Laundry care additive particles

Abstract

The present disclosure relates to laundry care additive particles and dryer sheets comprising a water-soluble carrier and a capsule featuring a substantially inorganic shell, such as a silica-based shell. The present disclosure also relates to methods of making and using such compositions.

Description

Technical Field

[0001] Laundry care additive granules. The composition comprises a plurality of granules, and the granules contain a water-soluble carrier and a capsule having a substantially inorganic shell (e.g., a silica-based shell). This disclosure also relates to methods for preparing and using such compositions. This disclosure also relates to a dryer paper comprising capsules having a substantially inorganic shell (e.g., a silica-based shell). Background Technology

[0002] Laundry care granule additives and dryer sheets are formulated with scented core / shell capsules. Typically, the core of such capsules contains fragrance, and the shell usually contains a polymeric material such as amino plastics, polyurea, or polyacrylate. These capsules are used to deliver the beneficial agent to a target surface, such as fabric. At various points of contact, the capsule then ruptures, releasing the fragrance. However, fragrance capsule leakage is known, thus reducing the efficiency of the fragrance delivery system.

[0003] Furthermore, flavor capsules typically encapsulate multiple flavor ingredients (“PRMs”). The problem is that different PRMs may leak through the capsule wall at different rates. Over time, such as when the product is transported or stored, the flavor profile may change because some PRMs leak more than others. When the freshness profile provided by the first dose of product differs from that provided by the last dose, this can lead to a less satisfying olfactory experience than the manufacturer-prepared formulation, quality control issues, and even consumer dissatisfaction.

[0004] The need includes garment care granule additives and dryer sheets that incorporate a fragrance delivery system with improved fragrance leakage characteristics. Summary of the Invention

[0005] This disclosure relates to a composition comprising a plurality of particles, wherein the particles comprise: a water-soluble carrier comprising about 25% to about 99% by weight; 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 flavoring ingredient;

[0006] The shell comprises about 90% to 100%, optionally about 95% to 100%, optionally about 99% to 100% inorganic material by weight of the shell.

[0007] This disclosure also relates to compositions comprising a plurality of particles, wherein the particles comprise: a water-soluble carrier comprising about 25% to about 99% by weight; 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 ingredient; wherein the shell comprises: a substantially inorganic first shell component comprising a condensation layer and a nanoparticle layer, wherein the condensation layer comprises a condensation product of a precursor, wherein the nanoparticle layer comprises inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer; and an inorganic second shell component surrounding the first shell component, wherein the inorganic second shell component surrounds the nanoparticle layer;

[0008] The precursor comprises at least one compound selected from the group consisting of formula (I), formula (II), and mixtures thereof; wherein formula (I) is (M v O z Y n ) w ;

[0009] Where equation (II) is (M) v O z Y n R 1 p ) w For formulas (I), (II), or mixtures thereof, each M is independently selected from the group consisting of silicon, titanium, and aluminum, v is the valence of M and is 3 or 4, z is 0.5 to 1.6, and each Y is independently selected from -OH, -OR 2 ,halogen, -NH2、-NHR 2 -N(R) 2 )2 and The group consisting of R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl or 5-12-membered heteroaryl, wherein the heteroaryl group comprises 1 to 3 cyclic heteroatoms selected from the group consisting of O, N, and S, wherein R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl or 5-12-membered heteroaryl, wherein the heteroaryl comprises 1 to 3 cyclic heteroatoms selected from O, N and S, w being 2 to 2000; wherein for formula (I), n is 0.7 to (v-1); and wherein for formula (II), n is 0 to (v-1), each R 1 Choose independently from the following groups: C1 to C 30 Alkyl, C1 to C30 C1 to C2 substituted with one or more of the following: alkylene, halogenated, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl. 30 Alkyl groups, and C1 to C2 groups substituted with one or more of halogens, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups. 30 Alkylene, and p is a positive number at most pmax, where pmax = 60 / [9*Mw(R 1 )+8], where Mw(R 1 ) is R 1 Molecular weight of the functional group.

[0010] This disclosure also relates to a dryer paper comprising: a nonwoven fiber layer; and a solid fabric softener composition carried on or within the nonwoven fiber layer;

[0011] The solid fabric softener composition comprises a plurality of capsules dispersed in the solid fabric softener composition, wherein the capsules include a core and a shell surrounding the core, and the core contains a fragrance ingredient; wherein the shell contains about 90% to 100%, optionally about 95% to 100%, optionally about 99% to 100% inorganic material by weight of the shell. Attached Figure Description

[0012] Figure 1 It is a pellet manufacturing equipment.

[0013] Figure 2 A schematic diagram of a method for preparing a capsule having a first shell component is shown, the capsule being prepared with a hydrophobic core.

[0014] Figure 3 A schematic diagram of a capsule having a first shell component and a second shell component is shown.

[0015] Figure 4 These are scanning electron microscope images of the capsule.

[0016] Figure 5 It is based on the capsule group disclosed herein.

[0017] Figure 6 It is a box plot of the WFHS / DFHS ratio measured as described in Example 3. Detailed Implementation

[0018] This disclosure relates to fabric care additive granules comprising a water-soluble carrier and a plurality of fragrance-containing capsules dispersed within the carrier. When dispersed in the carrier, the capsules exhibit consistent permeability to the various fragrance ingredients, providing the user with a consistent fragrance experience at all points of contact throughout the time of use of the fabric care additive packet and when the user handles or wears clothing treated with such a fabric care additive. This disclosure also relates to dryer paper comprising capsules.

[0019] Laundry care additive granules are intended to provide beneficial effects to clothes through washing. That is, the user can use the granules by dispensing them into the washing machine before starting a washing cycle, particularly a wash sub-cycle. The full wash compositions described herein differ from full rinse compositions. Full rinse compositions are designed to be dispensed during the rinse sub-cycle of the washing machine. In modern washing machines, the rinse sub-cycle starts automatically after the wash sub-cycle is completed, without any further input from the consumer. The composition to be dispensed during the rinse sub-cycle is typically dispensed into a separate dispensing compartment, which is part of the washing machine that dispenses the full rinse composition during the rinse sub-cycle, such as the dispensing drawer or the agitator in the tub.

[0020] It is believed that, when used in water-soluble carriers, capsules of the type disclosed herein work surprisingly well in controlling leakage of flavoring ingredients in the compositions disclosed herein, resulting in relatively low and consistent flavoring leakage. Not wishing to be bound by theory, it is believed that shells containing highly cross-linked inorganic materials drive flavoring ingredient leakage through a completely different mechanism compared to shells containing organic polymer materials. Specifically, the diffusion of small molecules such as flavoring ingredients (“PRMs”) through a homogeneous organic polymer shell is analogous to the diffusion mechanism through a homogeneous polymer membrane. In this case, the permeability of the polymer membrane to a given solute depends on the polymer free volume (affected by crystallinity and cross-linking density) and the relative solubility of the solute in the polymer. Since different PRMs will have different ranges of associated physical and chemical properties (e.g., molecular weight and polarity), and when the physical and chemical properties are also inhomogeneous, the diffusion rate is non-uniform for a given group of PRMs.

[0021] On the other hand, it is believed that the diffusion of small molecules through a highly cross-linked inorganic shell occurs primarily through microchannels formed by a permeation network of micropores present in the shell. As disclosed herein, such a highly cross-linked inorganic shell can be obtained by using a combination of a second shell component and a first shell component. In this case, it is believed that the permeability of the inorganic shell depends primarily on the number, density, and size of the microchannels effectively connecting the core and the continuous phase, which can result in a relatively uniform or consistent PRM leakage rate, and a relatively low permeation rate.

[0022] Because the various PRMs leak from the disclosed capsules in the disclosed compositions at a relatively consistent rate, it is further believed that the intended properties of the fragrance are preserved, resulting in more satisfactory and consistent olfactory performance.

[0023] This document may use the term "substantially free of" (or "substantially free from"). This means that the referred material is present in very small amounts, not intentionally added to the composition to form a portion of the composition, or optionally, the referred material is not present at analytically detectable levels. This means that the referred material is present in a composition only as an impurity among other intentionally added materials. If present, the referred material may be present at levels of less than 1%, less than 0.1%, less than 0.01%, or even 0% by weight of the composition.

[0024] Unless otherwise specified, all component or composition levels refer to the active portion of the component or composition and do not include impurities, such as residual solvents or byproducts, that may be present in commercially available sources of such components or compositions.

[0025] Unless otherwise specified, all temperatures in this document are in degrees Celsius (°C). Unless otherwise specified, all measurements in this document were taken at 20°C and atmospheric pressure.

[0026] As stated herein, unless otherwise specified, all percentages are based on the weight of the total composition. Unless otherwise specified, all ratios are by weight.

[0027] It should be understood that each maximum numerical limit given in this specification includes each lower numerical limit, as such lower numerical limits are explicitly stated herein. Each minimum numerical limit given in this specification will include each higher numerical limit, as such higher numerical limits are explicitly stated herein. Each numerical range given in this specification will include each narrower numerical range falling within such a wider numerical range, as all such narrower numerical ranges are explicitly stated herein.

[0028] Water-soluble carrier

[0029] The granules may contain a water-soluble carrier. The water-soluble carrier is used to carry the capsules into the washing liquid. As the water-soluble carrier dissolves, the capsules disperse into the washing liquid and deposit onto the clothing.

[0030] The water-soluble carrier can be a material that can dissolve in the washing liquid within a short time, for example, less than about 10 minutes.

[0031] Water solubility means that the material, carrier material, or particles are soluble or dispersible in water and optionally have a water solubility of at least 50%, optionally at least 75%, or even at least 95%, as measured by the method described below using a glass filter with a maximum pore size of 20 micrometers: 50 g ± 0.1 g of carrier is added to a pre-weighed 400 mL beaker, and 245 mL ± 1 mL of distilled water is added. The mixture is vigorously stirred for 30 minutes on a magnetic stirrer set to 600 rpm. The mixture is then filtered through a porous glass filter with the specified pore size (maximum 20 micrometers). This step is performed at a temperature of 23 °C ± 1.0 °C and a relative humidity of 50% ± 2%. The water in the collected filtrate is dried by any conventional method, and the weight of the remaining material (the dissolved or dispersed portion) is determined. The percentage of solubility or dispersion can then be calculated.

[0032] The water-soluble carrier may be selected from water-soluble inorganic alkali metal salts, water-soluble alkaline earth metal salts, water-soluble organic alkali metal salts, water-soluble organic alkaline earth metal salts, water-soluble carbohydrates, water-soluble silicates, water-soluble urea, and any combination thereof.

[0033] Alkali metal salts may be selected, for example, from lithium, sodium, and potassium salts, and any combination thereof. Available alkali metal salts may be selected, for example, from alkali metal fluorides, alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfates, alkali metal hydrogen sulfates, alkali metal phosphates, alkali metal monohydrogen phosphates, alkali metal dihydrogen phosphates, alkali metal carbonates, alkali metal monohydrogen carbonates, alkali metal acetates, alkali metal citrates, alkali metal lactates, alkali metal pyruvates, alkali metal silicates, alkali metal ascorbic acid salts, and combinations thereof.

[0034] Alkali metal salts may be selected from 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 acetate, sodium citrate, sodium lactate, sodium tartrate, sodium silicate, sodium ascorbate, 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 acetate, potassium citrate, potassium lactate, potassium tartrate, potassium silicate, potassium, ascorbic acid, and combinations thereof.

[0035] Alkaline earth metal salts can be selected from magnesium salts, calcium salts, and combinations thereof. Alkaline earth metal salts can also be selected from alkali metal fluorides, alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfates, alkali metal hydrogen sulfates, alkali metal phosphates, alkali metal monohydrogen phosphates, alkali metal dihydrogen phosphates, alkali metal carbonates, alkali metal monohydrogen carbonates, alkali metal acetates, alkali metal citrates, alkali metal lactates, alkali metal pyruvates, alkali metal silicates, alkali metal ascorbic acid salts, and combinations thereof. Alkaline earth metal salts may be selected from magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium phosphate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium carbonate, magnesium monohydrogen carbonate, magnesium acetate, magnesium citrate, magnesium lactate, magnesium tartrate, magnesium silicate, magnesium ascorbate, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium sulfate, calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium carbonate, calcium monohydrogen carbonate, calcium acetate, calcium citrate, calcium lactate, calcium tartrate, calcium silicate, calcium ascorbate, and combinations thereof.

[0036] Inorganic salts, such as inorganic alkali metal salts and inorganic alkaline earth metal salts, do not contain carbon. Organic salts, such as organic alkali metal salts and organic alkaline earth metal salts, contain carbon. Organic salts may be alkali metal salts or alkaline earth metal salts of sorbic acid (i.e., sorbates). Sorbicates may be selected from sodium sorbate, potassium sorbate, magnesium sorbate, calcium sorbate, and combinations thereof.

[0037] The water-soluble carrier may be or comprise materials selected from the following: water-soluble inorganic alkali metal salts, water-soluble organic alkali metal salts, water-soluble inorganic alkaline earth metal salts, water-soluble organic alkaline earth metal salts, water-soluble carbohydrates, water-soluble silicates, water-soluble urea, and combinations thereof. The water-soluble carrier may be selected from sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium citrate, potassium citrate, sodium tartrate, potassium tartrate, potassium sodium tartrate, calcium lactate, water glass, sodium silicate, potassium silicate, dextrose, fructose, galactose, isoglucose, glucose, sucrose, raffinose, isomaltitol, xylitol, confectionery, coarse sugar, and combinations thereof. In one embodiment, the water-soluble carrier may be sodium chloride. In one embodiment, the water-soluble carrier may be table salt.

[0038] The water-soluble carrier may be or contain materials selected from the following: sodium bicarbonate, sodium sulfate, sodium carbonate, sodium formate, calcium formate, sodium chloride, sucrose, maltodextrin, corn syrup solids, corn starch, wheat starch, rice starch, potato starch, cassava starch, clay, silicates, carboxymethyl cellulose citrate, fatty acids, fatty alcohols, diglycerides of hydrogenated tallow, glycerol, and combinations thereof.

[0039] The water-soluble carrier may be selected from water-soluble organic alkali metal salts, water-soluble inorganic alkaline earth metal salts, water-soluble organic alkaline earth metal salts, water-soluble carbohydrates, water-soluble silicates, water-soluble urea, starch, clay, water-insoluble silicates, carboxymethyl cellulose citrate, fatty acids, fatty alcohols, diglycerides of hydrogenated tallow, glycerol, polyethylene glycol, and combinations thereof.

[0040] The water-soluble carrier can be selected from disaccharides, polysaccharides, silicates, zeolites, carbonates, sulfates, citrates, and combinations thereof.

[0041] The water-soluble carrier may be selected from polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxyethylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, sodium sulfate, starch, and mixtures thereof.

[0042] The water-soluble carrier may be a water-soluble polymer. The water-soluble polymer may be selected from the group consisting of: C8-C22 alkyl polyalkoxylates comprising more than about 40 alkoxyl units, ethoxylated nonionic surfactants having an ethoxylation degree greater than about 30, polyalkylene glycols having a weight average molecular weight of about 2,000 to about 15,000, and combinations thereof.

