Treatment Composition

Abstract

A processing composition comprising a processing aid and a population of core / shell delivery particles, the shells of the particles being made in part from a biopolymer, and the particles being characterized by having certain ductile properties. 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, the shells of the particles being made in part from biopolymers, and the particles being characterized as having certain ductile properties. 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 having a shell made from naturally derived and / or biodegradable materials, such as biopolymers.

[0003] Core / shell delivery particles are typically intended to have frangible characteristics. When intact, the particle shell protects the benefit agent in the core for convenient delivery. Upon rupture, the particle releases the benefit agent.

[0004] Manufacturers of delivery particles have traditionally faced the challenge of creating a population of particles that burst at a desired time or touch point.In this field, emphasis has been placed on selecting materials and processing conditions that produce particles with a desired burst profile.For example, core / shell delivery particles can be classified by their fracture strength and / or burst stress, because these characteristics can predict the conditions under which the particle is likely to release beneficial agent.

[0005] Despite the industry's focus on frangible capsules, relying on rupture for release may have pitfalls. For example, despite manufacturers' best intentions, delivery particles may not rupture at the desired touch point. Additionally, given that the majority of the beneficial agent is released only upon rupture, frangible capsules tend to have an all-or-nothing release profile, which can result in users experiencing either too little or too much beneficial agent at any given time. These challenges can result in a suboptimal user / consumer experience. Summary of the Invention [Problem to be solved by the invention]

[0006] There remains a need for treatment compositions comprising core / shell delivery particles with improved or preferred release profiles, and it is further preferred that such delivery particles are made, at least in part, from naturally derived and / or biodegradable materials. [Means for solving the problem]

[0007] The present disclosure relates to treatment compositions that include a population of delivery particles, the delivery particles characterized by certain ductile properties.

[0008] For example, the present disclosure relates to 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 beneficial agent, and the shell comprising a polymeric material, the polymeric material comprising a reaction product of a biopolymer and a crosslinker, wherein the population of delivery particles is characterized by at least one, preferably at least two, and more preferably all three of the following: (a) a volume-weighted ductility energy greater than about 3.5, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s; (b) at least about 30% by number of the delivery particles being characterized as fully ductile particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s; and (c) less than 35% by number of the delivery particles being characterized as single-ruptured particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s.

[0009] The present disclosure also relates to a method of making a processing composition according to the present disclosure, the method comprising providing a base composition, the base composition including a processing aid, and combining a population of delivery particles with the base composition.

[0010] The present disclosure also relates to a method of treating a surface, the method comprising contacting the surface, preferably a fabric, with a treatment composition according to the present disclosure. [Brief explanation of the drawings]

[0011] The drawings herein are illustrative in nature and are not intended to be limiting. [Figure 1] 1 shows the basic setup for measuring the diameter of delivery particles. [Figure 2-1] 1 shows compression curves (eg, velocity-depth curves and load-depth curves) of exemplary delivery particles undergoing rupture. [Figure 2-2]1 shows compression curves (eg, velocity-depth curves and load-depth curves) of exemplary delivery particles undergoing rupture. [Figure 3-1] 1 shows the compression curve of a fully ductile particle. [Figure 3-2] 1 shows the compression curve of a fully ductile particle. [Figure 4-1] 1 shows the compression curve of a single burst particle. [Figure 4-2] 1 shows the compression curve of a single burst particle. [Figure 5-1] 1 shows the compression curves of multi-burst particles. [Figure 5-2] 1 shows the compression curves of multi-burst particles. [Figure 6] 1 shows the load-depth curve of an exemplary fully ductile particle. [Figure 7] 1 shows the load-depth curve of an exemplary single burst particle. [Figure 8] 1 shows the load-depth curve of an exemplary multi-burst particle. [Figure 9] 1 shows the distribution of measured ductile energy values ​​for a population of exemplary delivery particles. [Figure 10] 1 shows the distribution of log (ductile energy) values ​​for a population of exemplary delivery particles. [Figure 11] 1 shows the distribution of rescaled log(ductile energy) values ​​for a population of exemplary delivery particles. [Figure 12] A graph of grain size versus rescaled log (ductility energy) is shown. [Figure 13] 1 shows the volume fraction distribution by particle size of an exemplary population of delivery particles. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present disclosure relates to a treatment composition comprising a benefit agent-containing delivery particle having a shell made at least in part from a biopolymer. In contrast to the known brittle behavior of previous core / shell particles, the delivery particles of the present disclosure are characterized by desirable ductile properties. The ductile particles described herein can result in improved release profiles.

[0013] Without wishing to be bound by theory, it is believed that the delivery particles of the present disclosure, unlike particles having a relatively flexible shell and characterized by release via rupture, can, at least in some cases, provide a more desirable delivery or release profile. For example, due to having a relatively flexible shell, the particles of the present disclosure are believed to be more likely, at least at a population level, to survive processing processes that involve physical agitation, such as the washing and / or drying processes in an automatic washing machine. Furthermore, the ductile particles of the disclosed particle populations are not characterized by the hit-or-miss release profile of their burstable counterparts, thereby providing improved performance at one or more touchpoints.

[0014] It is believed that the ductile characteristics of the population of the present delivery particles can be provided and further tailored by the selection of certain materials, starting amounts, and / or processing conditions. For example, biopolymers according to the present disclosure, such as chitosan, are believed to provide useful starting materials for the formation of ductile particle shells. For example, certain biopolymers are characterized by desirable water-retention capabilities, due to the presence of hydroxyl groups, and may swell and / or exhibit increased elasticity in the presence of water. As an additional advantage, the biopolymers of the present disclosure are naturally derived and / or biodegradable, thereby improving the environmental footprint of the present delivery particles.

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

[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 includes compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material, if present at all, may be present at a concentration of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[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 and / or related methods for treating human hair, including bleaching, coloring, dyeing, conditioning, shampooing, styling, leave-on treatments, and boosters; 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, etc.). 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-cleaners, laundry pre-treatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatments, 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 may be used as laundry pre-treatments, laundry post-treatments, or may 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] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] Treatment Composition The present disclosure relates to treatment compositions (or simply "compositions" as used herein). The compositions of the present disclosure may include a processing aid and a population of delivery particles, 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.

[0026] The treatment composition is preferably a consumer product composition. The consumer product composition of the present disclosure can be useful in baby care, beauty care, fabric care, home care, family care, feminine care, and / or health care applications. The consumer product composition can be useful for treating surfaces such as fabric, hair, or skin. The consumer product composition can be intended to be used or consumed in the manner in which it is sold. The consumer product composition of the present disclosure is typically not intended for subsequent commercial manufacture or modification.

[0027] 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.

[0028] The consumer product composition may be a fabric care composition such as a laundry detergent composition (including a heavy-duty liquid cleaning detergent or unit dose article), a fabric conditioning composition (including a liquid fabric softening and / or enhancing composition), a laundry additive, a fabric pre-treatment composition (including a spray, pourable liquid, or spray), a fabric refresher composition (including a spray), or a mixture thereof. The treatment composition is preferably a fabric conditioning composition, even more preferably a liquid fabric conditioning composition.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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% by weight of the detergent composition, or less than about 15% by weight, or less than about 12% by weight, or less than about 10% by weight, or less than about 8% by weight. The composition may contain 0% water, or at least 0.1% water, or at least 1% water.

[0035] 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.

[0036] The treatment composition is applied for 20 seconds. -1 and 21°C, 1 to 1500 centipoise (1 to 1500 mPa * s), 100-1000 centipoise (100-1000 mPa * s), or 200 to 500 centipoise (200 to 500 mPa * s).

[0037] The treatment composition 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 composition of the present disclosure, preferably in the form of an aqueous liquid, may have a pH of about 2 to about 4, preferably about 2 to about 3.7, and more preferably about 2 to about 3.5. It is believed that such pH levels promote the stability of the quaternary ammonium ester compound, if present. On the other hand, conventional detergent compositions are typically characterized by a pH of about 7 to about 12, preferably about 7.5 to about 11. In some cases, an acidic detergent may be desirable, which may be characterized by a pH of about 2 to about 6, preferably about 2 to about 4. Compositions useful for certain beauty care applications, such as skin creams and / or shampoos, may be characterized by a pH of about 4 to about 7, preferably about 5 to about 6. The pH of the composition is measured by dissolving / dispersing the composition in deionized water to form a 10% solution at about 20°C.

[0038] Additional components and / or properties of the composition are discussed in more detail below.

[0039] 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 comprises a benefit agent (preferably a fragrance material) and, optionally, a partitioning modifier. The core can be liquid or solid, preferably liquid, at room temperature. The shell typically comprises a polymeric material that is the reaction product of a biopolymer and a crosslinker.

