useful as structuring agents. Another suitable structuring agent is sold under the trade name Rheovis CDE, available from BASF.

[0122] E. Other adjuvants The treatment compositions of the present disclosure may include other adjuvants suitable for inclusion in a product and / or end use. For example, the treatment compositions may include pure perfume, perfume delivery technology (such as secondary perfumes and / or encapsulates having non-polyisocyanate / chitosan wall materials), cationic surfactants, cationic polymers, solvents, suds suppressors, or combinations thereof.

[0123] Method for producing the treatment composition The present disclosure further relates to methods for making treatment compositions, such as the treatment compositions and / or consumer product compositions described herein.

[0124] The method may include providing a base composition including a processing aid and combining a population of delivery particles with the base composition. The population of delivery particles may preferably be provided as an aqueous slurry. The base composition is in the form of a liquid composition.

[0125] The delivery particles may be combined with one or more auxiliary ingredients when the delivery particles are in one or more forms including a slurry form, a neat particle form, and / or a spray-dried particle form, preferably a slurry form. The delivery particles may be combined with such auxiliary ingredients by methods including mixing and / or spraying.

[0126] The processing composition of the present disclosure can be formulated into any suitable form and can be prepared by any process selected by the formulator.One or more auxiliary ingredients and delivery particles can be combined in a batch process, a circulation loop process, and / or an in-line mixing process.Suitable equipment for use in the methods disclosed herein can include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, high shear mixers, static mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, if available, in continuous process configurations), spray dryers, and extruders.

[0127] As described herein, the treatment composition may be packaged in a container to form a consumer product. The container may be a bottle, preferably a plastic bottle. The treatment composition may be packaged in an aerosol or other spray container according to known methods.

[0128] Processing method The present disclosure also relates to a method of treating a surface, preferably a fabric. Generally, the method comprises contacting a surface, preferably a fabric, with a treatment composition according to the present disclosure, wherein the treatment composition comprises a population of delivery particles as described herein.

[0129] Additionally or alternatively, the method may comprise contacting a surface, preferably a fabric, with a population of delivery particles described herein, which may be included in a treatment composition, preferably a fabric care composition, according to the present disclosure.

[0130] The method may include contacting a fabric, such as clothing, with a treatment composition. The treatment composition includes a population of delivery particles. The contacting step results in one or more of the delivery particles being deposited on the surface of the fabric. The delivery particles include a core and a shell surrounding the core, where the core includes a benefit agent, preferably a fragrance material including one or more perfume ingredients. The shell includes a polymeric material that is, for example, the reaction product of chitosan of a specific molecular weight and a crosslinker. Suitable treatment compositions and delivery particles are described in more detail above.

[0131] The contacting step may occur during a manual laundry process, e.g., in a basin when fabrics are treated by hand, or during an automatic laundry process, e.g., in an automatic washing machine. The contacting step may occur during the wash cycle of an automatic washing machine. In such cases, the treatment composition may be a laundry detergent or a laundry additive. The contacting step may preferably occur during the rinse cycle of an automatic washing machine. In such cases, the treatment composition may be a fabric enhancer, preferably a liquid fabric enhancer. The contacting step may also occur during the drying step of the laundry process, e.g., in an automatic dryer. In such cases, the treatment composition may be in the form of a nonwoven dryer sheet or a dryer bar. The contacting step may occur as a result of the treatment composition being applied directly to the fabric, e.g., in a pre-treatment operation or a "refreshing" step (e.g., in the case of fabrics that have been used or worn since the last wash). In such cases, the treatment composition may be in the form of a liquid, stick, or spray, preferably a spray. Contacting the target fabrics relatively late in the laundering process, for example during the rinse cycle, improves the likelihood or efficiency of deposition on the fabrics, as the fabrics are less likely to be washed down the drain.

[0132] The contacting step may occur in the presence of water. The treatment composition can be diluted with water to form a treatment solution. The treatment composition can be diluted from about 100 to about 1500 times, preferably from 300 to about 1000 times.

[0133] Liquids containing the disclosed compositions may have a pH of about 3 to about 11.5. When diluted, such compositions are typically used at concentrations of about 500 ppm to about 15,000 ppm in solution. When the cleaning solvent is water, the water temperature typically ranges from about 5°C to about 90°C, and the water-to-fabric ratio may typically be about 1:1 to about 30:1.

[0134] The dilution may occur in the drum of an automatic washing machine. The treatment composition may be placed in a dispensing drawer of the automatic washing machine. The treatment composition may be dispensed from the dispensing drawer into the drum during the treatment process.

[0135] As alluded to above, the method may further comprise drying the fabric having one or more delivery particles on the surface of the fabric. The drying step may comprise a passive drying process, such as on a clothesline or drying rack. The drying step may comprise an automatic drying process, such as an automatic dryer.

[0136] combination Specifically contemplated combinations of the present disclosure are set forth herein in the following alphabetized sections, which are exemplary in nature and not intended to be limiting.

