Treatment composition having delivery particles made from acid-treated chitosan

Abstract

Provided are processing compositions that include a processing aid and a population of core / shell delivery particles, where the shell is made from acid-treated chitosan and a crosslinker, where the acid-treated chitosan results from treating the chitosan with a weak acid or a mixture of a strong acid and a weak acid. Also provided are related methods of making and using such compositions.

Description

[Technical Field]

[0001] The present disclosure relates to processing compositions comprising a processing aid and a population of core / shell delivery particles, the shell of which is made from acid-treated chitosan and a crosslinker, the acid-treated chitosan resulting from treating chitosan with a weak acid or a mixture of strong and weak acids. The disclosure also relates to related methods of making and using such compositions. [Background technology]

[0002] Delivery particles, particularly core / shell delivery particles, are a convenient way to deliver benefit agents in treatment compositions such as laundry products. For environmental reasons, it may be desirable to use delivery particles with walls made from naturally occurring and / or biodegradable materials.

[0003] Delivery particles having a shell made at least in part from chitosan-based materials are known. However, such particles may not provide the desired level of performance. Furthermore, chitosan can be a difficult material to work with due to its tendency to increase viscosity.

[0004] US Patent Application Publication No. 2020 / 0252469 discloses the treatment of chitosan in an acidic medium, for example, by adjusting the pH with hydrochloric acid (HCl) before forming microcapsules. However, such treatment methods have associated challenges. For example, under certain conditions, hydrochloric acid can be corrosive to manufacturing equipment, which is typically made of steel. Additionally or alternatively, improving the performance of delivery particles is still desired. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent Application Publication No. 2020 / 0252469 Summary of the Invention [Problem to be solved by the invention]

[0006] There is a need for improved treatment compositions and related methods that include delivery particles made from chitosan-based materials. [Means for solving the problem]

[0007] The present disclosure relates to treatment compositions comprising chitosan-based core / shell delivery particles, wherein the chitosan is treated with a weak acid, or even a mixture of a strong acid and a weak acid. For example, the present disclosure relates to treatment compositions comprising a processing aid and a population of delivery particles, wherein the delivery particles comprise a core and a shell surrounding the core, the core comprising a benefit agent, and the shell comprising a polymeric material that is the reaction product of chitosan and a crosslinker, wherein the acid-treated chitosan results from treating the chitosan with a mixture of a first acid and a second acid, wherein the first acid comprises a strong acid and the second acid comprises a weak acid, the first acid and the second acid are present in a normality ratio of about 20:80 to about 80:20, preferably about 35:65 to about 65:35, and the chitosan is treated with the mixture at a pH of 6.5 or less and a temperature of at least 25°C.

[0008] The present disclosure also relates to a treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, the shell comprising a polymeric material that is the reaction product of acid-treated chitosan and a crosslinker, the acid-treated chitosan resulting from treating chitosan with an acid, the acid comprising one or more weak acids, the chitosan being treated with the acid at a pH of 6.5 or less and a temperature of at least 25°C, and the processing aid comprising a conditioning active.

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

[0010] The present disclosure also relates to a method of treating a surface, comprising contacting the surface, preferably a fabric, with the treatment composition described herein. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure relates to a treatment composition comprising delivery particles having a shell made at least in part from a chitosan-based material. In particular, the delivery particles include a shell comprising the reaction product of chitosan and a crosslinker. Prior to shell formation, the chitosan used to make the particle shell is treated with a weak acid or a mixture of acids, i.e., a mixture comprising a strong acid and a weak acid.

[0012] Typically, when chitosan is dissolved in water during the process of preparing delivery particles, the resulting mixture tends to have a very high viscosity. This can cause problems with flowability and processing, and / or can prevent the proper formation of the delivery particle shell. It has been found that acid treatment can reduce the viscosity of the mixture. It is also believed that acid treatment of chitosan can have a beneficial effect on the molecular weight of chitosan, thereby improving shell formation and / or improving delivery performance.

[0013] On the other hand, it has been found that even when chitosan is processed at a consistent pH, the choice of acid can make a difference: for example, using a strong acid such as HCl alone can produce relatively good particles, but on the other hand, it can cause potential corrosive problems in the manufacturing plant.

[0014] It has been surprisingly found that treating chitosan with a weak acid or a mixture of acids including a weak acid can result in suitable delivery particles while reducing corrosion issues in manufacturing equipment. It has also been surprisingly found that careful selection of the acid (or acids) can provide benefits in one or more vectors. For example, treating chitosan with a mixed acid system including a strong acid and a weak acid, particularly in a specific ratio, is believed to result in delivery particles with good performance while reducing corrosion risks in manufacturing plants.

[0015] The acid-treated chitosan, delivery particles, treatment compositions, and related methods of the present disclosure are discussed in more detail below.

[0016] As used herein, the articles "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described. As used herein, the terms "include," "includes," and "including" are meant to be open-ended. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0017] The terms "substantially free of" or "substantially free from" may also be used herein. This means that the indicated material is in minimal amounts and has not been intentionally added to the composition to form part of the composition, or preferably is not present at analytically detectable concentrations. It means that the indicated material comprises a composition in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material, if present at all, may be present at a concentration of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0018] As used herein, "consumer product" means a baby care, beauty care, fabric and home care, family care, feminine care, or health care product or device that is intended for use or consumption in the form in which it is sold and not for subsequent commercial manufacture or modification. Such products include diapers, bibs, wipes; products for treating human hair and / or methods related to treating human hair, where the treatment includes bleaching, coloring, dyeing, conditioning, shampooing, and styling; deodorants and antiperspirants; personal cleansing; skin care, including the application of creams, lotions, and other topically applied products intended for consumer use; and shaving products, products for treating fabrics, hard surfaces, and any other surface in the fabric or home care field and / or related methods (e.g., air care, auto care, dishwashing, fabric cleaning, etc.). conditioning (including softening), laundry detergents, wash and rinse additives and / or care, hard surface cleaning and / or treatments, and other cleaning for consumer or commercial use); products and / or methods related to toilet paper, tissue, paper handkerchiefs, and / or paper towels; tampons, feminine napkins; adult incontinence products; products and / or methods related to oral care, including toothpaste, tooth gels, mouth rinses, denture adhesives, tooth whitening agents; non-prescription health care, including cough and cold treatments; pest control products, and water purification.

[0019] As used herein, the phrase "fabric care composition" includes compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric deodorizing compositions, laundry pre-cleaning agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions can be used as laundry pre-treatment agents, laundry post-treatment agents, or can be added during the rinse or wash cycle of laundry operations.

[0020] As used herein, "delivery particles," "particles," "encapsulations," "microcapsules," and "capsules" are used interchangeably unless otherwise indicated. As used herein, these terms typically refer to core / shell delivery particles.

[0021] Unless otherwise noted, all ingredient or composition concentrations are in terms of the active portion of that ingredient or composition and are exclusive of impurities, e.g., residual solvents or by-products, that may be present in commercial sources of such ingredient or composition.

[0022] All temperatures herein are in degrees Celsius (°C) unless otherwise specified. All measurements herein are made at 20°C and atmospheric pressure unless otherwise specified.

[0023] In all embodiments of the present disclosure, all percentages are by weight of the total composition unless specifically stated otherwise. All ratios are by weight unless specifically stated otherwise.

[0024] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0025] Treatment Composition The present disclosure relates to treatment compositions (or simply "compositions" as used herein). The compositions of the present disclosure may include a population of delivery particles and a treatment aid, each of which is described in more detail below. The treatment compositions may be useful in the methods of treating surfaces, such as fabrics, described herein.

[0026] The treatment composition is preferably a consumer product composition. The consumer product composition of the present disclosure can be useful in baby care, beauty care, fabric care, home care, family care, feminine care, and / or health care applications. The consumer product composition can be useful for treating surfaces such as fabrics, hair, or skin. The consumer product composition can be intended to be used or consumed in the manner in which it is sold. The consumer product composition of the present disclosure can typically be intended for subsequent commercial manufacture or modification.

[0027] The consumer product composition may preferably be a fabric care composition, a hard surface cleaner composition, a dish care composition, a hair care composition (such as a shampoo or conditioner), a body cleansing composition, or a mixture thereof, and may preferably be a fabric care composition.

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

[0029] The composition may be a beauty care composition, such as a hair treatment product (including shampoo and / or conditioner), a skin care product (including a cream, lotion, or other topically applied product for consumer use), a shaving care product (including a shaving lotion, foam, or pre- or post-shave treatment), a personal cleansing product (including a liquid body wash, liquid hand soap, and / or bar soap), a deodorant and / or antiperspirant, or mixtures thereof.

[0030] The compositions may be home care compositions such as air care, car care, dishwashing, hard surface cleaning and / or treatment, and other consumer or institutional cleaning.

[0031] The treatment composition may be in the form of a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, pastilles or beads, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven sheet, or mixtures thereof.

[0032] The treatment composition may be in the form of a liquid. The liquid composition may preferably comprise from about 50% to about 97%, preferably from about 60% to about 96%, more preferably from about 70% to about 95%, and even from about 80% to about 95% water by weight of the fabric treatment composition. The liquid composition may be a liquid fabric conditioner. The liquid may be packaged in a pourable bottle. The liquid may be packaged in an aerosol can or other spray bottle. Suitable containers are described in more detail below.

[0033] The treatment composition may be in solid form. The composition may be in the form of beads or tablets, which may be tableted from a liquid melt. The composition may be an extruded product. The treatment composition may be in the form of a powder or granules.

[0034] The composition may be in the form of a unit-dose article such as a tablet, pouch, sheet, or fiber article. Such pouches typically include a water-soluble film, e.g., a polyvinyl alcohol water-soluble film, that at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition may be enclosed in a single-compartment pouch or a multi-compartment pouch. A multi-compartment pouch may have at least two, at least three, or at least four compartments. A multi-compartment pouch may include compartments arranged side-by-side and / or stacked. The composition contained in the pouch or its compartments may be liquid, solid (e.g., powder), or a combination thereof. The pouch composition may have a relatively low amount of water, e.g., less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% by weight of the detergent composition.

[0035] The treatment composition may be in the form of a spray, for example, dispensed via an aerosol container having a trigger sprayer and / or a valve.

