Laundry care additive particles

Abstract

The present disclosure also relates to methods of making and using such compositions, and to methods of using such compositions.

Description

Technical Field

[0001] Laundry care additive particles. The composition includes a plurality of particles, which include a water-soluble carrier and capsules having a substantially inorganic shell, such as a silica-based shell. The present disclosure further relates to a method for manufacturing and a method for using such a composition. The present disclosure further relates to a dryer sheet including capsules having a substantially inorganic shell, such as a silica-based shell.

Background Art

[0002] Laundry care particle additives and dryer sheets are formulated using fragrance-containing core / shell capsules. Typically, the core of such capsules contains fragrance, and the shell often contains a polymeric material such as aminoplast, polyurea, or polyacrylate. These capsules are useful for delivering beneficial agents to a target surface such as fabric. Then, at various touch points, the capsules rupture and release the fragrance. However, it is known that fragrance capsules leak, thereby reducing the efficiency of the fragrance delivery system.

[0003] Furthermore, fragrance capsules typically encapsulate various fragrance raw materials ("perfume raw material, PRM"). The problem is that various PRMs can leak through the capsule wall at various rates. Over time, such as while the product is being transported or stored, the characteristics of the fragrance can change because some PRMs leak more than others. This can lead to an olfactory experience that is less desirable than what the manufacturer planned, quality control problems, and even consumer dissatisfaction if the freshness profile provided by the first administration of the product differs from that provided by the last administration.

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is a need for laundry care particle additives and dryer sheets that include a fragrance delivery system having an improved fragrance leakage profile.

Means for Solving the Problem

[0005] The present disclosure relates to a composition comprising a plurality of particles, the particles comprising from about 25 wt% to about 99 wt% of a water-soluble carrier and a plurality of capsules dispersed in the water-soluble carrier, the capsules comprising a core and a shell surrounding the core, the core comprising a flavoring ingredient, and a plurality of capsules, The shell comprises from about 90 wt% to 100 wt%, optionally from about 95 wt% to 100 wt%, optionally from about 99 wt% to 100 wt% of an inorganic material of the shell.

[0006] The present disclosure further relates to a composition comprising a plurality of particles, the particles comprising from about 25 wt% to about 99 wt% of a water-soluble carrier and a plurality of capsules dispersed in the water-soluble carrier, the capsules comprising a core and a shell surrounding the core, the core comprising a flavoring ingredient, and a plurality of capsules, the shell being a substantially inorganic first shell component comprising a condensation layer and a nanoparticle layer, the condensation layer comprising a condensation product of a precursor, the nanoparticle layer comprising inorganic nanoparticles, the condensation layer being disposed between the core and the nanoparticle layer, a substantially inorganic first shell component, and an inorganic second shell component surrounding the first shell component, the second shell component surrounding the nanoparticle layer, and an inorganic second shell component. The precursor comprises at least one compound selected from the group consisting of formula (I), formula (II), and mixtures thereof, formula (I) being (M v O z Y n ) w wherein, formula (II) is (M v O z Y n R 1 p ) wand for formula (I), formula (II), or a mixture 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 from 0.5 to 1.6, each Y is independently -OH, -OR 2 , halogen,

[0007]

Chemical formula

[0008]

Chemical formula

[0009] The present disclosure further relates to a dryer sheet comprising a nonwoven fiber layer and a solid fabric softening composition supported on or within the nonwoven fiber layer, wherein the solid fabric softening composition comprises a plurality of capsules dispersed in the solid fabric softening composition, the capsules comprising a core and a shell surrounding the core, the core comprising a fragrance raw material, and the shell comprising about 90 wt% to 100 wt%, optionally about 95 wt% to 100 wt%, optionally about 99 wt% to 100 wt% of an inorganic material of the shell.

Brief Description of the Drawings

[0010]

Figure 1

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Mode for Carrying Out the Invention

[0011] The present disclosure relates to laundry care additive particles comprising a water-soluble carrier and capsules containing a plurality of fragrances dispersed in the carrier. The capsules, when dispersed in the carrier, have consistent permeability to various fragrance raw materials, which provides a consistent fragrance experience to the user over the period during which the laundry care additive package is used and at various contact points where the user handles or wears laundry treated with such a laundry care additive. The present disclosure further relates to a dryer sheet containing the capsules.

[0012] The laundry care additive particles can be practical for providing benefits to the laundry through washing. That is, the particles can be used by the user by dispensing the particles into the washing machine before starting a washing machine cycle, particularly a washing sub-cycle. Through-the-wash compositions, such as those described herein, are different from through-the-rinse compositions. Through-the-rinse compositions are designed to be dispensed during the rinse sub-cycle of the washing machine. In recent washing machines, after the washing sub-cycle is completed, the rinse sub-cycle is automatically started without further input from the consumer. The composition dispensed during the rinse sub-cycle is generally dispensed into a separate input chamber, such as a dispensing drawer, which is part of the washing machine that dispenses the through-the-rinse composition during the rinse sub-cycle, or from an agitator within a tab.

[0013] The types of capsules disclosed herein, when used in a water-soluble carrier, are believed to control the leakage of fragrance ingredients in the compositions of the present disclosure surprisingly well, resulting in relatively low and consistent fragrance leakage. Without being bound by theory, it is believed that the leakage of fragrance ingredients is caused by fundamentally different mechanisms for shells containing highly cross-linked inorganic materials compared to shells containing organic polymer materials. Specifically, the diffusion of small molecules such as fragrance raw materials ("PRM") across a homogeneous organic polymer shell is similar to the diffusion mechanism across a homogeneous polymer membrane. In this case, the permeability of the polymer membrane to a given solute depends on both the free volume of the polymer (affected by crystallinity and cross-link density) and the relative solubility of the solute in the polymer. Since different PRMs have different ranges of relevant physical and chemical properties (e.g., molecular weight and polarity), the diffusion rates for a given set of PRMs are not uniform if the physical and chemical properties are also not uniform.

[0014] On the other hand, the diffusion of small molecules across a highly cross-linked inorganic shell is believed to occur primarily through microchannels formed by a permeation network of micropores present in the shell. Such highly cross-linked inorganic shells can be obtained by using a second shell component in combination with a first shell component, as disclosed in the present disclosure. In this case, the permeability of the inorganic shell depends primarily on the number, density, and dimensions of the microchannels that effectively connect the core phase and the continuous phase, which is believed to result in relatively uniform or consistent PRM leakage rates relative to each other and relatively low leakage rates.

[0015] Since 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 maintained, resulting in a more satisfactory and consistent olfactory performance.

[0016] In this specification, the terms "substantially free of" or "substantially free from" may be used. This means that the indicated material is present in minimal amounts and is not intentionally added to the composition to form part of the composition, or optionally, is not present at analytically detectable concentrations. It means that the composition includes the indicated material only as an impurity in one of the other materials that are intentionally included. The indicated material, if present, may be present at a concentration of less than 1% by weight, or less than 0.1% by weight, or less than 0.01% by weight, or even 0% by weight of the composition.

[0017] Unless otherwise noted, all component or composition levels are with respect to the active portion of that component or composition, and impurities that may be present in commercial sources of such components or compositions, such as residual solvents or by-products, are excluded.

[0018] All temperatures in this specification are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise stated, all measurements in this specification are carried out at 20 °C and atmospheric pressure.

[0019] As described herein, unless otherwise specified, all percentages are by weight of the total composition. Unless otherwise specified, all ratios are weight ratios.

[0020] All of the maximum numerical limitations given throughout this specification are to be understood as including all lower numerical limitations, as if such lower numerical limitations were expressly recited herein. All of the minimum numerical limitations given throughout this specification are to be assumed to include all higher numerical limitations, as if such higher numerical limitations were expressly recited herein. All numerical ranges given throughout this specification are to be assumed to include any and all sub-ranges subsumed therein, as if such sub-ranges were all expressly recited herein.

[0021] Water-soluble carrier The particles can include a water-soluble carrier. The water-soluble carrier serves to carry the capsules into the cleaning liquid. When the water-soluble carrier dissolves, the capsules are dispersed in the cleaning liquid and adhere to the laundry.

[0022] The water-soluble carrier can be a material that is soluble in the cleaning liquid in a short time, for example, less than about 10 minutes.

[0023] Water-soluble means that a material, carrier substance, or particle is soluble or dispersible in water and has a water solubility of optionally at least 50%, optionally at least 75%, or even at least 95% when measured by the method indicated hereinafter using a glass filter having a maximum pore size of 20 micrometers: Add 50 grams ± 0.1 gram of the carrier to a pre-weighed 400 mL beaker and add 245 mL ± 1 mL of distilled water. Stir this vigorously for 30 minutes with a magnetic stirrer set at 600 rpm. Then filter the mixture through a sintered glass filter having the pore size (maximum 20 micrometers) defined above. The procedure is carried out at a temperature of 23°C ± 1.0°C and a relative humidity of 50% ± 2%. Dry the water from the recovered filtrate by any conventional method and determine the weight of the remaining material (this is the dissolved or dispersed fraction). The solubility or dispersibility can then be calculated.

[0024] The water-soluble carrier can be selected from the group consisting of 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 ureas, and any combination thereof.

[0025] The alkali metal salts can be selected from the group consisting of, for example, salts of lithium, sodium, and potassium, and any combination thereof. Useful alkali metal salts can be selected from the group consisting of, for example, alkali metal fluorides, alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfates, alkali metal bisulfates, alkali metal phosphates, alkali metal monohydrogen phosphates, alkali metal dihydrogen phosphates, alkali metal carbonates, alkali metal bicarbonates, alkali metal acetates, alkali metal citrates, alkali metal lactates, alkali metal pyruvates, alkali metal silicates, alkali metal ascorbates, and combinations thereof.

[0026] The alkali metal salts can be selected from the group consisting of sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, sodium bisulfate, sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium carbonate, sodium bicarbonate, sodium 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 bicarbonate, potassium acetate, potassium citrate, potassium lactate, potassium tartrate, potassium silicate, potassium ascorbate, and combinations thereof.

[0027] The alkaline earth metal salt can be selected from the group consisting of salts of magnesium, salts of calcium, etc., and combinations thereof. The alkaline earth metal salt can be selected from the group consisting of alkali metal fluorides, alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfates, alkali metal bisulfates, alkali metal phosphates, alkali metal monohydrogen phosphates, alkali metal dihydrogen phosphates, alkali metal carbonates, alkali metal bicarbonates, alkali metal acetates, alkali metal citrates, alkali metal lactates, alkali metal pyruvates, alkali metal silicates, alkali metal ascorbates, and combinations thereof. The alkaline earth metal salt can be selected from the group consisting of magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium phosphate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium carbonate, magnesium bicarbonate, 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 bicarbonate, calcium acetate, calcium citrate, calcium lactate, calcium tartrate, calcium silicate, calcium ascorbate, and combinations thereof.

[0028] 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. The organic salt may be an alkali metal salt or an alkaline earth metal salt of sorbic acid (i.e., sorbate). The sorbate may be selected from the group consisting of sodium sorbate, potassium sorbate, magnesium sorbate, calcium sorbate, and combinations thereof.

[0029] The water-soluble carrier may be a substance selected from the group consisting of 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, or may contain the same. The water-soluble carrier may be selected from the group consisting of 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, isomalt, xylitol, rock sugar, raw 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.

[0030] The water-soluble carrier may be a substance selected from the group consisting of 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, tapioca starch, clay, silicate, carboxymethyl cellulose citrate, fatty acid, fatty alcohol, glyceryl diester of hydrogenated tallow, glycerol, and combinations thereof, or may contain the same.

[0031] The water-soluble carrier may be selected from the group consisting of 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 silicate, carboxymethyl cellulose citrate, fatty acid, fatty alcohol, glyceryl diester of hydrogenated tallow, glycerol, polyethylene glycol, and combinations thereof.

[0032] The water-soluble carrier can be selected from the group consisting of disaccharides, polysaccharides, silicates, zeolites, carbonates, sulfates, citrates, and combinations thereof.

[0033] The water-soluble carrier can be selected from the group consisting of polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxoalkylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, sodium sulfate, starch, and mixtures thereof.

[0034] The water-soluble carrier can be a water-soluble polymer. The water-soluble polymer can be selected from the group consisting of C8 - C22 alkyl polyalkoxylates containing more than about 40 alkoxylate units, ethoxylated nonionic surfactants having an ethoxylation degree of more than about 30, polyalkylene glycols having a weight average molecular weight of about 2000 - about 15000, and combinations thereof.

