Treatment composition with perfume-containing delivery particles

Abstract

A treatment composition comprising a processing aid and a population of core / shell delivery particles, wherein the shell comprises a polymeric material formed from a crosslinked amine-containing biopolymer and the core comprises a fragrance material comprising an ester-containing perfume raw material. Related methods of making and using such compositions.

Description

[Technical Field]

[0001] The present disclosure relates to treatment compositions comprising a processing aid and a population of core / shell delivery particles, wherein the shell comprises a polymeric material formed from a crosslinked amine-containing biopolymer and the core comprises a fragrance material comprising an ester-containing perfume raw material. The present disclosure also relates to related methods of making and using such compositions. [Background technology]

[0002] Delivery particles, especially core / shell delivery particles, are a convenient way to deliver benefit agents into treatment compositions such as laundry products.For environmental reasons, it may be desirable to use delivery particles with shells made from naturally occurring and / or biodegradable materials.Useful shell-forming materials often contain primary amine groups, and such materials react easily with some crosslinking agents, such as polyisocyanates, to form suitable polymeric materials.

[0003] However, when perfume is encapsulated in core-shell delivery particles, certain shell materials may interact with certain perfume raw materials, which results in capsules with relatively poor performance.For example, when making particles with polymer shells made from materials containing primary amines (such as chitosan), perfume raw materials containing aldehyde groups may react with amine groups, which may result in capsules that are relatively weak and / or leaky.In particular, it is known that the encapsulation of aldehyde-containing perfumes in polyurea shells is difficult. Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

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

[0006] For example, the present disclosure relates to a treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the shell comprising a polymeric material, the polymeric material comprising a reaction product of a biopolymer and a crosslinker, the biopolymer comprising primary amine groups, the core comprising a fragrance material, the fragrance material comprising (a) at least about 30% by weight of the fragrance material of an ester-containing perfume raw material (“PRM”), and (b) at least about 0.5% by weight of the fragrance material of an aldehyde-containing PRM.

[0007] The present disclosure also relates to a treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the shell comprising a polymeric material, the polymeric material comprising a reaction product of a biopolymer and a crosslinker, the biopolymer comprising primary amine groups, the core comprising a fragrance material, the fragrance material comprising one or more fragrance raw materials (“PRM”), the fragrance material 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) comprising at least about 30% by weight of the fragrance material of fragrance raw materials having an S-ESTER value of 13 or greater.

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

[0009] The present disclosure also relates to a method of making a treatment composition, the method comprising: providing a base composition, the base composition comprising a processing aid; and combining a population of delivery particles with the base composition, the delivery particles comprising a core and a shell surrounding the core, the shell comprising a polymeric material, the polymeric material comprising a reaction product of a biopolymer and a crosslinker, the biopolymer comprising primary amine groups, the core comprising a fragrance material, the fragrance material comprising: (a) at least about 30% by weight of the fragrance material of an ester-containing perfume raw material (“PRM”), and (b) at least about 0.5% by weight of the fragrance material of an aldehyde-containing PRM. Additionally or alternatively, the fragrance material may 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 ingredients; and / or (b) comprising at least about 30% by weight of the fragrance material of fragrance ingredients having an S-ESTER value of 13 or greater. DETAILED DESCRIPTION OF THE INVENTION

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

[0011] Without being bound by theory, it is believed that ester-containing PRMs create hydrogen bonds or dipole moments that "engage" with the amine groups of amine-containing biopolymers, thereby reducing the reaction of "available" or "free" amine groups with aldehyde and / or ketone-containing PRMs. While the groups may temporarily "engage," the temperatures at which such delivery particles are typically prepared (e.g., 50-95°C) are believed not to favor reactions between amine and ester groups. Furthermore, despite the relatively strong hydrogen-bonding ability of ester groups, amine / ester reactions are believed to be kinetically unfavorable compared to amine reactions with isocyanates (e.g., from a crosslinker) or aldehydes (e.g., from another PRM), which is reflected in the S-ESTER descriptor described herein.

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

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

[0014] As used herein, the articles "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described. As used herein, the terms "include," "includes," and "including" are meant to be open-ended. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0015] The terms "substantially free of" or "substantially free from" may be used herein. This means that the indicated material is in minimal amounts and has not been intentionally added to the composition to form part of the composition, or preferably is not present at analytically detectable concentrations. It includes compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material, if present at all, may be present at a concentration of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0016] As used herein, "consumer product" means a baby care, beauty care, fabric and home care, family care, feminine care, or health care product or device that is intended for use or consumption in the form in which it is sold and not for subsequent commercial manufacture or modification. Such products include diapers, bibs, wipes, products and / or related methods for treating human hair, including bleaching, coloring, dyeing, conditioning, shampooing, styling, deodorants and antiperspirants, personal cleansing, skin care, including the application of creams, lotions, and other topically applied products intended for consumer use, and shaving products, products and / or related methods for treating fabrics, hard surfaces, and any other surface in the fabric or home care category, including air care, auto care, dishwashing, fabric conditioning (including softening), and the like. products and / or methods relating to toilet paper, tissue, paper handkerchiefs, and / or paper towels; tampons, feminine napkins, adult incontinence products; oral care products and / or methods including toothpaste, tooth gels, mouth rinses, denture adhesives, tooth whitening agents; non-prescription health care including cough and cold treatments; pest control products; and water purification.

[0017] As used herein, the phrase "fabric care composition" includes compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric deodorizing compositions, laundry pre-cleaners, laundry pre-treatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatments, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions can be used as laundry pre-treatments, laundry post-treatments, or can be added during the rinse or wash cycle of laundry operations.

[0018] As used herein, "delivery particles," "particles," "encapsulations," "microcapsules," and "capsules" are used interchangeably unless otherwise indicated. As used herein, these terms typically refer to core / shell delivery particles.

[0019] Unless otherwise noted, all ingredient or composition concentrations are in terms of the active portion of that ingredient or composition and are exclusive of impurities, e.g., residual solvents or by-products, that may be present in commercial sources of such ingredient or composition.

[0020] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All measurements herein are made at 20°C and atmospheric pressure unless otherwise stated.

[0021] In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless specifically stated otherwise.

[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 includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0023] Treatment Composition The present disclosure relates to treatment compositions (or simply "compositions" as used herein). The compositions of the present disclosure may include a population of delivery particles and a treatment aid, each of which is described in more detail below. The treatment compositions may be useful in the methods of treating surfaces, such as fabrics, described herein.

[0024] The treatment composition is preferably a consumer product composition. The consumer product composition of the present disclosure can be useful in baby care, beauty care, fabric care, home care, family care, feminine care, and / or health care applications. The consumer product composition can be useful for treating surfaces such as fabric, hair, or skin. The consumer product composition can be intended to be used or consumed in the form in which it is sold. The consumer product composition of the present disclosure is usually not intended for subsequent commercial manufacture or modification.

[0025] The consumer product composition may be a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition (such as a shampoo or conditioner), a body cleansing composition, or a mixture thereof, preferably a fabric care composition.

[0026] The consumer product composition may be a fabric care composition such as a laundry detergent composition (including a heavy-duty liquid cleaning detergent or unit dose article), a fabric conditioning composition (including a liquid fabric softening and / or enhancing composition), a laundry additive, a fabric pre-treatment composition (including a spray, pourable liquid, or spray), a fabric refresher composition (including a spray), or a mixture thereof. The treatment composition is preferably a fabric conditioning composition, more preferably a liquid fabric conditioning composition.

[0027] The composition may be a beauty care composition, such as a hair treatment product (including shampoo and / or conditioner), a skin care product (including a cream, lotion, or other topically applied product for consumer use), a shaving care product (including a shaving lotion, foam, or pre- or post-shave treatment), a personal cleansing product (including a liquid body wash, liquid hand soap, and / or bar soap), a deodorant and / or antiperspirant, or mixtures thereof.

[0028] The compositions may be home care compositions such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other consumer or institutional cleaning.

[0029] The treatment composition may be in the form of a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, a pastille or bead, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven sheet, or mixtures thereof.

[0030] The treatment composition may be in the form of a liquid. The liquid composition may comprise from about 50% to about 97%, preferably from about 60% to about 96%, more preferably from about 70% to about 95%, or even from about 80% to about 95%, by weight of the fabric treatment composition, of water. The liquid composition may be a liquid fabric conditioner. The liquid may be packaged in a pourable bottle. The liquid may be packaged in an aerosol can or other spray bottle. Suitable containers are described in more detail below.

[0031] The treatment composition may be in the form of a solid. The composition may be in the form of beads or pastilles, which may be pastilles from a liquid melt. The composition may be an extruded product. The treatment composition may be in the form of a powder or granules.

[0032] The composition may be in the form of a unit-dose article such as a tablet, pouch, sheet, or fiber article. Such pouches typically include a water-soluble film, e.g., a polyvinyl alcohol water-soluble film, that at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition may be enclosed in a single-compartment pouch or a multi-compartment pouch. A multi-compartment pouch may have at least two, at least three, or at least four compartments. A multi-compartment pouch may include compartments arranged side-by-side and / or stacked. The composition contained in the pouch or its compartments may be liquid, solid (e.g., powder), or a combination thereof. The pouch composition may have a relatively low amount of water, e.g., less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% by weight of the detergent composition.

[0033] The treatment composition may be in the form of a spray, for example, dispensed from a bottle via an aerosol container having a trigger sprayer and / or a valve.

[0034] The treatment composition is applied for 20 seconds. -1and 21°C, 1 to 1500 centipoise (1 to 1500 mPa * s), 100-1000 centipoise (100-1000 mPa * s), or 200 to 500 centipoise (200 to 500 mPa * s).

[0035] Treatment compositions of the present disclosure may be characterized by a pH of about 2 to about 12, or about 2 to about 8.5, or about 2 to about 7, or about 2 to about 5. Treatment compositions of the present disclosure, preferably in the form of an aqueous liquid, may have a pH of about 2 to about 4, preferably about 2 to about 3.7, and more preferably about 2 to about 3.5. Such pH concentrations are believed to promote the stability of quaternary ammonium ester compounds, if present. Meanwhile, detergent compositions are typically characterized by a pH of about 7 to about 12, preferably about 7.5 to about 11. The pH of the composition is measured by dissolving / dispersing the composition in deionized water to form a 10% concentration solution at about 20°C.