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

[0037] The treatment compositions of the present disclosure may be characterized by a pH of about 2 to about 12, or about 2 to about 8.5, or about 2 to about 7, or about 2 to about 5. The treatment compositions of the present disclosure, preferably in aqueous liquid form, may have a pH of about 2 to about 4, preferably about 2 to about 3.7, and more preferably about 2 to about 3.5. It is believed that such pH levels promote the stability of the quaternary ammonium ester compound, if present. On the other hand, detergent compositions are typically characterized by a pH of about 7 to about 12, preferably about 7.5 to about 11. The pH of the composition is measured by dissolving / dispersing the composition in deionized water to form a 10% concentration solution at about 20°C.

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

[0039] Delivery particle population The treatment composition of the present disclosure comprises a group of delivery particles. The delivery particles comprise a core and a shell surrounding the core. The core may comprise a benefit agent and, optionally, a partitioning modifier. The core may be liquid or solid at room temperature, preferably liquid.

[0040] The treatment composition may comprise from about 0.05% to about 20%, or from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.2% to about 2% delivery particles by weight of the composition. The composition may comprise a sufficient amount of 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% encapsulated benefit agent, preferably perfume ingredient, based on the weight of the composition. As discussed herein, the amount or weight percent of delivery particles refers to the combined wall material and core material.

[0041] Populations of delivery particles according to the present disclosure can be characterized by a volume-weighted median particle size of about 1 to about 100 microns, preferably about 10 to about 100 microns, preferably about 15 to about 50 microns, more preferably about 20 to about 40 microns, and even more preferably about 25 to about 35 microns. For certain compositions, it may be preferred that the population of delivery particles be characterized by a volume-weighted median particle size of about 1 to about 50 microns, preferably about 5 to about 20 microns, and more preferably about 10 to about 15 microns. Different particle sizes can be obtained by controlling droplet size during emulsification.

[0042] The delivery particles can be characterized by a core-to-shell ratio of up to 99:1, or even 99.5:0.5, by weight. The shell may be present in a concentration of about 1% to about 25%, preferably about 1% to about 20%, preferably about 1% to about 15%, more preferably about 5% to about 15%, even more preferably about 10% to about 15%, and even more preferably about 10% to about 12% by weight of the delivery particle. The shell may be present in a concentration of at least 1%, preferably at least 3%, and more preferably at least 5% by weight of the delivery particle. The shell may be present in a concentration of up to about 25%, preferably up to about 20%, more preferably up to about 15%, and even more preferably up to about 12% by weight of the delivery particle.

[0043] 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 a pH of 4.5. The delivery particles may be configured to have a zeta potential of at least 15 millivolts (mV) at a pH of 4.5, or at least 40 mV at a pH of 4.5, or at least 60 mV at a pH of 4.5. Polyurea capsules prepared with chitosan typically exhibit a positive zeta potential. Such capsules have improved adhesion efficiency to fabrics. At higher pHs, the particles may be nonionic or anionic.

[0044] The delivery particles of the present disclosure comprise a shell surrounding a core. (As used herein, "shell" and "wall" are used interchangeably with respect to the delivery particles unless otherwise indicated.) The shell comprises a polymeric material, which is the reaction product of chitosan and a crosslinker.

[0045] Chitosan can be characterized by a weight-average molecular weight of about 100 kDa to about 600 kDa. Preferably, chitosan is characterized by a weight-average molecular weight (Mw) of about 100 kDa to about 500 kDa, preferably about 100 kDa to about 400 kDa, more preferably about 100 kDa to about 300 kDa, and even more preferably about 100 kDa to about 200 kDa. The method used to determine chitosan molecular weight and related parameters is provided in the Test Methods section below and uses gel permeation chromatography with multi-angle light scattering (MALS) and refractive index detection gel permeation chromatography (GPC) (GPC-MALS / RI) techniques. Selecting a chitosan with a preferred weight-average molecular weight can result in capsules with favorable shell formation and / or desirable processability.

[0046] A preferred chitosan for use in the materials of the present disclosure is acid-treated chitosan. For example, chitosan (before acid treatment, also referred to as raw chitosan or parent chitosan) can be treated with an acid, preferably at a pH of 6.5 or less, for at least 1 hour, preferably about 1 hour to about 3 hours, at a temperature of about 25°C to about 99°C, preferably about 75°C to about 95°C. The acid can be selected from strong acids (e.g., hydrochloric acid), weak acids (e.g., formic acid or acetic acid), or mixtures thereof. Chitosan can be acid-treated at a pH of preferably 2 to 6.5, preferably 3 to 6, and even more preferably 4 to 6.

[0047] Acid-treated chitosan can be formed by treating chitosan with a mixture of acids (e.g., a mixed acid system). Preferably, the acid-treated chitosan results from treating chitosan with a mixture comprising a first acid, which comprises a strong acid, and a second acid, which comprises a weak acid. As described in more detail above, using the mixtures of acids described herein is believed to provide delivery particles that exhibit adequate performance while minimizing risk to, for example, manufacturing equipment.

[0048] The chitosan is treated with the mixture at a pH of preferably 6.5 or less, preferably less than 6.5, more preferably between 3 and 6, and at a temperature of at least 25°C, preferably between about 25°C and about 99°C, preferably between about 75°C and about 95°C. If the temperature is too low, the reaction may be incomplete. If the temperature is too high, undesirable degradation of the chitosan may occur.

[0049] Acid treatment of chitosan can advantageously reduce the viscosity of the chitosan solution, with lower viscosity mixtures being easier to process and / or resulting in improved capsule formation. It is desirable to acid treat the chitosan for at least 1 hour, preferably from about 1 hour to about 3 hours. It is desirable to treat the chitosan for a length of time to obtain a chitosan solution having a viscosity of about 1500 cp or less, preferably 500 cp or less.

[0050] By treating chitosan according to the present disclosure, chitosan solutions at concentrations of 3%, preferably 3.5%, and more preferably 4% or greater can achieve a surprising reduction in viscosity measured at the same concentration. The viscosity of chitosan at such concentrations is typically in the 4000 centipoise (cP) range. When processed according to the process of the present disclosure, acid-treated chitosan at the same concentration can exhibit a 60% or even greater viscosity reduction to a viscosity of 1500 cP, or even 1000 cP, or even 500 cP. For example, chitosan at a 3.5% concentration, typically having a starting viscosity of 4000 cP, treated according to the present disclosure exhibits a 60% or even greater viscosity reduction to a viscosity of 1500 cP, or even 1000 cP, at the same concentration.

[0051] It has been found advantageous to use certain relative amounts of each acid in the mixture. For example, the first acid and the second acid are preferably present in a normality ratio of about 20:80 to about 80:20, preferably about 35:65 to about 65:35. Without being bound by theory, it is believed that selecting the correct ratio can result in delivery particles that are efficiently produced, exhibit good performance, and / or minimize the risk of corrosion.

[0052] The first acid may comprise, consist essentially of, or consist of a strong acid selected from the group consisting of hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, and mixtures thereof, preferably hydrochloric acid.

[0053] The weak acid and / or second acid may comprise, consist essentially of, or consist of a weak acid selected from the group consisting of formic acid, acetic acid, ascorbic acid, glutamic acid, lactic acid, maleic acid, malic acid, succinic acid, citric acid, acrylic acid, oxalic acid, tartaric acid, and mixtures thereof, preferably a weak acid selected from the group consisting of formic acid, acetic acid, and mixtures thereof.

[0054] The acid may be a monobasic, dibasic, or polybasic acid. For purposes of this disclosure, "polybasic acid" includes "tribasic acid." It should be understood that a dibasic or polybasic acid has two or more ionizable hydrogens and therefore has a first or initial pKa value and additional pKa values ​​for the additional ionizable hydrogens, respectively. For purposes of this specification, "first pKa" refers to the first or initial ionizable hydrogen when the acid is a dibasic or polybasic acid.

[0055] The first acid preferably has a first pKa of less than 1. The second acid preferably has a first pKa of from about 1 to about 5.5. Preferably, both are true: the first acid has a first pKa of less than 1 and the second acid has a first pKa of from about 1 to about 5.5.

[0056] Acid-treated chitosan can be formed by treating chitosan with a weak acid, as described above. To reduce the risk of corrosion, it may be preferable that the chitosan used to make the delivery particle shell is treated with only a weak acid. The weak acid may include a single weak acid or a mixture of weak acids. Suitable weak acids are described above.

[0057] Without being bound by theory, it is believed that the selection of the weak acid can affect the final shell formation and the resulting performance of the delivery particles, at least in certain product matrices. For example, as shown in the Examples section below, it is believed that chitosan treated with acetic acid can yield delivery particles that perform particularly well in liquid fabric enhancer compositions. Accordingly, the present disclosure relates to a treatment composition, e.g., a liquid fabric enhancer ("LFE") composition, comprising a population of delivery particles formed from the acid-treated chitosan described herein, the acid-treated chitosan resulting from treating the chitosan with an acid, the acid including one or more weak acids but no strong acid, and the chitosan treated with the acid at a pH of 6.5 or less and a temperature of at least 25°C. Preferably, the weak acid in such cases includes acetic acid or includes only acetic acid. Such compositions may include conditioning actives, such as esterquats, which may be present in the composition at a concentration of from about 1% to about 35%, preferably from 2% to about 20%, by weight of the composition. Suitable conditioning actives are described in more detail below.

[0058] The chitosan may comprise anionically modified chitosan, cationically modified chitosan, or a combination thereof. Anionic and / or cationic modification of chitosan can alter the surface charge and / or zeta potential, which can affect, for example, the deposition efficiency and / or formulation compatibility of the particles, thereby altering the shell characteristics of the delivery particles.

[0059] As noted above, the shell is a polymeric material that is the reaction product of chitosan and a crosslinking agent. Preferably, the crosslinking agent comprises a polyisocyanate. Thus, the shell of the delivery particle may comprise a polyurea resin, which comprises the reaction product of a polyisocyanate and chitosan.

[0060] For purposes of this specification, polyisocyanate materials useful in the present disclosure should be understood as isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. "Polyisocyanate" is intended to refer to materials or compounds containing two or more isocyanate moieties. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended to be encompassed by the term "polyisocyanate" herein. Polyisocyanates useful in the present disclosure include isocyanate monomers, oligomers, or prepolymers, or dimers or trimers thereof, having at least two isocyanate groups. Preferred crosslinking can be achieved using polyisocyanates with a functionality of at least three.

[0061] Aromatic polyisocyanates may be preferred. However, aliphatic polyisocyanates and their blends may also be useful. Aliphatic polyisocyanates are understood to be polyisocyanates that do not contain any aromatic moieties. Aromatic polyisocyanates are understood to be polyisocyanates that contain at least one aromatic moiety. The crosslinker may also comprise a mixture of aromatic and aliphatic polyisocyanates.

