Treatment composition

Abstract

A treatment composition comprising a treatment aid and a population of core / shell delivery particles wherein the shell of the particles is made in part from a biopolymer and wherein the particles are characterized by having certain ductile properties. Related methods of making and using such compositions.

Description

Technical Field

[0001] The present disclosure relates to a treatment composition comprising a treatment aid and a population of core / shell delivery particles, wherein the shell of the particles is made at least in part of a biopolymer, and wherein the particles are characterized by certain ductility properties. The present disclosure also relates to related methods of making and using such compositions. Background Art

[0002] Delivery particles, particularly core / shell delivery particles, are a convenient way to deliver beneficial agents in treatment compositions such as laundry products. For environmental reasons, it may be desirable to use delivery particles having a shell made of materials from natural sources and / or biodegradable materials such as biopolymers.

[0003] Core / shell delivery particles are generally designed to have brittle properties. When intact, the particle shell protects the beneficial agent in the core for easy delivery. When ruptured, the particle releases the beneficial agent.

[0004] Traditionally, the challenge faced by manufacturers of delivery particles has been to form a population of particles that rupture at a desired time or point of contact. The focus in the art has been more on selecting materials and processing conditions such that the particles have the desired rupture characteristics. For example, core / shell delivery particles can be classified according to their fracture strength and / or rupture stress, as such properties can predict the conditions under which the particles may release the beneficial agent.

[0005] Although the industry has focused on brittle capsules, it is believed that relying on rupture release may have drawbacks. For example, despite the best intentions of manufacturers, the delivery particles may not rupture at the desired point of contact. Additionally, given that the vast majority of beneficial agents are only released upon rupture, brittle capsules tend to have an all-or-nothing release profile, which can result in the user experiencing too little or too much of the beneficial agent at any given moment. These challenges can lead to a suboptimal user / consumer experience.

[0006] There remains a need for treatment compositions comprising core / shell delivery particles having improved or preferred release characteristics. Further preferably, such delivery particles are made at least in part of materials from natural sources and / or biodegradable materials. Summary of the Invention

[0007] The present disclosure relates to a treatment composition comprising a population of delivery particles, wherein the delivery particles are characterized by certain ductility properties.

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

[0009] The present disclosure also relates to a method of preparing a treatment composition according to the present disclosure, the method comprising the steps of: providing a base composition, wherein the base composition comprises a treatment aid; and combining a population of delivery particles with the base composition.

[0010] The present disclosure also relates to a method of treating a surface, the method comprising the step of: contacting the surface (preferably a fabric) with a treatment composition according to the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The figures herein are illustrative in nature and are not intended to be limiting.

[0012] Figure 1 A basic setup for measuring the diameter of delivery particles is shown.

[0013] FIG. 2 shows compression curves (e.g., velocity-depth and load-depth curves) of exemplary ruptured delivery particles.

[0014] FIG. 3 shows compression curves of fully ductile particles.

[0015] FIG. 4 shows compression curves of single-fracture particles.

[0016] FIG. 5 shows compression curves of multi-fracture particles.

[0017] Figure 6 A load-depth curve of an exemplary fully ductile particle is shown.

[0018] Figure 7 A load-depth curve of an exemplary single-fracture particle is shown.

[0019] Figure 8 A load-depth curve of an exemplary multi-fracture particle is shown.

[0020] Figure 9 Shows the distribution of measured ductile energy values for an exemplary population of delivery particles.

[0021] Figure 10 Shows the distribution of Log(ductile energy) values for an exemplary population of delivery particles.

[0022] Figure 11 Shows the distribution of rescaled Log(ductile energy) values for an exemplary population of delivery particles.

[0023] Figure 12 Shows a plot of particle size versus rescaled Log(ductile energy).

[0024] Figure 13 Shows the distribution of volume fractions of an exemplary population of delivery particles divided by particle size. DETAILED DESCRIPTION

[0025] The present disclosure relates to a treatment composition comprising delivery particles containing a beneficial agent, the delivery particles containing the beneficial agent having a shell made at least in part of a biopolymer. Contrary to the known brittle behavior of prior core / shell particles, the delivery particles of the present disclosure are characterized by having desired ductile properties. Particles having the ductility described herein can result in improved release characteristics.

[0026] Without wishing to be bound by theory, it is believed that the delivery particles of the present disclosure have a relatively flexible shell and can provide different delivery or release characteristics compared to particles characterized by release via rupture and in at least some cases more desirable delivery or release characteristics. For example, it is believed that due to the relatively flexible shell, the particles of the present disclosure are at least more likely to withstand processing procedures including physical agitation, such as washing and / or drying procedures in an automatic washing machine, at the population level. Additionally, the ductile particles of the disclosed particle population are not characterized by the all-or-nothing release characteristics of their rupturable counterparts, thereby providing improved performance at one or more points of contact.

[0027] It is believed that the ductile properties of the inventive delivery particle population can be provided, and even adjusted, by selecting certain materials, starting amounts, and / or processing conditions. For example, it is believed that biopolymers according to the present disclosure, such as chitosan, provide useful starting materials for forming ductile particle shells. For example, it is believed that certain biopolymers are characterized by a desired water retention capacity (e.g., due to the presence of hydroxyl groups) and can swell and / or increase elasticity in the presence of water. As an additional benefit, the biopolymers of the present disclosure are of natural origin and / or biodegradable, thereby improving the environmental footprint of the inventive delivery particles.

[0028] The delivery particles, treatment compositions, and related methods of the present disclosure are discussed in more detail below.

[0029] As used herein, the articles "a" and "an" are understood to mean one or more of the items claimed or described in the claims. As used herein, the terms "comprising," "including," and "containing" are intended to be non-limiting. The compositions of the present disclosure can comprise, consist essentially of, or consist of the components of the present disclosure.

[0030] The term "substantially free of" can be used herein. This means that the indicated material is present in very small amounts, not intentionally added to form part of the composition, or preferably is not present at levels detectable by analysis. This means compositions that include those in which the indicated material is present only as an impurity in one of the other materials intentionally added. If present at all, the indicated material can be present at levels less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0031] As used herein, "consumer product" means baby care products, beauty care products, fabric and home care products, household care products, feminine care products, and / or health care products or devices intended to be used or consumed in a sold form and not intended for subsequent commercial manufacture or modification. Such products include, but are not limited to, diapers, bibs, wipes; products and / or methods related to treating human hair, including bleaching, coloring, dyeing, conditioning, shampooing, styling, dry treatments, and boosters; deodorants and antiperspirants; personal cleansing; skin care, including the application of creams, lotions, and other topically applied products for consumer use; and shaving products, products and / or methods related to treating fabrics, hard surfaces, and any other surfaces in the fabric and home care areas, including: air care, automotive care, dishwashing, fabric conditioning (including softening), laundry detergency, laundry washing and rinse additives and / or care, hard surface cleaning and / or treatment, and other cleaning for consumer or business use; products and / or methods related to toilet paper, facial tissue, paper handkerchiefs, and / or paper towels; tampons, feminine sanitary pads; adult incontinence products; products and / or methods related to oral care, including toothpaste, teething gels, tooth cleaning, denture adhesives, teeth whitening; over-the-counter health care products, including cough and cold medicines; pest control products; and water purification.

[0032] As used herein, the phrase "fabric care composition" includes compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-wash compositions, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in a porous substrate or nonwoven sheet, and other suitable forms that would be apparent to one of ordinary skill in the art in light of the teachings herein. Such compositions can be used as laundry pre-treatment agents, laundry post-treatment agents, or can be added during the rinse cycle or wash cycle of a laundry operation.

[0033] As used herein, unless otherwise indicated, the terms "delivery particle", "particle", "encapsulate", "microcapsule", and "capsule" are used interchangeably. As used herein, these terms generally refer to core / shell delivery particles.

[0034] Unless otherwise indicated, all component or composition levels are based on the active portion of that component or composition and do not include impurities that may be present in commercially available sources of such components or compositions, such as residual solvents or by-products.

[0035] Unless otherwise indicated, all temperatures herein are in degrees Celsius (°C). Unless otherwise indicated, all measurements herein are made at 20 °C and atmospheric pressure.

[0036] In all embodiments of the present disclosure, unless otherwise specifically stated, all percentages are by weight of the total composition. Unless otherwise specifically stated, all ratios are weight ratios.

[0037] 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 will include 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 falling within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0038] Treatment composition

[0039] The present disclosure relates to treatment compositions (or simply "compositions" as used herein). The compositions of the present disclosure can include treatment aids and populations of delivery particles, each of which is described in more detail below. The treatment compositions can be used in the methods of treating surfaces, such as fabrics, described herein.

[0040] The treatment composition is preferably a consumer product composition. The consumer product compositions of the present disclosure can be used in baby care products, beauty care products, fabric care products, home care products, household care products, feminine care products, and / or healthcare applications. The consumer product composition can be used to treat surfaces such as fabrics, hair, or skin. The consumer product composition can be intended for use or consumption in its sold form. The consumer product compositions of the present disclosure are generally not intended for subsequent commercial manufacturing or modification.

[0041] The consumer product composition can preferably be a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition (such as a shampoo or conditioner), a body cleansing composition, or a mixture thereof, preferably a fabric care composition.

[0042] The consumer product composition can be a fabric care composition, such as a laundry detergent composition (including heavy-duty liquid detergents or unit dose products), a fabric conditioning composition (including liquid fabric softening and / or enhancing compositions), a laundry additive, a fabric pretreatment composition (including sprays, pourable liquids or sprays), a fabric refresher composition (including sprays), or a mixture thereof. The treatment composition is preferably a fabric conditioning composition, even more preferably a liquid fabric conditioning composition.

[0043] The composition can be a beauty care composition, such as a hair treatment product (including shampoo and / or conditioner), a skin care product (including creams, lotions or other topically applied products for consumer use), a shaving care product (including shaving lotions, foams, or pre- or post-shave treatments), a personal cleansing product (including liquid bath products, liquid hand soaps, and / or bar soaps), a deodorant and / or antiperspirant, or a mixture thereof.

[0044] The composition can be a home care composition, such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other cleaning for consumer or institutional use.

[0045] The treatment composition can be in the form of a liquid composition, a particulate composition, an aqueous colloid, a single-compartment sachet, a multi-compartment sachet, a soluble sheet, a lozenge or bead, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a non-woven sheet, or a mixture thereof.

[0046] The treatment composition may be in liquid form. The liquid composition may preferably comprise from about 50% to about 97%, preferably from about 60% to about 96%, more preferably from about 70% to about 95%, or even from about 80% to about 95% water, based on the 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 hereinafter.

[0047] The treatment composition may be in solid form. The composition may be in the form of beads or tablets, which may be made from a liquid melt. The composition may be an extruded product. The treatment composition may be in powder or granular form.

[0048] The composition may be in the form of a combined dose article such as a tablet, sachet, sheet or fibrous article. Such sachets typically comprise a water-soluble film, such as a polyvinyl alcohol water-soluble film, which at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition may be encapsulated in a single-compartment sachet or a multi-compartment sachet. The multi-compartment sachet may have at least two, at least three or at least four compartments. The multi-compartment sachet may include side-by-side and / or stacked compartments. The composition contained in the sachet or its compartments may be liquid, solid (such as powder), or a combination thereof. The sachet composition may have a relatively small amount of water, for example less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% water, based on the weight of the detergent composition. The composition may contain 0% water, or at least 0.1% water, or at least 1% water.

[0049] The treatment composition may be in spray form and may be dispensed from a bottle, for example via a trigger sprayer and / or an aerosol container with a valve.

[0050] The treatment composition may have a viscosity at 20 s -1 and 21 °C of from 1 centipoise to 1500 centipoise (1 mPa·s to 1500 mPa·s), from 100 centipoise to 1000 centipoise (100 mPa·s to 1000 mPa·s), or from 200 centipoise to 500 centipoise (200 mPa·s to 500 mPa·s).

[0051] The treatment composition of the present disclosure may be characterized by a pH of from about 2 to about 12, or from about 2 to about 8.5, or from about 2 to about 7, or from about 2 to about 5. The treatment composition of the present disclosure may have a pH of from about 2 to about 4, preferably from about 2 to about 3.7, more preferably from about 2 to about 3.5, and is preferably in the form of an aqueous liquid. It is believed that such pH levels are beneficial for the stability of the quaternary ammonium ester compound (when present). On the other hand, traditional detergent compositions are typically characterized by a pH of from about 7 to about 12, preferably from about 7.5 to about 11. In some cases, an acidic detergent may be desired and may be characterized by a pH of from about 2 to about 6, preferably from 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 from about 4 to about 7, preferably from about 5 to about 6. The pH of the composition is determined by dissolving / dispersing the composition in deionized water at about 20 °C to form a 10% concentration solution.

[0052] Additional components and / or features of the composition are discussed in more detail below.

[0053] Delivery particle population

[0054] The treatment composition of the present disclosure comprises a population of delivery particles. The delivery particles include a core and a shell surrounding the core. The core contains a beneficial agent (preferably an aromatic material) and optionally a dispensing modifier. The core can be liquid or solid at room temperature, preferably liquid. The shell contains a polymeric material which is typically a reaction product of a biopolymer and a crosslinking agent.

