Treatment composition with perfume-containing delivery particles

Abstract

A treatment composition comprising a treatment aid and a population of core / shell delivery particles wherein the shell comprises a polymeric material formed from a cross-linked amine-containing biopolymer and wherein the core comprises a fragrance material comprising an ester-containing fragrance raw material. The present disclosure also relates to 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 comprises a polymeric material formed from a crosslinked amine-containing biopolymer, and wherein the core comprises an aroma material comprising an ester-containing perfume raw material. The present disclosure also relates to related methods for preparing and using such compositions. Background Art

[0002] Delivery particles, particularly core / shell delivery particles, are a convenient way to deliver beneficial agents in treatment compositions such as laundry products. For environmental reasons, it may be desirable to use delivery particles having a shell made of naturally derived and / or biodegradable materials. Useful shell preparation materials typically include primary amine groups since such materials readily react with many crosslinking agents such as polyisocyanates to form suitable polymeric materials.

[0003] That is, when encapsulating an aroma in core-shell delivery particles, certain shell materials can interact with certain perfume raw materials, resulting in capsules with relatively poor performance. For example, when preparing particles having a polymeric shell made of a material containing a primary amine such as chitosan, perfume raw materials containing aldehyde groups can react with the amine groups, which can result in relatively weak and / or leaky capsules. In particular, it is known that encapsulating aldehyde-containing perfumes in polyurea shells is challenging.

[0004] There is a need for improved treatment compositions comprising perfume-containing delivery particles, preferably particles made at least in part from naturally derived or biodegradable materials. Summary of the Invention

[0005] The present disclosure relates to a treatment composition comprising delivery particles, wherein the particles comprise an ester-containing perfume raw material in the core.

[0006] For example, the present disclosure relates to a treatment composition comprising: a treatment aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the biopolymer comprises a primary amine group, wherein the core comprises an aroma material, and wherein the aroma material comprises: (a) at least about 30% by weight of an ester-containing perfume raw material ("PRM") based on the weight of the aroma material, and (b) at least about 0.5% by weight of an aldehyde-containing PRM based on the weight of the aroma material.

[0007] The present disclosure also 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 shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises an aroma material, wherein the aroma material comprises one or more perfume raw materials ("PRM"), and wherein the aroma material is characterized by one or more of the following: (a) having an S-ESTER value of at least about 5, wherein the S-ESTER value of the aroma material is calculated as the weight-average S-ESTER value of the perfume raw materials; and / or (b) comprising at least about 30% by weight of the aroma material of a perfume raw material having an S-ESTER value of 13 or greater.

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

[0009] The present disclosure also relates to a method of preparing a treatment composition, the method comprising the steps of: providing a base composition, wherein the base composition comprises a treatment aid; and combining a population of delivery particles with the base composition, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises an aroma material, wherein the aroma material comprises: (a) at least about 30% by weight of the aroma material of an ester-containing perfume raw material ("PRM"), and (b) at least about 0.5% by weight of the aroma material of an aldehyde-containing PRM. Additionally or alternatively, the aroma material may be characterized by one or more of the following: (a) having an S-ESTER value of at least about 5, wherein the S-ESTER value of the aroma material is calculated as the weight-average S-ESTER value of the perfume raw materials; and / or (b) comprising at least about 30% by weight of the aroma material of a perfume raw material having an S-ESTER value of 13 or greater. Detailed Description

[0010] The present disclosure relates to a treatment composition comprising fragrance-containing delivery particles having a shell made at least in part from a biopolymer comprising primary amine groups. It has been found that careful selection of the aroma material to be encapsulated in the core can result in improved freshness performance. In particular, it has been found that it is advantageous to select at least a certain amount of ester-containing perfume raw materials ("PRM").

[0011] Without wishing to be bound by theory, it is believed that the ester-containing PRM forms hydrogen bonds or dipole moments that "engage" with the amine groups of the amine-containing biopolymer, thereby reducing the reaction of the "available" or "free" amine groups with the aldehyde PRM and / or the ketone-containing PRM. Although the groups may be temporarily "engaged", it is believed that the temperatures typically used to prepare such delivery particles (e.g., 50 °C - 95 °C) are not conducive to the reaction between the amine groups and the ester groups. In addition, it is believed that the amine / ester reaction is kinetically unfavorable compared to the reaction of amines with isocyanates (e.g., from crosslinkers) or aldehydes (e.g., from another PRM), even though the hydrogen bonding ability of the ester groups is relatively strong, as reflected in the S-ESTER descriptor described herein.

[0012] To further improve the shell formation and the resulting properties of the capsules, it may be preferred to limit the amount of aldehyde-, ketone-, and hydroxyl-containing PRM in the fragrance to be encapsulated.

[0013] The fragrances, delivery particles, treatment compositions, and related methods of the present disclosure are discussed in more detail below.

[0014] As used herein, the articles "a" and "an" when used in the claims are understood to mean one or more of the things claimed or described. As used herein, the terms "comprising", "including", and "containing" are intended to be non-limiting. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0015] The term "substantially free of" may be used herein. This means that the indicated material is present in very small amounts, not intentionally added to form part of the composition, or preferably the indicated material is not present at an analytically detectable level. This means including compositions in which the indicated material is present only as an impurity in one of the other materials intentionally added. If present at all, the indicated material may be present at a level of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0016] 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 manufacturing or modification. Such products include, but are not limited to, diapers, bibs, wipes; products and / or methods involving the treatment of human hair, which treatment includes bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; skin care, including the application of creams, lotions, and other topically applied products for consumer use; and shaving products, products and / or methods involving the treatment of fabrics, hard surfaces, and any other surfaces in the fabric and home care areas, including: air care, automotive care, dishwashing, fabric conditioning (including softening), laundry detergency, laundry washing and rinse additives and / or care, hard surface cleaning and / or treatment, and other cleaning for consumer or business use; products and / or methods involving toilet paper, facial tissue, paper handkerchiefs, and / or paper towels; tampons, feminine sanitary napkins; adult incontinence products; products and / or methods involving 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.

[0017] As used herein, the phrase "fabric care composition" includes compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry 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 porous substrates or nonwoven sheets, 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.

[0018] As used herein, unless otherwise specified, "delivery particle", "particle", "encapsulate", "microcapsule", and "capsule" are used interchangeably. As used herein, these terms generally refer to core / shell delivery particles.

[0019] Unless otherwise specified, 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] Treatment composition

[0024] The present disclosure relates to treatment compositions (or simply "compositions" as used herein). The compositions of the present disclosure may comprise a population of delivery particles and a treatment aid, each described in more detail below. The treatment compositions can be used in the methods of treating surfaces (such as fabrics) described herein.

[0025] The treatment compositions are preferably consumer product compositions. The consumer product compositions of the present disclosure can be used in baby care products, beauty care products, fabric care products, home care products, household care products, feminine care products, and / or health care applications. The consumer product compositions can be used to treat surfaces such as fabrics, hair, or skin. The consumer product compositions are intended to be used or consumed in their sold form. The consumer product compositions of the present disclosure are generally not intended for subsequent commercial manufacture or modification.

[0026] The consumer product compositions can preferably be fabric care compositions, hard surface cleaner compositions, dish care compositions, hair care compositions (such as shampoos or conditioners), body cleansing compositions, or mixtures thereof, preferably fabric care compositions.

[0027] The consumer product compositions can be fabric care compositions, such as laundry detergent compositions (including heavy-duty liquid detergents or unit dose products), fabric conditioning compositions (including liquid fabric softening and / or enhancing compositions), laundry additives, fabric pretreatment compositions (including sprays, pourable liquids or sprays), fabric freshener compositions (including sprays), or mixtures thereof. The treatment compositions are preferably fabric conditioning compositions, even more preferably liquid fabric conditioning compositions.

[0028] 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 lotion, foam, or pre- or post-shave treatment), a personal cleansing product (including liquid bath, liquid hand soap, and / or bar soap), a deodorant and / or antiperspirant, or a mixture thereof.

[0029] The composition can be a household care composition, such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other cleaning compositions for consumer or institutional use.

[0030] 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 product, a tablet, a bar, a strip, a flake, a foam / mousse, a non-woven sheet, or a mixture thereof.

[0031] The treatment composition can be in liquid form. The liquid composition can preferably contain about 50% to about 97%, preferably about 60% to about 96%, more preferably about 70% to about 95%, or even about 80% to about 95% water by weight of the fabric treatment composition. The liquid composition can be a liquid fabric conditioner. The liquid can be packaged in a pourable bottle. The liquid can be packaged in an aerosol can or other spray bottle. Suitable containers are described in more detail below.

[0032] The treatment composition can be in solid form. The composition can be in the form of beads or lozenges, which can be made from a liquid melt. The composition can be an extruded product. The treatment composition can be in powder or particulate form.

[0033] The composition can be in the form of a combined dose article such as a tablet, sachet, sheet, or fibrous product. Such sachets typically include a water-soluble film, such as a polyvinyl alcohol water-soluble film, which at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition can be encapsulated in a single-compartment sachet or a multi-compartment sachet. The multi-compartment sachet can have at least two, at least three, or at least four compartments. The multi-compartment sachet can include compartments that are side-by-side and / or stacked. The composition contained in the sachet or its compartments can be liquid, solid (such as powder), or a combination thereof. The sachet composition can have a relatively small amount of water, for example less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% water by weight of the detergent composition.