[0036] Additional components and / or properties of the composition are discussed in more detail below.

[0037] Delivery particle population The treatment composition of the present disclosure includes a population of delivery particles. The delivery particles include a core and a shell surrounding the core. The core may include a fragrance material and, optionally, a partitioning modifier. The core can be liquid or solid at room temperature, preferably liquid.

[0038] The treatment composition may comprise from about 0.05% to about 20%, or from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.2% to about 2%, by weight of the composition, of delivery particles. The composition may comprise a sufficient amount of total delivery particles to provide the composition with from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 2%, by weight of the composition, of encapsulated benefit agent, preferably perfume raw material. As discussed herein, the amount or weight percent of delivery particles refers to the combined wall material and core material.

[0039] A population of delivery particles according to the present disclosure can be characterized by a volume-weighted median particle diameter of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 25 to about 35 microns. For certain compositions, it may be preferred that the population of delivery particles be characterized by a volume-weighted median particle diameter of about 1 to about 50 microns, preferably about 5 to about 20 microns, and more preferably about 10 to about 15 microns. Different particle sizes can be obtained by controlling droplet size during emulsification.

[0040] The delivery particles can be characterized by a core-to-shell ratio of up to 99:1, or even 99.5:0.5, by weight. The shell can be present in a concentration of about 1% to about 25%, preferably about 1% to about 20%, preferably about 1% to about 15%, more preferably about 5% to about 15%, even more preferably about 10% to about 15%, and even more preferably about 10% to about 12%, by weight of the delivery particle. The shell can be present in a concentration of at least 1%, preferably at least 3%, and more preferably at least 5% by weight of the delivery particle. The shell may be present in a concentration of up to about 25%, preferably up to about 20%, preferably up to about 15%, and more preferably up to about 12% by weight of the delivery particle.

[0041] The delivery particles may be cationic, preferably cationic at pH 4.5. The delivery particles may be characterized by a zeta potential of at least 15 millivolts (mV) at a pH of 4.5. The delivery particles may be configured to have a zeta potential of at least 15 millivolts (mV) at a pH of 4.5, or at least 40 mV at a pH of 4.5, or at least 60 mV at a pH of 4.5. Delivery particles prepared with chitosan typically exhibit a positive zeta potential. Such capsules have improved adhesion efficiency on fabrics. At higher pHs, the particles may be nonionic or anionic.

[0042] The delivery particles of the present disclosure comprise a shell surrounding a core. (As used herein, "shell" and "wall" are used interchangeably with respect to delivery particles unless otherwise indicated.) The shell comprises a polymeric material. The polymeric material is the reaction product of a biopolymer and a crosslinker.

[0043] Biopolymers typically contain primary amine groups that can be reacted with a cross-linking agent to form a polymeric material that can be described as a cross-linked biopolymer.

[0044] The biopolymer may preferably be selected from the group consisting of polysaccharides, proteins, nucleic acids, derivatives thereof, and combinations thereof. Preferably, the biopolymer is selected from the group consisting of: (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 fibronin, derivatives thereof, and combinations thereof; (b) a protein selected from the group consisting of gelatin (e.g., porcine gelatin), collagen, casein, sericin, fibroin, whey protein, pea protein, zein, soy protein, plant storage proteins (plant protein isolates, plant protein concentrates), gluten, peptides, actin, derivatives thereof, and combinations thereof; (c) a nucleic acid selected from the group consisting of polynucleotides, RNA, DNA, derivatives thereof, and combinations thereof; and (d) A combination of these.

[0045] Amine-containing polysaccharides may be preferred, for example, for reasons of convenient availability, biodegradability, and / or performance. A particularly preferred material is chitosan. Thus, the biopolymer may preferably be chitosan, a derivative thereof, or a combination thereof. Preferably, the biopolymer is acid-treated chitosan, a derivative thereof, or a combination thereof.

[0046] The chitosan may preferably be acid-treated. For example, chitosan (which may be referred to as raw chitosan or parent chitosan before acid treatment) may be treated with an acid at a pH of 6.5 or less for at least 1 hour, preferably about 1 hour to about 3 hours, or for the time required to obtain a chitosan solution viscosity of about 1500 cps or less, or even 500 cps or less, at a temperature of about 25°C to about 99°C, preferably about 75°C to about 95°C. The acid may be selected from a strong acid (such as hydrochloric acid), an organic acid (such as formic acid or acetic acid), or a mixture thereof. The chitosan may be acid-treated at a pH of 2 to 6.5, preferably about 3 to about 6, or even 4 to 6.

[0047] The biopolymer, preferably chitosan, more preferably acid-treated chitosan, can be characterized by a molecular weight of about 1 kDa to about 1000 kDa, preferably about 50 kDa to about 600 kDa, more preferably about 100 kDa to about 500 kDa, even more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa. Without wishing to be bound by theory, it is believed that biopolymers characterized by relatively low molecular weights are less effective at forming suitable delivery particles, while those with relatively high molecular weights tend to be more difficult to process. The method used to determine the molecular weight and related parameters of chitosan is described in the Test Methods section below and uses gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) techniques.

[0048] The chitosan may be characterized by a degree of deacetylation of at least 50%, preferably about 50% to about 99%, more preferably about 75% to about 90%, and even more preferably about 80% to about 85%. The degree of deacetylation can affect the solubility of the chitosan, which in turn can affect its reactivity or behavior in the process of forming the particle shell. For example, a degree of deacetylation that is too low (e.g., less than 50%) can result in a chitosan that is relatively insoluble and relatively unreactive. A relatively high degree of deacetylation can result in a chitosan that is very soluble, with relatively little chitosan migrating to the oil / water interface during shell formation.

[0049] When present, chitosan may comprise anionically modified chitosan, cationically modified chitosan, or a combination thereof. Anionic and / or cationic modification of chitosan can alter the shell characteristics of the delivery particles, for example, by changing the surface charge and / or zeta potential, which can affect the particle's adhesion efficiency and / or formulation compatibility.

[0050] As mentioned above, the shell is a polymeric material that is the reaction product of the biopolymer chitosan and a crosslinking agent. The crosslinking material is preferably a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxy compounds, polyphenols, carbonyl halides, aziridines, and combinations thereof. The crosslinking agent is more preferably selected from the group consisting of polyisocyanates, epoxy compounds, difunctional aldehydes, and combinations thereof.

[0051] The cross-linking agent is preferably a polyisocyanate. It is believed that such a material will react favorably with the amine groups of the biopolymer to form an effective cross-linked polymer wall. When the cross-linking agent is a polyisocyanate, the polymeric material of the shell can be understood to include a polyurea resin. The polyurea resin may include the reaction product of a polyisocyanate and chitosan.

[0052] Polyisocyanate materials useful in the present disclosure are understood herein to be isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. "Polyisocyanate" is intended to mean a material or compound containing two or more isocyanate moieties. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended to be encompassed by the term "polyisocyanate" herein. Polyisocyanates useful in the present invention include isocyanate monomers, oligomers, or prepolymers, or dimers or trimers thereof, having at least two isocyanate groups. Optimal crosslinking can be achieved using polyisocyanates with a functionality of at least three.

[0053] Aromatic polyisocyanates may be preferred. However, aliphatic polyisocyanates and their blends may also be useful. Aliphatic polyisocyanates are understood to be polyisocyanates that do not contain any aromatic moieties. Aromatic polyisocyanates are understood to be polyisocyanates that contain at least one aromatic moiety. The crosslinker may also comprise a mixture of aromatic and aliphatic polyisocyanates.

[0054] If the polyisocyanate is aromatic, it may be, but is not limited to, methylene diphenyl isocyanate, toluene diisocyanate, tetramethyl xylidene diisocyanate, polyisocyanurate of toluene diisocyanate (available from Bayer under the trade name Desmodur® RC), trimethylolpropane adduct of toluene diisocyanate (available from Bayer under the trade name Desmodur® L75), and phenylene diisocyanate, or trimethylolpropane adduct of xylylene diisocyanate (available from Mitsui Chemicals under the trade name Takenate® D-110N), naphthalene-1,5-diisocyanate.

[0055] Aliphatic polyisocyanates may include trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N 100).

[0056] Derivatives of polyisocyanates may include oligomers or polymers of isocyanate monomers. As a non-limiting example, the polyisocyanate may preferably include oligomers or polymers of diphenylmethane diisocyanate (MDI), such as Mondur® MR-Light.

[0057] The polyisocyanate may preferably be selected from the group consisting of polyisocyanurate of toluene diisocyanate, trimethylolpropane adduct of toluene diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, 2,2'-methylenediphenyl diisocyanate, 4,4'-methylenediphenyl diisocyanate, 2,4'-methylenediphenyl diisocyanate, [diisocyanato(phenyl)methyl]benzene, toluene diisocyanate, tetramethylxylidene diisocyanate, naphthalene-1,5-diisocyanate, 1,4-phenylene diisocyanate, 1,3-diisocyanatobenzene, derivatives thereof (such as prepolymers, oligomers, and / or polymers thereof), and combinations thereof.

[0058] The particle shell may also be reinforced using additional co-crosslinking agents such as polyfunctional amines and / or polyamines, such as diethylene triamine (DETA), polyethyleneimine, polyvinylamine, or mixtures thereof. Acrylates can also be used as additional co-crosslinking agents, for example, to reinforce the shell.

[0059] The polymeric material can be formed in a reaction in which the weight ratio of biopolymer, preferably a polysaccharide, more preferably chitosan or a derivative thereof (which can include acid-treated chitosan), to crosslinker present in the reaction is about 1:10 to about 1:0.1, preferably about 1:5 to about 5:1, preferably about 1:4 to about 5:1, more preferably about 1:1 to about 5:1, and more preferably about 3:1 to about 5:1. It is believed that selecting the desired ratio of biopolymer to crosslinker can provide the desired ductility benefits as well as improved biodegradability. It may be preferred that at least 21% by weight of the shell be comprised of moieties derived from chitosan, preferably acid-treated chitosan. The chitosan weight percentage of the shell may be about 21% to about 95% of the shell. The ratio of chitosan in the aqueous phase compared to isocyanate in the oil phase may be 21:79 to 90:10, or even 1:2 to 9:1, or even 1:1 to 7:1, by weight.