[0055] The delivery particles of the present disclosure can be described as having ductile properties at least at the population level. As used herein generally, "ductile" particles (or those having "ductility") are those that can be deformed without material failure or rupture. Without wishing to be bound by theory, it is believed that the shell of the particles described in the present invention is relatively flexible or pliable while still having appropriate robustness and generally being able to contain the beneficial agent in the core. It is believed that the ductile particles of the present disclosure release the encapsulated beneficial agent when squeezed or otherwise deformed without breaking, rather than by a rupture mechanism. This can result in a more sustained release profile since the beneficial agent is not necessarily released in a single rupture event. Additionally or alternatively, a relatively low force may be required to obtain the release of the encapsulated beneficial agent since the release event does not require complete rupture of the particle.

[0056] As described in more detail below, it is believed that the relative ductility of the particulate population according to the present invention can be affected by the choice 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 size and / or shell thickness, the use and amount 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 having desired ductility and performance characteristics.

[0057] The population of delivery particles of the present disclosure can be characterized by a volume-weighted ductility energy greater than about 3.5, preferably greater than about 3.8, based on the compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s. The population of delivery particles of the present disclosure can 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 the compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s.

[0058] It is believed that a population of delivery particles characterized by the volume-weighted ductility energy at the stated levels provides desired performance at certain contact points, such as dry fabric odor, and / or may distribute well over time, thus providing long-lasting and consistent benefits. Such populations can also be used in certain applications, particularly those where high shear exists during use, such as through the wash and / or rinse cycles of an automatic washing machine. At lower levels of volume-weighted ductility energy, the particles may not exhibit sufficient ductility to provide the desired benefits; for example, they may collapse prematurely during manufacture, transport, or use (e.g., during the wash cycle) and release the encapsulated benefit agent prematurely. More details on how to determine the volume-weighted ductility energy of a population of delivery particles can be found in the test methods section below.

[0059] When it is anticipated or intended to use a treatment composition under relatively high shear conditions, it may be preferred 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 combined dose detergent, and / or a laundry wash additive for the wash cycle, such as a fragrance bead) can contain such a population of delivery particles, which is 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 the compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s. It is believed that such particles can better withstand high shear conditions while retaining a sufficient amount of the benefit agent in the core.

[0060] When a treatment composition is expected or intended to be used under relatively low shear conditions, a population of delivery particles characterized by a relatively low volume-weighted ductility energy may be preferably used. For example, a treatment composition (such as a liquid fabric enhancer) intended to be used in the rinse cycle of an automatic washing machine may comprise such 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, more preferably about 4.0 to about 4.5 based on the compression of fifty randomly selected delivery particles by a blunt probe moving at 2 μm / s. It is believed that such particles can withstand the lower shear conditions while retaining a sufficient amount of the beneficial agent in the core and providing convenient release of the beneficial agent.

[0061] It may be desirable to vary the volume-weighted ductility energy of the particle population as the particle size changes. For example, a population with relatively large particles may be characterized by a relatively large volume-weighted ductility energy. Without wishing to be bound by theory, it is believed that larger particles generally have a greater mass and thus can absorb more energy. Accordingly, the size and volume-weighted ductility energy of the particle population can be selected for certain applications and / or release characteristics. For example, when the population of delivery particles is characterized by a volume-weighted median particle size of about 20 microns to about 40 microns, the volume-weighted ductility energy of the population may preferably be about 3.5 to about 7.5, more preferably about 4.5 to about 6.0. When the population of delivery particles is characterized by a volume-weighted median particle size of about 10 microns to about 25 microns, based on the compression of fifty randomly selected delivery particles by a blunt probe moving at 2 μm / s, the volume-weighted ductility energy of the population may preferably be about 3.0 to about 5.0, more preferably about 3.5 to about 4.0.

[0062] Any single delivery particle, when compressed by a blunt probe moving at 2 μm / s, can be classified as a fully ductile particle, a single fracture particle, or a multi-fracture particle, as described in more detail in the test methods section. By sampling a specific number of particles (e.g., fifty particles), the delivery particle population can be described in terms of the proportion (e.g., as a percentage by number) of particles falling into any one or more of these categories. The relative proportions can give an indication of the overall population behavior, which can help predict the relative performance of the population in the treatment composition. When classifying a delivery particle population using these categories, the respective percentages of fully ductile particles, single fracture particles, and multi-fracture particles will typically total 100%.

[0063] The characteristics of the population of delivery particles of the present disclosure may lie in that, based on compressing fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s, at least about 30%, preferably at least about 50% of the delivery particles, by number, are characterized as fully ductile particles. It is believed that a population with a relatively high proportion of fully ductile particles may provide desired performance. Without wishing to be bound by theory, it is believed that since the release of the encapsulated beneficial agent is not concentrated at a single time point (e.g., a rupture event), the release of the beneficial agent from the particles of the present disclosure tends to be more gradual and / or linear over time. More details on how to determine the relative proportion of fully ductile particles in the population can be found in the test methods section below.

[0064] The characteristics of the population of delivery particles of the present disclosure may lie in that, based on compressing fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s, less than 35%, preferably less than 25% of the delivery particles, by number, are characterized as single-rupture particles. It is believed that a population with a relatively low proportion of fully ductile particles may provide desired performance. More details on how to determine the relative proportion of single-rupture particles in the population can be found in the test methods section below.

[0065] The population of delivery particles of the present disclosure may comprise delivery particles that, based on compressing fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s, are characterized as multi-rupture particles. More details on how to determine the relative proportion of single-rupture particles in the population can be found in the test methods section below.

[0066] Preferably, the population of delivery particles is characterized by at least one, preferably at least two, more preferably all three of the following, where each is based on compressing fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s according to the following test method: (a) a volume-weighted ductility energy greater than about 3.5; (b) at least about 30% of the delivery particles, by number, are characterized as fully ductile particles; (c) less than 35% of the delivery particles, by number, are characterized as single-rupture particles.

[0067] 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% of delivery particles, by weight of the composition. The composition may comprise a sufficient amount of delivery particles to provide from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 2% of encapsulated beneficial agent, by weight of the composition, which may preferably be an aromatic material having one or more fragrance ingredients. When discussing the amount or weight percentage of delivery particles herein, it means the sum of the wall material and the core material.

[0068] The characteristics of the population of delivery particles according to the present disclosure may lie in a volume-weighted median particle size of from about 1 micron to about 100 microns, preferably from about 10 microns to about 100 microns, preferably from about 15 microns to about 50 microns, more preferably from about 20 microns to about 40 microns, and even more preferably from about 25 microns to about 35 microns. For certain compositions, it may be preferred that the population of delivery particles is characterized by a volume-weighted median particle size of from about 1 micron to about 50 microns, preferably from about 5 microns to about 20 microns, and more preferably from about 10 microns to about 15 microns. Different particle sizes can be obtained by controlling the droplet size during the emulsification process.

[0069] The characteristics of the delivery particles may lie in a core-to-shell ratio, based on weight, of up to 99:1, or even 99.5:0.5. The shell may be present at a level of from about 1% to about 25%, preferably from about 1% to about 20%, preferably from about 1% to 15%, more preferably from about 5% to about 15%, even more preferably from about 10% to about 15%, and even more preferably from about 10% to about 12% by weight of the delivery particles. The shell may be present at a level of at least 1%, preferably at least 3%, and more preferably at least 5% by weight of the delivery particles. The shell may be present at a level of up to about 20%, preferably up to about 15%, and more preferably up to about 12% by weight of the delivery particles.

[0070] The delivery particles may be cationic in nature, preferably cationic at a pH of 4.5. The characteristics of the delivery particles may lie in a ζ potential of at least 15 millivolts (mV) at a pH of 4.5. The delivery particles can be made to have a ζ potential of at least 15 millivolts (mV) at a pH of 4.5, or even a ζ potential of at least 40 mV at a pH of 4.5, or even a ζ potential of at least 60 mV at a pH of 4.5. Polyurea capsules prepared with chitosan generally exhibit a positive ζ potential. Such capsules have improved deposition efficiency on fabrics. At higher pH values, the particles can be made non-ionic or anionic.

[0071] The delivery particles of the present disclosure include a shell surrounding a core. (As used herein, "shell" and "wall" may be used interchangeably with respect to delivery particles, unless otherwise specified.) The shell contains a polymeric material. The polymeric material includes and preferably is a reaction product of a biopolymer and a crosslinking agent.

[0072] The biopolymer may preferably be selected from the group consisting of polysaccharides, proteins, nucleic acids, polyphenolic compounds, their derivatives, and combinations thereof. Preferably, the biopolymer is selected from the group consisting of:

[0073] (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, fibroin, their derivatives, and combinations thereof;

[0074] (b) A protein selected from the group consisting of gelatin, collagen, casein, sericin, fibroin, whey protein, zein, soy protein, plant storage proteins (protein isolates, protein concentrates), gluten, peptides, actin, their derivatives, and combinations thereof;

[0075] (c) A nucleic acid selected from the group consisting of polynucleotide, RNA, DNA, their derivatives, and combinations thereof;

[0076] (d) A polyphenolic compound selected from the group consisting of tannin, lignan, their derivatives, and combinations thereof; or

[0077] (e) Combinations thereof.

[0078] The biopolymer preferably contains primary amine groups. The primary amine groups can react with a crosslinking agent (preferably polyisocyanate) to form a polymeric material, which can be described as a crosslinked biopolymer.

[0079] For example, due to convenient availability, biodegradability, and / or performance reasons, amine-containing biopolymers (such as amine-containing or amine-modified saccharides) can be preferred. A particularly preferred material is chitosan. Thus, the biopolymer can preferably be chitosan, its derivatives, or combinations thereof. Preferably, the biopolymer is acid-treated chitosan, redox initiator-treated chitosan, their derivatives, or combinations thereof.

[0080] Chitosan can preferably be acid-treated chitosan. For example, chitosan (which can be referred to as raw chitosan or parent chitosan before acid treatment) can be acid-treated at a temperature of about 25°C to about 99°C, preferably about 75°C to about 95°C, at a pH of 6.5 or lower, preferably for at least one hour, preferably about one hour to about three hours. The acid can be selected from strong acids (such as hydrochloric acid), organic acids (such as formic acid or acetic acid), or mixtures thereof. Chitosan can preferably be acid-treated at a pH of 2 to 6.5 or even 4 to 6.

[0081] Chitosan can be treated with a redox initiator (e.g., redox-initiator-treated chitosan). For example, when forming delivery particles, a redox initiator (preferably comprising a persulfate or a peroxide) can be added to the aqueous phase and / or the emulsion. A redox initiator (which may comprise a persulfate or a peroxide) can be added to acid-treated chitosan. In an in-situ variation, after combining the oil phase and the aqueous phase under high-shear stirring, the redox initiator can be added to the emulsion. The redox initiator advantageously depolymerizes hydrolyzed chitosan or modified chitosan, reducing the viscosity and thus facilitating the formation of the polymer of the shell during the capsule formation process. Preferably, the modification of chitosan with an epoxide, an aldehyde, or an α,β-unsaturated compound is completed before adding the redox initiator, but the redox initiator (peroxide or persulfate) can be introduced simultaneously with or even before the modifying compound. The redox initiator can be selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof. The redox initiator (preferably a persulfate or a peroxide) can be present at a level of about 0.1 wt% to about 99 wt% of the chitosan.

[0082] The biopolymer (preferably chitosan, more preferably acid-treated chitosan) can preferably 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 a relatively low molecular weight are less effective in forming suitable delivery particles, while those with a relatively high molecular weight tend to be difficult to process. Methods for determining the molecular weight and related parameters of chitosan are provided in the test methods section below and use gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) technology.

[0083] Chitosan (when present) can 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 affects the solubility of chitosan, which in turn affects its reactivity or behavior during the formation of the particle shell. For example, too low a degree of deacetylation (e.g., below 50%) can result in relatively insoluble and relatively unreactive chitosan. A relatively high degree of deacetylation can result in very soluble chitosan, thus leading to relatively little chitosan reaching the oil / water interface during shell formation.

[0084] Chitosan (when present) may include anionically modified chitosan, cationically modified chitosan, or combinations thereof. Modifying chitosan in an anionic and / or cationic manner alters the characteristics of the shell of the delivery particles, such as by changing the surface charge and / or zeta potential, which can affect the deposition efficiency of the particles and / or formulation compatibility.

[0085] As described above, the shell is a polymeric material that is the reaction product of a biopolymer chitosan and a crosslinker. The crosslinking material is preferably a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxides, polyphenols, carbonyl halides, aziridines, and combinations thereof. The crosslinker is more preferably selected from the group consisting of polyisocyanates, epoxides, bifunctional aldehydes, and combinations thereof.

[0086] The crosslinker is preferably a polyisocyanate, especially when the biopolymer contains amine groups. It is believed that such materials advantageously react with the amine groups of the biopolymer to form an effective crosslinked polymer wall. The polymeric material of the shell may preferably contain a polyurea resin, which may contain the reaction product of a polyisocyanate and chitosan.

[0087] The polyisocyanate materials useful in the present disclosure are to be understood as isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. The term "polyisocyanate" is intended to denote a material or compound containing two or more isocyanate moieties. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended to be encompassed by the term "polyisocyanate" herein. The polyisocyanates useful in the present disclosure include isocyanate monomers, oligomers, or prepolymers having at least two isocyanate groups, or dimers or trimers thereof. Preferred crosslinking can be achieved using polyisocyanates having at least three functional groups.