[0034] The treatment composition can be in spray form and can be dispensed from a bottle, for example, via a trigger sprayer and / or an aerosol container with a valve.

[0035] 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).

[0036] 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, if present, such pH levels are beneficial to the stability of the quaternary ammonium ester compound. On the other hand, the detergent composition is generally characterized by a pH of from about 7 to about 12, preferably from about 7.5 to about 11. The pH of the composition is measured by dissolving / dispersing the composition in deionized water at about 20 °C to form a 10% concentration solution.

[0037] The additional components and / or features of the composition are discussed in more detail below.

[0038] Delivery particle population

[0039] 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 fragrance material and optionally a dispensing modifier. The core may be liquid or solid at room temperature, preferably liquid.

[0040] The treatment composition may comprise from about 0.05% to about 20%, or from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.2% to about 2% by weight of the composition of the delivery particles. The composition may comprise a sufficient amount of the delivery particles to provide from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 2% by weight of the composition of the encapsulated beneficial agent, which may preferably be a fragrance raw material. When discussing the amount or weight percentage of the delivery particles herein, it means the sum of the wall material and the core material.

[0041] The characteristics of the population of delivery particles according to the present disclosure can 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, even more preferably from about 25 microns to about 35 microns. For certain compositions, preferably, the population of delivery particles is characterized by a volume-weighted median particle size of from about 1 micron to about 50 microns, preferably from about 5 microns to about 20 microns, more preferably from about 10 microns to about 15 microns. Different particle sizes can be obtained by controlling the droplet size during the emulsification process.

[0042] The characteristics of the delivery particles can lie in a core-to-shell ratio, based on weight, of up to 99:1, or even 99.5:0.5. The shell can be present in an amount of from about 1% to about 25% by weight of the delivery particles, preferably from about 1% to about 20% by weight, preferably from about 1% to 15% by weight, more preferably from about 5% to about 15% by weight, even more preferably from about 10% to about 15% by weight, even more preferably from about 10% to about 12% by weight. The shell can be present in an amount of at least 1% by weight, preferably at least 3% by weight, more preferably at least 5% by weight of the delivery particles. The shell can be present in an amount of at most about 25% by weight, preferably at most about 20% by weight, preferably at most about 15% by weight, more preferably at most about 12% by weight of the delivery particles.

[0043] The delivery particles can be cationic in nature, preferably cationic at a pH of 4.5. The characteristics of the delivery particles can lie in a ζ potential of at least 15 millivolts (mV) at a pH of 4.5. The delivery particles can be made to have a ζ potential of at least 15 millivolts (mV) at a pH of 4.5, or even a ζ potential of at least 40 mV at a pH of 4.5, or even a ζ potential of at least 60 mV at a pH of 4.5. Delivery particles prepared with chitosan generally exhibit a positive ζ potential. Such capsules have improved deposition efficiency on fabrics. At higher pH values, the particles can be made non-ionic or anionic.

[0044] The delivery particles of the present disclosure include a shell surrounding a core. (As used herein, "shell" and "wall" can be used interchangeably with respect to the delivery particles, unless otherwise specified.) The shell contains a polymeric material. The polymeric material is a reaction product of a biopolymer and a crosslinking agent.

[0045] The biopolymer generally contains primary amine groups. The primary amine groups react with the crosslinking agent to form a polymeric material, which can be described as a crosslinked biopolymer.

[0046] The biopolymer can preferably be selected from the group consisting of polysaccharides, proteins, nucleic acids, their derivatives, and combinations thereof. Preferably, the biopolymer is selected from the group consisting of:

[0047] (a) A polysaccharide selected from the group consisting of chitosan, amine-modified starch, amine-modified dextran, amine-modified maltodextrin, amine-modified dextrin, amine-modified cellulose, amine-modified hemicellulose, chitin, amine-modified alginate, amine-modified lignin, amine-modified gum, amine-modified pectin, amine-modified agar, melanin, silk fibroin, their derivatives, and combinations thereof;

[0048] (b) A protein selected from the group consisting of gelatin (e.g., porcine gelatin), collagen, casein, sericin, fibroin, whey protein, pea protein, corn protein, soy protein, plant storage proteins (protein isolates, protein concentrates), gluten, peptides, actin, their derivatives, and combinations thereof;

[0049] (c) A nucleic acid selected from the group consisting of polynucleotides, RNA, DNA, their derivatives, and combinations thereof; and

[0050] (d) Combinations thereof.

[0051] For example, due to convenient availability, biodegradability, and / or performance reasons, amine-containing polysaccharides may be preferred. A particularly preferred material is chitosan. Thus, the biopolymer may preferably be chitosan, its derivatives, or combinations thereof. Preferably, the biopolymer is acid-treated chitosan, its derivatives, or combinations thereof.

[0052] Chitosan may preferably be acid-treated chitosan. For example, chitosan (which may be referred to as raw chitosan or parent chitosan before acid treatment) may be 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 with an acid for at least one hour, preferably about one hour to about three hours, or for a period of time required 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. The acid may be selected from strong acids (such as hydrochloric acid), organic acids (such as formic acid or acetic acid), or mixtures thereof. Chitosan may preferably be acid-treated under conditions where the pH is from 2 to 6.5, preferably from about 3 to about 6, or even from 4 to 6.

[0053] Biopolymers, preferably chitosan, more preferably acid-treated chitosan, may be 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. 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) techniques.

[0054] Chitosan may be characterized by a degree of deacetylation of at least 50%, preferably from about 50% to about 99%, more preferably from about 75% to about 90%, and even more preferably from about 80% to about 85%. The degree of deacetylation affects the solubility of chitosan, which in turn affects its reactivity or behavior during the formation of the particle shell. For example, too low a degree of deacetylation (e.g., below 50%) results in relatively insoluble and relatively unreactive chitosan. A relatively high degree of deacetylation can result in very soluble chitosan, leading to relatively little chitosan reaching the oil / water interface during shell formation.

[0055] When chitosan is present, it may include anion-modified chitosan, cation-modified chitosan, or a combination thereof. Modifying chitosan in anionic and / or cationic ways changes the characteristics of the shell of the delivery particles, e.g., by changing the surface charge and / or zeta potential, which affects the deposition efficiency of the particles and / or formulation compatibility.

[0056] As described above, the shell is a polymeric material that is the reaction product of a biopolymer chitosan and a crosslinking agent. The crosslinking material is preferably a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxides, polyphenols, carbonyl halides, aziridines, and combinations thereof. The crosslinking agent is more preferably selected from the group consisting of polyisocyanates, epoxides, bifunctional aldehydes, and combinations thereof.

[0057] The crosslinking agent is preferably a polyisocyanate. It is believed that such materials advantageously react with the amine groups of the biopolymer to form an effective crosslinked polymer wall. When the crosslinking agent is a polyisocyanate, the polymeric material of the shell can be understood to comprise a polyurea resin. The polyurea resin may comprise the reaction product of a polyisocyanate and chitosan.

[0058] The polyisocyanate materials useful in the present disclosure are understood to be isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. "Polyisocyanate" is intended to denote a material or compound containing two or more isocyanate moieties. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended to be covered by the term "polyisocyanate" herein. The polyisocyanates useful in the present disclosure include isocyanate monomers, oligomers, or prepolymers having at least two isocyanate groups, or their dimers or trimers. Preferred crosslinking can be achieved using polyisocyanates having at least three functional groups.

[0059] Aromatic polyisocyanates can be preferred; however, aliphatic polyisocyanates and their blends can be useful. Aliphatic polyisocyanates are understood to be polyisocyanates that do not contain any aromatic moieties. Aromatic polyisocyanates are understood to be polyisocyanates that contain at least one aromatic moiety. The crosslinking agent can comprise a mixture of aromatic polyisocyanates and aliphatic polyisocyanates.

[0060] Polyisocyanates, when aromatic, can be but are not limited to methylene diphenyl diisocyanate, toluene diisocyanate, tetramethylxylene diisocyanate, the polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name RC), the trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name L75), naphthalene-1,5-diisocyanate, and the trimethylolpropane adduct of phenylene diisocyanate or xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name D-110N).

[0061] Aliphatic polyisocyanates can include the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate, the trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or the biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name N 100).

[0062] Derivatives of polyisocyanates can include oligomers or polymers of isocyanate monomers. As a non-limiting example, the polyisocyanate can preferably contain oligomers or polymers of diphenylmethane diisocyanate (MDI), such as MR-Light.

[0063] The polyisocyanate may preferably be selected from the group consisting of: polyisocyanurates of tolylene diisocyanate; trimethylolpropane adducts of tolylene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; diphenylmethane diisocyanate; tolylene diisocyanate; tetramethyldimethylaniline diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; their derivatives (such as their prepolymers, oligomers and / or polymers); and combinations thereof.

[0064] Additional co-crosslinking agents such as polyfunctional amines and / or polyamines such as diethylenetriamine (DETA), polyethyleneimine, polyvinylamine or mixtures thereof can also be used to reinforce the particle shell. Acrylates can also be used as additional co-crosslinking agents, for example to reinforce the shell.

[0065] The polymeric material can be formed in a reaction in which the weight ratio of the biopolymer, preferably a polysaccharide, more preferably chitosan or its derivatives (which may include acid-treated chitosan), present in the reaction to the crosslinking agent present in the reaction is from about 1:10 to about 1:0.1, 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 crosslinking agent can provide the desired ductility benefit as well as improved biodegradability. Preferably, at least 21 wt% of the shell consists of a portion derived from chitosan, preferably derived from acid-treated chitosan. The weight percentage of chitosan in the shell can be from about 21% to about 95% of the shell. Based on weight, the ratio of chitosan in the aqueous phase to isocyanate in the oil phase can be from 21:79 to 90:10, or even from 1:2 to 9:1, or even from 1:1 to 7:1.

