Laundry care additive particles

Abstract

A composition comprising a plurality of particles, a method of treating laundry using such particles, and a method of preparing such particles wherein the particles comprise: from about 25% to about 99% by weight of a water soluble carrier; and a plurality of capsules dispersed in the water-soluble carrier wherein the capsules comprise a core and a shell surrounding the core and the core comprises a perfume raw material; wherein the shell comprises a polymeric material which is a reaction product of chitosan derived from an aqueous phase and a cross-linking agent.

Description

Technical Field

[0001] A laundry care particle comprising a polymeric material which is the reaction product of chitosan derived from an aqueous phase and a cross-linking agent. Background Art

[0002] Laundry care particles are formulated with scented core / shell capsules. Typically, the core of these capsules contains the fragrance, and the shell typically comprises a polymeric material such as aminoplasts, polyureas, or polyacrylates, or a naturally derived material such as gelatin, lysine, or chitosan. These capsules can be used to deliver beneficial agents to target surfaces, such as fabrics. The capsules then release the fragrance upon manipulation at various touch points.

[0003] One capsule technology is a combination of the reaction product of chitosan and a cross-linker, wherein the cross-linker comprises an isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates derived from an oil phase, each of which contains an aromatic moiety. Such capsules can be difficult to include in granular laundry products due to a lack of durability in some manufacturing processes.

[0004] In view of the above limitations, there is a continuing unmet need for granular laundry products having suitably durable capsules. Summary of the Invention

[0005] A composition comprising a plurality of particles, wherein the particles comprise: from about 25% to about 99% by weight of a water-soluble carrier; and a plurality of capsules dispersed in the water-soluble carrier, wherein the capsules include a core and a shell surrounding the core, and the core comprises a fragrance raw material; wherein the shell comprises from about 90% to 100%, optionally from about 95% to 100%, optionally from about 99% to 100%, by weight of the shell, of a polymeric material that is the reaction product of chitosan derived from an aqueous phase and a cross-linking agent, wherein the cross-linking agent comprises an isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates derived from an oil phase, each of the diisocyanates and / or polyisocyanates comprising an aromatic moiety; and wherein the mixture of diisocyanates and / or polyisocyanates comprising an aromatic moiety comprises at least one α-aromatic isocyanate and at least one β-aromatic isocyanate, optionally wherein the desired isocyanates are each present at least 20 mole percent of the total isocyanate component. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Figure 1 Schematic diagram of the granulation equipment used to prepare granules.

[0007] Figure 2: Perfume loss after preparation of laundry care granules comprising capsules prepared with different ratios of α-aromatic isocyanate and β-aromatic isocyanate.

[0008] Figure 3 : Oil-free capsules after spray drying prepared with different ratios of α-aromatic isocyanate and β-aromatic isocyanate and different shell (%) and volume-weighted median microcapsule size (μm). DETAILED DESCRIPTION

[0009] The present disclosure relates to laundry care additive particles comprising a water-soluble carrier and a plurality of fragrance-containing capsules dispersed in the carrier, wherein the capsules comprise a core and a shell surrounding the core, and the core comprises a fragrance raw material; wherein the shell comprises from about 90% to 100%, optionally from about 95% to 100%, optionally from about 99% to 100%, by weight of the shell, of a polymeric material that is the reaction product of chitosan derived from an aqueous phase and a cross-linking agent, wherein the cross-linking agent comprises an isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates derived from an oil phase, each of the diisocyanates and / or polyisocyanates comprising an aromatic moiety; and wherein the mixture of diisocyanates and / or polyisocyanates comprising an aromatic moiety comprises at least one α-aromatic isocyanate and at least one β-aromatic isocyanate, optionally wherein the desired isocyanates are each present at least 20 mole percent of the total isocyanate component.

[0010] The laundry care additive particles can be used to provide a beneficial effect for clothes by washing. That is, the user can use the particles by distributing the particles into the washing machine before starting the washing machine cycle, particularly the wash sub-cycle. Full wash compositions such as those described herein are different from full rinse compositions. Full rinse compositions are designed to be distributed during the rinse sub-cycle of the washing machine. In modern washing machines, the rinse sub-cycle is automatically started after the wash sub-cycle is completed without any further input from the consumer. The composition to be distributed during the rinse sub-cycle is usually dosed in a separate dosing chamber, which is a part of the washing machine that distributes the full rinse composition during the rinse sub-cycle, such as an agitator in a distribution drawer or tub.

[0011] It is believed that capsules of the type disclosed herein work surprisingly well in providing improved, consumer-acceptable freshness benefits on fabrics when used in a water-soluble carrier.

[0012] The term "substantially free" may be used herein. This means that the referenced material is very small and not intentionally added to the composition to form part of the composition, or optionally, the referenced material is not present at analytically detectable levels. This includes compositions in which the referenced material is present only as an impurity in one of the other materials intentionally added. If present, the referenced material may be present at a level of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0013] Unless otherwise indicated, all component or composition levels are in reference to the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

[0014] Unless otherwise indicated, all temperatures herein are in degrees Celsius (° C.) Unless otherwise indicated, all measurements herein are made at 20° C. and atmospheric pressure.

[0015] As used herein, all percentages are by weight of the total composition unless otherwise specifically stated. All ratios are by weight unless otherwise specifically stated.

[0016] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range falling within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0017] Water-soluble carrier

[0018] The granules of the present invention may comprise from 25% to 99% by weight of a water-soluble carrier.While any suitable material may be used as the water-soluble carrier, one preferred composition comprises a polyalkylene glycol.

[0019] The polyalkylene glycol water-soluble carrier can be a material selected from polyethylene glycol, polypropylene glycol, ethylene oxide / propylene oxide block copolymers and combinations thereof. For example, the water-soluble carrier can be polyethylene glycol (PEG). PEG has a lower cost, can be formed into many different shapes and sizes, minimizes the diffusion of free fragrances, and dissolves well in water. As used herein, the term "polyethylene glycol" or "PEG" includes homopolymers comprising repeating units of ethylene oxide, random copolymers comprising repeating units of ethylene oxide and propylene oxide, block copolymers comprising blocks of polyethylene oxide and polypropylene oxide, and combinations thereof.

[0020] The particles may comprise from about 25% to about 99% PEG by weight. Optionally, the particles may comprise from about 35% to about 99% PEG by weight of the respective particle, optionally from about 40% to about 99%, optionally from about 50% to about 99%, optionally combinations thereof, and any integer percentage or range of integer percentages within any of the foregoing ranges. Preferably, the PEG present in the particle is characterized by a weight average molecular weight (Mw) ranging from about 2,000 Daltons to about 20,000 Daltons, optionally from about 2,000 Da to about 15,000 Da, alternatively from about 4,000 Da to about 20,000 Da, alternatively from about 4,000 Da to about 15,000 Da, alternatively from about 4,000 Da to about 12,000 Da, alternatively from about 5,000 Da to about 11,000 Da, alternatively from about 6,000 Da to about 10,000 Da, alternatively from about 7,000 Da to about 9,000 Da, alternatively combinations thereof. Suitable PEGs include those available under the trade name E 8000 is a homopolymer commercially available from BASF.

[0021] While combinations of molecular weight PEGs can be used, it is believed that PEGs with a molecular weight below 4,000 Da should be used in relatively low weight percent amounts compared to PEGs with a molecular weight above 4,000 Da. It is believed that PEGs with a molecular weight below 4,000 Da have lower melting temperatures and may introduce processing difficulties. To compensate for this lower melting temperature of the lower molecular weight PEGs, higher molecular weight PEGs can be used in higher weight percents than the lower molecular weight PEGs. For example, the higher molecular weight PEGs can be introduced in a ratio of at least about 1.1:1.

[0022] For example, the polyalkylene glycol water-soluble carrier can be an ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymer, which preferably has an average ethylene oxide chain length of about 2 to about 90, preferably about 3 to about 50, more preferably about 4 to about 20 ethylene oxide units, and an average propylene oxide chain length of 20 to 70, preferably 30 to 60, more preferably 45 to 55 propylene oxide units. More preferably, the ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymer has a molecular weight of about 2,000 daltons to about 30,000 daltons, preferably about 3,000 daltons to about 20,000 daltons, more preferably about 4,000 daltons to about 15,000 daltons.

[0023] Preferably, the copolymer comprises from 10% to 90%, preferably from 15% to 50%, and most preferably from 15% to 25% of the combined ethylene oxide blocks by weight of the copolymer. Most preferably, the total ethylene oxide content is equally divided between the two ethylene oxide blocks. Equally divided herein means that each ethylene oxide block comprises, on average, from 40% to 60%, preferably from 45% to 55%, even more preferably from 48% to 52%, and most preferably 50% of the total number of ethylene oxide units, the % of the two ethylene oxide blocks totaling 100%. Some ethylene oxide-propylene oxide-ethylene oxide (EOx1POyEOx2) triblock copolymers improve cleaning.

[0024] Suitable ethylene oxide-propylene oxide-ethylene oxide triblock copolymers are commercially available from BASF Corporation under the tradename Pluronic series or from The Dow Chemical Company under the tradename Tergitol L series. Particularly suitable materials are PE 9200. Other suitable materials include F38, F68 and F108.

[0025] The polyalkylene glycol water-soluble carrier also includes "end-capped" polyalkylene glycol. Typically, the polyalkylene glycol has two -OH groups at both ends of the polymer chain, and "end-capped" means that at least one or both of the -OH groups react and are connected to an end-capping organic group different from the polyalkylene glycol. Preferably, the end-capping organic group R is connected to the -OH group of the polyalkylene glycol via an ether bond (-OR) and / or an ester bond (-O-(C=O)-R), wherein R is a linear or branched C1-C 30 Alkyl groups, cycloalkyl groups having 5 to 9 carbon atoms, C6-C 30 Arylalkyl group, C6-C 30 More preferably, R is a linear or branched C1-C 30 An alkyl group, even more preferably a straight-chain C1-C6 alkyl group, and even more preferably a methyl group (CH3).

[0026] Examples of suitable "end-capped" polyalkylene glycols include polyethylene glycol fatty alcohol ethers of the formula:

[0027] H3C-(CH2) t -O-[CH2-CH2-O] q -(CH2) t -CH3

[0028] in

[0029] q is a number ranging from 30 to 250 based on a molar average value.

[0030] t is a number ranging from 0 to 30 based on a molar average value.

[0031] Examples of suitable "end-capped" polyalkylene glycols include polyethylene glycol fatty alcohol esters of the formula:

[0032] H3C-(CH2) t -(C=O)-O-[CH2-CH2-O] q -(C=O)-(CH2) t -CH3

[0033] in

[0034] q is a number ranging from 30 to 250 based on a molar average value.

[0035] t is a number ranging from 0 to 30 based on a molar average value.

[0036] Additional choices of polyalkylene glycols include modified polyalkylene glycols having the formula:

[0037] HO-(C2H4O) s -(CH2) t )-CH3;

[0038] in

[0039] s is based on a number with a molar average value of 63 to 68,

[0040] t is a number ranging from 13 to 19, preferably 17, based on a molar average value.

[0041] The carrier composition comprising the above-mentioned formulation may contain from about 10% to about 60% by weight, preferably from about 20% to about 50% by weight, even more preferably from about 25% to about 45% by weight, and most preferably from about 30% to about 40% by weight of the above-mentioned modified polyalkylene glycol.

[0042] Other water-soluble carriers

[0043] The water-soluble carrier can be a material that dissolves in the wash liquor within a short period of time, for example, less than about 10 minutes.

[0044] The particles may also comprise other water-soluble carriers selected from inorganic alkali metal salts, inorganic alkaline earth metal salts, organic alkali metal salts, organic alkaline earth metal salts, carbohydrates and their derivatives, clays, zeolites, silica, silicates, citric acid and its salts, fatty alcohols, glycerol, diglycerides of hydrogenated tallow, water-soluble polymers, and combinations thereof.

[0045] Suitable inorganic alkali metal salts can be selected from the group consisting of sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, sodium bisulfate, sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium carbonate, sodium bicarbonate, sodium silicate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium sulfate, potassium bisulfate, potassium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, potassium carbonate, potassium monohydrogen carbonate, potassium silicate, and combinations thereof.

[0046] Suitable inorganic alkaline earth metal salts can be selected from the group consisting of magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium phosphate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium carbonate, magnesium monohydrogen carbonate, magnesium silicate, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium sulfate, calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium carbonate, calcium monohydrogen carbonate, calcium silicate, and combinations thereof.

