Treatment composition with perfume-containing delivery particles

Abstract

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

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] Joint Research Statement

[0003] Encapsys, LLC and The Procter & Gamble Company entered into a joint research agreement on or about July 29, 2021, and this invention is the result of activities conducted within the scope of the joint research agreement between the parties that was in effect on or before the date of this invention. Technical Field

[0004] The present disclosure relates to treatment compositions comprising a treatment adjuvant and a core / shell delivery particle population, wherein the shell comprises a polymer material formed from a cross-linked amine-containing biopolymer, and wherein the core comprises a fragrance material comprising an ester-containing fragrance raw material. The present disclosure also relates to related methods of making and using such compositions. Background Art

[0005] Delivery particles, particularly core / shell delivery particles, are a convenient way to deliver benefit agents in treatment compositions, such as laundry products. For environmental reasons, it may be desirable to use delivery particles having a shell made from naturally derived and / or biodegradable materials. Useful shell-forming materials often include primary amine groups, as such materials readily react with a variety of crosslinking agents, such as polyisocyanates, to form suitable polymeric materials.

[0006] That is, when encapsulating fragrances in core-shell delivery particles, some of the shell material may interact with some of the fragrance raw materials, resulting in relatively poor performing capsules. For example, when making particles having a polymer shell made from a material containing primary amines (e.g., chitosan), fragrance raw materials containing aldehyde groups may react with the amine groups, which may result in relatively weak and / or leaky capsules. In particular, encapsulating aldehyde-containing fragrances in polyurea shells is known to be challenging.

[0007] There is a need for improved delivery particles for improved treatment compositions comprising perfume-containing delivery particles, preferably particles made at least in part from naturally derived or biodegradable materials. Summary of the invention

[0008] The present disclosure relates to delivery particles and treatment compositions comprising the same, wherein the particle comprises an ester-containing perfume raw material in a core.

[0009] For example, the present disclosure is directed to a treatment composition comprising: a treatment adjuvant 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 the reaction product of a biopolymer and a cross-linking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises a fragrance material, wherein the fragrance material comprises: (a) at least about 30% by weight of an ester-containing fragrance raw material ("PRM"), based on the weight of the fragrance material, and (b) at least about 0.5% by weight of an aldehyde-containing PRM, based on the weight of the fragrance material.

[0010] The present disclosure also relates to treatment compositions comprising: a treatment adjuvant 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 the reaction product of a biopolymer and a cross-linking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises a fragrance material, wherein the fragrance material comprises one or more fragrance raw materials ("PRMs"), and 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 a fragrance raw material having an S-ESTER value of 13 or greater.

[0011] The present disclosure also relates to a method of treating a surface, the method comprising the step of contacting a surface, preferably a fabric, with a treatment composition according to the present disclosure.

[0012] The present disclosure also relates to a method of making a treatment composition, the method comprising the steps of providing a base composition, wherein the base composition comprises a treatment adjuvant, and combining a population of delivery particles with the base composition, wherein the delivery particles comprise a core and a shell surrounding the core, wherein the shell comprises a polymeric material, wherein the polymeric material comprises a reaction product of a biopolymer and a crosslinking agent, wherein the biopolymer comprises primary amine groups, wherein the core comprises a fragrance material, wherein the fragrance material comprises: (a) at least about 30% by weight of an ester-containing fragrance raw material ("PRM"), based on the weight of the fragrance material, and (b) at least about 0.5% by weight of an aldehyde-containing PRM, based on the weight of the fragrance material. 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, 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 a fragrance raw material having an S-ESTER value of 13 or greater. DETAILED DESCRIPTION

[0013] The present disclosure relates to treatment compositions comprising a fragrance-containing delivery particle having a shell made at least in part from a biopolymer comprising primary amine groups. 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 amount of ester-containing fragrance raw materials ("PRMs").

[0014] Without wishing to be bound by theory, it is believed that the ester-containing PRMs generate hydrogen bonds or dipole moments that "bond" to the amine groups of the amine-containing biopolymer, thereby reducing the reaction of "available" or "free" amine groups with aldehyde PRMs and / or ketone-containing PRMs. Although these groups may be temporarily "bonded", it is believed that the temperatures at which such delivery particles are typically made (e.g., 50-95° C.) are unfavorable for reactions between amine groups and ester groups. Furthermore, it is believed that amine / ester reactions are kinetically unfavorable compared to reactions of amines with isocyanates (e.g., from crosslinkers) or aldehydes (e.g., from other PRMs), although the hydrogen bonding ability of ester groups is relatively strong, which is reflected in the S-ESTER index described herein.

[0015] To further improve the shell formation and resulting performance of the capsules, it may be preferred to limit the amount of aldehyde-containing PRMs, ketone-containing PRMs and hydroxyl-containing PRMs in the aroma to be encapsulated.

[0016] The fragrances, delivery particles, treatment compositions and related methods of the present disclosure are discussed in more detail below.

[0017] 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 intended to be non-limiting. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0018] The terms "substantially free of" or "substantially free from" may be used herein. This means that the indicated material has at least not been intentionally added to the composition to form a part thereof, or preferably is not present at an analytically detectable level. This is meant to include 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, may be present at a level of less than 1%, or less than 0.1%, or less than 0.01%, or even 0%, by weight of the composition.

[0019] As used herein, "consumer product" means a baby care, beauty care, fabric & home care, household care, feminine care and / or health care product or device that is intended to be used or consumed in the form in which it is sold and is not intended for subsequent commercial manufacture or modification. Such products include, but are not limited to: diapers, bibs, wipes; products for and / or methods associated with treating human hair, including bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; skin care, including application of creams, lotions and other topically applied products for consumer use; and shaving products; products for and / or methods associated with treating fabrics, hard surfaces and any other surfaces in the fabric and home care fields, including : air care, car care, dishwashing, fabric conditioning (including softening), laundry detergents, laundry and rinse additives and / or care, hard surface cleaning and / or treatment, and other cleaning for consumer or institutional use; products and / or methods related to bath towels, facial tissues, paper handkerchiefs and / or paper towels; tampons, feminine hygiene products; adult incontinence products; products and / or methods related to oral care, including toothpaste, tooth gel, mouthwash, denture adhesives, teeth whitening; over-the-counter health care, including cough and cold medicines; pest control products; and water purification.

[0020] The phrase "fabric care composition" as used herein includes compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, laundry pre-washes, laundry pre-treaters, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, rinse-post 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 according to the teachings herein. Such compositions may be used as pre-treatments for laundry, post-treatments for laundry, or may be added during the rinse or wash cycle of a laundry operation.

[0021] Unless otherwise indicated, as used herein, "delivery particle," "particle," "encapsulate," "microcapsule," and "capsule" are used interchangeably. As used herein, these terms typically refer to a core / shell delivery particle.

[0022] Unless otherwise indicated, all component or composition levels refer to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such component or composition.

[0023] Unless otherwise stated, all temperatures herein are in degrees Celsius (° C.) Unless otherwise stated, all measurements herein are made at 20° C. and atmospheric pressure.

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

[0025] It should be understood that each maximum numerical limit given throughout this specification includes each lower numerical limit, as if such lower numerical limits were explicitly written herein. Each minimum numerical limit given throughout this specification will include each higher numerical limit, as if such higher numerical limits were explicitly written herein. Each numerical range given throughout this specification will include each narrower numerical range that falls within such a wider numerical range, as if such narrower numerical ranges were explicitly written herein.

[0026] Treatment composition

[0027] The present disclosure relates to treatment compositions (or simply "compositions" as used herein). Compositions of the present disclosure may include a population of delivery particles and a treatment adjuvant, each of which is described in more detail below. The treatment compositions can be used in the methods of treating surfaces (e.g., fabrics) described herein.

[0028] The treatment composition is preferably a consumer product composition. The consumer product composition of the present disclosure can be used for baby care, beauty care, fabric care, home care, family care, feminine care and / or health care applications. The consumer product composition can be used to treat surfaces, such as fabrics, hair or skin. The consumer product composition can be intended to be used or consumed in the form of its sale. The consumer product composition of the present disclosure is typically not intended to be used for subsequent commercial manufacturing or modification.

[0029] The consumer product composition may preferably be a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition (eg a shampoo or conditioner), a body cleansing composition, or mixtures thereof, preferably a fabric care composition.

[0030] The consumer product composition may be a fabric care composition, such as a laundry detergent composition (including heavy-duty liquid detergents or unit dose products), a fabric conditioning composition (including liquid fabric softening and / or enhancing compositions), a laundry additive, a fabric pretreatment composition (including sprays, pourable liquids or sprays), a fabric refresher composition (including sprays), or mixtures thereof. The treatment composition is preferably a fabric conditioning composition, even more preferably a liquid fabric conditioning composition.

[0031] The composition may be a beauty care composition, such as a hair treatment product (including shampoo and / or conditioner), a skin care product (including cream, lotion or other topically applied product for consumer use), a shaving care product (including shaving lotion, foam, or pre-shave or after-shave treatment), a personal cleansing product (including liquid body wash, hand soap and / or soap bar), a deodorant and / or an antiperspirant, or mixtures thereof.

[0032] The composition may be a household care composition, such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other cleaning compositions for consumer or institutional use.

[0033] The treatment composition may be in the form of a liquid composition, a granular composition, a hydrocolloid, a single compartment bag, a multi-compartment bag, a dissolvable sheet, a lozenge or bead, a fiber product, a tablet, a stick, a bar / block, a wafer, a foam / mousse, a nonwoven sheet, or a mixture thereof.