[0088] Aromatic polyisocyanates may be preferred; however, aliphatic polyisocyanates and their blends may 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 contain a mixture of aromatic polyisocyanates and aliphatic polyisocyanates.

[0089] Polyisocyanates, when aromatic, can be but are not limited to methylene diphenyl diisocyanate, toluene diisocyanate, tetramethylxylidene diisocyanate, the polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name RC), the trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name L75 (commercially available) or trimethylolpropane adducts of naphthalene-1,5-diisocyanate, phenylene diisocyanate or xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name D-110N).

[0090] Aliphatic polyisocyanates may include trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate (commercially available from Mitsui Chemicals) or biurets of hexamethylene diisocyanate (commercially available from Bayer under the trade name N 100).

[0091] Derivatives of polyisocyanates may include oligomers or polymers of isocyanate monomers. As non-limiting examples, polyisocyanates may preferably comprise oligomers or polymers of diphenylmethane diisocyanate (MDI), such as MR-Light.

[0092] Polyisocyanates may preferably be selected from the group consisting of: polyisocyanurates of toluene diisocyanate; trimethylolpropane adducts of toluene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4′-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethylxylylene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; their derivatives (such as their prepolymers, oligomers and / or polymers); and combinations thereof.

[0093] Additional co-crosslinkers such as polyfunctional amines and / or polyamines such as diethylenetriamine (DETA), polyethyleneimine, polyvinylamine or mixtures thereof may also be used to strengthen the particle shell. Acrylates may also be used as additional co-crosslinkers, for example to strengthen the shell.

[0094] The polymeric material may be formed in a reaction in which the weight ratio of the biopolymer present in the reaction, preferably a polysaccharide, more preferably chitosan or a derivative thereof (which may include acid-treated chitosan) to the 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 may provide the desired ductility benefits as well as improved biodegradability.

[0095] It may be preferred that at least 21% by weight of the shell is composed of a portion derived from a biopolymer, preferably derived from chitosan, more preferably derived from acid-treated chitosan. The weight percentage of the biopolymer (preferably chitosan or its derivative) in the shell may be from about 21% to about 95% of the shell. Based on weight, the ratio of the biopolymer (preferably chitosan) in the aqueous phase to the crosslinking agent (preferably polyisocyanate) in the oil phase may 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). The level of the biopolymer (preferably chitosan) contained in the shell may be: 21% by weight or even higher of the total shell, preferably from about 21% by weight to about 90% by weight, or even from 21% by weight to 85% by weight, or even from 21% by weight to 75% by weight, or from 21% by weight to 55% by weight is the biopolymer (preferably chitosan). The chitosan in this paragraph may preferably be acid-treated chitosan.

[0096] The reaction product forming at least a portion of the polymeric material may be formed in a reaction in which the biopolymer is initially present in the aqueous phase and the crosslinking agent is initially present in the oil phase. The crosslinking agent is preferably present in the oil phase at a level of about 1% to about 20% by weight of the oil phase, preferably about 2% to about 10% by weight, more preferably about 2.5% to about 5% by weight. The crosslinking agent may be a polyisocyanate present in the oil phase at a level greater than 1%, preferably 1.3%, preferably greater than 2%, more preferably greater than 2.5%, even more preferably greater than 2.9%.

[0097] A population of delivery particles may be prepared according to a method comprising the following steps: (a) forming an aqueous phase comprising chitosan as described herein, preferably wherein the aqueous phase has a pH of 6.5 or lower, 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 beneficial agent (preferably an aromatic material) and at least one crosslinking agent (preferably at least one polyisocyanate) and optionally a partitioning modifier; (c) forming an emulsion by mixing the aqueous phase and the oil phase under high-shear agitation, preferably a water-in-oil emulsion, optionally adjusting the pH of the emulsion to within the range of pH 2 to pH 6; (d) curing the emulsion by heating, preferably heating 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 will comprise a polymeric material that is the reaction product of chitosan and the crosslinking agent, and wherein the shell surrounds a core comprising the beneficial agent.

[0098] A population of delivery particles can be prepared by a method comprising the following steps: (a) forming an aqueous phase by treating chitosan with a mixture of a first acid and a second acid, the first acid comprising a strong acid and the second acid comprising a weak acid, wherein the chitosan is treated at a pH of 6.5 or less, or even less than pH 6.5, or even at a pH of 3 to 6 and at a temperature of at least 25 °C for at least one hour, or for a period of time sufficient to obtain a chitosan solution viscosity of no more than about 1500 cps or even no more than 500 cps of the acid-treated chitosan; (b) forming an oil phase by dissolving together at least one beneficial agent and at least one polyisocyanate, optionally with added oil (e.g., a partitioning modifier) and / or solvent; (c) forming an emulsion by mixing the aqueous phase and the oil phase into an excess of the aqueous phase under high-shear agitation, thereby forming droplets of the oil phase and the beneficial agent dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to within the range of pH 2 to pH 6; (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 aqueous phase, the shell comprising the reaction product of the polyisocyanate and the acid-treated chitosan, and the shell surrounding a core comprising the oil phase and the beneficial agent.

[0099] Chitosan can be added to water in a jacketed reactor and at a pH adjusted with an acid such as concentrated HCl of 2 or even 3 to 6.5. The chitosan in the mixture can be acid-treated by heating to an elevated temperature (such as 85 °C) for 60 minutes and then held at that temperature for 1 minute to 1440 minutes or even longer. The aqueous phase can then be cooled to 25 °C. Optionally, deacetylation can also be further promoted or enhanced by an enzyme to depolymerize or deacetylate the chitosan. The oil phase can be prepared by dissolving an isocyanate such as a trimer of xylylene diisocyanate (XDI) or a polymer of methylene diphenyl diisocyanate (MDI) in oil at 25 °C. The oil phase can then be added to the aqueous phase and ground at high speed to obtain the target size. The emulsion can then be cured 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 cure a shell at the interface of the droplets of the oil phase and the aqueous 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 cure the particles. The slurry can then be cooled to room temperature.

[0100] To form a population of capsules with appropriate ductility, it is preferable to adjust the pH of the aqueous phase and / or the emulsion to be greater than or equal to about 5.2, preferably greater than or equal to about 5.6, and at most about 6.5, preferably at most about 6. It is believed that the pH during particle shell formation can affect the final ductility of the particle population.

[0101] To form a population of capsules with appropriate ductility, the capsules may preferably be prepared by a method including at least one grinding step, which may preferably be carried out at a specific temperature. For example, the at least one grinding 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 about 25 °C to about 35 °C. The grinding may be carried out until the desired particle size is achieved. It is believed that the temperature during the grinding step affects the final ductility of the particle population.

[0102] When tested according to test method OECD 301B, 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 preferably degrade by at least 60% of its mass after 60 days (or less). The shell may degrade by 30% to 100%, preferably 40% to 100%, 50% to 100%, 60% to 100% or 60% to 95% after 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, more preferably 14 days.

[0103] The delivery particles of the present disclosure include a core. The core contains a beneficial agent, preferably an aromatic material. The core optionally contains a dispensing modifier.

[0104] The core of the particle is surrounded by a shell. When the ductile particle is compressed or otherwise deformed, it is believed that the beneficial agent (preferably an aromatic material) in the core exits the particle by extruding from the shell. Additionally or alternatively, at least some of the beneficial agent may diffuse through the shell. Even when there are ductile particles in the population of the present disclosure, some particles may rupture upon compression or deformation, resulting in the release of the beneficial agent. Suitable beneficial agents located in the core may include beneficial agents that provide beneficial effects to surfaces such as fabrics or hair, such as suitable aromatic materials.

[0105] The core may contain from about 5% to about 100% of the beneficial agent, preferably an aromatic material, by weight of the core. The core may contain from about 45% to about 95%, preferably from about 50% to about 80%, more preferably from about 50% to about 70% of the beneficial agent, preferably an aromatic material, by weight of the core.

[0106] The beneficial agent in the core may be relatively hydrophobic. Such reagents are compatible with the oil phase commonly found in the preparation of the delivery particles of the present disclosure.

[0107] Beneficial agents are selected to provide beneficial effects under the preferred uses of the treatment compositions. The beneficial agents in the core are optionally selected from the group consisting of: fragrance materials, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin coolants, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleaching granules, silica particles, malodor attenuators, odor control materials, chelating agents, antistatic agents, softeners, insect and moth repellents, colorants, thickeners, wrinkle and shape control agents, smoothing agents, wrinkle control agents, hygiene treatment agents, disinfectants, microbial control agents, mildew control agents, mold control agents, antiviral agents, desiccants, antifouling agents, detergents, fabric renovators and freshness extending agents, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color restoration / recovery agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, anti-wear agents, fabric integrity agents, anti-pilling agents, defoaming agents, ultraviolet protection agents, photo-fading inhibitors, anti-allergenic agents, enzymes, water repellents, fabric comfort agents, anti-shrinkage agents, anti-stretching agents, stretch recovery agents, skin care agents, synthetic or natural active substances, antibacterial active substances, antiperspirant active substances, cationic polymers, dyes, and mixtures thereof.

[0108] The beneficial agent in the core preferably comprises a fragrance material (or simply "fragrance"), which may comprise one or more perfume raw materials. The fragrance is particularly suitable for encapsulation in the delivery particles described in the present invention, since the fragrance-containing particles can provide a fresh beneficial effect across multiple contact points.

[0109] As used herein, the term "perfume raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mol, and which can be used alone or in combination with other perfume raw materials to impart an odor, aroma, essence, or fragrance. Typical PRMs particularly include alcohols, ketones, aldehydes, esters, ethers, nitrites, and olefins, such as terpenes. A list of common PRMs can be found in various references, such as "Perfume and Flavor Chemicals", Volumes I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology", Miller, P.M. and Lamparsky, D., Blackie Academic and Professional (1994).

[0110] The characteristics of the PRMs can lie in their boiling points (B.P.) measured at a normal pressure (760 mmHg), and their octanol / water partition coefficients (P), which can be described according to logP and determined according to the test methods below. Based on these characteristics, the PRMs can be classified as Quadrant I, Quadrant II, Quadrant III or Quadrant IV fragrances, as described in more detail in U.S. Patent 6,869,923. Suitable Quadrant I, Quadrant II, Quadrant III and Quadrant IV fragrance ingredients are disclosed therein.

[0111] Fragrance ingredients having a boiling point B.P. below about 250 °C and a logP less than about 3 are referred to as Quadrant I fragrance ingredients. Quadrant I fragrance ingredients are preferably limited to less than 30% of the fragrance material.

[0112] The fragrance can include fragrance ingredients having a logP of about 2.5 to about 4. It should be understood that other fragrance ingredients may also be present in the fragrance.

[0113] The core of the delivery particles of the present disclosure can include a partitioning modifier, which can promote a more robust shell formation. The partitioning modifier can be combined with the fragrance oil material of the core before incorporation into the wall-forming monomers. The partitioning modifier can be present in the core at a level of 0% to 95%, preferably about 5% to about 55%, preferably about 10% to about 50%, more preferably about 20% to about 50%, even more preferably about 25% to about 50% by weight of the core.

[0114] The partitioning modifier can include materials selected from the group consisting of vegetable oils, modified vegetable oils, mono-esters, di-esters and tri-esters of C4-C 24 fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning modifier can preferably include isopropyl myristate or even consist of isopropyl myristate. The modified vegetable oil can be esterified and / or brominated. The modified vegetable oil can preferably include castor oil and / or soybean oil. U.S. Patent Application Publication 20110268802, which is incorporated herein by reference, describes other partitioning modifiers that can be used in the delivery particles described in the present invention.

[0115] Optionally, the aqueous phase can include an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (such as alkyl sulfates, alkyl ether sulfates and / or alkyl benzene sulfonates), non-ionic surfactants (such as alkoxylated alcohols, preferably containing ethoxy), polyvinyl alcohol, and / or polyvinyl pyrrolidone. It is possible in the present application that dissolved chitosan can provide emulsifying benefits.

[0116] The emulsifier (if used) is typically present in an amount of from about 0.1% to 40% by weight, preferably from 0.2% to about 15% by weight, more typically from 0.5% to 10% by weight, based on the total weight of the aqueous phase.

[0117] The population of delivery particles can be provided as a slurry (preferably an aqueous slurry). The slurry can contain one or more processing aids, which can include water, aggregation-inhibiting substances such as divalent salts, or particulate-suspending polymers such as xanthan gum, guar gum, cellulose (preferably microcrystalline cellulose) and / or carboxymethyl cellulose.

[0118] The slurry can contain one or more carriers selected from the group consisting of: polar solvents including, but not limited to, water, ethylene glycol, propylene glycol, polyethylene glycol, glycerol; non-polar solvents including, but not limited to, mineral oil, perfume raw materials, silicone oil, hydrocarbon paraffin oil; and mixtures thereof. An aqueous slurry can be preferred. The slurry can contain unencapsulated ("free") perfume raw materials, which differ in properties and / or amount from those encapsulated in the core of the delivery particles.