[0047] Organic salts, such as organic alkali metal salts and organic alkaline earth metal salts, contain carbon.

[0048] Suitable organic alkali metal salts may be selected from the group consisting of sodium acetate, sodium citrate, sodium lactate, sodium tartrate, sodium ascorbate, sodium sorbate, potassium acetate, potassium citrate, potassium lactate, potassium tartrate, potassium ascorbate, potassium sorbate, and combinations thereof.

[0049] Suitable organic alkali metal salts may be selected from the group consisting of calcium acetate, calcium citrate, calcium lactate, calcium tartrate, calcium ascorbate, calcium sorbate, magnesium acetate, magnesium citrate, magnesium lactate, magnesium tartrate, magnesium ascorbate, magnesium sorbate, and combinations thereof.

[0050] The carbohydrate may be selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides, derivatives thereof, and combinations thereof.

[0051] Suitable monosaccharides may be selected from the group consisting of erythrose, ribose, arabinose, xylose, glucose, isoglucose, dextrose, galactose, mannose, erythrulose, ribulose, fructose, sorbose, rhamnose, fucose, deoxyribose, ribose, and combinations thereof.

[0052] Suitable disaccharides may be selected from the group consisting of sucrose, maltose, lactose, isomaltose, trehalose, cellobiose, melibiose, gentiobiose, and combinations thereof.

[0053] Suitable oligosaccharides may be selected from the group consisting of maltotriose, raffinose, stachyose and combinations thereof.

[0054] Preferably, the sugar is selected from the group consisting of fructose, glucose, isoglucose, galactose, raffinose and combinations thereof. More preferably, the sugar comprises or is sucrose.

[0055] Suitable polysaccharides can be selected from the group consisting of starch, corn starch, wheat starch, rice starch, potato starch, tapioca starch, modified starches, cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose esters, cellulose amides, glycogen, pectin, dextrin, maltodextrin, corn syrup solids, alginates, xyloglucans, xylans, glucuronoxylans, arabinoxylans, mannans, glucans, glucomannans, galactoglucomannans, xanthan gum, carrageenan, locust bean gum, gum arabic, gum tragacanth, and combinations thereof.

[0056] The carbohydrate derivative may be selected from the group consisting of amino sugars, deoxy sugars, sugar alcohols, sugar acids, and combinations thereof.

[0057] Suitable sugar alcohols can be selected from the group consisting of sorbitol, mannitol, isomalt, maltitol, lactitol, xylitol, erythritol and combinations thereof. Preferably, sugar alcohols are selected from the group consisting of mannitol, sorbitol, xylitol and combinations thereof. Sugar alcohol polyols are further described in detail in US11920111.

[0058] The water-soluble carrier may be selected from the group consisting of clay, zeolite, citric acid and its salts, fatty alcohols, diglycerides of hydrogenated tallow, and combinations thereof.

[0059] The water-soluble carrier can be a water-soluble polymer selected from the group consisting of polyvinyl alcohol (PVA), modified PVA; polyvinyl pyrrolidone; PVA copolymers, such as PVA / polyvinyl pyrrolidone and PVA / polyvinyl amine; partially hydrolyzed polyvinyl acetate; polyglycerol esters, acrylamide; polyvinyl acetate; polycarboxylic acids and their salts, sulfonated polyacrylates, polyamino acids or peptides, polyamides, polyacrylamides, maleic acid / acrylic acid copolymers, gelatin, and combinations thereof.

[0060] Some specific examples of suitable support materials may include combinations of the aforementioned. For example, the support material may comprise a mixture of a first weight percent polyethylene glycol; a second weight percent sodium bicarbonate; and a third weight percent sodium acetate trihydrate. In such a configuration, the first weight percent may be from about 30 to about 70, more preferably from about 40 to about 60, even more preferably from about 45 to about 58, or most preferably from about 52 to about 56.

[0061] The second weight percent may be from about 10 to about 30, more preferably from about 15 to about 25, and even more preferably from about 15 to about 20. It is worth noting that dissolution issues may arise when using higher percentages of sodium bicarbonate. For example, when hard water is used as part of the washing process, it is believed that a portion of the sodium carbonate may react with the hard water and form calcium carbonate. Because the calcium carbonate may not completely dissolve during the washing process, calcium carbonate flakes may appear on clothing, which may give consumers a negative impression of the particle's performance.

[0062] The third weight percent may be from about 10 to about 30, more preferably from about 15 to about 25, and even more preferably from about 15 to about 20. It is worth noting that discoloration and odor generation may occur when higher percentages of sodium acetate are used. It is believed that sodium acetate may degrade and form acetic acid. Acetic acid may cause discoloration of the particles and a sour taste to the particles. This may lead consumers to have a very negative impression of the performance of the particles, especially when the particles are advertised as providing a fragrant scent to clothing articles.

[0063] As another example, the support material may comprise polyethylene glycol, a block copolymer of ethylene oxide and propylene oxide, and a clay, such as bentonite and / or other organoclay materials.

[0064] As another example, the carrier material may comprise sodium chloride, propylene glycol, and sodium starch octenylsuccinate.

[0065] As another example, the support material may comprise sodium acetate, dipropylene glycol, cellulose, sodium hydroxide, and sodium acrylate copolymer.

[0066] As another example, the carrier material can include a modified polyethylene glycol as described herein and polyethylene glycol. The modified polyethylene glycol can have a higher molecular weight than the polyethylene glycol. Additionally, the modified polyethylene glycol can be present in a higher weight percentage than the polyethylene glycol.

[0067] As yet another example, the carrier material may comprise from about 45 to about 80%, preferably from about 50% to about 70%, preferably from about 50% to about 60% by weight of a sugar alcohol polyol selected from the group consisting of erythritol, xylitol, mannitol, isomalt, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof.

[0068] Fragrances / fragrances

[0069] The particles of the present disclosure may contain one or more fragrances / spices. At least a portion of the fragrances / spices may be provided in a plurality of capsules as described herein. Similarly, at least a portion of the fragrances / spices may be contained by a carrier outside the capsule. Regardless of whether the fragrances / spices are contained by a carrier or by a capsule, the fragrances / spices may be configured similarly. It is noteworthy that although the fragrances / spices contained by the carrier and the fragrances / spices contained by the plurality of capsules may be configured similarly, they may have different fragrances or different intensities. This paper further provides in detail the configuration of fragrances / spices suitable for use with the particles of the present disclosure.

[0070] capsule

[0071] The compositions of the present disclosure also include a plurality of capsules. As described in more detail below, the capsules can include a core surrounded by a shell, wherein the shell comprises a polymeric material that is the reaction product of chitosan and a cross-linking agent, wherein the cross-linking agent comprises an isocyanate component that comprises a mixture of two or more diisocyanates and / or polyisocyanates, each of which comprises an aromatic moiety; and wherein the mixture of diisocyanates and / or polyisocyanates comprising an aromatic moiety comprises at least one α-aromatic isocyanate and at least one β-aromatic isocyanate, optionally wherein each of the desired isocyanates is present at least 20 mole percent of the total isocyanate component.

[0072] The capsules may be present in the particles of the composition in an amount of from about 0.1% to about 20%, or from about 0.2% to about 10%, or from about 0.2% to about 5%, or from about 0.2% to about 3% by weight of the composition. The composition may contain a sufficient amount of capsules to provide the composition with from about 0.1% to about 20%, or from about 0.2% to about 10%, or from about 0.2% to about 5% of the fragrance raw material by weight of the composition. When discussing the amount or weight percentage of capsules herein, this refers to the sum of the shell material and the core material.

[0073] In order for capsules containing core materials to be functional and cost-effective in consumer product applications such as laundry care granular additives, they should: i) resist diffusion of the core during the shelf life of the liquid product (e.g., low leakage or permeability); ii) have the ability to deposit on a target surface during application (e.g., a washing machine cycle); and iii) be capable of releasing the core material by mechanical shell rupture at the appropriate time and place to provide the desired benefit to the end consumer.

[0074] i. core

[0075] The capsule comprises a core. The core may comprise a liquid or a solid. Preferably, the core comprises a liquid, which may be oil-based or aqueous. Preferably, in the finished product, the core comprises a liquid at room temperature.

[0076] The liquid includes fragrance. Based on the total weight of the liquid in the core, the liquid can contain from about 1% to 100% by weight of fragrance. Optionally, the liquid can contain from about 50% to 100% by weight of fragrance based on the total weight of the core, and optionally from 80% to 100% by weight of fragrance based on the total weight of the core. Generally, higher levels of fragrance are preferred to improve delivery efficiency.

[0077] A fragrance may comprise one or more, optionally two or more, fragrance raw materials. As used herein, the term "fragrance raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mol, and which can be used alone or in combination with other PRMs to impart an odor, aroma, flavor, or fragrance. Typical PRMs include, among others, alcohols, ketones, aldehydes, esters, ethers, nitriles, and alkenes, such as terpenes. Lists of common PRMs can be found in various references, for example, "Perfume and Flavor Chemistry," 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).

[0078] PRMs can be characterized by their boiling point (BP) measured at atmospheric pressure (760 mm Hg), and their octanol / water partition coefficient (P), which can be described in terms of logP, determined according to the test methods described in the Test Methods section. Based on these properties, PRMs can be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV PRMs, as described in detail below. A fragrance having multiple PRMs from different quadrants may be desirable, for example, to provide fragrance benefits at different contact points during normal use.

[0079] PRMs having a boiling point BP below about 250°C and a logP of less than about 3 are referred to as Quadrant I PRMs. Quadrant I PRMs are optionally limited to less than 30% of the fragrance composition. PRMs having a boiling point BP above about 250°C and a logP greater than about 3 are referred to as Quadrant IV PRMs, PRMs having a boiling point BP above about 250°C and a logP less than about 3 are referred to as Quadrant II PRMs, and PRMs having a boiling point BP below about 250°C and a logP greater than about 3 are referred to as Quadrant III PRMs. Suitable Quadrant I, II, III, and IV PRMs are disclosed in U.S. Patent No. 6,869,923 Bl.

[0080] A fragrance may contain a mixture of at least 3, or even at least 5, or at least 7 PRMs. A fragrance may contain at least 10 or at least 15 PRMs. A mixture of PRMs may provide, for example, a more complex and desirable aroma at multiple contact points, and / or better fragrance performance or longevity. However, it may be desirable to limit the number of PRMs in a fragrance to reduce or limit formulation complexity and / or cost.

[0081] The fragrance may comprise at least one fragrance raw material of natural origin (e.g., plant origin). Such components may be desirable for sustainability / environmental reasons. Naturally derived PRMs may include natural extracts or essences, which may include mixtures of PRMs. Such natural extracts or essential oils may include orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essences, sandalwood oil, pine oil, cedar, and the like. The PRM can be selected from the group consisting of almond oil, ambrette, angelica seed oil, artemisia oil, fragrant basil oil, benzoin extract, bergamot essential oil, bergamot oil, black pepper oil, black pepper essence, black currant essence, blood orange oil, bois des landes, brandy pure jungle essence, juniper, Roman chamomile, cardamom pulp extract, cardamom oil, carrot heart, caryophyllene extra, cedar, cedar leaf, cedar oil, Ceylon cinnamon bark, Ceylon cinnamon extract, beeswax, citronella, citronellal, clary sage essential oil, fractionated clove leaf oil, copaiba balsam, coriander, cos anethol, cos cos essence coriander russ ie), cucumber extract, fennel oil, cyperus heart, elemi heart, elemi oil, English white chamomile, cineole, lemon eucalyptus, eugenol, guava balsam heart, ginger, grapefruit alternative, guaiac oil, bitter rue oil, guaiac wood extract, helichrysum, isoeugenol, jasmine, juniper berry oil, lime, rock rose, lavender oil, lavender, lavender essential oil, lemon cedar, lemon oil, green lemon peel, lemongrass, lemongrass oil, litsea cubeba, magnolia oil, yellow mandarin Tangerine oil, crystallized menthol, peppermint pepper leaf, narcissus, neroli oil, nutmeg, orange blossom water, orange oil, orange phase oil, organic rose water, osmanthus, patchouli, patchouli heart, patchouli oil, black pepper oil, mint, pure peru balsam, petitgrain, allspice oil, pink peppercorns, raspberry essence, rose alcohol, rose, centifolia rose, sandalwood, Sichuan peppercorn extract, white benzoin, sweet orange oil, tangerine oil, vanilla, vetiver, violet leaf, violet leaf, wormwood oil, and combinations thereof.