[0066] The shell can contain chitosan in an amount of 21 wt% or even higher, preferably from about 21 wt% to about 90 wt%, or even from 21 wt% to 85 wt%, or even from 21 wt% to 75 wt%, or 21 wt% to 55 wt% of the total shell of chitosan. The chitosan in this paragraph can preferably be acid-treated chitosan.

[0067] A population of delivery particles can be prepared according to a method comprising the steps of: (a) forming an aqueous phase comprising chitosan as described herein, preferably wherein the aqueous phase is at a pH of 6.5 or lower, more preferably at a pH of 3 to 6, and at 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 a crosslinking agent, preferably a 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, preferably pH 3 to pH 6; (d) curing the emulsion by heating (preferably to at least 40 °C) for a time sufficient to form a shell at the interface of the oil droplets and the aqueous phase, wherein the shell 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.

[0068] A population of delivery particles can be prepared according to a method comprising the steps of: (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; (b) forming an oil phase by dissolving together at least one beneficial agent and at least one polyisocyanate optionally with added oil (e.g., 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 dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to within the range of pH 2 to pH 6, preferably pH 3 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 droplets of the oil phase and the beneficial agent.

[0069] Chitosan can be added to water in a jacketed reactor and adjusted using an acid such as concentrated HCl at a pH 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 can be held at that temperature for 1 minute to 1440 minutes or longer. Then the aqueous phase can be cooled to 25 °C. Optionally, deacetylation can also be further promoted or enhanced by an enzyme to depolymerize or deacetylate the chitosan. The oil phase can be prepared by dissolving an isocyanate such as a trimer of xylylene diisocyanate (XDI) or a polymer of methylene diphenyl diisocyanate (MDI) in oil at 25 °C. A diluent, such as isopropyl myristate, can be used to adjust the hydrophilicity of the oil phase. Then the oil phase can be added to the aqueous phase and ground at high speed to obtain the target size. Then the emulsion can be cured in one or more heating steps, such as heating to 40 °C in 30 minutes and holding at 40 °C for 60 minutes. The time and temperature are approximate. The temperature and time are selected to be sufficient to form and cure a shell at the interface of the droplets of the oil phase and the water continuous phase. For example, the emulsion can be heated to 85 °C in 60 minutes and then held at 85 °C for 360 minutes to cure the particles. Then the slurry can be cooled to room temperature.

[0070] When tested according to test method OECD 301B, the shell can degrade by at least 50% after 20 days (or less). When tested according to test method OECD 301B, the shell can degrade by at least 60% of its mass after 60 days (or less). When tested according to test method OECD 301B, the shell can preferably degrade by at least 60% of its mass after 60 days (or less). The shell can 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.

[0071] The delivery particles of the present disclosure include a core. The core contains an aroma material. The aroma material contains one or more perfume raw materials (PRM). The core optionally contains a dispensing modifier.

[0072] The core of the particle is surrounded by a shell. When the shell breaks, the aroma material in the core is released. Additionally or alternatively, the aroma material in the core can diffuse out of the particle, and / or it can be extruded. Suitable aroma materials located in the core can include aroma materials that provide beneficial effects to surfaces such as fabrics or hair.

[0073] The core can contain from about 5% to about 100% of the aroma material by weight of the core. The core can contain from about 45% to about 95%, preferably from about 50% to about 80%, more preferably from about 50% to about 70% of the aroma material by weight of the core.

[0074] The fragrance material can be relatively hydrophobic. Such reagents are compatible with the oil phase commonly found in the delivery particles of the present disclosure.

[0075] As described above, the core of the delivery particles of the present disclosure contains a fragrance, which can include one or more perfume raw materials. The fragrance is particularly suitable for encapsulation in the delivery particles of the present invention because the fragrance-containing particles can provide a fresh benefit across multiple contact points.

[0076] 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).

[0077] PRMs can be characterized by their boiling point (B.P.) measured at normal pressure (760 mmHg), and their octanol / water partition coefficient (P), which can be described by logP and is determined according to the test method below. Based on these properties, PRMs can be classified as first quadrant, second quadrant, third quadrant, or fourth quadrant fragrances, as detailed below.

[0078] The fragrance can include perfume raw materials having a logP of about 2.5 to about 4. It should be understood that other perfume raw materials can also be present in the fragrance.

[0079] The fragrance raw materials may include fragrance raw materials selected from the group consisting of: fragrance raw materials having a boiling point (B.P.) below about 250 °C and a logP less than about 3, fragrance raw materials having a B.P. above about 250 °C and a logP greater than about 3, fragrance raw materials having a B.P. above about 250 °C and a logP less than about 3, fragrance raw materials having a B.P. below about 250 °C and a logP greater than about 3, and mixtures thereof. The fragrance raw materials having a boiling point B.P. below about 250 °C and a logP less than about 3 are referred to as Quadrant I fragrance raw materials. The Quadrant I fragrance raw materials are preferably limited to less than 30% of the fragrance composition. The fragrance raw materials having a B.P. above about 250 °C and a logP greater than about 3 are referred to as Quadrant IV fragrance raw materials, the fragrance raw materials having a B.P. above about 250 °C and a logP less than about 3 are referred to as Quadrant II fragrance raw materials, and the fragrance raw materials having a B.P. below about 250 °C and a logP greater than about 3 are referred to as Quadrant III fragrance raw materials. Suitable Quadrant I, Quadrant II, Quadrant III, and Quadrant IV fragrance raw materials are disclosed in U.S. Patent 6,869,923 B1.

[0080] As described above, there are challenges associated with encapsulating certain PRMs in certain wall materials. It has surprisingly been found that effective delivery particles can be prepared by selecting certain PRMs to be encapsulated. For example, it has been found beneficial to select a certain minimum amount of ester-containing PRM as part of the fragrance material to be encapsulated. Additionally or alternatively, as described in more detail below, it has been found beneficial to select the components of the fragrance material such that the fragrance material is characterized by one or more S-ESTER values.

[0081] The fragrance material may comprise at least 30% by weight of the fragrance material of ester-containing fragrance raw materials (PRMs). Preferably, the fragrance material further comprises at least 0.5% by weight of the fragrance material of aldehyde-containing PRMs. It has surprisingly been found that including a relatively high amount of ester-containing PRMs in the fragrance material allows for the advantageous encapsulation of the entire fragrance material. This is the case even when the fragrance material contains aldehyde-containing PRMs, which are known to cause encapsulation challenges when using amine-containing shell precursors.

[0082] The fragrance material may comprise at least about 30%, preferably about 35%, more preferably at least about 40%, even more preferably at least about 50% by weight of the fragrance material of ester-containing PRMs. The fragrance material may comprise from 30% to 99.5% by weight of the fragrance material, preferably from 35% to about 80%, more preferably from about 40% to about 70%, even more preferably from about 50% to about 60%. It is believed that a relatively high amount of ester-containing PRMs will result in more effective encapsulation and / or performance.

[0083] It should be noted that some PRMs contain more than one functional group, such as ester groups and hydroxyl groups (see, for example, triethyl citrate). For the purposes of this disclosure, when determining the relative percentage of PRMs containing a given functional group in a given fragrance material, PRMs having more than one type of functional group are counted in each functional group category. Thus, the amount of triethyl citrate in a given fragrance will be counted in both the percentage of ester-containing PRMs and the percentage of hydroxyl-containing PRMs. When such materials are present, due to such double (or even triple, etc.) counting, the relative percentages of PRMs having each functional group, by weight of the fragrance material, can total greater than 100%.

[0084] Fragrance materials comprising a single PRM can be described according to their atom-level electrotopological state (E-state) indices. E-state values are molecular descriptors that can be found in the literature and / or determined using commercially available software programs. E-state values effectively look at each atom in a molecule and reflect the valence state electronegativity of the atom, which is affected by the atoms connected to it. The electrotopological state indices are discussed in more detail in Hall et al., Electrotopological State Indices for Atom Types: A Novel Combination of Electronic, Topological, and Valence State Information, J. Chem. Inf. Comput. Sci. 1995, 35, 1039 - 1045.

[0085] The S-ESTER value is the sum of the atom-level electrotopological state (E-state) values of all the carbonyl carbons and oxygens in the ester groups in a molecule. To determine the E-state and S-ESTER values for the purposes described in this disclosure, the E-state values are calculated using the software program winMolconn version 1.2.2.3 (purchased from Hall Associates Consulting of Quincy, MA) used according to the manufacturer's instructions. The method for determining the S-ESTER value is described in more detail in the Test Methods section below.

[0086] For a particular compound, a relatively high S-ESTER value can indicate, for example, more than one ester group. A relatively high S-ESTER value for a mixture of compounds (such as a fragrance material comprising more than one type of fragrance ingredient) can indicate a relatively high proportion of ester-containing compounds, including compounds containing more than one ester group.