[0040] The delivery particles of the present disclosure can be described as having ductile properties, at least at the mass level. As generally used herein, a "ductile" particle (or one having "ductility") is one that can be deformed without breaking or rupturing the material. Without wishing to be bound by theory, it is believed that the shell of the particles described herein is relatively soft or pliable, yet still suitably robust for generally containing a beneficial agent in the core. Instead of releasing the beneficial agent through a rupture mechanism, the ductile particles of the present disclosure are believed to release the encapsulated beneficial agent without disintegrating when squeezed or deformed. This may result in a longer-lasting release profile, as the beneficial agent is not necessarily released in a single rupture event. Additionally or alternatively, a relatively low force may be required to obtain release of the encapsulated beneficial agent, as complete rupture of the particle is not required for the release event.

[0041] As described in more detail below, it is believed that the relative ductility of the described particle populations can be influenced by the selection of certain starting materials, starting amounts, and / or processing conditions. For example, the use of certain starting materials and their amounts and / or ratios, particle sizes and / or shell thicknesses, the use and amounts of partitioning modifiers, and / or the use of certain pH or milling temperatures during particle formation can be utilized to provide a population of delivery particles with desirable ductility and performance characteristics.

[0042] A population of delivery particles of the present disclosure may be characterized by a volume-weighted ductility energy of greater than about 3.5, preferably greater than about 3.8, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. A population of delivery particles of the present disclosure may be characterized by a volume-weighted ductility energy of about 3.5 to about 10.0, preferably about 3.5 to about 7.5, more preferably about 3.8 to about 6.0, more preferably about 4.0 to about 5.5, and even more preferably about 4.5 to about 5.2, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s.

[0043] It is believed that a population of delivery particles characterized by a volume-weighted ductile energy at the stated concentration can provide desirable performance, such as dry fabric odor, at a certain touch point, and / or be well distributed over time to provide longevity and consistency benefits.Such populations can also be useful in certain applications, particularly when high shear is present during use, such as through the wash and / or rinse cycles of an automatic washing machine.If the level of volume-weighted ductile energy is low, the particles may not be sufficiently ductile to provide the desired benefit, and may, for example, collapse prematurely during manufacturing, transportation, or use (e.g., during the wash cycle), prematurely releasing the encapsulated benefit agent.Further details regarding how to determine the volume-weighted ductile energy of a population of delivery particles can be found in the Test Methods section below.

[0044] When a treatment composition is expected or intended to be used under relatively high shear conditions, it may be preferable to use a population of delivery particles characterized by a relatively high volume-weighted ductility energy. For example, a treatment composition intended for use in the wash cycle of an automatic washing machine (such as a heavy-duty liquid detergent, a unit-dose detergent, and / or a laundry additive for the wash cycle, such as scent beads) may include a population of delivery particles characterized by a volume-weighted ductility energy of about 4.5 to about 6.0, preferably about 5.0 to about 5.5, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / sec. Such particles are believed to be better able to withstand high shear conditions while maintaining an adequate amount of benefit agent in the core.

[0045] When a treatment composition is expected or intended to be used under relatively low shear conditions, it may be preferable to use a population of delivery particles characterized by a relatively low volume-weighted ductility energy. For example, a treatment composition (such as a liquid fabric enhancer) intended for use in the rinse cycle of an automatic washing machine may include a population of delivery particles characterized by a volume-weighted ductility energy of about 3.5 to about 5, preferably about 3.8 to about 4.8, and more preferably about 4.0 to about 4.5, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / sec. Such particles are believed to be able to withstand lower shear conditions while maintaining an adequate amount of benefit agent in the core and providing convenient release of the benefit agent.

[0046] It may be desirable to vary the volume-weighted ductile energy of a particle population as particle size varies. For example, a population having relatively large particles may be characterized by a relatively high volume-weighted ductile energy. Without wishing to be bound by theory, it is believed that larger particles typically have a greater mass and, therefore, can absorb more energy. Thus, the size and volume-weighted ductile energy of a particle population may be selected for a particular application and / or release profile. For example, if a population of delivery particles is characterized by a volume-weighted median particle size of about 20 to about 40 microns, the volume-weighted ductile energy of the population may preferably be about 3.5 to about 7.5, more preferably about 4.5 to about 6.0. If a population of delivery particles is characterized by a volume-weighted median particle size of about 10 to about 25 microns, the volume-weighted ductile energy of the population may preferably be about 3.0 to about 5.0, more preferably about 3.5 to about 4.0, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s.

[0047] Any single delivery particle, when compressed by a blunt probe moving at 2 μm / s, as described in more detail in the Test Methods section, can be classified as a fully ductile particle, a single-burst particle, or a multi-burst particle. By sampling a certain number of particles, e.g., 50 particles, the population of delivery particles can be described in terms of the proportion (e.g., as a percentage by number) of particles that fall into any one or more of these categories. The relative proportions can provide an indication of the behavior of the population as a whole, which can be useful in predicting the relative performance of the population in a treatment composition. When classifying a population of delivery particles using these categories, the respective percentages of fully ductile particles, single-burst particles, and multi-burst particles typically add up to 100%.

[0048] A population of delivery particles of the present disclosure may be characterized by at least about 30%, preferably at least about 50%, by number of delivery particles characterized as fully ductile particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. It is believed that a population having a relatively high proportion of fully ductile particles can provide desirable performance. Without wishing to be bound by theory, it is believed that because the release of the encapsulated benefit agent is not concentrated at a single point in time (e.g., a rupture event), the release of the benefit agent from particles of the present disclosure tends to be more gradual and / or linear over time. Further details regarding how to determine the relative proportion of fully ductile particles in a population can be found in the Test Methods section below.

[0049] A population of delivery particles of the present disclosure may be characterized as having less than 35%, preferably less than about 25%, by number of delivery particles characterized as single-ruptured particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. It is believed that a population having a relatively low percentage of fully ductile particles can provide desirable performance. Further details regarding methods for determining the relative percentage of single-ruptured particles in a population can be found in the Test Methods section below.

[0050] The population of delivery particles of the present disclosure may include delivery particles characterized as multi-burst particles based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. Further details regarding how to determine the relative proportion of single-burst particles in a population can be found in the Test Methods section below.

[0051] It is preferred that the population of delivery particles, when based on 50 randomly selected delivery particles each being compressed by a blunt probe moving at 2 μm / s according to the test method described below, be characterized by at least one, preferably at least two, and more preferably all three of the following: (a) a volume-weighted ductility energy greater than about 3.5; (b) at least about 30% by number of delivery particles characterized as fully ductile particles; and (c) less than 35% by number of delivery particles characterized as single-ruptured particles.

[0052] 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 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 delivery particles in an amount sufficient to provide the composition with an encapsulated benefit agent, which may preferably be a fragrance material having one or more perfume ingredients. As discussed herein, the amount or weight percent of delivery particles refers to the combined wall material and core material.

[0053] 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.

[0054] 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 20% by weight of the delivery particle, preferably up to about 15% by weight, and more preferably up to about 12% by weight.

[0055] 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. Polyurea capsules prepared with 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.

[0056] 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 comprises, and preferably is, the reaction product of a biopolymer and a crosslinker.

[0057] The biopolymer may preferably be selected from the group consisting of polysaccharides, proteins, nucleic acids, polyphenolic compounds, derivatives thereof, and combinations thereof. Preferably, the biopolymer is (a) a polysaccharide selected from the group consisting of chitosan, starch, modified starch, dextran, maltodextrin, dextrin, cellulose, modified cellulose, hemicellulose, chitin, alginate, lignin, gum, pectin, fructan, carrageenan, agar, pullulan, suberin, cutin, cutan, melanin, silk fibronin, derivatives thereof, and combinations thereof; (b) a protein selected from the group consisting of gelatin, collagen, casein, sericin, fibroin, whey protein, zein, soy protein, plant storage proteins (plant protein isolates, plant protein concentrates), gluten, peptides, actin, derivatives thereof, and combinations thereof; (c) a nucleic acid selected from the group consisting of polynucleotides, RNA, DNA, derivatives thereof, and combinations thereof; (d) a polyphenolic compound selected from the group consisting of tannins, lignans, derivatives thereof, and combinations thereof; or (e) combinations thereof.

[0058] The biopolymer preferably contains primary amine groups that can be reacted with a crosslinking agent, preferably a polyisocyanate, to form a polymeric material that may be described as a crosslinked biopolymer.

[0059] Amine-containing biopolymers, such as amine-containing or amine-modified polysaccharides, may be preferred due to, for example, convenient availability, biodegradability, and / or performance reasons. A particularly preferred material is chitosan. Thus, the biopolymer may preferably be chitosan, a derivative thereof, or a combination thereof. Preferably, the biopolymer is acid-treated chitosan, redox initiator-treated chitosan, a derivative thereof, or a combination thereof.

[0060] The chitosan may preferably be acid-treated chitosan. For example, chitosan (which may be referred to as raw chitosan or parent chitosan before acid treatment) may be treated with an acid, preferably at a pH of 6.5 or less, for at least 1 hour, preferably about 1 hour to about 3 hours, at a temperature of about 25°C to about 99°C, preferably about 75°C to about 95°C. The acid may be selected from a strong acid (such as hydrochloric acid), an organic acid (such as formic acid or acetic acid), or a mixture thereof. The chitosan may be acid-treated preferably at a pH of 2 to 6.5, or even at a pH of 4 to 6.