[0082] In addition to the PRM, the core may also include a pro-flavor, which may help improve the persistence of the freshness benefit. The pro-flavor may comprise a non-volatile material that is released or converted into a fragrance material, such as by simple hydrolysis, or may be a pro-flavor triggered by a pH change (e.g., triggered by a drop in pH), or may be an enzyme-released pro-flavor, or a light-triggered pro-flavor, or an oxidation-triggered pro-flavor. Depending on the pro-flavor selected, the pro-flavor may exhibit different release rates.

[0083] The core of the encapsulate of the present disclosure may contain a core modifier, such as a distribution modifier and / or a density modifier. In addition to the flavor, the core may also contain from greater than 0% to 80%, optionally from greater than 0% to 50%, optionally from greater than 0% to 30% of a core modifier based on the total core weight. The distribution modifier may comprise a material selected from the group consisting of vegetable oils, modified vegetable oils, C4-C 24 Monoesters, diesters, and triesters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partition modifier may optionally include or consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may optionally contain castor oil and / or soybean oil. U.S. Patent Application Publication No. 20110268802, incorporated herein by reference, describes other partition modifiers that can be used in the fragrance encapsulates of the present invention.

[0084] ii. Shell

[0085] The capsules of the present disclosure include a shell surrounding the core. The shell may include or may be a polymeric material comprising a reaction product of a cross-linking agent from an oil phase and chitosan derived from an aqueous phase. The cross-linking agent comprises a mixture of two or more diisocyanates and / or polyisocyanates derived from the oil phase, each of which contains an aromatic moiety. Surprisingly, it has been discovered that leakage can be controlled based on two isocyanates, each containing at least one aromatic moiety, which, when combined with chitosan, produces low-leakage capsules in different matrices and supports to a degree that has not been achieved with degradable constructs to date. More specifically, the cross-linking agent comprises an isocyanate component, wherein the isocyanate component comprises a mixture of two or more diisocyanates and / or polyisocyanates derived from the oil phase, each of which contains an aromatic moiety; and each isocyanate is independently selected from the group consisting of α-aromatic isocyanates and β-aromatic isocyanates. In embodiments, the mixture of diisocyanates and / or polyisocyanates may comprise at least one alpha isocyanate and at least one beta isocyanate.

[0086] Surprisingly, enhanced performance in terms of lower leakage and retention of the core material in the carrier material can be achieved, wherein the weighted %NCO of the aromatic isocyanate of the isocyanate component is 15% to 32% by weight, or even 20% to 26%, or even 20% to 25%, or even 21% to 25% by weight. The mass percentage of the α-aromatic isocyanate in the isocyanate component can be 1% to 99% by weight, optionally 5% to 90% by weight, or optionally 30% to 60% by weight. The mass percentage of the β-aromatic isocyanate in the isocyanate component is 1% to 99% by weight, optionally 5% to 10% by weight, or optionally 70% to 40% by weight. The isocyanate component has a ratio of α-aromatic isocyanate to β-aromatic isocyanate of 20% to 50% by weight, optionally 25% to 40% by weight, or optionally 30% to 35% by weight.

[0087] In addition to the composition, a method for preparing the composition is disclosed. The composition is a core-shell capsule population. The core comprises a beneficial agent, and the shell comprises a polymeric material that is the reaction product of a crosslinking agent of at least two isocyanate monomers, oligomers, or prepolymers and chitosan. The method for preparing the capsule comprises the following steps:

[0088] forming an aqueous phase in which chitosan is dissolved or dispersed in water. Optionally, prior to capsule shell formation, the chitosan may be pretreated with one or more reducing initiators such as persulfates or with one or more acids at a pH of from pH 3 to pH 6.5, or even at a pH of from 4 to 6.5, at a temperature of at least 25° C. for at least one hour or to a viscosity of less than 1500 centipoise (cp) and optionally less than 500 cp to form treated chitosan; and

[0089] forming an oil phase comprising dissolving together at least one benefit agent and an isocyanate component comprising at least two isocyanates having aromatic moieties, wherein the weighted % NCO of the aromatic isocyanates of the isocyanate component is from 15% to 32% by weight, or even from 20% to 26%, or even from 20% to 25%, or even from 21% to 25% by weight; and

[0090] forming an emulsion by mixing the aqueous phase and the oil phase into an excess of the aqueous phase under high shear agitation, thereby forming droplets of the oil phase dispersed in the aqueous phase, and optionally adjusting the pH of the emulsion to within the range of pH 3 to pH 6; and

[0091] The emulsion is solidified by heating to at least 40°C for a time sufficient to form a shell at the interface of the droplet with the aqueous phase, the shell comprising the reaction product of the cross-linking component and chitosan, and surrounding the core of the droplet comprising the oil phase. Optionally, the chitosan can be treated chitosan. The droplets of the oil phase contain the beneficial agent, either because the beneficial agent is itself an oil or is soluble in the added oil or is soluble in the cross-linking agent.

[0092] In some specific examples, at least 21% by weight of the shell comprises chitosan. In embodiments, the isocyanate component comprises methylene diphenyl isocyanate and xylylene diisocyanate in a weight ratio of 1:2 to 1:1.75. In embodiments, the isocyanate component comprises 30% to 40% methylene diphenyl isocyanate and 60% to 70% xylylene diisocyanate by weight.

[0093] The capsule may comprise a core material and a shell encapsulating the core material. The core material may comprise a beneficial agent. The shell comprises a polymeric material that is the reaction product of chitosan derived from the aqueous phase and a cross-linking agent comprising an isocyanate component, wherein the isocyanate component comprises a mixture of two or more diisocyanates and / or polyisocyanates derived from the oil phase, each of the diisocyanates and / or polyisocyanates comprising an aromatic moiety. The isocyanate is a diisocyanate, a triisocyanate, or a mixture of a diisocyanate and a triisocyanate.

[0094] Controlling leakage into matrix and carrier in the presence of water is challenging. In the presence of water, the storage stability of the product in terms of low leakage into the carrier or matrix is ​​important for maintaining the ability of delivering benefit agents such as fragrances at the required contact point. The benefit agent that leaks into the matrix or carrier too early is less available at the desired contact point later. Encapsulation is used to retain the benefit agent to increase the product shelf life. In some articles, such as treatment compositions for fabrics and textiles, it is desired to retain the benefit agent for expression at the later contact point, such as after washing, in the drying cycle, or during wearing. The benefit agent that leaks is usually not available for the expression of expectation in this type of later stage. Although this type of expression is extremely sought after, it is still difficult to successfully achieve. Surprisingly, it has been found that leakage can be controlled according to two isocyanates, each isocyanate comprising an aromatic moiety, which, when combined with chitosan, produces low leakage capsules in different matrices and carriers, reaching a degree that has been unattainable so far with degradable constructs.

[0095] Low leakage can be achieved by carefully selecting a mixture of diisocyanates and / or polyisocyanates comprising alpha isocyanates or beta isocyanates, especially those combinations comprising at least one alpha isocyanate and at least one beta isocyanate. In embodiments, surprisingly low leakage into the carrier material is observed when the weighted % NCO of the aromatic isocyanates of the isocyanate component is 15% to 32%, or even 20% to 26%, or even 20% to 25%, or even 21% to 25% by weight. In particular, the composition can comprise an isocyanate component comprising alpha-aromatic isocyanates and / or beta-aromatic isocyanates. The alpha-aromatic isocyanates are selected from the group consisting of:

[0096] wherein R is a biuret, a uretdione, an isocyanurate, a polyol having pendant carbamate groups, a polyamine having pendant urea groups, a polyacid having anhydride groups, a biuret-containing polyisocyanate, a uretdione-containing polyisocyanate, or an isocyanurate-containing polyisocyanate.

[0097] R in structures I, II, III, IV, XII, and XIII, for example, comprises a moiety having at least two or more functional groups that are linked to a corresponding diisocyanate or triisocyanate. R in structures I, II, III, IV, XII, and XIII, for example, can comprise a polyol; or a polyol having one or more pendant carbamate groups; or a polyamine, such as a polyamine having one or more pendant urea groups or other linking groups; a polyacid having anhydrous groups; a polyisocyanate comprising a biuret; a polyisocyanate comprising a uretdione; or a polyisocyanate comprising an isocyanurate. In structures I, II, III, IV, XII, and XIII, for example, the R moiety comprises at least two or more functional groups that are linked to a corresponding diisocyanate or triisocyanate.

[0098] The aromatic isocyanates of formulae I-XVI are based on derivative modifications of commonly commercially available isocyanates, such as xylylene diisocyanate (XDI), toluene diisocyanate (TDI), and methylene diphenyl diisocyanate (MDI).

[0099] The aromatic isocyanates selected above are generally commercially available. For example, Covestro, Leverkusen, Germany is a supplier of polyisocyanates and prepolymers under the trademark Desmodur. Polyisocyanates conforming to structures I-XVI disclosed herein are available under the trademark Desmodur E for isocyanates and prepolymers and / or may also be synthetically derived. Optionally, aromatic isocyanates are also commercially available from sources such as Mitsui Chemicals, Inc., Tokyo, Japan, such as isocyanates under the trademark Takenate, for example, Takenate D-110N adduct based on xylylene diisocyanate.

[0100] Specific examples of usable α-aromatic isocyanates may be selected from the following group:

[0101]

[0102] wherein n is an integer from 1 to 24, optionally from 1 to 18, or even from 1 to 12, or even from 1 to 8,

[0103]

[0104]

[0105] Useful β-aromatic isocyanates may be selected from the following group:

[0106]

[0107]

[0108] wherein R is a polyol having pendant carbamate groups, a polyamine having pendant urea groups, a polyacid having anhydrous groups, a polyisocyanate containing biuret, a polyisocyanate containing uretdione, or a polyisocyanate containing isocyanurate.

[0109] The α-aromatic isocyanate may also be selected from the group consisting of toluene diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, isomers thereof, adducts thereof, and combinations thereof, and is optionally selected from methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, isomers thereof, adducts thereof, and combinations thereof. Specific examples of useful β-aromatic isocyanates may be selected from the group consisting of:

[0110]

[0111]

[0112] The β-aromatic isocyanate may also be selected from the group consisting of xylylene diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, tetramethylxylylene diisocyanate, isomers thereof, adducts thereof, and combinations thereof.

[0113] The present disclosure relates to a treatment composition comprising a capsule having a shell made at least in part from a chitosan-based material. Specifically, the capsule includes a shell comprising the reaction product of chitosan and a cross-linking agent. The cross-linking agent comprises an isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates derived from an oil phase, each of the diisocyanates and / or polyisocyanates containing an aromatic moiety. The isocyanate component may comprise at least two diisocyanates and / or polyisocyanates selected from methylene diphenyl diisocyanate and xylylene diisocyanate. In an embodiment, the xylylene diisocyanate comprises a trimethylolpropane adduct of xylylene diisocyanate, and the methylene diphenyl diisocyanate may be selected from 2,2'-methylene diphenyl diisocyanate and 4,4'-methylene diphenyl diisocyanate. Optionally, the weight ratio of the isocyanate component is from 1:2 to 1:1.75. Ideally, the isocyanate component comprises 30% to 40% by weight of methylene diphenyl diisocyanate and 60% to 70% by weight of xylylene diisocyanate. Usefully, the isocyanate component comprises about 34% by weight of methylene diphenyl diisocyanate and about 66% by weight of xylylene diisocyanate. Within this isocyanate range or ratio, chitosan combined with the isocyanate component is surprisingly able to effectively deliver the beneficial agent at the desired contact point. Due to the combination of the two isocyanates with the chitosan, leakage into the matrix component and / or the carrier is surprisingly reduced. The mixture of isocyanates having an aromatic moiety can, for example, comprise a trimer of xylylene diisocyanate (XDI) or an oligomer or prepolymer of methylene diphenyl diisocyanate (MDI).

[0114] Optionally, prior to shell formation, the chitosan used to prepare the particle shell may be treated with an acid or even a mixture of acids, such as described in U.S. Serial No. 63,429,232 filed December 1, 2022, or with a redox initiator (optionally a persulfate), such as described in U.S. Serial No. 63,429,240 filed December 1, 2022, which are incorporated herein by reference. The redox initiator is selected from any of persulfates or peroxides. Optionally, the redox initiator is selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, cesium persulfate, benzoyl peroxide, hydrogen peroxide, and mixtures thereof.