[0062] If the polyisocyanate is aromatic, it can be, but is not limited to, methylene diphenyl isocyanate, toluene diisocyanate, tetramethylxylidene diisocyanate, polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® RC), trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® L75), naphthalene-1,5-diisocyanate, phenylene diisocyanate, or trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name Takenate® D-110N).

[0063] Aliphatic polyisocyanates can include trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N100).

[0064] Derivatives of polyisocyanates may include oligomers or polymers of isocyanate monomers. As a non-limiting example, the polyisocyanate may preferably include oligomers or polymers of diphenylmethane diisocyanate (MDI), such as Mondur® MR-Light.

[0065] The polyisocyanate may preferably be selected from the group consisting of polyisocyanurates of toluene diisocyanate; trimethylolpropane adducts of toluene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethylxylidene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (e.g., prepolymers, oligomers, and / or polymers thereof); and combinations thereof.

[0066] The particle shell may also be reinforced using additional co-crosslinking agents such as polyfunctional amines and / or polyamines, e.g., diethylene triamine (DETA), polyethyleneimine, polyvinylamine, or mixtures thereof. Acrylates can also be used as additional co-crosslinking agents, e.g., to reinforce the shell.

[0067] The polymeric material may be formed in a reaction in which the weight ratio of chitosan present in the reaction to the crosslinker present in the reaction is from about 1:10 to about 1:0.1. It is believed that selecting the desired ratio of biopolymer to crosslinker can provide the desired ductility benefits and improved biodegradability. It is preferred that at least 21% by weight of the shell be comprised of moieties derived from chitosan, preferably acid-treated chitosan. The chitosan as a weight percentage of the shell may be from about 21% to about 95% of the shell. The ratio of chitosan in the aqueous phase compared to isocyanate in the oil phase may be 21:79 to 90:10, or even 1:2 to 10:1, or even 1:1 to 7:1, by weight. The shell may comprise chitosan at a concentration of 21% or more by weight of the total shell, preferably from about 21% to about 90%, or even 21% to 85%, or even 21% to 75%, or even 21% to 55% by weight. The chitosan referred to in this paragraph may preferably be acid-treated chitosan.

[0068] The population of delivery particles can be prepared by: (a) forming an aqueous phase by treating chitosan with a mixture of a first acid and a second acid, wherein the first acid comprises a strong acid and the second acid comprises a weak acid, and wherein the chitosan is treated at a pH of 6.5 or less, or even a pH below 6.5, or even a pH between 3 and 6, at a temperature of at least 25°C, for at least 1 hour, preferably between 1 and 3 hours; and (b) forming an oil phase comprising dissolving at least one benefit agent and at least one crosslinking agent, preferably a polyisocyanate, optionally together with an added oil (e.g., partitioning modifier) ​​and / or solvent. (c) forming an emulsion by mixing the aqueous phase and oil phase into an excess of the aqueous phase under high shear agitation, thereby forming droplets of the oil phase (containing the benefit agent) dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to a range of pH 2 to pH 6; and (d) curing the emulsion by heating to at least 40°C for a time sufficient to form a shell at the interface of the droplets and the aqueous phase, the shell comprising the reaction product of a crosslinker and acid treated chitosan, the shell surrounding a core containing the benefit agent.

[0069] Chitosan may be added to water in a jacketed reactor at a pH of 2, or even 3-6.5, adjusted using a strong acid (such as concentrated HCl) and a weak acid (such as formic acid or acetic acid). The chitosan in this mixture may be acid-treated by heating to an elevated temperature, such as 85°C, for 60 minutes and then holding at this temperature for 1-1440 minutes or longer. The aqueous phase may then be cooled to 25°C. Optionally, deacetylation may be further facilitated or enhanced by an enzyme that depolymerizes or deacetylates chitosan. The oil phase may be prepared by dissolving an isocyanate, such as a trimer of xylylene diisocyanate (XDI) or a polymer of methylene diphenyl isocyanate (MDI), in oil at 25°C. A diluent, such as isopropyl myristate, may be used to adjust the hydrophobicity of the oil phase. The oil phase may then be added to the aqueous phase and milled at high speed to obtain the desired size. The emulsion may then be hardened in one or more heating steps, such as heating to 40°C in 30 minutes and holding at 40°C for 60 minutes. The times and temperatures are approximate. The temperature and time are selected to be sufficient to form and harden a shell at the interface between the oil phase droplets and the aqueous continuous phase. For example, the emulsion may be heated to 85°C in 60 minutes and then held at 85°C for 360 minutes to harden the particles. The slurry may then be cooled to room temperature.

[0070] The shell may degrade by at least 50% after 20 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by at least 60% of its mass after 60 days (or less) when tested according to test method OECD 301B. The shell may degrade by 30-100%, preferably 40-100%, 50-100%, 60-100%, or 60-95% in 60 days, preferably 50 days, more preferably 40 days, more preferably 28 days, or more preferably 14 days.

[0071] The delivery particles of the present disclosure comprise a core. The core comprises a benefit agent. The core optionally comprises a partitioning modifier.

[0072] The core of the particle is surrounded by a shell. When the shell ruptures, the benefit agent in the core is released. Additionally or alternatively, the benefit agent in the core may diffuse and / or be squeezed out of the particle. Suitable benefit agents disposed in the core may include benefit agents that provide a benefit to a surface such as fabric or hair.

[0073] The core may comprise from about 5% to about 100% benefit agent, preferably a fragrance, by weight of the core. The core may comprise from about 45% to about 95%, preferably from about 50% to about 80%, more preferably from about 50% to about 70% benefit agent, preferably a fragrance, by weight of the core.

[0074] The benefit agent may comprise an aldehyde-containing benefit agent, a ketone-containing benefit agent, or a combination thereof. Such benefit agents, such as aldehyde- or ketone-containing perfume ingredients, are known to provide desirable benefits, such as fresh-feel benefits. The benefit agent may comprise at least about 20%, preferably at least about 25%, more preferably at least about 40%, and even more preferably at least about 50% by weight of the benefit agent of the aldehyde-containing benefit agent, ketone-containing benefit agent, or a combination thereof.

[0075] The benefit agent may be a hydrophobic benefit agent, which is compatible with the oil phase typically used in making the delivery particles of the present disclosure.

[0076] The benefit agents are selected to provide a benefit under the preferred use of the treatment composition. The benefit agents in the core may be fragrances, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lubricants, lipids, skin cooling agents, vitamins, sunscreens, antioxidants, glycerin, catalysts, bleach particles, silicon dioxide particles, malodor reducing agents, odor control materials, chelating agents, antistatic agents, softening agents, insect and moth repellents, colorants, thickeners, drape and foam modifying agents, smoothing agents, wrinkle control agents, sanitizing agents, disinfectants, bacterial inhibitors, mold inhibitors, mildew inhibitors, antiviral agents, drying agents, stain resistant agents, soil release agents, fabric The active ingredient may be selected from the group consisting of refreshing and fresh-feel maintaining agents, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color retention agents, optical brighteners, color restoration / revitalization agents, anti-fade agents, whiteness enhancers, anti-abrasion agents, abrasion resistant agents, fabric integration agents, anti-abrasion agents, anti-pilling agents, foam suppressors, defoamers, UV protection agents, fade inhibitors, anti-allergy agents, enzymes, waterproofing agents, fabric comfort agents, shrink resistance agents, stretch resistance agents, stretch recovery agents, skin care agents, synthetic or natural actives, antibacterial actives, antiperspirant actives, cationic polymers, dyes, and mixtures thereof.

[0077] The benefit agent in the core may preferably comprise a fragrance (or simply "fragrance"), which may include one or more perfume raw materials. Fragrances are particularly suitable for encapsulation in the delivery particles described herein, as fragrance-containing particles can provide the benefit of fresh washing across multiple touch points.

[0078] As used herein, the term "perfume raw material" (or "perfume raw material, PRM") refers to a compound having a molecular weight of at least about 100 g / mole and useful for imparting an odor, fragrance, essence, or scent, either alone or in combination with other perfume raw materials. Typical PRMs include alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes, such as terpenes, among others. Lists of common PRMs can be found in various reference sources, such as, for example, "Perfume and Flavor Chemicals," 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).

[0079] PRMs may be characterized by their boiling point (BP) measured at atmospheric pressure (760 mmHg) and octanol / water partition coefficient (P), which may be described in terms of logP, determined according to the following test method. Based on these characteristics, PRMs may be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV perfumes, as described in more detail in U.S. Pat. No. 6,869,923. Suitable Quadrant I, II, III, and IV perfume raw materials are disclosed in U.S. Pat. No. 6,869,923.

[0080] Perfume raw materials having a boiling point BP below about 250° C. and a logP below about 3 are known as Quadrant I perfume raw materials. Quadrant I perfume raw materials are preferably limited to less than 30% of the fragrance materials.

[0081] The fragrance may include perfume raw materials having a logP of from about 2.5 to about 4. It is understood that other perfume raw materials may also be present in the fragrance.

[0082] The core of the delivery particles of the present disclosure may include a partitioning modifier, which may promote more robust shell formation. The partitioning modifier may be combined with the perfume oil material of the core prior to incorporation of the wall-forming monomer. The partitioning modifier may be present in the core at a concentration of from 0% to about 95% by weight of the core, preferably from about 5% to about 55% by weight, preferably from about 10% to about 50% by weight, more preferably from about 20% to about 50% by weight, and more preferably from about 25% to about 50% by weight.

[0083] Partition adjusters include vegetable oils, modified vegetable oils, and C4-C 24 The partitioning modifier may include a material selected from the group consisting of monoesters, diesters, and triesters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning modifier may preferably include isopropyl myristate, or may even consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably include castor oil and / or soybean oil. U.S. Patent Application Publication No. 20110268802, incorporated herein by reference, describes other partitioning modifiers that may be useful in the delivery particles described herein.

[0084] The oil phase can include a suitable carrier and / or solvent, especially when the benefit agent itself is insufficient to function as an oil phase or solvent for the wall-forming material during the process of forming the shell of the delivery particle. In this sense, oil is optional, since the benefit agent itself can sometimes be oil. These carriers or solvents are generally oils, preferably with a boiling point above about 80°C, low volatility, and non-flammable. Although not limited thereto, they preferably include one or more esters, preferably with a chain length of up to 18 carbon atoms or up to 42 carbon atoms, and / or triglycerides, such as esters of C6-C12 fatty acids with glycerol.