[0034] The treatment composition may be in liquid form. The liquid composition may preferably include about 50% to about 97%, preferably about 60% to about 96%, more preferably about 70% to about 95%, or even about 80% to about 95% water by weight of the fabric treatment composition. The liquid composition 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.

[0035] The treatment composition may be in solid form. The composition may be in the form of beads or pastilles, which may be made into pastilles from a liquid melt. The composition may be an extruded product. The treatment composition may be in the form of a powder or pellets.

[0036] The composition can be in the form of a unitized dosage product (e.g., tablet, bag, sheet or fiber product). Such a bag typically includes a water-soluble film such as a polyvinyl alcohol water-soluble film, which at least partially encapsulates the composition. Suitable films can be obtained from MonoSol, LLC (Indiana, USA). The composition can be encapsulated in a single or multi-compartment bag. The multi-compartment bag can have at least two, at least three, or at least four compartments. The multi-compartment bag can include compartments that are arranged side by side and / or stacked. The composition contained in the bag or its compartment can be a liquid, a solid (e.g., a powder) or a combination thereof. The bagged composition can have a relatively small amount of water, for example, less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% water by weight of the detergent composition.

[0037] The treatment composition may be in the form of a spray and may be dispensed, for example, from a bottle via a trigger sprayer and / or an aerosol container having a valve.

[0038] The treatment composition may have a -1 and a viscosity of 1-1500 centipoise (1-1500 mPa*s), 100-1000 centipoise (100-1000 mPa*s), or 200-500 centipoise (200-500 mPa*s) at 21°C.

[0039] The treatment composition of the present disclosure may be characterized by a pH of about 2 to about 12, or about 2 to about 8.5, or about 2 to about 7, or about 2 to about 5. The treatment composition of the present disclosure may have a pH of about 2 to about 4, preferably a pH of about 2 to about 3.7, more preferably a pH of about 2 to about 3.5, preferably in aqueous liquid form. It is believed that such a pH level promotes the stability of the quaternary ammonium ester compound (when present). On the other hand, the detergent composition is typically characterized by a pH of about 7 to about 12, preferably about 7.5 to about 11. The pH of the composition is determined by dissolving / dispersing the composition in deionized water at about 20°C to form a 10% concentration solution.

[0040] Additional components and / or features of the compositions are discussed in more detail below.

[0041] Delivery Particle Group

[0042] The treatment composition of the present disclosure comprises a population of delivery particles. The delivery particles comprise a core and a shell surrounding the core. The core comprises a fragrance material and an optional distribution modifier. At room temperature, the core may be liquid or solid, preferably liquid.

[0043] The treatment composition may comprise from about 0.05% to about 20%, or from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.2% to about 2% of the delivery particles by weight of the composition. The composition may comprise a sufficient amount of the 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% of the encapsulated benefit agent, which may preferably be a fragrance raw material, by weight of the composition. When the amount or weight percentage of the delivery particles is discussed herein, the sum of the wall material and the core material is meant.

[0044] A population of delivery particles according to the present disclosure may be characterized by a volume weighted median particle size of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 25 to about 35 microns. For some compositions, it may be preferred that the population of delivery particles be characterized by a volume weighted median particle size of about 1 to about 50 microns, preferably about 5 to about 20 microns, and more preferably about 10 to about 15 microns. Different particle sizes can be obtained by controlling the droplet size during emulsification.

[0045] The delivery particle may be characterized by a core to shell ratio of up to 99:1, or even 99.5:0.5 by weight. The shell may be present at a level of about 1% to about 25%, preferably about 1% to about 20%, preferably about 1% to 15%, more preferably about 5% to about 15%, even more preferably about 10% to about 15%, even more preferably about 10% to about 12%, by weight of the delivery particle. The shell may be present at a level of at least 1%, preferably at least 3%, more preferably at least 5%, by weight of the delivery particle. The shell may be present at a level of up to about 205%, preferably up to about 15%, more preferably up to about 12%, by weight of the delivery particle.

[0046] The delivery particles may be cationic in nature, preferably cationic at pH 4.5. The delivery particles may be characterized by a zeta potential of at least 15 millivolts (mV) at pH 4.5. The delivery particles may be made to have a zeta potential of at least 15 millivolts (mV) at pH 4.5, or even at least 40 mV at pH 4.5, or even at least 60 mV at pH 4.5. Polyurea capsules prepared with chitosan typically exhibit a positive zeta potential. Such capsules have improved deposition efficiency on fabrics. At higher pH, the particles may be able to be made nonionic or anionic.

[0047] 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 cross-linking agent.

[0048] Biopolymers typically contain primary amine groups. The primary amine groups react with a cross-linking agent to form a polymer material, which can be described as a cross-linked biopolymer.

[0049] The biopolymer may preferably be selected from the following: polysaccharides, proteins, nucleic acids, their derivatives, and combinations thereof. Preferably, the biopolymer is selected from the following:

[0050] (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;

[0051] (b) a protein selected from the group consisting of gelatin (e.g., porcine gelatin), collagen, casein, sericin, fibroin, whey protein, pea protein, corn protein, soy protein, plant storage protein (plant protein isolate, plant protein concentrate), gluten, peptides, actin, derivatives thereof, and combinations thereof;

[0052] (c) a nucleic acid selected from the group consisting of a polynucleotide, RNA, DNA, derivatives thereof, and combinations thereof; and

[0053] (d) combinations thereof.

[0054] Amine-containing polysaccharides may be preferred, for example due to convenient availability, biodegradability and / or performance reasons. A particularly preferred material is chitosan. Thus, the biopolymer may preferably be chitosan, a derivative thereof, or a combination thereof. Preferably, the biopolymer is acid-treated chitosan, a derivative thereof, or a combination thereof.

[0055] Preferably, the chitosan may be an acid-treated chitosan. For example, the chitosan (which may be referred to as the original chitosan or the parent chitosan before the acid treatment) may be treated with an acid preferably at a pH of 6.5 or less for at least one hour, preferably about one hour to about three hours, at a temperature of about 25°C to about 99°C, preferably about 75°C to about 95°C. The acid may be selected from a strong acid (e.g., hydrochloric acid), an organic acid (e.g., formic acid or acetic acid), or a mixture thereof. Preferably, the chitosan may be acid-treated at a pH of 2-6.5, or even at a pH of 4-6.

[0056] The biopolymer (preferably chitosan, more preferably acid-treated chitosan) may preferably be characterized by a molecular weight of about 1 kDa to about 1000 kDa, preferably about 50 kDa to about 600 kDa, more preferably about 100 kDa to about 500 kDa, even more preferably about 100 kDa to about 300 kDa, 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 in forming suitable delivery particles, while those with relatively high molecular weights are often difficult to process. Methods for determining chitosan molecular weight and related parameters are provided in the Test Methods section below, and use gel permeation chromatography with multi-angle light scattering and refractive index detection techniques (GPC-MALS / RI).

[0057] Chitosan can be characterized by a degree of deacetylation of at least 50%, preferably about 50% to about 99%, more preferably about 75% to about 90%, even more preferably about 80% to about 85%. The degree of deacetylation can affect the solubility of chitosan, which in turn can affect its reactivity or behavior during the formation of the particle shell. For example, too low a degree of deacetylation (e.g., less than 50%) results in relatively insoluble and relatively unreactive chitosan. A relatively high degree of deacetylation can result in very soluble chitosan, resulting in relatively little chitosan moving to the oil / water interface during shell formation.

[0058] When present, the chitosan may comprise anionically modified chitosan, cationically modified chitosan, or a combination thereof. Anionically and / or cationically modified chitosan may alter the properties of the shell of the delivery particle, for example by changing the surface charge and / or zeta potential, which may affect the deposition efficiency and / or formulation compatibility of the particle.

[0059] As described above, the shell is a polymer material, which is the reaction product of the biopolymer chitosan and a cross-linking agent. The cross-linking material is preferably selected from the following materials: polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxides, polyphenols, carbonyl halides, aziridines, and combinations thereof. More preferably, the cross-linking agent is selected from the following: polyisocyanates, epoxides, difunctional aldehydes, and combinations thereof.

[0060] The crosslinking agent is preferably a polyisocyanate. It is believed that such a material is conducive to reacting with the amine groups of the biopolymer to form an effective, crosslinked polymer wall. When the crosslinking agent is a polyisocyanate, the polymer material of the shell can be understood to include a polyurea resin. The polyurea resin can include the reaction product of a polyisocyanate and chitosan.

[0061] For purposes of the present invention, the polyisocyanate materials that can be used for the present disclosure are understood to be isocyanate monomers, isocyanate oligomers, isocyanate prepolymers or dimers or trimers of aliphatic or aromatic isocyanates. Monomers, prepolymers, oligomers or dimers or trimers of all such aliphatic or aromatic isocyanates are intended to be included in the term "polyisocyanates" herein. Polyisocyanates that can be used for the present disclosure comprise isocyanate monomers, oligomers or prepolymers, or their dimers or trimers, with at least two isocyanate groups. Preferred crosslinking can be realized with polyisocyanates with at least three functional groups.

[0062] Aromatic polyisocyanates may be preferred; however, aliphatic polyisocyanates and blends thereof may be useful. Aliphatic polyisocyanates are understood to be polyisocyanates that do not contain any aromatic moieties. Aromatic polyisocyanates are understood to be polyisocyanates that contain at least one aromatic moiety. The crosslinking agent may comprise a mixture of aromatic polyisocyanates and aliphatic polyisocyanates.