[0043] The water-soluble carrier can be a water-soluble polymer. The water-soluble polymer can be a block copolymer having formula (I), (II), (III), or (IV), i.e., R... 1 O-(EO)x-(PO)yR 2 (I), R 1 O--(PO)x-(EO)yR 2 (II), R 1 O-(EO)o-(PO)p-(EO)qR 2 (III) R 1 O--(PO)o-(EO)p-(PO)qR 2 (IV) or combinations thereof; wherein EO is a -CH2CH2O- group and PO is a -CH(CH3)CH2O- group; R 1 and R 2 Independently H or C1-C22 alkyl groups; x, y, o, p and q are independently 1-100; the precursor condition is that the sum of x and y is greater than 35, and the sum of o, p and q is greater than 35; wherein the block copolymer has a molecular weight in the range of about 3000 g / mol to about 15,000 g / mol.

[0044] The water-soluble polymer may be one or more block copolymers, such as block copolymers based on ethylene oxide and propylene oxide, selected from the group consisting of: PLURONIC-F38, PLURONIC-F68, PLURONIC-F77, PLURONIC-F87, PLURONIC-F88, and combinations thereof. PLURONIC materials are available from BASF.

[0045] The water-soluble polymer may be selected from the group consisting of: polyvinyl alcohol (PVA), modified PVA; polyvinylpyrrolidone; PVA copolymers, such as PVA / polyvinylpyrrolidone and PVA / polyvinylamine; partially hydrolyzed polyvinyl acetate; polyepoxides, such as ethylene oxide; polyethylene glycol; acrylamide; acrylic acid; cellulose, alkyl cellulose, such as methylcellulose, ethylcellulose and propylcellulose; cellulose ethers; cellulose esters; cellulose amides; polyvinyl acetate; polycarboxylic acids and salts; polyamino acids or peptides; polyamides; polyacrylamide; maleic acid / acrylic acid copolymers; polysaccharides, including starch, modified starch; gelatin; alginate; xylooligosaccharide, other hemicellulose polysaccharides, including xylan, glucuronic acid xylan, arabinoxylan, mannan, glucomannan and galactoglucomannan; natural gums, such as pectin, xanthan gum, carrageenan, locust bean gum, gum arabic, tragacanth gum; and combinations thereof. In one embodiment, the polymer comprises: polyacrylate, particularly sulfonated polyacrylate and water-soluble acrylate copolymer; and alkyl hydroxycellulose, such as methylcellulose, sodium carboxymethylcellulose, modified carboxymethylcellulose, dextrin, ethylcellulose, propylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, and polymethyl methacrylate. In another embodiment, the water-soluble polymer may be selected from PVA; PVA copolymers; hydroxypropyl methylcellulose (HPMC); and mixtures thereof.

[0046] Water-soluble polymers can be selected from polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl alcohol / polyvinylpyrrolidone, polyvinyl alcohol / polyvinylamine, partially hydrolyzed polyvinyl acetate, polyepoxides, polyethylene glycol, acrylamide, acrylic acid, cellulose, alkyl cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic acid / acrylic acid copolymers, polysaccharides, starch, modified starch, gelatin, alginate, xylooligosaccharide, and hemicellulose polysaccharides. Xylan, glucuronic acid xylan, arabinoxylan, mannan, glucomannan, galactoglucomannan, natural gums, pectin, xanthan gum, carrageenan, locust bean gum, gum arabic, tragacanth gum, polyacrylate, sulfonated polyacrylate, water-soluble acrylate copolymers, alkyl hydroxycellulose, methylcellulose, sodium carboxymethylcellulose, modified carboxymethylcellulose, dextrin, ethylcellulose, propylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, polymethyl acrylate, polyvinyl alcohol copolymers, hydroxypropyl methylcellulose, and mixtures thereof.

[0047] Water-soluble polymers can be organic materials. Organic water-soluble polymers can provide the beneficial effect of being easily soluble in water.

[0048] The water-soluble polymer may be selected from the group consisting of: polyethylene glycol, polypropylene glycol polyoxyethylene, polyethylene glycol fatty acid esters, polyethylene glycol ethers, starch, and mixtures thereof.

[0049] The water-soluble polymer may be polyethylene glycol (PEG). PEG can be a convenient material for preparing granules because, when the granules have the mass range disclosed herein, PEG has sufficient water solubility to dissolve during washing cycles. Furthermore, PEG can be readily processed in melt form. The melt initiation temperature of PEG can vary depending on the molecular weight of PEG. Granules may contain about 25% to about 94% PEG by weight, having a weight-average molecular weight of about 2000 to about 15000. PEG has a low cost, can be formed into many different shapes and sizes, minimizes the diffusion of unencapsulated fragrances, and is well soluble in water. PEG has a variety of weight-average molecular weights. Suitable weight-average molecular weights of PEG range from about 2,000 to about 13,000, or about 4,000 to about 13,000, or about 4,000 to about 12,000, or about 4,000 to about 11,000, or about 5,000 to about 11,000, or about 6,000 to about 10,000, or about 7,000 to about 9,000, or combinations thereof. PEG is available from BASF, such as PLURIOL E 8000, or other PLURIOL products. The water-soluble polymer may be a mixture of two or more polyethylene glycol compositions, one having a first weight-average molecular weight (e.g., 9,000) and the other having a second weight-average molecular weight (e.g., 4,000), the second weight-average molecular weight being different from the first weight-average molecular weight.

[0050] The particles may contain about 25% to about 99% water-soluble carrier by weight. The particles may contain about 35% to about 95%, optionally about 50% to about 80%, optionally combinations thereof, and any whole percentage or range of whole percentage carriers within any of the foregoing ranges by weight.

[0051] Multiple particles may comprise a single particle containing about 25% to about 99% of a water-soluble carrier by weight of the particle; and about 0.1% to about 20% of a capsule by weight of the particle; wherein the capsule is dispersed in a matrix of a water-soluble polymer.

[0052] The granules may contain about 25% to about 99% PEG by weight of a single granule. Optionally, a single granule may contain about 25% to about 95%, about 35% to about 95%, about 50% to about 80%, or combinations thereof, and any percentage integer or range of percentage integers of PEG within any of the foregoing ranges.

[0053] Water-soluble polymers may include materials selected from the group consisting of: formula H-(C2H4O) x -(CH(CH3)CH2O) y -(C2H4O) z-OH polyalkylene polymers, wherein x is about 50 to about 300, y is about 20 to about 100, and z is about 10 to about 200; formula (C2H4O) q -C(O)O-(CH2) r -CH3 polyethylene glycol fatty acid esters, wherein q is about 20 to about 200 and r is about 10 to about 30; formula HO-(C2H4O) s -(CH2) t Polyethylene glycol fatty alcohol ethers of formula H-(C2H4O), wherein s is about 30 to about 250 and t is about 10 to about 30; and mixtures thereof. x -(CH(CH3)CH2O) y -(C2H4O) z The polyalkylene polymer with -OH can be a block copolymer or a random copolymer, wherein x is about 50 to about 300, y is about 20 to about 100, and z is about 10 to about 200.

[0054] Water-soluble polymers may include: polyethylene glycol; formula H-(C2H4O) x -(CH(CH3)CH2O) y -(C2H4O) z -OH polyalkylene polymers, wherein x is about 50 to about 300, y is about 20 to about 100, and z is about 10 to about 200; formula (C2H4O) q -C(O)O-(CH2) r -CH3 polyethylene glycol fatty acid esters, wherein q is about 20 to about 200 and r is about 10 to about 30; and HO-(C2H4O) s -(CH2) t )-CH3 polyethylene glycol fatty alcohol ether, wherein s is about 30 to about 250 and t is about 10 to about 30.

[0055] The water-soluble polymer may contain about 20% to about 95% of the formula H-(C2H4O) based on the weight of a plurality of particles or on the weight of a single particle. x -(CH(CH3)CH2O) y -(C2H4O) z Polyalkylene polymers with -OH groups, wherein x is about 50 to about 300; y is about 20 to about 100; and z is about 10 to about 200.

[0056] The water-soluble polymer may contain about 1% to about 20% of the formula (C2H4O) based on the weight of multiple particles or on the weight of a single particle. q -C(O)O-(CH2) r-CH3 polyethylene glycol fatty acid esters, wherein q is about 20 to about 200 and r is about 10 to about 30.

[0057] The water-soluble polymer may contain about 1% to about 10% of the formula HO-(C2H4O) based on the weight of multiple particles or on the weight of a single particle. s -(CH2) t )-CH3 polyethylene glycol fatty alcohol ether, wherein s is about 30 to about 250 and t is about 10 to about 30.

[0058] The water-soluble carrier may contain a plasticizer polyol (0% to 3% by weight of the particles), wherein the plasticizer polymer is optionally liquid at 20°C and 1 atm; water (1% to 20%, or 1% to 12%, or 6% to 8% by weight of the particles); and sugar alcohol polyols selected from the group consisting of erythritol, xylitol, mannitol, isomaltitol, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof (45% to 80%, or 50% to 70%, or 50% to 60% by weight of the particles). The granules further comprise: (a) a modified starch having a dextrose equivalent of 15 to 20, wherein the sugar alcohol polyol and the modified starch are present in a weight ratio of 2:1 to 16:1, or 2:1 to 10:1, or 2:1 to 3:1; or (b) a modified starch having a dextrose equivalent of 4 to less than 15, wherein the sugar alcohol polyol and the modified starch are present in a weight ratio of 1.5:1 to 16:1, or 1.5:1 to 10:1, or 1.5:1 to 4. The modified starch may have a dextrose equivalent of 15 to 20, and the sugar alcohol polyol and the modified starch may be present in a ratio of 2:1 to 16:1, or 2:1 to 10:1, or 2:1 to 3:1. The modified starch may have a dextran equivalent of 4 to less than 15, and the sugar alcohol polyol and the modified starch may be present in a weight ratio of 1.5:1 to 16:1, or 1.5:1 to 10:1, or 1.5:1 to 4:1 to the modified starch. The modified starch may have a dextran equivalent of 4 to 12. The modified starch may be maltodextrin. The sugar alcohol polyol may be mannitol. The plasticizer polyol may be selected from the group consisting of glycerol, dipropylene glycol, propylene glycol, and mixtures thereof.

[0059] The particles may contain about 25% to about 99% water-soluble carrier by weight. Optionally, the particles may contain about 35% to about 85%, or even about 50% to about 80% water-soluble carrier by weight of the particles.

[0060] capsule

[0061] The compositions disclosed herein also comprise a plurality of capsules. As described in more detail below, the capsules may include a core surrounded by a substantially inorganic shell.

[0062] The capsules may be present in the particles of the composition in an amount of about 0.1% to about 20%, or about 0.2% to about 10%, or about 0.2% to about 5%, or about 0.2% to about 3% by weight of the composition. The composition may contain sufficient capsules to provide the composition with about 0.1% to about 20%, or about 0.2% to about 10%, or about 0.2% to about 5% of the flavoring ingredient by weight of the composition. When discussing the amount or weight percentage of capsules herein, it means the sum of the shell material and the core material.

[0063] The capsule may have an average shell thickness of 10 nm to 10,000 nm, optionally 170 nm to 1,000 nm, optionally 300 nm to 500 nm.

[0064] The capsules may have an average volume-weighted capsule diameter of 0.1 μm to 300 μm, optionally 10 μm to 200 μm, or optionally 10 μm to 50 μm. It has been advantageously found that large capsules (e.g., an average diameter of 10 μm or greater) can be provided according to the embodiments described herein without sacrificing the overall stability of the capsule and / or simultaneously maintaining good burst strength.

[0065] Surprisingly, it has been found that, in addition to the inorganic shell, the volumetric core-shell ratio can play a significant role in ensuring the physical integrity of the capsule. Shells that are too thin relative to the overall size of the capsule (core:shell ratio > 98:2) tend to lack self-integrity. On the other hand, extremely thick shells relative to the capsule diameter (core:shell ratio < 80:20) tend to have higher shell permeability in surfactant-rich matrices. While one might intuitively assume that a thick shell would lead to lower shell permeability (since this parameter affects the average diffusion path of the active substance through the shell), it has been surprisingly found that capsules of the present invention with shells having a thickness above a threshold exhibit higher shell permeability. This upper threshold is believed to depend in part on the capsule diameter.

[0066] The capsules may have a core-shell volume ratio of 50:50 to 99:1, optionally 60:40 to 99:1, optionally 70:30 to 98:2, or optionally 80:20 to 96:4.

[0067] Specific combinations of these capsule properties may be desired. For example, a capsule may have a volume core-shell ratio of about 99:1 to about 50:50, and an average volume-weighted capsule diameter of about 0.1 μm to about 200 μm and an average shell thickness of about 10 nm to about 10,000 nm. Another capsule may have a volume core-shell ratio of about 99:1 to about 50:50, and an average volume-weighted capsule diameter of about 10 μm to about 200 μm and an average shell thickness of about 170 nm to about 10,000 nm. A third capsule may have a volume core-shell ratio of about 98:2 to about 70:30, and an average volume-weighted capsule diameter of about 10 μm to about 100 μm and an average shell thickness of about 300 nm to about 1000 nm.

[0068] The method according to this disclosure can produce capsules with a low coefficient of variation in capsule diameter. Control over the capsule size distribution can advantageously allow the population to have improved and more uniform burst strength. The capsule population can have a coefficient of variation in capsule diameter of 40% or less, optionally 30% or less, optionally 20% or less.

[0069] In order for capsules containing nuclear material to function effectively and cost-effectively in consumer product applications such as laundry care granule additives, they should: i) resist nuclear diffusion (e.g., low leakage or permeability) during the shelf life of the liquid product; ii) have the ability to deposit on the target surface during application (e.g., washing machine cycle); and iii) be able to release the nuclear material to the end consumer by mechanical shell rupture at the appropriate time and place to provide the intended beneficial effects.

[0070] The capsules described herein may have an average burst strength of 0.1 MPa to 10 MPa, optionally 0.25 MPa to 5 MPa, optionally 0.25 MPa to 3 MPa. Completely inorganic capsules traditionally have poor burst strength, while the capsules described herein may have a burst strength greater than 0.25 MPa, thereby providing improved stability and triggered release of the beneficial agent at a specified burst stress.

[0071] In some embodiments, the average volume-weighted diameter of the capsule is from 1 micrometer to 200 micrometers, optionally from 1 micrometer to 10 micrometers, or optionally from 2 micrometers to 8 micrometers. In another embodiment, the shell thickness is from 1 nm to 10000 nm, from 1 nm to 1000 nm, or from 10 nm to 200 nm. In yet another embodiment, the capsule has an average volume-weighted diameter of 1 micrometer to 10 micrometers and a shell thickness of 1 nm to 200 nm. It has been found that capsules with an average volume-weighted diameter of 1 micrometer to 10 micrometers and a shell thickness of 1 nm to 200 nm have higher burst strength.

[0072] Unbound by theory, higher burst strength is believed to provide better durability during the washing process, which can cause mechanically weak capsules to burst prematurely due to mechanical constraints in the washing machine.