[0137] A. A treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, and the shell comprising a polymeric material that is the reaction product of a modified chitosan and a crosslinker, the modified chitosan being formed by treating the chitosan with a redox initiator, the redox initiator being selected from the group consisting of persulfates, peroxides, and combinations thereof. 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, and more preferably sodium persulfate. C. The treatment composition according to paragraph A or B, wherein the redox initiator and 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. D. A treatment composition according to any of paragraphs A-C, wherein the shell of the delivery particle comprises sulfur atoms, preferably wherein the sulfur atoms are present in the shell at a concentration of from about 0.1% to about 20% by weight of the shell, more preferably from about 0.1% to about 10% by weight, and even more preferably from about 0.1% to about 1% by weight. E. The treatment composition according to any of paragraphs A-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 less, preferably less than 6.5, even more preferably at a pH of about 3 to about 6, even more preferably at a pH of about 4 to about 6, preferably at a pH of about 5 to about 6, more preferably at a pH of 5.2 to 6, or preferably at a pH of 6.5 or less, preferably less than 6.5, even more preferably at a pH of 3 to 6.2, or even at a pH of 5 to 6.2. F. The treatment composition according to any of paragraphs A-E, wherein the modified chitosan is an acid-treated modified chitosan, and wherein the chitosan is 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 the second acid is a weak acid, and preferably the first acid and the second acid are present in a normality ratio of from about 20:80 to about 80:20, preferably from about 35:65 to about 65:35. G. A treatment composition according to any of paragraphs A-F, wherein at least one of the following is true: (a) the chitosan is characterized by a weight average molecular weight of about 100 kDa to about 600 kDa, preferably about 100 kDa to about 500 kDa, more preferably about 100 kDa to about 400 kDa, more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa, prior to treatment with a redox initiator and / or an acid; and / or (b) the modified chitosan is characterized by a weight average molecular weight of about 1 kDa to about 600 kDa, preferably about 5 kDa to about 300 kDa, more preferably about 10 kDa to about 200 kDa, more preferably about 15 kDa to about 150 kDa, and even more preferably about 20 kDa to about 100 kDa. H. The treatment composition according to any of paragraphs A-G, wherein the crosslinker 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'-methylene diphenyl diisocyanate, 4,4'-methylene diphenyl diisocyanate, 2,4'-methylene diphenyl diisocyanate, [diisocyanato(phenyl)methyl]benzene, toluene diisocyanate, tetramethylxylidene diisocyanate, naphthalene-1,5-diisocyanate, 1,4-phenylene diisocyanate, 1,3-diisocyanatobenzene, derivatives thereof (such as prepolymers, oligomers, and / or polymers thereof), and combinations thereof. I. The treatment composition according to any of paragraphs A-H, wherein a reaction product is formed in the reaction and the weight ratio of chitosan present in the reaction to crosslinker present in the reaction is from about 1:10 to about 1:0.1. J. The treatment composition according to any of paragraphs A-I, wherein the shell is present on the delivery particle at a concentration of about 15% or less by weight of the delivery particle. K. The treatment composition according to any of paragraphs A-J, wherein the benefit agent is a fragrance material, preferably a fragrance material comprising a perfume raw material characterized by a logP of from about 2.5 to about 4.5. L. The core optionally comprises a partitioning modifier, preferably a vegetable oil, a modified vegetable oil, a C4-C6 oil, optionally present in the core at a concentration of about 5% to about 55% by weight of the core, preferably about 10% to about 50% by weight, more preferably about 25% to about 50% by weight. 24 The treatment composition according to any of paragraphs A-K, further comprising a partitioning modifier selected from the group consisting of mono-, di-, and tri-esters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate. M. The treatment composition according to any of paragraphs A-L, wherein the delivery particles are characterized by a volume weighted median particle size of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 25 to about 35 microns. N. The delivery particles are prepared by treating chitosan with a redox initiator in the presence of water at a pH of 6.5 or less and at least 25°C, preferably for at least 1 hour, and / or until the aqueous phase is characterized by a viscosity of less than 1500 cp, preferably a viscosity of less than 500 cp, to form a modified chitosan, preferably wherein the aqueous phase further comprises a mixture of a first acid and a second acid; forming an oil phase, which comprises dissolving together at least one benefit agent and at least one crosslinking agent, preferably a polyisocyanate, optionally with an additive oil, preferably a partitioning control agent; forming an emulsion, which comprises dissolving the oil phase in excess of the aqueous phase, preferably a the treatment composition according to any of paragraphs A-M is obtainable from a process comprising the steps of: forming an emulsion by mixing under high shear agitation or high shear agitation to form droplets of an oil phase dispersed in an aqueous phase, and optionally adjusting the pH of the emulsion to a range of from 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, wherein the shell comprises a reaction product of a crosslinker and a modified chitosan, the shell surrounding a core comprising the droplets of the oil phase. O. The treatment composition according to any of paragraphs A-O, wherein the delivery particles are cationic, preferably wherein the delivery particles are characterized by a zeta potential of at least 15 mV at a pH of 4.5. P. The treatment composition according to any of paragraphs A-O, wherein the modified chitosan is further modified with a modifying compound, the modifying compound comprising an epoxide, an aldehyde, an α,β-unsaturated compound, or a combination thereof. Q. A treatment composition according to any of paragraphs A-P, wherein the shell of the delivery particles degrades by at least 60% in 60 days when tested according to test method OECD 301B. R. The treatment composition according to any of paragraphs A-Q, wherein the processing aid is selected from the group consisting of surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic metal complexes, polymeric dispersants, mud and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, undiluted fragrance, additional fragrance delivery systems, structural elasticizers, carriers, hydrotropes, processing aids, anti-flocculants, coatings, formaldehyde scavengers, pigments, and mixtures thereof. S. The treatment composition according to any of paragraphs A-R, wherein the treatment aid comprises an anionic surfactant, a cationic conditioning agent, or a mixture thereof. T. The treatment composition according to any of paragraphs A-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 laundry detergent composition, a fabric conditioning composition, a laundry additive, a fabric pre-treatment composition, a fabric refresher composition, or a mixture thereof. U. The treatment composition according to any of paragraphs A-T, wherein the treatment composition is in the form of a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, a pastille or bead, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven, or a mixture thereof, preferably a liquid composition. V. The treatment composition according to any of paragraphs A-U, wherein the treatment composition comprises from about 50% to about 99% water by weight of the treatment composition, preferably from about 60% to about 98% water by weight of the treatment composition, and more preferably from about 80% to about 96% water by weight. W. A method of making a processing composition according to any of paragraphs A-V, the method comprising the steps of providing a base composition comprising a processing aid, and combining a population of delivery particles with the base composition. X. A method of treating a surface, the method comprising contacting the surface, preferably a fabric, with a treatment composition according to any of paragraphs A-V.

[0138] Test Method It will be understood that the test methods disclosed in the Test Methods section of this application should be used to determine the values ​​of each of the parameters of the inventive subject matter claimed and described herein.

[0139] Determination of polymer molecular weight and related parameters The following method, which describes gel permeation chromatograph with multi-angle light scatter and refractive index (GPC-MALS / RI), is used to find molecular weight distribution measurements and related values ​​for the polymers described herein.

[0140] Gel Permeation Chromatography (GPC) with Multi-Angle Light Scattering (MALS) and Refractive Index (RI) detection (GPC-MALS / RI) allows the measurement of absolute molecular weights of polymers without the need for column calibration or standards. GPC systems allow the separation of molecules as a function of their molecular size. MALS and RI can provide information on number-average (Mn) and weight-average (Mw) molecular weights.

[0141] The Mw distribution of water-soluble polymers such as chitosan is typically measured using a liquid chromatography system (e.g., Agilent 1260 Infinity Pump System with OpenLab Chemstation software, Agilent Technology, Santa Clara, CA, USA) and a column set (e.g., 2 Tosoh TSKgel G6000WP 7.8 x 300 mm 13 μm pore size, guard column A0022 6 mm x 40 mm PW x1-cp, King of Prussia, PA), operated at 40°C. The mobile phase is 0.1 M sodium nitrate in water containing 0.02% sodium azide and 0.2% acetic acid. The mobile phase solvent is pumped isocratically at a flow rate of 1 mL / min. A multi-angle light scattering (18-Angle MALS) detector DAWN® and a refractive index (RI) detector (Wyatt Technology, Santa Barbara, Calif., USA) controlled by Wyatt Astra® software v8.0 are used.