[0063] Preferably, the polyisocyanate is selected from the group consisting of polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of toluene diisocyanate and trimethylolpropane adducts of xylylene diisocyanate, 2,2′-methylene diphenyl diisocyanate, 4,4′-methylene diphenyl diisocyanate, 2,4′-methylene diphenyl diisocyanate, toluene diisocyanate, tetramethylxylidine diisocyanate, naphthalene-1,5-diisocyanate, 1,4-phenylene diisocyanate, 1,3-diisocyanatobenzene, and combinations thereof.

[0064] Additional co-crosslinkers (e.g., multifunctional amines and / or polyamines, such as diethylenetriamine (DETA), polyethyleneimine, polyvinylamine, or mixtures thereof) may also be used to strengthen the particle shell. For example, acrylates may also be used as additional co-crosslinkers to strengthen the shell.

[0065] The polymer material may be formed in a reaction wherein the weight ratio of the biopolymer (preferably a polysaccharide, more preferably chitosan or a derivative thereof (which may include acid-treated chitosan)) present in the reaction to the cross-linking agent present in the reaction is from about 1:10 to about 1:0.1, preferably from about 1:5 to about 5:1, preferably from about 1:4 to about 5:1, more preferably from about 1:1 to about 5:1, more preferably from about 3:1 to about 5:1. It is believed that selecting a desired ratio of biopolymer to cross-linking agent may provide the desired ductility benefits as well as improved biodegradability. It may be preferred that at least 21% by weight of the shell is composed of moieties derived from chitosan, preferably acid-treated chitosan. Chitosan may be from about 21% to about 95% of the shell as a percentage of the weight of the shell. The ratio of chitosan in the aqueous phase to isocyanate in the oil phase may be from 21:79 to 90:10, or even 1:2 to 10:1, or even 1:1 to 7:1 on a weight basis. The shell may comprise chitosan at a level of 21 wt% or even more, preferably from about 21 wt% to about 90 wt%, or even 21 wt% to 85 wt%, or even 21 wt% to 75 wt%, or 21 wt% to 55 wt% of the total shell is chitosan. The chitosan of this paragraph may preferably be acid-treated chitosan.

[0066] The delivery particle population can be prepared according to a method comprising the following steps: (a) forming an aqueous phase comprising chitosan as described herein, preferably wherein the aqueous phase has a pH of 6.5 or 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 beneficial agent (preferably a fragrance material) and at least one cross-linking 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 phase and the oil phase under high shear agitation, optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6; (d) curing the emulsion by heating, preferably to at least 40°C, for a time sufficient to form a shell at the interface of the oil droplets and the aqueous phase, wherein the shell will comprise a polymeric material which is the reaction product of the chitosan and the cross-linking agent, and wherein the shell surrounds a core comprising the beneficial agent.

[0067] The delivery particle population may be prepared according to a method comprising the steps of: (a) forming an aqueous phase by treating chitosan with a mixture of a first acid and a second acid, the first acid comprising a strong acid and the second acid comprising a weak acid, wherein the chitosan is treated at a pH of 6.5 or less, or even below pH 6.5, or even at a pH of 3 to 6 and a temperature of at least 25° C. for at least one hour; (b) forming an oil phase comprising mixing at least one beneficial agent and at least one polyisocyanate, optionally with an added oil (e.g., a partitioning modifier) ​​and / or a solvent. (c) forming an emulsion by: mixing an aqueous phase and an oil phase into an excess of the aqueous phase under high shear agitation to form droplets of the oil phase and the beneficial agent, the droplets being dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to be in the range of pH 2 to pH 6; (d) curing the emulsion by heating to at least 40° C. for a time sufficient to form a shell at the interface of the droplets with the aqueous phase, the shell comprising the reaction product of the polyisocyanate and the acid-treated chitosan, and the shell surrounding a core comprising the droplets of the oil phase and the beneficial agent.

[0068] Chitosan can be added to water in a jacketed reactor and at a pH from 2 or even from 3 to 6.5, using acid (e.g., concentrated HCl) to adjust. The chitosan of this mixture can be acid treated by heating to an elevated temperature (e.g., 85°C) within 60 minutes, and then can be kept at this temperature for 1 minute-1440 minutes or longer. The aqueous phase can then be cooled to 25°C. Optionally, deacetylation can also be further promoted or enhanced by enzymes to depolymerize or deacetylate chitosan. The oil phase can be prepared by dissolving an isocyanate such as a trimer of xylene diisocyanate (XDI) or a polymer of methylene diphenyl diisocyanate (MDI) in oil at 25°C. A diluent (e.g., isopropyl myristate) can be used to adjust the hydrophilicity of the oil phase. The oil phase can then be added to the aqueous phase and ground at high speed to obtain a target size. The emulsion can then be solidified in one or more heating steps, for example, heated to 40°C within 30 minutes and kept at 40°C for 60 minutes. The time and temperature are approximate. The temperature and time are selected to be sufficient to form and solidify the shell at the interface of the oil phase droplets and the water continuous phase. For example, the emulsion can be heated to 85°C in 60 minutes and then maintained at 85°C for 360 minutes to solidify the particles. The slurry can then be cooled to room temperature.

[0069] The shell may degrade by at least 50% after 20 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may preferably degrade by at least 60% of its mass after 60 days (or less) 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% within 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, more preferably 14 days.

[0070] The delivery particles of the present disclosure include a core. The core includes a fragrance material. The fragrance material includes one or more fragrance raw materials (PRMs). The core optionally includes a distribution modifier.

[0071] The core of the particle is surrounded by the shell. When the shell breaks, the fragrance material in the core is released. Additionally or alternatively, the fragrance material in the core can diffuse out from the particle, and / or it can be squeezed out. The suitable fragrance material in the core can include a fragrance material that provides benefits to a surface (e.g., fabric or hair).

[0072] The core may comprise from about 5% to about 100% aroma material by weight of the core. The core may comprise from about 45% to about 95%, preferably from about 50% to about 80%, more preferably from about 50% to about 70% aroma material by weight of the core.

[0073] The fragrance material may be relatively hydrophobic. Such agents are compatible with the oil phase that is common in making the delivery particles of the present disclosure.

[0074] As described above, the core of the delivery particles of the present disclosure contains a fragrance, which may include one or more fragrance raw materials. Fragrances are particularly suitable for encapsulation in the delivery particles described herein because the fragrance-containing particles can provide freshness benefits across multiple contact points.

[0075] As used herein, the term "fragrance raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mol and which can be used to impart an odor, flavor, fragrance, or aroma, either alone or in combination with other fragrance raw materials. Typical PRMs include alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes, such as terpenes, among others. Lists of common PRMs can be found in various reference sources, such as "Perfume and Flavor Chemicals", Volumes I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology", Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0076] PRMs can be characterized by their boiling point (BP) measured at atmospheric pressure (760 mm Hg) and their octanol / water partition coefficient (P) (which can be described as logP, determined according to the following test method). Based on these characteristics, PRMs can be classified as Quadrant I, Quadrant II, Quadrant III or Quadrant IV fragrances, as described in more detail below.

[0077] The aroma may comprise a fragrance raw material having a logP of from about 2.5 to about 4. It is understood that other fragrance raw materials may also be present in the aroma.

[0078] The perfume raw material may comprise a perfume raw material selected from the following: perfume raw materials having a boiling point (BP) of less than about 250°C and a logP of less than about 3, perfume raw materials having a BP of greater than about 250°C and a logP of greater than about 3, perfume raw materials having a BP of greater than about 250°C and a logP of less than about 3, perfume raw materials having a BP of less than about 250°C and a logP of greater than about 3, and mixtures thereof. Perfume raw materials having a boiling point BP of less than about 250°C and a logP of less than about 3 are referred to as quadrant I perfume raw materials. It is preferred to limit quadrant I perfume raw materials to less than 30% of the perfume composition. Perfume raw materials having a BP of greater than about 250°C and a logP of greater than about 3 are referred to as quadrant IV perfume raw materials, perfume raw materials having a BP of greater than about 250°C and a logP of less than about 3 are referred to as quadrant II perfume raw materials, and perfume raw materials having a BP of less than about 250°C and a logP of greater than about 3 are referred to as quadrant III perfume raw materials. Suitable quadrant I, II, III and IV perfume raw materials are disclosed in U.S. Pat. No. 6,869,923B1.

[0079] As described above, there are challenges associated with encapsulating some PRMs in some wall materials. It was surprisingly found that effective delivery particles can be made by selecting some PRMs to be encapsulated. For example, it was found to be beneficial to select a certain minimum amount of ester-containing PRMs as part of the fragrance material to be encapsulated. Additionally or alternatively, it was found to be beneficial to select the components of the fragrance material so that the fragrance material is characterized by one or more S-ESTER values, as described in more detail below.

[0080] The fragrance material may comprise at least 30% by weight of the fragrance material of ester-containing perfume raw materials (PRMs). Preferably, the fragrance material also contains at least 0.5% by weight of the fragrance material of aldehyde-containing PRMs. It has surprisingly been found that including relatively high amounts of ester-containing PRMs in the fragrance material allows for advantageous encapsulation of the entire fragrance material. This is true even when the fragrance material comprises aldehyde-containing PRMs, which are known to cause encapsulation challenges when using amine-containing shell precursors.

[0081] The aroma material may contain at least about 30%, preferably about 35%, more preferably at least about 40%, even more preferably at least about 50% of an ester-containing PRM by weight of the aroma material. The aroma material may contain from 30% to 99.5%, preferably from 35% to about 80%, more preferably from about 40% to about 70%, even more preferably from about 50% to about 60% by weight of the aroma material. It is believed that relatively higher amounts of ester-containing PRMs will result in more effective encapsulation and / or performance.