[0073] Capsules having an average volume-weighted diameter of 1 to 10 micrometers and a shell thickness of 10 nm to 200 nm, when prepared with a specifically selected silica precursor, provide resistance to mechanical constraints. In some embodiments, the precursor has a molecular weight of 2 kDa to 5 kDa, optionally 2.5 kDa to 4 kDa. Furthermore, careful selection of the precursor concentration is required, wherein the concentration is 20% to 60% by weight, preferably 40% to 60% by weight, of the oil phase used during encapsulation.

[0074] Unbound by theory, higher molecular weight precursors are believed to have a much slower migration time from the oil phase to the aqueous phase. This slower migration time is thought to be caused by a combination of three phenomena: diffusion, partitioning, and reaction kinetics. This phenomenon can be important in the case of small-sized capsules because the total surface area between the oil and water in the system increases with decreasing capsule diameter. The higher surface area leads to greater migration of the precursor from the oil phase to the aqueous phase, which in turn reduces the polymerization yield at the interface. Therefore, higher molecular weight precursors can mitigate the effects of increased surface area and yield capsules according to the invention.

[0075] i. core

[0076] The capsule includes a core. The core may be oil-based or water-based. Optionally, the core is oil-based. The core may be liquid at the temperature at which the product is prepared. The core may be liquid at or near room temperature.

[0077] The core includes flavoring. Based on the total weight of the core, the core may contain from about 1% to 100% by weight of flavoring. Optionally, the core may contain from about 50% to 100% by weight of flavoring based on the total weight of the core, and optionally from 80% to 100% by weight of flavoring based on the total weight of the core. Generally, a higher level of flavoring is preferred to improve delivery efficiency.

[0078] Fragrances may contain one or more, optionally two or more fragrance ingredients. As used herein, the term "fragrance ingredient" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mol and which may be used alone or in combination with other PRMs to impart odor, aroma, flavor, or fragrance. Typical PRMs include, in particular, alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes, such as terpenes. A list of common PRMs can be found in various references, such as "Perfume and Flavor Chemicals," Volumes I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology," Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0079] PRMs are characterized by their boiling point (BP) measured at atmospheric pressure (760 mm Hg) and their octanol / water partition coefficient (P), which can be described by logP and determined according to the test methods described in the Test Methods section. Based on these properties, PRMs can be classified into Quadrant I, Quadrant II, Quadrant III, or Quadrant IV PRMs, as detailed below. It may be desirable for fragrances to have multiple PRMs from different quadrants, for example, to provide beneficial aromatic effects at different points of contact during normal use.

[0080] A flavoring compound (PRM) having a boiling point (BP) below about 250°C and less than about 3 logP is designated as a Quadrant I PRM. Quadrant I PRMs are optionally limited to less than 30% of the flavoring composition. A flavoring compound (PRM) having a BP above about 250°C and greater than about 3 logP is designated as a Quadrant IV PRM, a flavoring compound (PRM) having a BP above about 250°C and less than about 3 logP is designated as a Quadrant II PRM, and a flavoring compound (PRM) having a BP below about 250°C and greater than about 3 logP is designated as a Quadrant III PRM. Suitable Quadrant I, II, III, and IV PRMs are disclosed in U.S. Patent 6,869,923B1.

[0081] Flavorings may contain a mixture of at least three, or even at least five, or at least seven PRMs. Flavorings may contain at least ten or at least fifteen PRMs. A mixture of PRMs may, for example, provide a more complex and desired aroma at multiple contact points, and / or better flavor performance or persistence. However, it may be desirable to limit the number of PRMs in a flavoring to reduce or limit formulation complexity and / or cost.

[0082] Fragrances may contain at least one fragrance ingredient from a natural source. Such components may be desirable for sustainability / environmental reasons. Naturally sourced fragrance ingredients (PRMs) may include natural extracts or essential oils, which may comprise mixtures of PRMs. Such natural extracts or essential oils may include orange oil, lemon oil, rose extract, lavender, musk, green sage, balsam essence, sandalwood oil, pine oil, cedarwood, etc. PRM can be selected from the following blends: Almond Oil, Okra, Angelica Seed Oil, Artemisia Oil, Basil Oil, Benzoin Extract, Bergamot Essential Oil, Bergamot Oil, Black Pepper Oil, Black Pepper Flavor, Blackcurrant Flavor, Blood Orange Oil, Bois des Landes, Pure Juniper Brandy Flavor, Juniper, Roman Chamomile, Cardamom Pulp Extract, Cardamom Oil, Carrot Heart, Extra Caryophyllene, Cedarwood, Cedarwood Leaf, Cedarwood Oil, Ceylon Cinnamon Bark, Ceylon Cinnamon Extract, Beeswax, Citronellol, Citronellal, Clary Sage Essential Oil, Distilled Clove Leaf Oil, Bitter Croaker Balsam, Coriander, Cos Cos Anethol, Russian Coriander Essence (russie), cucumber extract, fennel oil, cyperus rotundus core, elegans core, elegans oil, English white chamomile, eucalyptol, lemon eucalyptus, eugenol, coumarin core, ginger, grapefruit substitute, guaiac oil, bitter rue oil, guaiac extract, immortelle, isoeugenol, jasmine semperflorens, juniper berry oil, lime, rock rose, bright lavender oil, mixed lavender, lavender essential oil, lemon cedarwood, lemon oil, green lemon peel, lemongrass, lemongrass oil, litsea cubeba, magnolia oil. Yellow mandarin oil, crystallized menthol, peppermint leaf, narcissus, neroli oil, nutmeg, neroli water, orange oil, orange saffron oil, organic rose water, osmanthus, patchouli, patchouli heart, patchouli oil, black pepper oil, peppermint, pure Peruvian balsam, petitgrain, allspice oil, pink pepper, raspberry essence, rose alcohol, rose, centifolia rose, sandalwood, Sichuan pepper extract, white benzoin, sweet orange oil, mandarin orange oil, vanilla, vetiver, violet leaf, violet foliage, wormwood oil, and combinations thereof.

[0083] In addition to the PRM, the core may also contain preflavorings, which can help improve the persistence of the beneficial effects of freshness. Preflavorings may contain non-volatile materials that are released or transformed into flavoring materials by, for example, simple hydrolysis, or may be preflavorings that are triggered by pH changes (e.g., by a decrease in pH), or may be preflavorings that are released by enzymes, or light-triggered preflavorings. Depending on the preflavorings selected, preflavorings may exhibit different release rates.

[0084] The core of the encapsulation disclosed herein may contain a core modifier, such as a partition modifier and / or a density modifier. In addition to fragrance, the core may also contain a core modifier comprising, based on the total core weight, greater than 0% to 80%, optionally greater than 0% to 50%, and optionally greater than 0% to 30%. The partition modifier may include materials 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 docosanoate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning 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 include castor oil and / or soybean oil. Other partitioning modifiers that can be used in the flavoring encapsulations described herein are described in U.S. Patent Application Publication 20110268802, which is incorporated herein by reference.

[0085] ii. Shell

[0086] The capsule disclosed herein includes a shell surrounding the core.

[0087] The shell may include a first shell component. The shell may optionally include a second shell component surrounding the first shell component. The first shell component may include a condensation layer formed from the condensation product of the precursor. As described in detail below, the precursor may comprise one or more precursor compounds. The first shell component may include a layer of nanoparticles. The second shell component may comprise an inorganic material.

[0088] The shell can be substantially inorganic (defined later). A substantially inorganic shell may include a first shell component comprising a condensation layer surrounding the core, and may also include a nanoparticle layer surrounding the condensation layer. A substantially inorganic shell may also include a second shell component surrounding the first shell component. The first shell component comprises an inorganic material, optionally a metal / semi-metal oxide, optionally SiO2, TiO2, and Al2O3, and optionally SiO2. The second shell component comprises an inorganic material, optionally comprising a material selected from the group consisting of metal / semi-metal oxides, metals, and minerals, optionally selected from the list of SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, clay, gold, silver, iron, nickel, and copper, and optionally selected from SiO2 and CaCO3. Optionally, the material of the second shell component has the same type of chemical properties as the first shell component to maximize chemical compatibility.

[0089] The first shell component may include a condensation layer surrounding the core. The condensation layer may be a condensation product of one or more precursors. One or more precursors may comprise at least one compound selected from the group consisting of formulas (I), (II), and mixtures thereof, wherein formula (I) is (M v O z Y n ) w And where equation (II) is (M) v O z Y n R 1 p ) w Preferably, the precursor contains only formula (I) and no compound according to formula (II), for example, to reduce the organic content of the capsule shell (i.e., no R). 1 Groups). Formulas (I) and (II) are described in more detail below.

[0090] One or more precursors may have formula (I):

[0091] (M v O z Y n ) w (Formula I),

[0092] Where M is one or more of silicon, titanium, and aluminum, v is the valence of M and is 3 or 4, z is 0.5 to 1.6, preferably 0.5 to 1.5, and each Y is independently selected from -OH, -OR 2 -NH2, -NHR 2 -N(R) 2 )2, where R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl, or 5-12 membered heteroaryl containing 1 to 3 cyclic heteroatoms selected from O, N, and S, R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 Aryl, or 5-12-membered heteroaryl containing 1 to 3 cyclic heteroatoms selected from O, N and S, n is 0.7 to (v-1) and w is 2 to 2000.

[0093] One or more precursors may have formula (I), where M is silicon. It is possible that Y is -OR 2 It is possible that n is 1 to 3. It is also possible that Y is -OR. 2 And n can be between 1 and 3. It is possible that n is at least 2, and one or more of Y are -OR. 2And one or more of Y are -OH.

[0094] R 2 It can be C1 to C 20 Alkyl group. R 2 It can be C6 to C 22 Aryl. R 2 It can be one or more of C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, and C8 alkyl. 2 It can be a C1 alkyl group. R 2 It can be a C2 alkyl group. R 2 It can be a C3 alkyl group. R 2 It can be a C4 alkyl group.

[0095] It is possible that z is 0.5 to 1.3, or 0.5 to 1.1, 0.5 to 0.9, or 0.7 to 1.5, or 0.9 to 1.3, or 0.7 to 1.3.

[0096] Optionally, M represents silicon, v represents 4, and each Y represents -OR. 2 n is 2 and / or 3, and each R 2 It is a C2 alkyl group.

[0097] The precursor may contain polyalkoxysilane (PAOS). The precursor may contain polyalkoxysilane (PAOS) ​​synthesized via a hydrolysis process.

[0098] The precursor may alternatively include one or more of the compounds of formula (II):

[0099] (M v O z Y n R 1 p ) w (Equation II)

[0100] Where M is one or more of silicon, titanium, and aluminum, v is the valence of M and is 3 or 4, z is 0.5 to 1.6, preferably 0.5 to 1.5, and each Y is independently selected from -OH, -OR 2 ,halogen, -NH2、-NHR 2 -N(R) 2 )2 and Where R 2 Selected from C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl, or 5-12 membered heteroaryl containing 1 to 3 cyclic heteroatoms selected from O, N, and S, R 3 H, C1 to C20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl, or 5-12 membered heteroaryl containing 1 to 3 cyclic heteroatoms selected from O, N, and S, n being 0 to (v-1), each R 1 Independently selected from C1 to C 30 Alkyl, C1 to C 30 C1 to C2 substituted with one or more of the following: alkylene, halogenated, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl. 30 Alkyl groups, or those substituted with one or more of halogens, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups, from C1 to C2. 30 Alkylene, p exists in an amount of at most pmax, and w is from 2 to 2000; and p is a positive number of at most pmax, where pmax = 60 / [9*Mw(R 1 )+8], where Mw(R 1 ) is R 1 Molecular weight of the functional group.

[0101] R 1 It can be a C1 to C2 column substituted with one to four independently selected groups selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups. 30 Alkyl group. R 1 It can be a C1 to C2 column substituted with one to four independently selected groups selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups. 30 Alkylene.

[0102] As described above, in order to reduce or even eliminate the organic content in the first shell component, it is preferable to reduce or even eliminate the presence of compounds of formula (II) having an R1 group. The precursor, condensation layer, first shell component, and / or shell may be free of compounds of formula (II).

[0103] The precursors of formula (I) and / or (II) may be characterized by one or more physical properties, namely molecular weight (Mw), degree of branching (DB), and polydispersity index (PDI) of the molecular weight distribution. It is believed that selecting a specific Mw and / or DB can be used to obtain capsules that retain their mechanical integrity after surface drying and have low shell permeability in a surfactant-based matrix. The precursors of formula (I) and (II) may be characterized by a DB of 0 to 0.6, preferably 0.1 to 0.5, optionally 0.19 to 0.4, and / or a Mw of 600 Da to 100,000 Da, preferably 700 Da to 60,000 Da, optionally 1,000 Da to 30,000 Da. This characteristic provides the useful properties of the precursors to obtain the capsules of the present invention. The precursors of formula (I) and / or (II) may have a PDI of 1 to 50.

[0104] The condensation layer comprising a metal / semi-metal oxide can be formed from the condensation product of a precursor comprising at least one compound of formula (I) and / or at least one compound of formula (II), optionally combined with a monomeric precursor of one or more metal / semi-metal oxides, wherein the metal / semi-metal oxide comprises TiO2, Al2O3, and SiO2, preferably SiO2. The monomeric precursor of the metal / semi-metal oxide may include formula M(Y). V-n R n The compound, wherein M, Y, and R are as defined in formula (II), and n can be an integer from 0 to 3. The monomeric precursor of the metal / semi-metal oxide is preferably in the form where M is silicon, and the compound has the general formula Si(Y). 4-n R n Where Y and R are as defined with respect to formula (II) and n can be an integer from 0 to 3. Examples of such monomers are TEOS (tetraethoxy orthosilicate), TMOS (tetramethoxy orthosilicate), TBOS (tetrabutoxy orthosilicate), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). These are not intended to limit the range of monomers that can be used, and it will be apparent to those skilled in the art what suitable monomers can be used in combination herein.

[0105] The first shell component may include an optional nanoparticle layer. The nanoparticle layer contains nanoparticles. The nanoparticles in the nanoparticle layer may be one or more of SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, clay, silver, gold, and copper. Optionally, the nanoparticle layer may contain SiO2 nanoparticles.

[0106] Nanoparticles may have an average diameter of 1 nm to 500 nm, optionally 50 nm to 400 nm.

[0107] The pore size of the capsule can be tuned by changing the shape of the nanoparticles and / or by using combinations of different nanoparticle sizes. For example, non-spherical, irregular nanoparticles can be used because they can have improved packing when forming nanoparticle layers, which is believed to produce a denser shell structure. This can be advantageous when limited permeability is required. The nanoparticles used can have more regular shapes, such as spheres. Any envisioned nanoparticle shape can be used herein.

[0108] Nanoparticles may be substantially free of hydrophobic modification. Nanoparticles may be substantially free of organic compound modification. Nanoparticles may contain organic compound modification. Nanoparticles may be hydrophilic.