[0035] The water-soluble carrier can be a water-soluble polymer. The water-soluble polymer is of formula (I), (II), (III) or (IV), R 1 O-(EO)x-(PO)y-R 2 (I), R 1 O--(PO)x-(EO)y-R 2 (II), R 1 O-(EO)o-(PO)p-(EO)q-R 2 (III), R 1 O--(PO)o-(EO)p-(PO)q-R 2 (IV), or a combination thereof (wherein EO is a -CH 2 CH 2 O- group, and PO is a -CH(CH 3 )CH 2 O- group; R 1 and R 2is, independently, H or a C1-C22 alkyl group; x, y, o, p, and q are, independently, from 1 to 100; provided that the sum of x and y is greater than 35 and the sum of o, p, and q is greater than 35; and the block copolymer may be a block copolymer having a molecular weight in the range of about 3000 g / mol to about 15,000 g / mol).

[0036] The water-soluble polymer can be a block copolymer or a plurality of block copolymers, for example, a block copolymer 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.

[0037] Water-soluble polymers can 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; polyalkylene oxides such as polyethylene oxide; polyethylene glycol; acrylamide; acrylic acid; alkyl cellulose-based materials such as cellulose, methyl cellulose, ethyl cellulose and propyl cellulose; cellulose ethers; cellulose esters; cellulose amides; polyvinyl acetate; polycarboxylic acids and salts; polyamino acids or peptides; polyamides; polyacrylamide; copolymers of maleic acid / acrylic acid; polysaccharides including starch, modified starch; gelatin; alginate; other hemicellulose-based polysaccharides including xyloglucan, xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan, and galactoglucomannan; and pectin, xanthan, and carrageenan, locust bean, arabic, tragacanth and other natural gums; and combinations thereof. In one embodiment, the polymer includes polyacrylate, particularly sulfonated polyacrylate and water-soluble acrylate copolymers; and alkyl hydroxycellulose-based materials such as methyl cellulose, sodium carboxymethyl cellulose, modified carboxymethyl cellulose, dextrin, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, maltodextrin, polymethacrylate. In yet another embodiment, the water-soluble polymer can be selected from the group consisting of PVA; PVA copolymers; hydroxypropyl methyl cellulose (HPMC); and mixtures thereof.

[0038] The water-soluble polymer can be selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl alcohol / polyvinyl pyrrolidone, polyvinyl alcohol / polyvinyl amine, partially hydrolyzed polyvinyl acetate, polyalkylene oxide, polyethylene glycol, acrylamide, acrylic acid, cellulose, alkyl cellulose-based materials, methyl cellulose, ethyl cellulose, propyl cellulose, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polycarboxylic acid and salts, polyamino acid or peptide, polyamide, polyacrylamide, copolymer of maleic acid / acrylic acid, polysaccharide, starch, modified starch, gelatin, alginate, xyloglucan, hemicellulosic polysaccharide, xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan, galactoglucomannan, natural gum, pectin, xanthan, carrageenan, locust bean, arabic, tragacanth, polyacrylate, sulfonated polyacrylate, water-soluble acrylate copolymer, alkyl hydroxycellulose-based materials, methyl cellulose, sodium carboxymethyl cellulose, modified carboxy-methyl cellulose, dextrin, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, maltodextrin, polymethacrylate, polyvinyl alcohol polymer, hydroxypropyl methyl cellulose, and mixtures thereof.

[0039] The water-soluble polymer can be an organic material. The organic water-soluble polymer can bring the benefit of being easily soluble in water.

[0040] The water-soluble polymer can be selected from the group consisting of polyethylene glycol, polypropylene glycol polyoxoalkylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, starch, and mixtures thereof.

[0041] The water-soluble polymer may be polyethylene glycol (PEG). PEG can be sufficiently water-soluble to dissolve during the washing cycle when the particles have a mass within the ranges disclosed herein, and can thus be a convenient material to use in making the particles. Further, PEG can be easily processed as a melt. The onset of the melting temperature of PEG can vary as a function of the molecular weight of PEG. The particles can contain from about 25 wt% to about 94 wt% of PEG having a weight average molecular weight of from about 2,000 to about 15,000. PEG is relatively low-cost, can be formed into many different shapes and sizes, minimizes the diffusion of unencapsulated fragrance, and dissolves well in water. PEG is available with a variety of weight average molecular weights. Suitable ranges of the weight average molecular weight of PEG include from about 2,000 to about 13,000, or from about 4,000 to about 13,000, or from about 4,000 to about 12,000, or from about 4,000 to about 11,000, or from about 5,000 to about 11,000, or from about 6,000 to about 10,000, or from about 7,000 to about 9,000, or combinations thereof. PEG is available, for example, as PLURIOL E8000, or other PLURIOL products, from BASF. 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., 9000) and the other having a second weight average molecular weight (e.g., 4000), where the second weight average molecular weight is different from the first weight average molecular weight.

[0042] The particles can contain from about 25 wt% to about 99 wt% of a water-soluble carrier. The particles can contain from about 35 wt% to about 95 wt%, optionally from about 50 wt% to about 80 wt%, optionally combinations thereof, and any total percentage or range of total percentages within any of the foregoing ranges, of the water-soluble carrier.

[0043] The plurality of particles can include individual particles containing from about 25 wt% to about 99 wt% of a water-soluble carrier and from about 0.1 wt% to about 20 wt% of particle capsules, where the capsules are dispersed in a matrix of the water-soluble polymer.

[0044] The particles may contain from about 25 wt% to about 99 wt% of PEG per individual particle. Optionally, each individual particle may contain from about 25 wt% to about 95 wt%, optionally from about 35 wt% to about 95 wt%, optionally from about 50 wt% to about 80 wt%, optionally a combination of these, and any total percentage or range of total percentages within any of the aforementioned ranges of PEG.

[0045] The water-soluble polymer can include materials selected from the group consisting of: polyalkylene polymers of the formula H-(C 2 H 4 O) x -(CH(CH 3 )CH 2 O) y -(C 2 H 4 O) z -OH (wherein x is from about 50 to about 300, y is from about 20 to about 100, and z is from about 10 to about 200); polyethylene glycol fatty acid esters of the formula (C 2 H 4 O) q -C(O)O-(CH 2 ) r -CH 3 (wherein q is from about 20 to about 200 and r is from about 10 to about 30); polyethylene glycol fatty alcohol ethers of the formula HO-(C 2 H 4 O) s -CH 2 ) t )-CH 3 (wherein s is from about 30 to about 250 and t is from about 10 to about 30); and mixtures thereof. The formula H-(C 2 H 4 O) x -(CH(CH 3 )CH 2 O) y -(C 2 H 4 O) z-OH (wherein x is from about 50 to about 300, y is from about 20 to about 100, and z is from about 10 to about 200) can be a block copolymer or a random copolymer.

[0046] The water-soluble polymer may include: polyethylene glycol; the formula H-(C 2 H 4 O) x -(CH(CH 3 )CH 2 O) y -(C 2 H 4 O) z -OH (wherein x is from about 50 to about 300, y is from about 20 to about 100, and z is from about 10 to about 200) of a polyalkylene polymer; the formula (C 2 H 4 O) q -C(O)O-(CH 2 ) r -CH 3 (wherein q is from about 20 to about 200 and r is from about 10 to about 30) of a polyethylene glycol fatty acid ester; and the formula HO-(C 2 H 4 O) s -(CH 2 ) t )-CH 3 (wherein s is from about 30 to about 250 and t is from about 10 to about 30) of a polyethylene glycol fatty alcohol ether.

[0047] The water-soluble polymer can be about 20 wt% to about 95 wt% of a plurality of particles or individual particles of the formula H-(C 2 H 4 O) x -(CH(CH 3 )CH 2 O) y -(C 2 H 4 O) z -OH (wherein x is from about 50 to about 300, y is from about 20 to about 100, and z is from about 10 to about 200) of a polyalkylene polymer.

[0048] The water-soluble polymer may contain from about 1 wt% to about 20 wt% of a polyethylene glycol fatty acid ester of the formula (C 2 H 4 O) q -C(O)O-(CH 2 ) r -CH 3 (wherein q is from about 20 to about 200 and r is from about 10 to about 30) based on a plurality of particles or individual particles.

[0049] The water-soluble polymer may contain from about 1 wt% to about 10 wt% of a polyethylene glycol fatty alcohol ether of the formula HO-(C 2 H 4 O) s -CH 2 ) t )-CH 3 (wherein s is from about 30 to about 250 and t is from about 10 to about 30) based on a plurality of particles or individual particles.

[0050] The water-soluble carrier can include a plasticizer polyol (0 wt% to 3 wt% of the particles), which is optionally a liquid at 20 °C and 1 atm, a plasticizer polymer, water (1 wt% to 20 wt% of the particles, or 1 wt% to 12 wt%, or 6 wt% to 8 wt%), and a sugar alcohol polyol selected from the group consisting of erythritol, xylitol, mannitol, isomalt, maltitol, lactitol, trehalose, lactose, tagatose, sucralose, and mixtures thereof (45 wt% to 80 wt% of the particles, or 50 wt% to 70 wt%, or 50 wt% to 60 wt%). The particles can further include (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, or 2:1 to 10:1, or 2:1 to 3:1, or (b) a modified starch having a dextrose equivalent of less than 4 to 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, or 1.5:1 to 10:1, or 1.5:1 to 4:1. The modified starch has a dextrose equivalent of 15 to 20, and the sugar alcohol polyol and the modified starch can 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 has a dextrose equivalent of less than 4 to 15, and the sugar alcohol polyol and the modified starch can be present in a weight ratio of the sugar alcohol polyol to the modified starch of 1.5:1 to 16:1, or 1.5:1 to 10:1, or 1.5:1 to 4:1. The modified starch can have a dextrose equivalent of 4 to 12. The modified starch can be maltodextrin. The sugar alcohol polyol can be mannitol. The plasticizer polyol can be selected from the group consisting of glycerin, dipropylene glycol, propylene glycol, and mixtures thereof.

[0051] The particles can contain from about 25 wt% to about 99 wt% of a water-soluble carrier. Optionally, the particles can contain from about 35 wt% to about 85 wt%, or even from about 50 wt% to about 80 wt% of the water-soluble carrier, based on the weight of the particles.

[0052] Capsules The compositions of the present disclosure further include a plurality of capsules. As described in more detail below, the capsules can include a core surrounded by a substantially inorganic shell.

[0053] The capsules can be present in the particles of the composition in an amount of from about 0.1 wt% to about 20 wt%, or from about 0.2 wt% to about 10 wt%, or from about 0.2 wt% to about 5 wt%, or from about 0.2 wt% to about 3 wt% of the composition. The composition can include an amount of capsules sufficient to provide from about 0.1 wt% to about 20 wt%, or from about 0.2 wt% to about 10 wt%, or from about 0.2 wt% to about 5 wt% of a fragrance ingredient to the composition. As discussed herein, the amount or weight percent of the capsules means the total of the shell material and the core material.

[0054] The capsules can have an average shell thickness of from 10 nm to 10,000 nm, optionally from 170 nm to 1000 nm, and optionally from 300 nm to 500 nm.

[0055] The capsules can have an average volume-weighted capsule diameter of from 0.1 micrometers to 300 micrometers, optionally from 10 micrometers to 200 micrometers, and optionally from 10 micrometers to 50 micrometers. Advantageously, according to the embodiments herein, it has been found that large capsules (e.g., having an average diameter of 10 µm or more) can be provided without sacrificing the overall stability of the capsules and / or while maintaining good breaking strength.

[0056] Surprisingly, it has been found that in addition to the inorganic shell, the volume core-to-shell ratio can also play an important role in ensuring the physical integrity of the capsule. A shell that is too thin relative to the overall size of the capsule (core:shell ratio > 98:2) tends to suffer from the adverse effects of lack of self-integrity. On the other hand, a shell that is extremely thick relative to the diameter of the capsule (core:shell ratio < 80:20) tends to have higher shell permeability in a surfactant-rich matrix. Intuitively, a thick shell would result in lower shell permeability (because this parameter affects the average diffusion path of the active substance across the shell), while surprisingly, it has been found that the capsules of the present invention having a shell with a thickness exceeding the threshold have higher shell permeability. This upper threshold is thought to depend, in part, on the capsule diameter.