[0082] Note that some PRMs contain more than one functional group, such as an ester group and a hydroxyl group (see, e.g., triethyl citrate). For purposes of this disclosure, when determining the relative percentages of PRMs (which include a given functional group) in a given fragrance material, 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 would be counted in 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 total more than 100% by weight of the fragrance material due to such double (or even triple, etc.) counting.

[0083] Aroma materials (including individual PRMs) can be described according to their atomic-level electrotopological state (E-State) index. E-State values ​​are molecular indices that can be found in the literature and / or determined using commercially available software programs. The E-State value effectively observes each atom in a molecule and reflects the valence electronegativity of the atom, which is affected by the atoms to which it is attached. The electrotopological state index is discussed more 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.

[0084] The S-ESTER value is the sum of the atomic-level electrotopological state (E-State) values ​​of all carbonyl carbons and oxygens in the ester groups in the molecule. To determine the E-State and S-ESTER values ​​for the purposes described in this disclosure, the software program winMolconn version 1.2.2.3 (available from Hall Associates Consulting in Quincy, MA, used according to the manufacturer's instructions) is used to calculate the E-State value. The method for determining the S-ESTER value is described in more detail in the Test Methods section below.

[0085] For example, a relatively high S-ESTER value for a particular compound may indicate more than one ester group. A relatively high S-ESTER value for a mixture of compounds (e.g., a fragrance material containing more than one type of fragrance raw material) may indicate a relatively high proportion of ester-containing compounds, including compounds containing more than one ester group.

[0086] The fragrance material encapsulated in the delivery particles of the present disclosure can be characterized according to the S-ESTER value of the entire fragrance material (e.g., a mixture of PRMs) and / or characterized by the relative amount of PRMs characterized by a certain S-ESTER value. For example, the fragrance material can be characterized by one or more of the following: (a) having an S-ESTER value of at least about 5, 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% of the fragrance raw materials by weight of the fragrance material, the fragrance raw materials having an S-ESTER value of 13 or greater.

[0087] The fragrance material may be characterized as having an S-ESTER value of at least about 5, preferably at least about 5.5, preferably at least about 6. Additionally, the fragrance material may preferably be characterized by an S-ESTER value of no greater than about 20, preferably no greater than about 13, more preferably no greater than about 10. Larger S-ESTER values ​​are associated with a relatively greater number of esters, which may be associated with relatively lower volatility and lower olfactory impact.

[0088] The fragrance material may comprise at least about 30%, preferably at least about 40%, more preferably at least about 50%, even more preferably at least about 55%, by weight of the fragrance material, of a fragrance raw material having an S-ESTER value of about 13 or greater, preferably a PRM having an S-ESTER value of from about 13 to about 80, more preferably from about 13 to about 35, even more preferably from about 13 to about 20. For clarity, it is understood that PRMs that do not include ester groups are assigned an S-ESTER value of zero.

[0089] The following table provides suitable ester-containing PRMs for use in the fragrance materials of the present disclosure. The fragrance materials of the present disclosure may contain any PRM listed in the following table or a combination thereof. The table also indicates the type of functional groups present, and the S-ESTER value specified for each PRM.

[0090]

[0091]

[0092] While it is believed that relatively higher amounts of ester-containing PRMs will result in more effective encapsulation and / or performance, from an olfactory perspective it may be desirable to include PRMs with non-ester moieties to form a well-rounded fragrance.

[0093] For example, the aroma material may comprise an aldehyde-containing PRM. The aroma material may comprise at least about 0.5%, preferably at least about 1%, more preferably at least about 5%, more preferably at least about 10% of an aldehyde-containing PRM by weight of the aroma material. Due to known problems associated with encapsulation, it may be desirable to limit the amount of aldehyde-containing PRM. For example, the aroma material may comprise from 0.5% to about 30%, preferably from about 1% to about 25%, more preferably from about 5% to about 20% of an aldehyde-containing PRM by weight of the aroma material. Aldehyde-containing fragrance raw materials may include: methylnonyl acetaldehyde: benzaldehyde; sea breeze aldehyde; isocyclic citral; privet aldehyde (triplal / ligustral); methyl citrus aldehyde B; lily aldehyde; decanal; undecenal; cyclamen aldehyde; cyclamen aldehyde; dupical; acacia aldehyde; adoc aldehyde; melon aldehyde; calypsone; anise aldehyde; jasmine aldehyde; cumin aldehyde; 3,6-dimethylcyclohex-3-ene-1-carboxaldehyde; α-4-dimethylphenylpropionaldehyde (satinaldehyde); conosin aldehyde; vanillin; ethyl vanillin; cinnamaldehyde; cis-4-decenal; trans-4-decenal; cis-7-decenal; undecenal; trans-2-hexenal; trans-2-octenal; 2-undecenal; 2,4-dodecadeienal; cis-4-heptanal; Florydral; butylcinnamaldehyde; limonelal; amylcinnamaldehyde; hexylcinnamaldehyde; citronellal; citral; cis-3-hexen-1-al; or mixtures thereof, as these materials are particularly desired by formulators and / or consumers.

[0094] The fragrance material may contain hydroxyl-containing PRMs. However, in order to promote effective shell formation, the relative amount of such PRMs may be limited. The fragrance material may contain no more than 30% hydroxyl-containing PRMs, preferably 1% to 30% hydroxyl-containing PRMs by weight of the fragrance material. Hydroxyl-containing fragrance raw materials may include: geraniol, nonadienol, cinnamyl alcohol, linalool, tricyclodecenyl acetate, their derivatives or mixtures thereof, as these materials are particularly desired by formulators and / or consumers.

[0095] The fragrance material may comprise a ketone PRM. Ketone-containing fragrance raw materials may include: 1-(3-methyl-benzofuranyl)ethanone (nerolione); 4-(4-methoxyphenyl)butan-2-one; 1-naphth-2-ylethanone; nectaryl; trimethylsuccinone (trimofix O); 2-heptylcyclopentanone; delta-damascone; beta-damascone; alpha-damascone; methylionone; 2-hexylcyclopent-2-en-1-one; galenone or mixtures thereof, as these materials are particularly desirable to formulators and / or consumers.

[0096] Preferred fragrance materials suitable for encapsulation in the delivery particles of the present disclosure may include the following types 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).

[0097] The core of the delivery particle of the present disclosure may include a partitioning modifier, which may promote more robust shell formation. The partitioning modifier may be combined with the fragrance oil material of the core prior to incorporation into the wall-forming monomers. The partitioning modifier may be present in the core at a level of 0% to 95%, preferably about 5% to about 55%, preferably about 10% to about 50%, more preferably about 25% to about 50%, by weight of the core.

[0098] The partitioning modifier may comprise a material selected from the group consisting of vegetable oils, modified vegetable oils, C4-C 24 Monoesters, diesters and triesters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The distribution modifier may preferably comprise isopropyl myristate or even consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably comprise castor oil and / or soybean oil. U.S. Patent Application Publication 20110268802 (incorporated herein by reference) describes other distribution modifiers that can be used for the delivery particles described herein.

[0099] Optionally, the core may contain additional benefit agents which may be selected from the following: silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin cooling agents, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleaching particles, silica particles, malodor reducers, odor control materials, antistatic agents, softeners, insect and moth repellents, colorants, antioxidants, chelating agents, thickeners, drape and shape control agents, smoothing agents, wrinkle control agents, disinfectants, bactericides, bacteria control agents, mold control agents, mildew control agents, antiviral agents, desiccant agents, stain repellents , fabric refreshers and freshness extenders, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color restoration / regeneration agents, anti-fading agents, whiteness enhancers, anti-wear agents, wear inhibitors, fabric integrity agents, anti-abrasion agents, anti-pilling agents, defoaming agents, anti-foaming agents, UV protectants, sunlight fade inhibitors, anti-allergic agents, enzymes, water repellents, fabric softeners, anti-shrinkage agents, anti-stretch agents, stretch recovery agents, skin care agents, synthetic or natural actives, antimicrobial actives, antiperspirant actives, cationic polymers, dyes, and mixtures thereof.

[0100] When the benefit agent itself is not sufficient to act as an oil phase or solvent, particularly for the wall forming material during the process of forming the shell of the delivery particle, the oil phase may include a suitable carrier and / or solvent. In this sense, the oil is optional, because the benefit agent itself may sometimes be an oil. These carriers or solvents are typically oils, preferably having a boiling point greater than about 80°C and having low volatility and are non-flammable. Although not limited thereto, they preferably include one or more esters, preferably having 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 and glycerol.

[0101] Optionally, the aqueous phase may include an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (e.g., alkyl sulfates / salts, alkyl ether sulfates / salts and / or alkyl benzene sulfonates / salts), nonionic surfactants (e.g., alkoxylated alcohols, preferably comprising ethoxy groups), polyvinyl alcohol and / or polyvinyl pyrrolidone. It may be that dissolved chitosan may provide emulsification benefits in the present application.

[0102] Emulsifiers, if used, typically comprise from about 0.1 to 40 weight percent, preferably from 0.2 to about 15 weight percent, more typically from 0.5 to 10 weight percent, based on the total weight of the aqueous phase.

[0103] The delivery particle population can be provided in the form of a slurry, preferably an aqueous slurry. The slurry may include one or more processing aids, which may include water, aggregation-inhibiting materials such as divalent salts, or particle suspending polymers, such as xanthan gum, guar gum, cellulose (preferably microfibrillated cellulose) and / or carboxymethyl cellulose. When the delivery particles are characterized by cationic properties (e.g., when the shell is at least partially derived from chitosan), non-anionic structurants (preferably nonionic structurants) may be preferred to avoid harmful charge interactions that may lead to undesirable aggregation.