[0109] Nanoparticles may contain surface modifications, such as, but not limited to, straight-chain or branched C1 to C2 groups. 20 Alkyl groups, surface amino groups, surface methacrylyl groups, surface halogens, or surface thiols. These surface modifications allow for the presence of covalently bonded organic molecules on the surface of the nanoparticles. When inorganic nanoparticles are disclosed in this document, this means either including or excluding any of the aforementioned surface modifications without explicit indication.

[0110] The capsule disclosed herein can be defined as comprising a substantially inorganic shell, which includes a first shell component and a second shell component. Substantially inorganic means that the first shell component may contain at most 10% by weight or at most 5% by weight of organic matter, preferably at most 1% by weight, as defined later in the calculation of organic matter content. It may be preferred that the first shell component, the second shell component, or both contain no more than about 5% by weight, preferably no more than about 2% by weight, and optionally about 0% by weight of organic matter, depending on the circumstances.

[0111] While the first shell component can be used to construct a mechanically stable scaffold or framework, it also provides low shell permeability in liquid products containing surfactants (such as laundry detergents, shower gels, cleaning agents, etc.) (see Surfactants in Consumer Products, J. Falbe, Springer-Verlag). The second shell component significantly reduces shell permeability, which improves capsule impermeability in surfactant-based matrices. The second shell component also significantly improves capsule mechanical properties, such as capsule bursting force and burst strength. Without being bound by theory, it is believed that the second shell component contributes to overall shell densification by depositing precursors in the pores retained in the first shell component. The second shell component also adds an additional inorganic layer to the capsule surface. These improved shell permeability and mechanical properties provided by the second shell component only occur when used in combination with a first shell component as defined in this invention.

[0112] More detailed descriptions of the shell structures, their materials, and how they interact with each other to provide optimal performance can be found in U.S. patent applications 16 / 851173, 16 / 851176, and 16 / 851194, the entire contents of which are incorporated herein by reference.

[0113] iii. Methods for preparing capsules

[0114] The capsules of this disclosure can be formed by first mixing a hydrophobic material with any of the precursors for the condensation layer as defined above to form an oil phase, wherein the oil phase may comprise an oil-based and / or oil-soluble precursor. The precursor / hydrophobic material mixture is then used as a dispersed phase or as a continuous phase bound to water, wherein in the former case an O / W (oil-in-water) emulsion is formed, and in the latter case a W / O (water-in-oil) emulsion is formed once the two phases are mixed and homogenized by methods known to those skilled in the art. Preferably, an O / W emulsion is formed. Nanoparticles may be present in the aqueous and / or oil phases, regardless of the desired emulsion type. The oil phase may comprise an oil-based core modifier and / or an oil-based beneficial agent, as well as the precursor for the condensation layer. Suitable core materials for the oil phase have been previously described herein.

[0115] Once any emulsion has been formed, the following steps can be performed:

[0116] (a) Nanoparticles migrate to the oil / water interface, thereby forming a nanoparticle layer.

[0117] (b) The precursor containing the metal / semi-metal oxide precursor will initiate a hydrolysis / condensation reaction with water at the oil / water interface to form a condensation layer surrounded by a nanoparticle layer. The precursor of the condensation layer can further react with the nanoparticles of the nanoparticle layer.

[0118] Based on the total weight of the oil phase, the precursor for forming the condensation layer may be present in an amount of 1% to 50% by weight, preferably 10% to 40% by weight.

[0119] The oil phase composition may include any compounds as defined in the core section above. Prior to emulsification, the oil phase may contain 10% by weight to about 99% by weight of a beneficial agent.

[0120] In the method for preparing capsules according to this disclosure, the oil phase may be a dispersed phase, and the continuous aqueous (or water) phase may include water, an acid or base, and nanoparticles. At least when both the oil phase and the aqueous phase are mixed together, the aqueous (or water) phase may have a pH of 1 to 11, preferably 1 to 7. The acid may be a strong acid. Strong acids may include one or more of HCl, HNO3, H2SO4, HBr, HI, HClO4, and HClO3, preferably HCl. The acid may be a weak acid. The weak acid may be acetic acid or HF. The concentration of the acid in the continuous aqueous phase may be 10. -7 M to 5M. The base can be an inorganic or organic base, preferably an inorganic base. Inorganic bases can be hydroxides, such as sodium hydroxide and ammonia. For example, minerals can be about 10. -5 M to 0.01M NaOH, or about 10 -5 M to approximately 1M ammonia. The list of acids and bases listed above, and their concentration ranges, is not intended to limit the scope of the invention, and other suitable acids and bases that allow control of the pH of the continuous phase are considered herein.

[0121] In the method for preparing the capsules according to this disclosure, the pH can be altered throughout the process by adding an acid and / or a base. For example, the method can be initiated with an aqueous phase at an acidic or neutral pH, and then a base can be added during the process to increase the pH. Alternatively, the method can be initiated with an aqueous phase at an alkaline or neutral pH, and then an acid can be added during the process to decrease the pH. Furthermore, the method can be initiated with an aqueous phase at an acidic or neutral pH, and then an acid can be added during the process to further decrease the pH. Alternatively, the method can be initiated with an aqueous phase at an alkaline or neutral pH, and then a base can be added during the process to further increase the pH. Any suitable pH variation can be used. Furthermore, any suitable combination of acid and base can be used in the method at any time to achieve the desired pH. Any of the above-described nanoparticles can be used in the aqueous phase. The nanoparticles can be present in an amount from about 0.01 wt% to about 10 wt% based on the total weight of the aqueous phase.

[0122] The method may include mixing an oil phase and an aqueous phase at a ratio of about 1:10 to about 1:1.

[0123] The second shell component can be formed by mixing a capsule having the first shell component with a solution of a second shell component precursor. The solution of the second shell component precursor may contain a water-soluble or oil-soluble second shell component precursor. The second shell component precursor may be one or more of a compound of formula (I) as defined above, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). The second shell component precursor may also contain Si(Y). 4-n R n One or more of the following type of silane monomers, wherein Y is a hydrolyzable group, R is a non-hydrolyzable group, and n can be an integer from 0 to 3. Examples of such monomers are given earlier in this paragraph, and these are not intended to limit the range of monomers that can be used. Second shell component precursors may comprise silicates, titanates, aluminates, zirconates, and / or zincates. Second shell component precursors may comprise carbonates and calcium salts. Second shell component precursors may comprise salts of iron, silver, copper, nickel, and / or gold. Second shell component precursors may comprise zinc, zirconium, silicon, titanium, and / or aluminum alkoxides. Second shell component precursors may comprise one or more of the following silicate solutions: sodium silicate, tetrasilyl alcohol solution, ferric sulfate and ferric nitrate, titanium alkoxide solution, aluminum trioxide solution, zinc glycol solution, zirconium alcohol solution, calcium salt solution, and carbonate solution. Second shell components containing CaCO3 can be obtained from the combined use of calcium salts and carbonates. Second shell components containing CaCO3 can be obtained from calcium salts by in-situ generation of carbonate ions from CO2 without the addition of carbonates.

[0124] The second shell component precursor may contain any suitable combination of any of the compounds listed above.

[0125] The solution of the second shell component precursor can be added dropwise to the capsule comprising the first shell component. The solution of the second shell component precursor and the capsule can be mixed together for 1 minute to 24 hours. The solution of the second shell component precursor and the capsule can be dissolved at room temperature or at high temperatures such as 20°C to 100°C.

[0126] Mixed together.

[0127] Based on the total weight of the solution of the second shell component precursor, the second shell component precursor solution may contain an amount of 1% to 50% by weight of the second shell component precursor.

[0128] The capsule having the first shell component can be mixed with a solution of the second shell component precursor at a pH of 1 to 11. The solution of the second shell component precursor may contain an acid and / or a base. The acid may be a strong acid. Strong acids may include one or more of HCl, HNO3, H2SO4, HBr, HI, HClO4, and HClO3, preferably HCl. In other embodiments, the acid may be a weak acid. In embodiments, the weak acid may be acetic acid or HF. The concentration of the acid in the second shell component precursor solution may be 10. -7 M to 5M. The base can be an inorganic or organic base, preferably an inorganic base. Inorganic bases can be hydroxides, such as sodium hydroxide and ammonia. For example, minerals can be about 10. -5 M to 0.01M NaOH, or about 10 -5 M to approximately 1M ammonia. The list of acids and bases provided above is not intended to limit the scope of the invention, and other suitable acids and bases that allow for control of the pH of the precursor solution for the second shell component are considered herein.

[0129] Methods for forming a second shell component may include pH variations during the process. For example, the process of forming a second shell component may be initiated at an acidic or neutral pH, and then a base may be added during the process to raise the pH. Alternatively, the process of forming a second shell component may be initiated at an alkaline or neutral pH, and then an acid may be added during the process to lower the pH. Furthermore, the process of forming a second shell component may be initiated at an acidic or neutral pH, and an acid may be added during the process to further lower the pH. Alternatively, the process of forming a second shell component may be initiated at an alkaline or neutral pH, and a base may be added during the process to further raise the pH. Any suitable pH variation may be used. Furthermore, any suitable combination of acid and base may be used at any time in the solution of the second shell component precursor to achieve the desired pH. Methods for forming a second shell component may include maintaining a stable pH with a maximum deviation of + / - 0.5 pH units during the process. For example, the process of forming a second shell component may be maintained at an alkaline, acidic, or neutral pH. Alternatively, the process of forming a second shell component may be maintained within a specific pH range by controlling the pH using an acid or base. Any suitable pH range may be used. Furthermore, any suitable combination of acid and base can be used at any time in the solution of the second shell component precursor to maintain a stable pH within the desired range.

[0130] A more detailed description of the method for preparing the capsule and the relevant properties of all shell component precursors (i.e., condensation layer precursors, nanoparticles, and second shell component precursors) can be found in U.S. Patent Applications 16 / 851173, 16 / 851176, and 16 / 851194, the full contents of which define the method for preparing the capsule of the present invention.

[0131] Whether preparing an oil-based core or an aqueous core, the emulsion can be cured under conditions that solidify the precursor, thereby forming a shell surrounding the core.

[0132] The reaction temperature used for curing can be increased to improve the rate of obtaining cured capsules. The curing process can cause condensation of the precursor. The curing process can be carried out at or above room temperature. The curing process can be carried out at temperatures from 30°C to 150°C, preferably from 50°C to 120°C, and optionally from 80°C to 100°C. The curing process can be completed within any suitable time period so that the capsule shell can be strengthened by the condensation of the precursor material. The curing process can be carried out from 1 minute to 45 days, preferably from 1 hour to 7 days, and optionally from 1 hour to 24 hours. The capsule is considered cured when it no longer collapses. The determination of capsule collapse is described in detail below. During the curing step, it is believed that hydrolysis of the Y portion (from formula (I) and / or (II) occurs, followed by subsequent condensation of the -OH group with another -OH group or another portion of the Y type (where the two Y portions are not necessarily the same). The hydrolyzed precursor portion will initially condense with the surface portion of the nanoparticles (provided that they contain such portions). As shell formation proceeds, the precursor portion will react with the pre-formed shell.

[0133] A curable emulsion causes the shell precursor to condense. The curable emulsion causes the shell precursor to react with nanoparticles and condense. An example of the hydrolysis and condensation steps of the silica-based shell described herein is shown below:

[0134] Hydrolysis: ≡Si-OR + H₂O → ≡Si-OH + ROH

[0135] Condensation: ≡Si-OH + ≡Si-OR → ≡Si-O-Si≡ + ROH

[0136] ≡Si-OH+≡Si-OH→≡Si-O-Si≡+H2O.

[0137] For example, when using the precursor of formula (I) or (II), the hydrolysis and condensation steps are described below:

[0138] Hydrolysis: ≡M-Y + H₂O → ≡M-OH + YH

[0139] Condensation: ≡M-OH+≡MY→≡MOM≡+YH

[0140] ≡M-OH+≡M-OH→≡MOM≡+H2O.

[0141] The capsules may be provided as a slurry composition (or simply "slurry" herein). The method described herein may result in a slurry containing capsules. The slurry may be formulated into products, such as consumer products.

[0142] The composition may comprise other flavor capsules. These capsules may be core-shell capsules and may contain more than 5% by weight of organic material based on the weight of the shell material. Such capsules may be considered “organic” capsules in this disclosure to distinguish them from the inorganic capsules described and claimed herein. The shell material of the organic capsule may include materials derived from melamine, polyacrylamide, silicone, polystyrene, polyurea, polyurethane, polyacrylate-based materials, gelatin, styrene malic anhydride, polyamide, and mixtures thereof, preferably polymeric materials. The organic capsule may be coated with a deposition aid, cationic polymer, nonionic polymer, anionic polymer, or mixture thereof. Suitable deposition polymers may be selected from the group consisting of: polyethylene formaldehyde, partially hydroxylated polyethylene formaldehyde, polyethyleneamine, polyethyleneimine, ethoxylated polyethyleneimine, polyvinyl alcohol, polyacrylate, cationic polysaccharides (such as chitosan), and combinations thereof. Organic capsules may have a volume-weighted average particle size of about 0.5 micrometers to about 100 micrometers, preferably about 1 micrometer to about 60 micrometers, or alternatively about 25 micrometers to about 60 micrometers, optionally about 25 micrometers to about 60 micrometers.

[0143] Methods for handling clothing

[0144] A method for treating clothing may include the following steps: providing clothing articles in a washing machine; dispensing a composition comprising multiple particles into the washing machine; and contacting the clothing articles with the composition during a wash sub-cycle of the washing machine. The washing machine may have a wash sub-cycle and a rinse sub-cycle. Approximately 5g to approximately 50g of the particle composition may be dispensed into the washing machine.

[0145] By delivering the beneficial fragrance effects via a wash subcycle, consumers only need to dispense the detergent composition and the multi-particle composition into a single location, such as the wash tub, before or shortly after starting the washing machine. This may be more convenient for consumers than using a rinse additive composition, which is dispensed separately into the wash tub after the wash subcycle is completed, such as before, during, or between two rinse cycles. Using the automatic dispensing units of modern vertical and high-efficiency machines can be inconvenient because it requires dispensing the rinse additive composition into a location that is not used for dispensing the detergent composition.

[0146] Optionally, the method may further include a step of contacting the garment with a detergent composition during a washing sub-cycle of the washing machine, the detergent composition comprising about 3% to about 60%, optionally 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 different from the granules. The detergent composition may optionally be provided separately from the granules. The detergent composition may be dispensed separately from a composition comprising a plurality of granules.

[0147] A washing machine has at least two basic sub-cycles within its operating cycle: a washing sub-cycle and a rinsing sub-cycle. The washing sub-cycle is the cycle that begins when water is first added or partially added to fill the washing tub. The main purpose of the washing sub-cycle is to remove and / or loosen dirt from the clothes and to suspend the dirt in the washing liquid. Typically, the washing liquid is drained at the end of the washing sub-cycle. The rinsing sub-cycle occurs after the washing sub-cycle and has the main purpose of rinsing away dirt and, optionally, removing some of the beneficial substances brought into the washing sub-cycle by the clothes.