[0057] The capsule can have a volume core-to-shell ratio of 50:50 to 99:1, optionally 60:40 to 99:1, optionally 70:30 to 98:2, optionally 80:20 to 96:4.

[0058] It may be desirable to have certain combinations of these capsule properties. For example, the capsule can have a volume core-to-shell ratio of about 99:1 to about 50:50, an average volume-weighted capsule diameter of about 0.1 Mm to about 200 Mm, and an average shell thickness of about 10 nm to about 10,000 nm. The capsule can have a volume core-to-shell ratio of about 99:1 to about 50:50, an average volume-weighted capsule diameter of about 10 Mm to about 200 Mm, and an average shell thickness of about 170 nm to about 10,000 nm. The capsule can have a volume core-to-shell ratio of about 98:2 to about 70:30, an average volume-weighted capsule diameter of about 10 Mm to about 100 Mm, and an average shell thickness of about 300 nm to about 1000 nm.

[0059] The method according to the present disclosure can produce capsules with a low coefficient of variation of capsule diameter. By controlling the size distribution of the capsules, it is possible to improve the fracture strength of the population and enable the population to have a more uniform fracture strength. The coefficient of variation of the capsule diameter of the capsule population can be 40% or less, optionally 30% or less, and optionally 20% or less.

[0060] In the case of capsules containing a core material that functions in consumer product applications such as laundry care particle additives and is cost-effective, the capsules should i) have resistance to core diffusion during the shelf life of the liquid product (e.g., low leakage or permeability), ii) have the ability to deposit on the targeted surface during application (e.g., during a washing machine cycle), and iii) have the ability to release the core material by mechanically rupturing the shell at the correct timing and location to provide the intended benefit to the end consumer.

[0061] The capsules described herein can have an average fracture strength of 0.1 MPa to 10 MPa, optionally 0.25 MPa to 5 MPa, and optionally 0.25 MPa to 3 MPa. Conventional completely inorganic capsules have inferior fracture strength, but in the capsules described herein, the fracture strength of the capsules can exceed 0.25 MPa, the stability is improved, and the release of the beneficial agent can be induced by receiving a rupture stress of a specified magnitude.

[0062] In certain embodiments, the average volume-weighted diameter of the capsules is 1 to 200 micrometers, optionally 1 to 10 micrometers, and optionally 2 to 8 micrometers. In another embodiment, the shell thickness is 1 to 10000 nm, 1 to 1000 nm, and 10 to 200 nm. In a further embodiment, the capsules have an average volume-weighted diameter of 1 to 10 micrometers and a shell thickness of 1 to 200 nm. Capsules having an average volume-weighted diameter of 1 to 10 micrometers and a shell thickness of 1 to 200 nm have been found to have a higher fracture strength.

[0063] Although not bound by theory, higher breaking strength is thought to provide better survivability during the washing process, which can cause premature rupture of mechanically weak capsules due to mechanical constraints in the washing machine.

[0064] Capsules having an average volume weighted diameter of 1 to 10 micrometers and a shell thickness of 10 to 200 nm provide resistance to mechanical constraints when made using a specific selection of silica precursors. In some embodiments, the precursor has a molecular weight of 2 to 5 kDa, optionally 2.5 to 4 kDa. Additionally, the concentration of the precursor needs to be carefully selected, and the concentration is 20 to 60 wt%, preferably 40 to 60 wt%, of the oil phase used during encapsulation.

[0065] Although not bound by theory, higher molecular weight precursors are thought to have a much slower transfer time from the oil phase to the water phase. The slower transfer time is thought to result from a combination of three phenomena: diffusion, partitioning, and reaction kinetics. This phenomenon can be important in the context of small capsules due to the fact that the total surface area between oil and water in the system increases as the capsule diameter decreases. The higher surface area results in a higher transfer of the precursor from the oil phase to the water phase, thereby reducing the yield of polymerization at the interface. Thus, higher molecular weight precursors mitigate the effects brought about by the increase in surface area and allow the capsules according to the invention to be obtained.

[0066] i. Core The capsule includes a core. The core may be oily or the core may be aqueous. Optionally, the core is oily. The core may be liquid at the temperature at which it is used in the formulated product. The core may be liquid at room temperature and near room temperature.

[0067] The core contains a fragrance. The core may contain from about 1 wt% to 100 wt% of the fragrance, based on the total weight of the core. Optionally, the core may contain from 50 wt% to 100 wt% of the fragrance, based on the total weight of the core, and optionally from about 80 wt% to 100 wt% of the fragrance, based on the total weight of the core. Typically, higher levels of fragrance are preferred for improved delivery efficiency.

[0068] The fragrance may contain one or more, optionally two or more, perfume raw materials. The term "perfume raw material" (or "perfume raw material, PRM") as used herein refers to a compound having a molecular weight of at least about 100 g / mol and useful for imparting odor, aroma, essence, or scent, either alone or in combination with other PRMs. Typical PRMs include, inter alia, 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, P.M. and Lamparsky, D., Blackie Academic and Professional (1994).

[0069] PRMs can be characterized by their octanol / water partition coefficient (P), which can be described in terms of their boiling points (B.P.) measured at normal pressure (760 mmHg) and the logP determined according to the test methods in the test methods section. As described in more detail below, based on these characteristics, the PRMs may be classified as PRMs in Quadrant I, Quadrant II, Quadrant III, or Quadrant IV. Fragrances having various PRMs from different quadrants may be desirable, for example, to provide aromatic effects at different touch points during normal use.

[0070] A PRM having a boiling point (B.P.) lower than about 250 °C and a logP lower than about 3 is known as quadrant IPRM. Quadrant IPRM is optionally limited to less than 30% of the fragrance composition. A PRM having a B.P. higher than about 250 °C and a logP higher than about 3 is known as quadrant IVPRM, a PRM having a B.P. higher than about 250 °C and a logP lower than about 3 is known as quadrant IIPRM, and a PRM having a B.P. lower than about 250 °C and a logP higher than about 3 is known as quadrant IIIPRM. Suitable quadrant I, II, III, and IV PRMs are disclosed in U.S. Patent No. 6,869,923 (B1).

[0071] The fragrance may comprise a mixture of at least 3, or even at least 5, or at least 7 PRMs. The fragrance may comprise at least 10 or at least 15 PRMs. The mixture of PRMs may provide a more complex and desirable aroma, and / or better fragrance performance or longevity, for example, at various touchpoints. However, it may be desirable to limit the number of PRMs in the fragrance to reduce or limit the complexity and / or cost of the formulation.

[0072] The fragrance may contain at least one fragrance raw material of natural origin. Such ingredients may be desirable for sustainability / environmental reasons. The PRM of natural origin may include natural extracts or essences that may contain a mixture of PRMs. Such natural extracts or essences may include orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essence, sandalwood oil, pine root oil, cedar, etc.The PRM can be selected from the group consisting of almond oil, ambra, angelica seed oil, almawood oil, basil oil Granville, benzoin resinoid, bergamot essential oil, bergamot oil, black pepper oil, black pepper essence, blackcurrant essence, blood orange oil, Bois de Lune, brandy pure jungle essence, cade, camomile roman he, cardamom Guatemala extract, cardamom oil, carrot heart, caryophyllene extra, cider, cider leaf, cider wood oil, cinnamon bark ceylon, cinnamon ceylan extract, beeswax, citronella, citronellal, clarisse essence, clove leaf oil rectified, copaiba balsam, coriander, cos cos anethole, cos cos essence coriandrol russey, cucumber extract, cumin oil, cypriol heart, elemi cool, elemi oil, English white camomile, eucalyptol, lemon eucalyptus, eugenol, galbanum heart, ginger, grapefruit replacer, guaiac wood oil, turmeric oil, healing wood bro, helichrysum, iso eugenol, jasmine sambac, juniper berry oil, key lime, labdanum resinoid, lavandin abrialis oil, lavandin grossa, lavender essential oil, lemon cedra, lemon oil, lemon peel barberry, lemon grass, lemon grass oil, lisea cubeba, magnolia flower oil, mandarin oil yellow, menthol crystallize, mint peperita cascade, narcissus, neroli oil, nutmeg, orange flower water, orange oil, orange phase oil, organic rose water, osmanthus, patchouli, patchouli heart, patchouli oil, pepper black oil, peppermint, peru balsam absolute, petitgrain less, pimento berry oil, pink pepper, raspberry essence, rhodinol, rose, rose centifolia, sandalwood, sichuan pepper extract, styrax white, sweet orange oil, tangerine oil, vanilla, vetiver, violet leaves, violet feuille, mugwort oil, and combinations thereof.

[0073] In addition to the PRM, the core may include a pro-fragrance that can contribute to improving the shelf life of the freshness effect. The pro-fragrance may include, for example, a non-volatile substance that releases or converts into a fragrance substance as a result of simple hydrolysis, or may be a pH change-inducing pro-fragrance (e.g., induced by a decrease in pH), or a pro-fragrance releasable by an enzyme, or a photo-induced pro-fragrance. The pro-fragrance may exhibit various release rates depending on the selected pro-fragrance.

[0074] The core of the encapsulating agent of the present disclosure may include a core modifier such as a partitioning regulator and / or a density regulator. In addition to the fragrance, the core may include a core modifier in an amount of more than 0% to 80%, optionally more than 0% to 50%, optionally more than 0% to 30% based on the total weight of the core. The partitioning regulator may include a material selected from the group consisting of vegetable oils, modified vegetable oils, mono-, di-, and tri-esters of C 4 ~C 24 fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning regulator may optionally include isopropyl myristate or may 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. U.S. Patent Application Publication No. 20110268802, which is incorporated herein by reference, describes other partitioning regulators that may be useful in the fragrance encapsulating agents described herein.

[0075] ii. Shell The capsules of the present disclosure include a shell surrounding the core.

[0076] The shell may include a first shell component. Optionally, the shell may include a second shell component surrounding the first shell component. The first shell component may include a condensation layer formed from a condensation product of a precursor. As described in detail below, the precursor may include one or more precursor compounds. The first shell component may include a nanoparticle layer. The second shell component may include an inorganic material.

[0077] The shell may be substantially inorganic (as defined later). A substantially inorganic shell may include a first shell component including a condensation layer surrounding the core, and may further include a nanoparticle layer surrounding the condensation layer. The substantially inorganic shell may further include a second shell component surrounding the first shell component. The first shell component includes an inorganic material, optionally a metal / semimetal oxide, optionally SiO2, TiO2, and Al2O3, and optionally SiO2. The second shell component includes a metal / semimetal oxide, a metal, and a mineral, optionally SiO 2 、TiO 2 、Al 2 O 3 、ZrO 2 、ZnO 2 、CaCO 3 、Ca 2 SiO 4 、Fe 2 O 3 、Fe 3 O 4 、a material selected from the list of clay, gold, silver, iron, nickel, and copper, optionally SiO 2 and CaCO 3 and includes an inorganic material optionally including a material from the group of materials selected from. Optionally, the material of the second shell component is the same type of chemical substance as the first shell component to maximize chemical compatibility.

[0078] 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. The one or more precursors may include at least one compound from the group consisting of formula (I), formula (II), and mixtures thereof, and formula (I) is (M v O z Yn ) w and formula (II) is (M v O z Y n R 1 p ) w . The precursor contains only formula (I) and, for example, may preferably not contain a compound according to formula (II) (i.e., no R 1 group) in order to reduce the organic component content of the capsule shell. Formulas (I) and (II) will be described in more detail below.

[0079] One or more precursors can be of formula (I): (M v O z Y n ) w (Formula I) wherein 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, each Y is independently -OH, -OR 2 , -NH 2 , -NHR 2 , -N(R 2 ) 2 selected from, R 2 is C 1 ~C 20 alkyl, C 1 ~C 20 alkylene, C 6 ~C 22 aryl, or 5- to 12-membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N, and S, R 3 is H, C 1 ~C 20 alkyl, C 1 ~C 20 alkylene, C 6 ~C 22 aryl, or 5- to 12-membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N, and S, and n is 0.7 to (v - 1) and w is 2 to 2000.

[0080] One or more precursors may be of formula (I), wherein M is silicon. Y is -OR 2 and may be. n may be from 1 to 3. Y is -OR 2 and n may preferably be from 1 to 3. n is at least 2, and one or more of Y are -OR 2 and one or more of Y may be -OH.