[0115] Typically, when chitosan is dissolved in water, for example during the preparation of capsules, the resulting mixture tends to be very viscous. This can lead to flowability and processing challenges and / or inhibit the full formation of the capsule shell. Acid treatment has been described in U.S. Serial No. 63,429,232 to reduce mixture viscosity and improve shell structure. Furthermore, it is believed that acid treatment of chitosan can beneficially affect the molecular weight of the chitosan, thereby improving shell formation and / or delivery performance.

[0116] The capsule has a shell at least partially made of a chitosan-based material. Specifically, the capsule includes a shell comprising a reaction product of chitosan and an isocyanate component.

[0117] Without wishing to be bound by theory, it is believed that careful selection of chitosan and isocyanate combinations within the disclosed weight ratios can contribute to surprisingly long shelf-life compositions containing capsules. For example, the disclosed selection of isocyanate components can result in capsules that perform better at certain contact points. It is believed that the disclosed combinations of isocyanates produce capsules with higher density. The surprising effect of reduced leakage is believed to be due not only to the density of the polymeric material, but also to the presence of aromatic moieties and the reactive sites of the isocyanate components.

[0118] In addition, chitosan often presents processing challenges in aqueous environments, particularly its viscosity. Viscosity can affect the fluidity of the solution and / or inhibit the full formation of the particle wall. Optionally, treatment with acid can help reduce the viscosity of the solution. Without wishing to be bound by theory, it is believed that careful selection of the molecular weight of the chitosan can be advantageous. For example, selecting chitosan with a molecular weight above a certain threshold can produce capsules that perform better at certain contact points than particles made from chitosan of lower molecular weight. Surprisingly, treatment with acid can produce chitosan at a concentration of 3.5% (typically with a starting viscosity of about 4000 cP) that shows a 60% or even greater reduction in viscosity compared to untreated chitosan, reaching a viscosity of 1500 cP or even 1000 cP at the same concentration.

[0119] Disclosed are compositions comprising core-shell encapsulates (also referred to as capsules), including methods for preparing such encapsulates or capsules. The core comprises a beneficial agent, optionally a fragrance, and the shell may comprise, for example, a polyurea resin polymer material, the reaction product of a cross-linking agent comprising a mixture of two or more diisocyanates and / or polyisocyanates derived from an oil phase, each of which comprises an aromatic moiety. When forming the composition, chitosan is dissolved or dispersed in an aqueous phase and optionally treated with an acid, optionally at a pH of 3 to about 6.5. At a pH of 6.5 or less, or even less than pH 6.0, or even at a pH of 3 to 6, or even at a pH of 3.5 to 6, or even at a pH of 4 to 6, and at a temperature of at least 25°C, the chitosan is treated with an acid for at least one hour. Typically, the treatment step can be measured as the period of time to obtain a chitosan solution having a viscosity of 1500 centipoise (cp) or less and optionally less than 500 cp.

[0120] Chitosan is characterized in that weight average molecular weight is about 100kDa to about 80,000kDa, or even 100kDa to about 600kDa. Optionally, chitosan is characterized in that weight average molecular weight (Mw) of about 100kDa to about 500kDa, optionally about 100kDa to about 400kDa, optionally about 100kDa to about 300kDa, optionally about 100kDa to about 200kDa. The method for determining chitosan molecular weight and related parameters is provided in the test method part below, and uses the gel permeation chromatography with multi-angle light scattering and refractive index detection (GPC-MALS / RI) technology. The chitosan with preferred weight average molecular weight is selected to produce the capsule with suitable shell formation and / or desired processability. For the sake of clarity, the chitosan weight average molecular weight is measured before processing, such as with acid and / or redox initiator as described herein.

[0121] The ratio of isocyanate component crosslinker to chitosan is from 79:21 to 10:90, or even from 2:1 to 1:10, or even from 1:1 to 1:7, based on weight.

[0122] The crosslinking agent of the composition optionally may comprise an additional polyisocyanate in addition to the mixture of two or more diisocyanates or polyisocyanates.The additional crosslinking agent may be an aliphatic or aromatic monomer, oligomer or prepolymer, usefully having two or more isocyanate functional groups. Additional crosslinkers of the isocyanate type can be chosen, for example, from aromatic toluene diisocyanate and its derivatives for capsule wall formation, or aliphatic monomers, oligomers or prepolymers, such as hexamethylene diisocyanate and its dimers or trimers, or 3,3,5-trimethyl-5-isocyanatomethyl-1-isocyanatocyclohexane tetramethylene diisocyanate, polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of toluene diisocyanate, toluene diisocyanate, tetramethylxylylene diisocyanate, naphthalene-1,5-diisocyanate, phenylene diisocyanate, 1,3-diisocyanato-2-methylbenzene, hydrogenated MDI, bis(4-isocyanatocyclohexyl)methane, dicyclohexylmethane-4,4′-diisocyanate and oligomers and prepolymers thereof. The additional isocyanates that can be used include isocyanate monomers, oligomers or prepolymers, or dimers or trimers thereof, having at least two isocyanate groups. Using isocyanates with at least three functional groups can achieve optimal crosslinking. This list is illustrative, not restrictive. Additional crosslinking agents of isocyanate types can be formed by adducts of polyisocyanates. Adducts are products of a molecule with itself and / or with another molecule. In the case of polyisocyanate and its own adducts, the isocyanate moieties of the polyisocyanate molecules can react with each other to form a larger polyisocyanate product containing biuret, uretdione and / or isocyanurate moieties. In the case of polyol adducts of polyisocyanates, the isocyanate moieties of the polyisocyanate molecules can react with the hydroxyl moieties of the polyols to form a larger polyisocyanate product containing a carbamate moiety. In the case of polyamine adducts of polyisocyanates, the isocyanate moieties of the polyisocyanate molecules can react with the amine moieties of the polyamines to form a larger polyisocyanate product containing a urea moiety. In the case of a polyacid adduct of a polyisocyanate, the isocyanate portion of the polyisocyanate molecule can react with the carboxyl portion of the polyacid to form a larger polyisocyanate product containing an anhydride portion, wherein a polyisocyanate is a molecule containing two or more isocyanate moieties.

[0123] When formulated as described herein, the shell degrades by at least 40%, or even at least 60%, of its mass after at least 60 days when tested according to test method OECD 301 B.

[0124] The core-shell encapsulate has a core to shell ratio of at least 75:25, or 85:15, or 90:10, or even up to 99:1, or even at least 99.5:0.5, based on weight. The shell may comprise 1% to 25% by weight of the core-shell encapsulate.

[0125] To produce capsules as described herein, an aqueous phase is prepared comprising an aqueous solution or dispersion of an amine-containing natural material having free amino moieties. The amine-containing natural material is a bio-based material. Examples of such materials include chitosan. The amine-containing natural material is dispersed in water. In the case of chitosan, in embodiments, the material can even be hydrolyzed, thereby protonating at least a portion of the amine groups and promoting dissolution in water. The hydrolysis is performed by heating at an acidic pH, such as about 3 to about 6.5, or even about 5 or 5.5, for a period of time.

[0126] The oil phase is prepared by dissolving the isocyanate component in oil at 25°C. A diluent, such as isopropyl myristate, can be used to adjust the hydrophilicity of the oil phase. The oil phase is then added to the aqueous phase and milled at high speed to achieve the target size. The emulsion is then cured in one or more heating steps, such as heating to 40°C over 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 solidify the shell at the interface of the oil phase droplets and the aqueous continuous phase. For example, the emulsion is heated to 85°C over 60 minutes and then held at 85°C for 360 minutes to solidify the capsules. The slurry is then cooled to room temperature.

[0127] The volume weighted median particle size of the capsules may be in the range of 5 microns to 150 microns, or even 10 microns to 50 microns, optionally 15 microns to 50 microns.

[0128] The crosslinking agent may be a mixture of difunctional or polyfunctional isocyanates. When referring to useful crosslinking agents, for the purposes of this document, reference to polyisocyanates should be understood to include isocyanate monomers, isocyanate oligomers, isocyanate prepolymers, or dimers or trimers of aliphatic or aromatic isocyanates. All such monomers, prepolymers, oligomers, or dimers or trimers of aliphatic or aromatic isocyanates are intended by the term "polyisocyanate" as used herein.

[0129] Additional co-crosslinkers such as multifunctional amines and / or polyamines such as diethylenetriamine (DETA), polyethyleneimine, and polyethyleneamine may also be used to strengthen the capsule shell.

[0130] Additional co-crosslinkers such as multifunctional amines and / or polyamines such as diethylenetriamine (DETA), polyethyleneimine, polyvinylamine or mixtures thereof may also be used to strengthen the shell. Acrylates may also be used as additional co-crosslinkers, for example to strengthen the shell.

[0131] The polymeric material can be formed in a reaction wherein the weight ratio of chitosan present in the reaction to the cross-linking agent 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 cross-linking agent can provide the desired ductility benefits as well as improved biodegradability. Preferably, at least 21% by weight of the shell is composed of moieties derived from chitosan, optionally derived from acid-treated chitosan. The weight percentage of chitosan in the shell can be from about 21% to about 95% of the shell. The ratio of chitosan in the aqueous phase to isocyanate in the oil phase can be from 21:79 to 90:10, or even from 1:2 to 10:1, or even from 1:1 to 7:1, based on weight. The shell can comprise chitosan at a level of 21% or even higher, optionally from about 21% to about 90%, or even from 21% to 85%, or even from 21% to 75%, or from 21% to 55%, of the total chitosan shell. The chitosan of this paragraph may optionally be acid treated chitosan or chitosan treated with a redox initiator such as persulfate, or both.

[0132] Chitosan can be added to water in a jacketed reactor and optionally pretreated with one or two redox initiators, or at a pH of 3 to 6.5, using an acid (such as one or more of HCl, formic acid, or acetic acid). The optional pretreatment step can be accomplished by heating to an elevated temperature (such as 85°C) over 60 minutes and then maintaining the temperature for 1 minute to 1440 minutes or longer. The aqueous phase can then be cooled to 25°C. Optionally, a deacetylation step can be added to further promote or enhance the depolymerization or deacetylation of the chitosan, such as by enzymes. The oil phase is prepared by dissolving a mixture of isocyanates containing aromatic moieties in oil at 25°C. A diluent, such as isopropyl myristate, can be used to adjust the hydrophobicity of the oil phase. The oil phase can then be added to the aqueous phase and milled at high speed to achieve the target size. The emulsion can then be solidified in one or more heating steps, such as heating to 40°C over 30 minutes and maintaining it at 40°C for 60 minutes. The times and temperatures are approximate. The temperature and time are selected to be sufficient to form and solidify the shell at the interface of the droplets of the oil phase and the continuous aqueous phase. For example, the emulsion can be heated to 85°C over 60 minutes and then held at 85°C for 360 minutes to solidify the particles. The slurry can then be cooled to room temperature.

[0133] When tested according to test method OECD 301B, the shell may degrade by at least 50% after 20 days (or less). When tested according to test method OECD 301B, the shell may degrade by at least 60% of its mass after 60 days (or less). When tested according to test method OECD 301B, the shell may optionally degrade by at least 60% of its mass after 60 days (or less). The shell may degrade by 30% to 100%, optionally 40% to 100%, 50% to 100%, 60% to 100%, or 60% to 95% after 60 days, optionally 50 days, optionally 40 days, optionally 28 days, or optionally 14 days.

[0134] Method for treating clothing

[0135] The method for treating clothing may include the steps of providing an article of clothing in a washing machine; dispensing a composition comprising a plurality of particles into the washing machine; and contacting the article of clothing with the composition during a wash cycle of the washing machine. The washing machine may have a wash cycle and a rinse cycle. From about 5 g to about 50 g of the particle composition may be dispensed into the washing machine.

[0136] By providing a fragrance benefit via the wash sub-cycle, the consumer need only dose the detergent composition and the composition comprising a plurality of particles into a single location, such as a wash tub, before or shortly after the washing machine is started. This may be more convenient for the consumer than using a rinse-added composition that is separately dispensed into the wash tub after the wash sub-cycle is completed, such as before, during, or between rinse cycles. Using the automatic dispensing features of modern vertical and high-efficiency machines may be inconvenient because it requires dispensing the rinse-added composition into a location other than where the detergent composition is dispensed.

