Water-soluble unit dose article containing core / shell capsules

Abstract

The present invention discloses a water-soluble unit dose article comprising a laundry detergent composition, the laundry detergent composition comprising capsules having a core and a shell.

Description

TECHNICAL FIELD

[0001] A water-soluble unit dose article comprising a laundry detergent composition, the laundry detergent composition comprising capsules having a core and a shell. BACKGROUND OF THE INVENTION

[0002] Water-soluble unit dose articles are popular with consumers due to their convenience and efficiency of use. Such water-soluble unit dose articles typically comprise a laundry detergent composition. Without being bound by theory, when the water-soluble unit dose article is added to water, the film dissolves / disintegrates, releasing the internal contents into the surrounding water to produce a washing liquid.

[0003] Encapsulated fragrance technologies are commonly formulated into the detergent compositions of water-soluble unit dose articles to provide fabric freshness benefits. These encapsulated fragrance technologies include a core comprising a fragrance ingredient surrounded by a shell. The shell is typically made from petrochemical-derived technologies, for example, melamine formaldehyde or polyacrylate-based technologies. Currently, due to environmental sustainability reasons, formulators are exploring ways to reduce the petrochemical-derived content within their formulations.

[0004] As non-petrochemical-derived capsule alternatives, encapsulated fragrance technologies comprising a shell mainly composed of inorganic materials have been proposed in the art. However, it has been found that their fabric freshness performance is poorer than that of traditional petrochemical-derived capsule technologies within traditional detergent compositions.

[0005] Accordingly, there is a need for a laundry detergent composition comprising fragrance capsules, wherein the fragrance capsules have a shell with a significantly reduced petrochemical-derived content, and wherein the laundry detergent composition comprising said capsules exhibits improved fabric freshness benefits compared to known laundry detergent compositions comprising fragrance capsules having a shell with a significantly reduced petrochemical-derived content.

[0006] Surprisingly, it has been found that when formulating a laundry detergent composition comprising fragrance capsules, wherein the fragrance capsules comprise a shell with a significantly reduced petrochemical-derived content, and wherein the laundry detergent composition is encapsulated within a polyvinyl alcohol water-soluble film, significantly improved fabric freshness performance is obtained when compared singly variably to the same detergent composition without the polyvinyl alcohol water-soluble film. SUMMARY OF THE INVENTION

[0007] One aspect of the present invention is a water-soluble unit dose article, wherein the water-soluble unit dose article comprises a water-soluble polyvinyl alcohol film and a laundry detergent composition, wherein the water-soluble film encapsulates the laundry detergent composition, wherein the laundry detergent composition comprises capsules, wherein the capsules have a core and a shell, and wherein the shell surrounds the core; wherein the core comprises a hydrophobic material, preferably, wherein the hydrophobic material comprises at least one fragrance ingredient; wherein the shell comprises between 90% and 100% water by weight of the shell. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 is a water-soluble unit dose article according to the present invention. DETAILED DESCRIPTION

[0009] Water-soluble unit-dose product

[0010] The present invention relates to a water-soluble unit dose article comprising a water-soluble polyvinyl alcohol film and a laundry detergent composition, wherein the water-soluble film encapsulates the laundry detergent composition. The water-soluble polyvinyl alcohol film and the laundry detergent composition are described in more detail below.

[0011] The water-soluble unit dose article includes a water-soluble film (i.e., a water-soluble polyvinyl alcohol film), which is shaped such that the unit dose article includes at least one internal compartment surrounded by the water-soluble film. The unit dose article may include a first water-soluble film and a second water-soluble film sealed to each other to define the internal compartment. The water-soluble unit dose article is constructed such that the detergent composition does not leak out of the compartment during storage. However, when the water-soluble unit dose article is added to water, the water-soluble film dissolves and releases the contents in the internal compartment into the washing liquid.

[0012] The compartment should be understood to mean an enclosed internal space within the unit dose article that holds the detergent composition. During manufacture, the first water-soluble film may be shaped to include an open compartment into which the detergent composition is added. Then a second water-soluble film is placed over the first film in an orientation adjacent to the opening of the compartment. Then the first film and the second film are sealed together along a sealing area.

[0013] The unit dose article may include more than one compartment, even at least two compartments, or even at least three compartments, or even at least four compartments. The compartments may be arranged in a stacked orientation, i.e., one positioned on top of the other. In such an orientation, the unit dose article will include at least three layers of film: a top, one or more intermediate, and a bottom. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e., one adjacent to the other. The compartments may even be oriented in a "tire and rim" arrangement, i.e., a first compartment is positioned adjacent to a second compartment, but the first compartment at least partially encloses the second compartment, but does not completely enclose the second compartment. Alternatively, one compartment may be completely enclosed within another compartment.