[0104] The slurry may include one or more carriers selected from the following: 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, fragrance raw materials, silicone oils, hydrocarbon paraffin oils; and mixtures thereof. Aqueous slurries may be preferred. The slurry may contain non-encapsulated ("free") fragrance raw materials, which are different in characteristics and / or amounts from those encapsulated in the core of the delivery particle.

[0105] The slurry may include a deposition aid, which may include a polymer selected from the group consisting of: polysaccharides, in one aspect, cationically modified starch and / or cationically modified guar gum; polysiloxanes; polydiallyldimethylammonium halides; copolymers of polydiallyldimethylammonium chloride and polyvinyl pyrrolidone; compositions comprising polyethylene glycol and polyvinyl pyrrolidone; acrylamide; imidazole; imidazolinium halides; polyvinylamine; copolymers of polyvinylamine and N-vinyl formamide; polyvinyl formamide, polyvinyl alcohol; polyvinyl alcohol cross-linked with boric acid; polyacrylic acid; polyglyceryl ether silicone cross-polymers; copolymers of polyacrylic acid, polyacrylate, polyvinylamine and polyvinyl alcohol, oligomers of amines. , on the one hand diethylenetriamine, ethylenediamine, bis(3-aminopropyl)piperazine, N,N-bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine, and mixtures thereof; polyethyleneimine, derivatized polyethyleneimine, on the one hand 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 on the backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile or combinations thereof; preformed coacervates of anionic surfactants in combination with cationic polymers; polyamines and mixtures thereof.

[0106] At least one population of delivery particles can be included in an agglomerate and then combined with a different population of delivery particles and at least one auxiliary material. The agglomerate can include a material selected from the group consisting of silicon dioxide, 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.

[0107] Suitable equipment for use in the methods disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow shear mixers, ribbon blenders, longitudinal axis granulators and drum mixers (both in batch and (when applicable) continuous process configurations), spray dryers and extruders. Such equipment can be obtained from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Kentucky, USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minnesota, USA), Arde Barinco (New Jersey, USA).

[0108] Auxiliary ingredients

[0109] In addition to the delivery particles, the treatment compositions of the present disclosure may also include one or more adjunct materials. The adjunct material may provide a benefit in the intended end use of the composition, or it may be a processing and / or stability aid.

[0110] Suitable adjunct materials may include surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleach systems, stabilizers, synergists, chelants, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, soil and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, additional fragrances and fragrance delivery systems, structure elasticizers, carriers, hydrotropes, processing aids, anti-agglomeration agents, coatings, formaldehyde scavengers and / or pigments. Preferably, the adjunct materials comprise additional fabric conditioners, dyes, pH control agents, solvents, rheology modifiers, structurants, cationic polymers, surfactants, fragrances, additional fragrance delivery systems, chelants, antioxidants, preservatives, or mixtures thereof.

[0111] 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, chelants, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, soil and soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizers, fabric softeners, carriers, hydrotropes, processing aids, structurants, anti-agglomeration agents, coatings, formaldehyde scavengers and / or pigments.

[0112] The precise nature of these additional components and the level at which they are incorporated will depend on the physical form of the composition and the nature of the operation for which it is used. However, when one or more adjuvants are present, such one or more adjuvants may be present as described in detail below. The following is a non-limiting list of suitable additional adjuvants.

[0113] A. Surfactants

[0114] The compositions of the present disclosure may include a surfactant. Surfactants can be used to provide, for example, cleaning benefits. The compositions may include a surfactant system, which may contain one or more surfactants.

[0115] The compositions of the present disclosure may include about 0.1% to about 70%, or about 2% to about 60%, or about 5% to about 50% of the surfactant system by weight of the composition. Liquid compositions may include about 5% to about 40% of the surfactant system by weight of the composition. Concentrated (compact) formulations (including concentrated liquids, gels and / or compositions suitable for unit dosage form) may include about 25% to about 70%, or about 30% to about 50% of the surfactant system by weight of the composition.

[0116] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include linear alkylbenzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, nonionic surfactants such as ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactant may be derived at least in part from a natural source, such as a natural raw material alcohol.

[0117] Suitable anionic surfactants may include any conventional anionic surfactants. This may include sulfate detergent surfactants, such as alkoxylated and / or non-alkoxylated alkyl sulfate materials and / or sulfonic acid detergent surfactants, such as alkylbenzene sulfonates. Anionic surfactants may be linear, branched or a combination thereof. Preferred surfactants include linear alkylbenzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS) or mixtures thereof. Other suitable anionic surfactants include branched modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES) and / or alkyl ethoxylated carboxylates (AEC). Anionic surfactants may exist in acid form, salt form or mixtures thereof. Anionic surfactants may be partially or completely neutralized, for example, by alkali metals (e.g., sodium) or amines (e.g., monoethanolamine). Due to the presence of the cationic esterquat material, it may be desirable to limit the amount of anionic surfactant to avoid undesirable interaction of the materials; for example the composition may comprise less than 5%, preferably less than 3%, more preferably less than 1%, even more preferably less than 0.1% anionic surfactant by weight of the composition.

[0118] Surfactant system can comprise nonionic surfactant. Suitable nonionic surfactant comprises alkoxylated fatty alcohol such as ethoxylated fatty alcohol. Other suitable nonionic surfactant comprises alkoxylated alkylphenol, alkylphenol condensate, mid-chain branched alcohol, mid-chain branched alkyl alkoxylate, alkyl polysaccharide (such as alkyl polyglycoside), polyhydroxy fatty acid amide, ether-terminated poly (oxyalkylated) alcohol surfactant, and their mixture. Alkoxylate unit can be ethyleneoxy unit, propyleneoxy unit or their mixture. Nonionic surfactant can be linear, branched (such as mid-chain branched) or their combination. Specific nonionic surfactant can comprise alcohol with average about 12-about 16 carbons and average about 3-about 9 ethoxy groups, such as C12-C14EO7 nonionic surfactant.

[0119] Suitable zwitterionic surfactants may include any conventional zwitterionic surfactants, such as betaines, including alkyl dimethyl betaine and coconut dimethyl amidopropyl betaine, C8-C 18 (For example, C 12 -C 18 ) amine oxides (such as C 12-14 dimethylamine oxide) and / or sulfonyl and hydroxy betaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonate / salt, in which the alkyl group can be C8-C 18 , or C 10 -C 14 The zwitterionic surfactant may include an amine oxide.

[0120] Depending on the formulation and / or intended end use, the composition may be substantially free of some surfactants. For example, a liquid fabric enhancer composition (e.g., a fabric softener) may be substantially free of anionic surfactants because such surfactants may interact adversely with cationic ingredients.

[0121] B. Conditioning Actives

[0122] 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.

[0123] Conditioning actives can be present at levels of about 1% to about 99% by weight of the composition. The composition can include conditioning actives from about 1%, or from about 2%, or from about 3% to about 99%, or to about 75%, or to about 50%, or to about 40%, or to about 35%, or to about 30%, or to about 25%, or to about 20%, or to about 15%, or to about 10% by weight of the composition. The composition can include conditioning actives from about 5% to about 30% by weight of the composition.

[0124] Conditioning actives suitable for the compositions of the present disclosure may include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof. Preferably the treatment composition is a fabric care composition wherein one or more of the adjunct ingredients comprises a quaternary ammonium ester material; such materials are particularly useful in fabric enhancing / conditioning / softening compositions.

[0125] The composition may include a quaternary ammonium ester compound, a silicone, or a combination thereof, preferably a combination. The total amount of the quaternary ammonium ester compound and the silicone may be about 5% to about 70%, or about 6% to about 50%, or about 7% to about 40%, or about 10% to about 30%, or about 15% to about 25% by weight of the composition. The composition may include a quaternary ammonium ester compound and 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.

[0126] The composition may contain a mixture of different types of conditioning actives. The composition of the present disclosure may contain some conditioning actives but be substantially free of others. For example, the composition may be free of quaternary ammonium ester compounds, silicones, or both. The composition may contain quaternary ammonium ester compounds but be substantially free of silicones. The composition may contain silicones but be substantially free of quaternary ammonium ester compounds.

[0127] C. Deposition Aid

[0128] The compositions of the present disclosure may include a deposition aid. As described above, due to the synergistic benefits generated by the esterquat materials and delivery particles of the present disclosure, relatively 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 compositions of the present disclosure to enhance performance even more.

[0129] Deposition aids can facilitate deposition of delivery particles, conditioning actives, perfumes, or combinations thereof, thereby improving the performance benefits of the composition and / or allowing for more efficient formulation of such benefit agents. The composition may comprise 0.0001% to 3%, preferably 0.0005% to 2%, more preferably 0.001% to 1%, or about 0.01% to about 0.5%, or about 0.05% to about 0.3% of a deposition aid by weight of the composition. The deposition aid may be a cationic or amphoteric polymer, preferably a cationic polymer.

[0130] Generally speaking, cationic polymers and methods for their manufacture are known in the literature. Suitable cationic polymers may include quaternary ammonium polymers, which are known as "polyquaternium" polymers, as designated by the International Nomenclature of Cosmetic Ingredients, for example, polyquaternium-6 (poly(diallyldimethylammonium chloride)), polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), polyquaternium-10 (quaternized hydroxyethylcellulose), polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride), and the like.