[0137] Optionally, the method may further include the step of contacting the clothing item with a detergent composition during a wash sub-cycle of the washing machine, the detergent composition comprising from about 3% to about 60%, optionally from about 3% to about 40%, by weight of an anionic surfactant. The anionic surfactant may be selected from sulfates, sulfonates, carboxylates, and mixtures thereof. The detergent composition is distinct from the particles. The detergent composition may optionally be provided separately from the particles. The detergent composition may be dispensed separately from the composition comprising the plurality of particles.

[0138] A washing machine has at least two basic sub-cycles within its operating cycle: a wash sub-cycle and a rinse sub-cycle. The wash sub-cycle of a washing machine is the cycle that begins when water is first added or partially added to fill the washtub. The main purpose of the wash sub-cycle is to remove and / or loosen soil from the clothing items and to suspend the soil in the wash liquid. Typically, the wash liquid is drained at the end of the wash sub-cycle. The rinse sub-cycle of a washing machine occurs after the wash sub-cycle and has the main purpose of rinsing away soil and, optionally, some benefit agents brought to the wash sub-cycle by the clothing items.

[0139] The method may optionally include a step of contacting the clothing items with a detergent composition comprising an anionic surfactant during the wash sub-cycle. Most consumers provide the detergent composition to the wash tub during the wash sub-cycle. The detergent composition may comprise anionic surfactants and optional other benefit agents, including but not limited to spices, bleaching agents, whitening agents, hueing dyes, enzymes, etc. During the wash sub-cycle, the benefit agent provided with the detergent composition contacts the clothing items placed in the wash tub or is applied to the clothing items. Typically, the benefit agent of the detergent composition is dispersed in a wash liquid of water and benefit agent.

[0140] During the washing sub-cycle, the washtub can be filled with water or at least partially filled. The individual particles of the composition can be dissolved or dispersed in water to form a wash liquid comprising a particle component. Optionally, if a detergent composition is used, the wash liquid can include components of the detergent composition and components of the particles. Before the clothing item is placed in the washtub of the washing machine, a plurality of particles can be placed in the washtub of the washing machine. After the clothing item is placed in the washtub of the washing machine, a plurality of particles can be placed in the washtub of the washing machine. A plurality of particles can be placed in the washtub before filling or partially filling the washtub with water or after filling the washtub with water has begun.

[0141] If the consumer uses detergent composition to implement the method for processing clothing products, the detergent composition and the particles of the composition can be provided by separate packaging. For example, the detergent composition can be the liquid detergent composition provided from the bottle, pouch, water-soluble pouch, measuring cup, quantitative ball or barrel associated with the washing machine. The particles of the composition can be provided by separate packaging, provided by a carton, bottle, water-soluble pouch, measuring cup, pouch etc. in a non-limiting example manner. If the detergent composition is a solid form such as powder, water-soluble fiber substrate, water-soluble sheet, water-soluble film, water-soluble film, the water-insoluble fiber web carrying the solid detergent composition, the particles of the composition can have a solid form detergent composition. For example, the particles of the composition can be provided by a container comprising a mixture of the particles of the solid detergent composition and the composition. Optionally, the particles of the composition can be provided by a pouch, which is formed by the detergent composition, and the detergent composition is a water-soluble fiber substrate, water-soluble sheet, water-soluble film, water-soluble film, the water-insoluble fiber web carrying the solid detergent composition.

[0142] Method for forming particles

[0143] Granules of the composition can be prepared by a multi-step process. Granules can be formed by tableting or melt processing. A melt composition can be prepared containing from about 25% to about 99% by weight of a water-soluble carrier and from about 0.1% to about 20% by weight of a capsule.

[0144] By using the particle manufacturing device 1 ( Figure 1 ) to form particles of the composition. The molten composition 20 can be prepared in a batch mixer 10 or a continuous mixer 10, or by manually mixing the component materials on a work surface. When the carrier is a water-soluble polymer, the water-soluble polymer can be heated to a temperature above the onset of melting of the water-soluble polymer and below the flash point or boiling point of the encapsulated fragrance.

[0145] The molten composition 20 comprising the water-soluble carrier and the capsules can be passed through one or more orifices 60 and deposited as an extrudate or as droplets onto a moving conveyor 80. The mixture can optionally be deposited into a recessed portion of a mold and cooled or allowed to cool so that the mixture solidifies into granules 90. The granules can be removed from the recessed portion of the mold to produce a finished product. A plurality of orifices can be provided in the distributor 30. The molten composition 20 can be delivered to the distributor via a feed tube 40. Optionally, a mixer 50, such as a static mixer 55, can be provided in line with the feed tube 40. Optionally, the feed tube 40 can be insulated or provided with a heating jacket.

[0146] Optionally, granules 90 can be formed by passing a mixture comprising a water-soluble carrier and capsules through one or more orifices 60 of a dispenser and depositing the mixture on a moving conveyor 80 below the one or more orifices 60. The mixture can solidify to form granules 90. The mixture can be deposited on the moving conveyor 80 as an extrudate, and the extrudate can be cut to form granules 90. Alternatively, the mixture can pass through the one or more orifices 60 to form droplets on the moving conveyor 80, and the droplets can solidify to form granules 90.

[0147] Optionally, a gas feed pipe may be included upstream of the distributor 30 to include gas in the molten composition. Downstream of the gas feed pipe, the molten composition 30 may be ground to destroy bubbles so that the melt is a melt with entrained gas. The particles formed by the melt with entrained gas may include bubbles. The gas feed pipe and the grinder may be an integrated unit, such as, for example, an OAKES bubbler (OAKES Corporation, 686 Old Willets Path, Hauppauge, NY 11788) 2MT1A continuous bubbler. Optionally, gas may be entrained into the molten composition 20 by mixing a gas generating material in the molten composition 20.

[0148] particles

[0149] The particles may each have a mass of about 1 mg to about 500 mg, alternatively about 5 mg to about 500 mg, alternatively about 5 mg to about 200 mg, alternatively about 10 mg to about 100 mg, alternatively about 20 mg to about 50 mg, alternatively about 35 mg to about 45 mg, alternatively about 38 mg. An individual particle may have a diameter of about 0.003 cm 3 to about 5cm 3 , optionally about 0.003 cm 3 to about 1cm 3 , optionally about 0.003 cm 3 to about 0.5cm 3 , optionally about 0.003 cm 3 to about 0.2cm 3 , optionally about 0.003 cm 3 to about 0.15cm 3 The composition may contain less than 10% by weight of particles having an individual mass of less than about 10 mg. This may reduce the likelihood of dusting.

[0150] In any disclosed embodiment or combination, the particles disclosed herein can have a shape selected from the group consisting of a sphere, a hemisphere, an oblate spheroid, a cylinder, a polyhedron, and an oblate hemispheroid. The particles can be hemispherical, a compressed hemispherical, or have at least one substantially flat or planar surface. Such particles can have a relatively high surface area to mass ratio compared to spherical particles. Dissolution time in water can decrease as surface area increases, with shorter dissolution times being preferred over longer dissolution times.

[0151] The particles disclosed herein may have a ratio of maximum dimension to minimum dimension of about 10:1, optionally about 8:1, optionally about 5:1, optionally about 3:1, optionally about 2:1. The particles disclosed herein may be shaped such that the particles are not flakes. Particles having a ratio of maximum dimension to minimum dimension greater than about 10 or flakes may tend to be brittle, making the particles prone to becoming dusty. The brittleness of the particles tends to decrease as the value of the ratio of maximum dimension to minimum dimension decreases.

[0152] The particles may comprise less than about 20% by weight of anionic surfactants, optionally less than about 10% by weight of anionic surfactants, optionally less than about 5% by weight of anionic surfactants, optionally less than about 3% by weight of anionic surfactants, optionally less than about 1% by weight of anionic surfactants. The particles may comprise from 0% to about 20% by weight, optionally from 0% to about 10%, optionally from about 0% to about 5%, optionally from about 0% to about 3%, optionally from about 0% to about 1% of anionic surfactants.

[0153] The granules may comprise less than about 10% by weight water.

[0154] The particles may contain gas bubbles. The gas bubbles may be spherical. Because the particles may contain gas bubbles entrained therein, the density of the particles may be less than the density or weighted average density of the constituent solid and / or liquid materials forming the particles. It may be advantageous for the particles including gas bubbles to contain an antioxidant because the gas bubbles may assist in oxidation reactions within the particles. Each particle may have a particle size of less than about 1 g / cm 3 Optionally, the particles may each have a density of less than about 0.98 g / cm 3 Optionally, the particles may each have a density of less than about 0.95 g / cm 3 Since the density of a typical washing solution is about 1 g / cm 3 , it may be desirable to provide each having less than about 1 g / cm 3 , or even less than about 0.95 g / cm 3 Each having a density of less than about 1 g / cm 3A density of particles of 1000 Å may be desirable to provide particles 90 that float in the wash liquid.

[0155] Each particle may have a certain volume, and the gas occlusions within the particle 90 may occupy from about 0.5% to about 50% of the volume of the particle, or even from about 1% to about 20% of the volume of the particle, or even from about 2% to about 15% of the volume of the particle, or even from about 4% to about 12% of the volume of the particle. Without being bound by theory, it is believed that if the volume of the gas occlusions is too large, the particle may not be strong enough and may break in an undesirable manner during packaging, transportation, storage, and use of the particle.

[0156] The occluded material can have an effective diameter of between about 1 micron and about 2000 microns, or even between about 5 microns and about 1000 microns, or even between about 5 microns and about 200 microns, or even between about 25 microns and about 50 microns. Generally speaking, it is believed that smaller gas occluded materials are more desirable than larger gas occluded materials. If the effective diameter of the gas occluded material is too large, it is believed that the particles may not be strong enough and may break in an undesirable manner when the particles are packaged, transported, stored, and used. The effective diameter is the diameter of a sphere having the same volume as the gas occluded material. The gas occluded material can be spherical.

[0157] Package

[0158] The compositions described herein can be provided in any suitable packaging. For example, plastic bottles can be used. In such configurations, preferably, the plastic can be recycled via a desired plastic recycling stream. For example, the container can comprise one or more plastic materials including polyethylene terephthalate, high-density polyethylene, low-density polyethylene, polypropylene, or any other plastic known in the art and recyclable.

[0159] Since the compositions described herein include a water-soluble carrier, it is useful to have reduced or no interaction with moisture during storage. Plastic containers can provide a good moisture barrier and can allow for a long shelf life during storage. However, other containers can also be used where an alternative to plastic is desired.

[0160] Another suitable container includes paper-based packaging. A paper-based material herein refers to a material comprising paper. Without wishing to be bound by theory, "paper" herein refers to a material made from cellulose-based pulp. Preferably, the paper-based material comprises paper, cardboard, or a mixture thereof, wherein preferably, the cardboard comprises paperboard, corrugated fiberboard, or a mixture thereof. The paper-based material may include a printed image thereon. Exemplary paper-based packaging is described in more detail below.

[0161] The paper-based package may comprise a first portion and a second portion, each portion comprising an inner surface and an outer surface, wherein the inner surface faces the inner compartment. The first portion and the second portion preferably comprise a paper-based material. Preferably, the entirety of the first portion and the second portion is formed of the paper-based material.

[0162] The paper-based material can be a laminate comprising paper comprising a first material and a second material. The first material can be cardboard or a mixture thereof, wherein preferably, the cardboard comprises paperboard, corrugated fiberboard or a mixture thereof. As previously mentioned, since the compositions of the present disclosure require reduced interaction with moisture and preferably do not require interaction with moisture, a suitable second material will be known to those skilled in the art. Preferably, the second material comprises a plastic material. Preferably, the plastic material comprises polyethylene, polyethylene terephthalate, polypropylene, polyvinyl alcohol or a mixture thereof. The second material can be biaxially oriented polypropylene, metallized polyethylene terephthalate or a mixture thereof. Alternatively, the second material can be a wax, a cellulosic material, polyvinyl alcohol or a mixture thereof. It is noteworthy that in some configurations, the second material can be separated from the paper-based material, for example, inserted into the paper-based material.

[0163] The inner surface of the first portion and preferably the inner surface of the second portion comprises the second material.The outer surface of the first portion and the second portion may comprise the first material, or vice versa.