[0060] The shell may comprise chitosan at a concentration of 21% or more by weight of the total shell being chitosan, preferably from about 21% to about 90%, or even from 21% to 85%, or even from 21% to 75%, or even from 21% to 55% by weight. The chitosan in this paragraph may preferably be acid-treated chitosan.

[0061] The population of delivery particles may be made according to a process comprising the following steps: (a) forming an aqueous phase comprising the chitosan described herein, preferably wherein the aqueous phase has a pH of 6.5 or less, more preferably a pH of 3 to 6, and a temperature of at least 25°C; (b) forming an oil phase comprising at least one benefit agent, preferably a fragrance material, and at least a crosslinking agent, preferably at least one polyisocyanate, and optionally a partitioning modifier; (c) forming an emulsion, preferably an oil-in-water emulsion, by mixing the aqueous and oil phases under high shear agitation, and optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6, preferably pH 3 to pH 6; and (d) curing the emulsion by heating, preferably to at least 40°C, for a time sufficient to form a shell at the interface of the oil droplets and the aqueous phase, wherein the shell comprises a polymeric material that is the reaction product of the chitosan and the crosslinking agent, the shell surrounding a core comprising the benefit agent.

[0062] The population of delivery particles may be made according to a process comprising the steps of: (a) forming an aqueous phase by treating chitosan with a mixture of a first acid and a second acid, wherein the first acid comprises a strong acid and the second acid comprises a weak acid, and wherein the chitosan is at a pH of 6.5 or less, or even less than pH 6.5; (b) forming an oil phase comprising dissolving at least one benefit agent and at least one polyisocyanate, optionally with added oil (e.g., partitioning modifier) ​​and / or solvent; (c) mixing the water phase and oil phase into an excess of water phase under high shear agitation to form an emulsion, thereby forming droplets of the oil phase dispersed in the water phase, and optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6, preferably pH 3 to pH 6; and (d) heating the emulsion to at least 40°C and curing for a time sufficient to form a shell at the interface of the droplets and the water phase, the shell comprising the reaction product of the polyisocyanate and acid treated chitosan, the shell surrounding the core comprising the oil phase and droplets of the benefit agent.

[0063] Chitosan can be added to water in a jacketed reactor at a pH of 2 or even 3-6.5 and adjusted using an acid such as concentrated HCl. The chitosan in this mixture can be acid-treated by heating to a high temperature, such as 85°C, for 60 minutes, then held at this temperature for 1 minute to 1440 minutes or more. The aqueous phase can then be cooled to 25°C. Optionally, deacetylation can be further promoted or enhanced by an enzyme that depolymerizes or deacetylates 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 isocyanate (MDI), in oil at 25°C. A diluent, such as isopropyl myristate, can be used to adjust the hydrophilicity of the oil phase. The oil phase is then added to the aqueous phase and milled at high speed to obtain the target size. The emulsion can then be hardened in one or more heating steps, such as heating to 40°C for 30 minutes and holding at 40°C for 60 minutes. The times and temperatures are approximate. The temperature and time are selected to be sufficient to form and harden a shell at the interface between the oil phase droplets and the aqueous continuous phase. For example, the emulsion can be heated to 85°C for 60 minutes and then held at 85°C for 360 minutes to harden the particles. The slurry can then be cooled to room temperature.

[0064] The shell may degrade by at least 50% after 20 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by 30-100%, preferably 40-100%, 50-100%, 60-100%, or 60-95% in 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, or more preferably 14 days.

[0065] The delivery particles of the present disclosure include a core. The core includes a fragrance material. The fragrance material may include one or more perfume raw materials ("PRMs"). The core also optionally includes a partitioning modifier.

[0066] The core of the particle is surrounded by a shell. When the shell ruptures, the fragrance material in the core is released. Additionally or alternatively, the fragrance material in the core may diffuse and / or be extruded from the particle. Suitable fragrance materials located within the core may include fragrance materials that provide a benefit to surfaces such as fabrics and hair.

[0067] The core may contain about 5% to about 100% of the fragrance material by weight of the core, and about 45% to about 95%, preferably about 50% to about 80%, and more preferably about 50% to about 70%, of the fragrance material by weight of the core.

[0068] The fragrance material may be relatively hydrophobic, and such agents are compatible with the oil phase typically used in making the delivery particles of the present disclosure.

[0069] As mentioned above, the core of the delivery particles of the present disclosure contains a fragrance, which may include one or more perfume ingredients. Fragrances are particularly suitable for inclusion in the delivery particles described herein because the fragrance-containing particles can provide freshness benefits across multiple touch points.

[0070] As used herein, the term "perfume raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mole and useful for imparting odors, fragrances, essences, or scents, either alone or in combination with other perfume raw materials. Typical PRMs include, among others, alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes such as terpenes. Lists of common PRMs can be found in various reference sources, such as, for example, "Perfume and Flavor Chemicals," Vol. I and Vol. II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology," Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0071] PRMs may be characterized by their boiling point (BP) measured at atmospheric pressure (760 mmHg) and octanol / water partition coefficient (P), which may be described in terms of logP, determined according to the following test method. Based on these characteristics, PRMs may be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV fragrances, as described in more detail below.

[0072] The fragrance may include perfume raw materials having a logP of from about 2.5 to about 4. It is understood that other perfume raw materials may also be present in the fragrance.

[0073] The perfume raw materials may include perfume raw materials selected from the group consisting of perfume raw materials having a boiling point (BP) below about 250°C and a logP below about 3, perfume raw materials having a BP above about 250°C and a logP above about 3, perfume raw materials having a BP above about 250°C and a logP below about 3, perfume raw materials having a BP below about 250°C and a logP below about 3, perfume raw materials having a BP below about 250°C and a logP above about 3, and mixtures thereof. Perfume raw materials having a boiling point BP below about 250°C and a logP below about 3 are known as Quadrant I perfume raw materials. Quadrant 1 perfume raw materials are preferably limited to less than 30% of the perfume composition. Perfume raw materials having a BP above about 250° C. and a log P above about 3 are known as Quadrant IV perfume raw materials, perfume raw materials having a BP above about 250° C. and a log P below about 3 are known as Quadrant II perfume raw materials, and perfume raw materials having a BP below about 250° C. and a log P above about 3 are known as Quadrant III perfume raw materials. Suitable Quadrant 1, Quadrant 2, Quadrant 3 and Quadrant 4 perfume raw materials are disclosed in U.S. Patent No. 6,869,923 B1.

[0074] As mentioned above, there are problems associated with encapsulating a specific PRM in a specific wall material.Surprisingly, it has been found that by selecting a specific PRM to be encapsulated, effective delivery particles can be made.For example, it has been found to be beneficial to select a specific minimum amount of ester-containing PRM that should be part of the fragrance material to be encapsulated.In addition or alternatively, it has been found to be beneficial to select the components of fragrance material so that the fragrance material is characterized by one or more S-ESTER values, as will be described in more detail below.

[0075] Fragrance material can comprise at least 30% by weight of ester-containing perfume raw material (PRM) of fragrance material.Preferably, fragrance material also comprises at least 0.5% by weight of aldehyde-containing PRM of fragrance material.Surprisingly, it has been found that by including a relatively large amount of ester-containing PRM in fragrance material, it is possible to favorably encapsulate the entire fragrance material.This is true even when fragrance material comprises aldehyde-containing PRM, which is known to cause encapsulation problems when using amine-containing shell precursor.

[0076] The fragrance material may comprise at least about 30%, preferably about 35%, more preferably at least about 40%, and even more preferably at least about 50% by weight of the ester-containing PRM. The fragrance material may comprise 30% to 99.5%, preferably 35% to about 80%, more preferably about 40% to about 70%, and even more preferably about 50% to about 60% by weight of the fragrance material. It is believed that higher amounts of the ester-containing PRM provide more effective encapsulation and / or performance.

[0077] Notably, certain PRMs contain one or more functional groups, such as ester and hydroxyl groups (see, for example, triethyl citrate). For purposes of this disclosure, when determining the relative percentage of PRMs in a given fragrance material that contain a given functional group, PRMs with more than one type of functional group are counted in each functional group category. Thus, the amount of triethyl citrate in a given fragrance is counted toward both the percentage of ester-containing PRMs and the percentage of hydroxyl-containing PRMs. When such materials are present, the relative percentages of PRMs with each functional group may add up to more than 100% by weight of the fragrance material due to such double (or triple, etc.) counting.

[0078] Fragrance materials, including individual PRMs, can be described in terms of their atomic-level electronic topological 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. The E-State value effectively considers each atom in a molecule and reflects the electronegativity of the atom's valence state, which is influenced by the atoms bonded to that atom. Electronic topological state indices are described in 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.

[0079] The S-ESTER value is the sum of the atomic-level electronic topology state (E-State) values ​​for all 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 (available from Hall Associates Consulting, Quincy, MA) and 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.

[0080] A relatively high S-ESTER value for a particular compound may indicate, for example, more than one type of ester group. A relatively high S-ESTER value for a mixture of compounds, such as a fragrance material containing more than one perfume raw material, may indicate a relatively high proportion of ester-containing compounds, including compounds containing more than one ester group.

[0081] The fragrance materials encapsulated in the delivery particles of the present disclosure may be characterized according to the S-ESTER value of the fragrance material as a whole (e.g., a mixture of PRMs) and / or by the relative amount of PRMs characterized by a particular S-ESTER value. For example, the fragrance material may 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 materials), and / or (b) comprising at least about 30% by weight of the fragrance material of fragrance materials having an S-ESTER value of 13 or greater.

[0082] Fragrance materials may be characterized by having an S-ESTER value of at least about 5, preferably at least about 5.5, and preferably at least about 6. Furthermore, fragrance materials may preferably be characterized by an S-ESTER value of no greater than about 20, preferably no greater than about 13, and more preferably no greater than about 10. Higher S-ESTER values ​​are associated with relatively higher amounts of esters, which may be associated with relatively lower volatility and lower olfactory impact.