[0061] Chitosan can be treated with a redox initiator (e.g., redox initiator-treated chitosan). For example, a redox initiator, preferably comprising a persulfate or peroxide, can be added to the aqueous phase and / or emulsion when forming delivery particles. A redox initiator, which may comprise a persulfate or peroxide, can be added to acid-treated chitosan. In an in situ variation, the redox initiator can be added to the emulsion after combining the oil and aqueous phases under high shear stirring. The redox initiator advantageously depolymerizes hydrolyzed or modified chitosan to reduce viscosity and facilitate shell polymer formation in the capsule formation process. Modification of chitosan with an epoxide, aldehyde, or α,β-unsaturated compound is preferably accomplished before adding the redox initiator, although the redox initiator (peroxide or persulfate) can be introduced simultaneously with or even before the modifying compound. The redox initiator may be selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof. The redox initiator, preferably a persulfate or peroxide, may be present in a concentration of about 0.1% to about 99% by weight of chitosan.

[0062] The biopolymer, preferably chitosan, more preferably acid-treated chitosan, can be characterized by a molecular weight of about 1 kDa to about 1000 kDa, preferably about 50 kDa to about 600 kDa, more preferably about 100 kDa to about 500 kDa, even more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa. Without wishing to be bound by theory, it is believed that biopolymers characterized by relatively low molecular weights are less effective at forming suitable delivery particles, while those with relatively high molecular weights tend to be more difficult to process. The method used to determine the molecular weight and related parameters of chitosan is provided in the Test Methods section below and uses gel permeation chromatograph with multi-angle light scattering and refractive index detection (GPC-MALS / RI) techniques.

[0063] When present, 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.

[0064] When present, chitosan may comprise anionically modified chitosan, cationically modified chitosan, or a combination thereof. The shell characteristics of the delivery particles can be altered by modifying chitosan in an anionic and / or cationic manner, for example, by changing the surface charge and / or zeta potential, which can affect the adhesion efficiency and / or formulation compatibility of the particles.

[0065] As mentioned above, the shell is a polymeric material that is the reaction product of the biopolymer chitosan and a crosslinking agent. The crosslinking material is preferably a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxy compounds, polyphenols, carbonyl halides, aziridines, and combinations thereof. The crosslinking agent is more preferably selected from the group consisting of polyisocyanates, epoxy compounds, difunctional aldehydes, and combinations thereof.

[0066] The crosslinking agent is preferably a polyisocyanate, particularly when the biopolymer contains amine groups. It is believed that such materials react favorably with the amine groups of the biopolymer to form an effective crosslinked polymer wall. The polymeric material of the shell may preferably comprise a polyurea resin, which may comprise the reaction product of a polyisocyanate and chitosan.

[0067] For purposes of this specification, polyisocyanate materials useful in the present disclosure are understood to be 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.

[0068] 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.

[0069] 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), or 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).

[0070] 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).

[0071] 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.

[0072] 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.

[0073] The particle shell may also be reinforced using additional co-crosslinking agents 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-crosslinking agents, for example, to reinforce the shell.

[0074] The polymeric material can be formed in a reaction in which the weight ratio of biopolymer, preferably a polysaccharide, more preferably chitosan or a derivative thereof (which may include acid-treated chitosan) present in the reaction to crosslinker present in the reaction is from about 1:10 to about 10:1, preferably from about 1:5 to about 5:1, preferably from about 1:4 to about 5:1, more preferably from about 1:1 to about 5:1, more preferably from about 3:1 to about 5:1. It is believed that selecting the desired ratio of biopolymer to crosslinker can provide the desired benefits of ductility, as well as improved biodegradability.

[0075] It may be preferred that at least 21% by weight of the shell be comprised of a portion derived from a biopolymer, preferably chitosan, more preferably acid-treated chitosan. The biopolymer, preferably chitosan or a derivative thereof, as a weight percentage of the shell can be from about 21% up to about 95% of the shell. The ratio of biopolymer, preferably chitosan, in the aqueous phase compared to the crosslinker, preferably polyisocyanate, in the oil phase can be from 21:79 (1:3.7) to 90:10 (1:0.11), or even from 33.3:66.6 (1:2) to 90:10 (9:1), or even from 50:50 (1:1) to 87.5:12.5 (7:1), by weight. The shell may comprise a biopolymer, preferably chitosan, at a concentration of 21% or more by weight of the total shell, preferably about 21% to about 90%, or even 21% to 85%, or even 21% to 75%, or 21% to 55% by weight of the biopolymer, preferably chitosan. The chitosan in this paragraph may preferably be acid-treated chitosan.

[0076] The reaction product that forms at least a portion of the polymeric material can be formed in a reaction in which the biopolymer is initially present in the aqueous phase and the crosslinker is initially present in the oil phase. The crosslinker is preferably present in the oil phase at a concentration of from about 1% to about 20%, preferably from about 2% to about 10%, and more preferably from about 2.5% to about 5% by weight of the oil phase. The crosslinker can be a polyisocyanate present in the oil phase at a concentration greater than 1%, preferably greater than 1.3%, preferably greater than 2%, more preferably greater than 2.5%, and even more preferably greater than 2.9%.

[0077] A population of delivery particles may be made according to a method comprising the following steps: (a) forming an aqueous phase comprising the chitosan described herein, preferably wherein the aqueous phase has a pH of 6.5 or less, more preferably a pH of 3 to 6, and a temperature of at least 25°C; (b) forming an oil phase comprising at least one benefit agent, preferably a fragrance material, and at least a crosslinking agent, preferably a polyisocyanate, and optionally a partitioning modifier; (c) forming an emulsion, preferably an oil-in-water emulsion, by mixing the aqueous and oil phases under high shear agitation, optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6; and (d) curing the emulsion by heating, preferably to at least 40°C, for a time sufficient to form a shell at the interface of the oil droplets and the aqueous phase, wherein the shell comprises a polymeric material that is the reaction product of the chitosan and the crosslinking agent, the shell surrounding a core comprising the benefit agent.

[0078] The population of delivery particles can be formed by the following steps: (a) forming an aqueous phase by treating chitosan with a mixture of a first acid and a second acid, wherein the first acid comprises a strong acid and the second acid comprises a weak acid, and wherein the chitosan is treated at a pH of 6.5 or less, or even a pH below 6.5, or even a pH of 3-6, and a temperature of at least 25°C, for at least 1 hour, or for a period of time required to obtain a chitosan solution viscosity of about 1500 cps or less, or even 500 cps or less, of the acid-treated chitosan; and (b) forming an aqueous phase of at least one benefit agent and at least one polyisocyanate, optionally with an additive oil (e.g., a partitioning modifier) ​​and / or a solvent. (c) forming an emulsion by mixing the water phase and oil phase into an excess of the water phase under high shear agitation, thereby forming droplets of the oil phase and benefit agent dispersed in the water phase, and optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6; and (d) curing the emulsion by heating to at least 40°C for a time sufficient to form a shell at the interface of the droplets and the water phase, wherein the shell comprises the reaction product of a polyisocyanate and acid treated chitosan, the shell surrounding the core comprising the oil phase and benefit agent droplets.

[0079] Chitosan can be added to water in a jacketed reactor at a pH of 2 or even 3-6.5 and adjusted using an acid such as concentrated HCl. The chitosan in this mixture can be acid-treated by heating to a high temperature, such as 85°C, for 60 minutes and then held at this temperature for 1 minute to 1440 minutes, or even longer. The aqueous phase can then be cooled to 25°C. Optionally, deacetylation can be further facilitated or enhanced with an enzyme that depolymerizes or deacetylates chitosan. An oil phase can 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. The oil phase is then added to the aqueous phase and milled at high speed to obtain the desired size. The emulsion can 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 times and temperatures 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 can be heated to 85°C in 60 minutes and then held at 85°C for 360 minutes to harden the particles. The slurry can then be cooled to room temperature.

[0080] To form a suitably ductile capsule population, it may be preferable to adjust the pH of the aqueous phase and / or emulsion to about 5.2 or greater, preferably about 5.6 or greater, and up to about 6.5, preferably up to about 6. It is believed that the pH during particle shell formation can affect the ultimate ductility of the particle population.

[0081] To form a suitably ductile capsule population, it may be preferable to prepare the capsules by a method including at least one milling step, which may preferably be carried out at a particular temperature. For example, at least one milling step may be carried out at a temperature of at least about 7°C, 15°C, preferably at least about 20°C, more preferably at least about 25°C, and even more preferably from about 25°C to about 35°C. Milling may be carried out until the desired particle size is achieved. The temperature during the milling step is believed to affect the ultimate ductility of the particle population.

[0082] 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.

[0083] The delivery particles of the present disclosure comprise a core. The core comprises a benefit agent, preferably a fragrance material. The core also optionally comprises a partitioning modifier.