[0164] Preferably, the paper-based laminate comprises greater than 50%, preferably greater than 85%, and more preferably greater than 95% by weight of a fiber-based material laminate. Preferably, the plastic material has a thickness between 10 and 40 microns, more preferably between 10 and 35 microns. As noted, the loaded substrate may contain aqueous hydrogen peroxide. Therefore, the second material should be selected to minimize evaporation of the aqueous hydrogen peroxide from the loaded substrate and to minimize leakage of the aqueous hydrogen peroxide into the paper-based material to avoid weakening the overall package.

[0165] Paper-based packaging is described in US 1 1821 142, US 1 1913173, US 1 1913174 and US 2022 / 0033158. The paper-based packaging described herein can be recycled in a paper recycling stream, which reduces the amount of material sent to landfills, and preferably eliminates it.

[0166] As described, the composition of the present disclosure may include a plurality of particles. A plurality of particles may include at least a first group of particles and a second group of particles. The first group and the second group may differ from each other in composition. For example, the first group may include a first dye, and the second group includes a second dye, wherein the first dye and the second dye are different so that the first group of particles and the second group of particles are different colors in the same package. Independently or in combination therewith, the first group of particles may generally have a first size, and the second group of particles may generally have a second size. The first size and the second size may be visually different so that the user can easily detect the presence of the first group of particles and the second group of particles in a single container.

[0167] Additionally, the first and second groups can include compositional differences, including or excluding the color of the particles. For example, at least one particle in the first group of particles can include a fabric softening active, an enzyme, or other functional ingredient useful in laundry applications that is not present in the second group of particles. This type of configuration can also accommodate particles of different sizes, shapes, and / or colors, such that the first group is distinctly different from the second group.

[0168] combination

[0169] Specific contemplated combinations of the present disclosure are described herein in the following lettered paragraphs. These combinations are illustrative in nature and not restrictive.

[0170] A. A composition comprising a plurality of particles, wherein the particles comprise:

[0171] from about 25% to about 99% by weight of a water-soluble carrier; and

[0172] A plurality of capsules dispersed in the water-soluble carrier, wherein the capsules include

[0173] a core and a shell surrounding the core, wherein the core comprises a flavor raw material;

[0174] wherein the shell comprises from about 90% to 100%, optionally from about 95% to 100%, optionally from about 99% to 100%, by weight of the shell, of a polymeric material which is the reaction product of chitosan derived from an aqueous phase and a cross-linking agent,

[0175] wherein the crosslinking agent comprises an isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates derived from an oil phase, each of the diisocyanates and / or polyisocyanates comprising an aromatic moiety; and

[0176] The mixture of diisocyanates and / or polyisocyanates containing aromatic moieties comprises at least one α-aromatic isocyanate and at least one β-aromatic isocyanate, optionally wherein the desired isocyanates are each present in at least 20 mole percent of the total isocyanate component.

[0177] B. The composition of paragraph A, wherein the weighted % NCO of the diisocyanate and / or polyisocyanate comprising aromatic moieties within the isocyanate component is from 15% to 32% by weight, or even from 20% to 26%, or even from 20% to 25%, or even from 21% to 25% by weight, and wherein:

[0178] The %NCO of an isocyanate compound is calculated as follows:

[0179]

[0180] wherein the number of isocyanate groups (NCO groups) is the count of isocyanate groups present in the compound, MW NCO groups is the molecular weight of a single NCO group, and MW isocyanate compound is the molecular weight of the entire isocyanate compound, excluding any solvent or other substances capable of miscibility with the isocyanate.

[0181] C. A composition according to paragraph A or B, wherein the α

[0182] The mass percentage of aromatic isocyanate is from 1% to 99% by weight, optionally from 5% to 90% by weight, optionally from 30% to 60% by weight.

[0183] D. The composition of any one of paragraphs A to C, wherein the mass percentage of the α-aromatic isocyanate in the isocyanate component is from 1% to 9% by weight.

[0184] 9%, optionally 5% to 90% by weight, optionally 30% to 60% by weight. E. The composition according to any of paragraphs A to D, wherein the α-aromatic isocyanate is selected from the group consisting of:

[0185]

[0186] wherein R is a biuret, a uretdione, an isocyanurate, a polyol, a polyol having urethane groups, urea, a polyamine, a polyamine having urea groups, a polyacid having anhydride groups, a polyisocyanate containing a biuret, a polyisocyanate containing a uretdione, or a polyisocyanate containing an isocyanurate,

[0187] Optionally, wherein the α-aromatic isocyanate is selected from the group consisting of:

[0188]

[0189] wherein n is an integer from 1 to 24,

[0190]

[0191]

[0192] Optionally, the α-aromatic isocyanate is selected from the group consisting of toluene diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, isomers thereof, adducts thereof, and combinations thereof.

[0193] F. The composition according to any of paragraphs A to E, wherein the beta-aromatic isocyanate is selected from the group consisting of:

[0194]

[0195] wherein R is a biuret, a uretdione, an isocyanurate, a polyol, a polyol having urethane groups, urea, a polyamine, a polyamine having urea groups, a polyacid having anhydride groups, a polyisocyanate containing a biuret, a polyisocyanate containing a uretdione, or a polyisocyanate containing an isocyanurate,

[0196] Optionally

[0197] wherein the β-aromatic isocyanate is selected from the group consisting of:

[0198]

[0199] Optionally, the β-aromatic isocyanate is selected from the group consisting of xylylene diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, tetramethylxylylene diisocyanate, isomers thereof, adducts thereof, and combinations thereof.

[0200] G. The composition of any of paragraphs A to F, wherein the isocyanate component comprises at least two diisocyanates and / or polyisocyanates selected from the group consisting of methylene diphenyl diisocyanate, polymeric methylene diphenyl isocyanate, and trimethylolpropane adducts of xylylene diisocyanate, optionally wherein the isocyanate component comprises methylene diphenyl diisocyanate, polymeric methylene diphenyl isocyanate, and trimethylolpropane adducts of xylylene diisocyanate in a weight ratio of 1:2 to 1:1.75, optionally wherein the isocyanate component comprises 3 by weight

[0201] 0% to 40%, optionally 34%, of a combination of methylene diphenyl isocyanate and polymeric methylene diphenyl isocyanate and 60% to 70%, optionally 66%, of a trimethylolpropane adduct of xylylene diisocyanate.

[0202] H. The composition of any of paragraphs A to G, wherein the chitosan is characterized by a weight average molecular weight of about 100 kDa to about 80,000 kDa, or even 100 kDa to about 600 kDa, optionally about 100 kDa to about 500 kDa, optionally about 100 kDa to about 400 kDa, optionally about 100 kDa to about 300 kDa, optionally about 100 kDa to about 200 kDa.

[0203] I. The composition of any of paragraphs A to H, wherein the ratio of the crosslinker to the chitosan is from 79:21 to 10:90, or even from 2:1 to 1:

[0204] 8, or even 1:1 to 1:7.

[0205] J. The composition of any of paragraphs A to I, wherein the core-shell encapsulate has a core to shell ratio of at least 75:25, or at least 99:1, or even at least 99.5:0.5, based on weight.

[0206] K. The composition of any of paragraphs A to J, wherein the fragrance comprises a fragrance raw material characterized by a logP of about 2.5 to about 4.5.

[0207] L. The composition of any of paragraphs A to K, wherein the capsules have a median particle size of 1 micron to 200 microns.

[0208] M. The composition of any of paragraphs A to L, wherein the water-soluble carrier is a water-soluble polymer.

[0209] N. A composition according to any one of paragraphs A to M, wherein the water-soluble carrier is selected from the group consisting of:

[0210] Formula H-(C2H4O) x -(CH(CH3)CH2O) y -(C2H4O) z -OH, wherein x is from 50 to 300, y is from 20 to 100, and z is from 10 to 200;

[0211] Formula (C2H4O) q -C(O)O-(CH2) r-CH3 polyethylene glycol fatty acid ester, wherein q is 20 to 200, and r is 10 to 30;

[0212] Formula HO-(C2H4O) s -(CH2) t )-CH3 polyethylene glycol fatty alcohol ether, wherein s is 30 to 250, and t is 10 to 30;

[0213] C8-C22 alkyl polyalkoxylates containing more than 40 alkoxylate units;

[0214] polyethylene glycol having a weight average molecular weight of 2,000 to 15,000;

[0215] EO / PO / EO block copolymer;

[0216] PO / EO / PO block copolymer;

[0217] EO / PO block copolymer;

[0218] PO / EO block copolymer;

[0219] Polypropylene glycol;

[0220] Ethoxylated nonionic surfactants with a degree of ethoxylation greater than 30;

[0221] Polyvinyl alcohol;

[0222] Polyalkylene glycols having a weight average molecular weight of 2,000 to 15,000; and mixtures thereof.

[0223] O. The composition of any of paragraphs A to M, wherein the water-soluble carrier is polyethylene glycol having a weight average molecular weight of about 2,000 to about 15,000.

[0224] P. A composition according to any one of paragraphs A to L, wherein the water-soluble carrier is selected from the group consisting of polyalkylene oxide, polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxyalkylene, polyethylene glycol fatty acid esters, polyethylene glycol ethers, sodium sulfate, starch, and mixtures thereof.

[0225] Q. The composition of any of paragraphs A to P, wherein the plurality of capsules is present at a level of about 0.1% to about 20% by weight of the composition.

[0226] R. The composition of any of paragraphs A to Q, wherein the particle has at least one planar surface.

[0227] S. The composition of any of paragraphs A to R, wherein the plurality of particles comprises a single particle, wherein the density of the individual particles is less than about 1 g / cm3 , optionally less than about 0.98 g / cm 3 .

[0228] T. The composition of any of paragraphs A to S, wherein the fragrance is a botanical fragrance.

[0229] U. The composition of any of paragraphs A to L, wherein the carrier comprises:

[0230] 0% to 3% by weight of a plasticizer polyol, wherein the plasticizer polyol is optionally a liquid at 20° C. and 1 atmosphere;

[0231] 1% to 20%, optionally 1% to 12%, optionally 6% to 8% by weight water;

[0232] 45% to 80%, optionally 50% to 70%, optionally 50% to 60% by weight of a sugar alcohol polyol selected from the group consisting of erythritol, xylitol, mannitol, isomalt, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof;

[0233] wherein the particles further comprise:

[0234] (a) a modified starch having a dextrose equivalent of 15 to 20, and the sugar alcohol polyol and the modified starch are present in a weight ratio of the sugar alcohol polyol to the modified starch of 2:1 to 16:1, optionally 2:1 to 10:1, optionally 2:1 to 3:1; or

[0235] (b) a modified starch having a dextrose equivalent of 4 to less than 15, and the sugar alcohol polyol and the modified starch are mixed at a ratio of 1.5:1 to 16:1, optionally 1.5:1 to 10:

[0236] 1, optionally present in a weight ratio of the sugar alcohol polyol to the modified starch of 1.5:1 to 4:1;

[0237] The capsules, the water and the sugar alcohol polyol are dispersed in the modified starch.

[0238] V. The composition of paragraph U, wherein the modified starch has a dextrose equivalent of 15 to 20, and the sugar alcohol polyol and the modified starch are present in a ratio of 2:1 to 16:1, optionally 2:1 to 10:1, optionally 2:1 to 3:1.

[0239] W. The composition according to paragraph U, wherein the modified starch has a dextrose equivalent of 4 to less than 15, and the sugar alcohol polyol and the modified starch are mixed at a ratio of 1.5:1 to 1

[0240] The sugar alcohol polyol is present in a weight ratio of 6:1, optionally 1.5:1 to 10:1, optionally 1.5:1 to 4:1 to the modified starch.

[0241] X. The composition of paragraph W, wherein the modified starch has a dextrose equivalent of 4 to 12.

[0242] Y. The composition of any of paragraphs U to X, wherein the modified starch is maltodextrin.

[0243] Z. The composition of any of paragraphs U to Y, wherein the sugar alcohol polyol is mannitol.

[0244] AA. A composition according to any of paragraphs A to L, wherein the carrier comprises:

[0245] 0% to 3% by weight of a plasticizer polyol, the plasticizer polyol being 2

[0246] It is liquid at 0°C and 1 atmosphere;

[0247] 1% to 20%, optionally 1% to 12%, optionally 6% to 8% by weight water;

[0248] 15% to 40%, optionally 20% to 30%, by weight of a sugar alcohol polyol selected from the group consisting of erythritol, xylitol, mannitol, isomalt, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof; and

[0249] a modified starch having a dextrose equivalent of 4 to less than 15, and the sugar alcohol polyol and the modified starch are present in a weight ratio of the sugar alcohol polyol to the modified starch of 1:5 to 1:1;

[0250] wherein the capsules, the water and the sugar alcohol polyol are dispersed in the modified starch; and

[0251] wherein each of the particles has an outer surface, and the anti-caking agent is located on the outer surface.