[0083] The fragrance material comprises at least about 30%, preferably at least about 40%, more preferably at least about 50%, and even more preferably at least about 55%, by weight of the fragrance material, of perfume ingredients having an S-ESTER value of about 13 or greater, and preferably from about 13 to about 80, more preferably from about 13 to about 35, and even more preferably from about 13 to about 20. For clarity, it is understood that PRMs that do not contain ester groups are assigned an S-ESTER value of zero.

[0084] Ester-containing PRMs suitable for use in the fragrance materials of the present disclosure are provided in the table below. The fragrance materials of the present disclosure may contain any of the PRMs listed in the table below, or a combination thereof. The table also indicates what types of functional groups are present, as well as the S-ESTER value assigned to each PRM.

[0085] [Table 1-1]

[0086] [Table 1-2]

[0087] Although relatively higher amounts of ester-containing PRMs are believed to provide more effective encapsulation and / or performance, from an olfactory perspective, it may be desirable to include PRMs with non-ester moieties to create a sufficiently rounded fragrance.

[0088] For example, the fragrance material may include an aldehyde-containing PRM. The fragrance material may comprise at least about 0.5%, preferably at least about 1%, more preferably at least about 5%, and more preferably at least about 10% of the 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 the aldehyde-containing PRM. For example, the fragrance material may comprise from 0.5% to about 30%, preferably from about 1% to about 25%, and more preferably from about 5% to about 20% of the aldehyde-containing PRM by weight of the fragrance material. Aldehyde-containing perfume raw materials include methyl nonylacetaldehyde, benzaldehyde, floralozone, isocyclocitral, triprolal (ligustral), precyclemone B, and the like. B), lilial, decyl aldehyde, undecylenic aldehyde, cyclamen homoaldehyde, cyclamen aldehyde, dupical, oncidal, adoxal, melonal, calypsone, anisaldehyde, heliotropin, cumin aldehyde, scentenal, 3,6-dimethylcyclohex-3-ene-1-carbaldehyde, satin aldehyde, canthoxal, vanilla The additives may include cinnamic aldehyde, ethyl vanillin, cinnamic aldehyde, cis-4-decenal, trans-4-decenal, cis-7-decenal, undecylenic aldehyde, trans-2-hexenal, trans-2-octenal, 2-undecenal, 2,4-dodecadienal, cis-4-heptenal, floridral, butyl cinnamaldehyde, limoneral, amyl cinnamaldehyde, hexyl cinnamaldehyde, citronellal, citral, cis-3-hexen-1-al, or mixtures thereof, because these materials are particularly desired by formulators and / or consumers.

[0089] The fragrance material may contain a hydroxyl-containing PRM. However, to promote effective shell formation, the relative amount of such PRM may be limited. The fragrance material may contain up to 30% by weight of the fragrance material of a hydroxyl-containing PRM, preferably 1% to 30%. Hydroxyl-containing perfume raw materials may include geraniol, nonadienol, cinnamic alcohol, linalool, furacetate, derivatives thereof, or mixtures thereof, as these materials are particularly desired by formulators and / or consumers.

[0090] The fragrance material may include a ketone-containing PRM. Preferred ketone-containing perfume raw materials may include nerolion, 4-(4-methoxyphenyl)butan-2-one, 1-naphthalen-2-ylethanone, nectaryl, trimofix O, fleuramone, delta-damascone, beta-damascone, alpha-damascone, methyl ionone, 2-hexylcyclopent-2-en-1-one, galbascone, or mixtures thereof, as these materials are particularly desired by formulators and / or consumers.

[0091] Preferred fragrance materials suitable for encapsulation in the delivery particles of the present disclosure may include the following categories of PRMs in the following amounts: about 45% to about 55% ester-containing PRMs, about 10% to about 25% aldehyde-containing PRMs, about 5% to about 20% hydroxyl-containing PRMs, and optionally, about 1% to about 40% additional PRMs (which may include PRMs that are ketone-containing PRMs).

[0092] The core of the delivery particles of the present disclosure may include a partitioning modifier, which may promote more robust shell formation. The partitioning modifier may be combined with the perfume oil material of the core prior to incorporation of the wall-forming monomer. The partitioning modifier may be present in the core at a concentration of about 0% to 95% by weight of the core, preferably about 5% to 55% by weight, preferably about 10% to 50% by weight, and more preferably about 25% to 50% by weight.

[0093] Partition modifiers include vegetable oils, modified vegetable oils, C4 to C 24 The partition modifier may include a material selected from the group consisting of mono-, di-, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partition modifier may preferably include isopropyl myristate, or may even consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably include castor oil and / or soybean oil. U.S. Patent Application Publication No. 20110268802, incorporated herein by reference, describes other partition modifiers that may be useful in the delivery particles described herein.

[0094] Optionally, the core comprises one or more additives selected from the group consisting of silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin cooling agents, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleach particles, silicon dioxide particles, odor reducers, odor control materials, antistatic agents, fabric softeners, insect and moth repellents, colorants, antioxidants, chelating agents, thickeners, drape and foam inhibitors, smoothing agents, wrinkle inhibitors, sanitizing agents, disinfectants, bacterial inhibitors, mold inhibitors, mildew inhibitors, antivirals, drying agents, stain resistant agents, soil release agents, fabric refreshing agents, and the like. and freshness maintaining agents, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color restoration / revitalization agents, anti-fade agents, whiteness enhancers, anti-abrasion agents, abrasion resistant agents, fabric integration agents, anti-abrasion agents, anti-pilling agents, foam suppressors, defoamers, UV protection agents, fade inhibitors, anti-allergy agents, enzymes, waterproofing agents, fabric comfort agents, shrink resistance agents, stretch resistance agents, stretch recovery agents, skin care agents, synthetic or natural actives, antibacterial actives, antiperspirant actives, cationic polymers, dyes, and mixtures thereof.

[0095] The oil phase may contain a suitable carrier and / or solvent, especially if the benefit agent itself is insufficient to function as an oil phase or solvent during the process of forming the shell of the delivery particle of the wall-forming material. In this sense, oil is optional, since the benefit agent itself may sometimes be oil. These carriers or solvents are generally oils, preferably with a boiling point above about 80°C, low volatility, and non-flammable. Although not limited thereto, they preferably include one or more esters, preferably with a chain length of up to 18 carbon atoms or even up to 42 carbon atoms, and / or triglycerides, such as esters of C6-C12 fatty acids with glycerol.

[0096] Optionally, the aqueous phase may contain an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (e.g., alkyl sulfates, alkyl ether sulfates, and / or alkylbenzene sulfonates), nonionic surfactants (e.g., alkoxylated alcohols, preferably alkoxylated alcohols containing ethoxy groups), polyvinyl alcohol, and / or polyvinylpyrrolidone. Solubilized chitosan can provide an emulsifying effect in this application.

[0097] When used, the emulsifier typically comprises about 0.1 to 40% by weight, preferably 0.2 to about 15% by weight, more typically 0.5 to 10% by weight, based on the total weight of the aqueous phase.

[0098] The population of delivery particles can be provided as a slurry, preferably an aqueous slurry. The slurry can include one or more processing aids, which can include water, an agglomeration inhibitor material such as a divalent salt, or a particle suspending polymer such as xanthan gum, guar gum, cellulose (preferably microfibrillated cellulose), and / or carboxymethyl cellulose. When the delivery particles are cationic in nature (e.g., when the shell is at least partially derived from chitosan), a non-anionic structuring agent, preferably a non-ionic structuring agent, can be preferred, for example, to avoid adverse charge interactions that can result in undesirable agglomeration.

[0099] The slurry may include one or more carriers selected from the group consisting of polar solvents, including but not limited to water, ethylene glycol, propylene glycol, polyethylene glycol, glycerol, non-polar solvents, including but not limited to mineral oil, perfume raw materials, silicone oil, hydrocarbon paraffin oil, and mixtures thereof. Aqueous slurries may be preferred. The slurry may also include non-encapsulated ("free") perfume raw materials that differ in identity and / or amount from those encapsulated in the core of the delivery particle.

[0100] The slurry may also include a deposition aid which may comprise a polymer selected from the group including: polysaccharides, in one embodiment cationically modified starch and / or cationically modified guar, polysiloxanes, polydiallyldimethylammonium halides, copolymers of polydiallyldimethylammonium chloride and polyvinylpyrrolidone, compositions comprising polyethylene glycol and polyvinylpyrrolidone, acrylamides, imidazoles, imidazolinium halides, polyvinylamines, copolymers of polyvinylamine and N-vinylformamide, polyvinylformamide, polyvinyl alcohols, polyvinyl alcohols crosslinked with boric acid, polyacrylic acid, polyglycerol ether silicone crosspolymers, polyacrylic acid, polyacrylates, amines, in one embodiment diethylenetriamine, ethylenediamine copolymers of polyvinylamine and polyvinyl alcohol oligomers, bis(3-aminopropyl)piperazine, N,N-bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine, and mixtures thereof; polyethyleneimine, derivatized polyethyleneimine, in one embodiment ethoxylated polyethyleneimine, polymeric compounds comprising at least two moieties selected from the group consisting of carboxylic acid moieties, amine moieties, hydroxyl moieties, and nitrile moieties in the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile, or combinations thereof; preformed coacervates of anionic surfactants combined with cationic polymers; polyamines and mixtures thereof.

[0101] At least one population of delivery particles may be contained in an agglomerate, which may then be combined with a separate population of delivery particles and at least one auxiliary material. The agglomerate may be comprised of a material selected from the group consisting of silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride, and a binder such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0102] Suitable equipment for use in the processes disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, where available, continuous process configurations), spray dryers, and extruders. Such equipment is available from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., USA), and Arde Barinco (New Jersey, USA).

[0103] Supplementary ingredients In addition to the delivery particles, the treatment compositions of the present disclosure may include one or more auxiliary materials that may provide a benefit in the intended end use of the composition or may be processing and / or stabilizing aids.

[0104] Suitable adjunct materials may include surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, additional perfumes and perfume delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-agglomerating agents, coating agents, formaldehyde scavengers, and / or pigments. Preferably, the adjunct materials include additional fabric conditioning agents, dyes, pH suppressants, solvents, rheology modifiers, structurants, cationic polymers, surfactants, perfumes, additional perfume delivery systems, chelating agents, antioxidants, preservatives, or mixtures thereof.