[0119] The slurry can contain a deposition aid, which can include polymers selected from the group consisting of: polysaccharides such as chitosan, cationically modified starch and / or cationically modified guar gum; polysiloxanes; diallyldimethylammonium halide; copolymers of diallyldimethylammonium chloride and polyvinylpyrrolidone; compositions containing polyethylene glycol and polyvinylpyrrolidone; acrylamide; imidazole; imidazoline halide; polyvinylamine; copolymers of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; polyglycerol ether silicone crosslinked polymer; copolymers of polyacrylic acid, polyacrylate, polyvinylamine and polyvinyl alcohol oligomers with amines, in one aspect, diethylenetriamine, ethylenediamine, bis(3-aminopropyl)piperazine, N,N-bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine and mixtures thereof; polyethyleneimine, derivatized polyethyleneimine, in one aspect, ethoxylated polyethyleneimine; polymeric compounds containing at least two moieties selected from the group consisting of carboxylic acid moieties, amine moieties, hydroxyl moieties and nitrile moieties on the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile or combinations thereof; preformed coacervates of anionic surfactants combined with cationic polymers; polyamines, and mixtures thereof.

[0120] At least one population of delivery particles can be included in an agglomerate and then combined with a different population of delivery particles and at least one adjuvant material. The agglomerate can comprise a material selected from silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride, and a base material such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0121] Suitable equipment for use in the methods disclosed herein can include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plowshare shear mixers, ribbon blenders, vertical axis granulators, and drum mixers (the latter two of which can be in batch process configurations and continuous process configurations (when available)), spray dryers, and extruders. Such equipment can be purchased from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., U.S.A.), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., U.S.A.), Arde Barinco (New Jersey, U.S.A.).

[0122] Auxiliary ingredient

[0123] In addition to the delivery particles, the treatment compositions of the present disclosure can further comprise one or more adjuvant materials. The adjuvant materials can provide beneficial effects in the intended end use of the composition, or they can be processing aids and / or stabilizing aids.

[0124] Suitable adjuvant materials can include: surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / antiredeposition agents, optical brighteners, antifoaming agents, silicones, hueing agents, aesthetic dyes, additional fragrances and fragrance delivery systems, structure elasticizers, carriers, hydrotropes, processing aids, antiagglomerants, coatings, formaldehyde scavengers, and / or pigments. Preferably, the adjuvant materials include additional fabric conditioners, dyes, pH control agents, solvents, rheology modifiers, structurants, cationic polymers, surfactants, fragrances, additional fragrance delivery systems, chelating agents, antioxidants, preservatives, or mixtures thereof.

[0125] Depending on the desired form, formulation, and / or end use, the compositions of the present disclosure may not include one or more of the following adjuvant materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / antiredeposition agents, optical brighteners, antifoaming agents, dyes, additional fragrances and fragrance delivery systems, structurants, fabric softeners, carriers, hydrotropes, processing aids, structuring agents, antiagglomerants, coatings, formaldehyde scavengers, and / or pigments.

[0126] The exact nature of these additional components and their levels of incorporation will depend on the physical form of the composition and the nature of the operations for which it is used. However, when one or more adjuvants are present, such one or more adjuvants may be present as detailed below. The following is a non-limiting list of suitable additional adjuvants.

[0127] A. Surfactant

[0128] The compositions of the present disclosure may include surfactants. For example, surfactants can be used to provide cleaning benefits. The composition may include a surfactant system, which may include one or more surfactants.

[0129] The compositions of the present disclosure may include from about 0.1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50% by weight of the composition of the surfactant system. Liquid compositions may include from about 5% to about 40% by weight of the composition of the surfactant system. Compact formulations, including compact liquids, gels, and / or compositions suitable for unit dosage forms, may include from about 25% to about 70% or from about 30% to about 50% by weight of the composition of the surfactant system.

[0130] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include linear alkylbenzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, nonionic surfactants such as ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactants may be at least partially derived from natural sources, such as natural raw material alcohols.

[0131] Suitable anionic surfactants can include any conventional anionic surfactant. This can include sulfate detergent surfactants (such as alkoxylated and / or non-alkoxylated alkyl sulfate materials) and / or sulfonate detergent surfactants (such as alkylbenzene sulfonates). The anionic surfactant can be straight-chain, branched-chain, or a combination thereof. Preferred surfactants include linear alkylbenzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched-chain modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactant can be present in acid form, salt form, or a mixture thereof. The anionic surfactant can be partially or fully neutralized with, for example, an alkali metal (such as sodium) or an amine (such as monoethanolamine). Due to the presence of cationic ester quaternary compound materials, it may be desirable to limit the amount of anionic surfactant to avoid undesirable interactions of the materials; for example, the composition can contain less than 5%, preferably less than 3%, more preferably less than 1%, and even more preferably less than 0.1% of anionic surfactant by weight of the composition.

[0132] The surfactant system can include nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (such as alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(alkoxylated) alcohol surfactants, and mixtures thereof. The alkoxide units can be ethyleneoxy units, propyleneoxy units, or a mixture thereof. The nonionic surfactant can be straight-chain, branched-chain (such as mid-chain branched), or a combination thereof. Specific nonionic surfactants can include alcohols having an average of about 12 to about 16 carbon atoms and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactant.

[0133] Suitable zwitterionic surfactants can include any conventional zwitterionic surfactant, such as betaines, including alkyl dimethyl betaines and coconut dimethylamidopropyl betaines, C8 to C 18 (e.g., C 12 to C 18 ) amine oxides (e.g., C 12-14 dimethylamine oxide), and / or sulfobetaines and hydroxybetaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonates, where the alkyl group can be C8 to C 18 or C 10 to C 14The zwitterionic surfactant may include amine oxide.

[0134] Depending on the formulation and / or intended end use, the composition may be substantially free of certain surfactants. For example, liquid fabric enhancer compositions, such as fabric softeners, may be substantially free of anionic surfactants because such surfactants can interact unfavorably with cationic components.

[0135] B. Conditioning active substance

[0136] The compositions of the present disclosure may contain conditioning actives. Compositions containing conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color and / or appearance benefits.

[0137] The conditioning actives may be present at a level of about 1% to about 99% by weight of the composition. The composition may contain about 1%, or about 2%, or about 3% to about 99%, or up to about 75%, or up to about 50%, or up to about 40%, or up to about 35%, or up to about 30%, or up to about 25%, or up to about 20%, or up to about 15%, or up to about 10% by weight of the composition of the conditioning actives. The composition may contain about 5% to about 30% by weight of the conditioning actives.

[0138] Conditioning actives suitable for the compositions of the present disclosure may include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes or combinations thereof. Preferably, the treatment composition is a fabric care composition, wherein one or more adjuvant components comprise a quaternary ammonium ester material; such materials are particularly useful in fabric enhancing / conditioning / softening compositions.

[0139] The composition may contain a quaternary ammonium ester compound, a silicone or a combination thereof, preferably a combination. The total amount of the combination of the quaternary ammonium ester compound and the silicone may be about 5% to about 70%, or about 6% to about 50%, or about 7% to about 40%, or about 10% to about 30%, or about 15% to about 25% by weight of the composition. The composition may contain the quaternary ammonium ester compound and the silicone in a weight ratio of 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.

[0140] The composition may contain a mixture of different types of conditioning actives. The compositions of the present disclosure may contain certain conditioning actives but be substantially free of other conditioning actives. For example, the composition may be free of quaternary ammonium ester compounds, silicones or both. The composition may contain a quaternary ammonium ester compound but be substantially free of silicones. The composition may contain silicones but be substantially free of quaternary ammonium ester compounds.

[0141] C. Deposition aid

[0142] The compositions of the present disclosure may include deposition aids. As described above, due to the synergistic beneficial effects from the ester quaternary ammonium compound materials and the delivery particles of the present disclosure, relatively little (or even no) deposition aid may be required to provide similar or even improved performance; alternatively, deposition aids may be used in the compositions of the present disclosure to further enhance performance.

[0143] Deposition aids may facilitate the deposition of delivery particles, conditioning actives, fragrances, or combinations thereof, thereby improving the performance benefits of the composition and / or allowing for more efficient formulation of such beneficial agents. The composition may include from 0.0001% to 3%, preferably from 0.0005% to 2%, more preferably from 0.001% to 1%, or about 0.01% to about 0.5%, or about 0.05% to about 0.3% by weight of the composition of the deposition aid. The deposition aid may be a cationic polymer or an amphoteric polymer, preferably a cationic polymer.

[0144] Generally speaking, cationic polymers and their manufacturing methods are known in the literature. Suitable cationic polymers may include quaternary ammonium polymers known as "polyquaternium" polymers, as designated by the International Nomenclature for Cosmetic Ingredients, such as polyquaternium-6 (poly(diallyldimethylammonium chloride)), polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), polyquaternium-10 (quaternized hydroxyethyl cellulose), polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride), etc.

[0145] The deposition aid may be selected from polyvinylformamide, partially hydroxylated polyvinylformamide, polyvinylamine, polyvinylimine, ethoxylated polyvinylimine, polyvinyl alcohol, polyacrylate, and combinations thereof. The cationic polymer may include cationic acrylate.

[0146] The deposition aid may be added simultaneously with the delivery particles (simultaneously with, for example, the encapsulated beneficial agent) or added directly / independently to the consumer product composition. As measured by size exclusion chromatography relative to a polyethylene oxide standard using refractive index (RI) detection, the weight average molecular weight of the polymer may be from 500 daltons to 5,000,000 daltons, or from 1,000 daltons to 2,000,000 daltons, or from 2,500 daltons to 1,500,000 daltons. The weight average molecular weight of the cationic polymer may be from 5,000 daltons to 37,500 daltons.

[0147] D. Rheology modifier / structurant

[0148] The compositions of the present disclosure may include rheology modifiers and / or structuring agents. Rheology modifiers can be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structuring agents can be used to promote phase stability and / or suspend or inhibit the aggregation of particles in a liquid composition, such as the delivery particles described herein.

[0149] Suitable rheology modifiers and / or structuring agents can include non-polymeric crystalline hydroxy-functionalized structuring agents (including those based on hydrogenated castor oil), polymeric structuring agents, cellulose fibers (e.g., microfibrillated cellulose, which can be derived from bacterial, fungal, or plant sources, including wood), diacylamino gelling agents, or combinations thereof.

[0150] Polymeric structuring agents can be of natural or synthetic origin. Natural origin polymeric structuring agents can include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives can include: pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structuring agents can include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated polyurethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers can include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates can include copolymers of unsaturated mono- or di-carboxylic acids with C1-C 30 alkyl esters of (meth)acrylic acid. Such copolymers are available from Noveon under the trade name Carbopol Aqua 30. Crosslinked polymers, such as crosslinked polyacrylates and / or polymers and / or copolymers, such as those further including nonionic monomers (such as acrylamide or methacrylamide monomers), can be used as structuring agents. Another suitable structuring agent is sold under the trade name Rheovis CDE and is available from BASF.

[0151] E. Other auxiliaries

[0152] The treatment compositions of the present disclosure may include other adjuvants suitable for inclusion in a product and / or suitable for end use. For example, the treatment compositions can include neat fragrances, fragrance delivery technologies (such as pre-fragrances and / or encapsulates having non-crosslinked biopolymer wall materials), cationic surfactants, cationic polymers, solvents, antifoaming agents, or combinations thereof.

[0153] Method for preparing treatment composition

[0154] The present disclosure also relates to methods for preparing treatment compositions, such as those treatment compositions and / or consumer product compositions described herein.

[0155] The method may include the following steps: providing a base composition, wherein the base composition comprises a processing aid; and combining a population of delivery particles with the base composition. The population of delivery particles may preferably be provided as an aqueous slurry. The base composition is in the form of a liquid composition.

[0156] When the delivery particles are in one or more forms (including slurry form, pure particle form, and / or spray-dried particle form), preferably slurry form, the delivery particles may be combined with one or more auxiliary components. The delivery particles may be combined with such auxiliary components by methods including mixing and / or spraying.

[0157] The treatment composition of the present disclosure can be formulated into any suitable form and prepared by any method selected by the formulator. One or more auxiliary components and delivery particles can be combined in a batch process, in a recycle loop process, and / or by an in-line mixing method. Suitable equipment for use in the methods disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recycle pumps, paddle mixers, high-shear mixers, static mixers, plow shear mixers, ribbon blenders, vertical axis granulators, and drum mixers (both of which may be in batch process configurations and continuous process configurations (when available)), spray dryers, and extruders.

[0158] The treatment composition can be placed in a container to form a consumer product as described herein. The container can be a bottle, preferably a plastic bottle. The treatment composition can be placed in an aerosol or other spray container according to known methods.

[0159] Treatment method

[0160] The present disclosure also relates to a method of treating a surface (preferably a fabric). Generally speaking, the method includes the step of contacting the surface (preferably a fabric) with a treatment composition according to the present disclosure, wherein the treatment composition comprises a population of delivery particles as described herein.

[0161] Additionally or alternatively, the method may include the step of contacting the surface (preferably a fabric) with a population of delivery particles as described herein. The population of delivery particles may be included in a treatment composition (preferably a fabric care composition) according to the present disclosure.

[0162] The method may include the step of contacting a fabric (such as a piece of clothing) with a treatment composition. The treatment composition comprises a population of delivery particles. The contacting step results in the deposition of one or more delivery particles on the surface of the fabric. The delivery particles include a core and a shell surrounding the core, wherein the core comprises a beneficial agent, preferably an aromatic material having one or more fragrance ingredients. The shell comprises a polymeric material, for example, which is a reaction product of chitosan of a specific molecular weight and a cross-linking agent. Suitable treatment compositions and delivery particles are described in more detail above.