[0087] The fragrance material encapsulated in the delivery particles of the present disclosure can be characterized according to the S-ESTER value of the overall fragrance material (e.g., a mixture of PRMs) and / or by the relative amount of PRMs characterized by a certain S-ESTER value. For example, the fragrance material can be characterized by one or more of the following: (a) having an S-ESTER value of at least about 5, where the S-ESTER value of the fragrance material is calculated as the weight-average S-ESTER value of the fragrance raw materials; and / or (b) containing at least about 30% by weight of the fragrance raw materials having an S-ESTER value of 13 or greater.

[0088] The fragrance material can be characterized by having an S-ESTER value of at least about 5, preferably at least about 5.5, preferably at least about 6. Additionally, the fragrance material can preferably be characterized by an S-ESTER value of no greater than about 20, preferably no greater than about 13, more preferably no greater than about 10. Larger S-ESTER values are associated with a relatively larger amount of esters, which may be associated with relatively lower volatility and lower olfactory impact.

[0089] The fragrance material can contain at least about 30% by weight, preferably at least about 40% by weight, more preferably at least about 50% by weight, even more preferably at least about 55% by weight of the fragrance raw materials having an S-ESTER value of about 13 or greater, preferably PRMs having an S-ESTER value of about 13 to about 80, more preferably about 13 to about 35, even more preferably about 13 to about 20. For clarity, it should be understood that PRMs that do not contain an ester group are assigned an S-ESTER value of zero.

[0090] Suitable ester-containing PRMs for the fragrance materials of the present disclosure are provided in the table below. The fragrance materials of the present disclosure can contain any of the PRMs listed in the table below or combinations thereof. The table also indicates what types of functional groups are present and the S-ESTER values assigned to each PRM.

[0091]

[0092]

[0093] Although it is believed that a relatively high amount of ester-containing PRMs will result in more effective encapsulation and / or performance, from an olfactory perspective, it may be necessary to include PRMs having a non-ester moiety in order to form a comprehensive fragrance.

[0094] For example, the fragrance material may contain an aldehyde-containing PRM. The fragrance material may contain at least about 0.5%, preferably at least about 1%, more preferably at least about 5%, and more preferably at least about 10% of an aldehyde-containing PRM by weight of the fragrance material. Due to known problems associated with encapsulation, it may be desirable to limit the amount of aldehyde-containing PRM. For example, the fragrance material may contain 0.5% to about 30%, preferably about 1% to about 25%, and more preferably about 5% to about 20% of an aldehyde-containing PRM by weight of the fragrance material. Aldehyde-containing fragrance raw materials may include: methylnonyl acetaldehyde: benzaldehyde; sea breeze aldehyde; isocyclic citral; (2,4-dimethylcyclohexene-3-yl) formaldehyde (privet aldehyde); methyl citrus aldehyde B; lily of the valley aldehyde; decanal; undecene aldehyde; cyclamen homoaldehyde; rabbit ear grass aldehyde; dobicar; oncidal; adoc aldehyde; melon aldehyde; 6-methoxy-2,6-dimethyloctanal; anise aldehyde; jasmine aldehyde; cumin aldehyde; qingfeng aldehyde; 3,6-dimethylcyclohex-3-ene-1-carboxaldehyde; 2-methyl-3-(p-methylphenyl) 1-decenal; cis-4-decenal; trans-4-decenal; cis-7-decenal; undecenal; trans-2-hexenal; trans-2-octenal; 2-undecenal; 2,4-dodecenal; cis-4-heptenal; cinnamaldehyde; butylcinnamaldehyde; limonelal; amylcinnamaldehyde; hexylcinnamaldehyde; citronellal; citral; cis-3-hexen-1-al; or mixtures thereof, as these materials are particularly desired by the formulator and / or consumer.

[0095] The fragrance material may contain hydroxyl-containing PRMs. However, in order to promote effective shell formation, the relative amount of such PRMs may be limited. The fragrance material may contain no more than 30% hydroxyl-containing PRMs, preferably 1% to 30% hydroxyl-containing PRMs by weight of the fragrance material. Hydroxyl-containing fragrance raw materials may include: geraniol, nonadienol, cinnamyl alcohol, linalool, yeast acetate, their derivatives or mixtures thereof, because these materials are particularly desired by formulators and / or consumers.

[0096] The fragrance material may include ketone PRMs. Ketone-containing fragrance raw materials may include: 1-(3-methyl-benzofuranyl)ethanone (nerolione); 4-(4-methoxyphenyl)butan-2-one; 1-naphthalene-2-ylethanone; safflowerone; trimofix O; jasmone; Δ-damascone; β-damascone; α-damascone; methylionone; 2-hexylcyclopent-2-ene-1-one; gerpentone; or mixtures thereof, as these materials are particularly desired by formulators and / or consumers.

[0097] Preferred fragrance materials suitable for encapsulation in the delivery particles of the present disclosure may comprise the following classes of PRMs in the following amounts: about 45% to about 55% ester-containing PRM; about 10% to about 25% aldehyde-containing PRM; about 5% to about 20% hydroxyl-containing PRM; and optionally about 1% to about 40% additional PRM, which may include PRMs that are ketone-containing PRMs.

[0098] The core of the delivery particles of the present disclosure may comprise a partitioning modifier that may facilitate more robust shell formation. The partitioning modifier may be combined with the fragrance oil material of the core prior to incorporation of the wall-forming monomers. The partitioning modifier may be present in the core in an amount of 0% to 95% by weight of the core, preferably about 5% to about 55%, preferably about 10% to about 50%, more preferably about 25% to about 50%.

[0099] The partitioning modifier may comprise a material selected from the group consisting of vegetable oils, modified vegetable oils, monoesters, diesters, and triesters of C4-C 24 fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning modifier may preferably comprise isopropyl myristate or even consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably include castor oil and / or soybean oil. U.S. Patent Application Publication 20110268802, which is incorporated herein by reference, describes other partitioning modifiers that may be used in the delivery particles described in the present invention.

[0100] Optionally, the core may comprise a beneficial agent selected from the group consisting of 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, antistatic agents, softeners, insect and moth repellents, colorants, antioxidants, chelating agents, bases, disinfecting drapes and morphology control agents, smoothing agents, wrinkle control agents, sanitation treatment agents, disinfectants, microbial control agents, mold control agents, mildew control agents, antiviral agents, desiccants, antifouling agents, detergents, fabric fresheners and freshness extenders, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color recovery / restoration agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, anti-wear agents, fabric integrity agents, anti-fuzzing 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.

[0101] When the beneficial agent itself is not sufficient to serve as the oil phase or solvent, especially in the process of forming the shell of the delivery particles for the wall-forming material, the oil phase may comprise a suitable carrier and / or solvent. In this sense, the oil is optional since the beneficial agent itself can sometimes be an oil. These carriers or solvents are generally oils, preferably having a boiling point greater than about 80 °C, low volatility and being non-flammable. Although not limited thereto, they preferably comprise one or more esters, preferably esters and / or triglycerides having a chain length of at most 18 carbon atoms or even at most 42 carbon atoms, such as esters of C6 to C12 fatty acids with glycerol.

[0102] Optionally, the aqueous phase may comprise an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (such as alkyl sulfates, alkyl ether sulfates and / or alkyl benzene sulfonates), non-ionic surfactants (such as alkoxylated alcohols, preferably comprising ethoxy groups), polyvinyl alcohol, and / or polyvinyl pyrrolidone. It is possible in the present application that dissolved chitosan can provide emulsification benefits.

[0103] The emulsifier (if employed) is generally from about 0.1 wt% to 40 wt%, preferably 0.2 wt% to about 15 wt%, more typically 0.5 wt% to 10 wt% based on the total weight of the aqueous phase.

[0104] The population of delivery particles can be provided as a slurry, preferably an aqueous slurry. The slurry may comprise one or more processing aids, which may include water, aggregation-inhibiting substances such as divalent salts, or particulate suspension polymers such as xanthan gum, guar gum, cellulose (preferably microfibrillated cellulose) and / or carboxymethyl cellulose. When the delivery particles are characterized by cationic properties (e.g., when the shell is at least partially derived from chitosan), non-anionic structuring agents, preferably non-ionic structuring agents, may be preferred, for example to avoid detrimental charge interactions that can lead to undesirable aggregation.

[0105] The slurry may comprise one or more carriers selected from the group consisting of: polar solvents, including but not limited to water, ethylene glycol, propylene glycol, polyethylene glycol, glycerol; non-polar solvents, including but not limited to mineral oil, perfume raw materials, silicone oil, hydrocarbon paraffin oil; and mixtures thereof. An aqueous slurry may be preferred. The slurry may comprise ("free") unencapsulated perfume raw materials, which differ in properties and / or amounts from those encapsulated in the core of the delivery particles.

[0106] The slurry may include a deposition aid, which may include a polymer selected from the group consisting of: polysaccharides, in one aspect, cationically modified starch and / or cationically modified guar gum; polysiloxanes; polydiallyldimethylammonium halide; a copolymer of polydiallyldimethylammonium chloride and polyvinylpyrrolidone; a composition comprising polyethylene glycol and polyvinylpyrrolidone; acrylamide; imidazole; imidazoline halide; polyvinylamine; a copolymer of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; a polyglycerol ether silicone crosslinked polymer; a copolymer of polyacrylic acid, polyacrylate, polyvinylamine and a polyvinyl alcohol oligomer of an amine, 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; a polymeric compound comprising at least two moieties on the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile, or combinations thereof, the at least two moieties selected from the group consisting of: carboxylic acid moieties, amine moieties, hydroxyl moieties, and nitrile moieties; a preformed condensate of an anionic surfactant in combination with a cationic polymer; polyamines, and mixtures thereof.