[0084] The core of the particle is surrounded by a shell. When the ductile particle is compressed or deformed, it is believed that the benefit agent in the core, preferably a fragrance material, leaves the particle by being squeezed through the shell. Additionally or alternatively, at least a portion of the benefit agent may diffuse through the shell. Even when ductile particles are present in the population of the present disclosure, some of the particles may rupture upon compression or deformation, resulting in the release of the benefit agent. Suitable benefit agents located in the core can include benefit agents, such as suitable fragrance materials, that provide a benefit to a surface, such as fabric or hair.

[0085] The core may comprise from about 5% to about 100% benefit agent, preferably fragrance material, 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 fragrance material, by weight of the core.

[0086] The benefit agent in the core can be relatively hydrophobic, and such an agent is compatible with the oil phase that is common in making the delivery particles of the present disclosure.

[0087] The benefit agent is selected to provide a benefit under the preferred use of the treatment composition.The benefit agent in the core can be selected from fragrance materials, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin cooling agents, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleach particles, silicon dioxide particles, malodor reducing agents, odor control materials, chelating agents, antistatic agents, softening agents, insect and moth repellents, colorants, thickeners, drape and foam inhibitors, smoothing agents, wrinkle inhibitors, sanitizing agents, disinfectants, bacterial inhibitors, mold inhibitors, mildew inhibitors, antiviral agents, drying agents, stain resistant agents, soil release agents, 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.

[0088] The benefit agent in the core preferably comprises a fragrance material (or simply "fragrance"), which may include one or more perfume raw materials. Fragrances are particularly suitable for encapsulation in the delivery particles described herein because fragrance-containing particles can provide odor-reducing benefits across multiple touch points.

[0089] As used herein, the term "perfume raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mole and useful for imparting odors, fragrances, essences, or scents, either alone or in combination with other perfume raw materials. Typical PRMs include 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," Vol. I and Vol. II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology," Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0090] 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.

[0091] 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.

[0092] 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.

[0093] The core of the delivery particles of the present disclosure may include a partitioning modifier, which may promote more robust shell formation. The partitioning modifier may be combined with the perfume oil material of the core prior to incorporation of the wall-forming monomer. The partitioning modifier may be present in the core at a concentration of from 0% to about 95% by weight of the core, preferably from about 5% to about 55%, preferably from about 10% to about 50%, more preferably from about 20% to about 50%, and even more preferably from about 25% to about 50%.

[0094] Partition modifiers include vegetable oils, modified vegetable oils, C4 to C 24 The partition modifier may include a material selected from the group consisting of mono-, di-, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partition 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 partition modifiers that may be useful in the delivery particles described herein.

[0095] 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 (such as alkoxylated alcohols, preferably containing ethoxy groups), polyvinyl alcohol, and / or polyvinylpyrrolidone. Solubilized chitosan may provide emulsification benefits in this application.

[0096] 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, more typically 0.5 to 10% by weight, based on the total weight of the aqueous phase.

[0097] The population of delivery particles may be provided as a slurry, preferably an aqueous slurry, which 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 carboxymethyl cellulose.

[0098] 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 include unencapsulated ("free") perfume raw materials that are different in identity and / or amount from those encapsulated in the core of the delivery particle.

[0099] 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- Copolymers of bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine, and mixtures thereof with polyvinyl alcohol oligomers; polyethyleneimine, derivatized polyethyleneimine, and in one aspect, ethoxylated polyethyleneimine; polymeric compounds comprising at least two moieties selected from the group consisting of carboxylic acid moieties, amine moieties, hydroxyl moieties, and nitrile moieties in a backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile, or combinations thereof; preformed coacervates of anionic surfactants combined with cationic polymers; polyamines, and mixtures thereof.

[0100] At least one population 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.

[0101] Suitable equipment for use in the methods 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).

[0102] Supplementary ingredients In addition to the delivery particles, the treatment compositions of the present disclosure may 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.

[0103] 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.

[0104] 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.

[0105] 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:

[0106] 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.

[0107] 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.

[0108] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include nonionic surfactants such as linear alkyl benzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactant may be derived, at least in part, from natural sources, such as natural feedstock alcohols.

[0109] Suitable anionic surfactants may include any conventional anionic surfactant. This may include, for example, sulfate detersive surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid-based detersive surfactants, such as alkyl benzene sulfonates. The anionic surfactant may be linear, branched, or a combination thereof. Preferred surfactants include linear alkyl benzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkyl benzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactant may be present in acid form, salt form, or a mixture thereof. The anionic surfactant may be partially or totally neutralized, for example, with an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine). Due to the presence of cationic ester quat materials, it may be desirable to limit the amount of anionic surfactant to avoid undesirable interactions of materials. For example, the composition may contain less than 5% by weight of the composition, preferably less than 3% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight of anionic surfactant.

[0110] 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. Particular 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.

[0111] 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

[0112] 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, since such surfactants may negatively interact with cationic components.

[0113] 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.

[0114] 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.

[0115] Suitable conditioning active materials for the compositions 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 improving / conditioning / softening compositions.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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).

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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 cross-linked biopolymer wall materials), cationic surfactants, cationic polymers, solvents, suds suppressors, or combinations thereof.

[0127] 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.

[0128] The method can include providing a base composition, the base composition including a processing aid, and combining a population of delivery particles with the base composition. The population of delivery particles can be preferably provided as an aqueous slurry. The base composition is in the form of a liquid composition.

[0129] 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.

[0130] The processing composition of the present disclosure can be formulated into any suitable form and can be prepared by any method selected by the formulator.One or more auxiliary components and delivery particles can be combined by batch method, circulation loop method, and / or in-line mixing method.The equipment suitable for use in the method disclosed herein can include continuous stirred tank reactor, homogenizer, turbine agitator, recirculation pump, paddle mixer, high shear mixer, static mixer, plow shear mixer, ribbon blender, vertical shaft granulator and drum mixer (both batch type and, if available, continuous method configuration), spray dryer, and extruder.

[0131] 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.

[0132] Processing method The present disclosure also relates to methods of treating a surface, preferably a fabric, generally comprising contacting the surface, preferably a fabric, with a treatment composition according to the present disclosure, wherein the treatment composition comprises a population of delivery particles as described herein.

[0133] 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.

[0134] The method can 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, the core including 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] The present disclosure also relates to a method for treating fabrics in an automatic washing machine. A typical treatment method in such machines typically includes a wash cycle involving relatively high shear agitation and one or more rinse cycles involving relatively low shear agitation. In such cases, it may be preferable to treat the fabrics with delivery particles designed to adequately deliver benefit agents under such conditions. For example, the method may include contacting the fabrics during the wash cycle with a population of delivery particles characterized by a volume-weighted ductility energy of about 4.5 to about 6.0, preferably about 5.0 to about 5.5. The method may include contacting the fabrics during the rinse cycle with a population of delivery particles characterized by a volume-weighted ductility energy of about 3.5 to about 5, preferably about 3.8 to about 4.8, and more preferably about 4.0 to about 4.5.

[0140] The method can include contacting a fabric with a first population of delivery particles during a wash cycle and a second population of delivery particles during a rinse cycle, wherein the first population has a volume weighted ductile energy relatively higher than the volume weighted ductile energy of the second population. The volume weighted ductile energy of the first population is preferably from about 4.5 to about 6.0, preferably from about 5.0 to about 5.5, and the volume weighted ductile energy of the second population is preferably from about 3.5 to about 5, preferably from about 3.8 to about 4.8, more preferably from about 4.0 to about 4.5.

[0141] 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.