[0105] Depending on the intended form, formulation, and / or end use, the compositions of the present disclosure may be free of one or more of the following adjunct materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural elastomers, fabric softeners, carriers, hydrotropes, processing aids, structurants, anti-agglomerating agents, coatings, formaldehyde scavengers, and / or pigments.

[0106] The exact nature of these additional components and the concentration at which they are incorporated depend on the physical form of the composition and the nature of the operation used. However, if one or more adjuvants are present, such one or more adjuvants can be present as detailed below. The following is a non-limiting list of suitable additional adjuvants:

[0107] A. Surfactants The composition of the present disclosure may include a surfactant. The surfactant may be useful, for example, to provide cleaning benefits. The composition may include a surfactant system, which may contain one or more surfactants.

[0108] Compositions of the present disclosure may comprise from about 0.1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50% by weight of the composition of a surfactant system. Liquid compositions may comprise from about 5% to about 40% by weight of the composition of a surfactant system. Compositions suitable for dense formulations, e.g., dense, liquid, gel, and / or unit dose forms, may comprise from about 25% to about 70%, or from about 30% to about 50% by weight of the composition of a surfactant system.

[0109] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include nonionic surfactants such as linear alkyl benzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactant may be derived, at least in part, from natural sources, such as natural feedstock alcohols.

[0110] Suitable anionic surfactants may include any conventional anionic surfactant. This may include, for example, sulfate detersive surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid-based detersive surfactants, such as alkyl benzene sulfonates. The anionic surfactant may be linear, branched, or a combination thereof. Preferred surfactants include linear alkyl benzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched-chain modified alkyl benzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactant may be present in acid form, salt form, or a mixture thereof. The anionic surfactant may be partially or totally neutralized, for example, with an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine). Due to the presence of cationic ester quat materials, it may be desirable to limit the amount of anionic surfactant to avoid undesirable interactions of the materials. For example, the composition may contain less than 5% by weight of the composition, preferably less than 3% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight of the composition of anionic surfactant.

[0111] The surfactant system may include a nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(oxyalkylated) alcohol surfactants, and mixtures thereof. The alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof. The nonionic surfactant may be linear, branched (e.g., mid-chain branched), or a combination thereof. Specific nonionic surfactants may include alcohols having an average of about 12 to about 16 carbons and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactants.

[0112] Suitable zwitterionic surfactants include betaines, C8-C9 alkyl dimethyl betaines, including alkyl dimethyl betaines and cocodimethylamidopropyl betaine. 18 (For example, C 12 ~C 18 ) amine oxides (e.g., C 12 ~ 14 dimethylamine oxide), and / or N-alkyl-N,N-dimethylamino-1-propanesulfonate (wherein the alkyl group is C8 to C 18 or C 10 ~C 14 The zwitterionic surfactant may include any conventional zwitterionic surfactant, such as sulfo and hydroxybetaines, such as (which may be

[0113] Depending on the formulation and / or intended end use, the composition may be substantially free of certain surfactants. For example, a liquid fabric strengthening composition such as a fabric softener may be substantially free of anionic surfactants, as such surfactants may negatively interact with cationic components.

[0114] B. Conditioning Actives The compositions of the present disclosure may include conditioning actives. Compositions containing conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color, and / or appearance benefits.

[0115] The conditioning active may be present at a concentration of about 1% to about 99% by weight of the composition. The composition may comprise from about 1%, or about 2%, or about 3%, to about 99%, or about 75%, or about 50%, or about 40%, or about 35%, or about 30%, or about 25%, or about 20%, or about 15%, or about 10% by weight of the composition. The composition may comprise from about 5% to about 30% by weight of the composition of the conditioning active.

[0116] Suitable conditioning active materials for the composition of the present disclosure can include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty acid esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof.Preferably, the treatment composition is a fabric care composition in which one or more adjunct ingredients comprise quaternary ammonium ester materials.Such materials are particularly useful in fabric enhancing / conditioning / softening compositions.

[0117] The composition may contain a quaternary ammonium ester compound, a silicone, or a combination of these, preferably a single combination. The total amount of the quaternary ammonium ester compound and the silicone may be about 5% to about 70% by weight of the composition, or about 6% to about 50% by weight, or about 7% to about 40% by weight, or about 10% to about 30% by weight, or about 15% to about 25% by weight. The composition may contain the quaternary ammonium ester compound and the silicone in a weight ratio of about 1:10 to about 10:1, or about 1:5 to about 5:1, or about 1:3 to about 1:3, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.

[0118] The composition may contain a mixture of different types of conditioning actives. The composition of the present disclosure may contain a specific conditioning active but may be substantially free of other conditioning actives. For example, the composition may be free of quaternary ammonium ester compounds, silicones, or both. The composition may contain a quaternary ammonium ester compound but may be substantially free of silicones. The composition may contain silicones but may be substantially free of quaternary ammonium ester compounds.

[0119] C. Adhesion aid The composition of the present disclosure may also include a deposition aid. As mentioned above, due to the synergistic effect of the ester quaternary material and the delivery particles of the present disclosure, less (or even no) deposition aid may be required to provide comparable or even improved performance. Alternatively, a deposition aid may be used in the composition of the present disclosure to further enhance performance.

[0120] The deposition aid may promote deposition of the delivery particles, conditioning actives, fragrance, or combinations thereof, which may improve the performance benefits of the composition and / or allow for more efficient incorporation of such benefit agents. The composition may comprise from 0.0001% to 3%, preferably from 0.0005% to 2%, more preferably from 0.001% to 1%, or from about 0.01% to about 0.5%, or from about 0.05% to about 0.3%, by weight of the composition, of the deposition aid. The deposition aid may be a cationic or amphoteric polymer, preferably a cationic polymer.

[0121] Cationic polymers in general and methods for their preparation are well known in the literature. Suitable cationic polymers include quaternary ammonium polymers known as "polyquaternium" polymers as designated in the International System of Nomenclature for Cosmetic Ingredients, such as Polyquaternium-6 (poly(diallyldimethylammonium chloride)), Polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), Polyquaternium-10 (quaternized hydroxyethylcellulose), and Polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride).

[0122] The deposition aid may be selected from the group consisting of polyvinyl formamide, partially hydroxylated polyvinyl formamide, polyvinyl amine, polyethylene imine, ethoxylated polyethylene imine, polyvinyl alcohol, polyacrylate, and combinations thereof. The cationic polymer may include a cationic acrylate.

[0123] The deposition aid can be added simultaneously with the delivery particles (e.g., simultaneously with the encapsulated benefit agent) or directly / independently into the consumer product composition. The weight average molecular weight of the polymer may be from 500 Daltons to 5,000,000 Daltons, or from 1,000 Daltons to 2,000,000 Daltons, or from 2,500 Daltons to 1,500,000 Daltons, as measured by size exclusion chromatography against polyethylene oxide standards using refractive index (RI) detection. The weight average molecular weight of the cationic polymer may be from 5,000 Daltons to 37,500 Daltons.

[0124] D. Rheology Modifiers / Structuring Agents The compositions of the present disclosure may include a rheology modifier and / or a structuring agent. Rheology modifiers may be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structuring agents may be used to promote phase stability and / or to suspend or inhibit aggregation of particles in the liquid composition, such as the delivery particles described herein.

[0125] Suitable rheology modifiers and / or structurants may include non-polymeric crystalline hydroxyl-functional structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulosic fibers (e.g., microfibrillated cellulose, which may be derived from bacterial, fungal, or plant sources, including wood), diamide gelling agents, or combinations thereof.

[0126] The polymeric structurant may be of natural or synthetic origin. Naturally derived polymeric structurants may include hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives may include pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structurants may include polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers may include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates are polymers of unsaturated mono- or dicarbonates and C1-C (meth)acrylic acid. 30 The structuring agent may include copolymers with alkyl esters. Such copolymers are available from Noveon Inc. under the trade name Carbopol Aqua 30. Crosslinked polymers, such as crosslinked polyacrylates, and / or polymers and / or copolymers, such as those further comprising nonionic monomers, such as acrylamide or methacrylamide monomers, may be useful as structuring agents. Another suitable structuring agent is sold under the trade name Rheovis CDE, available from BASF.

[0127] E. Other adjuvants The treatment compositions of the present disclosure may include other adjuvants suitable for inclusion in a product and / or end use. For example, the treatment compositions may include pure perfume, perfume delivery technology (such as pro-perfumes and / or encapsulations having non-crosslinked biopolymer wall materials), cationic surfactants, cationic polymers, solvents, suds suppressors, or combinations thereof.

[0128] Method for producing the treatment composition The present disclosure further relates to methods for making treatment compositions, such as the treatment compositions and / or consumer product compositions described herein.

[0129] The method can include providing a base composition including a processing aid and combining a population of delivery particles with the base composition. The population of delivery particles can be preferably provided as an aqueous slurry. The base composition is in the form of a liquid composition.

[0130] The delivery particles may be combined with one or more auxiliary ingredients when the delivery particles are in one or more forms including a slurry form, a neat particle form, and / or a spray-dried particle form, preferably a slurry form. The delivery particles may be combined with such auxiliary ingredients by methods including mixing and / or spraying.

[0131] The processing composition of the present disclosure can be formulated into any suitable form and prepared by any process selected by the formulator.One or more auxiliary ingredients and delivery particles can be combined in a batch process, a circulation loop process, and / or an in-line mixing process.Suitable equipment for use in the process disclosed herein can include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, high shear mixers, static mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, if available, in continuous process configurations), spray dryers, and extruders.

[0132] As described herein, the treatment composition may be packaged in a container to form a consumer product. The container may be a bottle, preferably a plastic bottle. The treatment composition may be packaged in an aerosol or other spray container according to known methods.

[0133] Processing method The present invention also relates to a method of treating a surface, preferably a fabric. Generally, the method comprises 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.

[0134] Additionally or alternatively, the method may comprise contacting a surface, preferably a fabric, with a population of delivery particles described herein, which may be contained in a treatment composition, preferably a fabric care composition, according to the present disclosure.