[0148] The method may optionally include the step of contacting the garment with a detergent composition containing an anionic surfactant during a wash cycle. Most consumers provide the detergent composition to the wash tub during a wash cycle. The detergent composition may contain anionic surfactants and optional other beneficial agents, including but not limited to fragrances, bleach, brighteners, color-correcting dyes, enzymes, etc. During the wash cycle, the beneficial agents provided with the detergent composition come into contact with or are applied to the garment in the wash tub. Typically, the beneficial agents of the detergent composition are dispersed in water and the wash liquid of the beneficial agents.

[0149] During the washing sub-cycle, the washing tub may be filled or at least partially filled with water. Individual particles of the composition may dissolve or disperse in water to form a washing liquid comprising the particle component. Optionally, if a detergent composition is used, the washing liquid may comprise components of the detergent composition and the particle component. Multiple particles may be placed in the washing tub of the washing machine before clothing articles are placed in it. Multiple particles may be placed in the washing tub of the washing machine after clothing articles are placed in it. Multiple particles may be placed in the washing tub before filling or partially filling the tub with water or after filling the tub with water has begun.

[0150] If a consumer uses a detergent composition to implement a method of treating clothing articles, the detergent composition and the particles of the composition may be provided in separate packaging. For example, the detergent composition may be a liquid detergent composition provided from a bottle, sachet, water-soluble sachet, measuring cup, measuring ball, or cartridge associated with a washing machine. The particles of the composition may be provided in separate packaging, in a non-limiting example, as a carton, bottle, water-soluble sachet, measuring cup, sachet, etc. If the detergent composition is in solid form such as powder, water-soluble fiber substrate, water-soluble sheet, water-soluble film, water-soluble membrane, or water-insoluble fiber web carrying the solid detergent composition, the particles of the composition may have a solid form of the detergent composition. For example, the particles of the composition may be provided in a container containing a mixture of the solid detergent composition and the particles of the composition. Optionally, the particles of the composition may be provided in sachets formed from the detergent composition, which may be a water-soluble fiber substrate, water-soluble sheet, water-soluble film, water-soluble membrane, or water-insoluble fiber web carrying the solid detergent composition.

[0151] Methods for forming particles

[0152] The granules of the composition can be prepared by a method comprising multiple steps. The granules can be formed by tableting or melt processing. A melt composition comprising about 25% to about 99% by weight of a water-soluble carrier and about 0.1% to about 20% by weight of capsules can be prepared.

[0153] This can be achieved by using pellet manufacturing equipment 11 ( Figure 1 The molten composition 20 can be formed into particles. The molten composition 20 can be prepared in a batch mixer 110 or a continuous mixer 110, or by manually mixing the component materials on a workbench surface. When the carrier is a water-soluble polymer, the water-soluble polymer can be heated to a temperature above the melting point of the water-soluble polymer and below the flash point or boiling point of the flavoring within the capsule.

[0154] A molten composition 20 comprising a water-soluble polymer carrier and a capsule can be deposited onto a moving conveyor 80 through one or more orifices 60 as an extruder or as droplets 85. The mixture may optionally be deposited into a recess in a mold and cooled or allowed to solidify into granules 90. The granules can be removed from the recess in the mold to produce a finished product. Multiple orifices may be provided in a dispenser 30. The molten composition 20 may be conveyed to the dispenser via a feed pipe 40. Optionally, a mixer 50, such as a static mixer 55, may be arranged in line with the feed pipe 40. Optionally, the feed pipe 40 may be insulated or provided with a heating jacket.

[0155] Optionally, granules 90 can be formed by passing a mixture comprising a water-soluble polymer carrier and a capsule through one or more orifices 60 of a dispenser and depositing the mixture onto a moving conveyor 80 below the one or more orifices 60. The mixture may solidify to form granules 90. The mixture may be deposited as an extrudate onto the moving conveyor 80, and the extrudate may be cut to form granules 90. Alternatively, the mixture may pass through one or more orifices 60 to form droplets on the moving conveyor 80, and the droplets may solidify to form granules 90.

[0156] Optionally, a gas feed pipe may be included upstream of the distributor 30 to include gas within the molten composition. Downstream of the gas feed pipe, the molten composition 30 may be abraded to break up bubbles, such that the melt is a gas-entrained melt. Particles formed from the gas-entrained melt may include bubbles. The gas feed pipe and a abrasive may be an integrated unit; as a non-limiting example, the OAKES bubbler (ETOakes 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 into the molten composition 20.

[0157] Particles

[0158] Each particle may 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, or alternatively about 38 mg. A single particle may have a mass of about 0.003 cm. 3 approximately 5cm 3 Optional, approximately 0.003cm 3 Approximately 1cm 3 Optional, approximately 0.003cm 3 To approximately 0.5cm 3 Optional, approximately 0.003cm 3 To approximately 0.2cm 3 Optional, approximately 0.003cm 3 To approximately 0.15cm 3 The volume of particles is considered important. Smaller particles are thought to provide better particle stacking in the container and faster dissolution during washing. The composition may contain less than 10% by weight of individual particles with a mass of less than about 10 mg. This can reduce the likelihood of dust accumulation.

[0159] In any of the disclosed embodiments or combinations, the particles disclosed herein may have a shape selected from spherical, hemispherical, oblate, cylindrical, polyhedral, and oblate-spherical. The particles may be hemispherical, compressed hemispherical, or have at least one substantially flat or flat surface. Compared to spherical particles, such particles may have a relatively high surface area to mass ratio. The dissolution time in water may decrease with increasing surface area, and a shorter dissolution time is preferred compared to a longer dissolution time.

[0160] The ratio of the maximum size to the minimum size of the particles disclosed herein can be approximately 10:1, optionally approximately 8:1, optionally approximately 5:1, optionally approximately 3:1, or optionally approximately 2:1. The particles disclosed herein can be formed such that the particles are not flakes. Particles with a maximum size to minimum size ratio greater than approximately 10, or flake-like particles, tend to be brittle, making them prone to turning into dust. The brittleness of the particles tends to decrease as the maximum size to minimum size ratio decreases.

[0161] The granules may comprise about 25% to 99% by weight of a water-soluble carrier and capsules dispersed in the water-soluble carrier. The granules may be provided from about 0.1% to about 20% by weight of the capsules in the composition.

[0162] The particles may contain less than about 20% anionic surfactant by weight, optionally less than about 10% anionic surfactant by weight, optionally less than about 5% anionic surfactant by weight, optionally less than about 3% anionic surfactant by weight, and optionally less than about 1% anionic surfactant by weight. The particles may also contain from 0% to about 20%, optionally from 0% to about 10%, optionally from about 0% to about 5%, optionally from about 0% to about 3%, and optionally from about 0% to about 1% anionic surfactant by weight.

[0163] The particles may contain less than about 10% water by weight.

[0164] The particles may include air bubbles. These bubbles may be spherical. Because the particles may include entrained air bubbles, 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 particles containing air bubbles to contain antioxidants, as the air bubbles can facilitate oxidation reactions within the particles. Each particle may have a density of less than about 1 g / cm³. 3 The density. Optionally, each particle may have a density of less than about 0.98 g / cm³. 3 The density. Optionally, each particle may have a density of less than about 0.95 g / cm³. 3 The density. Since the density of a typical washing solution is approximately 1 g / cm³. 3 Therefore, it may be desirable to provide each with a concentration of less than about 1 g / cm³. 3or even less than about 0.95 g / cm³ 3 Particles with a density of approximately 1 g / cm³. 3 A particle density of 90% is ideal for providing particles that float in the washing liquid.

[0165] Each particle may have a certain volume, and the gas adsorbate within the particle 90 may account for about 0.5% to about 50% of the particle volume, or even about 1% to about 20% of the particle volume, or even about 2% to about 15% of the particle volume, or even about 4% to about 12% of the particle volume. Without being bound by theory, it is believed that if the volume of the gas adsorbate 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.

[0166] Adsorbed particles can have an effective diameter ranging from about 1 micrometer to about 2000 micrometers, or even from about 5 micrometers to about 1000 micrometers, or even from about 5 micrometers to about 200 micrometers, or even from about 25 micrometers to about 50 micrometers. Generally, smaller gas adsorbed particles are considered more desirable than larger ones. If the effective diameter of the gas adsorbed particle is too large, it is believed that these particles may not be robust enough and may break in an undesirable manner during packaging, transportation, storage, and use. The effective diameter is the diameter of a sphere with the same volume as the gas adsorbed particle. Gas adsorbed particles can be spherical.

[0167] paper dryer

[0168] Capsules can also be practically used in dryer paper. Dryer paper may comprise a nonwoven fiber layer and a solid fabric softener composition loaded on or within said nonwoven fiber layer. The fabric softener composition may comprise multiple capsules dispersed within the solid fabric softener composition. The capsules may be those described herein.

[0169] Solid fabric softener compositions may contain quaternary ammonium compounds, optionally terpenoid quaternary ammonium compounds, optionally selected from the group consisting of: double tallow, dimethyl methyl ammonium sulfate, N,N-di(olenoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(low-erucic acid rapeseed oil-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(olenoyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)methyl ammonium sulfate, N,N-di(low-erucic acid rapeseed oil) N-methyl (2-hydroxyethyl)-N-methyl, N-(2-hydroxyethyl)methylammonium sulfate, N,N-di(oleylaminoethyl)-N-methyl, N-(2-hydroxyethyl)methylammonium sulfate, N,N-di(2-oleyloxyethyl)-N,N-dimethylammonium chloride, N,N-di(2-low erucic acid rapeseed oil oleyloxyethyl)-N,N-dimethylammonium chloride, N,N-di(2-oleyloxyethyl carbonyloxyethyl)-N,N-dimethylammonium chloride N,N-di(2-low erucic acid rapeseed oil oxyethyl carbonyl oxyethyl)-N,N-dimethylammonium chloride, N-(2-oleylenyl oxyethyl)-N-(2-oleylenyl oxyoxo-ethyl)-N,N-dimethylammonium chloride; N-(2-low erucic acid rapeseed oil oxyethyl)-N-(2-low erucic acid rapeseed oil oxyoxo-ethyl)-N,N-dimethylammonium chloride, N,N,N-tris(oleylenyl-oxy-ethyl)-N-methylammonium chloride, N,N,N-tris(oleylenyl-oxy-ethyl)-N-methylammonium chloride, N,N,N-tris (Low-erucic acid rapeseed oil-oxy-ethyl)-N-methylammonium chloride, N-(2-oleylenyloxyoxyethyl)-N-(oleylenyl)-N,N-dimethylammonium chloride, N-(2-low-erucic acid rapeseed oil-oxyoxyethyl)-N-(low-erucic acid rapeseed oil-)-N,N-dimethylammonium chloride, 1,2-dioleylenyloxyN,N,N-trimethylammonium propane chloride and 5,2-dioleylenyloxyN,N,N-trimethylammonium propane chloride, and combinations thereof. In one embodiment, the fabric conditioning active substance is N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)methylammonium sulfate, and mixtures thereof, wherein the fabric softening composition optionally comprises fatty acids.

[0170] Nonwoven fiber materials can have approximately 10 g / m 2 Approximately 50g / m 2 The basis weight. The nonwoven fiber material may be spunbond polyester terephthalate, optionally continuous filament spunbond terephthalate.

[0171] combination

[0172] The specific combinations contemplated in this disclosure are described herein in paragraphs indicated by the following letters. These combinations are illustrative in nature and not limiting.

[0173] A. A composition comprising a plurality of particles, wherein the particles comprise:

[0174] Water-soluble carrier comprising approximately 25% to approximately 99% by weight; and

[0175] Multiple capsules dispersed in the water-soluble carrier, wherein each capsule comprises a core and a shell surrounding the core, and the core contains a flavoring ingredient;

[0176] The shell comprises about 90% to 100%, optionally about 95% to 100%, optionally about 99% to 100% inorganic material by weight of the shell.

[0177] B. The composition according to paragraph A, wherein the inorganic material is selected from metal oxides, half-metal oxides, metals, minerals, and mixtures thereof, optionally selected from SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, clay, gold, silver, iron, nickel, copper, and mixtures thereof, optionally selected from SiO2, TiO2, Al2O3, CaCO3, and mixtures thereof, optionally SiO2.

[0178] C. The composition according to paragraph A or B, wherein the shell comprises a first shell component and a second shell component, the first shell component comprising a condensation layer and a nanoparticle layer, wherein the condensation layer comprises a condensation product of a precursor, and wherein the nanoparticle layer comprises inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer, the second shell component surrounding the first shell component, and wherein the second shell component surrounding the nanoparticle layer.

[0179] D. The composition according to any one of paragraphs A to C, wherein the capsule is characterized by one or more of the following:

[0180] Average volume-weighted capsule diameter from 10 μm to 200 μm, optionally from 10 μm to 190 μm;

[0181] Average shell thickness ranging from 170 nm to 1000 nm;

[0182] A core-shell volume ratio of approximately 50:50 to 99:1, optionally 60:40 to 99:1, optionally 70:30 to 98:2, optionally 80:20 to 96:4; and

[0183] The first shell component contains no more than 5% by weight, optionally no more than 2% by weight, and optionally 0% by weight of organic matter based on the weight of the first shell component.

[0184] E. The composition according to any one of paragraphs A to D, wherein the shell comprises:

[0185] The first shell component is essentially inorganic, consisting of a condensation layer and a nanoparticle layer.

[0186] The condensation layer comprises the condensation product of the precursor.

[0187] The nanoparticle layer comprises inorganic nanoparticles, and

[0188] The condensation layer is disposed between the core and the nanoparticle layer; and

[0189] An inorganic second shell component surrounding the first shell component.

[0190] The second shell component surrounds the nanoparticle layer;

[0191] The precursor comprises at least one compound selected from formula (I), formula (II), and mixtures thereof;

[0192] Where equation (I) is (M) v O z Y n ) w ;

[0193] Where equation (II) is (M) v O z Y n R 1 p ) w ;

[0194] For formulas (I), (II), or mixtures thereof, each M is independently selected from silicon, titanium, and aluminum, v is the valence of M and is 3 or 4, z is 0.5 to 1.6, and each Y is independently selected from -OH, -OR 2 ,halogen, -NH2、-NHR 2 -N(R) 2 )2, and

[0195] Where R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 Aryl or 5-12 heteroaryl,

[0196] The heteroaryl group comprises 1 to 3 cyclic heteroatoms selected from O, N, and S, wherein R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C22 Aryl or 5-12 heteroaryl,

[0197] The heteroaryl group comprises 1 to 3 cyclic heteroatoms selected from O, N and S, and w is 2 to 2000;

[0198] For equation (I), n ranges from 0.7 to (v-1); and

[0199] For equation (II), n is from 0 to (v-1), and each R 1 Independently selected from C1 to C 30 Alkyl, C1 to C 30 C1 to C2 substituted with one or more of the following: alkylene, halogenated, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl. 30 Alkyl groups, and C1 to C2 groups substituted with one or more of halogens, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups. 30 Alkylene, and p is a positive number at most pmax, where pmax = 60 / [9*Mw(R 1 )+8], where Mw(R 1 ) is R 1 Molecular weight of the functional group.

[0200] F. The composition according to paragraph E, wherein the precursor comprises at least one compound according to formula (I).