[0081] R 2 is optionally C 1 ~C 20 alkyl. R 2 is optionally C 6 ~C 22 aryl. R 2 is optionally C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, C 7 alkyl, and one or more of C 8 alkyl. R 2 is optionally C 1 alkyl. R 2 is optionally C 2 alkyl. R 2 is optionally C 3 alkyl. R 2 is optionally C 4 alkyl.

[0082] z may be from 0.5 to 1.3, from 0.5 to 1.1, from 0.5 to 0.9, from 0.7 to 1.5, from 0.9 to 1.3, or from 0.7 to 1.3.

[0083] M is silicon, v is 4, each Y is -OR 2 and n is 2 and / or 3, and each R 2 is optionally C 2 alkyl.

[0084] The precursor may include polyalkoxysilane (PAOS). The precursor may include polyalkoxysilane (PAOS) synthesized through a hydrolysis process.

[0085] Alternatively or additionally, the precursor may include one or more of the compounds of formula (II): (M v O z Y n R 1 p ) w (Formula II) Wherein M is one or more of silicon, titanium, and aluminum, v is the valence of M, which is 3 or 4, z is 0.5 to 1.6, preferably 0.5 to 1.5, and each Y is independently -OH, -OR 2 , halogen,

[0086]

Chemical formula

[0087]

Chemical formula

[0088] R 1 is a C 3 ~C 2 substituted with 1 to 4 groups independently selected from halogen, -OCF 2 , -NO 2 , -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO 1 ~C30 It may be alkyl. R 1 is halogen, -OCF 3 , -NO 2 , -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO 2 H, CO 2 C substituted with 1 to 4 groups independently selected from alkyl, aryl, and heteroaryl 1 ~C 30 It may be alkylene.

[0089] As shown above, in order to reduce or even eliminate the organic component content in the first shell component, it may be preferable to reduce or even eliminate the presence of the compound according to formula (II) having an R1 group. The precursor, the condensation layer, the first shell component, and / or the shell may not contain the compound according to formula (II).

[0090] The precursor of formula (I) and / or (II) can 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. Selecting a specific Mw and / or DB may be useful for obtaining capsules that maintain their mechanical integrity once left on the surface and have low shell permeability in a surfactant-based matrix. The precursors of formula (I) and (II) can be characterized as having a DB of 0 to 0.6, preferably 0.1 to 0.5, optionally 0.19 to 0.4, and / or an Mw of 600 Da to 100,000 Da, preferably 700 Da to 60,000 Da, optionally 1000 Da to 30,000 Da. The characteristics provide useful properties of the precursor for obtaining the capsules of the present invention. The precursor of formula (I) and / or (II) can have a PDI of 1 to 50.

[0091] The condensed layer containing the metal / semimetal oxide may be formed from the condensation product of a precursor containing at least one compound of formula (I) and / or at least one compound of formula (II), and optionally in combination with one or more monomer precursors of the metal / semimetal oxide, and the metal / semimetal oxide includes TiO2, Al2O3 and SiO2, preferably SiO2. The monomer precursor of the metal / semimetal oxide may be a compound of the formula M(Y) V-n R n (wherein M, Y, and R are the same as defined in formula (II), and n can be an integer from 0 to 3). The monomer precursor of the metal / semimetal oxide preferably has a form in which M is silicon and the compound has the general formula Si(Y) 4-n R n (wherein Y and R are the same as defined in formula (II), and n can be an integer from 0 to 3). Examples of such monomers are TEOS (tetraethoxysilicate), TMOS (tetramethoxysilicate), TBOS (tetrabutoxysilicate), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). These do not mean 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.

[0092] The first shell component may include any nanoparticle layer. The nanoparticle layer contains nanoparticles. The nanoparticles in the nanoparticle layer can be one or more of SiO 2 、TiO 2 、Al 2 O 3 、ZrO 2 、ZnO 2 、CaCO 3 、clay, silver, gold, and copper. Optionally, the nanoparticle layer may contain SiO 2 nanoparticles.

[0093] The nanoparticles can have an average diameter of 1 nm to 500 nm, optionally 50 nm to 400 nm.

[0094] The size of the pores of the capsule can be adjusted by changing the shape of the nanoparticles and / or by using a combination of nanoparticles of different sizes. For example, non-spherical and irregular nanoparticles can be used because their packing can be improved when forming a nanoparticle layer, thereby resulting in a higher density shell structure. This can be advantageous when it is necessary to limit permeability. The nanoparticles used can have a more regular shape, such as spherical. Any conceivable nanoparticle shape can be used herein.

[0095] The nanoparticles may substantially not contain a hydrophobic modification. The nanoparticles may substantially not contain a modification with an organic compound. The nanoparticles may contain a modification with an organic compound. The nanoparticles can be hydrophilic.

[0096] The nanoparticles can include a surface modification, examples of which include, but are not limited to, linear or branched C 1 ~C 20 alkyl groups, surface amino groups, surface methacrylo groups, surface halogens, or surface thiols. These surface modifications enable the nanoparticle surface to covalently bond organic molecules onto itself. When inorganic nanoparticles are disclosed herein for use, this means that, although not explicitly listed, they can include any of the aforementioned surface modifications or none at all.

[0097] The capsules of the present disclosure may be defined as comprising a substantially inorganic shell comprising a first shell component and a second shell component. Substantially inorganic means that the first shell component can contain up to 10 wt% or up to 5 wt% organic component content, preferably up to 1 wt% organic component content, as defined later in the calculation of the organic component content. The first shell component, the second shell component, or both may optionally contain an organic component content of about 5 wt% or less, preferably about 2 wt% or less, and optionally about 0 wt%, based on the weight of the first or shell component, in some cases.

[0098] The first shell component is useful for constructing a mechanically robust scaffold or framework, but in liquid products containing surfactants such as laundry detergents, shower gels, cleansers, etc., the permeability of the shell can be made low (see Surfactants in Consumer Products, J. Falbe, Springer-Verlag). The second shell component can significantly reduce the permeability of the shell and improve the impermeability of the capsules in a surfactant-based matrix. The second shell component can also significantly improve the mechanical properties of the capsules, such as the bursting force and breaking strength of the capsules. Without being bound by theory, it is believed that the second shell component contributes to the densification of the overall shell by depositing precursors within the pores remaining within the first shell component. The second shell component also adds an additional inorganic layer on the surface of the capsule. These improved shell permeability and mechanical properties provided by the second shell component occur only when used in combination with the first shell component, as defined in the present invention.

[0099] A more detailed description of the shell structures, their materials, and how they interact with each other to provide optimal performance can be found in U.S. Patent Application Nos. 16 / 851,173, 16 / 851,176, and 16 / 851,194, the entire disclosures of which are incorporated herein by reference.

[0100] iii. Capsule manufacturing process The capsules of the present disclosure may be formed by first mixing a hydrophobic material with any of the precursors of the condensation layer defined above, thereby forming an oil phase, which may contain an oily and / or oil-soluble precursor. The precursor / hydrophobic material mixture is then used with an aqueous phase either as a dispersed phase or as a continuous phase. When the two phases are mixed and homogenized via methods known to those skilled in the art, an O / W (oil-in-water) emulsion is formed in the former case and a W / O (water-in-oil) emulsion is formed in the latter case. Preferably, an O / W emulsion is formed. Nanoparticles may be present in the aqueous phase and / or the oil phase, regardless of the type of emulsion desired. The oil phase may contain an oily core modifier and / or an oily beneficial agent as well as a precursor of the condensation layer. Suitable core materials used in the oil phase are described earlier herein.

[0101] When any emulsion is formed, the following steps may occur. (a) The nanoparticles move to the oil / water interface, thereby forming a nanoparticle layer. (b) The precursor of the condensation layer containing the precursor of the metal / semimetal oxide begins to undergo a hydrolysis / condensation reaction with water at the oil / water interface, thus forming a condensation layer surrounded by the nanoparticle layer. The precursor of the condensation layer can further react with the nanoparticles of the nanoparticle layer.

[0102] The precursor for forming the condensation layer may be present in an amount of 1 wt% to 50 wt%, preferably 10 wt% to 40 wt%, based on the total weight of the oil phase.

[0103] The oil phase composition may include any of the compounds defined in the core section above. The oil phase may contain from 10 wt% to about 99 wt% of the beneficial agent before emulsification.

[0104] In the method for producing the capsules according to the present disclosure, the oil phase may be the dispersed phase, and the continuous aqueous (or water) phase may contain water, an acid or a base, and nanoparticles. The aqueous (or water) phase may have a pH of 1 to 11, preferably 1 to 7, at least at the time when at least both the oil phase and the water phase are mixed together. The acid may be a strong acid. The strong acid may be one or more of HCl, HNO 3 , H 2 SO 4 , HBr, HI, HClO 4 , and HClO 3 , preferably including 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 from 10 -7 M to 5M. The base may be an inorganic base or an organic base, preferably an inorganic base. The inorganic base may be hydroxides such as sodium hydroxide and ammonia. For example, the inorganic base may be about 10 -5 M to 0.01M NaOH, or about 10 -5 M to about 1M ammonia. The list of acids and bases and their concentration ranges exemplified above is not meant to limit the scope of the present invention, and other suitable acids and bases that enable control of the pH of the continuous phase are contemplated herein.

[0105] In the method for producing capsules according to the present disclosure, the pH can be varied throughout the process by adding an acid and / or a base. For example, the method can be started with an aqueous phase at an acidic or neutral pH, and later, a base can be added during the process to increase the pH. Alternatively, the method can be started with an aqueous phase at a basic or neutral pH, and later, an acid can be added during the process to decrease the pH. Further, the method can be started with an aqueous phase at an acidic or neutral pH, and an acid can be added during the process to further decrease the pH. Still further, the method can be started with an aqueous phase at a basic or neutral pH, and a base can be added during the process to further increase the pH. Any suitable pH shift can be used. Further, any suitable combination of an acid and a base can be used at any point in the method to achieve the desired pH. Any of the nanoparticles described above can be used in the aqueous phase. The nanoparticles can be present in an amount of about 0.01 wt% to about 10 wt% based on the total weight of the aqueous phase.

[0106] The method can include mixing an oil phase and an aqueous phase at a ratio of the oil phase to the aqueous phase of about 1:10 to about 1:1.

[0107] The second shell component can be formed by mixing a capsule having a first shell component with a solution of a second shell component precursor. The solution of the second shell component precursor can include a water-soluble or oil-soluble second shell component precursor. The second shell component precursor can be one or more of the compounds of formula (I) defined above, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). The second shell component precursor can also be Si(Y) 4-n R nIt may contain one or more of the silane monomers of the formula (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 have been shown previously in this paragraph, and these do not mean to limit the range of monomers that can be used. The second shell component precursor may contain silicate, titanate, aluminate, zirconate, and / or zincate. The second shell component precursor may contain carbonate and calcium salt. The second shell component precursor may contain salts of iron, silver, copper, nickel, and / or gold. The second shell component precursor may contain alkoxides of zinc, zirconium, silicon, titanium, and / or aluminum. The second shell component precursor may contain one or more of, for example, a silicate solution such as sodium silicate, a silicon tetraalkoxide solution, iron sulfate salt and iron nitrate salt, a titanium alkoxide solution, an aluminum trialkoxide solution, a zinc dialkoxide solution, a zirconium alkoxide solution, a calcium salt solution, and a carbonate solution. CaCO 3 The second shell component containing CaCO can be obtained by using a combination of a calcium salt and a carbonate. CaCO 3 The second shell component containing CaCO can generate carbonate ions in situ from CO 2 and can be obtained from a calcium salt without adding a carbonate.

[0108] The second shell component precursor may contain any suitable combination of any of the compounds listed above.

[0109] The solution of the second shell component precursor can be added dropwise to the capsules containing the first shell component. The solution of the second shell component precursor and the capsules can be mixed together for 1 minute to 24 hours. The solution of the second shell component precursor and the capsules can be mixed together at room temperature or high temperature, for example, at a temperature of 20°C to 100°C.

[0110] The solution of the second shell component precursor may contain the second shell component precursor in an amount of 1 wt% to 50 wt% based on the total weight of the solution of the second shell component precursor.