[0131] The deposition aid may be selected from the group consisting of polyvinylformamide, partially hydroxylated polyvinylformamide, polyvinylamine, polyethyleneimine, ethoxylated polyethyleneimine, polyvinyl alcohol, polyacrylate, and combinations thereof.The cationic polymer may comprise a cationic acrylate.

[0132] The deposition aid may be added simultaneously with the delivery particle (with, for example, the encapsulated benefit agent) or directly / separately to the consumer product composition. The weight average molecular weight of the polymer may be 500-5000000 or 1000-2000000 or 2500-1500000 Daltons, as determined by size exclusion chromatography relative to polyethylene oxide standards using refractive index (RI) detection. The weight average molecular weight of the cationic polymer may be 5000-37500 Daltons.

[0133] D. Rheology modifier / structurant

[0134] The compositions of the present disclosure may contain rheology modifiers and / or structurants. Rheology modifiers can be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structurants can be used to promote phase stabilization and / or delay or inhibit agglomeration of particles (e.g., delivery particles as described herein) in a liquid composition.

[0135] Suitable rheology modifiers and / or structurants may include non-polymeric crystalline hydroxy-functional structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulosic fibers (e.g., microfibrillated cellulose, which may be derived from bacteria, fungi, or plant sources, including from wood), diamido gelling agents, or combinations thereof.

[0136] Polymer structurants can be naturally derived or synthetic in origin. Naturally derived polymer structurants can include hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives can include pectin, alginate / esters, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymer structurants can include polycarboxylates, polyacrylates, hydrophobically modified ethoxylated polyurethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers can include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates can include unsaturated mono- or di-carbonic acids with C1-C12 of (meth) acrylic acid. 30 Copolymers of 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, can be used as structuring agents. Another suitable structuring agent is sold under the trade name Rheovis CDE, available from BASF.

[0137] E. Other auxiliary agents

[0138] The treatment compositions of the present disclosure may contain other adjuvants suitable for inclusion in the product and / or for end use. For example, the treatment compositions may include neat perfume, perfume delivery technology (e.g., encapsulates and / or pro-perfumes with non-crosslinked biopolymer wall materials), cationic surfactants, cationic polymers, solvents, foam suppressors, or combinations thereof.

[0139] Method for preparing treatment composition

[0140] The present disclosure also relates to methods for making treatment compositions, such as those treatment compositions and / or consumer product compositions described herein.

[0141] The method may comprise the steps of providing a base composition, wherein the base composition comprises a processing adjuvant, and combining a population of delivery particles with the base composition. The population of delivery particles may preferably be provided in the form of an aqueous slurry. The base composition is in the form of a liquid composition.

[0142] When the delivery particles are in one or more forms (including slurry form, pure particle form and / or spray-dried particle form, preferably slurry form), the delivery particles can be combined with one or more auxiliary ingredients. The delivery particles can be combined with such auxiliary agents by methods including mixing and / or spraying.

[0143] The treatment composition of the present disclosure can be formulated into any suitable form and prepared by any method selected by the formulator. One or more auxiliary components and delivery particles can be in batch method, in the circulation loop method and / or by online mixing method combination. Suitable equipment for use in the method disclosed herein may include a continuous stirred tank reactor, a homogenizer, a turbine agitator, a recirculation pump, a paddle mixer, a high shear mixer, a static mixer, a plough shear mixer, a ribbon blender, a longitudinal axis granulator and a drum mixer (all adopting batch and (when available) continuous method structure), a spray dryer and an extruder.

[0144] The treatment composition can be placed in a container to form a consumer product, as described herein. The container can be a bottle, preferably a plastic bottle. The treatment composition can be placed in an aerosol or other spray container according to known methods.

[0145] Treatment methods

[0146] The present disclosure also relates to a method of treating a surface, preferably a fabric. Generally, the method comprises the steps of contacting a surface, preferably a fabric, with a treatment composition according to the present disclosure, wherein the treatment composition comprises a population of delivery particles as described herein.

[0147] Additionally or alternatively, the method may comprise the step of contacting a surface, preferably a fabric, with a population of delivery particles as described herein.The population of delivery particles may be contained in a treatment composition, preferably a fabric care composition, according to the present disclosure.

[0148] The method may include the step of contacting a fabric (e.g., clothing) with a treatment composition. The treatment composition comprises a population of delivery particles. The contacting step causes one or more of the delivery particles to be deposited on the fabric surface. The delivery particles comprise a core and a shell around the core, wherein the core comprises a benefit agent, preferably a fragrance material comprising one or more flavor raw materials. The shell comprises a polymeric material, such as a reaction product of chitosan of a specific molecular weight and a crosslinking agent. Suitable treatment compositions and delivery particles are described in more detail above.

[0149] The contacting step may occur during a manual laundry process (e.g., in a wash tub when the fabric is treated by hand) or an automatic laundry process (e.g., in an automatic washing machine). The contacting step may occur during the wash cycle of an automatic washing machine; in such a case, the treatment composition may be a laundry detergent or a laundry additive. The contacting step may preferably occur during the rinse cycle of an automatic washing machine; in such a case, the treatment composition may be a fabric enhancer, preferably a liquid fabric enhancer. The contacting step may even occur during the drying step of the laundry process, such as in an automatic dryer; in such a case, the treatment composition may be in the form of a non-fabric drying sheet or a drying bar / block. The contacting step may occur as a result of applying the treatment composition directly to the fabric, such as in a pretreatment operation or in a "refreshing" step (e.g., for fabrics that have been used or worn since the last wash); in such a case, the treatment composition may be in the form of a liquid, a stick, or a spray (preferably a spray). Contacting the target fabric relatively late in the laundry process (e.g., during the rinse cycle) improves the likelihood or efficiency of deposition on the fabric because they are less likely to be washed down the drain.

[0150] The contacting step may occur in the presence of water. The treatment composition may be diluted with water to form a treatment solution. The treatment composition may be diluted from about 100 times to about 1500 times, preferably from 300 times to about 1000 times.

[0151] The liquid containing the disclosed composition may have a pH of about 3 to about 11.5. When diluted, such compositions are typically employed in a concentration of about 500 ppm to about 15,000 ppm in solution. When the wash 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.

[0152] The dilution may occur in the drum of an automatic washing machine. The treatment composition may be placed in a dispensing drawer of an automatic washing machine. The treatment composition may be dispensed from the dispensing drawer to the drum during the treatment process.

[0153] As mentioned above, the method may further include the step of drying the fabric (having one or more delivery particles on the surface of the fabric). The drying step may include a passive drying process, such as on a clothesline or clothes rack. The drying step may include an automatic drying process, such as in an automatic dryer.

[0154] Test Method

[0155] It is understood that the test methods disclosed in the Test Methods section of this application should be used to determine the various values ​​of the parameters of applicant's claimed subject matter as claimed and described herein.

[0156] Method for determining S-ESTER value

[0157] S-ESTER value is based on the atomic level electrotopological state (E-State) index of one or more compounds. E-State value is a molecular index that can be found in the literature and / or determined using a commercially available software program. E-State value effectively observes each atom in the molecule and reflects the valence electronegativity of the atom, which is affected by the atom connected thereto. Electrotopological state index is discussed more 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.

[0158] To determine E-State and S-ESTER values ​​for the purposes described in this disclosure, the software program winMolconn version 1.2.2.3 (available from Hall Associates Consulting of Quincy, MA, used according to the manufacturer's instructions) was used to calculate E-State values. The structure was prepared using a 2D connection table (SDF format or SMILES). The value labels used in the model test method calculations are the same labels reported by winMolconn; their descriptions and definitions can be found listed in the winMolconn documentation associated with the software.

[0159] To determine the S-ESTER value of a particular fragrance raw material or other compound, the software program winMolconn version 1.2.2.3 is used to calculate the E-State value of each atom. The S-ESTER value is the sum of the atomic-level electrotopological state (E-State) values ​​of all carbonyl carbons and oxygens in the ester groups in the molecule. If the compound includes multiple ester groups, the E-State values ​​of all ester groups are added. If the compound has no ester groups, the S-ESTER value of the compound is zero.

[0160] For example, the table below shows the SMILES input for an ester-containing PRM (tricyclodecenyl acetate), and the resulting S-ESTER values ​​provided by the software.

[0161]

[0162] To determine the S-ESTER value of a mixture of compounds (e.g., a fragrance material containing more than one fragrance raw material), first determine the S-ESTER value of each compound as described above. The S-ESTER value of the mixture is calculated by finding the weight average S-ESTER value based on the relative proportion (in weight percent) of each individual compound in the mixture.

[0163] Determination of molecular weight and related parameters of polymers

[0164] The following method describes gel permeation chromatography with multi-angle light scatterer and refractive index detection (GPC-MALS / RI) used to study molecular weight distribution measurements and related values ​​for the polymers described herein.

[0165] Gel permeation chromatography (GPC) with multi-angle light scattering (MALS) and refractive index (RI) detection (GPC-MALS / RI) allows the absolute molecular weight of polymers to be measured without the need for column calibration methods or standards. The GPC system allows molecules to be separated according to their molecular size. MALS and RI allow information on number average (Mn) and weight average (Mw) molecular weights to be obtained.

[0166] The Mw distribution of water-soluble polymers such as chitosan is typically measured by using a liquid chromatography system (e.g., Agilent 1260 Infinity pump system using OpenLab Chemstation software, Agilent Technology, Santa Clara, CA, USA) and a column set (e.g., 2 Tosoh TSKgel G6000WP 7.8×300mm 13um pore size, guard column A0022 6mm×40mm PW xl-cp, King of Prussia, PA) operating 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. The column is prepared using a Wyatt Multi-angle light scattering (18-angle MALS) detector controlled by software v8.0 and a differential refractive index (RI) detector (Wyatt Technology of Santa Barbara, California, USA).