[0142] Samples are typically prepared by dissolving chitosan material at approximately 1 mg per ml in the mobile phase, mixing the solution, and allowing it to hydrate overnight at room temperature. Prior to GPC analysis, samples are filtered using a 3 ml syringe through a 0.8 μm Versapor membrane filter (PALL, Life Sciences, NY, USA) into an LC autosampler vial.

[0143] The dn / dc value (differential change in refractive index with concentration, 0.15) is used to determine the number average molecular weight (Mn), weight average molecular weight (Mw), Z-average molecular weight (Mz), molecular weight at the peak maximum (Mp), and polydispersity (Mw / Mn) by the Astra detector software.

[0144] viscosity The viscosity of the final liquid product is measured using an AR550 rheometer / viscometer from TA instruments (New Castle, DE, USA) using parallel steel plates with a diameter of 40 mm and a gap size of 500 μm. -1 High shear viscosity at 0.05 seconds -1 The low shear viscosity at 21°C for 3 minutes is 0.01 s -1 ~25 seconds -1 is obtained from a logarithmic shear rate sweep.

[0145] Test Method for Determining logP For each material tested (e.g., each PRM in a fragrance mixture), the logarithm of the octanol / water partition coefficient (logP) is calculated. The logP values ​​of individual materials (e.g., PRMs) are calculated using the Consensus logP Computational Model, version 14.02 (Linux), available from Advanced Chemistry Development Inc. (ACD / Lab) (Toronto, Canada), which yields unitless logP values. The ACD / Labs Consensus logP Computational Model is part of the ACD / Labs model suite.

[0146] Volume-weighted particle size and size distribution Volume-weighted particle size distributions were determined by single-particle optical sensing (SPOS), also known as optical particle counting (OPC), using an AccuSizer 780 AD instrument and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent. The instrument was configured with the following conditions and options: flow rate = 1 ml / s, small diameter threshold = 0.50 μm, sensor model number = LE400-05 or equivalent, autodilution = on, collection time: 60 seconds, number of channels = 512, reservoir fluid volume = 50 ml, and maximum coincidence count = 9200. Measurements were initiated by cold-conditioning the sensor by flushing with water until the background count was less than 100. A sample of delivery capsules in suspension is introduced, and the capsule density is adjusted, if necessary, via automated dilution with deionized water to achieve a capsule count of at least 9200 per ml. The suspension is analyzed for 60 seconds. The resulting volume-weighted PSD data is plotted and recorded, and desired volume-weighted particle size values ​​(e.g., median / 50th percentile, 5th percentile, and / or 90th percentile) are determined.

[0147] Procedure for determining decomposition % To determine % degradation, the procedure described in the "OECD Guideline for Testing of Chemicals" 301B CO2 Evolution (Modified Sturm Test), adopted on July 17, 1992, is used. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0148] Fabric treatment methods The fabrics were treated using a Miele washing machine. For each treatment, 3 kg of fabric was added to the machine, including 1100 g of knitted cotton fabric and 1100 g of polyester-cotton (50 / 50) fabric. In addition, 18 terry towel cotton tracers, weighing approximately 780 g in total, were also added.

[0149] Prior to the test treatment, the load is pre-conditioned twice with 79 g of unscented IEC A-based detergent (ex WFK, Testgewebe GmbH), each time using a short cotton cycle at 95°C, followed by two additional 95°C washes without detergent.

[0150] For the test treatment, the load is washed using a short cotton cycle at 40°C, a spin speed of 1200 rpm, and 79 g of IEC A-based detergent, which is added to the appropriate dispenser at the beginning of the wash cycle. A dose of 35 g of the test fabric treatment composition (e.g., LFE according to the example) is added to the appropriate dispenser. At the end of the treatment cycle, the terry towel tracer is removed from the washing machine and line-dried overnight.

[0151] The next day, the dried terry towel tracer is analyzed by a rapid headspace GC / MS (gas chromatography mass spectrometry) technique as described below. For comparison purposes, all treatments washed and analyzed on the same day are reported as "single wash tests."

[0152] Method for determining headspace concentrations above treated dry fabrics The cotton tracer was analyzed by fast headspace GC / MS (gas chromatography mass spectrometry) technique. A 4 x 4 cm aliquot of terry cotton towel tracer was transferred to a 25 ml headspace vial. The fabric sample was equilibrated at 65°C for 10 minutes. The headspace above the fabric was sampled by SPME (50 / 30 μm DVB / Carboxen / PDMS) technique for 5 minutes. The SPME fibers were then thermally desorbed online into the GC. The analytes were analyzed in full scan mode by fast GC / MS. Ion extraction of specific masses of PRM was used to calculate the total HS reaction and perfume headspace composition above the tested leg.

[0153] EDX method 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 also provide the spatial distribution of elements via mapping, as element concentrations can be collected from points, along lines, or as maps.

[0154] The instrument used in the methods described herein is a Scanning Electron Microscope (SEM) ZEISS 300 equipped with a Bruker Quantax 400 EDX detector.

[0155] To analyze the delivered particles in the premix or slurry, 2 μl of the slurry solution is deposited onto an SEM stub (sample holder) that has been thoroughly pre-cleaned using acetone and alcohol in sequence.

[0156] To analyze the delivery particles in the product composition, the particles may be extracted according to the "Extraction of Delivery Particles from the Final Product" method provided below.

[0157] Use the EDX detector according to the manufacturer's instructions to collect the desired data, using the guidance for qualitative and quantitative analysis given below.

[0158] The data produced by EDX analysis includes a spectrum reported on a graph where the x-axis is the reported X-ray energy (keV) and the y-axis is the intensity of the signal. The graph features different peaks, each corresponding to the characteristic energies of the elements detected, which then allows the chemical composition of the analyzed sample to be defined.

[0159] A. Image Analysis For a given sample, perform elemental mapping to identify the surface location of the detected elements using a resolution of 600 x 400 pixels for 3 min, acquiring an area of ​​140 x 95 µm (corresponding to a magnification of 800x).