[0111] The capsule having the first shell component can be mixed with the solution of the second shell component precursor at a pH of 1 to 11. The solution of the second shell precursor may contain an acid and / or a base. The acid can be a strong acid. The strong acid can be one or more of HCl, HNO 3 、H 2 SO 4 、HBr, HI, HClO 4 、and HClO 3 、preferably including HCl. In other embodiments, the acid can be a weak acid. In an embodiment, the weak acid can be acetic acid or HF. The concentration of the acid in the solution of the second shell component precursor can be 10 -7 M to 5M. The base can be an inorganic base or an organic base, preferably an inorganic base. The inorganic base can be hydroxides such as sodium hydroxide and ammonia. For example, the inorganic base can be about 10 -5 M to 0.01M NaOH, or about 10 -5 M to about 1M ammonia. The list of acids and bases exemplified above is not meant to limit the scope of the present invention, and other suitable acids and bases that enable control of the pH of the solution of the second shell component precursor are contemplated herein.

[0112] The process of forming the second shell component can include a change in pH during the process. For example, the process of forming the second shell component can start at an acidic or neutral pH and later, a base can be added during the process to increase the pH. Alternatively, the process of forming the second shell component can start at a basic or neutral pH and later, an acid can be added during the process to decrease the pH. Still further, the process of forming the second shell component can start at an acidic or neutral pH and an acid can be added during the process to further decrease the pH. Yet still further, the process of forming the second shell component can start at a basic or neutral pH and a base can be added during the process to further increase the pH. Any suitable pH shift may be used. Further, any suitable combination of acid and base can be used at any point in the solution of the second shell component precursor to achieve the desired pH. The process of forming the second shell component can include maintaining a stable pH during the process with a deviation of up to ±0.5 pH units. For example, the process of forming the second shell component can be maintained at a basic, acidic, or neutral pH. Alternatively, the process of forming the second shell component can be maintained within a specific pH range by controlling the pH using an acid or a base. Any suitable pH range may be used. Further, any suitable combination of acid and base can be used at any point in the solution of the second shell component precursor to maintain a stable pH within the desired range.

[0113] A more detailed description of the method of making the capsules and the related properties of all shell component precursors (i.e., the condensation layer precursor, the nanoparticles, and the second shell component precursor) can be found in U.S. Patent Application Nos. 16 / 851173, 16 / 851176, and 16 / 851194, and the entire disclosure thereof defines the method of making the capsules of the present invention.

[0114] Regardless of whether an oil core or an aqueous core is produced, the emulsion can be cured under conditions that solidify the precursor, thereby forming a shell surrounding the core.

[0115] To increase the rate at which solidified capsules are obtained, the reaction temperature for curing can be increased. The curing process can induce the condensation of the precursor. The curing process can be carried out at room temperature or at a temperature higher than room temperature. The curing process can be carried out at a temperature of 30°C to 150°C, preferably 50°C to 120°C, optionally 80°C to 100°C. The curing process can be carried out over any suitable period to allow the shell of the capsule to be strengthened through the condensation of the precursor material. The curing process can be carried out over a period of 1 minute to 45 days, preferably 1 hour to 7 days, optionally 1 hour to 24 hours. The capsule is considered cured when it no longer disintegrates. The determination of capsule disintegration is described in detail below. During the curing step, hydrolysis of the Y moiety (from formula (I) and / or (II)) occurs, followed by subsequent condensation of an -OH group with another -OH group or with another moiety of type Y (in this case, the two Y moieties are not necessarily the same). The hydrolyzed portion of the precursor first condenses with the surface portion of the nanoparticles (if the nanoparticles contain such a portion). As the formation of the shell progresses, the precursor portion becomes reactive with the previously formed shell.

[0116] The emulsion can be cured such that the shell precursor condenses. The emulsion can be cured such that the shell precursor reacts with the nanoparticles and condenses. Examples of the hydrolysis step and the condensation step described herein for a silica-based shell are shown below:

[0117]

Table 1

[0118] For example, when a precursor of formula (I) or (II) is used, the following describes the hydrolysis step and the condensation step:

[0119] [Table 2]

[0120] The capsules can be provided as a slurry composition (or simply "slurry" herein). The result of the methods described herein can be a slurry containing the capsules. The slurry can be formulated into a product such as a consumer product, for example.

[0121] The composition may include other fragrance capsules. These capsules may be core - shell capsules and may contain more than 5% by weight of an organic material in the shell relative to the weight of the shell material. Such capsules can be considered "organic" capsules in the present disclosure to distinguish them from the inorganic capsules described and claimed herein. The shell material of the organic capsules may include materials derived from melamine, polyacrylamide, silicone, polystyrene, polyurea, polyurethane, polyacrylate - based materials, gelatin, styrene maleic anhydride, polyamide, and mixtures thereof, preferably polymeric materials. The organic capsules may be coated with an adhesion aid, a cationic polymer, a non - ionic polymer, an anionic polymer, or a mixture thereof. Suitable adhesion polymers may be selected from the group consisting of polyvinyl formal, partially hydroxylated polyvinyl formal, polyvinylamine, polyethyleneimine, ethoxylated polyethyleneimine, polyvinyl alcohol, polyacrylate, cationic polysaccharides (e.g., chitosan), and combinations thereof. The organic capsules may have a volume - weighted average particle size of from about 0.5 micrometers to about 100 micrometers, preferably from about 1 micrometer to about 60 micrometers, alternatively from about 25 micrometers to about 60 micrometers, optionally from about 25 micrometers to about 60 micrometers.

[0122] Method for treating laundry A process for treating laundry may include providing laundry articles to a washing machine, dispensing a composition containing a plurality of particles into the washing machine, and contacting the laundry articles with the composition during a washing sub-cycle of the washing machine. The washing machine may have a washing sub-cycle and a rinsing sub-cycle. About 5 g to about 50 g of the particulate composition can be dispensed into the washing machine.

[0123] By providing a fragrance benefit throughout the washing sub-cycle, the consumer only needs to add the detergent composition and the composition containing the plurality of particles to a single location, e.g., the wash tub, before or immediately after starting the washing machine. This can be more convenient for the consumer than using a rinse additive composition that is separately dispensed into the wash tub, e.g., before, during, or between rinse cycles, after the washing sub-cycle is completed. It can be inconvenient to use the automatic dispensing mechanisms of the latest upright and high-efficiency machines because the rinse additive composition needs to be dispensed at a location other than where the detergent composition is dispensed.

[0124] Optionally, the process may further include contacting the laundry items with a detergent composition containing from about 3 wt% to about 60 wt%, optionally from about 3 wt% to about 40 wt% of an anionic surfactant during the washing sub-cycle of the washing machine. The anionic surfactant may be selected from sulfates, sulfonates, carboxylates, and mixtures thereof. The detergent composition is different from the particles. The detergent composition may optionally be provided separately from the particles. The detergent composition may be dispensed separately from the composition containing the plurality of particles.

[0125] The washing machine has at least two basic sub - cycles within an operating cycle, namely, a washing sub - cycle and a rinsing sub - cycle. The washing sub - cycle of the washing machine is a cycle that starts when initially filling or partially filling the washing tub with water. The main purpose of the washing sub - cycle is to remove or loosen dirt from the laundry items and suspend this dirt in the washing liquid. Typically, the washing liquid is drained at the end of the washing sub - cycle. The rinsing sub - cycle of the washing machine occurs after the washing sub - cycle and mainly aims to rinse the dirt and optionally any beneficial agents provided to the laundry items in the washing sub - cycle.

[0126] The process can optionally include the step of contacting the laundry items with a detergent composition containing an anionic surfactant during the washing sub - cycle. Most consumers provide the detergent composition to the washing tub during the washing sub - cycle. The detergent composition can include an anionic surfactant and other beneficial agents such as, but not limited to, fragrances, bleaching agents, brightening agents, hue dyes, enzymes, etc. During the washing sub - cycle, the beneficial agents provided with the detergent composition are brought into contact with or applied to the laundry items placed in the washing tub. Typically, the beneficial agents of the detergent composition are dispersed in the washing liquid of water and the beneficial agents.

[0127] During the washing sub - cycle, the washing tub may be filled with water or at least partially filled with water. The individual particles of the composition can dissolve or disperse in water to form a washing liquid containing the components of the particles. Optionally, if a detergent composition is used, the washing liquid can contain the components of the detergent composition and the components of the particles. The plurality of particles can be placed in the washing tub of the washing machine before the laundry items are placed in the washing tub of the washing machine. The plurality of particles can be placed in the washing tub of the washing machine after the laundry items are placed inside the washing tub of the washing machine. The plurality of particles can be placed in the washing tub before filling the washing tub with water or partially filling it, or after the start of filling the washing tub with water.

[0128] In the implementation of a process for treating fabrics, when a consumer uses a detergent composition, the detergent composition and the particles of the composition can be provided from separate packages. For example, the detergent composition can be a liquid detergent composition provided from a bottle, sachet, water-soluble pouch, dosing cup, dosing ball, or cartridge associated with a washing machine. The particles of the composition can be provided from separate packages such as, by way of non-limiting example, cartons, bottles, water-soluble pouches, dosing cups, sachets, etc. When the detergent composition is in a solid form such as powder, water-soluble fibrous substrate, water-soluble sheet, water-soluble film, water-soluble film, water-insoluble fibrous web carrying a solid detergent composition, the particles of the composition can be provided together with the solid detergent composition. For example, the particles of the composition may be provided from a container containing a mixture of the solid detergent composition and the particles of the composition. Optionally, the particles of the composition can be provided from a pouch formed of the detergent composition, which is a water-soluble fibrous substrate, water-soluble sheet, water-soluble film, water-soluble film, water-insoluble fibrous web carrying a solid detergent composition.

[0129] Process for forming particles The particles of the composition can be made by a process comprising a plurality of steps. The particles can be formed by tableting or melt processing. A melt composition can be prepared comprising from about 25 wt% to about 99 wt% of a water-soluble carrier and from about 0.1 wt% to about 20 wt% of capsules.

[0130] The particles of the composition can be formed by using a particle production apparatus 11 (FIG. 1). The melt composition 20 can be prepared in a batch mixer 110 or a continuous mixer 110, or can be prepared on a bench top by manually mixing the constituent materials. When the carrier is a water-soluble polymer, the water-soluble polymer can be heated to a temperature above the melting onset point of the water-soluble polymer and below the flash point or boiling point of the fragrance within the capsules.

[0131] The melt composition 20 comprising the water-soluble carrier and the capsules can pass through one or more openings 60 and be deposited on the movable conveyor 80 as an extrudate or droplet 85. The mixture can optionally be deposited in the recesses of the mold and cooled or allowed to cool so that the mixture can solidify into particles 90. The particles can be removed from the recesses of the mold to obtain the finished product. The dispenser 30 can be provided with a plurality of openings. The melt composition 20 can be transported to the dispenser via the supply pipe 40. Optionally, a mixer 50 such as a static mixer 55 can be provided alongside the supply pipe 40. Optionally, the supply pipe 40 can be insulated or provided with a heated jacket.

[0132] Optionally, the particles 90 can be formed by passing a mixture comprising the water-soluble carrier and the capsules through one or more openings 60 of the dispenser and depositing the mixture on the movable conveyor 80 below the one or more openings 60. The mixture can be solidified to form the particles 90. The mixture can be deposited on the movable conveyor 80 as an extrudate and the extrudate can be cut to form the particles 90. Alternatively, the mixture can pass through one or more openings 60 to form droplets on the movable conveyor 80 and the droplets can be solidified to form the particles 90.

[0133] Optionally, a gas supply line can be included upstream of the dispenser 30 to include gas in the melt composition. Downstream of the gas supply line, the melt composition 30 can be pulverized to break the gas bubbles so that the melt is a gas-mixed melt. The particles formed from the gas-mixed melt can contain gas bubbles. The gas supply line and the mill can be an integrated unit, and as a non-limiting example, there is the OAKES FOAMER (E.T.Oakes Corporation, 686 Old Willets Path, Hauppauge, NY 11788) 2MT1A continuous foamer. Optionally, the gas can be incorporated into the melt composition 20 by mixing a gas-generating material into the melt composition 20.

[0134] Particles Each particle can have a mass of from about 1 mg to about 500 mg, alternatively from about 5 mg to about 500 mg, alternatively from about 5 mg to about 200 mg, alternatively from about 10 mg to about 100 mg, alternatively from about 20 mg to about 50 mg, alternatively from about 35 mg to about 45 mg, alternatively about 38 mg. Each particle is about 0.003 cm 3 to about 5 cm 3 optionally from about 0.003 cm 3 to about 1 cm 3 optionally from about 0.003 cm 3 to about 0.5 cm 3 optionally from about 0.003 cm 3 to about 0.2 cm 3 optionally from about 0.003 cm 3 to about 0.15 cm 3 and can have a volume of. Smaller particles are thought to provide better packing of the particles into the container and more rapid solubility in wash water. The composition can include less than 10 wt% of particles having an individual mass of less than about 10 mg. This can reduce the potential for dust.