[0135] The method may include contacting a fabric, such as clothing, with a treatment composition. The treatment composition includes a population of delivery particles. The contacting step results in one or more of the delivery particles being deposited on the surface of the fabric. The delivery particles include a core and a shell surrounding the core, the core including a benefit agent, preferably a fragrance material including one or more perfume ingredients. The shell includes a polymeric material that is, for example, the reaction product of chitosan of a specific molecular weight and a crosslinker. Suitable treatment compositions and delivery particles are described in more detail above.

[0136] The contacting step may be carried out during a manual laundry process, e.g., in a basin when fabrics are treated by hand, or during an automatic laundry process, e.g., in an automatic washing machine. The contacting step may be carried out during the wash cycle of an automatic washing machine. In such cases, the treatment composition may be a laundry detergent or a laundry additive. The contacting step may preferably be carried out during the rinse cycle of an automatic washing machine. In such cases, the treatment composition may be a fabric enhancer, preferably a liquid fabric enhancer. The contacting step may also be carried out during the drying step of the laundry process, e.g., in an automatic dryer. In such cases, the treatment composition may be in the form of a nonwoven dryer sheet or a dryer bar. The contacting step may be carried out as a result of the treatment composition being applied directly to the fabric, e.g., in a pre-treatment operation or a "refreshing" step (e.g., in the case of fabrics that have been used or worn since the last wash). In such cases, the treatment composition may be in the form of a liquid, stick, or spray, preferably a spray. Contacting the target fabrics relatively late in the laundering process, for example during the rinse cycle, improves the likelihood or efficiency of deposition on the fabrics, as the fabrics are less likely to be washed down the drain.

[0137] The contacting step may occur in the presence of water. The treatment composition can be diluted with water to form a treatment solution. The treatment composition can be diluted from about 100 to about 1500 times, preferably from 300 to about 1000 times.

[0138] Liquids containing the disclosed compositions may have a pH of about 3 to about 11.5. When diluted, such compositions are typically used at concentrations of about 500 ppm to about 15,000 ppm in solution. When the cleaning solvent is water, the water temperature typically ranges from about 5°C to about 90°C, and the water-to-fabric ratio may typically be about 1:1 to about 30:1.

[0139] The dilution may occur in the drum of an automatic washing machine. The treatment composition may be placed in a dispensing drawer of the automatic washing machine. The treatment composition may be dispensed from the dispensing drawer into the drum during the treatment process.

[0140] As alluded to above, the method may further comprise drying the fabric having one or more delivery particles on the surface of the fabric. The drying step may comprise a passive drying process, such as on a clothesline or drying rack. The drying step may comprise an automatic drying process, such as an automatic dryer.

[0141] combination Specifically contemplated combinations of the present disclosure are set forth herein in the following alphabetized paragraphs, which are exemplary in nature and not intended to be limiting.

[0142] A. A treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the shell comprising a polymeric material, the polymeric material comprising a reaction product of a biopolymer and a crosslinker, the biopolymer comprising primary amine groups, the core comprising a fragrance material, the fragrance material comprising (a) at least about 30% by weight of the fragrance material of an ester-containing perfume raw material ("PRM"), and (b) at least about 0.5% by weight of the fragrance material of an aldehyde-containing PRM.

[0143] B. A treatment composition comprising a processing 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 crosslinker, wherein the biopolymer comprises primary amine groups, wherein the core comprises a fragrance material, wherein the fragrance material comprises one or more perfume raw materials ("PRM"), wherein the fragrance 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 fragrance material is calculated as the weight average S-ESTER value of the fragrance raw materials, and / or (b) comprising at least about 30% by weight of the fragrance material of perfume raw materials having an S-ESTER value of 13 or greater.

[0144] C. The treatment composition of paragraph A or B, wherein the fragrance material comprises at least about 35%, preferably at least about 40%, preferably at least about 50% ester-containing PRM by weight of the fragrance material.

[0145] D. The treatment composition of any of paragraphs A-C, wherein the fragrance material has an S-ESTER value of at least about 5.5, preferably at least about 6, and preferably has an S-ESTER value of about 20 or less, preferably about 13 or less, and more preferably about 10 or less.

[0146] E. The treatment composition of any of paragraphs A-D, wherein the fragrance material comprises at least about 40%, preferably at least about 50%, more preferably at least about 55% by weight of the fragrance material of perfume raw materials 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, and even more preferably from about 13 to about 20.

[0147] F. Ester-containing fragrance ingredients: 4-tert-butylcyclohexyl acetate, allyl amyl glycolate, allyl caproate, allyl cyclohexane propionate, allyl heptanoate, amyl acetate (isomer blend), cis-3-hexenyl acetate, cis-3-hexenyl salicylate, cyclobutate, cyclogalbanate, cyclobutanate, dihydroterpinyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, exaltolide total, ethyl 2-methylpentanoate, ethyl acetate, ethyl butyrate, ethylene brassylate, ethyl isovalerate, ethyl lyton, ethyl methylphenyl glycidate, ethyl methylphenyl glycidate, ethyl-2-methyl butyrate, flora The treatment composition of any of paragraphs A-E, comprising one or more materials selected from the group consisting of acetate, fructalate, fultene, gamma-decalactone, geranyl acetate, habanolide, helbetolide, hexyl acetate, isobornyl acetate, isononyl acetate, isoamyl butyrate, jasmal, methyl anthranilate, methyl benzoate, methyl dihydrojasmonate, methyl dioxolane, methyl lightone, methylphenylcarbinyl acetate, musk RI, octahydrocoumarin, phenoxyethyl isobutyrate, phenylethyl tiglate, prenyl acetate, romandlide, sclareol, terpinyl acetate, thesalone, triethyl citrate, undecalactone, verdox, biolf, xenolide, and combinations thereof.

[0148] G. The treatment composition of any of paragraphs A-F, wherein the fragrance material comprises at least about 1% aldehyde-containing PRM by weight of the fragrance material, preferably at least about 5%, more preferably at least about 10% aldehyde-containing PRM by weight of the fragrance material.

[0149] H. The treatment composition of any of paragraphs A through G, wherein the fragrance material further comprises up to about 30% by weight of the fragrance material of a hydroxyl-containing PRM, preferably from about 1% to about 30%.

[0150] I. The treatment composition of any of paragraphs A-H, wherein the perfume material comprises 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.

[0151] J. The core further comprises a partitioning modifier, optionally present in the core at a concentration of about 10% to about 50% by weight of the core, preferably the partitioning modifier is selected from the group consisting of vegetable oil, modified vegetable oil, C4 to C6 24 The treatment composition of any of paragraphs A-I, wherein the surfactant is selected from the group consisting of mono-, di-, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate.

[0152] The treatment composition of any of paragraphs A-J, wherein the biopolymer is selected from the group consisting of polysaccharides, proteins, nucleic acids, derivatives thereof, 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, zein, soy protein, plant storage protein, gluten, peptides, actin, polynucleotides, RNA, DNA, derivatives thereof, and combinations thereof.

[0153] L. The treatment composition of any of paragraphs A-K, wherein the biopolymer is chitosan, a derivative thereof, or a combination thereof, preferably, the biopolymer is acid-treated chitosan.

[0154] M. The treatment composition of any of paragraphs A-L, wherein the biopolymer, preferably chitosan, more preferably acid-treated chitosan, has a molecular weight of about 1 kDa to about 1000 kDa, preferably about 50 kDa to about 600 kDa, more preferably about 100 kDa to about 500 kDa, even more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa.

[0155] N. The crosslinking agent is a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxy compounds, polyphenols, carbonyl halides, aziridines, and combinations thereof, preferably selected from the group consisting of polyisocyanates, epoxy compounds, difunctional aldehydes, and combinations thereof, more preferably polyisocyanates, and even more preferably polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of toluene diisocyanate, trimethylolpropane adducts of xylylene diisocyanate, the treatment composition of any of paragraphs A-M, wherein the polyisocyanate is selected from the group consisting of 1,3-diisocyanatobenzene, 1,3-diisocyanatobenzoate ...

[0156] O. The treatment composition of any of paragraphs A-N, wherein the delivery particles are characterized by a volume weighted median particle size of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 20 to about 30 microns.

[0157] P. The treatment composition of any of paragraphs A-O, wherein the shell of the delivery particles degrades by at least 60% in 60 days when tested according to test method OECD 301B.

[0158] Q. The treatment composition of any of paragraphs A-P, wherein the processing aid is selected from the group consisting of surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, undiluted fragrance, additional fragrance delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-agglomerating agents, coatings, formaldehyde scavengers, pigments, and mixtures thereof.

[0159] R. The treatment composition of any of paragraphs A-Q, wherein the treatment aid comprises an anionic surfactant, a cationic conditioning agent, or a mixture thereof.

[0160] S. The treatment composition of any of paragraphs A-R, wherein the composition is a fabric care composition, a hard surface cleaning composition, a dish care composition, a hair care composition, a body cleansing composition, or a mixture thereof, preferably a fabric care composition, more preferably a laundry detergent composition, a fabric conditioning composition, a laundry additive, a fabric pre-treatment composition, a fabric refresher composition, or a mixture thereof.

[0161] T. The treatment composition of any of paragraphs A-S, wherein the treatment composition is a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, a pastille or bead, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven, or a mixture thereof, preferably a liquid composition.

[0162] U. The treatment composition of any of paragraphs A-T, wherein the consumer product composition further comprises about 50% to about 99% water by weight of the treatment composition, preferably about 60% to about 98% water by weight of the consumer product composition, and more preferably about 80% to about 96% water by weight of the consumer product composition.

[0163] V. A method of treating a surface, the method comprising contacting the surface, preferably a fabric, with the treatment composition of any of paragraphs A-U.

[0164] W. A method of making a treatment composition, the method comprising: providing a base composition, the base composition comprising a processing aid; and combining a population of delivery particles with the base composition, the delivery particles comprising a core and a shell surrounding the core, the shell comprising a polymeric material, the polymeric material comprising a reaction product of a biopolymer and a crosslinker, the biopolymer comprising primary amine groups, the core comprising a fragrance material, the fragrance material comprising: (a) at least about 30% by weight of the fragrance material of an ester-containing perfume raw material ("PRM"), and (b) at least about 0.5% by weight of the fragrance material of an aldehyde-containing PRM.