[0142] 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. 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 beneficial agent, and the shell comprising a polymeric material, the polymeric material comprising a reaction product of a biopolymer and a crosslinker, wherein the population of delivery particles is characterized by at least one, and preferably at least two, of the following: (a) a volume-weighted ductility energy of greater than about 3.5, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s; (b) at least about 30% by number of the delivery particles being characterized as fully ductile particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s; and (c) less than 35% by number of the delivery particles being characterized as single-ruptured particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. B. The treatment composition according to paragraph A, wherein the population of delivery particles is characterized by a volume-weighted ductility energy of from about 3.5 to about 10.0, preferably from about 3.5 to about 7.5, more preferably from about 3.8 to about 6.0, more preferably from about 4.0 to about 5.5, and even more preferably from about 4.5 to about 5.2, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. C. The treatment composition according to either paragraph A or B, wherein the population of delivery particles is characterized as at least about 50% by number of delivery particles as fully ductile particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. D. The treated composition according to any of paragraphs A-C, wherein the population of delivery particles is characterized as having less than 25% by number of delivery particles characterized as single-burst particles based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s. E. The treatment composition according to any of paragraphs A-D, wherein the biopolymer is selected from the group consisting of polysaccharides, proteins, nucleic acids, polyphenolic compounds, derivatives thereof, and combinations thereof. F. The treatment composition according to any of paragraphs A-E, wherein the biopolymer is selected from the group consisting of chitosan, starch, modified starch, dextran, maltodextrin, dextrin, cellulose, modified cellulose, hemicellulose, chitin, alginate, lignin, gum, pectin, fructan, carrageenan, agar, pullulan, suberin, cutin, cutan, melanin, silk fibroin, gelatin, collagen, casein, sericin, fibroin, whey protein, zein, soy protein, plant storage proteins, gluten, peptides, actin, polynucleotides, RNA, DNA, tannins, lignans, derivatives thereof, and combinations thereof. G. The treatment composition according to any of paragraphs A-F, wherein the biopolymer is chitosan, a derivative thereof, or a combination thereof, preferably, the biopolymer is acid-treated chitosan, redox initiator-treated chitosan, a derivative thereof, or a combination thereof. H. The treatment composition according to any of paragraphs A-G, wherein the biopolymer is characterized by a molecular weight of about 1 kDal to about 1000 kDal, preferably about 50 kDal to about 600 kDal, more preferably about 100 kDal to about 500 kDal, even more preferably about 100 kDal to about 300 kDal, and even more preferably about 100 kDal to about 200 kDal. I. The crosslinking agent is selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxy compounds, polyphenols, carbonyl halides, aziridines, and combinations thereof, preferably polyisocyanates, epoxy compounds, bifunctional aldehydes, and combinations thereof, more preferably polyisocyanates, and even more preferably polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of toluene diisocyanate, trimethylolpropane adducts of xylylene diisocyanate, 2,2'-methylenediphenyl diisocyanates, The treatment composition according to any of paragraphs A-H, wherein the material is selected from the group consisting of isocyanates, polyisocyanates selected from the group consisting of 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. J. The treatment composition according to any of paragraphs A-I, wherein the reaction product is formed in the reaction wherein the biopolymer is initially present in the aqueous phase and the crosslinker is initially present in the oil phase, the crosslinker being present in the oil phase at a concentration of from about 1% to about 20%, preferably from about 2% to about 10%, more preferably from about 2.5% to about 5% by weight of the oil phase, and preferably the biopolymer and crosslinker are present in the reaction in a weight ratio of from about 1:10 to about 1:0.1. K. The treatment composition according to any of paragraphs A-J, wherein the benefit agent is a fragrance material. L. The core further comprises a partitioning modifier, preferably present at a concentration of about 10% to about 50% by weight of the core, more preferably about 20% to about 50% by weight, and even more preferably about 30% to about 50% by weight, and preferably the partitioning modifier is selected from the group consisting of vegetable oil, modified vegetable oil, C4 to C6 24 The treatment composition according to any of paragraphs A-K, wherein the surfactant is 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 population of delivery particles is produced by a method including at least one milling step, and wherein the at least one milling step is performed at a temperature of at least about 15°C, preferably at least about 20°C, more preferably at least about 25°C, and even more preferably from about 25°C to about 35°C. N. The treatment composition according to any of paragraphs A-M, 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. O. A treatment composition according to any of paragraphs A-N, wherein the shell of the delivery particles degrades by at least 60% in 60 days when tested according to test method OECD 301B. P. The treatment composition according to any of paragraphs A-O, 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-agglomerating agents, coatings, formaldehyde scavengers, pigments, and mixtures thereof. Q. The treatment composition according to any of paragraphs A-P, wherein the treatment aid comprises an anionic surfactant, a cationic conditioning agent, or a mixture thereof. R. The treatment composition according to any of paragraphs A-Q, 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. S. A treatment composition according to any of paragraphs A-R, 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. T. A treatment composition according to any of paragraphs A through S, 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. U. A method of making a processing composition according to any of paragraphs A-T, the method comprising: providing a base composition, the base composition including a processing aid; and combining a population of delivery particles with the base composition. V. The method according to paragraph U, wherein the population of delivery particles is provided as an aqueous slurry. W. The method according to either paragraph U or V, wherein the base composition is in the form of a liquid 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-T. Y. A method of treating fabrics in an automatic washing machine, the method comprising contacting the fabric with a first population of delivery particles during a wash cycle and with a second population of delivery particles during a rinse cycle, wherein the volume weighted ductile energy of the first population is relatively higher than the volume weighted ductile energy of the second population, preferably the volume weighted ductile energy of the first population is from about 4.5 to about 6.0, preferably from about 5.0 to about 5.5, and preferably the volume weighted ductile energy of the second population is preferably from about 3.5 to about 5, preferably from about 3.8 to about 4.8, more preferably from about 4.0 to about 4.5.

[0143] 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.

[0144] Mechanical properties of delivery particles The mechanical properties of the core:shell delivery particles described herein are determined according to the following method.

[0145] The general technique is a well-known methodology already defined in the literature: Zhang, Z., Saunders, R. and Thomas, C.R., Micromanipulation measurements of the bursting strength of single microcapsules, Journal of Microencapsulation 16(1), 117-124 (1999). Based on the measurements obtained via the methodology, several useful features can be observed and described, as provided in more detail below.

[0146] 1. Extracting Particles If the population of delivery particles is provided as part of a final product composition, the particles will need to be extracted in order to perform the analyses described herein.

[0147] Unless otherwise specified herein, a preferred method for isolating delivery particles from a 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, wash, and / or concentrate the delivery particles. An optical microscope equipped with a cross-polarization filter or differential interference contrast (DIC) is used to observe the delivery particles at, for example, 10x and 40x total magnification. Microscopic observation provides an early indication of the presence, size, and aggregation of delivery particles.

[0148] 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 at a 1:1 ratio (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 times).

[0149] 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.

[0150] If the fabric enhancer is white or the delivery particle-rich layer is difficult to distinguish, add 4 drops of dye (e.g., Liquitint Blue JH 5% premix from Milliken & Company, Spartanburg, South Carolina, USA) to the centrifuge tube from step 1. Add and proceed with isolation as described.

[0151] 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.

[0152] 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.

[0153] 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 deodorant diluent in 1.8 ml tubes and spun at 20,000 x g for 5 minutes per round.

[0154] 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.

[0155] 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.

[0156] 1. Preparation of Particles for Mechanical Property Measurements A 10 μl sample of the capsule population, typically in the form of a slurry, is diluted with 1.5 ml of distilled water. The sample is mixed for a few seconds to ensure it is homogenous. Once mixed / homogeneous, 5 μl of the diluted capsule population is spread onto a glass microslide in the Nanoindenter.

[0157] 3. Methodology for the Measurement of Mechanical Properties The measurements are carried out using an iNano® Nanoindenter (available from KLA, USA) equipped with a Poisson's ratio of 0.07, an elastic modulus of 1140 GPa, and a flat-end probe with a diameter of 100 μm. The frame stiffness is 8.8 * 10 5 N / m. The probe speed is set to 2 μm / s.

[0158] Fifty capsules of a given population of delivery particles are randomly selected from the population, and various characteristics of each capsule are measured, as described in more detail below. Briefly, the diameter of each particle is measured, and then each particle is compressed with the probe of an iNano® Nanoindenter. Measurements such as compression speed, compression depth, and associated load are recorded.

[0159] Based on the measurements, the diameter and burst rate of the individual capsules can be determined as described below.

[0160] A. Determining Individual Particle Diameter For purposes of the measurements described in this paragraph, the diameter of an individual delivery particle is defined as the height of the capsule measured along a vertical axis perpendicular to the microslide or substrate on which the delivery particle population is placed.

[0161] FIG. 1 shows a basic setup for measuring the diameter of delivery particles (or capsules as used herein). The diameter of each delivery particle 1 is calculated by determining the height 2 of the top surface 3 of the delivery particle 1 relative to the surface 4 of the substrate 5 on which the delivery particle 1 is placed using the probe 6 of the iNano® Nanoindenter. The arrow indicates the direction of compression 7. The dashed line indicates the vertical axis 8 of the delivery particle 1. The height 2 of the surface 4 of the substrate 5 is measured 150 μm to the right and 150 μm below the center of the delivery particle 1 on the microslide. Diameters are typically reported in microns.

[0162] The diameter can be calculated by the following equation: Diameter = height of capsule top surface - height of base material

[0163] B. Determining the burst velocity For each delivery particle, the burst rate (if present) is determined. Based on the burst rate (if present) measured during the capsule compression test, the particle is assigned to one of three categories, described in more detail below.

[0164] As mentioned above, for each capsule measurement, the probe compression speed is set to 2 μm / s. The probe speed, depth, and load are recorded while the capsule is compressed.

[0165] From the measurements, velocity-depth curves and load-depth curves can be constructed. Figure 2 shows such curves for an exemplary particle bursting. Graph 2A shows the velocity-depth curve 100, and Graph 2B shows how the load (measured in mN) varies throughout the measurement as a function of depth, presented as load-depth curve 102. Each depth corresponds to the amount of probe travel throughout the compression.

[0166] As shown in Graph 2A, the compression rate can vary by a magnitude of approximately 50 nm / s throughout the measurement due to variations in the mechanical resistance exerted by the capsule on the probe. At the zero depth point, the probe makes contact with the capsule, and this point on the curve is identified by triangle 104.