[0201] G. The composition according to paragraph F, wherein the precursor does not contain a compound according to formula (II).

[0202] H. The composition according to paragraph E or F, wherein the precursor comprises at least one compound according to formula (II).

[0203] I. The composition according to any one of paragraphs A to H, wherein the plurality of capsules are characterized by one or more of the following:

[0204] Average volume-weighted capsule diameter from approximately 10 μm to approximately 200 μm;

[0205] Average shell thickness from approximately 170 nm to approximately 1000 nm;

[0206] A core-shell ratio of approximately 50:50 to 99:1;

[0207] The first shell component contains no more than about 5% by weight of organic matter based on the weight of the first shell component.

[0208] J. The composition according to any one of paragraphs E to I, wherein the compound of formula (I), formula (II), or both is characterized by one or more of the following:

[0209] The equivalent weight-average molecular weight (Mw) of polystyrene is approximately 700 Da to approximately 30,000 Da.

[0210] Branching degree from 0.2 to approximately 0.6;

[0211] The molecular weight polydispersity index is approximately 1 to approximately 20.

[0212] K. The composition according to any one of paragraphs E to J, wherein M is silicon.

[0213] L. The composition according to any one of paragraphs E to K, wherein for formula (I), formula (II), or both formula (I) and formula (II), Y is OR, wherein R is selected from methyl, ethyl, propyl or butyl groups, optionally ethyl groups.

[0214] M. The composition according to any one of paragraphs E to L, wherein the second shell component comprises a material selected from calcium carbonate, silicon dioxide, and combinations thereof.

[0215] N. The composition according to any one of paragraphs E to M, wherein the inorganic nanoparticles of the first shell component comprise at least one of metal nanoparticles, mineral nanoparticles, metal oxide nanoparticles, or half-metal oxide nanoparticles.

[0216] Optionally, the inorganic nanoparticles comprise one or more materials selected from SiO2, TiO2, Al2O3, Fe2O3, Fe3O4, CaCO3, clay, silver, gold, or copper.

[0217] Optionally, the inorganic nanoparticles comprise one or more materials selected from SiO2, CaCO3, Al2O3, and clay.

[0218] O. The composition according to any one of paragraphs E to N, wherein the inorganic second shell component comprises at least one of SiO2, TiO2, Al2O3, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, iron, silver, nickel, gold, copper or clay, optionally at least one of SiO2 or CaCO3, optionally SiO2.

[0219] P. The composition according to any one of paragraphs A to O, wherein the water-soluble carrier is a water-soluble polymer.

[0220] Q. The composition according to any one of paragraphs A to P, wherein the water-soluble carrier is selected from:

[0221] Formula H-(C2H4O) x -(CH(CH3)CH2O) y -(C2H4O) z -OH polyalkylene polymers, wherein x is 50 to 300, y is 20 to 100, and z is 10 to 200;

[0222] Formula (C2H4O) q -C(O)O-(CH2) r -CH3 polyethylene glycol fatty acid esters, wherein q is 20 to 200 and r is 10 to 30;

[0223] Formula HO-(C2H4O) s -(CH2) t Polyethylene glycol fatty alcohol ethers of )-CH3, wherein s is 30 to 250 and t is 10 to 30;

[0224] C8-C22 alkyl polyalkoxylates containing more than 40 alkoxyl units; polyethylene glycol with a weight-average molecular weight of 2,000 to 15,000;

[0225] EO / PO / EO block copolymer;

[0226] PO / EO / PO block copolymer;

[0227] EO / PO block copolymer;

[0228] PO / EO block copolymer;

[0229] Polypropylene glycol;

[0230] Ethoxylated nonionic surfactants with a degree of ethoxylation greater than 30;

[0231] Polyvinyl alcohol;

[0232] Polyalkylene glycols with a weight average molecular weight of 2,000 to 15,000; and mixtures thereof.

[0233] R. The composition according to any one of paragraphs A to Q, wherein the water-soluble carrier is polyethylene glycol with a weight-average molecular weight of about 2,000 to about 15,000.

[0234] S. The composition according to any one of paragraphs A to R, wherein the water-soluble carrier is selected from polyepoxide, polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxyethylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, sodium sulfate, starch, and mixtures thereof.

[0235] T. The composition according to any one of paragraphs A to S, wherein the plurality of capsules are present at a level of about 0.1% to about 20% by weight of the composition.

[0236] U. The composition according to any one of paragraphs A to T, wherein the particles have at least one flat surface.

[0237] V. The composition according to any one of paragraphs A to U, wherein the plurality of particles comprises a single particle, wherein the density of the single particle is less than about 1 g / cm³. 3 Optionally less than approximately 0.98 g / cm³ 3 .

[0238] W. The composition according to any one of paragraphs A to V, wherein the fragrance is a plant-derived aromatic agent.

[0239] X. The composition according to any one of paragraphs A to W, wherein the carrier comprises:

[0240] 0% to 3% by weight of plasticizer polyol, wherein the plasticizer polymer is optionally liquid at 20°C and 1 atm;

[0241] 1% to 20%, optionally 1% to 12%, optionally 6% to 8% water by weight;

[0242] The sugar alcohol polyol comprises 45% to 80%, optionally 50% to 70%, optionally 50% to 60% by weight, wherein the sugar alcohol polyol is selected from erythritol, xylitol, mannitol, isomaltitol, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof;

[0243] The particles further comprise:

[0244] a. A modified starch having a dextrose equivalent of 15 to 20, wherein 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

[0245] b. A modified starch having a dextrose equivalent of 4 to less than 15, wherein the sugar alcohol polyol and the modified starch are present in a weight ratio of the sugar alcohol polyol to the modified starch of 1.5:1 to 16:1, optionally 1.5:1 to 10:1, optionally 1.5:1 to 4:1.

[0246] The capsule, the water, and the sugar alcohol polyol are dispersed in the modified starch.

[0247] Y. The composition according to paragraph X, 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.

[0248] Z. The composition according to paragraph X, wherein the modified starch has 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 1.5:1 to 16:1, optionally 1.5:1 to 10:1, optionally 1.5:1 to 4:1.

[0249] AA. The composition according to paragraph Z, wherein the modified starch has a dextrose equivalent of 4 to 12.

[0250] BB. The composition according to any one of paragraphs X to AA, wherein the modified starch is maltodextrin.

[0251] CC. The composition according to any one of paragraphs X to BB, wherein the sugar alcohol polyol is mannitol.

[0252] DD. The composition according to any one of paragraphs A to W, wherein the carrier comprises:

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

[0254] 1% to 10% by weight, optionally 3% to 8% water;

[0255] The sugar alcohol polyol comprises 15% to 40%, optionally 20% to 30% by weight, said sugar alcohol polyol being selected from erythritol, xylitol, mannitol, isomaltitol, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof; and

[0256] The modified starch has a dextran equivalent of 4 to less than 15, and the sugar alcohol polyol and the modified starch are present in a weight ratio of 1:5 to 1:1 of the sugar alcohol polyol to the modified starch.

[0257] The capsule, the water, and the sugar alcohol polyol are dispersed in the modified starch; and

[0258] Each of the particles has an outer surface, and an anti-caking agent is located on the outer surface.

[0259] EE. A method for treating clothing, the method comprising the following steps:

[0260] Provide clothing items in the washing machine;

[0261] Dispensing a plurality of particles according to any one of paragraphs A to D into the washing machine; and

[0262] The garment is brought into contact with the plurality of particles during the washing sub-cycle of the washing machine.

[0263] FF. According to the method described in paragraph EE, the method further includes the step of dispensing a laundry detergent containing about 3% to about 60% by weight of anionic or nonionic surfactant into the washing machine.

[0264] GG. The method according to paragraph EE or FF, wherein about 5g to about 50g of the plurality of particles are dispensed into the washing machine.

[0265] HH. A method for forming a plurality of particles according to any one of paragraphs A to DD, the method comprising the following steps:

[0266] Provide a melt composition comprising the water-soluble carrier and the capsule;

[0267] The molten composition is passed through one or more orifices of the dispenser; and

[0268] The molten composition is deposited on a moving conveyor below one or more of the orifices.

[0269] II. A dryer paper, the dryer paper comprising:

[0270] Nonwoven fiber layer; and

[0271] A solid fabric softener composition carried on or within the nonwoven fiber layer;

[0272] The solid fabric softener composition comprises a plurality of capsules dispersed in the solid fabric softener composition, wherein the capsules include a core and a shell surrounding the core, and the core contains a fragrance ingredient;

[0273] The shell comprises about 90% to 100%, optionally about 95% to 100%, optionally about 99% to 100% inorganic material by weight of the shell.

[0274] JJ. The dryer paper according to paragraph II, wherein the inorganic material is selected from metal oxides, semi-metal oxides, metals, minerals and mixtures thereof, optionally selected from SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, clay, gold, silver, iron, nickel, copper and mixtures thereof, optionally selected from SiO2, TiO2, Al2O3, CaCO3 and mixtures thereof, optionally SiO2.

[0275] KK. According to paragraph II or JJ, the dryer paper, wherein the shell includes a first shell component and a second shell component, the first shell component includes a condensation layer and a nanoparticle layer, wherein the condensation layer contains a condensation product of a precursor, and wherein the nanoparticle layer contains inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer, the second shell component surrounds the first shell component, and wherein the second shell component surrounds the nanoparticle layer.

[0276] LL. Dryer paper according to any one of paragraphs II to KK,

[0277] The shell includes:

[0278] The first shell component is essentially inorganic, consisting of a condensation layer and a nanoparticle layer.

[0279] The condensation layer comprises the condensation product of the precursor.

[0280] The nanoparticle layer comprises inorganic nanoparticles, and

[0281] The condensation layer is disposed between the core and the nanoparticle layer; and

[0282] An inorganic second shell component surrounding the first shell component.

[0283] The second shell component surrounds the nanoparticle layer;

[0284] The precursor comprises at least one compound selected from formula (I), formula (II), and mixtures thereof;

[0285] Where equation (I) is (M) v O z Y n ) w ;

[0286] Where equation (II) is (M) v O z Y n R 1 p ) w ;

[0287] For formulas (I), (II), or mixtures thereof, each M is independently selected from silicon, titanium, and aluminum, v is the valence of M and is 3 or 4, z is 0.5 to 1.6, and each Y is independently selected from -OH, -OR 2 ,halogen, -NH2、-NHR 2 -N(R) 2 )2, and

[0288] Where R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 Aryl or 5-12 heteroaryl,

[0289] The heteroaryl group comprises 1 to 3 cyclic heteroatoms selected from O, N, and S.

[0290] Where R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 Aryl or 5-12 heteroaryl,

[0291] The heteroaryl group comprises 1 to 3 cyclic heteroatoms selected from O, N and S, and w is 2 to 2000;

[0292] For equation (I), n ranges from 0.7 to (v-1); and

[0293] For equation (II), n is from 0 to (v-1), and each R 1 Independently selected from C1 to C 30 Alkyl, C1 to C 30 C1 to C2 substituted with one or more of the following: alkylene, halogenated, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl. 30 Alkyl groups, and C1 to C2 groups substituted with one or more of halogens, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups. 30 Alkylene, and p is a positive number at most pmax, where pmax = 60 / [9*Mw(R 1 )+8], where Mw(R 1 ) is R 1 Molecular weight of the functional group.

[0294] MM. Dryer paper according to any one of paragraphs II to LL, wherein the solid fabric softener composition comprises a quaternary ammonium compound, optionally a terpineol quaternary ammonium compound, optionally selected from bis-tallow, dimethyl methyl ammonium sulfate, N,N-di(olenoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(low-erucic acid rapeseed oil-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(olenoyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)methyl sulfate Ammonium, N,N-di(low erucic acid rapeseed oil-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)methylammonium sulfate-, N,N-di(oleylaminoethyl)-N-methyl, N-(2-hydroxyethyl)methylammonium sulfate, N,N-di(2-oleyloxyoxy-ethyl)-N,N-dimethylammonium chloride, N,N-di(2-low erucic acid rapeseed oil-oxyoxy-ethyl)-N,N-dimethylammonium chloride-, N,N-di(2-oleyloxyethylcarbonyloxyethyl)-N N-Dimethylammonium chloride, N,N-Di(2-lowererinyl erucic acid rapeseed oil oxyethyl carbonyl oxyethyl)-N,N-Dimethylammonium chloride, N-(2-oleylenyl oxyethyl)-N-(2-oleylenyl oxyoxy-ethyl)-N,N-Dimethylammonium chloride; N-(2-lowererinyl erucic acid rapeseed oil oxyethyl)-N-(2-lowererinyl erucic acid rapeseed oil oxyoxy-ethyl)-N,N-Dimethylammonium chloride, N,N,N-Tris(oleylenyl-oxy-ethyl)-N-methylammonium chloride, N, N,N-tris(hypoerucic acid rapeseed oil-oxy-ethyl)-N-methylammonium chloride, N-(2-oleylenyloxyoxyethyl)-N-(oleylenyl)-N,N-dimethylammonium chloride, N-(2-hypoerucic acid rapeseed oil-oxyoxyethyl)-N-(hypoerucic acid rapeseed oil-)-N,N-dimethylammonium chloride, 1,2-dioleylenyloxyN,N,N-trimethylammonium propane chloride, and 5,2-dioleylenyloxyN,N,N-trimethylammonium propane chloride, and combinations thereof. In one embodiment, the fabric conditioning active ingredient is N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)methylammonium sulfate, and mixtures thereof, wherein the fabric softening composition optionally comprises fatty acids.

[0295] NN. Dryer paper according to any one of paragraphs II to MM, wherein the nonwoven fiber material has about 10 g / m 2 Approximately 50g / m 2 The base weight.

[0296] OO. Dryer paper according to any one of paragraphs II to NN, wherein the nonwoven fiber material is spunbond polyester terephthalate, optionally continuous filament spunbond terephthalate.

[0297] Test methods

[0298] It should be understood that the test methods disclosed in the Test Methods section of this application should be used to determine the corresponding parameter values ​​of the subject matter claimed by the applicant as claimed and described herein.

[0299] i. Allocation coefficient method

[0300] The partition coefficient P is the concentration ratio of a compound in a mixture of two immiscible phases at equilibrium, in this case, n-octanol / water. The log value (logP) of the n-octanol / water partition coefficient can be experimentally measured using well-known methods, such as the "shake flask" method, or by measuring the solute distribution using UV / VIS spectroscopy (e.g., as described in Dearden JC, Bresnan, "The Measurement of Partition Coefficients", Molecular Informatics, Vol. 7, No. 3, 1988, pp. 133-144). Alternatively, the logP of each PRM in the tested flavor mixture can be calculated. Preferably, the logP of individual PRMs is calculated using the Consensus logP calculation model version 14.02 (Linux), available from Advanced Chemistry Development Inc. (ACD / Labs) (Toronto, Canada), to provide dimensionless logP values. The ACD / Labs Consensus logP calculation model is part of the ACD / Labs model suite.