[0165] Test Method It will be understood that the test methods disclosed in the Test Methods section of this application should be used to determine the values ​​of each of the parameters of Applicant's subject matter claimed and described herein.

[0166] How to determine the S-ESTER value S-ESTER values ​​are based on atomic-level electronic topological state (E-State) indices of one or more compounds. 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 electronegativity of the atom's valence state, as influenced by the atoms bonded to it. Electronic topological state indices are described in 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.

[0167] To determine E-State and S-ESTER values ​​for the purposes described in this disclosure, E-State values ​​are calculated using the software program winMolconn version 1.2.2.3 (available from Hall Associates Consulting, Quincy, MA) and used according to the manufacturer's instructions. Structures are created using 2D connectivity tables (SDF format or SMILES). Value labels used in model test method calculations are the same labels reported by winMolconn. Their descriptions and definitions are provided in the winMolconn documentation associated with the software.

[0168] To determine the S-ESTER value of a particular fragrance raw material or other compound, the E-State value of each atom is calculated using the software program winMolconn version 1.2.2.3. The S-ESTER value is the sum of the atomic-level electrotopological state (E-State) values ​​for all carbonyl carbons and oxygens in the ester groups in the molecule. If a compound contains multiple ester groups, the E-State values ​​for all of the ester groups are added. If a compound has no ester groups, the S-ESTER value of the compound is zero.

[0169] As an example, the table below shows the SMILES input for the ester-containing PRM, furacetate, as well as the resulting S-ESTER value provided by the software.

[0170] [Table 2]

[0171] To determine the S-ESTER value for a mixture of compounds, e.g., a fragrance material containing one or more perfume raw materials, the S-ESTER value for each compound is first determined as described above. The S-ESTER value of the mixture is calculated by taking a weighted average of the S-ESTER values ​​based on the relative proportions (by weight percent) of the individual compounds in the mixture.

[0172] Determination of polymer molecular weight and related parameters The following method, which describes gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI), is used to find molecular weight distribution measurements and related values ​​for the polymers described herein.

[0173] Gel Permeation Chromatography (GPC) with Multi-Angle Light Scattering (MALS) and Refractive Index (RI) detection (GPC-MALS / RI) allows for the measurement of absolute molecular weights of polymers without the need for column calibration or standards. GPC systems allow for the separation of molecules as a function of their molecular size. MALS and RI can provide information on number-average (Mn) and weight-average (Mw) molecular weights.

[0174] The Mw distribution of water-soluble polymers such as chitosan is typically measured using a liquid chromatography system (e.g., Agilent 1260 Infinity Pump System with OpenLab Chemstation software, Agilent Technology, Santa Clara, CA, USA) and a column set (e.g., 2 Tosoh TSKgel G6000WP 7.8 x 300 mm 13 μm pore size, guard column A0022 6 mm x 40 mm PW x1-cp, King of Prussia, PA) operated at 40 °C. The mobile phase is 0.1 M sodium nitrate in water containing 0.02% sodium azide and 0.2% acetic acid. The mobile phase solvent is pumped isocratically at a flow rate of 1 mL / min. A multi-angle light scattering (18-angle MALS) detector DAWN® and a refractive index (RI) detector (Wyatt Technology of Santa Barbara, Calif., USA) controlled by Wyatt Astra® software v8.0 are used.

[0175] Samples are typically prepared by dissolving approximately 1 mg / ml of chitosan material in the mobile phase, mixing the solution, and allowing it to hydrate overnight at room temperature. Samples are filtered using a 3 ml syringe through a 0.8 μm Versapor membrane filter (PALL, Life Sciences, NY, USA) into an LC autosampler vial prior to GPC analysis.

[0176] The dn / dc value (differential change in refractive index with concentration, 0.15) is used to determine the number average molecular weight (Mn), weight average molecular weight (Mw), Z-average molecular weight (Mz), molecular weight at the peak maximum (Mp), and polydispersity (Mw / Mn) by the Astra detector software.

[0177] viscosity The viscosity of the final liquid product is measured using an AR550 rheometer / viscometer from TA instruments (New Castle, DE, USA) using parallel steel plates with a diameter of 40 mm and a gap size of 500 μm.-1 High shear viscosity at 0.05 seconds -1 The low shear viscosity at 21°C for 3 minutes is 0.01 s -1 ~25 seconds -1 is obtained from a logarithmic shear rate sweep.

[0178] Test Method for Determining logP For each material tested (e.g., each PRM in a fragrance mixture), the logarithm of the octanol / water partition coefficient (logP) is calculated. The logP values ​​of individual materials (e.g., PRMs) are calculated using the Consensus logP Computational Model, version 14.02 (Linux), available from Advanced Chemistry Development Inc. (ACD / Lab) (Toronto, Canada), which yields unitless logP values. The ACD / Labs Consensus logP Computational Model is part of the ACD / Labs model suite.

[0179] Volume-weighted particle size and size distribution Volume-weighted particle size distributions were determined by single-particle optical sensing (SPOS), also known as optical particle counting (OPC), using an AccuSizer 780 AD instrument and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent. The instrument was configured with the following conditions and options: flow rate = 1 ml / s, minor threshold = 0.50 μm, sensor model number = LE400-05 or equivalent, autodilution = on, collection time: 60 s, number of channels = 512, reservoir fluid volume = 50 ml, and maximum coincidence count = 9200. Measurements were initiated by cold-conditioning the sensor by flushing with water until background counts were below 100. A sample of delivery capsules in suspension is introduced, and the capsule density is adjusted, if necessary, via automated dilution with deionized water to achieve a capsule count of at least 9200 per ml. The suspension is analyzed for 60 seconds. The resulting volume-weighted PSD data is plotted and recorded, and desired volume-weighted particle size values ​​(e.g., median / 50th percentile, 5th percentile, and / or 90th percentile) are determined.

[0180] Procedure for determining decomposition % To determine % degradation, the procedure described in the "OECD Guideline for Testing of Chemicals" 301B CO2 Evolution (Modified Sturm Test), adopted on July 17, 1992, is used. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0181] Fabric Treatment The fabrics were treated using a Miele washing machine. For each treatment, the machine was loaded with 3 kg of fabric (1100 g of knitted cotton fabric and 1100 g of 50 / 50 polyester-cotton fabric). Eighteen terry towel cotton tracers were also added, weighing a total of approximately 780 g. Prior to treatment, the load was preconditioned twice in a short cotton wash cycle at 95°C using 79 g of unscented IECA-based detergent provided by WFK Testgewebe GmbH, followed by two additional washes at 95°C without detergent.

[0182] Prior to the test treatment, the load is preconditioned twice with 79 g of unscented IEC A-based detergent (ex WFK, Testgewebe GmbH), each time using a short cotton cycle at 95°C, followed by two additional 95°C washes without detergent.

[0183] In the test treatment, the load is washed using a short cotton cycle at 40°C, a spin speed of 1200 rpm, and 79 g of IEC A-based detergent, which is added into a suitable dispenser at the beginning of the wash cycle. A 35 g dose (for example, according to the example) of the test fabric treatment composition is added to a suitable dispenser. At the end of the wash cycle, the terry towel tracer is removed from the washing machine and line-dried overnight. The next day, a professional perfumer performs an olfactory evaluation of the perfume intensity on the dried terry towel tracer. For comparison, a reference treatment is also performed, using the same fragrance as the test sample, but using polyacrylate capsules as delivery particles. All comparison treatments are washed and analyzed on the same day.

[0184] Olfactory evaluation method After the fabrics are treated, a professional perfumer performs an olfactory assessment of the perfume intensity of the dry fabrics at the DRY touchpoint (Dry Fabric Odor = DFO) and averages the scores. The scores are 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 = very strong perfume odor.

[0185] Method for determining headspace concentrations on treated dry fabrics The cotton tracer was analyzed by fast headspace GC / MS (gas chromatography mass spectrometry) technique. A 4x4cm aliquot of terry towel cotton tracer was transferred to a 25ml headspace vial. The fabric sample was equilibrated at 65°C for 10 minutes. The headspace above the fabric was sampled by SPME (50 / 30μm DVB / Carboxen / PDMS) technique for 5 minutes. The SPME fibers were then thermally desorbed online into the GC. The analytes were analyzed in full scan mode by fast GC / MS. Ion extraction of specific masses of PRM was used to calculate the total HS reaction and perfume headspace composition above the tested leg.

[0186] Total weight % of degraded PRM in delivery particle composition To determine the total amount of decomposed PRM in the delivery particle composition, the total fragrance (encapsulated + unencapsulated) is measured using the fragrance raw material as reference.For this purpose, gas chromatography (GC-MS) with mass spectrometry detector is used.Suitable equipment includes Agilent GC8890 equipped with Agilent 5977B mass spectrometer or equivalent, capillary column operation, quantification based on extracted ion capacity, autosampler, and 30m x 0.25mm nominal diameter column, 1 μm film thickness, J&W 122-5533 DB-5MS or equivalent.

[0187] Approximately 0.1 g of the delivery particle composition is weighed and the weight is recorded, and then an internal standard (Tonalid, ex. Merck) and 10 mL of ethanol are added to the sample. The suspension is heated at 60°C for 45 minutes, and then placed in an ultrasonic bath (such as Branson 3510) for 15 minutes. The cooled solution is then filtered through a 0.45 μm pore size PTFE syringe filter and analyzed by GC-MS. The amount of measured PRM is determined from the response of each PRM, and the total wt% PRM decomposition can be determined as follows:

[0188]

number

[0189] The examples provided below are intended to be illustrative and not limiting in nature.

[0190] Example 1. Exemplary Fragrance Materials Table 1 shows exemplary fragrance materials according to the present disclosure. The fragrance raw materials are listed along with the relative weight percent (by weight of the fragrance material) and S-ESTER value of each fragrance raw material. From these values, the S-ESTER value of all fragrance materials can be calculated as a weighted average S-ESTER value.

[0191] [Table 3] E = Material containing ester functional groups A = Materials containing aldehyde functional groups

[0192] Based on the information in Table 1, an exemplary fragrance material comprises 37% ester-containing material and 37% aldehyde-containing material, by weight of the fragrance material.