[0167] Samples were typically prepared at room temperature by dissolving chitosan material at ~1 mg / ml in the mobile phase and hydrated by mixing the solution overnight. Samples were filtered through a 0.8 μm Versapor membrane filter (PALL, Life Sciences, New York, USA) using a 3-ml syringe into an LC autosampler vial prior to GPC analysis.

[0168] The dn / dc value (differential change of refractive index with concentration, 0.15) was used for number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), peak maximum molecular weight (Mp) and polydispersity (Mw / Mn) determinations by the Astra detector software.

[0169] Viscosity

[0170] The viscosity of the liquid final product was measured using an AR 550 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. The viscosity was measured from 0.01 s / min in 3 min at 21 °C. -1 Up to 25s -1 The logarithmic shear rate scan was acquired for 20 s -1 High shear viscosity and 0.05s -1 Low shear viscosity.

[0171] Test Method for Determination of logP

[0172] The log value of the octanol / water partition coefficient (logP) was calculated for each material tested (e.g., each PRM in a fragrance blend). The logP of individual materials (e.g., PRMs) was calculated using the Consensus logP calculation model, version 14.02 (Linux), available from Advanced Chemistry Development Inc. (ACD / Labs) (Toronto, Canada) to provide dimensionless logP values. The Consensus logP calculation model from ACD / Labs is part of the ACD / Labs model suite.

[0173] Volume-weighted particle size and size distribution

[0174] Volume weighted particle size distribution was determined via single particle optical sensing (SPOS) (also known as optical particle counting (OPC)) using an AccuSizer 780AD instrument and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent. The instrument was configured to the following conditions and options: flow rate = 1 ml / sec; lower size threshold = 0.50 μm; sensor model = sensor model = LE400-05 or equivalent; automatic dilution = on; collection time = 60 seconds; number of channels = 512; container flow volume = 50 ml; maximum consistency = 9200. The measurement was started by placing the sensor in a cold state by flushing with water until the background count was less than 100. The delivery capsule sample in the suspension was introduced and the density of its capsule was adjusted with DI water via automatic dilution if necessary to produce a capsule count of at least 9200 / ml. The suspension was analyzed during a time period of 60 seconds. The resulting volume-weighted PSD data is plotted and recorded, and the desired volume-weighted particle size value (eg, median / 50th percentile, 5th percentile, and / or 90th percentile) is determined.

[0175] Procedure for determining % degradation

[0176] To determine the % degradation, the procedure described in "OECD Guideline for Testing Chemicals" 301B CO2 Release (Modified Sturm Test), adopted on July 17, 1992, was used. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0177] Fabric treatment

[0178] The fabrics were treated using a Miele washing machine. For each treatment, the washing machine was loaded with 3 kg of fabric, including 1100 g of knitted cotton fabric, 1100 g of polyester-cotton fabric (50 / 50). 18 towel cotton tracers were also added, with a total weight of about 780 g. Prior to treatment, the load was preconditioned twice with 79 g of IEC A Base detergent (unperfumed and provided by WFK Testgewebe GmbH), using a 95 ° C short cotton cycle, followed by two additional 95 ° C washes without detergent.

[0179] Prior to the test treatment, the load was preconditioned twice, each time using a 95°C short cotton cycle with 79 g of unperfumed IEC A Base detergent (ex WFK Testgewebe GmbH), followed by two additional 95°C washes without detergent.

[0180] For the test treatments, the load was washed using a 40°C short cotton cycle, 1200 rpm, and 79 g of IEC A Base detergent, which was added to an appropriate dispenser at the beginning of the wash cycle. A dose of 35 g of the test fabric treatment composition (e.g., according to the Examples) was added to an appropriate dispenser. At the end of the wash cycle, the towel tracer was removed from the washing machine and air-dried overnight. The next day, a professional perfumer performed an olfactory evaluation of the fragrance intensity on the dry towel cotton tracer. For comparison purposes, a reference treatment was also performed in which the same fragrance as the test sample was used but polyacrylate capsules were used as delivery particles. All comparison treatments were cleaned and analyzed on the same day.

[0181] Methods of Olfactory Evaluation

[0182] After the fabrics were treated, professional perfumers performed an olfactory evaluation of the dry fabric perfume intensity (Dry Fabric Odor = DFO) at the DRY contact point and averaged the scores. The scores were based on a perfume odor intensity scale of 0 to 100, where 0 = no perfume odor, 25 = slight perfume odor, 50 = medium perfume odor, 75 = strong perfume odor, and 100 = very strong perfume odor.

[0183] Method for determination of headspace concentration above treated dry fabrics

[0184] Cotton tracers were analyzed by a fast headspace GC / MS (gas chromatography mass spectrometry) method. 4×4 cm aliquots of towel cotton tracers were transferred to 25 ml headspace bottles. Fabric samples were equilibrated at 65°C for 10 minutes. The headspace above the fabric was sampled for 5 minutes via the SPME (50 / 30 μm DVB / Carboxen / PDMS) method. The SPME fiber was then thermally desorbed online into the GC. Analytes were analyzed by fast GC / MS in full scan mode. Specific mass ion extraction of PRMs was used to calculate the fragrance headspace composition and total HS response above the tested leg.

[0185] Total PRM weight % degraded in delivery particle composition

[0186] To determine the total amount of degraded PRMs in the delivery particle composition, the total aroma (encapsulated + non-encapsulated) was measured using the aroma raw material as a reference. For this purpose, gas chromatography with a mass spectrometer detector (GC-MS) was used. Suitable equipment includes: Agilent GC8890 equipped with an Agilent 5977B mass spectrometer or equivalent, capillary column operation, quantification based on extracted ion capability, autosampler; and 30m×0.25mm nominal diameter column, 1μm film thickness, J&W122-5533DB-5MS or equivalent.

[0187] Weigh approximately 0.1 g of the delivery particle composition and record the weight, then add an internal standard (Tonalid, formerly Merck) and 10 mL of ethanol 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 via GC-MS. The amount of the measured PRM is determined by the response of each PRM, and the total PRM degradation weight % can be determined as follows:

[0188]

[0189] wherein i is each individual PRM that is part of the fragrance composition and n is the total number of PRMs in the fragrance composition.

[0190] Example

[0191] The examples provided below are intended to be illustrative in nature and are not intended to be limiting.

[0192] Example 1. Exemplary Fragrance Materials

[0193] Table 1 shows exemplary aroma materials according to the present disclosure. The aroma raw materials are listed along with the relative weight percentage (based on the weight of the aroma material) and the S-ESTER value of each aroma raw material. Based on these values, the S-ESTER value of the total aroma material can be calculated as the weight average S-ESTER value.

[0194] Table 1.

[0195]

[0196] E =Material contains ester functional groups

[0197] A =Material contains aldehyde functional groups

[0198] Based on the information in Table 2, an exemplary fragrance material comprises 37% ester-containing material and 37% aldehyde-containing material by weight of the fragrance material.

[0199] Additionally, the S-ESTER value of the total aroma material was determined to be 7.913 based on the weight average calculation of the S-ESTER values ​​of the PRMs.

[0200] Example 2. Illustrative Particle Synthesis

[0201] In the following examples, the abbreviations correspond to the materials listed in Table 2.

[0202] Table 2

[0203]

[0204] The aqueous phase is prepared by dispersing 92.19g ChitoClear into 1956.6g water while mixing in a jacketed reactor. The pH of the aqueous phase is then adjusted to between 5.0 and 5.3 using concentrated HCl under stirring. The aqueous phase temperature is then raised to 85°C in 60 minutes, and then kept at 85°C for 2 hours to acid-treat ChitoClear. After the hydrolysis step, the aqueous phase temperature is then reduced to 25°C over a period of 90 minutes. The oil phase is prepared by mixing 716.37g of a fragrance oil according to the present disclosure (e.g., the fragrance material of Example 1) and 179.11g of isopropyl myristate and 19.54g of Takenate D-110N together at room temperature. The oil phase is added to the aqueous phase under high shear grinding to obtain an emulsion. The emulsion is heated to 40°C in 30 minutes and kept for 60 minutes. The emulsion is then heated to 85°C and kept at this temperature for 6 hours while mixing.

[0205] Example 3. Effect of Encapsulated Flavor Selection

[0206] To compare different chitosan delivery particles, liquid fabric enhancer ("LFE") samples were prepared with different particles. The same fragrance was used in the delivery particles evaluated in the reference treatment, and each core also included approximately 20%-35% of a partitioning modifier (i.e., isopropyl myristate). The LFE composition included a softening active (diesterquat) present at 6%, the associated delivery particles added at a level sufficient to provide 0.2% encapsulated fragrance, 0.11% structurant (cationic polymer - Flosoft FS222, formerly SNF), and different processing aids, with the pH adjusted to approximately 3.

[0207] For this example, a liquid fabric enhancer product was prepared having a general formulation according to Table 3 below.

[0208] Table 3.

[0209]

[0210]

[0211] Seven different fragrances were encapsulated in both delivery particles according to the present disclosure (e.g., walls made of chitosan and crosslinked with isocyanate) and reference polyacrylate ("PAC") delivery particles. The composition of the tested fragrances is generally described in Table 3 below; note that fragrance raw materials with more than one type of functional moiety are counted in each "functional group" category, which can result in PRMs being counted more than once and percentages that appear to add up to more than 100%. The S-ESTER value for each fragrance is also provided in Table 4. Fragrances 1-4 are fragrance materials according to the present disclosure; Fragrances 5-7 are comparative fragrance materials.