[0301] ii. Measurement of average shell thickness

[0302] Capsule shells, including a first shell component and a second shell component, were measured in nanometers on delivery capsules containing twenty beneficial agents, when present, using a focused ion beam scanning electron microscope (FIB-SEM; FEI HELIOS NANOLAB 650) or equivalent. Samples were prepared by diluting a small amount of liquid capsule dispersion (20 μl) with distilled water (1:10). The suspension was then deposited onto an ethanol-cleaned aluminum rod and transferred to a carbon coating machine (LEICA EM ACE600 or equivalent). The sample was then subjected to vacuum (vacuum level: 1) in the coating machine. 0-5(mbar) drying. Next, 25nm-50nm carbon was rapidly deposited onto the sample to deposit a conductive carbon layer on the surface. An aluminum rod was then transferred to a FIB-SEM to prepare the cross-section of the capsule. The cross-section was prepared by ion milling at an accelerating voltage of 30kV with an emission current of 2.5nA using cross-section cleaning mode. Images were acquired in immersion mode at 5.0kV and 100pA (holding time approximately 10μs) at a magnification of approximately 10,000.

[0303] Images of fractured shells were acquired in cross-sectional view form from 20 useful delivery capsules selected in a random manner, unbiased by their size, to form a representative sample showing the capsule size distribution. The shell thickness of each of the 20 capsules was measured at three different random locations by plotting measurement lines perpendicular to the tangent to the outer surface of the capsule shell. Sixty independent thickness measurements were recorded and used to calculate the average thickness.

[0304] iii. Mean and coefficient of variation of volume-weighted capsule diameter

[0305] Capsule size distribution was determined using an ACCUSIZER 780AD instrument or equivalent and the accompanying software CW788 version 1.82 (ParticleSizing Systems, Santa Barbara, California, USA) or equivalent, via single-particle optical sensing (SPOS) (also known as optical particle counting (OPC)). The instrument was configured with the following conditions and selections: flow rate = 1 mL / sec; lower size threshold = 0.50 μm; sensor model = LE400-05SE or equivalent; autodilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 mL; maximum overlap = 9200. Measurements were initiated by rinsing the sensor with water until the background count was less than 100. A sample was introduced into the suspension of the delivery capsules, and the capsule density was adjusted with DI water via autodilution as needed to obtain a capsule count of up to 9200 capsules / mL. The suspension was analyzed over a 60-second time period. The size range used was 1 μm to 493.3 μm.

[0306] Volume distribution :

[0307]

[0308]

[0309]

[0310] in:

[0311] CoV v– Coefficient of variation of volume-weighted size distribution

[0312] σ v –Standard deviation of volume-weighted size distribution

[0313] μ v – Average value of volume-weighted size distribution

[0314] d i – Diameter in class i

[0315] x i,v – Frequency in the level i (corresponding to diameter i) of the volume-weighted size distribution

[0316]

[0317] iv. Core-shell ratio assessment

[0318] The volume core-shell ratio is determined as follows, depending on the average shell thickness as measured by a shell thickness testing method. The volume core-shell ratio of a capsule for which its average shell thickness is measured is calculated using the following formula:

[0319]

[0320] The thickness is the average shell thickness of the capsule population measured by FIBSEM, and D 胶囊 It is the average volume-weighted diameter of the capsule population, measured by optical particle counting.

[0321] The core weight percentage can be calculated using the following formula, and this ratio can be converted into a core-shell ratio fraction:

[0322]

[0323] The shell percentage can be calculated based on the following formula:

[0324] %shell = 100 - %core.

[0325] Branching method

[0326] The branching degree of the precursor was determined as follows: the branching degree was measured using (29Si) nuclear magnetic resonance spectroscopy (NMR).

[0327] a. Sample preparation

[0328] Each sample was diluted to a 25% solution using deuterated benzene (benzene-D6 "100%" (D, 99.96%, purchased from Cambridge Isotope Laboratories Inc., Tewksbury, MA, or equivalent). 0.015 M chromium acetylacetone(III) (99.99% purity, purchased from Sigma-Aldrich, St. Louis, MO, or equivalent) was added as a paramagnetic relaxation reagent. If analysis was performed using glass NMR tubes (Wilmed-LabGlass, Vineland, NJ, or equivalent), blank samples must also be prepared by filling the NMR tubes with the same type of deuterated solvent used to dissolve the samples. The same glass tubes must be used for both the blank and the sample analysis.

[0329] b. Sample Analysis

[0330] Branching degree was determined using a BRUKER 400MHz nuclear magnetic resonance (NMR) instrument or equivalent. The standard silicon (29Si) method was used (e.g., from Bruker, with default parameters set to a minimum of 1000 scans and a relaxation time of 30 seconds).

[0331] c. Sample processing

[0332] Samples were stored and processed using system software suitable for NMR spectroscopy, such as MESTRENOVA version 12.0.4-22023 (purchased from Mestrelab Research) or equivalents. Phase adjustment and background correction were applied. A large, broad signal was observed extending from -70 ppm to -136 ppm, a result of using a glass NMR tube and the glass present in the probe housing. This signal was suppressed by subtracting the spectrum of the blank sample from the spectrum of the synthesized sample, provided that the same tube and method parameters were used to analyze both the blank and the sample. To further illustrate any slight differences in data collection, tubes, etc., the region outside the peak of interest was integrated and normalized to a consistent value. For example, for all blanks and samples, the integration was performed from -117 ppm to -115 ppm and the integration value was set to 4.

[0333] The resulting spectra produce a maximum of five main peak areas. The first peak (Q0) corresponds to unreacted TAOS. The second set of peaks (Q1) corresponds to terminal groups. The next set of peaks (Q2) corresponds to straight-chain groups. The next set of broad peaks (Q3) is a semi-dendritic unit. The last set of broad peaks (Q4) is a dendritic unit. When analyzing PAOS and PBOS, each set falls within a defined ppm range. Representative ranges are described in Table 1 below.

[0334] Table 1.

[0335] Group ID Number of bridging oxygen per silicon ppm range Q0 0 -80 to -84 Q1 1 -88 to -91 Q2 2 -93 to -98 Q3 3 -100 to -106 Q4 4 -108 to -115

[0336] Polyoxysilanes have different chemical shifts for Q0 and Q1, have overlapping signals for Q2, and have unchanged Q3 and Q4, as shown in Table 2 below.

[0337] Table 2.

[0338] Group ID Number of bridging oxygen per silicon ppm range Q0 0 -78 to -80 Q1 1 -85 to -88 Q2 2 -91 to -96 Q3 3 -100 to -106 Q4 4 -108 to -115

[0339] The ppm ranges shown in the table above may not apply to all monomers. Other monomers may cause changes in chemical shifts; however, the correct partitioning of Q0-Q4 should not be affected.

[0340] Using MESTRENOVA, integrate for each group of peaks, and the degree of branching can be calculated using the following formula:

[0341]

[0342] d. Methods for determining molecular weight and polydispersity index

[0343] The molecular weight (weight-average molecular weight of polystyrene equivalent (Mw)) and polydispersity index (Mw / Mn) of the condensation layer precursor described in this article were determined using size exclusion chromatography with refractive index detection. Mn is the number-average molecular weight.

[0344] Sample preparation

[0345] Weigh the sample and then dilute it to the target concentration of 10 mg / mL using the solvent used in the instrument system. For example, weigh 50 mg of polyalkoxysilane into a 5 mL volumetric flask, dissolve it, and dilute it to volume with toluene. After the sample has dissolved in the solvent, pass it through a 0.45 μm nylon filter and load it into the instrument's autosampler.

[0346] Sample Analysis

[0347] Polymer analysis was performed using an HPLC system with an autosampler (e.g., a WATERS 2695 HPLC separation module, Waters Corporation, Milford MA, or equivalent) connected to a refractive index detector (e.g., a WYATT 2414 refractive index detector, Santa Barbara, CA, or equivalent). Separation was performed on three columns, each 7.8 mm I.D. × 300 mm long, packed with 5 μm polystyrene-divinylbenzene media, connected in series, with molecular weight cutoffs of 1 kDA, 10 kDA, and 60 kDA, respectively. Suitable columns were TSKGEL G1000HHR, G2000HHR, and G3000HHR columns (purchased from TOSOH Bioscience, King of Prussia, PA) or equivalents. The analytical columns were protected using 6 mm I.D. × 40 mm long 5 μm polystyrene-divinylbenzene guard columns (e.g., TSKGEL Guardcolumn HHR-L, TOSOH Bioscience, or equivalents). Toluene (HPLC grade or equivalent) was pumped isocratically at 1.0 mL / min while maintaining the column and detector at 25 °C. 100 μL of the prepared sample was injected for analysis. Sample data were stored and processed using software with GPC calculation capabilities (e.g., ASTRA version 6.1.7.17, available from Wyatt Technologies, Santa Barbara, CA, or equivalent).

[0348] The system was calibrated using ten or more narrowly dispersed polystyrene standards (e.g., standard READYCAL Set, such as Sigma Aldrich PN 76552 or equivalent) with known molecular weights (in the range of approximately 0.250 kDa to 70 kDa) and a third-order fit of the Mp versus retention time curve.

[0349] Using this system software, the weight-average molecular weight (Mw) and polydispersity index (Mw / Mn) are calculated and recorded.

[0350] v. Method for calculating the organic matter content in the first shell component

[0351] As used herein, according to the definition of an organic portion in the inorganic shell of a capsule of this disclosure: any portion X that cannot be cleaved from a metal precursor containing metal M (where M belongs to the group consisting of metals and half-metals, and X belongs to the group consisting of non-metals) via the hydrolysis of the MX bond connecting said portion to an inorganic precursor of metal or half-metal M, and under specific reaction conditions, is considered organic. A minimum degree of hydrolysis of 1% was set as the reaction condition when exposed to neutral pH distilled water for 24 hours without stirring.

[0352] This method allows for the calculation of theoretical organic content under the assumption that all hydrolyzable groups are fully converted. Therefore, it allows for the assessment of the theoretical organic percentage of any silane mixture, and the result represents only the precursor mixture itself, not the actual organic content in the first shell component. Therefore, when a certain percentage of the organic content of the first shell component is disclosed anywhere in this document, it should be understood that any mixture containing unhydrolyzed or prepolymerized precursors has a theoretical organic content lower than the disclosed amount, calculated according to the following method.

[0353] The following example calculations are for silanes. These are followed by calculations for the general case.

[0354] Consider a mixture of silanes, where the mole fraction of each is Y. i , where i is the ID number of each silane. The mixture can be represented as follows:

[0355] Si(XR) 4-n R n

[0356] Where XR is a hydrolyzable group under the conditions mentioned in the above definition, and R i ni Under the above conditions, it is non-hydrolyzable, and n i = 0, 1, 2 or 3.

[0357] This silane mixture will produce a shell with the following general formula:

[0358]

[0359] Then, the weight percentage of the organic portion, as previously defined, can be calculated as follows:

[0360] 1) Determine the mole fraction of each precursor (including nanoparticles).

[0361] 2) Determine the general formula for each precursor (including nanoparticles).

[0362] 3) General formula for calculating the mixture of precursor and nanoparticles based on mole fraction

[0363] 4) The silane is converted into a reactive silane (all hydrolyzable groups are converted into oxygen groups).

[0364] 5) Calculate the weight ratio of the organic portion to the total mass (assuming the skeleton is 1 mole of Si).

[0365] Example calculations are shown in Table 3.

[0366] Table 3.

[0367] raw material Chemical formula Mw(g / mol) Weight (g) Amount (mmol) mole fraction Sample AY <![CDATA[SiO(OEt)2]]> 134 1 7.46 0.57 TEOS <![CDATA[Si(OEt)4]]> 208 0.2 0.96 0.07 DEDMS <![CDATA[Si(OEt)2Me2]]> 148.27 0.2 1.35 0.10 SiO2 NP <![CDATA[SiO2]]> 60 0.2 3.33 0.25

[0368] To calculate the general formula for a mixture, multiply the index of each atom in the individual chemical formula by its respective mole fraction. Then, for mixtures, when similar indices appear (typically for ethoxy groups), sum the fractional indices.

[0369] Note: According to the calculation method (the sum of all mole fractions of Si is 1), the sum of all Si fractions in the general formula of the mixture will always be added to 1.

[0370] SiO 1*0.57+2*0.25 (OEt) 2*0.57+4*0.07+2*0.10 Me 2*0.10

[0371] SiO 1.07 (OEt) 1.62 Me 0.20

[0372] To convert an unreacted chemical formula into a reacted one, simply divide the index of all hydrolyzable groups by 2 and then add them together (with any pre-existing oxygen groups, if applicable) to obtain a fully reacted silane.

[0373] SiO 1.88 Me 0.20

[0374] In this case, the expected result is SiO 1.9 Me 0.2 Because the sum of all exponents must satisfy the following formula:

[0375] A + B / 2 = 2,

[0376] Where A is the oxygen atom index, and B is the sum of all non-hydrolyzable indices. Small rounding errors may occur during the calculation and should be corrected. Then, the indices on the oxygen atom are readjusted to satisfy the chemical formula.

[0377] Therefore, the final chemical formula is SiO 1.9 Me 0.2 The weight ratio of organic matter is calculated as follows:

[0378] Weight ratio = (0.20*15) / (28+1.9*16+0.20*15) = 4.9%

[0379] General situation :

[0380] The above chemical formula can be summarized by considering the valence of the metal or half-metal M, thus giving the following modified chemical formula:

[0381] M(XR)V-ni R i ni

[0382] And a similar method is used, but the valence V of the corresponding metal must be taken into account.

[0383] Example

[0384] The embodiments provided below are intended to be illustrative in nature and are not intended to be limiting.

[0385] Example 1. Synthesis of non-hydrolyzed precursors

[0386] Under a nitrogen atmosphere, 1000 g of tetraethoxysilane (TEOS, purchased from Sigma Aldrich) was added to a clean, dry round-bottom flask equipped with a stir bar and distillation apparatus. 490 ml of acetic anhydride (purchased from Sigma Aldrich) and 5.8 g of tetrakis(trimethylsiloxy)titanium (purchased from Gelest) were added, and the contents of the flask were stirred at 135 °C for 28 hours. During this time, ethyl acetate, generated from the reaction of the ethoxysilane group with acetic anhydride, was distilled off. The reaction flask was cooled to room temperature and placed on a rotary evaporator (BUCHI Rotovapor R110) used in conjunction with a water bath and a vacuum pump (WELCH 1402 DuoSeal) to remove any residual solvent and volatile compounds. The resulting polyethoxysilane (PEOS) was a yellow, viscous liquid with the following specifications found in Table 4. The ratio of TEOS to acetic anhydride can be varied to control the parameters presented in Table 4.

[0387] Table 4.