[0085] Optionally, the aqueous phase may contain an emulsifier. Non-limiting examples of emulsifiers include anionic surfactants (e.g., alkyl sulfates, alkyl ether sulfates, and / or alkylbenzene sulfonates), nonionic surfactants (e.g., alkoxylated alcohols, preferably alkoxylated alcohols containing ethoxy groups), polyvinyl alcohol, and / or polyvinylpyrrolidone. Solubilized chitosan can provide emulsification benefits in this application. When used, the emulsifier is typically present in an amount of about 0.1 to 40 wt %, preferably 0.2 to about 15 wt %, more typically 0.5 to 10 wt %, based on the total weight of the aqueous phase.

[0086] The population of delivery particles can be provided as a slurry, preferably an aqueous slurry. The slurry can include one or more processing aids, which can include water, an agglomeration inhibitor such as a divalent salt, or a particle-suspending polymer such as xanthan gum, guar gum, cellulose (preferably microfibrillated cellulose), and / or carboxymethylcellulose. When the delivery particles are cationic in nature (e.g., when the shell is at least partially derived from chitosan), non-anionic structuring agents, preferably nonionic structuring agents, are preferred, for example, to avoid deleterious charge interactions that can result in undesirable agglomeration.

[0087] The slurry may include one or more carriers selected from the group consisting of polar solvents, including but not limited to water, ethylene glycol, propylene glycol, polyethylene glycol, and glycerol; and non-polar solvents, including but not limited to mineral oil, perfume raw materials, silicone oil, and hydrocarbon paraffin oil, and mixtures thereof. Aqueous slurries may be preferred. The slurry may include non-encapsulated ("free") perfume raw materials of different identity and / or amount than those encapsulated in the core of the delivery particle.

[0088] The slurry may also include a deposition aid which may comprise a polymer selected from the group including: polysaccharides, such as chitosan, cationically modified starch, and / or cationically modified guar; polysiloxanes; polydiallyldimethylammonium halides; copolymers of polydiallyldimethylammonium chloride and polyvinylpyrrolidone; compositions comprising polyethylene glycol and polyvinylpyrrolidone; acrylamides; imidazoles; imidazolinium halides; polyvinylamines; copolymers of polyvinylamine and N-vinylformamide; polyvinylformamide, polyvinyl alcohol; polyvinyl alcohol crosslinked with boric acid; polyacrylic acid; polyglycerol ether silicone crosspolymers; polyacrylic acid, polyacrylates, polyvinylamine and amines, and in one embodiment diethylenetriamine. copolymers of N,N-bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine, and mixtures thereof with polyvinyl alcohol oligomers; polyethyleneimine, derivatized polyethyleneimine, and in one aspect, ethoxylated polyethyleneimine; polymeric compounds comprising at least two moieties selected from the group consisting of carboxylic acid moieties, amine moieties, hydroxyl moieties, and nitrile moieties in a backbone of polybutadiene, polyisoprene, polybutadiene / styrene, polybutadiene / acrylonitrile, carboxyl-terminated polybutadiene / acrylonitrile, or combinations thereof; preformed coacervates of anionic surfactants combined with cationic polymers; polyamines, and mixtures thereof.

[0089] At least one group of delivery particles may be contained in an agglomerate, which may then be combined with a separate group of delivery particles and at least one auxiliary material. The agglomerate may include a material selected from the group consisting of silica, citric acid, sodium carbonate, sodium sulfate, sodium chloride, and a binder, such as sodium silicate, modified cellulose, polyethylene glycol, polyacrylate, polyacrylic acid, zeolite, and mixtures thereof.

[0090] Suitable equipment for use in the processes disclosed herein includes continuous stirred tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow shear mixers, ribbon blenders, vertical shaft granulators and drum mixers (both batch and, where available, continuous process configurations), spray dryers, and extruders. Such equipment is available from Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Ky., USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex Corp. (Minneapolis, Minn., USA), and Arde Barinco (New Jersey, USA).

[0091] Supplementary ingredients In addition to the delivery particles, the treatment compositions of the present disclosure may also include one or more auxiliary materials that may provide a benefit in the intended end use of the composition or may be processing and / or stabilizing aids.

[0092] Suitable adjunct materials may include surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, additional perfumes and perfume delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-agglomerating agents, coating agents, formaldehyde scavengers, and / or pigments. Preferably, the adjunct materials include additional fabric conditioning agents, dyes, pH control agents, solvents, rheology modifiers, structurants, cationic polymers, surfactants, perfumes, additional perfume delivery systems, chelating agents, antioxidants, preservatives, or mixtures thereof.

[0093] Depending on the intended form, formulation, and / or end use, the compositions of the present disclosure may be free of one or more of the following adjunct materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural elastomers, fabric softeners, carriers, hydrotropes, processing aids, structurants, anti-agglomerating agents, coatings, formaldehyde scavengers, and / or pigments.

[0094] The exact nature of these additional components and the concentration at which they are incorporated depend on the physical form of the composition and the nature of the work to be used. However, if one or more adjuvants are present, such one or more adjuvants can be present as detailed below. The following is a non-limiting list of suitable additional adjuvants:

[0095] A. Surfactants The composition of the present disclosure may include a surfactant. The surfactant may be useful, for example, to provide cleaning benefits. The composition may include a surfactant system, which may contain one or more surfactants.

[0096] Compositions of the present disclosure may comprise from about 0.1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50% by weight of the composition of a surfactant system. Liquid compositions may comprise from about 5% to about 40% by weight of the composition of a surfactant system. Compositions suitable for dense formulations, e.g., dense, liquid, gel, and / or unit dose forms, may comprise from about 25% to about 70%, or from about 30% to about 50% by weight of the composition of a surfactant system.

[0097] The surfactant system may include anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. The surfactant system may include nonionic surfactants such as linear alkyl benzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, ethoxylated alcohols, amine oxides, or mixtures thereof. The surfactant may be derived, at least in part, from natural sources, such as natural feedstock alcohols.

[0098] Suitable anionic surfactants may include any conventional anionic surfactant. This may include, for example, sulfate detersive surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid-based detersive surfactants, such as alkyl benzene sulfonates. The anionic surfactant may be linear, branched, or a combination thereof. Preferred surfactants include linear alkyl benzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkyl benzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and / or alkyl ethoxylated carboxylates (AEC). The anionic surfactant may be present in acid form, salt form, or a mixture thereof. The anionic surfactant may be partially or totally neutralized, for example, with an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine). Due to the presence of cationic ester quat materials, it may be desirable to limit the amount of anionic surfactant to avoid undesirable interactions of materials. For example, the composition may contain less than 5% by weight of the composition, preferably less than 3% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight of anionic surfactant.

[0099] The surfactant system may also include a nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-capped poly(oxyalkylated) alcohol surfactants, and mixtures thereof. The alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof. The nonionic surfactant may be linear, branched (e.g., mid-chain branched), or a combination thereof. Specific nonionic surfactants may include alcohols having an average of about 12 to about 16 carbons and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactants.

[0100] Suitable zwitterionic surfactants include betaines, C8-C9 alkyl dimethyl betaines, including alkyl dimethyl betaines and cocodimethylamidopropyl betaine. 18 (For example, C 12 ~C 18 ) amine oxides (e.g., C 12 ~ 14 dimethylamine oxide), and / or N-alkyl-N,N-dimethylamino-1-propanesulfonate (wherein the alkyl group is C8 to C 18 or C 10 ~C 14 The zwitterionic surfactant may include any conventional zwitterionic surfactant, such as sulfo and hydroxybetaines, such as (which may be

[0101] Depending on the formulation and / or intended end use, the composition may be substantially free of certain surfactants. For example, a liquid fabric strengthening composition, such as a fabric softener, may be substantially free of anionic surfactants, as such surfactants may negatively interact with cationic components.

[0102] B. Conditioning Actives The compositions of the present disclosure may include conditioning actives. Compositions containing conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color, and / or appearance benefits.

[0103] The conditioning active may be present at a level of about 1% to about 99% by weight of the composition. The composition may comprise from about 1%, or about 2%, or about 3%, to about 99%, or about 75%, or about 50%, or about 40%, or about 35%, or about 30%, or about 25%, or about 20%, or about 15%, or about 10% by weight of the composition of the conditioning active. The composition may comprise from about 5% to about 30% by weight of the composition of the conditioning active.

[0104] Suitable conditioning active materials for the composition of the present disclosure can include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty acid esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof.Preferably, the treatment composition is a fabric care composition in which one or more adjunct ingredients comprise quaternary ammonium ester materials.Such materials are particularly useful in fabric enhancing / conditioning / softening compositions.

[0105] The composition may contain a quaternary ammonium ester compound, a silicone, or a combination of these, preferably a single combination. The total amount of the quaternary ammonium ester compound and the silicone may be about 5% to about 70% by weight, or about 6% to about 50% by weight, or about 7% to about 40% by weight, or about 10% to about 30% by weight, or about 15% to about 25% by weight of the composition. The composition may contain the quaternary ammonium ester compound and the silicone in a weight ratio of about 1:10 to about 10:1, or about 1:5 to about 5:1, or about 1:3 to about 1:3, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.

[0106] The composition may contain a mixture of different types of conditioning actives. The composition of the present disclosure may contain a specific conditioning active but may be substantially free of other conditioning actives. For example, the composition may be free of quaternary ammonium ester compounds, silicones, or both. The composition may contain a quaternary ammonium ester compound but may be substantially free of silicones. The composition may contain silicones but may be substantially free of quaternary ammonium ester compounds.

[0107] C. Adhesion aid The composition of the present disclosure may also include a deposition aid. As mentioned above, due to the synergistic effect of the ester quaternary material and the delivery particles of the present disclosure, less (or even no) deposition aid may be required to provide comparable or even improved performance. Alternatively, a deposition aid may be used in the composition of the present disclosure to further enhance performance.

[0108] The deposition aid may promote deposition of the delivery particles, conditioning actives, fragrance, or combinations thereof, which may improve the performance benefits of the composition and / or allow for more efficient incorporation of such benefit agents. The composition may comprise from 0.0001% to 3%, preferably from 0.0005% to 2%, more preferably from 0.001% to 1%, or from about 0.01% to about 0.5%, or from about 0.05% to about 0.3%, by weight of the composition, of the deposition aid. The deposition aid may be a cationic or amphoteric polymer, preferably a cationic polymer.