[0160] The chemical information produced by EDX techniques can be visualized in several ways, including elemental mapping. For a particular region of interest (ROI), a digital image can be acquired in which the intensity of each location (pixel) is proportional to the intensity of each peak. Figure 1 shows a digital image of a particular ROI using a delivery particle slurry sample, showing a number of delivery particles 100. Figure 2 shows various images (originally in color) relating to the intensity of each peak. Typically, the images are in color, with brighter colors associated with greater peak intensity. In Figure 2, a first image 110 shows a representative sample of delivery particles 100. A second image 111 shows an image representing the carbon present. A third image 112 shows an image representing the oxygen present. A fourth image 113 shows an image representing the nitrogen present. A fifth image 114 shows an image representing the sulfur present. A sixth image 115 shows an image representing the chlorine present.

[0161] B. Quantitative analysis 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% by weight for the quantified elements, and if the mass concentration is lower than the MDL, the element will not be quantified.

[0162] For quantitative analysis, EDX spectra are acquired over a 50 μm × 40 μm area for 3 minutes. The output is a spectrum, where peaks are identified as corresponding to the detected elements, and a table showing the mass fraction and atomic distribution fraction (stoichiometric ratio) is also generated. Figure 3 shows a graph of the spectrum for a given sample.

[0163] Extraction of delivery particles from the final product Unless otherwise specified herein, the preferred method for isolating delivery particles from the final product is based on the fact that the density of the majority of such delivery particles is different from that of water. The final 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 final product. A pipette or spatula is used to remove the top and bottom layers of this suspension, which is then subjected to further rounds of dilution and centrifugation to separate and concentrate the delivery particles. The delivery particles are observed using an optical microscope equipped with a cross-polarization filter or differential interference contrast (DIC) at a total magnification of 100x and 400x. Microscopic observation provides an early indication of the presence, size, and aggregation of delivery particles.

[0164] To extract the delivery particles from the final liquid fabric enhancer product, the following procedure is performed: 1. Place three approximately 20 ml aliquots of the liquid fabric enhancer into three separate 50 ml centrifuge tubes, dilute each with aliquot:deionized water = 1:1 (e.g., 20 ml fabric enhancer + 20 ml deionized water), mix each aliquot well, and centrifuge each aliquot for 30 minutes at approximately 10,000 x g. 2. After the centrifugation in step 1, discard the bottom aqueous layer (approximately 10 ml) in each 50 ml centrifuge tube, and then add 10 ml of deionized water to each 50 ml centrifuge tube. 3. Repeat the process of centrifugation, removal of the bottom aqueous layer, and then adding 10 ml of deionized water to each 50 ml centrifuge tube two more times for each aliquot. 4. Remove the top layer with a spatula or pipette. 5. Transfer this top layer to a 1.8 ml centrifuge tube and centrifuge at approximately 20,000 x g for 5 minutes. 6. Remove the top layer with a spatula and transfer to a new 1.8 ml centrifuge tube, add deionized water until the tube is completely filled, then centrifuge at approximately 20,000 x g for 5 minutes. 7. Remove the bottom layer with a fine pipette, add deionized water until the tube is completely filled, and centrifuge at approximately 20,000 x g for 5 minutes. 8. Repeat step 7 five more times (total of six).

[0165] If both the top and bottom layers appear rich in delivery particles in step 1 above, proceed immediately to step 3 (i.e., skip step 2) and proceed with steps 4-8. Once those steps are complete, use a spatula and / or pipette to remove the bottom layer from the 50 ml centrifuge tube from 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 in the new tube and add deionized water until the tube is completely filled, then centrifuge at approximately 20,000 x g for 5 minutes. Remove the top layer (water) and add deionized water until the tube is again full. Repeat this five more times (for a total of six). Combine the isolated top and bottom layers, rich in delivery particles, back together.

[0166] If the fabric enhancer is white or the delivery particle-rich layer is difficult to distinguish, add 4 drops of a dye (such as Liquitint Blue JH 5% premix from Milliken & Company, Spartanburg, South Carolina, USA) to the centrifuge tube from step 1 and proceed with isolation as described.

[0167] To extract delivery particles from solid end products that disperse readily in water, 1 L of deionized water is mixed with 20 g of the end product (e.g., detergent foams, films, gels, and granules, or water-soluble polymers; soap flakes and bars; and other matrices that dissolve readily in water, such as salts, sugars, clays, and starches). When extracting delivery particles from end products that do not disperse readily in water, such as waxes, dryer sheets, dryer bars, and greasy materials, it may be necessary to add detergent to the product and diluent, and to stir and / or gently heat the product to release the delivery particles from the matrix. The use of organic solvents or drying of the delivery particles during the extraction process should be avoided, as these operations may damage the delivery particles during this stage.

[0168] For extraction of delivery particles from liquid final 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), 20 ml of the final product is mixed with 20 ml of deionized water. If necessary, NaCl (e.g., 1-4 g NaCl) may be added to the diluted suspension to increase the density of the solution and facilitate floating of the delivery particles to the top layer. If the product has a white color that makes it difficult to distinguish the layers of delivery particles formed during centrifugation, a water-soluble dye may be added to the diluent to provide visual contrast.

[0169] The water / product mixture is subjected to successive rounds of centrifugation, involving removal of the top and bottom layers and resuspension of those layers in fresh diluent, followed by further centrifugation, isolation, and resuspension. Each round of centrifugation is performed in tubes with a volume of 1.5 to 50 ml, using a centrifugal force of up to 20,000 x g for 5 to 30 minutes. At least six rounds of centrifugation are typically required to extract and purify enough delivery particles for testing. For example, the first round of centrifugation may be performed in a 50 ml tube spun at 10,000 x g for 30 minutes, followed by five more rounds of centrifugation, in which material from the top and bottom layers is separately resuspended in fresh diluent in 1.8 ml tubes and spun at 20,000 x g for 5 minutes per round.

[0170] If delivery particles are observed microscopically in both the top and bottom layers, the delivery particles from these two layers are recombined after a final centrifugation step to create 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 may be stored as a deionized water suspension for up to 14 days before analysis.

[0171] Those skilled in the art will recognize that various other protocols can be devised for extracting and isolating delivery particles from the final product, and that such methods require validation through comparison of measurements taken before and after adding and extracting delivery particles from the final product.