[0163] The contacting step can occur during a manual laundering process, such as in a laundry basin when handling fabrics by hand, or during an automatic laundering process, such as in an automatic washing machine. The contacting step can occur during the wash cycle of an automatic washing machine; in such cases, the treatment composition can be a laundry detergent or a laundry washing additive. The contacting step can preferably occur during the rinse cycle of an automatic washing machine; in such cases, the treatment composition can be a fabric softener, preferably a liquid fabric softener. The contacting step can even occur during the drying step of the laundering process, such as in an automatic dryer; in such cases, the treatment composition can be in the form of a non-woven dryer sheet or a dryer bar. The contacting step can occur due to the direct application of the treatment composition onto the fabric, such as in a pre-treatment operation or in a "refreshing" step (e.g., for fabrics that have been used or worn since the last wash); in such cases, the treatment composition can be in the form of a liquid, bar, or spray, preferably a spray. Contacting the target fabric at a relatively late stage of the laundry process (e.g., during the rinse cycle) increases the likelihood or efficiency of deposition onto the fabric because they are less likely to be flushed down the drain.

[0164] The contacting step can be carried out in the presence of water. The treatment composition can be diluted with water to form a treatment liquid. The treatment composition can be diluted from about 100-fold to about 1500-fold, preferably from 300-fold to about 1000-fold.

[0165] The liquid containing the disclosed composition can have a pH of about 3 to about 11.5. Such compositions are typically used at a concentration of about 500 ppm to about 15,000 ppm in solution when diluted. When the washing solvent is water, the water temperature is generally in the range of about 5°C to about 90°C, and the ratio of water to fabric can generally be about 1:1 to about 30:1.

[0166] Dilution can occur in the drum of an automatic washing machine. The treatment composition can be placed in the dispenser drawer of an automatic washing machine. During the treatment process, the treatment composition can be dispensed from the dispenser drawer into the drum.

[0167] The present disclosure also relates to a method of treating a fabric in an automatic washing machine. Typical treatment methods in such machines include a washing cycle and one or more rinsing cycles, the washing cycle generally including relatively high shear agitation and the one or more rinsing cycles generally including relatively low shear agitation. In such cases, it may be preferred to treat the fabric with delivery particles designed to adequately deliver a beneficial agent under such conditions. For example, the method may include contacting the fabric with a population of delivery particles during the washing cycle, the population of delivery particles being characterized by a volume weighted extensibility energy of from about 4.5 to about 6.0, preferably from about 5.0 to about 5.5. The method may include contacting the fabric with a population of delivery particles during the rinsing cycle, the population of delivery particles being characterized by a volume weighted extensibility energy of 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.

[0168] The method may include contacting the fabric with a first population of delivery particles during the washing cycle and with a second population of delivery particles during the rinsing cycle, wherein the volume weighted extensibility energy of the first population is relatively greater than the volume weighted extensibility energy of the second population. The volume weighted extensibility 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 extensibility 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.

[0169] As described above, the method may further include a step of drying the fabric having one or more delivery particles on the surface of the fabric. The drying step may include a passive drying process, such as on a clothesline or drying rack. The drying step may include an automatic drying process, such as in an automatic dryer.

[0170] Combination

[0171] Specifically contemplated combinations of the present disclosure are described herein in the following lettered paragraphs. These combinations are exemplary in nature and not restrictive.

[0172] A. A treatment composition, the treatment composition comprising: a treatment aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, wherein the shell comprises a reaction product of a biopolymer and a crosslinking agent, and wherein the population of delivery particles is characterized by at least one, preferably at least two, of the following: (a) a volume weighted extensibility energy greater than about 3.5 based on compression of fifty randomly selected delivery particles 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 compression of fifty randomly selected delivery particles by a blunt probe moving at 2 μm / s;

[0173] (c) Based on the compression of fifty randomly selected delivery particles by a blunt probe moving at 2 μm / s, less than about 35% of said delivery particles, by number, are characterized as single rupture particles.

[0174] B. The treated composition according to paragraph A, wherein the population of delivery particles is 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

[0175] 6.0, more preferably about 4.0 to about 5.5, even more preferably about 4.5 to about 5.2, based on the compression of fifty randomly selected delivery particles by a blunt probe moving at 2 μm / s.

[0176] C. The treated composition according to any one of paragraphs A or B, wherein the population of delivery particles is characterized by at least about 50% of said delivery particles, by number, being characterized as fully ductile particles, based on the compression of fifty randomly selected delivery particles by a blunt probe moving at 2 μm / s.

[0177] D. The treated composition according to any one of paragraphs A to C, wherein the population of delivery particles is characterized by less than 25% of said delivery particles, by number, being characterized as single rupture particles, based on the compression of fifty randomly selected delivery

[0178] delivery particles by a blunt probe moving at 2 μm / s. E. The treated composition according to any one of paragraphs A to D, wherein the biopolymer

[0179] is selected from the group consisting of polysaccharides, proteins, nucleic acids, polyphenolic compounds, their derivatives, and combinations thereof.

[0180] F. The treated composition according to any one of paragraphs A to 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, gums, pectin, fructan, carrageenan, agar, pullulan, suberin, cutin, cuticle, melanin, fibroin, gelatin, collagen, casein, sericin, fibroin, whey protein, zein, soy protein, vegetative storage protein, gluten, peptides, actin, polynucleotides, RNA, DNA, tannins, lignans, their derivatives, and combinations thereof.

[0181] G. The treated composition according to any one of paragraphs A to F, wherein the biopolymer is chitosan, its derivatives, or combinations thereof, preferably wherein the biopolymer is acid-treated chitosan, redox initiator-treated chitosan, their derivatives, or combinations thereof.

[0182] H. A treating composition according to any one of paragraphs A to G, wherein the biopolymer is characterized by a molecular weight of from about 1 kDa to about 1000 kDa, preferably from about 50 kDa to about 600 kDa, more preferably from about 100 kDa to about 500 kDa, even more preferably from about 100 kDa to about 300 kDa, and even more preferably from about 100 kDa to about 200 kDa.

[0183] I. A treating composition according to any one of paragraphs A to H, wherein the crosslinking agent is a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxides, polyphenols, carbonyl halides, aziridines, and combinations thereof, preferably polyisocyanates, epoxides, bifunctional aldehydes, and combinations thereof, more preferably polyisocyanates, and even more preferably polyisocyanates selected from the group consisting of polyisocyanurates of toluene diisocyanate; trimethylolpropane adducts of toluene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4′-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethylxylylene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (such as their prepolymers, oligomers, and / or polymers); and combinations thereof.

[0184] J. A treating composition according to any one of paragraphs A to I, wherein the reaction product is formed in a reaction in which the biopolymer is initially present in an aqueous phase and the crosslinking agent is initially present in an oil phase, wherein the crosslinking agent is present in the oil phase at a level 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 wherein the biopolymer and the crosslinking agent are present in the reaction at a weight ratio of from about 1:10 to about 1:0.1.

[0185] K. A treating composition according to any one of paragraphs A to J, wherein the beneficial agent is an aromatic material.

[0186] L. A treating composition according to any one of paragraphs A to K, wherein the core further comprises a dispensing modifier, which is preferably present at a level 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, and preferably wherein the dispensing modifier is selected from the group consisting of vegetable oils, modified vegetable oils, C4-C 24Mono-esters, di-esters and tri-esters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate and mixtures thereof, more preferably isopropyl myristate.

[0187] M. A treatment composition according to any one of paragraphs A to L, wherein the population of delivery particles is prepared by a method comprising at least one grinding step, wherein the at least one grinding 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, even more preferably from about 25 °C to about 35 °C.

[0188] N. A treatment composition according to any one of paragraphs A to M, wherein the delivery particles are characterized by a volume-weighted median particle size of from about 1 micron to about 100 microns, preferably from about 10 microns to about 100 microns, preferably from about 15 microns to about 50 microns, more preferably from about 20 microns to about 40 microns, even more preferably from about 25 microns to about 35 microns.

[0189] O. A treatment composition according to any one of paragraphs A to N, wherein when tested according to test method OECD 301B, the shell of the delivery particles degrades by at least 60% after 60 days.

[0190] P. A treatment composition according to any one of paragraphs A to O, wherein the treatment aid is selected from the group consisting of: surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / anti-redeposition agents, optical brighteners, antifoaming agents, silicones, colorants, aesthetic dyes, perfume bases, additional perfume delivery systems, structuring elastifiers, carriers, hydrotropes, processing aids, anti-agglomerants, coatings, formaldehyde scavengers, pigments and mixtures thereof.

[0191] Q. A treatment composition according to any one of paragraphs A to P, wherein the treatment aid comprises an anionic surfactant, a cationic conditioner or a mixture thereof.

[0192] R. A treatment composition according to any one of paragraphs A to 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 fabric care composition as a laundry detergent composition, a fabric conditioner composition, a laundry additive, a fabric pretreatment composition, a fabric refresher composition or a mixture thereof.

[0193] S. A treatment composition according to any one of paragraphs A to R, wherein the treatment composition is in the form of a liquid composition, a particulate composition, an aqueous colloid, a single-compartment sachet, a multi-compartment sachet, a soluble sheet, a lozenge or bead, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a non-woven sheet, or a mixture thereof, preferably in the form of a liquid composition.

[0194] T. A treatment composition according to any one of paragraphs A to S, wherein the treatment composition comprises from about 50% to about 99% by weight of the treatment composition of water, preferably from about 60% to about 98% by weight of the treatment composition of water, more preferably from about 80% to about 96% by weight of the treatment composition of water.

[0195] U. A method of preparing a treatment composition according to any one of paragraphs A to T, the method comprising the steps of: providing a base composition, wherein the base composition comprises the treatment aid; and combining the delivery particle population with the base composition.

[0196] V. The method according to paragraph U, wherein the delivery particle population is provided as an aqueous slurry.

[0197] W. The method according to any one of paragraphs U or V, wherein the base composition is in the form of a liquid composition.

[0198] X. A method of treating a surface, the method comprising the step of: contacting the surface, preferably a fabric, with a treatment composition according to any one of paragraphs A to T.

[0199] Y. A method of treating a fabric in an automatic washing machine, the method comprising the steps of: contacting the fabric with a first delivery particle population during a wash cycle and with a second delivery particle population during a rinse cycle, wherein the volume-weighted extensional energy of the first population is relatively greater than the volume-weighted extensional energy of the second population, preferably wherein the volume-weighted extensional 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 wherein the volume-weighted extensional 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.

[0200] Test method

[0201] It should be understood that the test methods disclosed in the test methods section of this application should be used to determine the corresponding parameter values of the subject matter claimed by the applicant as claimed and described herein.

[0202] Mechanical properties of delivery particles

[0203] Determine the mechanical properties of the core:shell delivery particles as described herein according to the following method.

[0204] The general technique is a well-known method that has been defined in the literature of 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 measurement results obtained by this method, many useful properties can be observed and described, as provided in more detail below.

[0205] 1. Extraction of particles

[0206] When the delivery particle population is provided as part of a finished composition, the particles need to be extracted for the analysis described herein.

[0207] Unless otherwise specified herein, the preferred method for separating the delivery particles from the finished product is based on the fact that the density of most such delivery particles is different from that of water. Mix the finished product with water to dilute and / or release the delivery particles. Centrifuge the diluted product suspension to accelerate the separation of the delivery particles. Such delivery particles tend to float or sink in the diluted solution / dispersion of the finished product. Using a pipette or spatula, remove the top and bottom layers of the suspension, and undergo additional dilution and centrifugation cycles to separate, clean, and / or enrich the delivery particles. Observe the delivery particles using an optical microscope equipped with a cross-polarized filter or differential interference contrast (DIC), for example, at a total magnification of 10x and 40x. Microscopic observation provides an initial indication of the presence, size, quality, and aggregation of the delivery particles.

[0208] To extract the delivery particles from a liquid fabric enhancer, the finished product undergoes the following procedures:

[0209] 1. Place three aliquots of approximately 20 ml of the liquid fabric enhancer into three separate 50 ml centrifuge tubes, and dilute each aliquot 1:1 with deionized water (e.g., 20 ml of fabric enhancer + 20 ml of deionized water), mix each aliquot well, and centrifuge each aliquot at approximately 10000×g for 30 minutes.

[0210] 2. After centrifugation according to step 1, discard the bottom water layer (about 10 ml) in each 50 ml centrifuge tube, and then add 10 ml of deionized water to each 50 ml centrifuge tube.

[0211] 3. For each aliquot, repeat the process of centrifuging, removing the bottom aqueous layer, and then adding 10 ml of deionized water to each 50 ml centrifuge tube two more times.

[0212] 4. Remove the top layer with a spatula or pipette, and

[0213] 5. Transfer the top layer to a 1.8 ml centrifuge tube and centrifuge at approximately 20,000 × g for 5 minutes.

[0214] 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 full, then centrifuge at approximately 20,000 x g for 5 minutes.

[0215] 7. Remove the bottom layer with a fine pipette, add deionized water until the tube is completely full, and centrifuge at approximately 20,000 × g for 5 minutes.

[0216] 8. Repeat step 7 five more times (for a total of six times).