[0109] Cationic polymers in general and methods for their preparation are well known in the literature. Suitable cationic polymers include quaternary ammonium polymers known as "polyquaternium" polymers as designated in the International System of Nomenclature for Cosmetic Ingredients, such as Polyquaternium-6 (poly(diallyldimethylammonium chloride)), Polyquaternium-7 (copolymer of acrylamide and diallyldimethylammonium chloride), Polyquaternium-10 (quaternized hydroxyethylcellulose), and Polyquaternium-22 (copolymer of acrylic acid and diallyldimethylammonium chloride).

[0110] The deposition aid may be selected from the group consisting of polyvinyl formamide, partially hydroxylated polyvinyl formamide, polyvinyl amine, polyethylene imine, ethoxylated polyethylene imine, polyvinyl alcohol, polyacrylate, and combinations thereof. The cationic polymer may include a cationic acrylate.

[0111] The deposition aid can be added simultaneously with the delivery particles (e.g., simultaneously with the encapsulated benefit agent) or directly / independently into the consumer product. The weight average molecular weight of the polymer may be 500 to 5,000,000 daltons, or 1,000 to 2,000,000 daltons, or 2,500 to 1,500,000 daltons, as measured by size exclusion chromatography against polyethylene oxide standards using refractive index (RI) detection. The weight average molecular weight of the cationic polymer may be 5,000 to 37,500 daltons.

[0112] D. Rheology Modifiers / Structuring Agents The compositions of the present disclosure may include a rheology modifier and / or a structuring agent. Rheology modifiers may be used to "thicken" or "thin" a liquid composition to a desired viscosity. Structuring agents may be used to promote phase stability and / or to suspend or inhibit aggregation of particles in the liquid composition, such as the delivery particles described herein.

[0113] Suitable rheology modifiers and / or structurants may include non-polymeric crystalline hydroxyl-functional structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulosic fibers (e.g., microfibrillated cellulose, which may be derived from bacterial, fungal, or plant sources, including wood), diamide gelling agents, or combinations thereof.

[0114] The polymeric structurant may be of natural or synthetic origin. Naturally derived polymeric structurants may include hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Polysaccharide derivatives may include pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Synthetic polymeric structurants may include polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes, hydrophobically modified nonionic polyols, and mixtures thereof. Polycarboxylate polymers may include polyacrylates, polymethacrylates, or mixtures thereof. Polyacrylates are polymers of unsaturated mono- or dicarbonates and C1-C (meth)acrylic acid. 30 The structuring agent may include copolymers with alkyl esters. Such copolymers are available from Noveon Inc. under the trade name Carbopol Aqua 30. Crosslinked polymers, such as crosslinked polyacrylates, and / or polymers and / or copolymers, such as those further comprising nonionic monomers, such as acrylamide or methacrylamide monomers, may be useful as structuring agents. Another suitable structuring agent is sold under the trade name Rheovis CDE, available from BASF.

[0115] E. Other adjuvants The treatment compositions of the present disclosure may include other adjuvants suitable for inclusion in a product and / or end use. For example, the treatment compositions may include pure perfume, perfume delivery technology (such as secondary perfumes and / or encapsulates having non-polyisocyanate / chitosan wall materials), cationic surfactants, cationic polymers, solvents, suds suppressors, or combinations thereof.

[0116] Method for producing the treatment composition The present disclosure further relates to methods for making treatment compositions, such as the treatment compositions and / or consumer product compositions described herein.

[0117] The method can include providing a base composition including a processing aid and combining a population of delivery particles with the base composition. The population of delivery particles can be provided preferably as an aqueous slurry. The base composition is in liquid form.

[0118] The delivery particles may be combined with one or more auxiliary ingredients when the delivery particles are in one or more forms including a slurry form, a neat particle form, and / or a spray-dried particle form, preferably a slurry form. The delivery particles may be combined with such auxiliary ingredients by methods including mixing and / or spraying.

[0119] At least a portion of the process for producing the treatment composition may be carried out in a manufacturing apparatus comprising stainless steel, preferably 316L stainless steel. The population of delivery particles may be part of an aqueous slurry that contacts at least a portion of the stainless steel, preferably 316L stainless steel. Because stainless steel is susceptible to corrosion in the presence of, for example, chloride ions, it may be desirable to keep the amount of chloride ions to a minimum. Thus, the slurry may contain less than 0.4 wt. % chloride ions (Cl) by weight of the slurry, preferably 0.37 wt. % or less, preferably less than 0.2 wt. %, and more preferably 0.17 wt. % or less. - The relative amount of chloride ions can be reduced by reducing the amount of HCl used to treat the chitosan in forming the delivery particles and / or by using a weaker acid.

[0120] The processing composition of the present disclosure can be formulated into any suitable form and can be prepared by any process selected by the formulator.One or more auxiliary ingredients and delivery particles can be combined in a batch process, a circulation loop process, and / or an in-line mixing process.Suitable equipment for use in the method disclosed herein can 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 plow shear mixer, a ribbon blender, a vertical shaft granulator and a drum mixer (both batch and, if available, in a continuous process configuration), a spray dryer, and an extruder.

[0121] As described herein, the treatment composition may be packaged in a container to form a consumer product. The container may be a bottle, preferably a plastic bottle. The treatment composition may be packaged in an aerosol or other spray container according to known methods.

[0122] Processing method The present disclosure also relates to a method of treating a surface, preferably a fabric. Generally, the method comprises contacting the surface, preferably a fabric, with a treatment composition according to the present disclosure, comprising a population of delivery particles as described herein.

[0123] Additionally or alternatively, the method may comprise contacting a surface, preferably a fabric, with a population of delivery particles described herein, which may be contained in a treatment composition, preferably a fabric care composition, according to the present disclosure.

[0124] The method may include contacting a fabric, such as a garment, with a treatment composition. The treatment composition includes a group of delivery particles. The contacting step results in one or more of the delivery particles being deposited on the surface of the fabric. The delivery particles include a core and a shell surrounding the core, the core including a benefit agent, preferably a fragrance material including one or more perfume ingredients. The shell includes a polymeric material that is, for example, the reaction product of chitosan of a specific molecular weight and a crosslinker. Suitable treatment compositions and delivery particles are described in more detail above.

[0125] The contacting step may occur during a manual laundry process, e.g., in a basin when fabrics are treated by hand, or during an automatic laundry process, e.g., in an automatic washing machine. The contacting step may occur during the wash cycle of an automatic washing machine. In such cases, the treatment composition may be a laundry detergent or a laundry additive. The contacting step may preferably occur during the rinse cycle of an automatic washing machine. In such cases, the treatment composition may be a fabric enhancer, preferably a liquid fabric enhancer. The contacting step may also occur during the drying step of the laundry process, e.g., in an automatic dryer. In such cases, the treatment composition may be in the form of a nonwoven dryer sheet or a dryer bar. The contacting step may occur as a result of the treatment composition being applied directly to the fabric, e.g., in a pre-treatment operation or a "refreshing" step (e.g., in the case of fabrics that have been used or worn since the last wash). In such cases, the treatment composition may be in the form of a liquid, stick, or spray, preferably a spray. Contacting the target fabric relatively late in the laundry process, e.g., during the rinse cycle, improves the likelihood or efficiency of deposition on the fabric, as the fabric is less likely to be washed down the drain.

[0126] The contacting step may occur in the presence of water. The treatment composition can be diluted with water to form a treatment solution. The treatment composition can be diluted from about 100 to about 1500 times, preferably from 300 to about 1000 times.

[0127] Liquids containing the disclosed compositions may have a pH of about 3 to about 11.5. When diluted, such compositions are typically used at concentrations of about 500 ppm to about 15,000 ppm in solution. When the cleaning solvent is water, the water temperature typically ranges from about 5°C to about 90°C, and the water-to-fabric ratio may typically be about 1:1 to about 30:1.

[0128] The dilution may occur in the drum of an automatic washing machine. The treatment composition may be placed in a dispensing drawer of the automatic washing machine. The treatment composition may be dispensed from the dispensing drawer into the drum during the treatment process.

[0129] As alluded to above, the method may further comprise drying the fabric having one or more delivery particles on the surface of the fabric. The drying step may comprise a passive drying process, such as on a clothesline or drying rack. The drying step may comprise an automatic drying process, such as an automatic dryer.