[0014] In the case where the unit dose article includes at least two compartments, one of the compartments may be smaller than the other compartment. In the case where the unit dose article includes at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are stacked on top of the larger compartment. The stacked compartments are preferably in a side-by-side orientation. The unit dose article may include at least four compartments, three of the compartments may be smaller than the fourth compartment, and preferably the smaller compartments are stacked on top of the larger compartment. The stacked compartments are preferably in a side-by-side orientation.

[0015] In a multi-compartment orientation, the detergent composition according to the present invention may be contained in at least one of the compartments. It may, for example, be contained in only one compartment, or may be contained in two compartments, or even may be contained in three compartments, or even may be contained in four compartments.

[0016] Each compartment may contain the same or different compositions. The different compositions may all be in the same form, or they may be in different forms.

[0017] The water-soluble unit dose article may include at least two internal compartments, wherein a liquid laundry detergent composition is contained in at least one of the compartments, and preferably, wherein the unit dose article includes at least three compartments, wherein the detergent composition is contained in at least one of the compartments.

[0018] Figure 1 There is disclosed a water-soluble unit dose article (1) according to the present invention. The water-soluble unit dose article (1) includes a first water-soluble film (2) and a second water-soluble film (3) sealed together at a sealing area (4). A liquid laundry detergent composition (5) is contained within the water-soluble unit dose article (1).

[0019] Without being bound by theory, it is believed that there is a synergistic effect between polyvinyl alcohol and the perfume capsules having an inorganic shell material according to the present invention. When compared to these perfume capsules having a shell material according to the present invention formulated inside a non-water-soluble polyvinyl alcohol film-encapsulated detergent composition, this synergistic effect results in improved capsule deposition during washing and retention on the fabric, and accordingly an overall improved fabric freshness performance.

[0020] This is even more surprising when compared to capsules having a higher petrochemical-derived content formulated in a detergent composition (where the detergent composition is not encapsulated in a water-soluble polyvinyl alcohol film), considering the negative interaction found between petrochemical-derived encapsulated perfume technologies and polyvinyl alcohol, resulting in impaired fabric freshness.

[0021] Water-soluble film

[0022] The film of the present invention is soluble or dispersible in water. The water-soluble film preferably has a thickness of 20 micrometers to 150 micrometers, preferably 35 micrometers to 125 micrometers, even more preferably 50 micrometers to 110 micrometers, and most preferably about 76 micrometers.

[0023] Preferably, as measured by the method presented herein, after using a glass filter having a maximum pore size of 20 micrometers, the film has at least 50%, preferably at least 75%, or even at least 95% water solubility:

[0024] Add 5 grams ± 0.1 gram of the film material to a pre-weighed 3L beaker and add 2L ± 5 mL of distilled water. Stir it vigorously at 30 °C for 30 minutes on a magnetic stirrer Labline (model 1250) or equivalent and a 5 cm magnetic stirrer (set at 600 rpm). Then, filter the mixture through a folded qualitative porous glass filter having the above-specified pore size (maximum 20 micrometers). Dry the water in the collected filtrate by any conventional method and determine the weight of the remaining material (the dissolved or dispersed part). Then, the percentage of solubility or dispersibility can be calculated.

[0025] The preferred film material is preferably a polymeric material. As is known in the art, the film material can be obtained, for example, by casting, blowing, extruding, or blow-extruding the polymeric material.

[0026] The water-soluble film contains polyvinyl alcohol. Preferably, the water-soluble film contains at least 50%, preferably at least 60% by weight of the water-soluble film of polyvinyl alcohol. The water-soluble film can contain between 50% and 100%, or even between 60% and 99% by weight of the water-soluble film of polyvinyl alcohol.

[0027] Preferably, the water-soluble film comprises a polyvinyl alcohol homopolymer or copolymer, preferably a blend of a polyvinyl alcohol homopolymer and / or a polyvinyl alcohol copolymer, preferably selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, especially carboxylated anionic polyvinyl alcohol copolymers, most preferably a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer. Preferably, the water-soluble film comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer, preferably an anionic polyvinyl alcohol copolymer, or a blend of a polyvinyl alcohol homopolymer and / or a polyvinyl alcohol copolymer (preferably an anionic polyvinyl alcohol copolymer). More preferably, the water-soluble film comprises an anionic polyvinyl alcohol copolymer, even more preferably selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, especially carboxylated anionic polyvinyl alcohol copolymer, and most preferably the water-soluble film comprises a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer.