[0107] At least one population of delivery particles may be included in an agglomerate, and then combined with a different population of delivery particles and at least one adjuvant material. The agglomerate may include a material selected from the following: 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.

[0108] Suitable apparatuses for use in the methods disclosed herein can include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plowshare shear mixers, belt blenders, vertical axis granulators, and tumbling mixers (both of which can be in batch process configurations and continuous process configurations when available), spray dryers, and extruders. Such apparatuses can be purchased from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., U.S.A.), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., U.S.A.), Arde Barinco (New Jersey, U.S.A.).

[0109] Auxiliary component

[0110] In addition to delivering 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.

[0111] 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.

[0112] Depending on the desired form, formulation, and / or end use, the compositions of the present disclosure may not contain one or more of the following adjuvant materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / antiredeposition agents, optical brighteners, defoamers, dyes, additional fragrances and fragrance delivery systems, structurants, fabric softeners, carriers, hydrotropes, processing aids, structuring agents, anti-caking agents, coatings, formaldehyde scavengers, and / or pigments.

[0113] 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.

[0114] A. Surfactant

[0115] The compositions of the present disclosure may contain surfactants. For example, surfactants can be used to provide cleaning benefits. The composition may contain a surfactant system, which may contain one or more surfactants.

[0116] The compositions of the present disclosure may contain from about 0.1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50% by weight of the composition of the surfactant system. Liquid compositions may contain from about 5% to about 40% by weight of the composition of the surfactant system. Compact formulations, including compact liquids, gels, and / or compositions suitable for unit dosage forms, may contain from about 25% to about 70% or from about 30% to about 50% by weight of the composition of the surfactant system.

[0117] 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.

[0118] 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 linear, branched, or a combination thereof. Preferred surfactants include linear alkylbenzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactant can be present in acid form, salt form, or a mixture thereof. The anionic surfactant can be partially or fully neutralized with, for example, an alkali metal (such as sodium) or an amine (such as monoethanolamine). Due to the presence of the cationic ester quaternary compound material, it may be desirable to limit the amount of the anionic surfactant to avoid undesirable interactions of the materials; for example, the composition can contain less than 5%, preferably less than 3%, more preferably less than 1%, and even more preferably less than 0.1% of the anionic surfactant by weight of the composition.

[0119] The surfactant system can include nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (such as alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(alkoxylated) alcohol surfactants, and mixtures thereof. The alkoxylate units can be ethyleneoxy units, propyleneoxy units, or a mixture thereof. The nonionic surfactant can be linear, branched (such as mid-chain branched), or a combination thereof. Specific nonionic surfactants can include alcohols having an average of about 12 to about 16 carbon atoms and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactant.

[0120] Suitable zwitterionic surfactants can include any conventional zwitterionic surfactant, such as betaines, including alkyl dimethyl betaines and coconut dimethylamidopropyl betaines, C8 to C 18 (e.g., C 12 to C 18 ) amine oxides (e.g., C 12-14 dimethylamine oxide), and / or sulfobetaines and hydroxybetaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonates, wherein the alkyl group can be C8 to C 18 or C 10 to C 14The zwitterionic surfactant may include amine oxide.

[0121] 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, as such surfactants may interact unfavorably with cationic components.

[0122] B. Conditioning active substance

[0123] The compositions of the present disclosure may include conditioning actives. Compositions containing conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color, and / or appearance benefits.

[0124] The conditioning actives may be present at a level of about 1% to about 99% by weight of the composition. The composition may include 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 include about 5% to about 30% by weight of the conditioning actives.

[0125] 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 include quaternary ammonium ester materials; such materials are particularly suitable for fabric enhancing / conditioning / softening compositions.

[0126] The composition may include 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 include a quaternary ammonium ester compound and a 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.

[0127] The composition may include a mixture of different types of conditioning actives. The compositions of the present disclosure may include 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 include a quaternary ammonium ester compound, but be substantially free of silicones. The composition may include a silicone, but be substantially free of quaternary ammonium ester compounds.

[0128] C. Deposition aid

[0129] 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.

[0130] 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.

[0131] Generally speaking, cationic polymers and their methods of manufacture are known in the literature. Suitable cationic polymers may include quaternary ammonium polymers referred to as "polyquaternium" polymers, as designated by the International Nomenclature for Cosmetic Ingredients, such as polyquaternium-6 (poly(diallyldimethylammonium chloride)), polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), polyquaternium-10 (quaternized hydroxyethyl cellulose), polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride), and the like.

[0132] The deposition aid may be selected from polyvinylformamide, partially hydroxylated polyvinylformamide, polyvinylamine, polyvinylimine, ethoxylated polyvinylimine, polyvinyl alcohol, polyacrylate esters, and combinations thereof. The cationic polymer may include cationic acrylates.

[0133] 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.

[0134] D. Rheology modifier / structurant

[0135] The compositions of the present disclosure may comprise rheology modifiers and / or structurants. Rheology modifiers can be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structurants can be used to promote phase stability and / or suspend or inhibit aggregation of particles in a liquid composition, such as the delivery particles described herein.

[0136] Suitable rheology modifiers and / or structurants can include non-polymeric crystalline hydroxy-functionalized structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulose fibers (e.g., microfibrillated cellulose, which can be derived from bacterial, fungal, or plant sources, including wood), diacylamino gelling agents, or combinations thereof.

[0137] Polymeric structuring agents can be of natural or synthetic origin. Natural origin polymeric structurants can include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives can include: pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structurants can include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated polyurethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers can include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates can include copolymers of unsaturated mono- or di-carboxylic acids with C1-C 30 alkyl esters of (meth)acrylic acid. Such copolymers are available from Noveon under the trade name Carbopol Aqua 30. Crosslinked polymers, such as crosslinked polyacrylates and / or polymers and / or copolymers, such as those further comprising nonionic monomers (such as acrylamide or methacrylamide monomers), can be used as structurants. Another suitable structurant is sold under the trade name Rheovis CDE and is available from BASF.

[0138] E. Other auxiliaries

[0139] The treatment compositions of the present disclosure may comprise other adjuvants suitable for inclusion in a product and / or suitable for end use. For example, the treatment compositions can comprise neat fragrances, fragrance delivery technologies (such as pre-fragrances and / or encapsulates with non-crosslinked biopolymer wall materials), cationic surfactants, cationic polymers, solvents, antifoaming agents, or combinations thereof.

[0140] Method for preparing treatment composition

[0141] The present disclosure further relates to methods for preparing treatment compositions, such as those treatment compositions and / or consumer product compositions described herein.

[0142] The method may comprise the steps of: 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.

[0143] 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 adjuvant components. The delivery particles may be combined with such adjuvants by methods including mixing and / or spraying.

[0144] The treatment composition of the present disclosure may be formulated into any suitable form and prepared by any method chosen by the formulator. The one or more adjuvant components and the delivery particles may be combined in a batch process, in a recycle loop process, and / or by an in-line mixing method. Suitable equipment for use in the methods disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recycle pumps, paddle mixers, high-shear mixers, static mixers, plow shear mixers, belt 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.

[0145] The treatment composition may be placed in a container to form a consumer product as described herein. The container may be a bottle, preferably a plastic bottle. The treatment composition may be placed in an aerosol or other spray container according to known methods.

[0146] Treatment method

[0147] The present disclosure also relates to a method of treating a surface, preferably a fabric. Generally speaking, the method comprises the step of contacting the surface (preferably a fabric) with a treatment composition according to the present disclosure, wherein the treatment composition comprises a population of delivery particles as described herein.

[0148] Additionally or alternatively, the method may comprise the step of contacting the surface (preferably a fabric) with a population of delivery particles as described herein. The population of delivery particles may be included in a treatment composition according to the present disclosure, preferably a fabric care composition.

[0149] The method may comprise the step of contacting a fabric (such as a garment) with a treatment composition. The treatment composition comprises a population of delivery particles. The contacting step results in the deposition of one or more of the delivery particles on the surface of the fabric. The delivery particles comprise a core and a shell surrounding the core, wherein the core comprises a beneficial agent, preferably an aromatic material comprising one or more fragrance ingredients. The shell comprises a polymeric material, such as the reaction product of chitosan of a specific molecular weight with a crosslinking agent. Suitable treatment compositions and delivery particles are described in more detail above.

[0150] The contacting step can occur during a manual laundry washing process (e.g., in a laundry basin when handling the fabric by hand), or an automatic laundry washing 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 laundry washing process, such as in an automatic dryer; in such cases, the treatment composition can be in the form of a nonwoven dryer sheet or a dryer bar. The contacting step can occur due to the direct application of the treatment composition to the fabric, such as in a pretreatment operation or in a "refreshing" step (e.g., for 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, a bar, or a spray, preferably a spray. Contacting the target fabric relatively late in the washing process (e.g., during the rinse cycle) improves the likelihood or efficiency of deposition onto the fabric as they are less likely to be rinsed down the drain.

[0151] The contacting step can be carried out in the presence of water. The treatment composition can be diluted with water to form a treatment liquid. The treatment composition can be diluted from about 100-fold to about 1500-fold, preferably 300-fold to about 1000-fold.

[0152] 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 typically in the range of about 5 °C to about 90 °C, and the ratio of water to fabric can typically be about 1:1 to about 30:1.

[0153] 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.