[0167] As shown in Graph 2B, the load of the exemplary capsule increases up to the capsule's burst point, which is characterized by a maximum load; this point on the curve is identified by a square in Graph 2B. The parallel point on the velocity-depth curve of Graph 2A is also identified by a square (the "burst point").

[0168] After the rupture point, the capsule no longer exerts significant resistance to probe compression, and the compression rate suddenly increases. After the capsule rupture point, a point of maximum probe velocity can be identified; this point on the curve is represented by circle 108 in Graph 2A.

[0169] As used herein, burst velocity is defined as the difference in velocity between the maximum probe velocity (after burst) and the probe velocity at the point of burst (which correlates to the probe depth at which the maximum load is observed). The formula for calculating burst velocity is reported in equation (1.1). Rupture velocity = maximum probe velocity - probe velocity at rupture point (1.1)

[0170] It can be seen that the burst velocity in terms of maximum probe velocity (represented by the circle) of the exemplary capsule in Graph 2A has a value of about 5 μm / s.

[0171] 4. Determination of Volume-Weighted Ductile Energy and Ductile Capsule Fraction To determine the volume-weighted ductile energy of a population of delivered particles, 50 capsules are randomly selected from the population and various characteristics of each capsule are measured as described in more detail below. Based on the rupture velocity (if present), each individual capsule is assigned to one of three categories (ductile, single-rupture, or multiple-rupture) described below. The area under the load versus depth curve is used to determine the measured ductile energy of the individual capsule. From these measurements, the volume-weighted ductile energy of the delivered particle population is determined. Furthermore, the relative proportion of particles that are ductile or exhibit "single-rupture" behavior can be determined from the data.

[0172] A. Classification of individual capsules Based on the fracture velocity and the number of maximum peaks in the load-depth curve, each individual capsule is classified in terms of one of three categories: fully ductile behavior, single-burst behavior, or multiple-burst behavior.

[0173] i. Definition of a fully ductile capsule A "fully ductile" capsule, as defined herein, when compressed by a blunt probe moving at 2 μm / s, is characterized by a difference between the maximum probe velocity and the standard probe velocity that does not exceed 200 nm, and therefore no fracture velocity can be defined.

[0174] 3 shows the compression curves of a fully ductile particle. As can be seen from the velocity-depth curve 110 in Graph 3A, the compression velocity does not exceed the standard compression velocity of 2 μm / s throughout the measurement. Additionally, no load drop or peak maximum is observed in the load-depth curve 112 in Graph 3B.

[0175] Based on curves 110, 112 of Graphs 3A and 3B, the particle does not exhibit any rupture point, e.g., there is no relative increase in compression rate, no decrease in load, and no maximum peak, and therefore the particle is defined as completely ductile.

[0176] At the zero depth point, the probe contacts the particle, and this point on curves 110, 112 is identified by triangle 114. It can be noted that during the final portion of the measurement at a probe depth of approximately 6500 nm, the compression rate approaches 0 nm / s as the entire diameter of the capsule is compressed and the tip exerts pressure toward the substrate on which the capsule is located. Diamond 116 in Graph 3B represents the point at which the probe contacts the substrate, which is associated with an exponential increase in load, considering that the substrate is a very hard material, such as a glass microslide.

[0177] ii. Definition of single-rupture capsule As defined herein, a "single burst" capsule is characterized by exhibiting a single capsule rupture point. A "single burst" capsule is characterized by a rate of rupture of greater than 200 nm when compressed by a blunt probe moving at 2 um / s.

[0178] 4 shows the compression curve of a single-burst particle. At the zero depth point, the probe contacts the particle, and this point on curves 120, 122 is identified by triangle 124. In velocity-depth curve 120 of Graph 4A, it can be seen that after detecting the burst point, the compression velocity exceeds 2 μm / s, which is indicated by square 126 in Graphs 4A and 4B. The maximum velocity of the probe is then identified by circle 128 in Graph 4A. As shown in Graph 4B, load-depth curve 122 is characterized by a single maximum peak (indicated by square 126), suggesting that the particle exhibits single-burst behavior.

[0179] iii. Definition of multiple rupture capsules "Multiple-burst" capsules are characterized by exhibiting multiple capsule ruptures when compressed by a blunt probe moving at 2 um / s. "Multiple-burst" capsules are characterized by a rate of rupture exceeding 200 nm multiple times when compressed by a blunt probe moving at 2 um / s. Typically, multiple-burst capsules are characterized by two or three rupture points, although more are possible.

[0180] 5 shows the compression curves of a multi-burst particle. At the zero depth point, the probe contacts the particle, and this point on curves 130, 132 is identified by triangle 134. As can be seen in velocity-depth curve 130 of Graph 5A and load-depth curve 132 of Graph 5B, there are multiple burst points. More precisely, the curves show three maximum peaks in maximum load (squares 136a, 136b, 136c) and three burst points associated with three relative increases in compression velocity, with maximum probe velocity indicated by circles 138a, 138b, 138c.

[0181] B. Determining Category Proportions Based on the number of capsules that fell into each category, the population can be characterized as to the relative amount of capsules in any given category.

[0182] For example, the population can be described by the proportion and / or percentage of capsules that are completely ductile (e.g., the number of capsules classified as completely ductile divided by the total number of capsules measured [i.e., 50]).

[0183] The population can be described by the proportion and / or percentage of capsules exhibiting single burst behavior (e.g., the number of capsules classified as single burst capsules divided by the total number of capsules measured [i.e., 50]).

[0184] The population can be described by the proportion and / or percentage of capsules exhibiting multiple burst behavior (e.g., the number of capsules classified as multiple burst capsules divided by the total number of capsules measured [i.e., 50]).

[0185] C. Calculation of capsule ductility energy by category To calculate the ductile energy of each individually measured delivery particle in the population, the area under a particular point on the capsule's load-depth curve is determined. The area is calculated according to Equations 1.2-1.4 below and can be calculated automatically by any suitable program, for example, by exporting the data points to MICROSOFT EXCEL® and using the program to determine the area under the relevant point.

[0186] i. Ductility energy of a perfectly ductile capsule The ductility energy of a fully ductile capsule is calculated as the area under the load versus depth curve from the point where the surface of the capsule is contacted by the probe to the point where the substrate is contacted by the probe.

[0187] Figure 6 shows a load-depth curve 140 for an exemplary fully ductile particle. The points where the surface of the capsule is contacted by the probe are represented in Figure 6 as triangles 142. The points where the substrate is contacted by the probe are represented in Figure 6 as diamonds 144. The area under the relevant portion of the curve is represented by the shaded region 146 in Figure 6.

[0188] The area is calculated via the integral of the load multiplied by the derivative of the depth over the interval extending from the surface of the capsule to the substrate point, as shown in equation (1.2):

[0189]

number

[0190] ii. Ductile energy of a single burst capsule The ductile energy of a single ruptured capsule is calculated as the area under the load versus depth curve from the point where the capsule surface is contacted by the probe to the (first and only) rupture point of the capsule.

[0191] Figure 7 shows an exemplary load-depth 150 curve for a single burst particle. The point at which the surface of the capsule is contacted by the probe is represented in Figure 7 as a triangle 152. The point at which the capsule bursts is represented in Figure 7 as a square 154. The area under the relevant portion of the curve 150 is represented by the shaded area 156 in Figure 7.

[0192] The area is calculated via the integral of the load multiplied by the derivative of the depth over an interval extending from the capsule surface to the rupture point, as shown in equation (1.3):

[0193]

number

[0194] iii. Ductile energy of multiple burst capsules The ductile energy of a multiple-rupture capsule is calculated as the area under the load versus depth curve from the point where the surface of the capsule is contacted by the probe to the point of the last rupture experienced by the capsule.

[0195] Figure 8 shows an exemplary load-depth curve 160 for a multi-burst particle. The point at which the capsule surface is contacted by the probe is represented in Figure 8 as a triangle 162. The three points at which the capsule ruptures are represented in Figure 8 as three squares 164a, 164b, and 164c, with the third and final rupture point 164c occurring at a probe depth of approximately 8000 nm. The area under the relevant portion of curve 160 is represented by a shaded region 166 in Figure 8.

[0196] The area is calculated via the integral of the load multiplied by the derivative of the depth over the interval extending from the capsule surface to the final rupture point, as shown in equation (1.4):

[0197]

number

[0198] D. Calculation of volume weighted ductile energy The volume weighted ductile energy of the population of delivered particles is determined using the diameter and ductile energy values ​​calculated for the individual particles, followed by logarithmic transformation and rescaling of the ductile energy values.

[0199] i. Logarithmic transformation Figure 9 shows a distribution 170 of measured ductile energy values ​​(in Joules) for an exemplary population of delivered particles. As can be seen in Figure 9, the distribution of measured ductile energy data does not follow a normal distribution. To remove skew from the data, a logarithmic transformation is performed. The resulting distribution 172 of log(ductile energy) values ​​is shown in Figure 10.