[0252] AA1. A composition according to any of paragraphs A to L, wherein the carrier comprises:

[0253] 0% to 3% by weight of a plasticizer polyol, wherein the plasticizer polyol is optionally a liquid at 20° C. and 1 atmosphere;

[0254] 1% to 20%, optionally 1% to 12%, optionally 6% to 8% by weight water;

[0255] 45% to 80%, optionally 50% to 70%, optionally 50% to 60% by weight of a sugar alcohol polyol selected from the group consisting of erythritol, xylitol, mannitol, isomalt, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof;

[0256] wherein the particles further comprise:

[0257] (a) a modified starch having a dextrose equivalent of 15 to 20, and the sugar alcohol polyol and the modified starch are present in a weight ratio of the sugar alcohol polyol to the modified starch of 2:1 to 16:1, optionally 2:1 to 10:1, optionally 2:1 to 3:1; or

[0258] (b) a modified starch having a dextrose equivalent of 4 to less than 15, and the sugar alcohol polyol and the modified starch are mixed at a ratio of 1.5:1 to 16:1, optionally 1.5:1 to 10:

[0259] 1, optionally present in a weight ratio of the sugar alcohol polyol to the modified starch of 1.5:1 to 4:1;

[0260] The capsules, the water and the sugar alcohol polyol are dispersed in the modified starch.

[0261] AA2. The composition according to paragraph AA1, wherein the modified starch has a dextrose equivalent of 15 to 20, and the sugar alcohol polyol and the modified starch are mixed in a ratio of 2:1 to 16:

[0262] 1, optionally 2:1 to 10:1, optionally 2:1 to 3:1.

[0263] AA3. A composition according to paragraph AA1, wherein the modified starch has a

[0264] 5 dextrose equivalent, and the sugar alcohol polyol and the modified starch are mixed at a ratio of 1.5:1 to

[0265] The sugar alcohol polyol is present in a weight ratio of 16:1, optionally 1.5:1 to 10:1, optionally 1.5:1 to 4:1 to the modified starch.

[0266] AA4. The composition of paragraph AA3, wherein the modified starch has a dextrose equivalent of 4 to 12.

[0267] AA5. The composition of any of paragraphs AA1 to AA4, wherein the modified starch is maltodextrin.

[0268] AA6. The composition of any of paragraphs AA1 to AA5, wherein the sugar alcohol polyol is mannitol.

[0269] AA7. The composition of any of paragraphs A to L, wherein the carrier comprises:

[0270] 0% to 3% by weight of a plasticizer polyol, the plasticizer polyol being 2

[0271] It is liquid at 0°C and 1 atmosphere;

[0272] 1 to 10%, optionally 3 to 8%, by weight, of water;

[0273] 15% to 40%, optionally 20% to 30%, by weight of a sugar alcohol polyol selected from the group consisting of erythritol, xylitol, mannitol, isomalt, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof; and

[0274] a modified starch having a dextrose equivalent of 4 to less than 15, and the sugar alcohol polyol and the modified starch are present in a weight ratio of the sugar alcohol polyol to the modified starch of 1:5 to 1:1;

[0275] wherein the capsules, the water and the sugar alcohol polyol are dispersed in the modified starch; and

[0276] wherein each of the particles has an outer surface, and the anti-caking agent is located on the outer surface.

[0277] BB. A method for treating laundry, comprising the steps of:

[0278] providing articles of clothing in a washing machine;

[0279] dispensing a plurality of particles according to any of paragraphs A to AA7 into the washing machine; and

[0280] The clothing items are contacted with the plurality of particles during a wash sub-cycle of the washing machine.

[0281] CC. The method according to paragraph BB, further comprising:

[0282] The step of dispensing up to about 60% of anionic or nonionic surfactant laundry detergent into the washing machine.

[0283] DD. The method of paragraph BB or CC, wherein about 5 g to about 50 g of the plurality of particles are dispensed into the washing machine.

[0284] EE. A method for forming a plurality of particles according to any of paragraphs A to AA, the method comprising the steps of:

[0285] providing a molten composition comprising the water-soluble carrier and the capsule;

[0286] passing the molten composition through one or more orifices of a distributor; and depositing the molten composition on a moving conveyor below the one or more orifices.

[0287] Test Method

[0288] It should be understood that the test methods disclosed in the Test Methods section of this application should be used to determine corresponding parameter values ​​for applicants' claimed subject matter as claimed and described herein.

[0289] Volume-weighted particle size and size distribution

[0290] Volume-weighted particle size distribution was determined by single particle optical sensing (SPOS), also known as optical particle counting (OPC), using an AccuSizer 780AD instrument and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent. The instrument was configured with the following conditions and options: flow rate = 1 ml / sec; lower size threshold = 0.50 μm; sensor model = LE400-05 or equivalent; autodilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 ml; maximum overlap = 9200. The measurement was started by cooling the sensor by flushing with water until the background count was less than 100. The sample in the suspension of delivery capsules was introduced, and the density of the capsules was adjusted with DI water by autodilution as needed to obtain a capsule count of at least 9200 / ml. The suspension was analyzed over a 60-second period. The resulting volume-weighted PSD data is plotted and recorded, and the desired volume-weighted particle size value (e.g., median / 50th percentile, 5th percentile, and / or 90th percentile) is determined.

[0291] Procedure for determining % degradation

[0292] The % degradation is determined by the "OECD Guideline for Testing of Chemicals" 301B CO2 Emission (Modified Sturm Test), adopted on July 17, 1992. For ease of reference, this test method is referred to herein as Test Method OECD 301B.

[0293] Spray drying process

[0294] This method converts a microcapsule slurry into a powder by removing water from the slurry via spray drying. The slurry is diluted to 19%-21% solids with RO water. The slurry is then spray dried on a Buchi Mini Spray Dryer B-290 with an inlet temperature of 180°C, an aspirator at 90%, and a pump at 20%-65%, with a target outlet temperature of 90°C. The resulting spray-dried microcapsule powder is collected from a collection vessel.

[0295] Preparation procedure for laundry care particles

[0296] PEG 8000 was melted in an oven at 80°C. After the PEG 8000 was completely melted, it was removed from the oven and allowed to cool to 60°C. The delivery particle slurry was added to the molten PEG 8000, blended with a spatula. The blend was returned to the oven for 3 hours to simulate the production process. It was then removed from the oven and poured onto a mold to form laundry care particles. The blend was allowed to cool and demolded to obtain the final laundry care particle product containing delivery particles.

[0297] Determining the amount of perfume loss after making laundry care particles

[0298] 1.25g of laundry care particles containing (encapsulated) spices were dissolved in 100g of water. A 1.00g sample was taken from the solution and pipetted into a 20ml headspace vial. The headspace above the solution was analyzed using an SPME headspace GC / MS (gas chromatography-mass spectrometry) method. The sample was incubated at 30°C for 10 minutes. The headspace above the solution was sampled for 1 minute via SPME (50 / 30μm DVB / Carboxen / PDMS). The SPME fiber was then thermally desorbed into the GC for 5 minutes. The analytes were analyzed by GC / MS in full scan mode with a split ratio of 1:10. The total spices HS response and spices headspace composition above the test group can be determined.

[0299] For samples of beads containing a certain type and amount of unencapsulated fragrance material, the total fragrance HS response obtained via the method described above was measured. This was considered to be a reference value representing 100% leakage of fragrance from the delivery particle.

[0300] This total fragrance HS response is compared to the total HS response obtained for a sample of beads containing the same type and amount of encapsulated fragrance material. When these two values ​​are compared to each other, the amount of fragrance leaked from the delivery particle can be determined by the following formula:

[0301]

[0302] Procedure for Determining Free Oil in Spray Drying

[0303] This method determines the "free oil of spray-dried powder" of microcapsule powder. 200mg-250mg of powder is placed in a 20mL scintillation vial and measured. 10mL of hexane is added. The vial is capped and vortexed at 3000RPM for 5 seconds and then left to stand for 2 minutes to allow the solid to settle. At least 2mL of solvent solution is extracted via a syringe and then filtered into a gas chromatography (GC) injection vial through a 0.45um syringe filter. The solution is injected into the GC instrument and the concentration of the fragrance in the solvent is determined by reference to a calibration curve generated by a serial dilution of the fragrance dissolved in hexane. The "free oil of spray-dried powder" is then calculated as the mass fraction of the fragrance relative to the mass of the powder in 10mL of hexane. For the powder sample, two repetitions of this procedure are performed and the results are averaged. The standard deviation is calculated from the two points and the average value is provided.

[0304] Sample preparation for biodegradability measurements

[0305] The water-soluble or water-dispersible material was purified by crystallization until a purity of more than 95% was achieved and dried before biodegradability measurements.

[0306] To analyze only the polymer wall, the oily medium containing the beneficial agent needs to be extracted from the capsule slurry. Therefore, the capsule slurry is freeze-dried to obtain a powder. This powder is then further washed with an organic solvent using the Soxhlet extraction method to extract the oily medium containing the beneficial agent until the weight percentage of the oily medium, based on the total capsule polymer wall, is less than 5%. Finally, the polymer wall is dried and analyzed.

[0307] The weight ratio of capsules to solvent is 1:3. The residual oily medium is determined by thermogravimetric analysis (isotherm at 100° C. for 60 minutes and isotherm at 250° C. for another 60 minutes). The weight loss determined must be less than 5%.

[0308] Leakage Procedure

[0309] The beneficial agent leakage of the beneficial agent-containing capsules was determined according to the following method:

[0310] i) Two 1 g samples of capsules containing beneficial agent were obtained.

[0311] ii) 1 g of the benefit agent-containing capsules was added to 99 g of the consumer product matrix in which the particles were to be employed and the mixture was labeled Sample 1. A second 1 g sample of the benefit agent-containing capsules in pure form, without contact with the consumer product matrix, was used immediately in step d below and was labeled Sample 2.

[0312] iii) The product matrix containing the capsules (Sample 1) was aged in a sealed glass jar at 35°C for 1 week.

[0313] iv) Capsules were recovered from both samples by filtration. The particles from Sample 1 (in the consumer product matrix) were recovered after the aging step. The particles from Sample 2 (pure raw material slurry) were recovered at the same time as the aging step for Sample 1 was initiated.

[0314] v) treating the recovered particles with a solvent to extract the benefit agent material from the particles.

[0315] vi) Analyze the solvent containing the beneficial agent extracted from each sample via chromatography.

[0316] vii) Integrate the resulting benefit agent peak areas under the curve and sum these areas to determine the total amount of benefit agent extracted from each sample.

[0317] viii) Determine the benefit agent leakage percentage by calculating the difference between the total amount of benefit agent extracted from Sample 2 (S2) and the total amount of benefit agent extracted from Sample 1 (S1), expressed as a percentage of the total amount of benefit agent extracted from Sample 2 (S2), as represented by the following formula:

[0318]

[0319] The procedure was repeated twice and the results were averaged. The standard deviation was calculated from the two points and the mean value was provided.

[0320] Method for determining the headspace concentration above treated dry fabrics.

[0321] Cotton tracers were analyzed by a fast headspace GC / MS (gas chromatography mass spectrometry) method. 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 for 5 minutes via an SPME (50 / 30 μm DVB / Carboxen / PDMS) method. The SPME fiber was then thermally desorbed immediately into the GC. Analytes were analyzed by fast GC / MS in full scan mode. Specific mass ion extraction of the PRM was used to calculate the total HS response and fragrance headspace composition above the test leg.

[0322] %NCO

[0323] The %NCO of an isocyanate compound is calculated as follows:

[0324]

[0325] where the number of NCO groups is the count of isocyanate groups present in the compound, MW NCO groups is the molecular weight of a single NCO group, and MW isocyanate compound is the molecular weight of the entire isocyanate compound, excluding any solvent or other substances capable of miscible with the isocyanate.

[0326] When the isocyanate is used as a mixture of multiple isocyanates, the % NCO is reported as the weighted sum of the mass percentages of each individual isocyanate in the mixture.