[0172] Procedure for determining the compatibility of delivery particles in a laundry matrix The suitability of the delivery particles in the laundry matrix is ​​measured by the percentage of agglomerates formed in the laundry detergent matrix. The slurry containing the delivery particles is homogenized by stirring for at least 1 minute using an overhead mixer. The homogenized slurry is then added to the laundry matrix, for example, a single unit dose (SUD) matrix, at a ratio of 1:40, for example, 1 g of slurry in 40 g of matrix, while mixing. The mixture is mixed using an overhead mixer at 350 rpm for at least 15 minutes. The mixture of delivery particles and laundry matrix is ​​then poured through a 425 μm sieve after mixing. The particle agglomerates on the sieve are washed with a large amount of deionized (DI) water until no visible laundry matrix is ​​observed. The original water-washed filtrate is then collected and passed through a 212 μm sieve to collect any particle agglomerates remaining on the 212 μm sieve. The particle agglomerates are then washed with a large amount of DI water until no visible matrix is ​​observed. The particle agglomerates from the 212 μm sieve and the particle agglomerates from the 425 μm sieve were combined and washed again with DI water to remove any residual matrix. The particle agglomerates were then collected and dried to a constant weight in a CEM oven to determine the weight of the particle agglomerates in the washed matrix. The percent agglomerates was calculated as follows:

[0173]

number

[0174] The examples provided below are intended to be illustrative in nature and not limiting.

[0175] In the following examples, the abbreviations correspond to the materials listed in Table 1.

[0176] [Table 1]

[0177] Comparative Example 1 Comparative Example 1 is the same as Example 13 of U.S. Patent Application Publication No. 20210252469(A1). An aqueous phase is prepared by dispersing 20.66 g of ChitoClear in 439.00 g of water while mixing in a jacketed reactor. The pH of the aqueous phase is then adjusted to 4.9 using concentrated HCl under stirring. The aqueous phase temperature is then increased to 85°C over 60 minutes and then held at 85°C for a period to hydrolyze the ChitoClear. After the hydrolysis step over a period of 90 minutes, the aqueous phase temperature is then reduced to 25°C. An oil phase is prepared by mixing 159.38 g of perfume oil and 23.91 g of isopropyl myristate with 4.00 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion. The emulsion is heated to 40°C over 30 minutes and held for 60 minutes. The pH of the emulsion was then adjusted to 2.97 using hydrochloric acid. The emulsion was then heated to 85°C and kept at this temperature for 6 hours with mixing. According to OECD 301B, the % degradability is 64.26% in 28 days.

[0178] Comparative Example 2 Comparative Example 2 is the same as Example 10 of U.S. Patent Application Publication No. 20210252469(A1). An aqueous phase is prepared by dispersing 20.66 g of ChitoClear in 439.00 g of water while mixing in a jacketed reactor. The pH of the aqueous phase is then adjusted to 6.0 using concentrated HCl under stirring. The aqueous phase temperature is then increased to 85°C over 60 minutes and then held at 85°C for a period to hydrolyze the ChitoClear. After the hydrolysis step over a period of 90 minutes, the aqueous phase temperature is then reduced to 25°C. An oil phase is prepared by mixing 159.38 g of perfume oil and 23.91 g of isopropyl myristate with 4.00 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion. The emulsion is heated to 40°C over 30 minutes and held for 60 minutes. The emulsion is then heated to 85°C and maintained at this temperature for 6 hours with mixing. Inclusion bodies are obtained, the degradability % of the inclusion bodies is 11.07% in 28 days according to OECD 301B.

[0179] Various data points relating to Comparative Examples 1 and 2 are reported in Table 2.

[0180] [Table 2]

[0181] As can be seen from Table 2, the inclusion bodies obtained at a relatively low pH (4.9) in Comparative Example 1 degrade to a greater extent in the OECD degradability test. However, these inclusion bodies suffer from relatively high leakage. Inclusion bodies prepared at a slightly higher pH (6) perform better in terms of leakage, but suffer from relatively poor performance in the degradability test. Inclusion bodies with low leakage are needed. Inclusion bodies that simultaneously have relatively high degradability are even more desirable. Achieving a balance between low leakage and high degradability has been difficult to achieve prior to the present invention. Inclusion bodies with low leakage, high degradability, and compatibility with laundry matrices have been even more difficult to achieve.

[0182] Example 1 An acid- and potassium persulfate-treated chitosan stock solution was prepared as follows: First, a potassium persulfate solution was prepared by dissolving 1.55 g of potassium persulfate in 3287.5 g of deionized water at 70°C. Next, 154.89 g of chitosan (ChitoClear) was dispersed into the potassium persulfate solution while mixing in a jacketed reactor. The pH of the chitosan dispersion was then adjusted to 4.30 using 68.37 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 85°C over 60 minutes and then held at 85°C for a period of time to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of the chitosan solution was 5.1. The resulting chitosan stock solution was used to prepare capsules in Examples 1, 3, 5, and 7.

[0183] An aqueous phase is prepared by mixing 420.27 g of the above chitosan stock solution in a jacketed reactor. An oil phase is prepared by mixing 128.30 g of fragrance and 54.99 g of isopropyl myristate with 4.01 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 11.71 microns.

[0184] Example 2. A chitosan stock solution treated with acid and potassium persulfate was prepared as follows: First, potassium persulfate solution ("KPS") was prepared by dissolving 1.55 g of potassium persulfate in 3287.97 g of deionized water at 70°C. Then, 154.90 g of chitosan (ChitoClear) was dispersed in the potassium persulfate solution while mixing in a jacketed reactor. The pH of the chitosan dispersion was then adjusted to 5.10 using 51.72 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 85°C over 60 minutes and then held at 85°C for a period of time to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain a chitosan solution treated with acid and potassium persulfate. The pH of the chitosan solution was 5.93. The resulting chitosan stock solution was used to prepare capsules in Examples 2, 4, 6, and 8.

[0185] An aqueous phase is prepared by mixing 422.15 g of the above chitosan stock solution in a jacketed reactor. An oil phase is prepared by mixing 128.30 g of fragrance and 54.99 g of isopropyl myristate with 4.01 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 17.64 microns.

[0186] Various data points relating to Examples 1 and 2 are reported in Table 3.

[0187] [Table 3]

[0188] As seen in Table 3, encapsulations based on the addition of persulfate exhibit degradability, but as seen in Example 2, leakage is also improved relative to Example 1 with a slight change in pH. Furthermore, Example 2, in addition to improving leakage relative to Example 1, also exhibits 39.81% degradability over 28 days. This illustrates how the addition of persulfate can achieve a surprising balance of properties by resulting in degradable capsules with relatively low leakage. Desired properties for encapsulations include one or more of low leakage or degradability, or compatibility with matrices such as laundry detergent environments. Example 2 illustrates low leakage and degradability. Example 1 illustrates degradability.

[0189] Example 3. An aqueous phase is prepared by mixing 420.27 g of chitosan stock solution from Example 1 in a jacketed reactor. An oil phase is prepared by mixing 146.63 g of fragrance and 36.66 g of isopropyl myristate with 5.55 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 13.32 microns.