[0135] In any of the disclosed embodiments or combinations, the particles disclosed herein can have a shape selected from the group consisting of spherical, hemispherical, oblate, cylindrical, polyhedral, and semi-oblate. The particles can be hemispherical, compressed hemispherical, or can have at least one substantially flat or flat surface. Such particles can have a relatively large surface area relative to their mass compared to spherical particles. The dissolution time in water can decrease as a function of the increase in surface area, and a shorter dissolution time is preferred over a long dissolution time.

[0136] The particles disclosed herein can have a ratio of maximum dimension to minimum dimension of from about 10 to 1, optionally from about 8 to 1, optionally from about 5 to 1, optionally from about 3 to 1, optionally from about 2 to 1. The particles disclosed herein can be of a shape such that the particles are not flakes. Particles having a ratio of maximum dimension to minimum dimension greater than about 10, or particles that are flakes, tend to be brittle and tend to become powdery. The brittleness of the particles tends to decrease as the value of the ratio of maximum dimension to minimum dimension decreases.

[0137] The particles can comprise from about 25% to 99% by weight of a water-soluble carrier and capsules dispersed in the water-soluble carrier. The particles can be provided at from about 0.1% to about 20% by weight of the composition capsules.

[0138] The particles can contain less than about 20% by weight of an anionic surfactant, optionally less than about 10% by weight of an anionic surfactant, optionally less than about 5% by weight of an anionic surfactant, optionally less than about 3% by weight of an anionic surfactant, optionally less than about 1% by weight of an anionic surfactant. The particles can contain from 0% to about 20% by weight, optionally from 0% to about 10% by weight, optionally from about 0% to about 5% by weight, optionally from about 0% to about 3% by weight, optionally from about 0% to about 1% by weight of an anionic surfactant.

[0139] The particles can contain less than about 10% by weight of water.

[0140] The particles can contain air bubbles. The air bubbles can be spherical air bubbles. Since the particles can contain air bubbles incorporated therein, the particles can have a density less than the density or weighted average density of the constitutive solid and / or liquid materials forming the particles. Since the air bubbles can contribute to the oxidation reaction within the particles, it can be advantageous for the particles containing air bubbles to contain an antioxidant. Each particle can have a density of less than about 1 g / cm 3 Optionally, the particles can each have a density of less than about 0.98 g / cm 3 Optionally, the particles can each have a density of less than about 0.95 g / cm 3 Since the density of a typical cleaning liquid is about 1 g / cm 3 it may be desirable to provide particles each having a density of less than about 1 g / cm 3 or even less than about 0.95 g / cm 3 Individually, particles having a density of less than about 1 g / cm 3 may be desirable to provide particles 90 that float in the cleaning solution.

[0141] Each particle may have a volume, and the gas storage body within particle 90 may constitute from about 0.5 volume % to about 50 volume % of the particle, or further from about 1 volume % to about 20 volume % of the particle, or further from about 2 volume % to about 15 volume % of the particle, or further from about 4 volume % to about 12 volume % of the particle. Without being bound by theory, if the volume of the gas storage body is too large, it is considered that the particles may not have sufficient strength to be packaged, shipped, stored, and used without breaking in an undesirable manner.

[0142] The storage body may have an effective diameter of from about 1 micrometer to about 2000 micrometers, or further from about 5 micrometers to about 1000 micrometers, or further from about 5 micrometers to about 200 micrometers, or further from about 25 to about 50 micrometers. Generally, smaller gas storage bodies are considered more desirable. If the effective diameter of the gas storage body is too large, it is considered that the particles may not have sufficient strength to be packaged, shipped, stored, and used without breaking in an undesirable way. The effective diameter is the diameter of a sphere having the same volume as the gas storage body. The gas storage body may be a spherical gas storage body.

[0143] Dryer sheet The capsules can also be used in actuality for a dryer sheet. The dryer sheet can include a nonwoven fiber layer and a solid fabric softening agent composition supported on or within the nonwoven fiber layer. The fabric softening agent composition can include a plurality of capsules dispersed in the solid fabric softening agent composition. The capsules can be those described herein.

[0144] The solid softening agent composition can contain a quaternary ammonium compound, optionally an ester quaternary ammonium compound, and optionally, di-tallow, dimethyl ammonium methyl sulfate, N,N-di(oleyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(oleyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate-, N,N-di(oleylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(2-oleyl-oxyoxo-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyl-oxyoxo-ethyl)-N,N-dimethyl ammonium chloride-, N,N-di(2-oleyl-oxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyl-oxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride, N-(2-oleyl-oxyethyl)-N-(2-oleyl-oxyoxo-ethyl)-N,N-dimethyl ammonium chloride; N-(2-canolyl-oxyethyl)-N-(2-canolyl-oxyoxo-ethyl)-N,N-dimethyl ammonium chloride, N,N,N-tri(oleyl-oxy-ethyl)-N-methyl ammonium chloride, N,N,N-tri(canolyi-oxy-ethyl)-N-methyl ammonium chloride-, N-(2-oleyl-oxyoxoethyl)-N-(oleyl)-N,N-dimethyl ammonium chloride, N-(2-canolyl-oxyoxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride, 1,2-dioleyloxy N,N,N-trimethylammoniopropane chloride, and 5,2-dicanolyloxy N,N,N-trimethylammoniopropane chloride, and combinations thereof, selected from the group consisting of.In one embodiment, the fabric conditioning active agent is N,N-di(tallowoyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)ammonium methyl sulfate, and mixtures thereof, and the fabric softening composition optionally contains a fatty acid.

[0145] The nonwoven fiber material can have a basis weight of about 10 g / m 2 to about 50 g / m 2 The nonwoven fiber material may be spunbond polyester terephthalate, optionally continuous filament spunbond terephthalate.

[0146] Combination The specifically contemplated combinations of the present disclosure are described herein in the following alphabetically lettered paragraphs. These combinations are essentially for illustrative purposes and are not intended to be limiting.

[0147] A. A composition comprising a plurality of particles, wherein the particles are from about 25 wt% to about 99 wt% of a water-soluble carrier, and a plurality of capsules dispersed in the water-soluble carrier, the capsules comprising a core and a shell surrounding the core, the core containing a fragrance raw material, and the shell contains from about 90 wt% to 100 wt% of the shell, optionally from about 95 wt% to 100 wt%, optionally from about 99 wt% to 100 wt% of an inorganic material, a composition. B. The inorganic material is selected from metal oxides, metalloid oxides, metals, minerals, and mixtures thereof, optionally SiO 2 , TiO 2 , Al 2 O 3 , ZrO 2 , ZnO 2 , CaCO 3 , Ca 2 SiO 4 , Fe 2 O 3 , Fe 3 O 4, selected from clay, gold, silver, iron, nickel, copper, and mixtures thereof, optionally SiO 2 , TiO 2 , Al 2 O 3 , CaCO 3 , and mixtures thereof, optionally SiO 2 , the composition according to paragraph A. C. The shell is a first shell component including a condensation layer and a nanoparticle layer, the condensation layer includes a condensation product of a precursor, the nanoparticle layer includes inorganic nanoparticles, and the condensation layer is disposed between the core and the nanoparticle layer; a first shell component, and a second shell component surrounding the first shell component, surrounding the nanoparticle layer, the composition according to paragraph A or B. D. The capsule is 10 Mm to 200 Mm, optionally 10 Mm to 190 Mm average volume weighted capsule diameter, 170 nm to 1000 nm average shell thickness, about 50:50 to 99:1, optionally 60:40 to 99:1, optionally 70:30 to 98:2, optionally 80:20 to 96:4 volume core-to-shell ratio, characterized by one or more of, The first shell component contains an organic component content of 5% by weight or less, optionally 2% by weight or less, optionally 0% by weight, based on the weight of the first shell component, the composition according to any one of paragraphs A to C. E. The shell is a substantially inorganic first shell component including a condensation layer and a nanoparticle layer, the condensation layer includes a condensation product of a precursor, the nanoparticle layer includes inorganic nanoparticles, the condensation layer is disposed between the core and the nanoparticle layer, a substantially inorganic first shell component, and an inorganic second shell component surrounding the first shell component, the second shell component surrounds the nanoparticle layer, an inorganic second shell component, including, The precursor contains at least one compound selected from formula (I), formula (II), and mixtures thereof. Formula (I) is (M v O z Y n ) w wherein Formula (II) is (M v O z Y n R 1 p ) w wherein For formula (I), formula (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 from 0.5 to 1.6; each Y is independently -OH, -OR 2 , halogen,

[0148]

Chemical formula

[0149]

Chemical formula

[0150]

Chemical formula

[0151]

Chemical formula

[0152] Test methods It will be understood that each value of the parameters of the subject matter claimed by the applicant claimed and described herein should be measured using the test methods disclosed in the test methods section of this application.

[0153] i. Partition coefficient method The partition coefficient P is the concentration ratio of a compound in a two-phase immiscible mixture at equilibrium (in this case, n-octanol / water). The log value of the n-octanol / water partition coefficient (logP) can be experimentally measured using well-known means such as the "shake flask" method that measures the distribution of solutes by UV / VIS spectroscopy (for example, described in "The Measurement of Partition Coefficient", Molecular Informatics, Volume 7, Issue 3, 1988, Pages 133-144, Dearden J C, Bresnan). Alternatively, logP can be calculated for each PRM in the flavor mixture to be tested. The logP values of individual PRMs are preferably calculated using the Consensus logP Computational Model, Version 14.02 (Linux (registered trademark)) available from Advanced Chemistry Development Inc. (ACD / Lab) (Toronto, Canada), and unitless logP values are obtained. The ACD / Labs Consensus logP Computational Model is part of the ACD / Labs model suite.

[0154] ii. Measurement of average shell thickness The shell of the capsule containing the first shell component and, if present, the second shell component is measured in nanometers using a focused ion beam scanning electron microscope (FIB-SEM, HELIOS NANOLAB 650 manufactured by FEI Company) or equivalent equipment for 20 delivery capsules containing the beneficial agent. The sample is prepared by diluting a small amount of the liquid capsule dispersion (20 mL) with distilled water (1:10). The suspension is then attached to an ethanol-washed aluminum stub and transferred to a carbon coating device (EM ACE600 manufactured by LEICA Company or equivalent equipment). The sample is dried under vacuum in the coating device (vacuum level: 10 -5mbar). Next, carbon with a size of 25 nm to 50 nm is flash-deposited on the sample to deposit a conductive carbon layer on its surface. Then, the aluminum stub is transferred to the FIB-SEM to prepare a cross-section of the capsule. The cross-section is prepared by ion milling using a cross-section cleaning pattern with an acceleration voltage of 30 kV and an emission current of 2.5 nA. Images are acquired at 5.0 kV and 100 pA using the immersion mode (dwell time: about 10 microseconds) at a magnification of approximately 10,000 times.

[0155] Images of the broken shells are obtained in cross-section from 20 randomly selected beneficial agent delivery capsules that are free of size bias to create a representative sample of the size distribution of the capsules present. The shell thickness of each of the 20 capsules is measured at three different randomly selected locations using calibrated microscope software by drawing a measurement line perpendicular to the tangent of the outer surface of the capsule shell. Sixty independent thickness measurements are recorded, and the average thickness is calculated using them.

[0156] iii. Average and coefficient of variation of the volume-weighted capsule diameter The capsule size distribution is determined by the single-particle optical sensing (SPOS), also known as optical particle counting (OPC), using an ACCUSIZER 780 AD instrument or equivalent, and the accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, U.S.A.) or equivalent software. The instrument is configured using the following conditions and options: flow rate = 1 mL / sec; small diameter side threshold = 0.50 Mm; sensor model number = LE400-05SE or equivalent; automatic dilution = on; collection time: 60 seconds; number of channels = 512; fluid volume of the container = 50 mL; maximum simultaneous count = 9200. The measurement is started by flushing with water until the background count is less than 100 and by bringing the sensor to a low temperature state. A sample of the delivery capsules in suspension is introduced, and if necessary, the density of the capsules is adjusted via automatic dilution using deionized water so that the count of the capsules is maximized to 9200 per 1 mL. The suspension is analyzed over 60 seconds. The size range used was 1 Mm to 493.3 Mm.