[0327] Unless otherwise indicated, all temperatures herein are in degrees Celsius (° C.) Unless otherwise indicated, all measurements herein are made at 20° C. and atmospheric pressure.

[0328] Unless otherwise indicated, all percentages and ratios are calculated by weight. Unless otherwise indicated, all percentages and ratios are calculated based on the total composition.

[0329] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range falling within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0330] In the following examples, abbreviations, materials, or trade names correspond to the materials listed in Table 3. These examples are illustrative in nature and not limiting.

[0331] Table 3

[0332]

[0333] Diisocyanates and / or polyisocyanates contain aromatic moieties. The isocyanates used have two functional groups: an isocyanate group and an aromatic moiety. For ease of reference, isocyanate molecules can be subdivided into several categories.

[0334] The first grouping can be based on the presence or absence of aromatic moieties within the entire molecule; thus, the following two categories are defined:

[0335] 1- Isocyanates containing at least one aromatic moiety.

[0336] 2- Isocyanates that do not contain any aromatic moieties.

[0337] For convenience, the presence of an aromatic moiety can be further classified as alpha or beta based on the carbon atom designation. Thus, isocyanates containing aromatic moieties can be further subdivided.

[0338] 1.i) an isocyanate containing an α-aromatic moiety; and

[0339] 1.ii) Isocyanates containing a β-aromatic moiety.

[0340] For ease of reference, Group 1, i) and ii) categories are referred to as:

[0341] 1.i) α-aromatic

[0342] 1.ii) β-aromatic

[0343] And group 2 is

[0344] 2. "Non-aromatic"

[0345] This naming convention is reflected in Table 4 below:

[0346] Table 4

[0347]

[0348] It is inferred that aromatic rings can affect reactivity. It was surprisingly found that isocyanates comprising α-aromatic moieties are more reactive than isocyanates comprising β-aromatic moieties. This is believed to be due to the nature of the electron-withdrawing aromatic ring, which enhances the electrophilic properties of the isocyanate group (NCO). Isocyanates comprising one or more α-aromatic moieties have a benzene ring attached to the NCO group, which theoretically enhances reactivity. It is believed that the delocalization of electrons in the aromatic ring makes the α-carbon even more electron-deficient, making it a stronger electrophile and therefore more susceptible to nucleophilic interactions with amines (such as chitosan amine groups). On the other hand, isocyanates comprising one or more β-aromatic moieties are less affected by the electron-withdrawing aromatic ring and are attached to the β-carbon. Although they are still reactive, they are generally less reactive than their α-aromatic isocyanate counterparts. This can lead to faster reaction rates, making α-aromatic isocyanates (such as the α-aromatic isocyanates of Group 1i) more effective in certain applications. However, their high reactivity can also make them more difficult to handle and may require additional precautions, such as potential undesirable reactivity with PRMs. Surprising, unexpected improvements were found when the isocyanate component was selected to comprise a mixture of two or more isocyanates, each containing an aromatic moiety; and each isocyanate was independently selected from the group consisting of α-aromatic isocyanates and β-aromatic isocyanates. It will be understood that the isocyanate can be a diisocyanate or a polyisocyanate.

[0349] Example

[0350] The examples provided below are intended to be illustrative in nature and not intended to be limiting.

[0351] Example 1

[0352] Determining the amount of perfume loss after making laundry care particles

[0353] Laundry care particles were prepared according to the above-mentioned preparation method (Laundry Care Particle Preparation Procedure). Table 5 below shows the laundry care particles comprising the fragrance capsules as described herein.

[0354] Table 5

[0355]

[0356] Perfume loss after making the laundry care particles was assessed according to the method provided in the Test Methods section above, "Determining the Amount of Perfume Loss After Making the Laundry Care Particles."

[0357] Table 6 highlights that Comparative Example 1, featuring a single beta-aromatic isocyanate, exhibits the highest amount of perfume loss after making the laundry care particles. Figure 2 It is highlighted that by increasing the amount of α-aromatic isocyanate, the fragrance loss decreases until minimum values ​​of α-aromatic isocyanate weighted concentration of approximately 20% and 40% are reached.

[0358]

[0359] Example 2

[0360] A population of capsules that has undergone a drying process involving heating to remove moisture.

[0361] The fragrance capsules as described herein were subjected to a spray drying process as described in the method "Spray Drying Procedure" provided in the Methods section above.

[0362] Free oil after spray drying was assessed according to the method "Procedure for determination of free oil after spray drying" provided in the Methods section above.

[0363] Table 7 highlights that Comparative Example 1, featuring a single β-aromatic isocyanate, exhibits the highest amount of free oil after spray drying. Figure 3 It is highlighted that increasing the amount of α-aromatic isocyanate leads to a decrease in free oil after spray drying, reaching minimum values ​​of approximately 15% and 40% in terms of α-aromatic isocyanate weighted concentration. Figure 3 It is emphasized that reducing the volume weighted median microcapsule size from 29±4 um to 16±4 um and increasing the shell (%) further helped in reducing the free oil after spray drying to a value of 2.9±0.0%.

[0364]

[0365] Example 4

[0366] Laundry care granular composition

[0367] In Table 8, examples of laundry care granular compositions are reported.

[0368]

[0369] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

[0370] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the present inventions disclosed or claimed herein, or an admission that it, by itself or in combination with any one or more references, proposes, suggests, or discloses any such invention. Further, 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 govern.

[0371] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the invention. It is therefore intended that all such changes and modifications within the scope of the invention be encompassed in the appended claims.

Claims

1. A composition comprising a plurality of particles, wherein the particles comprise: from about 25% to about 99% by weight of a water-soluble carrier; and a plurality of capsules dispersed in the water-soluble carrier, wherein the capsules comprise a core and a shell surrounding the core, and the core comprises a fragrance raw material; wherein the shell comprises from about 90% to 100%, optionally from about 95% to 100%, optionally from about 99% to 100%, by weight of the shell, of a polymeric material which is the reaction product of chitosan derived from an aqueous phase and a cross-linking agent, wherein the crosslinking agent comprises an isocyanate component comprising a mixture of two or more diisocyanates and / or polyisocyanates derived from an oil phase, each of the diisocyanates and / or polyisocyanates comprising an aromatic moiety; and wherein said mixture of diisocyanates and / or polyisocyanates comprising aromatic moieties comprises at least one α-aromatic isocyanate and at least one β-aromatic isocyanate, Optionally, the desired isocyanates are each present at at least 20 mole percent of the total isocyanate component.

2. The composition of claim 1 , wherein the weighted % NCO of the diisocyanate and / or polyisocyanate comprising aromatic moieties within the isocyanate component is from 15% to 32% by weight, or even from 20% to 26%, or even from 20% to 25%, or even from 21% to 25% by weight, and wherein: The %NCO of an isocyanate compound is calculated as follows: wherein the number of isocyanate groups (NCO groups) is the count of isocyanate groups present in the compound, MWNCO groups is the molecular weight of a single NCO group, and MW isocyanate compound is the molecular weight of the entire isocyanate compound, excluding any solvent or other substances capable of miscibility with the isocyanate.

3. The composition according to claim 1 or claim 2, wherein the mass percentage of the α-aromatic isocyanate in the isocyanate component can be 1% to 99% by weight, optionally 5% to 90% by weight, optionally 30% to 60% by weight.

4. The composition according to any preceding claim, wherein the mass percentage of the beta-aromatic isocyanate in the isocyanate component is from 1% to 99% by weight, optionally from 5% to 10% by weight, optionally from 70% to 40% by weight.

5. The composition according to any one of the preceding claims, wherein the α-aromatic isocyanate is selected from the group consisting of: wherein R is a biuret, a uretdione, an isocyanurate, a polyol, a polyol having urethane groups, urea, a polyamine, a polyamine having urea groups, a polyacid having anhydride groups, a polyisocyanate containing a biuret, a polyisocyanate containing a uretdione, or a polyisocyanate containing an isocyanurate, Optionally, wherein the α-aromatic isocyanate is selected from the group consisting of: wherein n is an integer from 1 to 24, Optionally, the α-aromatic isocyanate is selected from the group consisting of toluene diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, isomers thereof, adducts thereof, and combinations thereof.

6. The composition according to any one of the preceding claims, wherein the β-aromatic isocyanate is selected from the group consisting of: wherein R is a biuret, a uretdione, an isocyanurate, a polyol, a polyol having urethane groups, urea, a polyamine, a polyamine having urea groups, a polyacid having anhydride groups, a polyisocyanate containing a biuret, a polyisocyanate containing a uretdione, or a polyisocyanate containing an isocyanurate, Optionally wherein the β-aromatic isocyanate is selected from the group consisting of: Optionally, the β-aromatic isocyanate is selected from the group consisting of xylylene diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, tetramethylxylylene diisocyanate, isomers thereof, adducts thereof, and combinations thereof.

7. The composition of any one of the preceding claims, wherein the isocyanate component comprises at least two diisocyanates and / or polyisocyanates selected from methylene diphenyl diisocyanate, polymeric methylene diphenyl isocyanate and trimethylolpropane adduct of xylylene diisocyanate, optionally wherein the isocyanate component comprises methylene diphenyl diisocyanate, polymeric methylene diphenyl isocyanate and trimethylolpropane adduct of xylylene diisocyanate in a weight ratio of 1:2 to 1:1.75, optionally wherein the isocyanate component comprises 30% to 40%, optionally 34%, by weight of the combination of methylene diphenyl isocyanate and polymeric methylene diphenyl isocyanate and 60% to 70%, optionally 66%, by weight of trimethylolpropane adduct of xylylene diisocyanate.

8. The composition of any one of the preceding claims, wherein the chitosan is characterized by a weight average molecular weight of about 100 kDa to about 80,000 kDa, or even 100 kDa to about 600 kDa, optionally about 100 kDa to about 500 kDa, optionally about 100 kDa to about 400 kDa, optionally about 100 kDa to about 300 kDa, optionally about 100 kDa to about 200 kDa.

9. A composition according to any preceding claim, wherein the ratio of the cross-linker to the chitosan is from 79:21 to 10:90, or even from 2:1 to 1:8, or even from 1:1 to 1:7, based on weight.

10. The composition of any preceding claim, wherein the core-shell encapsulate has a core to shell ratio of at least 75:25, or at least 99:1, or even at least 99.5:0.5, based on weight.

11. The composition of any preceding claim, wherein the capsules have a volume weighted median particle size of capsules from about 5 microns to about 150 microns, or even from about 10 microns to about 50 microns, optionally from about 15 microns to about 50 microns.

12. A composition according to any one of the preceding claims, wherein the water-soluble carrier is selected from the group consisting of: Formula H-(C2H4O) x -(CH(CH3)CH2O) y -(C2H4O) z -OH, wherein x is from 50 to 300, y is from 20 to 100, and z is from 10 to 200; Formula (C2H4O) q -C(O)O-(CH2) r -CH3 polyethylene glycol fatty acid ester, wherein q is 20 to 200, and r is 10 to 30; Formula HO-(C2H4O) s -(CH2) t )-CH3 polyethylene glycol fatty alcohol ether, wherein s is 30 to 250, and t is 10 to 30; C8-C22 alkyl polyalkoxylates containing more than 40 alkoxylate units; polyethylene glycol having a weight average molecular weight of 2,000 to 15,000; EO / PO / EO block copolymer; PO / EO / PO block copolymer; EO / PO block copolymer; PO / EO block copolymer; Polypropylene glycol; Ethoxylated nonionic surfactants with a degree of ethoxylation greater than 30; Polyvinyl alcohol; Polyalkylene glycols having a weight average molecular weight of 2,000 to 15,000; and mixtures thereof, preferably polyethylene glycol having a weight average molecular weight of about 2,000 to about 15,000, and even more preferably a mixture of two polyethylene glycols having different molecular weights.

13. The composition according to any one of claims 1 to 12, wherein the water-soluble carrier is selected from the group consisting of polyalkylene oxide, polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxyalkylene, polyethylene glycol fatty acid esters, polyethylene glycol ethers, sodium sulfate, starch, and mixtures thereof.

14. The composition of any one of the preceding claims, wherein the plurality of capsules is present at a level of from about 0.1% to about 20% by weight of the composition.

15. The composition of any of the preceding claims, wherein the plurality of particles comprises individual particles, wherein the density of the individual particles is less than about 1 g / cm 3 , optionally less than about 0.98g / cm 3 。

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