[0217] If both a top layer and a bottom layer enriched in delivery particles appear in step 1 above, immediately proceed to step 3 (i.e., skip step 2) and continue with steps 4 through 8. Once those steps are complete, additionally use a spatula or / and pipette to remove the bottom layer from the 50 ml centrifuge tube of step 1. Transfer the bottom layer to a 1.8 ml centrifuge tube and centrifuge at approximately 20,000 × g for 5 minutes. Remove the bottom layer from the new tube and add deionized water until the tube is completely full, then centrifuge at approximately 20,000 × g for 5 minutes. Remove the top layer (water) and add deionized water again until the tube is full. Repeat this five more times (for a total of six times). Recombine the enriched delivery particles with the separated top and bottom layers.

[0218] If the fabric enhancer has a white color or it is difficult to distinguish the layer enriched in delivery particles, add 4 drops of dye (such as Liquitint Blue JH 5% premix from Milliken & Company (Spartanburg, South Carolina, USA)) to the centrifuge tube of step 1 and perform the separation as described above.

[0219] For extracting delivery particles from solid finished products that are easily dispersible in water, 1 L of deionized water is combined with 20 g of the finished product (e.g., detergent foam, film, gel, and particles; or water-soluble polymers; soap flakes and bars; and other water-soluble matrices such as salts, sugars, clays, and starches). When extracting delivery particles from finished products that are not easily dispersible in water such as waxes, dryer sheets, dryer bars, and greasy materials, it may be necessary to add detergent, stir and / or gently heat the product, and dilute it in order to release the delivery particles from the matrix. The use of organic solvents or drying of the delivery particles should be avoided during the extraction step as these actions can damage the delivery particles during this stage.

[0220] To extract delivery particles from liquid finished products that are not fabric softeners or fabric enhancers (e.g., liquid laundry detergents, liquid dish detergents, liquid hand soaps, lotions, shampoos, conditioners, and hair dyes), 20 ml of the finished product is mixed with 20 ml of deionized water. If desired, NaCl (e.g., 1 g to 4 g of NaCl) can be added to the diluted suspension to increase the density of the solution and facilitate the floating of the delivery particles to the top layer. If the product has a white color that makes it difficult to distinguish the layer of delivery particles formed during centrifugation, a water-soluble dye can be added to the diluent to provide visual contrast.

[0221] The water and product mixture is subjected to successive centrifugation cycles involving removal of the top and bottom layers, resuspending those layers in fresh diluent, and then further centrifuging, separating, and resuspending. Each centrifugation cycle occurs in a tube with a volume of 1.5 ml to 50 ml, using a centrifugal force of up to 20,000×g for a period of 5 minutes to 30 minutes. Typically, at least six centrifugation cycles are required to extract and clean sufficient delivery particles for testing. For example, the initial centrifugation cycle can be performed in a 50 ml tube, spinning at 10,000×g for 30 minutes, followed by five additional centrifugation cycles where the material from the top and bottom layers is separately resuspended in fresh diluent in 1.8 ml tubes and each cycle is spun at 20,000×g for 5 minutes.

[0222] If delivery particles are microscopically observed in both the top and bottom layers, the delivery particles from these two layers are recombined after the final centrifugation step to form a single sample containing all of the delivery particles extracted from the product. The extracted delivery particles should be analyzed as soon as possible, but they can be stored in the form of a suspension in deionized water for up to 14 days before analysis.

[0223] Those skilled in the art will recognize that various other protocols can be designed for extracting and separating delivery particles from finished products and will recognize that such methods need to be confirmed by comparing the resulting measurements taken before and after adding the delivery particles to the finished product and extracting the delivery particles from the finished product.

[0224] 1. Preparation of particles for measuring mechanical properties

[0225] Dilute 10 μl of the capsule population, usually in the form of a slurry, in 1.5 ml of distilled water. To ensure that the sample is homogeneous, mix the sample for a few seconds. Once mixed / homogeneous, spread 5 μl of the diluted capsule population on the glass microslide of the nanoindenter.

[0226] 3. Method for measuring mechanical properties

[0227] Measurements were carried out using a nanoindenter (purchased from KLA, United States) equipped with a flat-ended probe with a Poisson's ratio of 0.07, a modulus of 1140 GPa and a diameter of 100 μm. The frame stiffness was equal to 8.8*10 5 N / m. The probe speed was set to 2 μm / s.

[0228] For a given population of delivery particles, 50 capsules were randomly selected from the population and various properties of each capsule were measured, as described in more detail below. Briefly, the diameter of each particle was measured and then each particle was compressed with the probe of the nanoindenter. The measurement results, such as compression speed, compression depth and associated load, were recorded.

[0229] Based on the measurement results, the diameter and rupture speed of individual capsules can be determined, as described below.

[0230] A. Determination of individual particle size

[0231] For the purposes of the measurements described in this section, the diameter of an individual delivery particle is defined as the height of the capsule, which is measured along the vertical axis perpendicular to the microslide or substrate on which the population of delivery particles is placed.

[0232] Figure 1 The basic setup for measuring the diameter of a delivery particle (or capsule, as used herein) is shown. 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 nanoindenter. The arrow indicates the compression direction 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 at a position 150 μm to the right and 150 μm down from the center of the delivery particle 1 relative to the microslide. Typically, the diameter is reported in micrometers.

[0233] The diameter can be calculated by the following formula.

[0234] Diameter = height of the top surface of the capsule - height of the substrate

[0235] B. Determination of rupture speed

[0236] For each delivery particle, the rupture velocity (if any) is determined. Based on the rupture velocity (if any) measured during the capsule compression test, the particles are classified into one of three categories, as described in more detail below.

[0237] As described above, for each capsule measured, the compression speed of the probe was set to 2 μm / s. As the capsule was compressed, the speed, depth, and load of the probe were recorded.

[0238] Based on the measurements, a velocity-depth curve and a load-depth curve can be created. Figure 2 shows such curves for exemplary ruptured particles. The curve Figure 2A shows the velocity-depth curve 100, while the curve Figure 2B shows how the load (measured in mN) changes with depth throughout the measurement, presented as the load-depth curve 102. For each, the depth corresponds to the amount the probe travels throughout the compression.

[0239] As shown in the curve Figure 2A the compression speed can vary by approximately 50 nm / s throughout the measurement due to changes in the mechanical resistance exerted by the capsule on the probe. At the zero-depth point, the probe contacts the capsule; this point on the curve is identified by the triangle 104.

[0240] As shown in the curve Figure 2B for the exemplary capsule, the load increases until the rupture point of the capsule, which is characterized by the maximum load; this point on the curve is identified by the square in the curve Figure 2B The parallel point on the velocity-depth curve of the curve Figure 2A is also identified by the square ("rupture point").

[0241] After the rupture point, the compression speed suddenly increases because the capsule no longer exerts significant resistance to the probe compression. After the rupture point of the capsule, the point of maximum probe speed can be identified; this point on the curve is represented by the circle 108 in the curve Figure 2A As used herein, the rupture velocity is defined as the velocity difference between the maximum probe velocity (after rupture) and the probe velocity at the rupture point (which is related to the probe depth at the point where the maximum load is observed). The equation for calculating the rupture velocity is reported in Equation (1.1).

[0242] Rupture velocity = maximum probe velocity - probe velocity at rupture point (1.1)

[0243]

[0244] For the curve Figure 2A ​In the exemplary capsules, it can be seen that the rupture speed has a value of about 5 μm / s in terms of the maximum probe speed (represented by the circle).

[0245] 4. Determination of volume-weighted ductility energy and ratio of ductile capsules

[0246] To determine the volume-weighted ductile energy of the delivery particle population, 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 speed (if any), each individual capsule is classified into one of three categories (ductile, single rupture, or multiple ruptures), as described below. The measured ductile energy of an individual capsule is determined using the area under the load-versus-depth curve. Based on these measurements, the volume-weighted ductile energy of the delivery particle population is determined. In addition, the relative proportion of particles that are ductile or exhibit "single rupture" behavior can be determined from this data.

[0247] A. Classification of individual capsules

[0248] Based on the rupture speed and the number of maximum peaks on the load-depth curve, each individual capsule is classified according to its behavior into the following three categories: fully ductile behavior; single rupture behavior; or multiple rupture behavior.

[0249] i. Definition of fully ductile capsules

[0250] A "fully ductile" capsule, as defined herein, is characterized in that when compressed by a blunt probe moving at 2 μm / s, the difference between the maximum probe speed and the standard probe speed does not exceed 200 nm, and thus the rupture speed cannot be defined.

[0251] Figure 3 shows the compression curve of a fully ductile particle. As can be seen in the velocity-depth curve 110 of the curve Figure 3A throughout the measurement, the compression speed does not exceed the standard compression speed of 2 μm / s. Additionally, no drop or peak maximum of the load is observed in the load-depth curve 112 of the curve Figure 3B Based on the curves 110 and 112 of the curve

[0252] Based on curves Figure 3A and 3B 110, 112, the particle does not show any rupture points; for example, the compression speed does not increase relatively, and there is no drop in the load, and no maximum peak is generated. Therefore, the particle is defined as fully ductile.

[0253] At the zero-depth point, the probe contacts the particle; this point on curves 110, 112 is identified by triangle 114. During the last part of the measurement at a probe depth of approximately 6500 nm, it can be noted that when the entire diameter of the capsule is compressed and pressure is applied by the tip towards the substrate on which the capsule lies, the compression speed approaches 0 nm / s. CurveFigure 3B The diamond 116 in [description] indicates the point where the probe contacts the substrate, which is associated with an exponential increase in load given that the substrate is a highly rigid material such as a glass microcarrier.

[0254] ii. Definition of single-rupture capsules

[0255] A "single rupture" capsule as defined herein is characterized by exhibiting a single capsule rupture point. A "single rupture" capsule is characterized in that when compressed by a blunt probe moving at 2 μm / s, the rupture speed exceeds 200 nm once.

[0256] Figure 4 shows the compression curve of a single rupture particle. At the zero depth point, the probe contacts the particle; this point on curves 120, 122 is identified by triangle 124. In the Figure 4A velocity-depth curve 120 of the curve, it can be seen that after the rupture point is detected, the compression speed exceeds 2 μm / s; the rupture point is indicated by the square 126 in the curve Figure 4A and 4B . Then, the maximum speed of the probe is identified by the circle 128 in the curve Figure 4A . As shown in the curve Figure 4B , the load-depth curve 122 is characterized by a single maximum peak (shown at square 126), indicating that the particle exhibits single rupture behavior.

[0257] iii. Definition of multi-rupture capsules

[0258] A "multiple rupture" capsule is characterized by exhibiting multiple capsule rupture points when compressed by a blunt probe moving at 2 μm / s. A "multiple rupture" capsule is characterized in that when compressed by a blunt probe moving at 2 μm / s, the rupture speed exceeds 200 nm multiple times. Typically, a multiple rupture capsule is characterized by two or three rupture points, although more rupture points are possible.

[0259] Figure 5 shows the compression curve of a multiple rupture particle. At the zero depth point, the probe contacts the particle; this point on curves 130, 132 is identified by triangle 134. As can be seen in the Figure 5A velocity-depth curve 130 of the curve and the Figure 5B load-depth curve 132 of the curve, there are multiple rupture points. More precisely, these curves indicate three rupture points associated with three maximum peaks (squares 136a, 136b, 136c) of the maximum load and three relative increases in the compression speed; the maximum probe speeds are indicated by circles 138a, 138b, 138c.

[0260] B. Determination of category ratio

[0261] Based on the number of capsules assigned to each category, the population can be characterized by the relative amount of capsules in any given category.

[0262] For example, the population can be described by the proportion and / or percentage of fully ductile capsules (e.g., the number of capsules classified as fully ductile divided by the total number of capsules measured [i.e., 50]).

[0263] The population can be described by the proportion and / or percentage of capsules exhibiting single rupture behavior (e.g., the number of capsules classified as single rupture capsules divided by the total number of capsules measured [i.e., 50]).

[0264] The population can be described by the proportion and / or percentage of capsules exhibiting multiple rupture behavior (e.g., the number of capsules classified as multiple rupture capsules divided by the total number of capsules measured [i.e., 50]).

[0265] C. Calculation of ductility energy of capsules by category

[0266] To calculate the ductility energy of the individually measured delivery particles in the population, the area under certain points on the load-depth curve of the capsule is determined. This area is calculated according to the following formulas 1.2 to 1.4 and can be automatically calculated by any suitable program, such as by exporting the data points to MICROSOFT and using the program to determine the area under the relevant points.

[0267] i. Ductility energy of fully ductile capsules

[0268] For fully ductile capsules, the ductility energy is calculated as the area under the load-depth curve from the point where the probe contacts the capsule surface to the point where the probe contacts the substrate.

[0269] Figure 6 The load-depth curve 140 of an exemplary fully ductile particle is shown. The point where the probe contacts the capsule surface is represented as a triangle 142 in Figure 6 The point where the probe contacts the substrate is represented as a rhombus 144 in Figure 6 The area under the relevant part of the curve is represented by the shaded region 146 in Figure 6 This area is calculated by integrating the product of the load and the depth differential over the interval from the capsule surface to the substrate point, as shown in formula (1.2).

[0270] where the depth

[0271]

[0272] is the depth value when the capsule is contacted by the probe (triangle 142 in 表面 ), and the depth Figure 6 while the depth 基底is the depth value when the base is contacted ( Figure 6 the diamond 144 in), and F is the load measured by the probe during compression.