[0154] As described above, the method can further include a step of drying the fabric that has one or more delivery particles on the surface of the fabric. The drying step can include a passive drying process, such as on a clothesline or a drying rack. The drying step can include an automatic drying process, such as in an automatic dryer.

[0155] Combination

[0156] Specifically contemplated combinations of the present disclosure are described herein in the following lettered paragraphs. These combinations are illustrative in nature and not restrictive.

[0157] 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 shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises an aroma material, wherein the aroma material comprises: (a) at least about 30% by weight of the aroma material of an ester-containing perfume raw material ("PRM"), and (b) at least about 0.5% by weight of the aroma material of an aldehyde-containing PRM.

[0158] B. 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 shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises an aroma material, wherein the aroma material comprises one or more perfume raw materials ("PRM"), and wherein the aroma material is characterized by one or more of the following: (a) having an S-ESTER value of at least about 5, wherein the S-ESTER value of the aroma material is calculated as the weight-average S-ESTER value of the perfume raw materials; and / or (b) comprising at least about 30% by weight of the aroma material of a perfume raw material having an S-ESTER value of 13 or greater.

[0159] C. The treatment composition according to any one of paragraphs A or B, wherein the aroma material comprises at least about 35%, preferably at least about 40%, preferably at least about 50% by weight of the aroma material of an ester-containing PRM.

[0160] D. The treatment composition according to any one of paragraphs A to C, wherein the aroma material is characterized by having an S-ESTER value of at least about 5.5, preferably at least about 6, preferably wherein the S-ESTER value is not greater than about 20, preferably not greater than about 13, more preferably not greater than about 10.

[0161] E. The treatment composition according to any one of paragraphs A to D, wherein the aroma material comprises at least about 40%, preferably at least about 50%, more preferably at least about 55% by weight of a perfume raw material having an S-ESTER value of about 13 or greater, preferably about 13 to about 80, more preferably about 13 to about 35, even more preferably about 13 to about 20.

[0162] F. The treatment composition according to any one of paragraphs A to E, wherein the ester-containing fragrance raw material comprises one or more materials selected from the group consisting of: 4-tert-butylcyclohexyl acetate; allyl pentyl glycolate; allyl hexanoate; allyl cyclohexanepropionate; allyl heptanoate; amyl acetate (isomer blend); cis-3-hexenyl acetate; cis-3-hexenyl salicylate; cyclobutane; cyclogopone ester; cyclobutyrate; dihydroterpinyl acetate; dimethyl benzyl carbinyl acetate; dimethyl benzyl carbinyl butyrate; total amount of cyclopentadecanolide; ethyl 2-methyl pentanoate; ethyl acetate; ethyl butyrate; ethylene glycol brassylate; ethyl isovalerate; ethyl lactone; ethyl methyl phenyl glycidate; ethyl methyl phenyl glycidate; ethyl 2-methylbutyrate; ethyl yeastate; ethyl berry; fruitene; γ-decalactone; geranyl acetate; cyclopentadecenolide; galaxolide; hexyl acetate; isobornyl acetate; isononyl acetate; isopentyl butyrate; benzyl acetate; methyl anthranilate; methyl benzoate; methyl dihydrojasmonate; methyl dioxolane; methyl lactone; methyl phenyl carbinyl acetate; musk RI; octahydrocoumarin; phenoxyethyl isobutyrate; phenethyl tiglate; isoprenyl acetate; romandolide; sclareolide; terpinyl acetate; thesaron; triethyl citrate; undecanolide; o-tert-butylcyclohexyl acetate; violiff; zenolide; and combinations thereof.

[0163] G. The treatment composition according to any one of paragraphs A to F, wherein the fragrance material comprises at least about 1% of aldehyde-containing PRM by weight of the fragrance material, preferably at least about 5%, more preferably at least about 10% of aldehyde-containing PRM.

[0164] H. The treatment composition according to any one of paragraphs A to G, wherein the fragrance material further comprises no more than about 30% of hydroxyl-containing PRM by weight of the fragrance material, preferably about 1% to about 30% of hydroxyl-containing PRM.

[0165] I. The treatment composition according to any one of paragraphs A to H, wherein the fragrance material comprises: about 45% to about 55% of ester-containing PRM; about 10% to about 25% of aldehyde-containing PRM; about 5% to about 20% of hydroxyl-containing PRM; and optionally about 1% to about 40% of additional PRM.

[0166] J. The treatment composition according to any one of paragraphs A to I, wherein the core further comprises a dispensing modifier optionally present in the core in an amount of about 10% to about 50% by weight of the core, preferably a dispensing modifier selected from the group consisting of: vegetable oil, modified vegetable oil, C4-C 24Mono-esters, di-esters and tri-esters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate and mixtures thereof, more preferably isopropyl myristate.

[0167] K. The treatment composition according to any one of paragraphs A to J, wherein the biopolymer is selected from the group consisting of polysaccharides, proteins, nucleic acids, their derivatives and combinations thereof; preferably wherein the biopolymer is selected from the group consisting of: chitosan, amine-modified starch, amine-modified dextran, amine-modified maltodextrin, amine-modified dextrin, amine-modified cellulose, amine-modified hemicellulose, chitin, amine-modified alginate, amine-modified lignin, amine-modified gum, amine-modified pectin, amine-modified agar, melanin, fibroin, gelatin, collagen, casein, sericin, fibroin, whey protein, pea protein, corn protein, soy protein, plant storage protein, gluten, peptide, actin, polynucleotide, RNA, DNA, their derivatives and combinations thereof.

[0168] L. The treatment composition according to any one of paragraphs A to K, wherein the biopolymer is chitosan, its derivatives or combinations thereof, preferably wherein the biopolymer is acid-treated chitosan.

[0169] M. The treatment composition according to any one of paragraphs A to L, wherein the biopolymer, preferably chitosan, more preferably acid-treated chitosan, is 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, even more preferably about 100 kDa to about 200 kDa.

[0170] N. A treating composition according to any one of paragraphs A to M, 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 selected from the group consisting of 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; diphenylmethane diisocyanate; toluene diisocyanate; tetramethyldimethylaniline diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (such as their prepolymers, oligomers, and / or polymers); and combinations thereof.

[0171] O. A treating composition according to any one of paragraphs A to N, 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 20 microns to about 30 microns.

[0172] P. A treating composition according to any one of paragraphs A to O, wherein when tested according to test method OECD 301B, the shell of the delivery particles degrades by at least 60% after 60 days.

[0173] Q. A treating composition according to any one of paragraphs A to P, wherein the treatment aids are selected from the group consisting of surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clays and soil removal / anti-redeposition agents, optical brighteners, defoamers, silicones, colorants, aesthetic dyes, perfume bases, additional perfume delivery systems, structure elasticizers, carriers, hydrotropes, processing aids, anti-caking agents, coatings, formaldehyde scavengers, pigments, and mixtures thereof.

[0174] R. A treating composition according to any one of paragraphs A to Q, wherein the treatment aids include anionic surfactants, cationic conditioners, or mixtures thereof.

[0175] S. A treatment composition according to any one of paragraphs A to R, wherein the treatment composition is a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition, a body cleansing composition, or a mixture thereof, preferably a fabric care composition, more preferably a fabric care composition in the form of a laundry detergent composition, a fabric conditioning composition, a laundry washing additive, a fabric pretreatment composition, a fabric freshener composition, or a mixture thereof.

[0176] T. A treatment composition according to any one of paragraphs A to S, 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 tablet, a bead, a fibrous article, a tablet, a bar, a strip, a flake, a foam / mousse, a non-woven sheet, or a mixture thereof, preferably in the form of a liquid composition.

[0177] U. A treatment composition according to any one of paragraphs A to T, wherein the consumer product composition further comprises from about 50% to about 99% by weight of water, preferably from about 60% to about 98% by weight, more preferably from about 80% to about 96% by weight of water, based on the weight of the treatment composition.

[0178] V. 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 U.

[0179] W. A method of preparing a treatment composition, the method comprising the steps of: providing a base composition, wherein the base composition comprises a treatment aid; and combining a population of delivery particles with the base composition, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises an aroma material, and wherein the aroma material comprises: (a) at least about 30% by weight of an ester-containing perfume raw material ("PRM") based on the weight of the aroma material, and (b) at least about 0.5% by weight of an aldehyde-containing PRM based on the weight of the aroma material.

[0180] Test method

[0181] It should be understood that the test methods disclosed in the test methods section of the present application should be used to determine the corresponding parameter values of the subject matter claimed by the applicant as claimed and described herein.

[0182] Method for determining S-ESTER value

[0183] The S-ESTER value is based on the atom-level electrotopological state (E-state) index of one or more compounds. The E-state value is a molecular descriptor that can be found in the literature and / or determined using commercially available software programs. The E-state value effectively examines each atom in the molecule and reflects the valence electronegativity of the atom, which is affected by the atoms connected to it. The electrotopological state index is discussed in more detail in Hall et al., Electrotopological State Indices for Atom Types: A Novel Combination of Electronic, Topological, and Valence State Information, J. Chem. Inf. Comput. Sci. 1995, 35, 1039-1045.

[0184] To determine the E-state and S-ESTER values for the purposes described in this disclosure, the E-state values were calculated using the software program winMolconn version 1.2.2.3 (purchased from Hall Associates Consulting of Quincy, MA) according to the manufacturer's instructions. A 2D connection table (SDF format or SMILES) was used to prepare the structures. The value labels used in the model test method calculations were the same as those reported by winMolconn; their descriptions and definitions can be found in the winMolconn documentation associated with the software.