[0193] Furthermore, the S-ESTER value of all fragrance materials is determined to be 7.913, calculated according to the weighted average of the S-ESTER values ​​of the PRMs.

[0194] Example 2. Exemplary Delivery Particle Synthesis In the following examples, the abbreviations correspond to the materials listed in Table 2.

[0195] [Table 4]

[0196] An aqueous phase is prepared by dispersing 92.19 g of ChitoClear in 1956.6 g of water while mixing in a jacketed reactor. The pH of the aqueous phase is then adjusted to 5.0-5.3 using concentrated HCl while stirring. The temperature of the aqueous phase is then increased to 85°C over 60 minutes and then held at 85°C for 2 hours to acidify the ChitoClear. After a 90-minute hydrolysis step, the aqueous phase temperature is then reduced to 25°C. An oil phase is prepared by mixing 716.37 g of a perfume oil according to the present disclosure (e.g., the fragrance material of Example 1) and 179.11 g of isopropyl myristate with 19.54 g of Takenate D-110N at room temperature. The oil phase is added to the aqueous phase under high shear milling to obtain an emulsion. The emulsion is heated to 40°C over 30 minutes and held for 60 minutes. The emulsion is then heated to 85°C and maintained at this temperature with mixing for 6 hours.

[0197] Example 3. Effect of selection of encapsulated fragrance To compare different chitosan delivery particles, liquid fabric enhancer ("LFE") samples were prepared using different particles. The delivery particles evaluated in the reference treatment also contained the same fragrance, and each core also contained approximately 20% to 35% of a partitioning modifier (isopropyl myristate). The LFE composition included a softening active (diester quat) present at 6%, the associated delivery particles added at a concentration sufficient to provide 0.2% encapsulated fragrance, 0.11% structurant (cationic polymer - Flosoft FS222, exSNF), and various processing minor ingredients, with the pH adjusted to approximately 3.

[0198] For the purposes of the examples, liquid fabric enhancer products are prepared having the general formula in Table 3 below.

[0199] [Table 5]

[0200] Seven different fragrances are encapsulated in both delivery particles according to the present disclosure (e.g., walls made from chitosan and crosslinked with isocyanate) and reference polyacrylate ("PAC") delivery particles. The compositions of the fragrances tested are generally set forth in Table 3 below. Note that perfume raw materials with more than one functional moiety are counted in each "functionality" category, which may result in a PRM being counted more than once and the percentages appearing to total more than 100%. The S-ESTER values ​​for each fragrance are also provided in Table 4. Fragrances 1-4 (e.g., "Fragrance 1") are fragrance materials according to the present disclosure, and Fragrances 5-7 (e.g., "Fragrance 5") are comparative fragrance materials.

[0201] The walls of the delivery particles used in the experiments are made from an amine-containing biopolymer (acid-treated chitosan) and a crosslinker (polyisocyanate) (target volume-weighted median particle size = 28 microns). Reference polyacrylate delivery particles are made substantially according to the method described in U.S. Patent Application Publication No. 2011 / 0268802. Notably, the walls of the PAC delivery particles are not made from monomers containing primary amines, and therefore, significant reactivity with aldehyde PRMs is not expected. Reference PAC particles with fragrances 1-5 are characterized by a core:shell weight ratio of about 90:10. Reference PAC particles with fragrances 6 and 7 are characterized by a core:shell weight ratio of about 97:3 to about 98:2.

[0202] The composition of the fragrance in the delivery particles is analyzed using the analytical filtration method as described in the Test Methods section above and compared to the fragrance oil before encapsulation. From this analysis, the total weight percent of the degraded PRM is calculated according to the method above.

[0203] The results are provided below in Table 4. For comparison purposes, the olfactory DFO data for chitosan-based delivery particles are reported as delta values ​​relative to the DFO obtained from reference polyacrylate delivery particles containing the same fragrance according to the following formula:

[0204] Delta DFO = DFO chitosan delivery particles (test) - DFO PAC delivery particles (reference) asterisk( *) are statistically significant compared to the reference value.

[0205] [Table 6]

[0206] As shown in Table 4, delivery particles of the present invention featuring cores containing greater than 30% esters and / or fragrances with S-ESTER values ​​greater than 5 perform substantially equivalently on an olfactory basis compared to reference polyacrylate capsules. Furthermore, they exhibit a total % degradation of the PRM in the core of less than 5%. Meanwhile, comparative delivery particles with similar walls but featuring cores containing less than 30% esters and / or fragrances with S-ESTER values ​​less than 5 perform significantly worse compared to the reference polyacrylate capsules. Furthermore, they exhibit a total % degradation of the PRM in the core of more than 5%.

[0207] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0208] All documents cited herein, including cross-referenced or related patents or applications, and patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest, or disclose any such invention, either alone or in combination with any other reference or references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control.

[0209] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

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

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

3. 3. The treatment composition of claim 1 or 2, wherein the fragrance material comprises at least about 35%, preferably at least about 40%, preferably at least about 50% ester-containing PRM by weight of the fragrance material.

4. the fragrance material has an S-ESTER value of at least about 5.5, preferably at least about 6; The treatment composition according to any one of claims 1 to 3, characterized in that the S-ESTER value is preferably about 20 or less, preferably about 13 or less, more preferably about 10 or less.

5. the fragrance material comprises at least about 40%, preferably at least about 50%, and more preferably at least about 55%, by weight of the fragrance material, of perfume raw materials having an S-ESTER value of about 13 or greater; The treating composition of any one of claims 1 to 4, wherein the Mn is preferably from about 13 to about 80, more preferably from about 13 to about 35, and even more preferably from about 13 to about 20.

6. The ester-containing fragrance raw material is 4-tert-butylcyclohexyl acetate, allyl amyl glycolate, allyl caproate, allyl cyclohexane propionate, allyl heptanoate, amyl acetate (isomer blend), cis-3-hexenyl acetate, cis-3-hexenyl salicylate, cyclobutate, cyclogalbanate, cyclobutanate, dihydroterpinyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, exaltolide total, ethyl 2-methylpentanoate, ethyl acetate, ethyl butyrate, ethylene brassylate, ethyl isovalerate, ethyl light, ethyl methylphenyl glycidate, ethyl methylphenyl glycidate, ethyl-2-methyl butyrate, furacetate, fulvic acid, 6. The treatment composition of any one of claims 1 to 5, comprising one or more materials selected from the group consisting of tallate, fultene, gamma-decalactone, geranyl acetate, habanolide, helbetolide, hexyl acetate, isobornyl acetate, isononyl acetate, isoamyl butyrate, jasmal, methyl anthranilate, methyl benzoate, methyl dihydrojasmonate, methyl dioxolane, methyl lightone, methylphenylcarbinyl acetate, musk RI, octahydrocoumarin, phenoxyethyl isobutyrate, phenylethyl benzoate, phenylethyl tiglate, prenyl acetate, romandlide, sclareol, terpinyl acetate, thesalone, triethyl citrate, undecalactone, verdox, biolif, xenolide, and combinations thereof.

7. the fragrance material comprises at least about 1% by weight of the fragrance material of an aldehyde-containing PRM; A treating composition according to any preceding claim, preferably comprising at least about 5%, more preferably at least about 10%, by weight of said fragrance material, of an aldehyde-containing PRM.

8. 8. The treatment composition of any one of claims 1 to 7, wherein the fragrance material further comprises up to about 30% by weight of the fragrance material of a hydroxyl-containing PRM, preferably from about 1% to about 30%.

9. The fragrance material is about 45% to about 55% ester-containing PRM; about 10% to about 25% aldehyde-containing PRM; about 5% to about 20% of a hydroxyl-containing PRM, and The treatment composition of any one of claims 1 to 8, optionally comprising from about 1% to about 40% of an additional PRM.

10. the core further comprises a partitioning modifier, optionally present in the core at a concentration of about 10% to about 50% by weight of the core; Preferably, the partitioning modifier is a vegetable oil, a modified vegetable oil, C ４ ~C ２４ 10. The treatment composition according to any one of claims 1 to 9, wherein the surfactant is selected from the group consisting of mono-, di-, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate.

11. the biopolymer is selected from the group consisting of polysaccharides, proteins, nucleic acids, derivatives thereof, and combinations thereof; Preferably, the biopolymer is 11. The treatment composition according to any one of claims 1 to 10, wherein the treating composition 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, zein, soy protein, plant storage protein, gluten, peptides, actin, polynucleotides, RNA, DNA, derivatives thereof, and combinations thereof.

12. the biopolymer is chitosan, a derivative thereof, or a combination thereof; A treatment composition according to any one of claims 1 to 11, wherein the biopolymer is preferably acid-treated chitosan.

13. the biopolymer, preferably chitosan, more preferably acid-treated chitosan, has a molecular weight of about 1 kDa to about 1000 kDa; The treatment composition according to any one of claims 1 to 12, characterized in that it has a molecular weight of 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 crosslinking agent is a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxy compounds, polyphenols, carbonyl halides, aziridines, and combinations thereof; Preferably, the compound is selected from the group consisting of polyisocyanates, epoxy compounds, difunctional aldehydes, and combinations thereof; More preferably, it is a polyisocyanate. Even more preferably, the treatment composition according to any one of claims 1 to 13 is a polyisocyanate selected from the group consisting of polyisocyanurate of toluene diisocyanate, a trimethylolpropane adduct of toluene diisocyanate, a trimethylolpropane adduct of xylylene diisocyanate, 2,2'-methylenediphenyl diisocyanate, 4,4'-methylenediphenyl diisocyanate, 2,4'-methylenediphenyl diisocyanate, [diisocyanato(phenyl)methyl]benzene, toluene diisocyanate, tetramethylxylidene diisocyanate, naphthalene-1,5-diisocyanate, 1,4-phenylene diisocyanate, 1,3-diisocyanatobenzene, derivatives thereof (such as prepolymers, oligomers, and / or polymers thereof), and combinations thereof.

15. the delivery particles are from about 1 to about 100 microns; 15. The treating composition of any one of claims 1 to 14, characterized by a volume weighted median particle size of preferably from about 10 to about 100 microns, preferably from about 15 to about 50 microns, more preferably from about 20 to about 40 microns, and even more preferably from about 20 to about 30 microns.

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