[0190] Example 4. An aqueous phase is prepared by mixing 422.15 g of chitosan stock solution from Example 2 in a jacketed reactor. An oil phase is prepared by mixing 146.63 g of fragrance and 36.66 g of isopropyl myristate with 5.55 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 14.29 microns.

[0191] Various data points relating to Examples 3 and 4 are reported in Table 4.

[0192] [Table 4]

[0193] As seen in Table 4, the encapsulated bodies based on the addition of persulfate exhibit one-week leakage values ​​of 44.25% and 27.20%, respectively. Even more surprisingly, subtle adjustment of the pH increases the % degradability in these samples from 13.14% to 39.97%. The encapsulated bodies of the present invention consistently demonstrate surprising improvements in leakage or degradability or matrix compatibility. In preferred embodiments, an improvement is observed in one category of attributes, such as leakage or degradability. More desirably, an improvement is observed in two categories, such as leakage and degradability, as shown to be achievable in Example 4 or, prior to that, Example 2. Most desirably, an improvement is observed in all three categories: leakage, degradability, and compatibility. For example, appropriate selections can be made from the examples illustrated in Table 8. The parameters of the present invention surprisingly allow for the construction of encapsulated bodies with high performance in terms of leakage or degradability or matrix compatibility.

[0194] Example 5. An aqueous phase is prepared by mixing 420.27 g of chitosan stock solution from Example 1 in a jacketed reactor. An oil phase is prepared by mixing 146.63 g of fragrance and 36.66 g of isopropyl myristate with 2.49 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 18.06 microns.

[0195] Example 6 An aqueous phase is prepared by mixing 422.15 g of chitosan stock solution from Example 2 in a jacketed reactor. An oil phase is prepared by mixing 146.63 g of fragrance and 36.66 g of isopropyl myristate with 2.49 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 11.85 microns.

[0196] Various data points relating to Examples 5 and 6 are reported in Table 5.

[0197] [Table 5]

[0198] Examples 5 and 6 illustrate the improved degradability of capsules according to the present invention. In addition to improved degradability, a surprising reduction in leakage is observed as the pH is adjusted closer to pH 6. These examples reinforce the trend observed in the previous examples that the present invention can provide improvements in properties in more than one category of attributes, more specifically in terms of the attributes of leakage, degradability, and compatibility.

[0199] Example 7 An aqueous phase is prepared by mixing 420.27 g of chitosan stock solution from Example 1 in a jacketed reactor. An oil phase is prepared by mixing 164.96 g of fragrance and 18.33 g of isopropyl myristate with 4.01 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 20.54 microns.

[0200] Example 8 An aqueous phase is prepared by mixing 422.15 g of chitosan stock solution from Example 2 in a jacketed reactor. An oil phase is prepared by mixing 164.96 g of fragrance and 18.33 g of isopropyl myristate with 4.01 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 40°C over 30 minutes and then held for an additional 60 minutes. The resulting emulsion is then heated to 90°C in 60 minutes and maintained at this temperature with mixing for 8 hours, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 12.56 microns.

[0201] Various data points relating to Examples 7 and 8 are reported in Table 6.

[0202] [Table 6]

[0203] Examples 7 and 8 illustrate the improved degradability of capsules according to the present invention. As the pH is adjusted closer to pH 6, a reduction in leakage is observed in addition to improved degradability. These examples reinforce the trend observed in the previous examples that the present invention can provide improvements in more than one category of properties in terms of leakage, degradability, and compatibility.

[0204] Example 9. A chitosan stock solution treated with acid and potassium persulfate was prepared as follows: First, a potassium persulfate solution was prepared by dissolving 1.56 g of potassium persulfate in 3303.96 g of deionized water at room temperature. Next, 155.68 g of chitosan (ChitoClear) was dispersed in the potassium persulfate solution while mixing in a jacketed reactor. The pH of the chitosan dispersion was then adjusted to 5.80 using 53.88 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 85°C over 60 minutes and then held at 85°C for a period of time, such as 2 hours, to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain a chitosan solution treated with acid and potassium persulfate. The pH of the chitosan solution was 5.97.

[0205] An aqueous phase is prepared by mixing 2101.81 g of the above chitosan stock solution in a jacketed reactor. An oil phase is prepared by mixing 716.14 g of fragrance and 179.05 g of isopropyl myristate with 19.58 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes. The emulsion is then heated to 85°C in 60 minutes and maintained at this temperature for 6 hours with mixing, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 15.69 microns.

[0206] Example 10. A chitosan stock solution treated with acid and potassium persulfate was prepared as follows: First, a potassium persulfate solution was prepared by dissolving 1.56 g of potassium persulfate in 3303.96 g of deionized water at room temperature. Next, 155.68 g of chitosan (ChitoClear) was dispersed in the potassium persulfate solution while mixing in a jacketed reactor. The pH of the chitosan dispersion was then adjusted to 5.81 using 52.68 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 85°C over 60 minutes and then held at 85°C for a period of time, such as 2 hours, to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain a chitosan solution treated with acid and potassium persulfate. The pH of the chitosan solution was 5.90.

[0207] An aqueous phase is prepared by mixing 2456.58 g of the above chitosan stock solution in a jacketed reactor. An oil phase is prepared by mixing 714.38 g of fragrance and 178.6 g of isopropyl myristate with 27.07 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes. The emulsion is then heated to 85°C in 60 minutes and maintained at this temperature for 6 hours with mixing, after which it is cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 20.54 microns.

[0208] Various data points relating to Examples 9 and 10 are reported in Table 7.

[0209] [Table 7]

[0210] Examples 9 and 10 illustrate the improvement in multiple property categories in terms of improved degradability and improved leakage values ​​(lower is better) in capsules according to the present invention. As the pH is adjusted closer to pH 6, a surprising reduction in leakage is observed in addition to improved degradability. These examples illustrate that the present invention can provide improvements in more than one category of properties in terms of leakage, degradability, and compatibility. Compared to Comparative Examples 1 and 2, it is observed that better performance and degradability are observed when a redox initiator (KPS) is present.

[0211] Comparative Example 3. 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 with 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. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, then to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain an acid-treated chitosan solution. The pH of the chitosan solution was 5.40.

[0212] An oil phase is prepared by mixing 635.63g of fragrance and 158.92g of isopropyl myristate with 24.06g of Takenate D-110N at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 85°C in 60 minutes, and then held at 85°C for 6 hours, before being cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 10.06 microns.