[0273] ii. Ductility energy of single-rupture capsules

[0274] For a single - rupture capsule, the ductility energy is calculated as the area under the load - depth curve from the point where the capsule surface is contacted by the probe to the (first and only) rupture point of the capsule.

[0275] Figure 7 shows the load - depth 150 curve of an exemplary single - rupture particle. The point where the capsule surface is contacted by the probe is at Figure 7 represented as triangle 152 in. The point where the capsule ruptures is at Figure 7 represented as square 154 in. The area under the relevant part of curve 150 is represented by Figure 7 the shaded region 156 in.

[0276] This area is calculated by integrating the product of the load and the depth differential over the interval from the capsule surface to the rupture point, as shown in formula (1.3).

[0277]

[0278] where the depth 表面 is the depth value when the capsule is contacted by the probe ( Figure 7 the triangle 152 in), and the depth 破裂 is the depth value at the rupture point ( Figure 7 the square 154 in).

[0279] iii. Ductility energy of multi-rupture capsules

[0280] For a multi - rupture capsule, the ductility energy is calculated as the area under the load - depth curve from the point where the capsule surface is contacted by the probe to the last rupture point the capsule experiences.

[0281] Figure 8 shows the load - depth curve 160 of an exemplary multi - rupture particle. The point where the capsule surface is contacted by the probe is at Figure 8 represented as triangle 162 in. The three points where the capsule ruptures are at Figure 8 represented as three squares 164a, 164b, 164c in; the third and last rupture point 164c occurs at a probe depth of approximately 8000 nm. The area under the relevant part of curve 160 is represented by Figure 8 the shaded region 166 in.

[0282] This area is calculated by integrating the product of the load and the depth differential over the interval from the capsule surface to the last rupture point, as shown in formula (1.4).

[0283]

[0284] where Disp 表面 is the depth value when the capsule is contacted by the probe ( Figure 8 triangle 162 in 最后破裂 ), and Disp Figure 8 is the depth value at the last rupture point experienced by the capsule (

[0285] D. Calculation of volume-weighted ductility energy

[0286] Using the diameter and ductility energy values calculated for individual particles, the volume-weighted ductility energy of the delivery particle population is determined after logarithmic transformation and rescaling of the ductility energy values.

[0287] i. Logarithmic transformation

[0288] Figure 9 Shows the distribution 170 of the measured ductility energy values (in joules) of an exemplary delivery particle population. As Figure 9 seen, the distribution of the measured ductility energy data does not follow a normal distribution. To remove the skewness of the data, a logarithmic transformation is performed. The distribution 172 of the resulting log(ductility energy) values is shown in Figure 10 .

[0289] ii. Rescaling

[0290] To ensure that the data points are non-negative for modeling purposes, the Log(ductility energy) values are rescaled and transformed into rescaled Log(ductility energy) values by adding a ductility energy rescaling factor to each data point, as shown in Equation 1.5. The ductility energy rescaling factor is equal to the negative logarithm of the minimum measured ductility energy. In the exemplary sample, this corresponds to 13, which is related to the minimum measurable ductility energy of 10 -13 J. The resulting distribution 174 of the rescaled Log(ductility energy) values is shown in Figure 11 .

[0291] Rescaled Log(ductility energy) = log(ductility energy) + 13 (1.5)

[0292] iii. Prediction of rescaled logarithmic ductility energy by diameter

[0293] For the entire capsule population analyzed, predictions of the rescaled Log(ductility energy) data based on diameter are obtained in order to extrapolate the volume-weighted ductility energy of the capsules.

[0294] In this calculation, for the following formula, the rescaled Log(elongation energy) data will be defined as the response variable (y), and the diameter will be defined as the regression variable (x).

[0295] The predictive formula for the rescaled Log(elongation energy) is shown in Equation (1.6). In Figure 12 the regression line 176 is represented as a function of the rescaled Log(elongation energy) experimental data.

[0296]

[0297] The coefficients and

[0298]

[0299]

[0300] where SS xx and SS x y are defined based on Equations (1.9) and (1.10) respectively:[[]]END]]

[0301]

[0302]

[0303] where is the average of all x values (where the x values are the capsule diameter values), is the average of all y values (where the y values are the rescaled Log(elongation energy) values of the single capsule elongation energy), and n is the number of capsules measured in the dataset.

[0304] iv. Volume fraction

[0305] The volume fraction (φ i)。The instrument is configured with the following conditions and selections: flow rate = 1 mL / sec; lower size threshold = 0.50 μm; sensor model = LE400-05SE or equivalent; auto-dilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 ml; maximum coincidence = 9200. Measurement is started by flushing the sensor with water until the background count is less than 100 to bring it to a cold state. A sample in suspension of the delivery capsule is introduced and the density of the capsule is adjusted with DI water by auto-dilution as needed to obtain a capsule count of at most 9200 capsules / mL. The suspension is analyzed over a 60-second period. The size range used is from 1 μm to 493.3 μm.

[0306] Volume distribution :

[0307]

[0308] Where:

[0309] CoV v = coefficient of variation of the volume-weighted size distribution

[0310] σ v = standard deviation of the volume-weighted size distribution

[0311] μ v = mean of the volume-weighted size distribution

[0312] d i = diameter in fraction i

[0313] x i,v = frequency in fraction i (corresponding to diameter i) of the volume-weighted size distribution

[0314]

[0315] In Figure 13 the volume fraction is plotted as a function of the particle size of an exemplary population, resulting in distribution 178.

[0316] v. Volume-weighted ductility energy

[0317] Finally, the volume-weighted elongation energy is determined as the sum of the values provided by the rescaled Log(elongation energy) predictions provided at each diameter i weighted by the corresponding volume fraction φ i as shown in equation (1.11):

[0318]

[0319] where d min equals 1 μm, and d max equals 493 μm.

[0320] Determination of polymer molecular weight and related parameters

[0321] The method described below for gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) is used to find the molecular weight distribution measurements and related values of the polymers described herein.

[0322] Gel permeation chromatography (GPC) with multi-angle light scattering (MALS) and refractive index (RI) detection (GPC-MALS / RI) allows the measurement of the absolute molecular weight of polymers without the need for column calibration methods or standards. The GPC system allows molecules to be separated according to their molecular size. MALS and RI allow the obtainment of information on the number-average (Mn) and weight-average (Mw) molecular weights.

[0323] The Mw distribution of water-soluble polymers such as chitosan is typically measured using a liquid chromatography system (e.g., an Agilent 1260 Infinity pump system with OpenLab Chemstation software, Agilent Technology, Santa Clara, CA, USA) and a column set operating at 40 °C (e.g., 2 Tosoh TSKgel G6000WP 7.8×300 mm 13 um pore size, guard column A0022 6 mmx40 mm PW xl-cp, King of Prussia, PA). The mobile phase is an aqueous solution of 0.1 M sodium nitrate containing 0.02% sodium azide and 0.2% acetic acid. The mobile phase solvent is pumped isocratically at a flow rate of 1 mL / min. Using a multi-angle light scattering (18-Angle MALS) detector controlled by Wyatt software v8.0 and a differential refractive index (RI) detector (Wyatt Technology, Santa Barbara, California, USA).

[0324] Typically, a sample is prepared by dissolving the chitosan material at about 1 mg / ml in the mobile phase and hydrating the solution by mixing overnight at room temperature. Before GPC analysis, the sample is filtered through a 0.8 μm Versapor membrane filter (PALL, Life Sciences, NY, USA) into an LC autosampler vial using a 3 ml syringe.

[0325] The number-average molecular weight (Mn), weight-average molecular weight (Mw), z-average molecular weight (Mz), molecular weight at the peak maximum (Mp), and polydispersity (Mw / Mn) are determined using the dn / dc value (differential change of refractive index with concentration, 0.15) by the Astra detector software.

[0326] Viscosity

[0327] The viscosity of the liquid finished product was measured using an AR 550 rheometer / viscometer from TA Instruments (New Castle, DE, USA) with parallel steel plates having a diameter of 40 mm and a gap size of 500 μm. The high-shear viscosity at 20 s -1 and the low-shear viscosity at 0.05 s -1 were obtained from a logarithmic shear rate sweep from 0.01 s -1 to 25 s -1 over a 3-minute period at 21 °C.

[0328] Test method for determining logP

[0329] The logarithm of the octanol / water partition coefficient (logP) was calculated for each material tested (e.g., each PRM in the flavor mixture). The logP of individual materials (e.g., PRM) was calculated using the Consensus logP Computational Model version 14.02 (Linux) purchased from Advanced Chemistry Development Inc. (ACD / Labs) (Toronto, Canada) to provide a dimensionless logP value. The Consensus logP Computational Model from ACD / Labs is part of the ACD / Labs model suite.

[0330] Volume-weighted particle size and size distribution

[0331] Determine the volume-weighted particle size distribution by single particle optical sensing (SPOS) (also known as optical particle counting (OPC)) using an AccuSizer 780AD instrument and the accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, U.S.A.) or equivalent. The instrument is configured with the following conditions and selections: flow rate = 1 ml / sec; lower size threshold = 0.50 μm; sensor model = LE400-05 or equivalent; auto dilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 ml; maximum coincidence = 9200. Start the measurement by flushing the sensor with water until the background count is less than 100 to bring it to a cold state. Introduce the sample in suspension from the delivery capsule and adjust the density of the capsule with DI water by auto dilution as needed to obtain a capsule count of at least 9200 / ml. Analyze the suspension over a 60-second period. Plot and record the resulting volume-weighted PSD data and determine the desired volume-weighted particle size values (e.g., mean, median / 50th percentile, 5th percentile, and / or 90th percentile).

[0332] Procedure for determining % degradation

[0333] To determine % degradation, use the procedure described in the "OECD Guideline for Testing of Chemicals" 301B CO2 Evolution (Modified Sturm Test) adopted on July 17, 1992. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0334] Fabric treatment

[0335] Use a Miele washing machine to process the fabric. For each treatment, the washing machine loads 3 kg of fabric, which consists of 1100 g of knitted cotton fabric and 1100 g of polyester cotton fabric (50 / 50). Also add 18 thick terrycloth cotton tracers, with a total weight of approximately 780 g. Before this treatment, pre-treat the load twice with 79 g of IEC A basic detergent using a short cotton cycle at 95 °C, and then perform two additional washes at 95 °C without detergent. The basic detergent is fragrance-free and supplied by WFK Testgewebe GmbH.

[0336] Before the test treatment, the load was pre-treated twice, each time using a 95 °C short cotton cycle with 79 g of unperfumed IEC A basic detergent (purchased from WFK Testgewebe GmbH), followed by two additional 95 °C washes without detergent.

[0337] For the test treatment, a short cotton cycle at 40 °C, a spin speed of 1200 rpm and 79 g of IEC A basic detergent were used to wash the load, which was added to a suitable dispenser at the start of the wash cycle. A 35 g dose of the test fabric treatment composition (e.g., according to the examples) was added to a suitable dispenser. At the end of the wash cycle, the terry cloth towel tracer was removed from the washing machine and air-dried overnight. The next day, a professional perfumer performed an olfactory assessment of the fragrance intensity of the dried terry cloth towel tracer. For comparison purposes, a reference treatment was also carried out, in which the same fragrance as in the test samples was used, but polyacrylate capsules were used as delivery particles. All comparative treatments were washed and analyzed on the same day.

[0338] Olfactory evaluation method

[0339] After the fabric had been treated, a professional perfumer performed an olfactory assessment of the fragrance intensity of the dried fabric at the DRY contact point (dried fabric odor = DFO) and at the RUB contact point (rubbed fabric odor = RFO); the fabric was dried for one day, the DFO was smelled, then the fabric was manually manipulated to rub against itself, and the RFO was smelled again), and the scores were averaged. The scores were based on a fragrance odor intensity scale from 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. "ΔRFO" could be reported, which is the difference between RFO and DFO.

[0340] Method for determining headspace concentration above treated dry fabric

[0341] The cotton tracer was analyzed by the rapid headspace GC / MS (gas chromatography - mass spectrometry) method. A 4×4 cm aliquot of the terry cloth towel cotton tracer was transferred to a 25 mL headspace vial. The fabric sample was equilibrated at 65 °C for 10 minutes. The headspace above the fabric was sampled for 5 minutes via the SPME (50 / 30 μm DVB / Carboxen / PDMS) method. Subsequently, the SPME fiber was thermally desorbed immediately into the GC. The analytes were analyzed by rapid GC / MS in full scan mode. The total HS response and the fragrance headspace composition above the test leg were calculated using ion extraction of specific masses with PRM.

[0342] In addition to the test capsules, a similar method can be used to determine parallel headspace data, but using reference capsules, such as polyacrylate wall ("PAC") capsules outside the scope of the present disclosure, such as delivery particles prepared substantially according to the method described in U.S. Publication 2011 / 0268802. The data obtained from the reference capsules can be used as a comparison of the results of the capsules of the present invention. This can be reported as a ratio (e.g., the ratio of the results of the particles of the present invention to the results of the reference capsules).

[0343] In the following examples, the data results of different tests can be reported as "RFO headspace [normalized]", which is the ratio of the headspace result of the test (e.g., total HS response) to the headspace result of Test 1 of that test. Thus, Test 1 is "normalized" to 1.0, and other results are reported relative to this normalized level. Test 1 is used as the baseline below because, for example, it employs the lowest levels of each influencing factor of the particle preparation process (e.g., IPM%, crosslinker% in the oil phase, etc.).