[0130] combination Specifically contemplated combinations of the present disclosure are set forth herein in the following alphabetized sections, which are exemplary in nature and not intended to be limiting. A. A treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, and the shell comprising a polymeric material that is the reaction product of acid-treated chitosan and a crosslinker, the acid-treated chitosan resulting from 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, the first acid and the second acid being present in a normality ratio of about 20:80 to about 80:20, preferably about 35:65 to about 65:35, and the chitosan being treated with the mixture at a pH of 6.5 or less and at a temperature of at least 25°C. B. The treatment composition of paragraph A, wherein the first acid comprises a strong acid selected from the group consisting of hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, and mixtures thereof, preferably hydrochloric acid. C. The treatment composition of paragraph A or B, wherein the second acid comprises a weak acid selected from the group consisting of formic acid, acetic acid, ascorbic acid, glutamic acid, lactic acid, maleic acid, malic acid, succinic acid, citric acid, acrylic acid, oxalic acid, tartaric acid, and mixtures thereof, preferably selected from the group consisting of formic acid, acetic acid, and mixtures thereof. D. The processing composition of any one of paragraphs A-C, wherein the first acid has a first pKa of less than 1 and the second acid has a first pKa of from about 1 to about 5.5. E. The treatment composition of any one of paragraphs A-D, wherein the chitosan is characterized by a weight average molecular weight of from about 100 kDa to about 600 kDa, preferably from about 100 kDa to about 500 kDa, more preferably from about 100 kDa to about 400 kDa, more preferably from about 100 kDa to about 300 kDa, and even more preferably from about 100 kDa to about 200 kDa. F. The treatment composition of any one of paragraphs A-E, wherein the crosslinker comprises a polyisocyanate, preferably a polyisocyanate selected from the group consisting of polyisocyanurates of toluene diisocyanate; trimethylolpropane adducts of toluene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethylxylidene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (e.g., prepolymers, oligomers, and / or polymers thereof); and combinations thereof. G. The treatment composition of any one of paragraphs A through F, wherein a reaction product is formed in the reaction, and the weight ratio of chitosan present in the reaction to crosslinker present in the reaction is from about 1:10 to about 1:0.1. H. The treatment composition of any one of paragraphs A through G, wherein the benefit agent is a fragrance material, preferably a fragrance material comprising a perfume raw material characterized by a logP of from about 2.5 to about 4.5. I. The core optionally comprises a partitioning modifier, preferably vegetable oil, modified vegetable oil, C4-C6, present in the core at a concentration of about 5% to about 55% by weight, preferably about 10% to about 50% by weight, more preferably about 25% to about 50% by weight of the core. 24 The treatment composition of any one of paragraphs A-H, further comprising a partitioning modifier selected from the group consisting of mono-, di-, and tri-esters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof, more preferably isopropyl myristate. J. The treatment composition of any one of paragraphs AI, wherein the delivery particles are characterized by a volume weighted median particle size of about 1 to about 100 microns, 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. K. The delivery particles are prepared by treating chitosan with a mixture of a first acid and a second acid to form an aqueous phase, wherein the chitosan is treated at a pH of 6.5 or less, preferably a pH less than 6.5, more preferably a pH between 3 and 6, at a temperature of at least 25°C, for at least 1 hour, thereby forming acid-treated chitosan; forming an oil phase, comprising dissolving at least one benefit agent and at least one crosslinking agent, preferably a polyisocyanate, optionally with an added oil, preferably a partitioning control agent; and dissolving the oil phase in an excess of the aqueous phase. 10. The treatment composition of any one of paragraphs A-J, obtainable by a process comprising: forming an emulsion by mixing, preferably under high shear agitation, thereby forming droplets of an oil phase dispersed in an aqueous phase; and optionally adjusting the pH of the emulsion to be within the range of pH 2 to pH 6; and curing the emulsion at a temperature of at least 40°C for a time sufficient to form a shell at the interface between the droplets and the aqueous phase, the shell comprising a reaction product of a crosslinker and acid-treated chitosan, the shell surrounding a core comprising the droplets of the oil phase. L. The treatment composition of any one of paragraphs A-K, wherein the delivery particles are cationic, preferably the delivery particles are characterized by a zeta potential of at least 15 mV at pH 4.5. M. A treatment composition according to any one of paragraphs A-L, wherein the shell of the delivery particles degrades by at least 60% in 60 days when tested according to test method OECD 301B. N. The treatment composition of any one of paragraphs A-M, wherein the processing aid is selected from the group consisting of surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic metal complexes, polymeric dispersants, mud and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, undiluted fragrance, additional fragrance delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-flocculants, coatings, formaldehyde scavengers, pigments, and mixtures thereof. O. The treatment composition of any one of paragraphs A-N, wherein the treatment aid comprises an anionic surfactant, a cationic conditioning agent, or a mixture thereof. P. The treatment composition of any one of paragraphs A-O, wherein the treatment composition is a fabric care composition, a hard surface cleaning composition, a dish care composition, a hair care composition, a body cleansing composition, or a mixture thereof, preferably a fabric care composition, more preferably a fabric care composition that is a laundry detergent composition, a fabric conditioning composition, a laundry additive, a fabric pre-treatment composition, a fabric refresher composition, or a mixture thereof. Q. The treatment composition of any one of paragraphs A-P, wherein the treatment composition is a liquid composition, a granular composition, a hydrocolloid, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, a tablet or bead, a fibrous article, a tablet, a stick, a bar, a flake, a foam / mousse, a nonwoven, or a mixture thereof, preferably a liquid composition. R. The treatment composition of any one of paragraphs A-Q, wherein the treatment composition comprises from about 50% to about 99% water, preferably from about 60% to about 98%, and more preferably from about 80% to about 96% water, by weight of the treatment composition. S. A method of making a processing composition described in any one of paragraphs A-R, comprising the steps of providing a base composition comprising a processing aid, and combining a population of delivery particles with the base composition. T. The population of delivery particles is part of an aqueous slurry, the slurry having less than 0.4 wt. % chloride ions (Cl) by weight of the slurry, preferably 0.37 wt. % or less, preferably 0.2 wt. % or less, more preferably 0.17 wt. % or less. - ) The method of paragraph S, comprising: U. The method of paragraph S or T, wherein the method is carried out in a manufacturing apparatus comprising 316L stainless steel and the slurry contacts at least a portion of the 316L stainless steel. V. A method of treating a surface, comprising contacting the surface, preferably a fabric, with a treatment composition described in any one of paragraphs A-R. W. A treatment composition comprising a processing aid and a population of delivery particles, the delivery particles comprising a core and a shell surrounding the core, the core comprising a benefit agent, and the shell comprising a polymeric material that is a reaction product of acid-treated chitosan and a crosslinker, the acid-treated chitosan resulting from treating chitosan with an acid, the acid comprising one or more weak acids, the chitosan being treated with the acid at a pH of 6.5 or less and a temperature of at least 25°C, and the processing aid comprising a conditioning active. X. The treatment composition of paragraph W, wherein the acid does not comprise a strong acid. Y. The treatment composition of paragraph W or X, wherein the weak acid is selected from the group consisting of formic acid, acetic acid, ascorbic acid, glutamic acid, lactic acid, maleic acid, malic acid, succinic acid, citric acid, acrylic acid, oxalic acid, tartaric acid, and mixtures thereof, preferably formic acid, acetic acid, and mixtures thereof, and even more preferably acetic acid.

[0131] Test Method It will be understood that the test methods disclosed in the Test Methods section of this application should be used to determine the values ​​of each of the parameters of the inventive subject matter claimed and described herein.

[0132] Determination of polymer molecular weight and related parameters The following method, which describes gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI), is used to obtain molecular weight distribution measurements and related values ​​for the polymers described herein.

[0133] Gel permeation chromatography with multi-angle light scattering (MALS) and refractive index (RI) detection (GPC-MALS / RI) allows the measurement of the absolute average molecular weight of a polymer without the need for column calibration or standards. GPC systems allow the separation of molecules as a function of their molecular size. MALS and RI can provide information on the number average molecular weight (Mn) and weight average molecular weight (Mw).

[0134] The Mw distribution of water-soluble polymers such as chitosan is typically measured using a liquid chromatography system (e.g., Agilent 1260 Infinity Pump System with OpenLab Chemstation software, Agilent Technologies, Santa Clara, CA, USA) and a column set (e.g., two TSKgel G6000WP 7.8 x 300 mm 13 μm pore size, guard column A0022 6 mm x 40 mm PW xl-cp (Tosoh, King of Prussia, PA)) operated at 40°C. The mobile phase is 0.1 M sodium nitrate in water containing 0.02% sodium azide and 0.2% acetic acid. The mobile phase solvent is pumped isocratically at a flow rate of 1 mL / min. A multi-angle light scattering (18-angle MALS) detector DAWN® and a differential refractive index (RI) detector (Wyatt) controlled by Wyatt Astra® software v.8.0 are used. The ion exchanger is manufactured by Technology, Inc. (Santa Barbara, California, USA).

[0135] Samples are typically prepared by dissolving chitosan material in the mobile phase at approximately 1 mg / mL, mixing the solution, and allowing it to hydrate overnight at room temperature. Prior to GPC analysis, samples are filtered through 0.8 μm Versapor filters (PALL Life Sciences, NY, USA) using a 3 mL syringe into LC autosampler vials.

[0136] The dn / dc value (differential change in refractive index with concentration, 0.15) is used to determine the number average molecular weight (Mn), weight average molecular weight (Mw), Z-average molecular weight (Mz), molecular weight at the peak maximum (Mp), and polydispersity (Mw / Mn) by the Astra detector software.

[0137] viscosity Measure the viscosity of the liquid final product using an AR550 rheometer / viscometer from TA instruments (New Castle, Delaware, USA) using parallel steel plates with a diameter of 40 mm and a gap size of 500 μm. -1 High shear viscosity at 0.05 seconds -1 The low shear viscosity at 21°C for 3 minutes is 0.01 s -1 ~25 seconds -1 is obtained from a logarithmic shear rate sweep.

[0138] Test Method for Determining logP For each material tested (e.g., each PRM in a fragrance mixture), the logarithm of the octanol / water partition coefficient (logP) is calculated. The logP values ​​of individual materials (e.g., PRMs) are calculated using the Consensus logP Computational Model, version 14.02 (Linux), available from Advanced Chemistry Development Inc. (ACD / Lab) (Toronto, Canada), which yields unitless logP values. The ACD / Labs Consensus logP Computational Model is part of the ACD / Labs model suite.

[0139] Volume-weighted particle size and size distribution Volume-weighted particle size distributions were determined by single-particle optical sensing (SPOS), also known as optical particle counting (OPC), using an AccuSizer 780 AD instrument and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent. The instrument was configured with the following conditions and options: flow rate = 1 mL / s, minor threshold = 0.50 μm, sensor model number = LE400-05 or equivalent, autodilution = on, collection time: 60 seconds, number of channels = 512, reservoir fluid volume = 50 mL, and maximum coincidence count = 9200. Measurements were initiated by cold-conditioning the sensor by flushing with water until the background count was less than 100. A sample of delivery capsules in suspension is introduced, and the capsule density is adjusted, if necessary, via automated dilution with deionized water to achieve a capsule count of at least 9200 per mL. The suspension is analyzed for 60 seconds. The resulting volume-weighted PSD data is plotted and recorded, and desired volume-weighted particle size values ​​(e.g., median / 50th percentile, 5th percentile, and / or 90th percentile) are determined.

[0140] Procedure for determining decomposition % To determine % degradation, the procedure described in the "OECD Guideline for Testing of Chemicals" 301B CO2 Evolution (Modified Sturm Test), adopted on July 17, 1992, is used. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0141] Fabric treatment methods The fabrics were treated using a Miele washing machine. For each treatment, 3 kg of fabric was loaded into the washing machine, including 1100 g of knitted cotton fabric and 1100 g of polyester-cotton (50 / 50) fabric. Additionally, 18 terry towel cotton tracers were added, totaling approximately 780 g.

[0142] Prior to the test treatment, the laundry is preconditioned twice with 79 g of unscented IEC A-based detergent (e.g., WFK, Testgewebe GmbH) using a short cotton cycle at 95°C each time, followed by two additional 95°C washes without detergent.

[0143] In the test treatment, laundry is washed using a short cotton cycle at 40°C, a spin speed of 1200 rpm, and 79 g of IEC A base detergent, which is added to the appropriate dispenser at the beginning of the wash cycle. A 35 g dose of the test fabric treatment composition (i.e., LFE according to the example) is added to the appropriate dispenser. At the end of the treatment cycle, the terry towel tracer is removed from the washing machine and line dried overnight.