[0213] Example 11 An aqueous phase containing an acid- and potassium persulfate-treated chitosan stock solution is prepared as follows: Potassium persulfate (KPS) solution is 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. 96.43 g of chitosan ChitoClear is then added to the KPS solution. The pH of the chitosan dispersion is then adjusted to 5.91 using 32.96 g of concentrated HCl under stirring. The temperature of the chitosan solution is then increased to 85°C over 60 minutes and then held at 85°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature is then reduced to 25°C after the 90-minute hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of the chitosan solution is 6.04.

[0214] An oil phase is prepared by mixing 636.92g of fragrance and 159.24g of isopropyl myristate with 24.11g of Takenate D-110N at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 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 have a volume-weighted median particle size of 33.97 microns.

[0215] Example 12 A chitosan stock solution treated with acid and potassium persulfate was prepared as follows: 42.08 g of chitosan ChitoClear was dispersed in 893.0 g of deionized water at 25°C with mixing in a jacketed reactor. 0.42 g of potassium persulfate was added and dissolved. The pH of the chitosan dispersion was then adjusted to 5.87 using 14.40 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, then to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain a chitosan solution treated with acid and potassium persulfate. The pH of the chitosan solution was 5.90.

[0216] An aqueous phase is prepared by mixing 433.6 g of the above chitosan stock solution in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 95°C in 60 minutes, then held at 95°C for 4 hours, then 1.38 g of potassium persulfate is added and dissolved, then held at 95°C for 2 hours, then cooled to 25°C in 90 minutes. The formed capsules have a volume-weighted median particle size of 36.25 microns.

[0217] Example 13 A chitosan stock solution treated with acid and potassium persulfate was prepared as follows: 42.08 g of chitosan ChitoClear was dispersed in 893.1 g of deionized water at 25°C with mixing in a jacketed reactor. 4.20 g of potassium persulfate was added and dissolved. The pH of the chitosan dispersion was then adjusted to 5.94 using 14.35 g of concentrated HCl under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, and then held at 85°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain a chitosan solution treated with acid and potassium persulfate. The pH of the chitosan solution was 5.36.

[0218] An aqueous phase is prepared by mixing 433.6 g of chitosan stock solution from Example 13 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 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 have a volume-weighted median particle size of 50.79 microns.

[0219] Example 14. A chitosan stock solution treated with acid and potassium persulfate 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. The pH of the chitosan dispersion was then adjusted to 5.91 using 11.48 g of concentrated HCl and 1.25 g of 90% formic acid under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, then to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain a chitosan solution treated with acid and potassium persulfate. The pH of the chitosan solution was 5.99. The resulting chitosan stock solution was used to prepare capsules in Examples 14 and 15.

[0220] An aqueous phase is prepared by mixing 433.6 g of chitosan stock solution from Example 14 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 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 have a volume-weighted median particle size of 33.48 microns.

[0221] Example 15. An aqueous phase is prepared by mixing 433.6 g of chitosan stock solution from Example 14 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 95°C in 60 minutes, then held at 95°C for 4 hours, then 1.38 g of potassium persulfate is added and dissolved, then held at 95°C for 2 hours, then cooled to 25°C in 90 minutes. The formed capsules have a volume-weighted median particle size of 36.25 microns.

[0222] Example 16. A chitosan stock solution treated with acid and potassium persulfate was prepared as follows: 42.15 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. The pH of the chitosan dispersion was then adjusted to 5.92 using 8.66 g of concentrated HCl and 2.52 g of 90% formic acid under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, then to 95°C over 30 minutes, and then held at 95°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain a chitosan solution treated with acid and potassium persulfate. The pH of the chitosan solution was 6.01. The resulting chitosan stock solution was used to prepare capsules in Examples 16 and 17.

[0223] An aqueous phase is prepared by mixing 433.6 g of chitosan stock solution from Example 16 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 95°C in 60 minutes, then held at 95°C for 4 hours, then 1.38 g of potassium persulfate is added and dissolved, then held at 95°C for 2 hours, then cooled to 25°C in 90 minutes. The formed capsules have a volume-weighted median particle size of 31.68 microns.

[0224] Example 17. An aqueous phase is prepared by mixing 433.6 g of chitosan stock solution from Example 16 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 95°C in 60 minutes, then held at 95°C for 4 hours, then 3.90 g of potassium persulfate is added and dissolved, then held at 95°C for 2 hours, then cooled to 25°C in 90 minutes. The formed capsules have a volume-weighted median particle size of 31.68 microns.

[0225] Example 18. An 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. The pH of the chitosan dispersion was then adjusted to 5.93 using 32.05 g of concentrated HCl and 9.29 g of 90% formic acid under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, and then held at 85°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The solution was combined with 360 g of the stock solution from Example 19 and homogenized. The pH of the chitosan solution was 5.99. The resulting chitosan stock solution was used to prepare capsules in Examples 18 and 19.

[0226] An aqueous phase is prepared by mixing 433.5 g of chitosan stock solution from Example 18 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 85°C in 60 minutes, followed by the addition of 0.32 g of 30% hydrogen peroxide (H2O2) solution, and then held at 85°C for 6 hours, followed by cooling to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 33.89 microns.

[0227] Example 19. An aqueous phase is prepared by mixing 433.5 g of chitosan stock solution from Example 18 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 85°C in 60 minutes, followed by the addition of 0.65 g of 30% hydrogen peroxide solution, and then held at 85°C for 6 hours, then cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 30.42 microns.

[0228] Example 20. An 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 with mixing in a jacketed reactor. 1.58 g of potassium persulfate was added and dissolved. The pH of the chitosan dispersion was then adjusted to 5.95 using 32.05 g of concentrated HCl and 9.27 g of 90% formic acid under stirring. The temperature of the chitosan solution was then increased to 65°C over 30 minutes, then to 85°C over 30 minutes, and then held at 85°C for 2 hours to hydrolyze and depolymerize the chitosan. The temperature was then reduced to 25°C after the 90-minute hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of the chitosan solution was 6.00. The resulting chitosan stock solution was used to prepare capsules in Examples 20 and 21.

[0229] An aqueous phase is prepared by mixing 433.5 g of chitosan stock solution from Example 20 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 85°C in 60 minutes, followed by the addition of 1.30 g of 30% hydrogen peroxide solution, and then held at 85°C for 6 hours, then cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 25.87 microns.