[0157] Volume distribution:

[0158]

Number

[0159]

Number

[0160] iv. Evaluation of volume core-to-shell ratio The value of the volume core-to-shell ratio is determined as follows and depends on the average shell thickness measured by the shell thickness test method. The volume core-to-shell ratio of the capsules for which the average shell thickness has been measured is calculated by the following equation:

[0161]

Number

[0162] This ratio can be converted to a core-to-shell fraction value by calculating the core weight percentage using the following equation.

[0163]

Number

[0164] Degree of branching determination method The degree of branching of the precursor was determined as follows: The degree of branching was measured using (29Si) nuclear magnetic resonance spectroscopy (NMR).

[0165] a. Sample preparation Each sample is diluted to a 25% solution using deuterated benzene (Benzene-D6 “100%” (D, 99.96%, available from Cambridge Isotope Laboratories Inc. (Tewksbury, MA)) or an equivalent. 0.015 M chromium(III) acetylacetonate (purity 99.99%, available from Sigma-Aldrich (St. Louis, MO), or an equivalent) is added as a paramagnetic relaxation reagent. When using a glass NMR tube (manufactured by Wilmad-LabGlass (Vineland, NJ) or an equivalent) for analysis, a blank sample must also be prepared by filling the NMR tube with the same type of deuterated solvent used to dissolve the sample. The same glass tube must be used for analyzing both the blank and the sample.

[0166] b. Analysis of the sample The branching degree is determined using a BRUKER 400 MHz nuclear magnetic resonance spectroscopy (NMR) instrument, or an equivalent instrument. The standard silicon (29Si) method (e.g., from Bruker) is used with default parameter settings involving a minimum of 1000 scans and a relaxation time of 30 seconds.

[0167] c. Processing of the sample The samples are stored and processed using system software suitable for NMR spectroscopy, such as MESTRENOVA version 12.0.4-22023 (available from Mestrelab Research) or equivalents. Phase adjustment and background correction are applied. There is a large, broad signal extending from -70 to -136 ppm, which is the result of using a glass NMR tube and the glass present within the probe housing. This signal is suppressed by subtracting the spectrum of the blank sample from the spectrum of the composite sample, provided that the same tube and the same method parameters are used to analyze the blank and the sample. To further account for minor differences in data collection, tubes, etc., the regions outside the peaks in the region of interest should be integrated and normalized to a consistent value. For example, integrate from -117 to -115 ppm and set the integrated value to 4 for all blanks and samples.

[0168] The resulting spectra generate up to five main peak regions. The first peak (Q0) corresponds to unreacted TAOS. The second peak set (Q1) corresponds to end groups. The next set of peaks (Q2) corresponds to linear groups. The next broad set of peaks (Q3) is semi-dendritic units. The last broad set of peaks (Q4) is dendritic units. When PAOS and PBOS are analyzed, each group falls within a defined ppm range. Representative ranges are listed in Table 1 below.

[0169]

Table 3

[0170] Polymethoxysilane has different chemical shifts for Q0 and Q1, overlapping signals for Q2, and Q3 and Q4 are invariant, as described in Table 2 below.

[0171]

Table 4

[0172] The ppm ranges shown in the above table do not have to be applied to all monomers. However, other monomers may cause different chemical shifts, but the appropriate assignment of Q0 to Q4 should not be affected.

[0173] Using MESTRENOVA, each peak group can be integrated and the branching degree can be calculated by the following formula.

[0174]

Equation

[0175] d. Method for Determining Molecular Weight and Polydispersity Index The molecular weight (polystyrene-equivalent weight-average molecular weight (Mw)) and polydispersity index (Mw / Mn) of the condensation layer precursor described in this specification are determined using size exclusion chromatography with refractive index detection. Mn is the number-average molecular weight.

[0176] Preparation of Sample The sample is weighed and then diluted with the solvent used in the instrument system to a target concentration of 10 mg / mL. For example, 50 mg of polyalkoxysilane is weighed into a 5 mL volumetric flask, dissolved, and diluted to a predetermined volume with toluene. After the sample is dissolved in the solvent, it is passed through a 0.45 Mm nylon filter and loaded into the automatic sampler of the instrument.

[0177] Analysis of Sample An HPLC system using an autosampler (e.g., WATERS 2695 HPLC separation module, or equivalent, manufactured by Waters (Milford, MA)) connected to a refractive index detector (e.g., 2414 refractive index detector, or equivalent, manufactured by Wyatt (Santa Barbara, CA)) is used for polymer analysis. Separation is carried out on three columns, each with an inner diameter of 7.8 mm × length of 300 mm, filled with a 5 Mm polystyrene-divinylbenzene medium, connected in series, and having cutoffs at molecular weights of 1, 10, and 60 kDa, respectively. Suitable columns are the TSKGEL G1000HHR, G2000HHR, and G3000HHR columns (available from TOSOH Bioscience (King of Prussia, PA)) or equivalents. A guard column of 5 Mm polystyrene-divinylbenzene with an inner diameter of 6 mm × length of 40 mm (e.g., TSKGEL Guardcolumn HHR-L manufactured by TOSOH BIOSCIENCE, or equivalent) is used to protect the analytical column. Toluene (HPLC grade or equivalent) is pumped at a uniform rate of 1.0 mL / min with both the column and the detector maintained at 25°C. 100 mL of the prepared sample is injected for analysis. Sample data is stored and processed using software with GPC calculation capabilities (e.g., ASTRA Version 6.1.7.17 software or equivalent available from Wyatt Technologies (Santa Barbara, CA)).

[0178] The system is calibrated using more than 10 narrowly dispersed polystyrene standards (e.g., Standard READYCAL Set, e.g., PN76552 manufactured by Sigma-Aldrich, or equivalent) having known molecular weights in the range of about 0.250 - 70 kDa, using a cubic fit to the Mp vs. retention time curve.

[0179] The system software is used to calculate and report the weight average molecular weight (Mw) and the polydispersity index (Mw / Mn).

[0180] v. Method for calculating the organic component content in the first shell component As used herein, definition of the organic part in the inorganic shell of the capsule according to the present disclosure: Any part X that cannot be cleaved from a metal precursor carrying a metal M under specified reaction conditions via hydrolysis of an M-X bond (where M belongs to the group of metals and metalloids, X belongs to the group of non-metals, and connects the part to the inorganic precursor of the metal or metalloid M) is regarded as an organic part. It is set as the above reaction condition that it has a hydrolysis degree of at least 1% when exposed to distilled water having a neutral pH without stirring for 24 hours.

[0181] This method makes it possible to calculate the theoretical organic component content assuming complete conversion of all hydrolyzable groups. Therefore, it becomes possible to evaluate the theoretical proportion of the organic component for any mixture of silanes, and the result shows only the organic component content of this precursor mixture itself, not the actual organic component content in the first shell component. Therefore, if a specific ratio for the organic component content of the first shell component is disclosed anywhere in this document, that ratio should be understood as containing any mixture of non-hydrolyzed or pre-polymerized precursors that gives a theoretical organic content smaller than the disclosed number according to the following calculation.

[0182] The following calculation example is for silanes. Then, the calculation in the general case follows.

[0183] Each molar fraction Y i Consider a mixture of silanes having. Here, i is the identification number of each silane. The mixture can be represented as follows: Si(XR) 4-n R n In the formula, XR is a hydrolyzable group under the conditions described in the above definition, and R i ni is non-hydrolyzable under the above conditions, and n i = 0, 1, 2, or 3.

[0184] Such a mixture of silanes results in a shell having the following general formula.

[0185]

Number

[0186] Next, the weight percentage of the organic moiety as defined above can be calculated as follows. 1) Find the mole fraction of each precursor (including nanoparticles). 2) Determine the general formula of each precursor (including nanoparticles). 3) Calculate the general formula of the mixture of precursors and nanoparticles based on the mole fraction. 4) Convert to the reacted silane (convert all hydrolyzable groups to oxygen groups). 5) Calculate the weight ratio of the organic moiety to the total mass (assuming 1 mole of Si relative to the framework).

[0187] A calculation example is shown in Figure 3.

[0188]

Table 5

[0189] To calculate the general formula of the mixture, the exponent of each atom in the individual formula is multiplied by its respective mole fraction. Then, in the case of the mixture, when the same exponents occur, the sum of the fractional exponents is adopted (typically for ethoxy groups).

[0190] Note: The sum of all Si fractions is always 1 in the mixture general formula due to the calculation method (the sum of the total mole fractions of Si is 1).

[0191]

Number

[0192] To convert the unreacted formula to the post-reaction formula, simply divide the exponent of all hydrolyzable groups by 2 and then sum them up together (along with any existing oxygen groups if applicable) to obtain the fully reacted silane. SiO 1.88 Me 0.20

[0193] In this case, the expected result is that since the sum of all exponents must follow the following formula, for SiO 1.9 Me 0.2 it is: A + B / 2 = 2, where A is the oxygen atom exponent and B is the sum of all non-hydrolyzable exponents. Small errors occur from taking approximate numbers during the calculation, but they should be corrected. Then, readjust the exponent of the oxygen atom to satisfy this formula.

[0194] Thus, the final formula is SiO 1.9 Me 0.2 and the weight ratio of the organic component is calculated as follows. Weight ratio := (0.20 * × 15) / (28 + 1.9 * × 16 + 0.20 * × 15) = 4.9%

[0195] General case The above formula can be generalized by considering the valence of the metal or metalloid M, and thus the following modified formula can be obtained: M(XR) V-ni R i ni The same method is used, but the valence V of each metal is considered.

Example

[0196] The examples provided below are in fact intended to be illustrative and not intended to be limiting.

[0197] Example 1. Synthesis of non-hydrolyzable precursor 1000 g of tetraethoxysilane (TEOS, available from Sigma Aldrich) was added to a clean, dry round-bottom flask equipped with a stir bar and a distillation apparatus under a nitrogen atmosphere. 490 mL of acetic anhydride (available from Sigma Aldrich) and 5.8 g of tetrakis(trimethylsiloxy)titanium (available from Gelest) were added, and the contents of the flask were stirred at 135 °C for 28 hours. During this time, ethyl acetate produced by the reaction of ethoxysilane groups with acetic anhydride was distilled off. The reaction flask was cooled to room temperature and placed on a rotary evaporator (Rotovapor R110 manufactured by BUCHI), and this rotary evaporator was used together with a water bath and a vacuum pump (1402 DuoSeal manufactured by WELCH) to remove all of the remaining solvent and volatile compounds. The resulting polyethoxysilane (PEOS) was a yellow viscous liquid having the following specifications shown in Table 4. The ratio of TEOS to acetic anhydride can be varied to control the parameters shown in Table 4.

[0198]

Table 6

[0199] Example 2. Silica Shell-based Flavor Capsules The oil phase was prepared by mixing and homogenizing the precursor with the beneficial agent and / or the core modifier (2 parts of the beneficial agent and / or the core modifier per 1 part of the non-hydrolyzable precursor). The aqueous phase was prepared by adding 1.25 wt% of Aerosil 300 (available from Evonik) in 0.1 M HCl aqueous solution and dispersed in an ultrasonic bath for at least 30 minutes. After each phase was prepared separately, they were combined (1 part of the oil phase to 4 parts of the aqueous phase), and the oil phase was dispersed into the aqueous phase at 13400 RPM / 1 minute using an IKA ULTRATURRAX S25N-10G mixing tool. After the emulsification process was completed, the resulting emulsion was cured with the following temperature profile: 4 hours at 22 °C, 16 hours at 50 °C, and 96 hours at 70 °C. To attach the second shell component, the capsules were post-treated with the second shell component solution: the slurry was diluted twice in 0.1 M HCl and treated with a controlled addition of 10 wt% aqueous sodium silicate solution (40 mL / min, 0.16 mL / 1 g of slurry) using a suspension magnetic stirrer reactor at 22 °C and 250 RPM. 1 M HCl (aqueous solution) was used to keep the pH constant at pH 7. After the injection of the second shell component solution was completed, the capsules were centrifuged at 2500 rpm for 10 minutes and redispersed in deionized water. The population of the capsules had an average size of 29.22 Mm and a CoV of 38%.