[0344] Examples

[0345] The examples provided below are intended to be illustrative in nature and not limiting.

[0346] Example 1. Illustrative delivery particle synthesis

[0347] In the following examples, the abbreviations correspond to the materials listed in Table 1.

[0348] Table 1.

[0349]

[0350] 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. Then, 154.90 g of chitosan ChitoClear was dispersed into the potassium persulfate solution while mixing in a jacketed reactor. Then, the pH of the chitosan dispersion was adjusted to 5.10 using 51.72 g of concentrated HCl with stirring. Then, the temperature of the chitosan solution was raised to 85 °C over 60 minutes and then held at 85 °C for a period of time to hydrolyze and depolymerize the chitosan. Then, the temperature was lowered to 25 °C over 90 minutes after the hydrolysis step to obtain an acid- and potassium persulfate-treated chitosan solution. The pH of the chitosan solution was 5.93.

[0351] The aqueous phase was prepared by mixing 422.15 g of the above chitosan stock solution in a jacketed reactor. The oil phase was prepared by mixing 146.63 g of fragrance, 36.66 g of isopropyl myristate, and 5.55 g of Takenate D-110N at room temperature. The oil phase was added to the aqueous phase under high-shear milling to obtain an emulsion having a desired particle size at 25 °C. The emulsion was heated to 40 °C within 30 minutes and then held for an additional 60 minutes. The resulting emulsion was then heated to 90 °C within 60 minutes and held at that temperature for 8 hours with mixing, after which it was cooled to 25 °C within 90 minutes. The capsules formed had a volume-weighted median particle size of 14.29 microns.

[0352] Example 2. Illustrative treatment composition (liquid fabric enhancer)

[0353] The following table (Table 2) provides exemplary treatment compositions according to the present disclosure. Specifically, the table shows formulations of a liquid fabric enhancer ("LFE") suitable for, for example, the rinse cycle of an automatic washing machine. The following compositions are also suitable for the fabric treatment methods provided in the above test methods section. The delivery particles of the following formulations are delivery particles according to the present disclosure, including those of Example 1.

[0354] The delivery particles are present in the test LFE composition at a level providing an encapsulated fragrance of approximately 0.2% by weight of the LFE composition. The pH of the test LFE composition was adjusted to approximately 3.

[0355] Table 2.

[0356] Ingredient Active substance % (w / w) <![CDATA[DiEster Quat 1 > 6％ Encapsulated perfume oil provided in chitosan-based delivery particles 0.2％ Formic acid 0.045％ Hydrochloric acid 0.0075％ Sodium hydroxyethanediphosphonate 0.0071％ <![CDATA[Structuring agent (cationic polymer) 2 > 0.11％ Defoamer (silicone) 0.004％ Water Balance pH Approximately 3

[0357] 1 N,N-bis(tallowoyloxyethyl)-N,N-dimethylammonium chloride, delivered by Evonik

[0358] 2 Flosoft FS222, delivered by SNF

[0359] Example 3. Determination of ductility energy

[0360] For the following examples, a population of delivery particles was prepared according to Example 1. Fifty delivery particles selected to represent the diameter distribution were analyzed for mechanical properties and classified by particle type according to the method provided in the test methods section.

[0361] Table 3 shows the analysis results, including particle size, classification of individual capsules based on rupture characteristics, rupture velocity (if any), and rescaled Log (ductility energy).

[0362] Table 3.

[0363]

[0364]

[0365] Based on the classification of fifty individual capsules, the number and relative proportion (as a percentage) of each category are provided in Table 4 below.

[0366] Table 4.

[0367] Category Number of capsules Ratio [%] Fully ductile 34 68 Single-rupture 12 24 Multi-rupture 4 8

[0368] Based on the protocol described in the test methods section, the volume-weighted extension energy of the population was 4.64.

[0369] Example 4. Effect of distribution modifier level on ductility energy and freshness performance

[0370] In the following experiment, a population of fragrance delivery particles was prepared substantially according to Example 1, but with different levels of partitioning modifier, specifically isopropyl myristate ("IPM"). The volume-weighted extension energy of the population was analyzed and the results are reported in Table 5 below.

[0371] In addition, the delivery particles were provided to a liquid fabric enhancer and then used to treat a fabric according to the fabric treatment method provided in the test methods section above. The friction fabric odor (RFO) headspace performance of the treated fabric was evaluated by the fragrance headspace method and the ΔRFO was evaluated by a professional perfumer. The headspace data was compared to data from reference PAC capsules and then normalized to the results of Trial 1. The results are reported in Table 5.

[0372] Table 5.

[0373] Test IPM level [%] Volume-weighted ductility energy RFO headspace [normalized] ΔRFO (perfumer) 1 10 3.55 1x 0 2 20 4.30 4.3x 2.5 3 30 4.37 3.8x 1.25

[0374] Based on the data in Table 5, a relatively large amount of partitioning modifier results in a relatively large volume-weighted extension energy value for the population of delivery particles.

[0375] In addition, those particles with a relatively large volume-weighted extension energy value provide a relatively large RFO headspace value on the treated fabric, as well as a higher ΔRFO score according to the professional perfumer.

[0376] Example 5. Effect of crosslinker level on ductility energy and freshness performance

[0377] In the following experiment, a population of fragrance delivery particles was prepared substantially according to Example 1, but with different levels of crosslinking agent in the oil phase, specifically polyisocyanate (Takenate D110). The volume-weighted extension energy of the population was analyzed and the results are reported in Table 6 below.

[0378] In addition, delivery particles are provided to a liquid fabric enhancer and then used to treat a fabric according to the fabric treatment method provided in the above test methods section. The rubbed fabric odor (RFO) of the treated fabric is evaluated by the perfume headspace method, and the ΔRFO is evaluated by a professional perfumer. The headspace data is compared with the data from the reference PAC capsules and then normalized to the results of Trial 1. The results are reported in Table 6.

[0379] Table 6.

[0380]

[0381] Based on the data in Table 6, a relatively large amount of crosslinker (e.g., polyisocyanate) in the oil phase results in a relatively large volume-weighted ductility energy value for the population of delivery particles.

[0382] In addition, those particles with a relatively large volume-weighted ductility energy value provide a relatively large RFO headspace value on the treated fabric, as well as a higher ΔRFO score according to the professional perfumer.

[0383] Example 6. Effect of pH on category ratio and freshness performance

[0384] In the following experiment, a population of perfume delivery particles is prepared substantially according to Example 1, but the aqueous phase has a different pH. In this example, the grinding temperature of the particles is 25 °C. The relative proportion of fully ductile capsules in the population is analyzed and the results are reported in Table 7 below.

[0385] In addition, delivery particles are provided to a liquid fabric enhancer and then used to treat a fabric according to the fabric treatment method provided in the above test methods section. The rubbed fabric odor (RFO) of the treated fabric is evaluated by the perfume headspace method. The headspace data is compared with the data from the reference PAC capsules and then normalized to the results of Trial 1. The results are reported in Table 7.

[0386] Table 7.

[0387]

[0388] Based on the data in Table 7, a population of particles prepared with an aqueous phase of relatively high pH results in a relatively large proportion of capsules characterized by fully ductile behavior and a relatively small proportion of capsules characterized by single rupture behavior.

[0389] In addition, a population with a relatively large proportion of capsules characterized by fully ductile behavior is associated with a relatively large RFO headspace value on the treated fabric.

[0390] Example 7. Effect of grinding temperature on category ratio and freshness performance

[0391] In the following experiments, fragrance delivery particle populations were prepared substantially according to Example 1, but with different milling temperatures. The relative proportions of fully ductile capsules in the populations were analyzed, and the results are reported in Tables 8 and 9 below. The aqueous phase of the particles used to form Table 8 was characterized by a pH of 5.6. The aqueous phase of the particles used to form Table 9 was characterized by a pH of 5.2.

[0392] In addition, the delivery particles were provided to a liquid fabric enhancer and then used to treat a fabric according to the fabric treatment method provided in the above Test Methods section. The rubbed fabric odor (RFO) of the treated fabric was evaluated by the fragrance headspace method. The headspace data was compared to data from reference PAC capsules and then normalized to the results of Trial 1. The results are reported in Tables 8 and 9.

[0393] Table 8.

[0394]

[0395] Based on the data in Table 8, particle populations prepared with a relatively high milling temperature resulted in a relatively large proportion of capsules characterized by fully ductile behavior, a relatively small proportion of capsules characterized by single rupture behavior, and a relatively high volume-weighted ductility energy.

[0396] In addition, populations with a relatively large proportion of particles characterized by fully ductile behavior (and a relatively high volume-weighted ductility energy) were associated with relatively large RFO headspace values on the treated fabric.

[0397] Table 9.

[0398]

[0399] Based on the data in Table 9, particle populations prepared with a relatively high milling temperature resulted in a relatively small proportion of capsules characterized by single rupture behavior and a relatively high volume-weighted ductility energy. Notably, the particles of Trial 2 showed a relatively low proportion of fully ductile particles compared to Trial 1; this change is believed to be associated with the relatively low pH of the aqueous phase.

[0400] In addition, populations with a relatively small proportion of particles characterized by single rupture behavior (and a relatively high volume-weighted ductility energy) were associated with relatively large RFO headspace values on the treated fabric.

[0401] The dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values recited. Instead, each such dimension is intended to represent the recited value and a range functionally equivalent around that value. For example, a dimension disclosed as "40 mm" is intended to represent "about 40 mm".

[0402] Unless expressly excluded or otherwise limited, each document cited in this application, including any cross-references or related patents or patent applications and any patent application or patent to which this application claims priority or the benefit of its useful effects, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art with respect to any invention disclosed in this application or claimed in the claims herein, or that it alone or in any combination with any one or more other references teaches, suggests or discloses any such invention. Further, when any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this invention shall govern.

[0403] While the specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended that all such changes and modifications that fall within the scope of the present invention be covered by the appended claims.

Claims

1. A treatment composition, the treatment composition comprising: a treatment aid, and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, wherein the shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the population of delivery particles is characterized by at least one, preferably at least two, of the following: (a) A volume-weighted ductility energy greater than about 3.5 based on compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s; (b) At least about 30% of the delivery particles, by number, being characterized as fully ductile particles based on compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s; (c) Less than 35% of the delivery particles, by number, being characterized as single-fracture particles based on compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s.

2. The treatment composition according to claim 1, wherein the population of delivery particles is 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, even more preferably about 4.5 to about 5.2, based on compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s.

3. The treatment composition according to any one of claims 1 or 2, wherein the population of delivery particles is characterized by at least about 50% of the delivery particles, by number, being characterized as fully ductile particles based on compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s.

4. The treatment composition according to any one of the preceding claims, wherein the population of delivery particles is characterized by less than 25% of the delivery particles, by number, being characterized as single-fracture particles based on compression of fifty randomly selected delivery particles with a blunt probe moving at 2 μm / s.

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

6. The treatment composition according to any one of the preceding claims, 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, cuticle, melanin, fibroin, gelatin, collagen, casein, sericin, fibroin, whey protein, zein, soy protein, phytohemagglutinin, gluten, peptide, actin, polynucleotide, RNA, DNA, tannin, lignan, their derivatives, and combinations thereof.

7. The treatment composition according to any one of the preceding claims, wherein the biopolymer is chitosan, its derivatives, or combinations thereof, Preferably, the biopolymer is acid-treated chitosan, redox initiator-treated chitosan, their derivatives, or combinations thereof.

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

9. The treatment composition according to any one of the preceding claims, wherein the crosslinking agent is a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxides, polyphenols, carbonyl halides, aziridines, and combinations thereof, preferably polyisocyanates, epoxides, bifunctional aldehydes, and combinations thereof, more preferably polyisocyanates selected from the group consisting of polyisocyanurates of tolylene diisocyanate; trimethylolpropane adducts of tolylene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenebiphenyl diisocyanate; 4,4'-methylenebiphenyl diisocyanate; 2,4'-methylenebiphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; tolylene diisocyanate; tetramethylxylene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; their derivatives; and combinations thereof.

10. The treatment composition according to any one of the preceding claims, wherein the reaction product is formed in a reaction in which the biopolymer is initially present in an aqueous phase and the crosslinking agent is initially present in an oil phase, wherein the crosslinking agent is present in the oil phase at a level 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, preferably wherein the biopolymer and the crosslinking agent are present in the reaction in a weight ratio of from about 1:10 to about 1:0.

1.

11. The treatment composition according to any one of the preceding claims, wherein the beneficial agent is an aromatic material.

12. The treatment composition according to any one of the preceding claims, wherein the core further comprises a dispensing modifier, which is preferably present at a level 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 dispensing modifier is selected from the group consisting of: vegetable oil, modified vegetable oil, mono-, di- and triesters of C4-C 24 monoesters, diesters and triesters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate and mixtures thereof, more preferably isopropyl myristate.

13. The treatment composition according to any one of the preceding claims, wherein the population of delivery particles is prepared by a method comprising at least one grinding step, wherein the at least one grinding 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 treatment composition according to any one of the preceding claims, wherein the delivery particles are characterized by a volume weighted median particle size of from about 1 micron to about 100 microns, preferably from about 10 microns to about 100 microns, preferably from about 15 microns to about 50 microns, more preferably from about 20 microns to about 40 microns, and even more preferably from about 25 microns to about 35 microns.

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

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