[0388] PEOS parameters result Branching degree (DB) 0.26 Molecular weight (Mw) 1.2 Multidispersion Index (PDI) 3.9

[0389] Example 2. Fragrance capsules based on silica shells

[0390] The oil phase was prepared by mixing and homogenizing the precursor with a beneficial agent and / or a nuclear modifier (one part non-hydrolyzed precursor to two parts beneficial agent and / or nuclear modifier). The aqueous phase was prepared by adding 1.25 w% AEROSIL 300 (purchased from Evonik) to a 0.1 M HCl aqueous solution and dispersing in an ultrasonic bath for at least 30 minutes. Once the phases were prepared separately, they were combined (one part oil to four parts water) and the oil phase was dispersed into the aqueous phase using an IKA ULTRATURRAX S25N-10G mixing tool at 13400 RPM / 1 minute. Once the emulsification step was complete, the resulting emulsion was cured at the following temperature distributions: 22°C for 4 hours, 50°C for 16 hours, and 70°C for 96 hours. To deposit the second shell component, the capsules underwent post-treatment with the second shell component solution: the slurry was diluted 2-fold in 0.1M HCl and treated with a controlled addition of 10% (w / w) sodium silicate aqueous solution at 22°C using a suspended magnetically stirred reactor at 250 RPM (40 μl / min, 0.16 ml / g slurry). The pH was maintained constant at pH 7 using 1M HCl (aqueous solution). After the second shell component solution was added, the capsules were centrifuged at 2500 rpm for 10 min and redispersed in deionized water. The average size of the capsule cluster was 29.22 μm, and the CoV content was 38%.

[0391] Figure 2 A schematic diagram of a method for preparing a capsule 8 having a first shell component 6 is shown, the capsule being prepared with a hydrophobic core 4. For example, in the first box 100, an oil phase 1 is provided to an aqueous phase 2. The oil phase 2 contains a hydrophobic beneficial agent, such as one or more fragrance ingredients, and a liquid precursor material. Nanoparticles 3 have already surrounded the oil phase 1, for example, forming a Pickering emulsion. In the second box 101, a hydrolyzed precursor 5 begins to form at the interface surrounding the core 4, wherein the core 4 contains the oil phase containing the beneficial agent. In the third box 102, the first shell component 6 is formed around the core 4, wherein the first shell component is formed by the nanoparticles 3 and the hydrolyzed precursor 5.

[0392] Figure 3 A schematic diagram of a capsule 9 with a shell 10 is shown in block 103. The shell 10 has a first shell component 6 and a second shell component 7 surrounding a core 4. The capsule 9 is shown in an aqueous phase 2. The core 4 contains one or more flavoring ingredients. Figure 4 A scanning electron microscope image of a cross-section of this capsule 9 is shown. The core 4 is surrounded by a shell 10, wherein the shell 10 includes a first shell component 6 surrounded by a second shell component 7.

[0393] Figure 5 Scanning electron microscope images of a group of flavor capsules based on silica shells as described in this disclosure are shown.

[0394] Example 3. Exemplary Granular Formulation

[0395] Two distinct granule samples were prepared: one containing a flavor capsule based on a silica shell (Example 3A of the present invention), and the other containing a flavor capsule based on a polyacrylate shell (Comparative Example 3B). The general procedure for preparing the granules involved setting a hot plate to 85°C, weighing a beaker on the hot plate and allowing the contents to reach the desired temperature, and then manually transferring the mixture into a mold to prepare uniformly sized granules and allowing them to cool. The size of the individual granules thus formed was such that the weight of four such granules was approximately 0.140 g–0.145 g. The compositions of the two granules are shown in Table 5 below.

[0396] The following Embodiment 3A (Table 5) of the present invention is a group of fragrance capsules prepared according to Table 5 below, which encapsulate a mixture of fragrance raw material "Fragrance 1". According to this disclosure, the capsules of this group comprise a first shell component and a second shell component based on silica.

[0397] Comparative Example 3B (Table 5) below is a group of fragrance capsules containing polyacrylate shells encapsulating the same fragrance raw material mixture (“Fragrance 1”) prepared according to the method disclosed in PCTUS Publication WO2020 / 117996.

[0398] Table 5 PA230713C

[0399]

[0400] Under usage conditions, fabrics from Examples 3A and Comparative Example 3B of the present invention were tested to determine the top space of wet and dry fabrics. A MIELE HONEYCOMB CARE W1724 washing machine was used, and the cycle was set to a rapid cycle program of 30°C and 1000 RPM for 30 minutes. The fabric used in the test was a 420g terry cotton test fabric. Each of the 14 terry cotton test fabric pieces was 30cm × 15cm and had a mass of 30g. The test also included a ballast load. The ballast load consisted of 1369g of Calderon cotton (10 pieces) and 1220g of Calderon polyester cotton (10 pieces). Each of the 10 Calderon cotton pieces was 52cm × 42cm and had a mass of 137g. Each of the 10 Calderon polyester cotton pieces was 46cm × 46cm and had a mass of 122g. Granules and liquid detergent were delivered to the machine's drum at specified levels: 9 g of granules and 58.47 g of the liquid detergent formulation listed in Table 6 were placed at the bottom of the drum before the fabric was loaded. The liquid detergent was metered onto the top of the fabric. After washing, a sample of the terry cotton test fabric was obtained for wet headspace testing, and the remaining portion of the terry cotton test fabric was air-dried every 24 hours at controlled temperature and humidity (22°C / 50% RH).

[0401] Table 6.

[0402]

[0403] PA230713C

[0404]

[0405] Fragrance headspace analysis (wet fabric headspace, WFHS) was performed on the terry cotton test fabric immediately after the washing cycle, while the terry cotton test fabric was still wet. Six 4 cm × 4 cm samples of the terry cotton test fabric from each washing test were analyzed by rapid headspace GC / MS. Each 4 × 4 cm sample of the terry cotton test fabric was transferred to a 25 mL headspace vial. The samples of the terry cotton test fabric were equilibrated at 65 °C for 10 min. The headspace above the samples of the terry cotton test fabric was sampled for 5 min using the SPME (50 / 30 μm DVB / Carboxen / PDMS) method. The SPME fibers were then immediately thermally desorbed into the GC. The analytes were analyzed by rapid GC / MS in full scan mode. The total headspace response (expressed as nmol / L) was calculated using the specific mass ion extraction of the fragrance raw materials. After the terry cotton test fabric was dried at controlled temperature and humidity (22°C / 50% RH) for 24 hours, the dry terry cotton test fabric was tested in the same manner, the only difference being that the terry cotton test fabric was dry (dry fabric top space, DFHS) instead of wet.

[0406] The granules of Example 3A and Comparative Example 3B of the present invention each provided the same mass of fragrance. The wet fabric head space (WFHS) and dry fabric head space (DFHS) of each individual fragrance ingredient were measured. For each fragrance ingredient, the WFHS / DFHS ratio was calculated (see Table 7). The relative standard deviation of WFHS / DFHS for Example 3A and Comparative Example 3B of the present invention was also calculated. Figure 6 As shown (box plots of the center line, the first and third quartiles of the box edge, and the largest and smallest whiskers), the capsule of Example 3A according to the present invention has a lower relative standard deviation of the top space ratio compared to Comparative Example 3B. This indicates that the capsule of Example 3A of the present invention has a more consistent fragrance character between wet and dry fabrics compared to Comparative Example 3B.

[0407] Table 7.

[0408]

[0409] Example 4. Exemplary granule formulations are provided in Table 8 below.

[0410] Table 8.

[0411]

[0412]

[0413] Example 5

[0414] Non-hydrolyzed PEOS synthesis: Under a nitrogen atmosphere, 1000 g of TEOS (purchased from Sigma Aldrich) was added to a clean, dry round-bottom flask equipped with a stir bar and distillation apparatus. Next, 564 g of acetic anhydride (purchased from Sigma Aldrich) and 5.9 g of tetra(trimethylsiloxane)titanium (purchased from Gelest, Sigma Aldrich) were added, and the contents of the flask were heated to 135 °C with stirring. The reaction temperature was maintained at 135 °C for 30 hours with vigorous stirring, during which time the organic esters generated by the reaction of alkoxysilyl groups with acetic anhydride, as well as additional organic esters generated by the condensation of silyl acetate groups with other alkoxysilyl groups, occurred during the formation of polyethoxysilane (PEOS), were distilled off. The reaction flask was cooled to room temperature and placed on a rotary evaporator (BUCHI ROTOVAPOR R110) used in conjunction with a water bath and a vacuum pump (WELCH 1402 DUOSEAL) to remove any residual solvent. The degree of branching (DB), molecular weight (Mw), and polydispersity index (PDI) of the synthesized PEOS polymer were 0.42, 2.99, and 2.70, respectively.

[0415] Capsule Synthesis: Five batches were prepared following the procedure below, and these five batches were combined after the curing step to produce a combined slurry. The oil phase was prepared by mixing and homogenizing (or even dissolving, if all compounds are miscible) 3g of the synthesized PEOS precursor with 2g of a beneficial agent and / or core modifier (fragrance oil in this case). A 100g aqueous phase was prepared by mixing 0.5g NaCl, 3.5g of AEROSIL 300 pyrolytic silica from EVONIK, and 96g of deionized water. The pyrolytic silica was dispersed in the aqueous phase at 20000 RPM for 15 min using an IKA ULTRA-TURRAX (S25N). Once each phase was prepared individually, 5g of the oil phase was dispersed in 16g of the aqueous phase at 25000 RPM for 5 min using an IKA ULTRA-TURRAX mixer (S25N-10g) to achieve the desired average droplet diameter. The pH was then adjusted to 1 by adding 0.1M HCl dropwise. Once the emulsification step was complete, the resulting emulsion was allowed to stand at room temperature for 4 hours without stirring, and then at 90°C for 16 hours, until sufficient solidification occurred to prevent the capsules from collapsing. After the solidification step, five batches were combined to obtain a combined capsule slurry.

[0416] To deposit the second shell component, the combined capsule slurry was post-treated with a second shell component solution. 50 g of the combined slurry was diluted with 50 g of 0.1 M HCl (aqueous solution). The pH was adjusted to 7 using dropwise addition of 1 M NaOH (aqueous solution). The diluted slurry was then treated at room temperature using a suspended magnetically stirred reactor at 300 RPM with controlled addition (40 μl / min) of the second shell component precursor solution (20 ml of 15 wt% sodium silicate (aqueous solution)). The pH was maintained constant at pH 7 by continuous injection of 1.6 M HCl (aqueous solution) and 1 M NaOH (aqueous solution). The capsules were then centrifuged at 2500 RPM every 10 minutes. The supernatant was discarded, and the capsules were redispersed in deionized water.

[0417] To test for capsule collapse, the slurry was diluted 10-fold with deionized water. Several drops of subsequent dilution were added to a microscope slide and allowed to dry overnight at room temperature. The next day, the dried capsules were observed under transmitted light through an optical microscope to assess whether they maintained their spherical shape (without a coverslip). The capsules remained intact after drying and did not collapse. The measured average volume-weighted diameter of the capsules was 5.3 μm, and the CoV content was 46.2%. The percentage of organic matter in the shell was 0%.

[0418] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​cited. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0419] Unless expressly excluded or otherwise limited, every reference cited herein, including any cross-references or related patents or patent applications, and any patent application or patent claiming priority to or benefiting from it, is incorporated herein by reference in its entirety. Reference to any reference is not an endorsement of it as prior art to any disclosed or protected art herein, nor is it an endorsement of any such invention, either on its own or in combination with any one or more references. Furthermore, where any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in referenced documents, the meaning or definition given to that term in this invention shall prevail.

[0420] While specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications falling within the scope of the invention be covered in the appended claims.

Claims

1. A composition comprising a plurality of particles (90), wherein the particles comprise: The water-soluble carrier comprises 25% to 99% by weight, wherein the water-soluble carrier is a polyalkylene glycol with a weight-average molecular weight of 2000 to 15000; and Multiple capsules (8) dispersed in the water-soluble carrier, wherein the capsules include a core (4) and a shell (10) surrounding the core, and the core contains a flavoring ingredient; The shell comprises 90% to 100% inorganic material by weight of the shell, the inorganic material being silicon dioxide. The shell comprises: The first shell component is substantially inorganic, comprising a condensation layer and a nanoparticle layer, wherein "substantially inorganic" means that the first shell component contains at most 10% by weight of organic matter. The condensation layer comprises the condensation product of the precursor. The nanoparticle layer comprises inorganic nanoparticles, which in turn comprise silicon dioxide. The condensation layer is disposed between the core and the nanoparticle layer; and An inorganic second shell component surrounding the first shell component, wherein the inorganic second shell component comprises silicon dioxide. The inorganic second shell component surrounds the nanoparticle layer; The precursor comprises at least one compound selected from formula (I), formula (II), and mixtures thereof; Where equation (I) is (M) v O z Y n ) w ; Where equation (II) is (M) v O z Y n R 1 p ) w ; For formulas (I), (II), or mixtures thereof, each M is independently selected from silicon, titanium, and aluminum, v is the valence of M and is 3 or 4, z is 0.5 to 1.6, and each Y is independently selected from -OH, -OR 2 ,halogen, -NH2, -NHR 2 -N(R) 2 )2 and , Where R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 Aryl or 5-12 heteroaryl, The heteroaryl group comprises 1 to 3 cyclic heteroatoms selected from O, N, and S. Where R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 Aryl or 5-12 heteroaryl, The heteroaryl group comprises 1 to 3 cyclic heteroatoms selected from O, N and S, and w is 2 to 2000; For equation (I), n ranges from 0.7 to (v-1); and For equation (II), n ranges from 0 to (v-1), and each R 1 Independently selected from C1 to C 30 Alkyl, C1 to C 30 Alkylene, C1 to C2 substituted with one or more of halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups. 30 Alkyl groups, and C1 to C2 groups substituted with one or more of halogens, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, CO2alkyl, aryl, and heteroaryl groups. 30 Alkylene, and p is a positive number at most pmax, where pmax = 60 / [9*Mw(R 1 ) + 8], where Mw(R 1 ) is R 1 Molecular weight of the functional group.

2. The composition according to claim 1, wherein the precursor comprises at least one compound according to formula (I).

3. The composition according to claim 1, wherein the precursor comprises at least one compound according to formula (II).

4. The composition according to claim 1, wherein the plurality of capsules is characterized by one or more of the following: Average volume-weighted capsule diameter from 10µm to 200µm; Average shell thickness ranging from 170 nm to 1000 nm; Core-shell ratios ranging from 50:50 to 99:1; The first shell component contains no more than 5% by weight of organic matter based on the weight of the first shell component.

5. The composition according to claim 1, wherein the compound of formula (I), formula (II), or both is characterized by one or more of the following: Polystyrene equivalent weight-average molecular weight (Mw) from 700 Da to 30,000 Da. Branching degree of 0.2 to 0.6; and Molecular weight polydispersity index from 1 to 20.

6. The composition according to claim 1, wherein M is silicon.

7. The composition according to claim 1, wherein for formula (I), formula (II), or both formula (I) and formula (II), Y is OR, wherein R is selected from methyl groups, ethyl groups, propyl groups and butyl groups.

8. The composition according to claim 1, wherein for formula (I), formula (II), or both formula (I) and formula (II), Y is OR, wherein R is an ethyl group.

9. A method for treating clothing, the method comprising the following steps: Provide clothing items in the washing machine; The composition according to any one of the preceding claims is dispensed into the washing machine; as well as The garment is brought into contact with the plurality of particles during the washing sub-cycle of the washing machine.

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