[0144] The next day, the dried terry towel tracer is analyzed by a rapid headspace GC / MS (gas chromatography mass spectrometry) technique as described below. For comparison, all treatments are washed on the same day, and all treatments analyzed on the same day are reported as a "single wash test."

[0145] Olfactory evaluation method After the fabrics were treated, a professional perfumer performed an olfactory assessment of the perfume intensity of the dry fabric at the DRY touchpoint (Dry Fabric Odor = DFO) and the RUB touchpoint (Rubbed Fabric Odor = RFO). The fabrics were allowed to dry for one day, smelled for DFO, then manually manipulated by rubbing the fabric against itself and smelled again for RFO. The scores were averaged. The score was based on a perfume odor intensity scale of 0 to 100, where 0 = no perfume odor, 25 = slight perfume odor, 50 = moderate perfume odor, 75 = strong perfume odor, and 100 = very strong perfume odor.

[0146] Method for determining headspace concentrations above treated dry fabrics The cotton tracer was analyzed by fast headspace GC / MS (gas chromatography mass spectrometry) technique. A 4 x 4 cm aliquot of terry towel cotton tracer was transferred to a 25 mL headspace vial. The fabric sample was equilibrated at 65°C for 10 minutes. The headspace above the fabric was sampled by SPME (50 / 30 μm DVB / Carboxen / PDMS) technique for 5 minutes. The SPME fibers were then thermally desorbed online into the GC. The analytes were analyzed in full scan mode by fast GC / MS. Ion extraction of specific masses from the PRM was used to calculate the total HS reaction and perfume headspace composition above the tested leg. [Example]

[0147] The examples provided below are intended to be illustrative and not limiting in nature.

[0148] Comparative Example 1 An aqueous phase is prepared by dispersing 92.19 g of chitosan (ULV grade, Primex, Siglufjörður, Iceland) in 1956.6 g of water with mixing in a jacketed reactor. The pH of the aqueous phase is then adjusted to 5.37 with 39.16 g of concentrated HCl (hydrochloric acid, 32-38%, Avantor Performance Materials, LLC, Radnor, PA) with stirring. The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acidify the chitosan. After the 90 minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0149] The oil phase is prepared by mixing 716.36 g of fragrance oil and 179.10 g of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 19.59 g of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The delivery particle population of the final slurry has a volume-weighted median particle size of 28.84 microns.

[0150] Comparative Example 2 An aqueous phase is prepared by dispersing 101.26 g of chitosan (ULV grade, available from Primex EHF, Siglufjörður, Iceland) in 2153.18 g of water while mixing in a jacketed reactor. Then, 8.42 g of concentrated HCl (hydrochloric acid, 32-38%, available from Avantor Performance Materials, LLC, Radnor, Pennsylvania) is added to the chitosan mixture while stirring. The pH of the aqueous phase is then adjusted to 5.43 using 16.26 g of 90% formic acid (available from Brenntag Great Lakes, LLC, Wauwatosa, Wisconsin) while stirring. The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acid treat the chitosan. After the 90 minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0151] The oil phase is prepared by mixing 786.74 g of fragrance oil and 196.71 g of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 21.53 g of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The delivery particle population of the final slurry has a volume-weighted median particle size of 26.26 microns.

[0152] Comparative Example 3. An aqueous phase is prepared by dispersing 12.35 pounds of chitosan (ULV grade, Primex, Siglufjörður, Iceland) in 262.10 pounds of water while mixing in a jacketed tank. The pH of the aqueous phase is then adjusted to 5.19 with 2.7 pounds of 90% formic acid (Brenntag Great Lakes, LLC, Wauwatosa, Wisconsin) while stirring. The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acidify the chitosan. After the 90-minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0153] The oil phase is prepared by mixing 78.2 pounds of fragrance oil and 42 pounds of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 2.6 pounds of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) in a jacketed tank at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The delivery particle population of the final slurry has a volume-weighted median particle size of 32.11 microns.

[0154] Example 1 An aqueous phase is prepared by dispersing 101.31 g of chitosan (ULV grade, available from Primex, Siglufjörður, Iceland) in 2149.03 g of water while mixing in a jacketed reactor. Then, 25.19 g of concentrated HCl (hydrochloric acid, 32-38%, available from Avantor Performance Materials, LLC, Radnor, Pennsylvania) is added to the chitosan mixture while stirring. The pH of the aqueous phase is then adjusted to 5.43 with 8.5 g of 90% formic acid (available from Brenntag Great Lakes, LLC, Wauwatosa, Wisconsin) while stirring. The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acid treat the chitosan. After the 90 minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0155] The oil phase is prepared by mixing 786.70 g of fragrance oil and 196.68 g of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 21.57 g of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The delivery particle population of the final slurry has a volume-weighted median particle size of 25.65 microns.

[0156] Example 2. An aqueous phase is prepared by dispersing 12.31 pounds of chitosan (ULV grade, manufactured by Primex, Siglufjörður, Iceland) in 261.33 pounds of water while mixing in a jacketed tank. Then, with stirring, 3.07 pounds of concentrated HCl (hydrochloric acid, 32-38%, manufactured by Avantor Performance Materials, LLC, Radnor, Pennsylvania) is added to the chitosan mixture. The pH of the aqueous phase is then adjusted to 5.22 with stirring using 1.11 pounds of 90% formic acid (manufactured by Brenntag Great Lakes, LLC, Wauwatosa, Wisconsin). The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acidify the chitosan. Following the 90-minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0157] The oil phase is prepared by mixing 95.68 pounds of fragrance oil and 23.92 pounds of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 2.62 pounds of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) in a jacketed tank at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The population of delivery particles in the final slurry has a volume-weighted median particle size of 28.82 microns. According to the 301B test, the percent degradability of the shell is 54.95% at 28 days.

[0158] Example 3. An aqueous phase is prepared by dispersing 101.30 g of chitosan (ULV grade, available from Primex, Siglufjörður, Iceland) in 2148.95 g of water while mixing in a jacketed reactor. Then, with stirring, 16.80 g of concentrated HCl (hydrochloric acid, 32-38%, available from Avantor Performance Materials, LLC, Radnor, Pennsylvania) is added to the chitosan mixture. The pH of the aqueous phase is then adjusted to 5.43 with stirring using 12.44 g of 90% formic acid (available from Brenntag Great Lakes, LLC, Wauwatosa, Wisconsin). The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acid treat the chitosan. After the 90 minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0159] The oil phase is prepared by mixing 786.73 g of fragrance oil and 196.69 g of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 21.56 g of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The delivery particle population of the final slurry has a volume-weighted median particle size of 26.57 microns.

[0160] Example 4. An aqueous phase is prepared by dispersing 101.26 g of chitosan (ULV grade, available from Primex, Siglufjörður, Iceland) in 2149.6 g of water while mixing in a jacketed reactor. Then, 25.22 g of concentrated HCl (hydrochloric acid, 32-38%, available from Avantor Performance Materials, LLC, Radnor, Pennsylvania) is added to the chitosan mixture while stirring. The pH of the aqueous phase is then adjusted to 5.45 with 24.34 g of 40% acetic acid (available from Columbus Chemical Industries, Inc., Columbus, Wisconsin) while stirring. The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acid treat the chitosan. After the 90 minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0161] The oil phase is prepared by mixing 786.71 g of fragrance oil and 196.68 g of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 21.51 g of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The delivery particle population of the final slurry has a volume-weighted median particle size of 30.93 microns.

[0162] Example 5. An aqueous phase is prepared by dispersing 101.28 g of chitosan (ULV grade, available from Primex, Siglufjörður, Iceland) in 2139.74 g of water while mixing in a jacketed reactor. Then, with stirring, 16.82 g of concentrated HCl (hydrochloric acid, 32-38%, available from Avantor Performance Materials, LLC, Radnor, Pennsylvania) is added to the chitosan mixture. The pH of the aqueous phase is then adjusted to 5.45 with stirring using 36.78 g of 40% acetic acid (available from Columbus Chemical Industries, Inc., Columbus, Wisconsin). The aqueous phase temperature is then increased to 95°C over 90 minutes and then held at 95°C for a period of time (e.g., 2 hours) to acid treat the chitosan. After the 90 minute acid treatment step, the temperature of the aqueous phase is then reduced to 25°C.

[0163] The oil phase is prepared by mixing 786.74 g of fragrance oil and 196.68 g of isopropyl myristate (manufactured by Acme-Hardesty Co., Blue Bell, Pennsylvania) with 21.51 g of Takenate D-110N (manufactured by Mitsui Chemicals America, Inc., Rye Brook, New York) at room temperature. The oil phase is added to the water phase under high shear milling to obtain an emulsion. The emulsion is heated to 65°C over 45 minutes, then to 85°C over 60 minutes. The emulsion is then maintained at this temperature for 6 hours with mixing. The delivery particle population of the final slurry has a volume-weighted median particle size of 28.84 microns.

[0164] Example 6. Chitosan treated with a single acid To compare the performance of delivery particles made from chitosan materials subjected to various treatments with a single acid, three populations of delivery particles are made.

[0165] Chitosan is treated with hydrochloric acid, formic acid, and acetic acid, respectively. Perfume delivery particles are produced according to the present disclosure, and the shell is made from acid-treated chitosan and crosslinked with polyisocyanate. The core of the delivery particles contains, on average, about 80% of the first perfume and about 20% of a partitioning modifier (i.e., isopropyl myristate). The volume-weighted median particle size of the particle population is about 12-14 microns.

[0166] To test the freshness performance of the resulting delivery particles, liquid fabric enhancer ("LFE") samples are prepared using the different delivery particles described above. The test LFE compositions contain about 6% by weight of a diester quat. The chitosan-based delivery particles are present in the test LFE compositions at a concentration to provide about 0.2% by weight of encapsulated fragrance by weight of the LFE composition. The pH of the test LFE compositions is adjusted to about 3.

[0167] The fabric is treated according to the fabric treatment method provided in the Test Methods section above. The fabric is evaluated for dry fabric odor (DFO) and rub fabric odor (RFO) according to the olfactory evaluation method provided in the Test Methods section above. The results are provided in Table 1 below.

[0168] Additionally, the delivery particles are provided in a heavy duty liquid (HDL) detergent matrix and tested for leakage after one week of storage. The percentage leakage is provided in Table 1.