[0230] Example 21. An aqueous phase is prepared by mixing 433.5 g of chitosan stock solution from Example 20 in a jacketed reactor. An oil phase is prepared by mixing 128.86 g of fragrance and 32.22 g of isopropyl myristate with 4.88 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion with the desired particle size. The emulsion is heated to 60°C over 45 minutes, then to 85°C in 60 minutes, followed by the addition of 3.25 g of 30% hydrogen peroxide solution, and then held at 85°C for 6 hours, then cooled to 25°C in 90 minutes. The capsules formed have a volume-weighted median particle size of 25.87 microns.

[0231] Various data points relating to Comparative Example 3 and Examples 11-21 are reported in Table 8.

[0232] [Table 8]

[0233] Examples 11-21 illustrate the relative compatibility of delivery particles according to the present disclosure with product matrices such as laundry detergents (e.g., SUD = soluble unit dose article). These are compared to Comparative Example 3. Examples 12 and 17, in which redox initiator was added to the aqueous phase and emulsion, exhibit surprisingly low leakage and matrix compatibility attributes. Particles according to the present disclosure also appear to exhibit favorable degradation attributes. The table further suggests that % aggregates can be tuned or adjusted by the amount of redox initiator introduced. A high level of compatibility attribute is achieved when redox initiator is added to the aqueous phase and, optionally, the emulsion.

[0234] Additionally, Figure 4 shows the difference in charge of delivery particles made by various processes, such as acid treatment and the addition of a redox initiator to the aqueous phase or emulsion, as described in the examples shown (i.e., Comparative Example 3, and Examples 13, 14, 17, and 21). As shown by the examples, the disclosed process allows for tailoring of the zeta potential. For example, the disclosed process allows for lowering or mitigating the zeta potential at the pH conditions of use, usefully resulting in more controllable delivery particles that are less prone to aggregation and may be more compatible with the product matrix in the end-use application.

[0235] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

[0236] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest, or disclose any such invention, either alone or in combination with any other reference or references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control.

[0237] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. 1. A processing composition comprising a processing aid and a population of delivery particles, the delivery particle comprises a core and a shell surrounding the core; the core comprises a benefit agent; the shell comprises a polymeric material that is the reaction product of modified chitosan and a crosslinker; the modified chitosan is formed by treating chitosan with a redox initiator; The treatment composition, wherein the redox initiator is selected from the group consisting of persulfates, peroxides, and combinations thereof.

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

3. 3. The treating composition of claim 1, 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, and more preferably from about 30:70 to about 3:

97.

4. the shell of the delivery particle comprises sulfur atoms; 4. The treating composition of claim 1, wherein the sulfur atoms are preferably present in the shell at a concentration of from about 0.1% to about 20% by weight of the shell, more preferably from about 0.1% to about 10% by weight, and even more preferably from about 0.1% to about 1% by weight.

5. The modified chitosan is subjected to a process comprising the steps of:

5. The treatment composition of any one of claims 1 to 4, which is preferably formed 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 modified chitosan is an acid-treated modified chitosan; the chitosan is further treated with an acid, preferably a mixture of acids, more preferably a mixture of a first acid and a second acid; the first acid is a strong acid; the second acid is a weak acid; 6. The treatment composition of any one of claims 1 to 5, wherein preferably the first acid and the second acid are present in a normality ratio of from about 20:80 to about 80:20, preferably from about 35:65 to about 65:

35.

7. below, (a) the chitosan has a molecular weight of about 100 kDa to about 600 kDa prior to treatment with the redox initiator and / or acid; preferably characterized by a weight average molecular weight of about 100 kDa to about 500 kDa, more preferably about 100 kDa to about 400 kDa, more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa; (b) the modified chitosan is from about 1 kDa to about 600 kDa; The processing composition according to any one of claims 1 to 6, characterized by a weight average molecular weight of preferably from about 5 kDa to about 300 kDa, more preferably from 10 kDa to about 200 kDa, more preferably from about 15 kDa to about 150 kDa, and even more preferably from about 20 kDa to about 100 kDa.

8. The crosslinking agent is a polyisocyanate, The treatment composition according to any one of claims 1 to 7, preferably comprising 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, tetramethylxylidene diisocyanate, naphthalene-1,5-diisocyanate, 1,4-phenylene diisocyanate, 1,3-diisocyanatobenzene, derivatives thereof, and mixtures thereof.

9. 9. The treating composition of any one of claims 1 to 8, wherein the reaction product is formed in a reaction wherein the weight ratio of the chitosan present in the reaction to the crosslinker present in the reaction is from about 1:10 to about 1:0.

1.

10. The treatment composition of any one of claims 1 to 9, wherein the shell is present on the delivery particle at a concentration of about 15% or less by weight of the delivery particle.

11. The benefit agent comprises a fragrance material, A treatment composition according to any one of claims 1 to 10, which is a fragrance material comprising a perfume raw material preferably characterized by a log P of from about 2.5 to about 4.

5.

12. a partitioning modifier, optionally present in said core at a concentration of from about 5% to about 55%, preferably from about 10% to about 50%, more preferably from about 25% to about 50% by weight of said core; Preferably, vegetable oil, modified vegetable oil, C ４ ~C ２４ selected from the group consisting of mono-, di-, and tri-esters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof; The treatment composition according to any one of claims 1 to 11, further comprising a partitioning modifier, more preferably isopropyl myristate.

13. the delivery particles have a volume weighted median particle size of about 1 to about 100 microns; 13. The treating composition of any one of claims 1 to 12, characterized by a volume weighted median particle size of preferably from about 10 to about 100 microns, preferably from about 15 to about 50 microns, more preferably from about 20 to about 40 microns, and even more preferably from about 25 to about 35 microns.

14. The delivery particles include: forming an aqueous phase by treating the chitosan with the redox initiator in the presence of water at a pH of 6.5 or less and at least 25°C, preferably for at least 1 hour, and / or until the aqueous phase is characterized by a viscosity of less than 1500 cp, preferably a viscosity of less than 500 cp, to form the modified chitosan; forming an aqueous phase, preferably wherein said aqueous phase further comprises said mixture of said first acid and said second acid; forming an oil phase, said forming step comprising dissolving together at least one benefit agent and at least one crosslinking agent, preferably a polyisocyanate, optionally with an additive oil, preferably a partitioning control agent; forming an emulsion by mixing the oil phase with an excess of the aqueous phase, preferably under high shear agitation, to form droplets of the oil phase dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6; Optionally, providing a second redox initiator to the emulsion, 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 comprises the reaction product of the crosslinker and the modified chitosan; and hardening, wherein the shell surrounds the core comprising the droplets of the oil phase.

15. the delivery particles are cationic; Preferably, the treatment composition according to any one of claims 1 to 14, wherein the delivery particles are characterized by a zeta potential of at least 15 mV at a pH of 4.5.

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