[0185] To determine the S-ESTER value of a particular fragrance ingredient or other compound, the E-state value of each atom was calculated using the software program winMolconn version 1.2.2.3. The S-ESTER value is the sum of the atom-level electrotopological state (E-state) values of all the carbonyl carbons and oxygens in the ester groups in the molecule. If the compound contains multiple ester groups, the E-state values of all the ester groups are added together. If the compound does not have an ester group, the S-ESTER value of the compound is zero.

[0186] As an example, the following table shows the SMILES input for the ester-containing PRM, ethyl acetate, and the resulting S-ESTER value provided by the software.

[0187] SMILES input in winMolconn software Nme SEster CC(OC1C2C3C(C=CC3)C(C2)C1)=O Yeast acetate 16.2105

[0188] To determine the S-ESTER value of a compound mixture (such as an aromatic material containing more than one fragrance ingredient), the S-ESTER value of each compound was first determined as described above. Based on the relative proportions (by weight percentage) of each individual compound in the mixture, the S-ESTER value of the mixture was calculated by finding the weighted average of the S-ESTER values.

[0189] Determination of polymer molecular weight and related parameters

[0190] 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.

[0191] 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

[0192] the obtaining of information on the number-average (Mn) and weight-average (Mw) molecular weights.

[0193] The Mw distribution of water-soluble polymers such as chitosan is typically measured using a liquid chromatography system (e.g., an Agilent 1260 Infinity pump system with OpenLab Chemstation software, Agilent Technology, Santa Clara, CA, USA) and a column set operating at 40 °C (e.g., 2 Tosoh TSKgel G6000WP 7.8 x 300 mm 13 um pore size, guard column A0022 6 mm x 40 mm PW xl-cp, King of Prussia, PA). The mobile phase is an aqueous 0.1 M sodium nitrate solution containing 0.02% sodium azide and 0.2% acetic acid. The mobile phase solvent is pumped isocratically at a flow rate of 1 mL / min. Using a multi-angle light scattering (18-Angle MALS) detector controlled by Wyatt software v8.0 and a differential refractive index (RI) detector (Wyatt Technology, Santa Barbara, California, USA).

[0194] Typically, a sample is prepared by dissolving the chitosan material in the mobile phase at about 1 mg / ml 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.

[0195] The number-average molecular weight (Mn), weight-average molecular weight (Mw), z-average molecular weight (Mz), molecular weight at the peak maximum (Mp), and polydispersity (Mw / Mn) were determined using the dn / dc value (differential change of refractive index with concentration, 0.15) by Astra detector software.

[0196] Viscosity

[0197] The viscosity of the liquid finished product was measured using an AR 550 rheometer / viscometer from TA Instruments (New Castle, DE, USA) with parallel steel plates having a diameter of 40 mm and a gap size of 500 μm. -1 The high-shear viscosity at 20 s -1 and the low-shear viscosity at 0.05 s -1 were obtained from a logarithmic shear rate sweep from 0.01 s -1 to 25 s

[0198] Test method for determining logP

[0199] 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.

[0200] Volume-weighted particle size and size distribution

[0201] Determine the volume-weighted particle size distribution by single particle optical sensing (SPOS) (also known as optical particle counting (OPC)) using an AccuSizer 780AD instrument and the accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, U.S.A.) or equivalent. The instrument is configured with the following conditions and selections: flow rate = 1 ml / sec; lower size threshold = 0.50 μm; sensor model = LE400-05 or equivalent; automatic dilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 ml; maximum coincidence = 9200. Start the measurement by flushing the sensor with water until the background count is less than 100 to bring it to a cold state. Introduce the sample in suspension from the delivery capsule and adjust the density of the capsule with DI water by automatic dilution as needed to obtain a capsule count of at least 9200 / ml. Analyze the suspension over a 60-second period. Plot and record the resulting volume-weighted PSD data and determine the values of the volume-weighted particle size as required (e.g., median / 50th percentile, 5th percentile, and / or 90th percentile).

[0202] Procedure for determining % degradation

[0203] 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.

[0204] Fabric treatment

[0205] Process the fabric using a Miele washing machine. For each process, 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 processing, pretreat 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.

[0206] 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.

[0207] For the test treatment, the load was washed using a short cotton cycle at 40 °C, a spin speed of 1200 rpm and 79 g of IEC A basic detergent 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 perfume intensity on the dry terry cloth towel tracer. For comparative purposes, a reference treatment was also carried out, where the same perfume as in the test sample was used, but polyacrylate capsules were used as the delivery particles. All comparative treatments were washed and analyzed on the same day

[0208] Olfactory evaluation method

[0209] After treatment of the fabric, a professional perfumer performed an olfactory assessment of the perfume intensity at the DRY contact point on the dry fabric (dry fabric odor = DFO), and the scores were averaged. The scores were based on a perfume odor intensity scale of 0 to 100, where 0 = no perfume odor, 25 = slight perfume odor, 50 = moderate perfume odor, 75 = strong perfume odor, and 100 = extremely strong perfume odor.

[0210] Method for determining headspace concentration above treated dry fabric

[0211] The cotton tracer was analyzed by the fast headspace GC / MS (gas chromatography - mass spectrometry) method. A 4X4 cm aliquot of the terry cloth towel cotton tracer was transferred to a 25 mL headspace vial. The fabric sample was equilibrated at 65 °C for 10 minutes. The headspace above the fabric was sampled for 5 minutes via the SPME (50 / 30μm DVB / Carboxen / PDMS) method. Subsequently, the SPME fiber was instantaneously thermally desorbed into the GC. The analytes were analyzed by fast GC / MS in full scan mode. The total HS response and perfume headspace composition above the test leg were calculated using ion extraction of specific masses with PRM.

[0212] Total weight % of degraded PRM in delivery particle composition

[0213] To determine the total amount of degraded PRM in the delivered particulate composition, an aroma raw material was used as a reference to measure the total fragrance (encapsulated + unencapsulated). For this purpose, gas chromatography with a mass spectrometry detector (GC-MS) was used. Suitable equipment includes: Agilent GC8890 equipped with an Agilent 5977B mass spectrometer or equivalent, capillary column operation, quantification based on the ability to extract ions, an autosampler; and a 30 m × 0.25 mm nominal diameter column, 1 μm film thickness, J&W 122-5533 DB-5MS or equivalent.

[0214] Weigh approximately 0.1 g of the delivered particulate composition and record the weight. Then, add the internal standard (Tonalid, from Merck) and 10 mL of ethanol to the sample. Heat the suspension at 60 °C for 45 minutes and then place it in an ultrasonic bath (such as Branson 3510) for 15 minutes. Then, filter the cooled solution through a 0.45 μm pore size PTFE syringe filter and analyze it via GC-MS. The amount of PRM measured is determined by the response of each PRM, and the total weight percentage of PRM degradation can be determined as follows:

[0215]

[0216] where i is each individual PRM that is part of the aroma composition and n is the total number of PRMs in the aroma composition.

[0217] Example

[0218] The examples provided below are essentially intended to be illustrative and not restrictive.

[0219] Example 1. Exemplary fragrance material

[0220] Table 1 shows exemplary aroma materials according to the present disclosure. The fragrance raw materials are listed, along with the relative weight percentages (by weight of the aroma material) and the S-ESTER values of each fragrance raw material. Based on these values, the S-ESTER value of the total aroma material can be calculated as the weight-average S-ESTER value.

[0221] Table 1.

[0222]

[0223]

[0224] E = material containing an ester functional group

[0225] A = material containing an aldehyde functional group

[0226] Based on the information in Table 1, the exemplary fragrance material comprises 37% ester-containing material and 37% aldehyde-containing material by weight of the fragrance material.

[0227] In addition, based on the weighted average calculation of the S-ESTER value of the PRM, the S-ESTER value of the total fragrance material was determined to be 7.913.

[0228] Example 2. Illustrative delivery particle synthesis

[0229] In the following examples, the abbreviations correspond to the materials listed in Table 2.

[0230] Table 2

[0231]

[0232] The aqueous phase was prepared by dispersing 92.19 g of ChitoClear into 1956.6 g of water while mixing in a jacketed reactor. Then the pH of the aqueous phase was adjusted to between 5.0 and 5.3 using concentrated HCl with stirring. Then the temperature of the aqueous phase was raised to 85 °C within 60 minutes and then held at 85 °C for 2 hours to acid-treat ChitoClear. Then the temperature of the aqueous phase was lowered to 25 °C within 90 minutes after the hydrolysis step. The oil phase was prepared by mixing 716.37 g of the fragrance oil according to the present disclosure (e.g., the fragrance material of Example 1), 179.11 g of isopropyl myristate, and 19.54 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. The emulsion was heated to 40 °C within 30 minutes and held for 60 minutes. Then the emulsion was heated to 85 °C and held at this temperature for 6 hours while mixing.

[0233] Example 3. Effect of encapsulation fragrance selection

[0234] To compare different chitosan delivery particles, samples of liquid fabric enhancer ("LFE") were prepared with different particles. The same fragrance was used in the delivery particles evaluated in the reference treatment, and each core also contained approximately 20%-35% of a partitioning modifier (i.e., isopropyl myristate). The LFE composition contains a softening active substance (diester quaternary ammonium salt) present at 6%, the relevant delivery particles added in an amount sufficient to provide 0.2% encapsulated fragrance, 0.11% structuring agent (cationic polymer - Flosoft FS222, from SNF), and various processing trace components, with the pH adjusted to approximately 3.