[0200] ii. Rescaling For modeling purposes, to ensure that the data points are non-negative, the log(ductile energy) values ​​are rescaled and converted to rescaled log(ductile energy) values ​​by adding a ductile energy rescaling factor to each data point, as shown in Equation 1.5. The ductile energy rescaling factor is equal to the negative log of the minimum measured ductile energy. Within the exemplary specimen, this corresponds to 13, which is 10 -13 This relates to the minimum measurable ductile energy of J. The resulting distribution 174 of rescaled log(ductile energy) values ​​is shown in FIG. Rescaling log(ductile energy) = log(ductile energy) + 13 (1.5)

[0201] iii. Prediction of rescaled logarithmic ductility energy with diameter For the entire population of capsules analyzed, a prediction of the rescaled log(ductile energy) data as a function of diameter is obtained to extrapolate the volume-weighted ductile energy from the capsules.

[0202] In this calculation, the rescaled log ductility energy data is defined as the response variable (y) and diameter is defined as the regression variable (x) in the following equation:

[0203] The predictive formula for Rescaled Log(Ductile Energy) is shown in Equation (1.6): In Figure 12, a regression line 176 represents the Rescaled Log(Ductile Energy) function of the experimental data.

[0204]

number

[0205] coefficient

[0206]

number

[0207]

number

[0208]

number

[0209]

number

[0210]

number

[0211] iv.Volume fraction The volume fraction (Φ of the population) was measured via single-particle optical sensing (SPOS), also known as optical particle counting (OPC), using an AccuSizer 780 AD instrument or equivalent and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent software. i ) was determined. The instrument is configured with the following conditions and options: flow rate = 1 mL / sec; minor threshold = 0.50 μm; sensor model number = LE400-05SE or equivalent; autodilution = on; collection time: 60 seconds; number of channels = 512; reservoir fluid volume = 50 ml; maximum coincidence count = 9200. Measurements are initiated by cold-conditioning the sensor by flushing with water until the background count is less than 100. A sample of delivery capsules in suspension is introduced, and the capsule density is adjusted, if necessary, via autodilution with deionized water to achieve a maximum capsule count of 9200 per mL. The suspension is analyzed over a 60-second period. The size range used was 1 μm to 493.3 μm.

[0212] Volume distribution:

[0213]

number

[0214]

number

[0215] In FIG. 13, volume fraction is plotted as a function of particle diameter for an exemplary population, resulting in distribution 178.

[0216] v. Volume weighted ductile energy Finally, the volume-weighted ductile energy is the sum of the values ​​Φ provided by the rescaled log(ductile energy) predictions provided for each diameter i weighted by the corresponding volume fraction, as shown in equation (1.11). i It was decided that

[0217]

number

[0218] Determination of polymer molecular weight and related parameters The following method, which describes gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI), is used to find molecular weight distribution measurements and related values ​​for the polymers described herein.

[0219] 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.

[0220] 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 of Santa Barbara, Calif., USA) controlled by Wyatt Astra® software v8.0 are used.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] 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 automatic dilution with deionized water to ensure 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., mean, median / 50th percentile, 5th percentile, and / or 90th percentile) are determined.

[0226] 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.

[0227] Fabric Treatment The fabrics were treated using a Miele washing machine. For each treatment, 3 kg of fabric was loaded into the washing machine, including 1100 g of knitted cotton fabric and 1100 g of polyester-cotton fabric (50 / 50). Eighteen terry towel cotton tracers, weighing approximately 780 g in total, were also added. Prior to treatment, the load was preconditioned twice with 79 g of IEC A Base detergent, unscented and supplied by WFK Testgewebe GmbH, using a short cotton cycle at 95°C, followed by two additional washes at 95°C without detergent.

[0228] Prior to the test treatment, the load is preconditioned twice with 79 g of unscented IEC A-based detergent (ex WFK, Testgewebe GmbH), each time using a short cotton cycle at 95°C, followed by two additional 95°C washes without detergent.

[0229] In 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 into a suitable dispenser at the beginning of the wash cycle. A dosage of 35 g of test fabric treatment composition (for example, according to the example) is added into a suitable dispenser. At the end of the wash cycle, the terry towel tracer is removed from the washing machine and hung to dry overnight. The next day, a professional perfumer performs an olfactory evaluation of the perfume intensity of the dried terry towel tracer. For comparison purposes, a reference treatment is also carried out, which uses the same fragrance as the test sample, but uses polyacrylate capsules as delivery particles. All comparison treatments are washed and analyzed on the same day.

[0230] Olfactory assessment method After the fabrics are treated, expert perfumers perform an olfactory assessment of the dry fabric perfume intensity for DRY touchpoints (Dry Fabric Odor = DFO) and RUB touchpoints (Rubbing Fabric Odor = RFO). The fabrics are allowed to dry for a day, smelled for DFO, then manually manipulated by rubbing the fabric against itself, and smelled again for RFO, and the scores are averaged. The scores are based on a fragrance odor intensity scale of 0 to 100, where 0 = no fragrance odor, 25 = slight fragrance odor, 50 = moderate fragrance odor, 75 = strong fragrance odor, and 100 = extremely strong fragrance odor. The difference between the RFO and DFO, "Delta RFO," can be reported.

[0231] 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.

[0232] In addition to the test capsules, parallel headspace data may be determined using a similar method but using a reference capsule, e.g., a polyacrylate-walled capsule ("PAC") capsule beyond the scope of this disclosure, such as delivery particles made substantially according to the method described in U.S. Patent Application Publication No. 2011 / 0268802. Data obtained from the reference capsule can be used as a comparison for the results of the capsules of the present invention. This can be reported as a ratio (e.g., results for particles of the present invention vs. results for the reference capsule).

[0233] In the following examples, data results from different tests can be reported as "RFO Headspace [Normalized]," which is the ratio of the headspace result of a test (e.g., total HS response) to the headspace result of Test 1 for that test. Thus, Test 1 is "normalized" to 1.0, and other results are reported relative to that normalized level. Below, Test 1 is used as the baseline, for example, since it uses the lowest level of each influencing factor of the particle preparation method (e.g., % IPM in the oil phase, % crosslinker, etc.). [Example]

[0234] The examples provided below are intended to be illustrative and not limiting in nature.

[0235] Example 1. Exemplary Delivery Particle Synthesis In the following examples, the abbreviations correspond to the materials listed in Table 1.

[0236] [Table 1]

[0237] A chitosan stock solution was prepared as follows: First, a potassium persulfate solution was prepared by dissolving 1.55 g of potassium persulfate in 3287.97 g of deionized water at 70°C. Next, 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. After the 90-minute hydrolysis step, the temperature was then reduced to 25°C to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of the chitosan solution was 5.93.

[0238] 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 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 at 25°C. 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 for 8 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 14.29 microns.

[0239] Example 2. Exemplary Treatment Composition (Liquid Fabric Enhancer) The following table (Table 2) provides exemplary treatment compositions according to the present disclosure. Specifically, the table shows liquid fabric enhancer ("LFE") formulations suitable for use in, for example, the rinse cycle of an automatic washing machine. The following compositions are also suitable for use in the fabric treatment method provided in the Test Methods section above. The delivery particles in the following formulations are delivery particles according to the present disclosure, including those in Example 1.

[0240] The delivery particles are present in the test LFE composition at a concentration to provide about 0.2% encapsulated fragrance by weight of the LFE composition. The pH of the test LFE composition is adjusted to about 3.

[0241] [Table 2] 1 N,N-di(tallowoyloxyethy)-N,N-dimethylammonium chloride, manufactured by Evonik 2 Flosoft FS222, manufactured by SNF

[0242] Example 3. Determination of ductility energy In the following examples, a population of delivery particles is prepared according to Example 1. Fifty delivery particles selected to represent the diameter distribution are analyzed for mechanical properties and classified by particle type according to the methods provided in the Test Methods section.

[0243] Table 3 shows the results of the analysis, including particle diameter, classification of individual capsules based on rupture profile, rupture velocity (if present), and rescaled log (ductile energy).

[0244] [Table 3]

[0245] Based on 50 individual capsule categories, the number and relative proportion (as a percentage) of each category is provided in Table 4 below.

[0246] [Table 4]

[0247] The volume weighted ductile energy of the population based on the protocol described in the Test Methods section is 4.64.

[0248] Example 4. Effect of Partitioning Modifier Concentration on Ductile Energy and Deodorizing Performance In the following experiments, populations of perfume delivery particles are prepared substantially according to Example 1, but with different concentrations of a partitioning modifier, specifically isopropyl myristate ("IPM"). The populations are analyzed for volume-weighted ductile energy, which is reported in Table 5 below.

[0249] Furthermore, the delivery particles are provided in a liquid fabric enhancer, which is then used to treat fabric according to the fabric treatment method provided in the Test Methods section above. The treated fabric is evaluated for Rubbed Fabric Odor (RFO) headspace performance via the perfume headspace method, and for delta RFO by a professional perfumer. The headspace data is compared with the data from the reference PAC capsule, and then normalized to the results of Test 1. The results are reported in Table 5.