[0169] [Table 1] * =Comparative example

[0170] As shown in Table 1, delivery particles made from chitosan treated with weak acids, i.e., formic acid or acetic acid, provide comparable or even better freshness performance based on olfactory evaluation compared to delivery particles made from chitosan treated with strong acids, i.e., hydrochloric acid. Weak acids are also expected to result in improved corrosion profiles for associated slurries.

[0171] Interestingly, when delivery particles are provided in LFE products, acetic acid appears to provide improved fresh-wash feel performance compared to formic acid. However, as shown in Table 2, particles made from acetic acid-treated chitosan exhibit a relatively poor leakage profile in HDL products compared to particles made from formic acid-treated chitosan. Furthermore, slurries of particles made from acetic acid-treated chitosan were found to exhibit some gelation, which may pose processing challenges.

[0172] Example 7. Effect of mixed acid treatment on freshly washed sensory performance of particles To compare the freshness performance of delivery particles made from chitosan materials that have undergone various acid treatments, liquid fabric enhancer ("LFE") samples are prepared using the different delivery particles described above.

[0173] For each test, the core of the delivery particle contained, on average, about 65% to 80% second flavor and about 20% to 35% partitioning modifier (ie, isopropyl myristate).

[0174] A test LFE composition is prepared having the general formula shown in Table 2. The chitosan-based delivery particles are present in the test LFE composition at a concentration to provide about 0.2% by weight of the encapsulated fragrance material based on the weight of the LFE composition. The pH of the test LFE composition is adjusted to about 3.

[0175] [Table 2] 1 N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride (e.g., manufactured by Evonik) 2 Flosoft FS222 (e.g., manufactured by SNF)

[0176] The fabrics are treated according to the fabric treatment method provided in the Test Methods section above. The fabrics are evaluated for dry fabric odor (DFO) and rub fabric odor (RFO) according to the olfactory evaluation method provided in the Test Methods section above.

[0177] A. Formic acid The results for capsules made from chitosan that was at least partially treated with formic acid are shown in Table 3 below.

[0178] [Table 3] * =Comparative example

[0179] According to the data in Table 3, delivery particles formed from chitosan treated with mixed acid systems (e.g., strong acid:weak acid normality ratios of 80:20 to 20:80, where the weak acid is formic acid) provide comparable olfactory performance (e.g., RFO greater than 50) to delivery particles formed from chitosan treated with HCl alone. However, due to the presence of the weak acid, such systems are considered relatively less corrosive.

[0180] The data in Table 3 also show that delivery particles made from chitosan treated with acid systems having relatively high amounts of formic acid (a weak acid) (e.g., a normality ratio of less than 20:80) result in relatively poor performance (e.g., an RFO of less than 46).

[0181] B. Acetic acid The results for capsules made from chitosan that was at least partially treated with acetic acid are provided in Table 3 below.

[0182] [Table 4] * =Comparative example

[0183] According to the data in Table 4, delivery particles formed from chitosan treated with mixed acid systems (e.g., strong acid:weak acid normality ratios of 80:20 to 20:80, where the weak acid is acetic acid) provide comparable or even improved olfactory performance (e.g., RFO greater than 50) relative to delivery particles formed from chitosan treated with HCl alone. However, due to the presence of the weak acid, such systems are considered relatively less corrosive.

[0184] Furthermore, in light of separate data collected by applicant, delivery particles formed from chitosan treated with acetic acid alone are believed to be suboptimal with respect to leakage, for example, in a liquid detergent matrix. Therefore, the presence of a certain minimum level of a strong acid, such as HCl, is believed to be desirable for performance reasons.

[0185] Example 8. Effect of Slurry Chloride Concentration on Corrosion The following tests were conducted to investigate the effect of chloride concentration in the delivery particle slurry on the corrosion of stainless steel materials commonly used in manufacturing equipment.

[0186] Chitosan is treated with formic acid and used to make perfume delivery particles according to the methods described in this disclosure. Samples of the resulting particle slurries are doped with magnesium chloride (MgCl) to provide slurries with various chloride concentrations.

[0187] Stainless steel test samples (Grade = 316L SS; Size = 3 / 4" x 2" x 1 / 8", 120 grit sanded finish) were placed in a tray at approximately 38°C and subjected to a wet / dry test. The test involved periodically wetting the test sample with a slurry sample (i.e., immersion on day 1, then every 7 days) over a 28 day period. At the end of treatment, the test sample is inspected for corrosion pits. The total number of pits on the front and back of the test sample are counted and reported in Table 5 below.

[0188] [Table 5] * =Comparative example

[0189] A relatively low amount of chloride ions in the slurry results in fewer pits and less corrosion, as shown in Table 5. Based on the data in Table 5, slurries with chloride concentrations of less than 0.4% are preferred, with concentrations of less than 0.2% being even more preferred.

[0190] Dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0191] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest, or disclose any such invention, either alone or in combination with any other reference or references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control.

[0192] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A processing composition comprising a processing aid and a population of delivery particles, The delivery particle comprises a core and a shell surrounding the core; the core comprises a benefit agent; the shell comprises a polymeric material that is the reaction product of acid-treated chitosan and a crosslinker; the acid-treated chitosan results from treating chitosan with a mixture of a first acid and a second acid; the first acid comprises a strong acid; the second acid comprises a weak acid; the ratio of the first acid to the second acid is from about 20:80 to about 80:20; Preferably present in a normality ratio of about 35:65 to about 65:35; The chitosan is treated with the mixture at a pH of 6.5 or less and at a temperature of at least 25°C.

2. the first acid is a strong acid selected from the group consisting of hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, and mixtures thereof; 10. The treatment composition of claim 1, preferably comprising hydrochloric acid.

3. the second acid is a weak acid selected from the group consisting of formic acid, acetic acid, ascorbic acid, glutamic acid, lactic acid, maleic acid, malic acid, succinic acid, citric acid, acrylic acid, oxalic acid, tartaric acid, and mixtures thereof; 3. The treatment composition of claim 1 or 2, comprising a weak acid, preferably selected from the group consisting of formic acid, acetic acid, and mixtures thereof.

4. the first acid has a first pKa less than 1; and The treatment composition of any one of claims 1 to 3, wherein the second acid has a first pKa of from about 1 to about 5.

5.

5. The chitosan has a molecular weight of about 100 kDa to about 600 kDa, 5. The treatment composition according to any one of claims 1 to 4, characterized by a weight average molecular weight of preferably from about 100 kDa to about 500 kDa, more preferably from about 100 kDa to about 400 kDa, more preferably from about 100 kDa to about 300 kDa, and even more preferably from about 100 kDa to about 200 kDa.

6. The crosslinking agent is a polyisocyanate.

6. The treatment composition of any one of claims 1 to 5, comprising a polyisocyanate preferably selected from the group consisting of polyisocyanurates of toluene diisocyanate; trimethylolpropane adducts of toluene diisocyanate; trimethylolpropane adducts of xylylene diisocyanate; 2,2'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; [diisocyanato(phenyl)methyl]benzene; toluene diisocyanate; tetramethylxylidene diisocyanate; naphthalene-1,5-diisocyanate; 1,4-phenylene diisocyanate; 1,3-diisocyanatobenzene; derivatives thereof (e.g., prepolymers, oligomers, and / or polymers thereof); and combinations thereof.

7. 7. The treating composition of any one of claims 1 to 6, wherein the reaction product is formed in a reaction wherein the weight ratio of the chitosan present in the reaction to the crosslinker present in the reaction is from about 1:10 to about 1:0.

1.

8. The benefit agent may comprise a fragrance material, A treatment composition according to any one of claims 1 to 7, which is a fragrance material comprising a perfume raw material preferably characterized by a log P of from about 2.5 to about 4.

5.

9. The core optionally comprises a partitioning modifier present in the core at a concentration of from about 5% to about 55%, preferably from about 10% to about 50%, more preferably from about 25% to about 50% by weight of the core; Preferably vegetable oil, modified vegetable oil, C ４ ~C ２４ a partitioning modifier selected from the group consisting of mono-, di-, and tri-esters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof; More preferably, the treatment composition according to any one of claims 1 to 8 further comprises isopropyl myristate.

10. The delivery particles have a volume weighted median particle size of about 1 to about 100 microns; 10. The treating composition of any one of claims 1 to 9, characterized by a volume weighted median particle size of preferably from about 10 to about 100 microns, preferably from about 15 to about 50 microns, more preferably from about 20 to about 40 microns, and even more preferably from about 25 to about 35 microns.

11. The delivery particles include: forming an aqueous phase by treating the chitosan with the mixture of the first acid and the second acid; treating the chitosan at a pH of 6.5 or less, preferably a pH of less than 6.5, more preferably a pH of 3-6, at a temperature of at least 25°C for at least 1 hour, thereby forming an acid-treated chitosan; forming an oil phase comprising dissolving at least one benefit agent and at least one crosslinking agent, preferably a polyisocyanate, optionally together with an additive oil, preferably a partitioning control agent; forming an emulsion by mixing an oil phase into an excess of an aqueous phase, preferably under high shear agitation, thereby forming droplets of the oil phase dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to be within the range of pH 2 to pH 6; curing the emulsion at a temperature of at least 40°C for a time sufficient to form a shell at the interface between the droplets and the aqueous phase; the shell comprises the reaction product of the crosslinker and the acid-treated chitosan; and The treatment composition according to any one of claims 1 to 10, wherein the shell surrounds the core comprising the droplets of the oil phase.

12. the delivery particles are cationic; The treatment composition of any one of claims 1 to 11, wherein the delivery particles are preferably characterized by a zeta potential of at least 15 mV at pH 4.

5.

13. 13. The treatment composition of any one of claims 1 to 12, wherein the shell of the delivery particles degrades by at least 60% in 60 days when tested according to test method OECD 301B.

14. 14. The treatment composition of any one of claims 1 to 13, wherein the processing aid is selected from the group consisting of surfactants, conditioning actives, deposition aids, rheology modifiers or structurants, bleaching systems, stabilizers, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, enzyme stabilizers, catalytic metal complexes, polymeric dispersants, mud and soil removal / anti-redeposition agents, brighteners, suds suppressors, silicones, hueing agents, aesthetic dyes, undiluted perfume, additional perfume delivery systems, structural elastomers, carriers, hydrotropes, processing aids, anti-agglomerating agents, coatings, formaldehyde scavengers, pigments, and mixtures thereof.

15. The treatment composition of any one of claims 1 to 14, wherein the treatment aid comprises an anionic surfactant, a cationic conditioning agent, or a mixture thereof.

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