[0235] For the examples, liquid fabric enhancer products having the general formula according to Table 3 below were prepared.

[0236] Table 3 .

[0237]

[0238] Seven different fragrances were encapsulated in both delivery particles according to the present disclosure (e.g., walls made of chitosan and cross-linked with isocyanate) and reference polyacrylate (“PAC”) delivery particles. The components of the tested fragrances are generally described in Table 3 below; note that fragrance raw materials with more than one type of functional moiety are counted in each “functionality” category, which may result in the PRM being counted more than once, and the percentages may appear to total more than 100%. The S-ESTER values for each fragrance are also provided in Table 4. Fragrances 1-4 (“Fragrance 1,” etc.) are fragrance materials according to the present disclosure; fragrances 5-7 (“Fragrance 5,” etc.) are comparative fragrance materials.

[0239] The walls of the delivery particles according to the present disclosure used in the experiments were made of an amine-containing biopolymer (acid-treated chitosan) and a cross-linking agent (polyisocyanate) (target volume-weighted median particle size = 28 microns). The reference polyacrylate delivery particles were prepared substantially according to the method described in U.S. Publication 2011 / 0268802. Notably, the walls of the PAC delivery particles were not made of monomers with primary amines, and thus the reactivity with aldehyde-based PRMs was not significantly expected. The reference PAC particles for fragrances 1-5 were characterized by a core:shell weight ratio of approximately 90:10. The reference PAC particles for fragrances 6 and 7 were characterized by a core:shell weight ratio of approximately 97:3 to approximately 98:2.

[0240] The components of the fragrances in the delivery particles were analyzed using the analytical filtration method described in the test method section above and compared with the fragrance oils before encapsulation. From this analysis, the total weight % of the degraded PRM was calculated according to the method described above.

[0241] The results are provided in Table 4 below. For comparison purposes, the olfactory DFO data for the chitosan-based delivery particles were reported as Δ values relative to the DFO generated by the reference polyacrylate delivery particles containing the same fragrance according to the following formula.

[0242] ΔDFO = DFOchitosan delivery particle (test) - DFO PAC delivery particle (reference)

[0243] The ΔDFO entries with an asterisk (*) are statistically significant compared to the reference values.

[0244] Table 4

[0245]

[0246] As shown in Table 4, the delivery particles of the present invention (characterized in that the core contains an aroma having more than 30% esters and / or an S-ESTER value greater than 5) perform substantially the same on an olfactory basis compared to reference polyacrylate capsules. In addition, they show that the total degradation % of PRM in the core is less than 5%. On the other hand, the comparative delivery particles (which have a similar wall but are characterized in that the core contains an aroma having less than 30% esters and / or an S-ESTER value less than 5) perform significantly worse compared to reference polyacrylate capsules. In addition, they show that the total degradation % of PRM in the core is greater than 5%.

[0247] The dimensions and values disclosed herein should not be understood as being strictly limited to the exact values recited. Instead, each such dimension is intended to mean the recited value and a range functionally equivalent around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0248] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application, and any patent application or patent to which this application claims priority or for which it claims benefit of the advantage, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, or that it alone, or in any combination with any one or more other references, 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.

[0249] While specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended that all such changes and modifications that fall within the scope of the invention be covered by the appended claims.

Claims

1. A treatment composition comprising: a treatment aid, and a population of delivery particles, wherein said delivery particles comprise a core and a shell surrounding said core, wherein said shell comprises a polymeric material, wherein said polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein said biopolymer comprises primary amine groups, wherein said core comprises an aroma material, wherein said aroma material comprises: (a) at least about 30% by weight of the aroma material of an ester-containing perfume raw material ("PRM"), and (b) at least about 0.5% by weight of the aroma material of an aldehyde-containing PRM.

2. A treatment composition comprising: a treatment aid, and a population of delivery particles, wherein said delivery particles comprise a core and a shell surrounding said core, wherein said shell comprises a polymeric material, wherein said polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein said biopolymer comprises primary amine groups, wherein said core comprises an aroma material, wherein said aroma material comprises one or more perfume raw materials ("PRM"), and wherein said aroma material is characterized by one or more of the following: (a) having an S-ESTER value of at least about 5, wherein the S-ESTER value of said aroma material is calculated as the weight-average S-ESTER value of the perfume raw materials; and / or (b) comprising at least about 30% by weight of the aroma material of a perfume raw material having an S-ESTER value of 13 or greater.

3. The treatment composition according to any one of claims 1 or 2, wherein said aroma material comprises at least about 35%, preferably at least about 40%, preferably at least about 50% by weight of the aroma material of an ester-containing PRM.

4. The treatment composition according to any one of the preceding claims, wherein said aroma material is characterized by having an S-ESTER value of at least about 5.5, preferably at least about 6, preferably wherein said S-ESTER value is not greater than about 20, preferably not greater than about 13, more preferably not greater than about 10.

5. The treatment composition according to any one of the preceding claims, wherein said aroma material comprises at least about 40%, preferably at least about 50%, more preferably at least about 55% by weight of a perfume raw material having an S-ESTER value of about 13 or greater, preferably from about 13 to about 80, more preferably from about 13 to about 35, even more preferably from about 13 to about 20.

6. The treatment composition according to any one of the preceding claims, wherein the ester-containing fragrance raw material comprises one or more materials selected from the group consisting of: 4-tert-butylcyclohexyl acetate; allyl pentyl glycolate; allyl hexanoate; allyl cyclohexanepropionate; allyl heptanoate; amyl acetate (isomer blend); cis-3-hexenyl acetate; cis-3-hexenyl salicylate; cyclobutane; cyclogopone ester; cyclobutyrate; dihydroterpinyl acetate; dimethylbenzyl carbinyl acetate; dimethylbenzyl carbinyl butyrate; total amount of cyclopentadecanolide; ethyl 2-methylvalerate; ethyl acetate; ethyl butyrate; ethylene glycol brazileinate; ethyl isovalerate; ethyl lactone; ethyl methylphenylglycidate; ethyl methylphenylglycidate; ethyl 2-methylbutyrate; yeast acetate; ethyl berry; fruitene; γ-decalactone; geranyl acetate; cyclopentadecenolide; galaxolide; hexyl acetate; isobornyl acetate; isononyl acetate; isopentyl butyrate; benzyl acetate; methyl anthranilate; methyl benzoate; methyl dihydrojasmonate; methyldioxolane; methyl lactone; methylphenyl carbinyl acetate; musk RI; octahydrocoumarin; phenoxyethyl isobutyrate; phenethyl tiglate; isoprenyl acetate; romandolide; sclareolide; terpinyl acetate; thesaron; triethyl citrate; undecanolide; o-tert-butylcyclohexyl acetate; violiff; zenolide; and combinations thereof.

7. The treatment composition according to any one of the preceding claims, wherein the fragrance material comprises at least about 1% of aldehyde-containing PRM by weight of the fragrance material, preferably at least about 5% and more preferably at least about 10% of aldehyde-containing PRM by weight of the fragrance material.

8. The treatment composition according to any one of the preceding claims, wherein the fragrance material further comprises up to about 30% of hydroxyl-containing PRM by weight of the fragrance material, preferably about 1% to about 30% of hydroxyl-containing PRM.

9. The treatment composition according to any one of the preceding claims, wherein the fragrance material comprises: about 45% to about 55% of ester-containing PRM; about 10% to about 25% of aldehyde-containing PRM; about 5% to about 20% of hydroxyl-containing PRM; and optionally about 1% to about 40% of additional PRM.

10. The treatment composition according to any one of the preceding claims, wherein the core further comprises a dispensing modifier optionally present in the core in an amount of about 10% to about 50% by weight of the core, Preferably select a dispensing modifier from the group consisting of: vegetable oil, modified vegetable oil, mono-esters, di-esters and tri-esters 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.

11. 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, their derivatives, and combinations thereof; preferably wherein the biopolymer is selected from the group consisting of: Chitosan, amine-modified starch, amine-modified dextran, amine-modified maltodextrin, amine-modified dextrin, amine-modified cellulose, amine-modified hemicellulose, chitin, amine-modified alginate, amine-modified lignin, amine-modified gum, amine-modified pectin, amine-modified agar, melanin, silk fibroin, gelatin, collagen, casein, sericin, fibroin, whey protein, pea protein, corn protein, soy protein, plant storage protein, gluten, peptide, actin, polynucleotide, RNA, DNA, their derivatives, and combinations thereof.

12. The treatment composition according to any one of the preceding claims, wherein the biopolymer is chitosan, its derivatives, or a combination thereof, preferably wherein the biopolymer is acid-treated chitosan.

13. The treatment composition according to any one of the preceding claims, wherein the biopolymer, preferably chitosan, more preferably acid-treated chitosan, has 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.

14. 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 selected from the group consisting of polyisocyanates, epoxides, bifunctional aldehydes, and combinations thereof, more preferably polyisocyanates, 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'-methylenebiphenyl diisocyanate; 4,4'-methylenebiphenyl diisocyanate; 2,4'-methylenebiphenyl diisocyanate; diphenylmethane diisocyanate; toluene diisocyanate; tetramethylxylenediamine 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.

15. The treatment composition according to any one of the preceding claims, wherein the delivery particles have 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 20 microns to about 30 microns.

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