[0200] Figure 2 shows a schematic diagram of a method for producing capsules 8 having a first shell component 6 prepared using a hydrophobic core 4. For example, in the first box 100, the oil phase 1 is provided to the aqueous phase 2. The oil phase 2 contains a hydrophobic beneficial agent such as one or more flavor raw materials, and a liquid precursor material. The nanoparticles 3 surround the oil phase 1 and, for example, form a Pickering emulsion. In the second box 101, the hydrolyzed precursor 5 begins to form at the interface around the core 4, and the core 4 contains an oil phase containing the beneficial agent. In the third box 102, the first shell component 6 is formed around the core 4, and the first shell component is formed from the nanoparticles 3 and the hydrolyzed precursor 5.

[0201] Figure 3 shows a schematic view inside box 103 of capsule 9 having shell 10, and shell 10 has a first shell component 6 and a second shell component 7 around core 4. Capsule 9 is shown in aqueous phase 2. Core 4 contains one or more perfume raw materials. Figure 4 shows a scanning electron microscope image of a cross-section of such a capsule 9. Core 4 is surrounded by shell 10, and shell 10 includes a first shell component 6 surrounded by a second shell component 7.

[0202] Figure 5 shows a scanning electron microscope image of a population of silica shell-based perfume capsules described in the present disclosure.

[0203] Example 3. Exemplary Particle Formulations Two distinct samples of particles were prepared, one containing silica shell-based perfume capsules (Example 3A of the present invention) and the other containing polyacrylate shell-based perfume capsules (Comparative Example 3B). The general procedure for preparing the particles involved setting a hot plate to a temperature of 85 °C, weighing a beaker on the hot plate, bringing the contents to the appropriate temperature, and then pipetting the mixture by hand into a mold to create particles of uniform size, followed by allowing it to cool. The individual particles thus formed were sized such that four of such particles weighed approximately 0.140 - 0.145 g. The compositions of the two particles are shown in Table 5 below.

[0204] Example 3A of the present invention below (Table 5) was a population of perfume capsules prepared by encapsulating a mixture of the perfume raw material "Perfume 1" according to Table 5 below. The capsules of this population contained a silica-based first shell component and a second shell component according to the present disclosure.

[0205] The following Comparative Example 3B (Table 5) was a population of perfume capsules containing a polyacrylate shell, encapsulating the same mixture of perfume raw material ("Perfume 1") with an encapsulating agent prepared according to the process disclosed in International Publication No. WO 2020 / 117996.

[0206]

Table 7

[0207] Example 3A and Comparative Example 3B of the present invention were tested under use conditions using fabric to determine the wet fabric headspace and the dry fabric headspace. A MIELE HONEYCOMB CARE W1724 washing machine was used, and the cycle setting was an express cycle program at 30°C and 1000 RPM for 30 minutes. The fabric used in the test was a 420 g terry cotton test fabric. Each of the 14 terry cotton test fabrics was 30 cm × 15 cm and had a mass of 30 g. The test included a ballast load. The ballast load was 1369 g of Calderon cotton (10 pieces) and 1220 g of Calderon polyester cotton (10 pieces). Each of the 10 pieces of Calderon cotton was 52 cm × 42 cm and had a mass of 137 g. Each of the 10 pieces of Calderon polyester cotton was 46 cm × 46 cm and had a mass of 122 g. Particles and liquid detergent were delivered to the drum of the machine at the specified levels, i.e., 9 g of particles at the bottom of the drum before loading the fabric, and 58.47 g of the liquid detergent formulation in Table 6 below. The liquid detergent was administered onto the fabric. After washing, samples of the terry cotton test fabric were obtained for the wet fabric headspace test, and the remainder of the terry cotton test fabric was line dried at a controlled temperature and humidity (22°C / 50% rH) every 24 hours.

[0208]

Table 8

[0209] The fragrance headspace analysis was carried out on the Terry cotton test fabric immediately after the washing cycle while the Terry cotton test fabric was still wet (wet fabric headspace, WFHS (Wet Fabric Headspace)). For each washing test, six 4 cm × 4 cm samples of the Terry cotton test fabric were analyzed by high-speed 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 minutes. The headspace above the samples of the Terry cotton test fabric was sampled for 5 minutes by the SPME (50 / 30 Mm DVB / Carboxen / PDMS) technique. Subsequently, the SPME fiber was thermally desorbed online into the GC. The specimens were analyzed in the full scan mode of high-speed GC / MS. The total headspace response (expressed in nmol / L) was determined by the extraction of ions of specific masses of the fragrance raw materials. After the Terry cotton test fabric was line dried for 24 hours at a controlled temperature and humidity (22 °C / 50% rH), the dry Terry cotton test fabric was tested in the same manner, except that the Terry cotton test fabric was dry instead of wet (dry fabric headspace, DFHS (Dry Fabric Headspace)).

[0210] The particles of Example 3A and Comparative Example 3B of the present invention each provided the same mass of fragrance. For each individual fragrance raw material, the wet fabric headspace (WFHS) and the dry fabric headspace (DFHS) were measured. For each fragrance raw material, the ratio of WFHS / DFHS was calculated (see Table 7). The relative standard deviation of WFHS / DFHS was also calculated for Example 3A and Comparative Example 3B of the present invention. As shown in Figure 6 (box plot showing the median line, the first and third quartiles at the ends of the box, and the whiskers for the maximum and minimum), the capsules according to Example 3A of the present invention had a lower relative standard deviation of the headspace ratio compared to Comparative Example 3B. This indicates more consistent fragrance characteristics between the wet fabric and the dry fabric for the capsules of Example 3A of the present invention compared to Comparative Example 3B.

[0211]

Table 9

[0212] Example 4. An exemplary particle formulation is shown in Table 8 below.

[0213] [Table 10]

[0214] Example 5 Synthesis of non-hydrolyzable PEOS: 1000 g of TEOS (available from Sigma Aldrich) was added to a clean, dry round-bottom flask equipped with a stir bar and a distillation apparatus under a nitrogen atmosphere. Next, 564 g of acetic anhydride (available from Sigma Aldrich) and 5.9 g of tetrakis(trimethylsiloxide)titanium (available from Gelest, Sigma Aldrich) were added, and the contents of the flask were heated to 135 °C while stirring. While stirring vigorously, the reaction temperature was maintained at 135 °C for 30 hours. During this time, the organic esters produced by the reaction of the alkoxysilane groups with acetic anhydride were distilled off together with additional organic esters produced by the condensation of other alkoxysilane groups and silyl-acetate groups that occurred when polyethoxysilane (PEOS) was formed. The reaction flask was cooled to room temperature and placed on a rotary evaporator (Rotovapor R110 manufactured by Buchi), and this rotary evaporator was used together with a water bath and a vacuum pump (1402 DUOSEAL manufactured by WELCH) to remove all the remaining 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.

[0215] Capsule Synthesis: Five batches were prepared according to the following procedure. After the curing process, the five batches were combined to obtain a combined slurry. The oil phase was prepared by mixing 3 g of the PEOS precursor synthesized above, 2 g of the beneficial agent and / or core modifier, here a fragrance oil, and homogenizing (or dissolving if all compounds are miscible). A 100 g aqueous phase was prepared by mixing 0.5 g of NaCl, 3.5 g of EVONIK's AEROSIL 300 fumed silica, and 96 g of DI water. The fumed silica was dispersed in the aqueous phase at 20,000 RPM for 15 minutes using an IKA ULTRA-TURRAX (S25N). After each phase was prepared separately, 5 g of the oil phase was dispersed in 16 g of the aqueous phase at 25,000 RPM for 5 minutes using an IKA ULTRA-TURRAX mixer (S25N - 10 g) to reach the desired average oil droplet diameter. Then, 0.1 M HCl was added dropwise to adjust the pH to 1. After the emulsification process was completed, 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 curing occurred without capsule disintegration. The five batches were combined after the curing process to obtain a combined capsule slurry.

[0216] To attach the second shell component, the combined capsule slurry was post-treated with the second shell component solution. 50 g of the combined slurry was diluted with 50 g of 0.1 M HCl (aqueous solution). 1 M NaOH (aqueous solution) was added dropwise to adjust the pH to 7. Then, the diluted slurry was treated at room temperature using a suspended magnetic stirrer reactor at 300 RPM while controlling the addition of the solution of the second shell component precursor (20 mL of 15 wt% sodium silicate (aqueous solution)) (40 mL per minute). 1.6 M HCl (aqueous) solution and 1 M NaOH (aqueous) solution were continuously injected to keep the pH constant at pH 7. Then, the capsules were centrifuged at 2,500 RPM every 10 minutes. The supernatant was discarded and the capsules were redispersed in deionized water.

[0217] To test whether the capsules would disintegrate, the slurry was diluted 10-fold with deionized water. Droplets of the resulting dilution were added onto a microscope microslide and dried overnight at room temperature. The next day, the dried capsules were observed under an optical microscope by light transmission to evaluate whether the capsules maintained their spherical shape (no cover slide was used). The capsules withstood drying and did not disintegrate. The measured average volume-weighted diameter of the capsules was 5.3 Mm and the CoV was 46.2%. The organic component content rate in the shell was 0%.

[0218] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and the functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0219] All documents cited herein, including any patents or patent applications that are cross-referenced or related, and any patent application or patent for which this application claims priority or the benefit thereof, are hereby incorporated by reference in their entirety, unless expressly excluded or otherwise limited. The citation of any document is not to be construed as an admission that it is prior art to any invention disclosed or claimed herein, nor that it alone or in any combination with any other reference or references teaches, suggests or discloses any such invention. Further, in the event that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition given to the term in this document shall apply.

[0220] While specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the present invention. Accordingly, it is intended that all such changes and modifications within the scope of the present invention be covered by the appended claims.

Claims

1. A composition for use as a laundry care additive, comprising a plurality of particles, wherein said particles comprise from 25% to 99% by weight of a water-soluble carrier of the particles, and a plurality of capsules dispersed in said water-soluble carrier, said capsules comprising a core and a shell surrounding said core, said core comprising a fragrance raw material, a plurality of capsules; said water-soluble carrier is polyethylene glycol, said shell comprises from 90% to 100% by weight of an inorganic material of said shell, said shell is an inorganic first shell component comprising a condensation layer and a nanoparticle layer, said condensation layer comprises a condensation product of a precursor, said nanoparticle layer comprises inorganic nanoparticles, said condensation layer is an inorganic first shell component disposed between said core and said nanoparticle layer; an inorganic second shell component surrounding said first shell component, said second shell component comprises an inorganic second shell component surrounding said nanoparticle layer; said precursor comprises at least one compound of formula (I), Formula (I) is (M v O z Y n ) w and is For formula (I), each M represents silicon, v is the valence of M and is 4, z is from 0.5 to 1.6, Y is OR, R is selected from a methyl group, an ethyl group, a propyl group, and a butyl group, n is 2 and / or 3, and w is from 2 to 2000, The inorganic second shell component includes SiO 2 and A composition, wherein said inorganic nanoparticles comprise a material that is SiO2.

2. The inorganic material is SiO 2 The composition according to claim 1, wherein the inorganic material is SiO 2 .

3. Said capsules are characterized by one or more of an average volume-weighted capsule diameter of 10 micrometers to 200 micrometers, an average shell thickness of 170 nm to 1000 nm, a volume core-to-shell ratio of 50:50 to 99:1; The composition according to claim 1 or 2, wherein said first shell component comprises an organic component content of 5% by weight or less based on the weight of said first shell component.

4. Said plurality of capsules are characterized by one or more of an average volume-weighted capsule diameter of 10 micrometers to 200 micrometers, an average shell thickness of 170 nm to 1000 nm, a volume core-to-shell ratio of 50:50 to 99:1; The composition according to any one of claims 1 to 3, wherein said first shell component comprises an organic component content of 5% by weight or less based on the weight of said first shell component.

5. Said compound of formula (I) has a polystyrene equivalent weight average molecular weight (Mw) of 700 Da to 30,000 Da, A degree of branching of 0.2 to 0.6, and a polydispersity index of 1 to 20, the composition according to any one of claims 1 to 4, characterized by one or more of these. **Claim 6** For formula (I), the composition according to any one of claims 1 to 5, wherein Y is OR and R is an ethyl group. **Claim 7** A process for treating laundry, comprising: providing a laundry article to a washing machine; distributing the plurality of particles according to any one of claims 1 to 6 to the washing machine; and contacting the laundry article with the plurality of particles during a washing sub-cycle of the washing machine.

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