[0250] [Table 5]

[0251] According to the data in Table 5, higher amounts of partitioning modifier result in higher volume weighted ductile energy values ​​for the delivery particle population.

[0252] Additionally, particles with higher volume weighted ductile energy values ​​provide higher RFO headspace values ​​on treated fabrics as well as higher delta RFO scores by expert perfumers.

[0253] Example 5. Effect of crosslinker concentration on ductility energy and deodorizing performance In the following experiments, populations of perfume delivery particles are prepared substantially according to Example 1, but with different concentrations of a crosslinker, specifically a polyisocyanate (Takenate D110), in the oil phase. The populations are analyzed for volume-weighted ductile energy, which is reported in Table 6 below.

[0254] The delivery particles are then provided in a liquid fabric enhancer, which is then used to treat fabric according to the fabric treatment method provided in the Test Methods section above. The treated fabric is evaluated for rub fabric odor (RFO) via the perfume headspace method and for delta RFO by a professional perfumer. The headspace data is compared to data from a reference PAC capsule and then normalized to the results of Test 1. The results are reported in Table 6.

[0255] [Table 6]

[0256] According to the data in Table 6, a relatively high amount of crosslinker (eg, polyisocyanate) in the oil phase results in a relatively high volume weighted ductile energy value for the delivery particle population.

[0257] Additionally, particles with higher volume weighted ductile energy values ​​provide higher RFO headspace values ​​on treated fabrics as well as higher delta RFO scores by expert perfumers.

[0258] Example 6. Effect of pH on category ratio and deodorizing performance In the following experiments, populations of perfume delivery particles are prepared substantially according to Example 1, but with aqueous phases having different pHs. The particle milling temperature in this example is 25° C. The populations are analyzed for the relative percentage of fully ductile capsules, which are reported in Table 7 below.

[0259] Furthermore, the delivery particles are provided in a liquid fabric enhancer, which is then used to treat fabric according to the fabric treatment method provided in the Test Methods section above. The treated fabric is evaluated for rub fabric odor (RFO) via the perfume headspace method. The headspace data is compared to the data from the reference PAC capsule and then normalized to the results of Test 1. The results are reported in Table 7.

[0260] [Table 7]

[0261] According to the data in Table 7, particle populations made with aqueous phases having higher pH have a higher percentage of capsules characterized by fully ductile behavior and a lower percentage of capsules characterized by single burst behavior.

[0262] Furthermore, populations with a relatively high percentage of capsules characterized by fully ductile behavior are associated with relatively high RFO headspace values ​​on the treated fabrics.

[0263] Example 7. Effect of grinding temperature on category ratio and deodorizing performance In the following experiments, populations of perfume delivery particles are prepared substantially according to Example 1, but with different milling temperatures. The populations are analyzed for the relative proportion of fully ductile capsules, which are reported below in Tables 8 and 9. The aqueous phase used to form the particles in Table 8 is characterized by a pH of 5.6. The aqueous phase used to form the particles in Table 9 is characterized by a pH of 5.2.

[0264] Furthermore, the delivery particles are provided in a liquid fabric enhancer, which is then used to treat fabric according to the fabric treatment method provided in the Test Method section above. The treated fabric is evaluated for rub fabric odor (RFO) via the perfume headspace method. The headspace data is compared with the data from the reference PAC capsule, and then normalized to the results of Test 1. The results are reported in Tables 8 and 9.

[0265] [Table 8]

[0266] According to the data in Table 8, particle populations produced at higher milling temperatures have a higher proportion of capsules characterized by fully ductile behavior, a lower proportion of capsules characterized by single-rupture behavior, and a higher volume-weighted ductile energy.

[0267] Furthermore, populations with a higher proportion of particles characterized by fully ductile behavior (and higher volume-weighted ductile energy) are associated with higher RFO headspace values ​​on the treated fabric.

[0268] [Table 9]

[0269] According to the data in Table 9, the particle population produced at the higher milling temperatures had a lower percentage of capsules characterized by single burst behavior and a higher volume-weighted ductile energy. Notably, the particles from Test 2 exhibited a lower percentage of fully ductile particles compared to Test 1, a change believed to be associated with the lower pH of the aqueous phase.

[0270] Furthermore, populations with a relatively low percentage of particles characterized by single burst behavior (and relatively high volume-weighted ductile energy) are associated with relatively high RFO headspace values ​​on the treated fabrics.

[0271] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0272] 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.

[0273] 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 treatment composition comprising: a processing aid; 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; the polymeric material comprises a reaction product of a biopolymer and a crosslinker; The population of delivery particles comprises: (a) a volume-weighted ductility energy of greater than about 3.5, based on 50 randomly selected delivered particles being compressed by a blunt probe moving at 2 μm / s; (b) characterized in that, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s, at least about 30% of the delivery particles are fully ductile by number; (c) a population of delivery particles characterized by at least one, and preferably at least two, of the following: based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s, less than 35% of the number of delivery particles are single-burst particles.

2. 10. The treatment composition of claim 1, wherein the population of delivery particles is characterized by a volume-weighted ductility energy of from about 3.5 to about 10.0, preferably from about 3.5 to about 7.5, more preferably from about 3.8 to about 6.0, more preferably from about 4.0 to about 5.5, and even more preferably from about 4.5 to about 5.2, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s.

3. 3. The treatment composition of claim 1 or 2, wherein the population of delivery particles is characterized as at least about 50% by number as fully ductile particles, based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s.

4. 4. The treatment composition of claim 1, wherein the population of delivery particles is characterized as having less than 25% by number of delivery particles characterized as single-burst particles based on 50 randomly selected delivery particles being compressed by a blunt probe moving at 2 μm / s.

5. The treatment composition of any one of claims 1 to 4, wherein the biopolymer is selected from the group consisting of polysaccharides, proteins, nucleic acids, polyphenolic compounds, derivatives thereof, and combinations thereof.

6. 6. The treatment composition of any one of claims 1 to 5, wherein the biopolymer is selected from the group consisting of chitosan, starch, modified starch, dextran, maltodextrin, dextrin, cellulose, modified cellulose, hemicellulose, chitin, alginate, lignin, gum, pectin, fructan, carrageenan, agar, pullulan, suberin, cutin, cutan, melanin, silk fibroin, gelatin, collagen, casein, sericin, fibroin, whey protein, zein, soy protein, plant storage protein, gluten, peptide, actin, polynucleotide, RNA, DNA, tannin, lignan, derivatives thereof, and combinations thereof.

7. the biopolymer is chitosan, a derivative thereof, or a combination thereof; The treatment composition of any one of claims 1 to 6, wherein the biopolymer is preferably an acid-treated chitosan, a redox initiator-treated chitosan, a derivative thereof, or a combination thereof.

8. the biopolymer is between about 1 kDal and about 1000 kDal; 8. The treatment composition according to any one of claims 1 to 7, characterized by a molecular weight of preferably from about 50 kDal to about 600 kDal, more preferably from about 100 kDal to about 500 kDal, even more preferably from about 100 kDal to about 300 kDal, even more preferably from about 100 kDal to about 200 kDal.

9. The crosslinking agent may be selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxy compounds, polyphenols, carbonyl halides, aziridines, and combinations thereof; Preferably, polyisocyanates, epoxy compounds, difunctional aldehydes, and combinations thereof; More preferably, 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, and combinations thereof. The treatment composition of any one of claims 1 to 8, wherein the material is selected from the group consisting of polyisocyanates selected from the group consisting of:

10. the reaction product is formed in a reaction in which the biopolymer is initially present in an aqueous phase and the crosslinker is initially present in an oil phase; the crosslinker is present in the oil phase at a concentration of from about 1% to about 20%, preferably from about 2% to about 10%, and more preferably from about 2.5% to about 5%, by weight of the oil phase; The treatment composition of any one of claims 1 to 9, wherein the biopolymer and the cross-linking agent are preferably present in the reaction in a weight ratio of about 1:10 to about 1:0.

1.

11. The treatment composition of any one of claims 1 to 10, wherein the benefit agent is a fragrance material.

12. the core further comprises a partitioning modifier, preferably present at a concentration of from about 10% to about 50%, more preferably from about 20% to about 50%, and even more preferably from about 30% to about 50% by weight of the core; Preferably, the partitioning modifier is a vegetable oil, a modified vegetable oil, C ４ ~C ２４ 12. The treating composition of any one of claims 1 to 11, wherein the surfactant is selected from the group consisting of mono-, di-, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate.

13. 13. The treatment composition of any one of claims 1 to 12, wherein the population of delivery particles is made by a process comprising at least one milling step, and wherein the at least one milling step is carried out at a temperature of at least about 15°C, preferably at least about 20°C, more preferably at least about 25°C, and even more preferably from about 25°C to about 35°C.

14. the delivery particles are from about 1 to about 100 microns; 14. The treatment composition of any one of claims 1 to 13, 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.

15. 15. The treatment composition of any one of claims 1 to 14, wherein the shell of the delivery particles degrades by at least 60% in 60 days when tested according to test method OECD 301B.

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