[0212] The walls of the delivery particles of the present disclosure used in the experiments were made of an amine-containing biopolymer (acid-treated chitosan) and a crosslinker (polyisocyanate) (target volume weighted median particle size = 28 microns). Reference polyacrylate delivery particles were made essentially according to the methods described in U.S. Publication 2011 / 0268802. It is noted that the walls of the PAC delivery particles are not made of monomers with primary amines, so reactivity with aldehyde PRMs is not significantly expected. The reference PAC particles of fragrances 1-5 are characterized by a core:shell weight ratio of about 90:10. The reference PAC particles of fragrances 6 and 7 are characterized by a core:shell weight ratio of about 97:3 to about 98:2.

[0213] The composition of the fragrance in the delivery particles was 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 weight percent of total PRM degraded was calculated according to the method described above.

[0214] The results are provided below in Table 4. For comparison purposes, the olfactory DFO data for the chitosan based delivery particles are reported as Delta values ​​compared to the DFO produced by a reference polyacrylate delivery particle comprising the same fragrance according to the following formula.

[0215] Delta DFO = DFO chitosan delivery particles (test) - DFO PAC delivery particles (reference)

[0216] Delta DFO entries with an asterisk (*) are statistically significant compared to the reference value.

[0217] Table 4

[0218]

[0219] As shown in Table 4, the delivery particles of the present invention (characterized by a core comprising a fragrance having greater than 30% ester and / or an S-ESTER value greater than 5) performed substantially the same based on olfactory aspects compared to the reference polyacrylate capsules. In addition, they also showed a total degradation % of PRMs in the core of less than 5%. On the other hand, the comparative delivery particles (which have similar walls but are characterized by a core comprising a fragrance having less than 30% ester and / or an S-ESTER value less than 5) performed significantly worse compared to the reference polyacrylate capsules. In addition, they also showed a total degradation % of PRMs in the core of greater than 5%.

[0220] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact values ​​recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0221] Each document recorded herein (including any cross-referenced or related patents or applications and any patent applications or patents to which this application claims priority or the benefit of) is hereby incorporated by reference in its entirety, unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, nor is it an admission that it alone or in combination with any other reference or references teaches, suggests or discloses any such invention. In addition, in the event 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 the term in this document shall prevail.

[0222] Although particular embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the present invention. Therefore, the appended claims are intended to cover all such changes and modifications within the scope of the present invention.

Claims

1. A composition comprising: Delivery particle group, wherein the delivery particle comprises 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 cross-linking agent, wherein the biopolymer comprises secondary or primary amine groups, wherein the core comprises a fragrance material, wherein the fragrance material comprises: (a) at least about 30%, by weight of said fragrance material, of an ester-containing fragrance raw material ("PRM"), and (b) at least about 0.5 wt. %, based on the weight of the aroma material, of an aldehyde-containing PRM.

2. A composition comprising: Delivery particle group, wherein the delivery particle comprises 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 cross-linking agent, wherein the biopolymer comprises secondary or primary amine groups, wherein the core comprises a fragrance material, wherein the aroma material comprises one or more flavor raw materials ("PRMs"), and Wherein the aroma material is characterized by one or more of the following: (a) having an S-ESTER value of at least about 5, wherein the S-ESTER value of the 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 said aroma material, of a fragrance raw material having an S-ESTER value of 13 or greater.

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

4. A composition according to any preceding claim, wherein the aroma material is characterised by having an S-ESTER value of at least about 5.5, preferably at least about 6, Preferably, the S-ESTER value is no greater than about 20, preferably no greater than about 13, more preferably no greater than about 10.

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

6. A composition according to any preceding claim, wherein the ester-containing fragrance raw material comprises one or more materials selected from the group consisting of 4-tert-butyl cyclohexyl acetate, allyl isopentoxy acetate, allyl hexanoate, allyl cyclohexanepropionate, allyl heptanoate, amyl acetate (isomer blend), cis-3-hexenyl acetate, cis-3-hexenyl salicylate, cyclobutane, cyclogalactone, cyclobutane ester, dihydropinyl acetate, dimethylbenzyl acetate, dimethylbenzyl butyrate, cyclopentadecalactone, ethyl 2-methylvalerate, ethyl acetate, ethyl butyrate, ethylene glycol brazilate, ethyl isovalerate, ethyl lactone, ethyl methyl phenyl glycidate, ethyl methyl phenyl glycidate, ethyl-2-methylbutyrate, Tricyclodecenyl acetate, diethyl 1,4-cyclohexanedicarboxylate, tricyclodecenyl propionate, gamma-decanoic acid lactone, geranyl acetate, cyclopentadecenolide, hexyl acetate, isobornyl acetate, isononyl acetate, isoamyl butyrate, benzyl acetate, methyl anthranilate, methyl benzoate, methyl dihydrojasmonate, methyl dioxolane, methyl lactone, methyl phenyl acetate, musk RI, octahydrocoumarin, phenoxyethyl isobutyrate, phenylethyl tiglate, isoprenyl acetate, musk roman, clarylidene, pinyl acetate, ethyl 2,2,6-trimethylcyclohexanecarboxylate, triethyl citrate, undecanoic acid lactone, o-tert-butylcyclohexyl acetate, methyl 4-cycloocten-1-yl carbonate, zen musk, and combinations thereof.

7. A composition according to any preceding claim, wherein the aroma material comprises at least about 1% by weight of the aroma material of an aldehyde-containing PRM, Preferably at least about 5%, more preferably at least about 10%, by weight of the aroma material, of the aldehyde-containing PRM.

8. A composition according to any preceding claim, wherein the fragrance material further comprises no more than about 30% hydroxyl-containing PRM, preferably from about 1% to about 30% hydroxyl-containing PRM by weight of the fragrance material.

9. A composition according to any preceding claim, wherein the aroma material comprises: about 45% to about 55% of an ester-containing PRM; about 10% to about 25% aldehyde-containing PRMs; from about 5% to about 20% of a hydroxyl-containing PRM; and Optionally from about 1% to about 40% of additional PRMs.

10. A composition according to any preceding claim, wherein the core further comprises a partitioning modifier, optionally present in the core at a level of from about 10% to about 50% by weight of the core, Preferably the partitioning modifier is selected from the following: vegetable oils, modified vegetable oils, C4-C 24 Monoesters, diesters and triesters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate.

11. The composition of any preceding claim, wherein the biopolymer is selected from the group consisting of polysaccharides, proteins, nucleic acids, derivatives thereof, and combinations thereof; Preferably, the biopolymer is selected from the following: A polysaccharide selected from the group consisting of chitosan, amine-modified starch, amine-modified dextran, amine-modified maltodextrin, amine-modified dextrin, amine-modified cellulose, amine-modified hemicellulose, chitin, amine-modified alginate, amine-modified lignin, amine-modified gum, amine-modified pectin, amine-modified agar, melanin, silk fibroin, derivatives thereof, and combinations thereof; A protein selected from the group consisting of gelatin (e.g., porcine gelatin), collagen, casein, sericin, fibroin, whey protein, pea protein, corn protein, soy protein, plant storage protein (plant protein isolate, plant protein concentrate), gluten, peptides, actin, derivatives thereof, and combinations thereof; A nucleic acid selected from the group consisting of: polynucleotides, RNA, DNA, their derivatives, and combinations thereof; and A combination of them.

12. The composition of any preceding claim, wherein the biopolymer is chitosan, a derivative thereof, or a combination thereof, Preferably, the biopolymer is acid-treated chitosan.

13. The composition according to any preceding claim, wherein the biopolymer, preferably chitosan, more preferably acid-treated chitosan, is characterized by a molecular weight of about 1 kDa to about 1000 kDa, preferably about 50 kDa to about 600 kDa, more preferably about 100 kDa to about 500 kDa, even more preferably about 100 kDa to about 300 kDa, even more preferably about 100 kDa to about 200 kDa.

14. The composition of any preceding claim, wherein the crosslinking agent is a material selected from the group consisting of polyisocyanates, polyacrylates, poly(meth)acrylates, polyisothiocyanates, aldehydes, epoxides, polyphenols, carbonyl halides, aziridines, and combinations thereof, Preferably selected from the group consisting of polyisocyanates, epoxy compounds, difunctional aldehydes, and combinations thereof, More preferred are polyisocyanates selected from the group consisting of polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of toluene diisocyanate and trimethylolpropane adducts of xylylene diisocyanate, 2,2′-methylene diphenyl diisocyanate, 4,4′-methylene diphenyl diisocyanate, 2,4′-methylene diphenyl diisocyanate, toluene diisocyanate, tetramethylxylidine diisocyanate, naphthalene-1,5-diisocyanate, 1,4-phenylene diisocyanate, 1,3-diisocyanatobenzene, and combinations thereof.

15. The composition of any preceding claim, wherein the delivery particles are characterized by a volume weighted median particle size of about 1 to about 100 microns, Preferably, it is from about 10 to about 100 microns, preferably from about 15 to about 50 microns, more preferably from about 20 to about 40 microns, even more preferably from about 20 to about 30 microns.

16. A composition according to any preceding claim, wherein the shell of the delivery particle degrades by at least 60% within 60 days when tested according to test method OECD 301 B.

17. A composition according to any preceding claim, wherein the population of delivery particles is provided in the form of an aqueous slurry.

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