[0028] Preferred films exhibit good solubility in cold water (which means distilled water that has not been heated). Preferably, such films exhibit good solubility at a temperature of 24 °C, and even more preferably at 10 °C. By "good solubility" is meant, as described above, after using a glass filter with a maximum pore size of 20 microns, measured by the method described herein, the film exhibits a water solubility of at least 50%, preferably at least 75%, or even at least 95%.

[0029] Preferred films are those supplied by Monosol under trade references M8630, M8900, M8779, M8310.

[0030] The film can be opaque, transparent or translucent. The film can include printed areas.

[0031] The printed areas can be achieved using standard techniques such as flexographic printing or inkjet printing.

[0032] The film can contain an aversive agent, such as a bittering agent. Suitable bittering agents include but are not limited to naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate or mixtures thereof. Any suitable amount of the aversive agent can be used in the film. Suitable amounts include but are not limited to 1 ppm to 5000 ppm, or even 100 ppm to 2500 ppm, or even 250 ppm to 2000 ppm.

[0033] Preferably, the water-soluble film or the water-soluble unit dose article or both are coated with a lubricant, preferably, wherein the lubricant is selected from talc, zinc oxide, silica, siloxane, zeolite, silicic acid, alumina, sodium sulfate, potassium sulfate, calcium carbonate, magnesium carbonate, sodium citrate, sodium tripolyphosphate, potassium citrate, potassium tripolyphosphate, calcium stearate, zinc stearate, magnesium stearate, starch, modified starch, clay, kaolin, gypsum, cyclodextrin or mixtures thereof.

[0034] Preferably, the water-soluble film and its individual components independently contain between 0 ppm and 20 ppm, preferably between 0 ppm and 15 ppm, more preferably between 0 ppm and 10 ppm, even more preferably between 0 ppm and 5 ppm, even more preferably between 0 ppm and 1 ppm, even more preferably between 0 ppb and 100 ppb, and most preferably 0 ppb of dioxane. Those skilled in the art will be aware of the known methods and techniques for determining the dioxane content in water-soluble films and their components.

[0035] Laundry detergent composition

[0036] Laundry detergent compositions can have any suitable components. The compositions can be in the form of powders, liquids, or mixtures thereof.

[0037] The solid can be in the form of free-flowing granules, compacted solids, or mixtures thereof. It should be understood that the solid may contain some water, but is substantially water-free. In other words, except for the water from adding various raw materials, no water is deliberately added.

[0038] With respect to the laundry detergent compositions of the present invention, the term "liquid" encompasses forms such as dispersions, gels, pastes, etc. Liquid compositions can also include gases in a suitable subdivided form. The term "liquid laundry detergent composition" refers to any laundry detergent composition that contains a liquid capable of wetting and treating fabrics (e.g., cleaning clothes in a domestic washing machine). For example, a dispersion is a liquid that includes solids or particulate matter contained therein.

[0039] Laundry detergent compositions can be used as fully formulated consumer products, or can be added to one or more additional ingredients to form fully formulated consumer products. Laundry detergent compositions can be "pretreatment" compositions that are added to fabrics (preferably fabric stains) before adding the fabrics to the washing liquid.

[0040] The laundry detergent composition contains capsules, and the capsules are described in more detail below.

[0041] Preferably, the laundry detergent composition contains a non-soap surfactant. The non-soap surfactant is preferably selected from non-soap anionic surfactants, nonionic surfactants, or mixtures thereof. Preferably, the laundry detergent composition contains between 10% and 60% by weight of the laundry detergent composition, more preferably between 20% and 55% of the non-soap surfactant.

[0042] Preferably, the anionic non-soap surfactant contains linear alkylbenzene sulfonates, alkyl sulfates, alkoxylated alkyl sulfates, or mixtures thereof. Preferably, the alkoxylated alkyl sulfate is ethoxylated alkyl sulfate.

[0043] Preferably, the laundry detergent composition comprises a non-soap anionic surfactant in an amount of from 5% to 60% by weight of the detergent composition, preferably from 15% to 55% by weight, more preferably from 25% to 50% by weight, and most preferably from 30% to 45% by weight.

[0044] Preferably, the non-soap anionic surfactant comprises linear alkylbenzene sulfonate and alkoxylated alkyl sulfate, wherein the ratio of linear alkylbenzene sulfonate to alkoxylated alkyl sulfate, preferably the weight ratio of linear alkylbenzene sulfonate to ethoxylated alkyl sulfate, is from 1:10 to 10:1, preferably from 6:1 to 1:6, more preferably from 4:1 to 1:4, and even more preferably from 3:1 to 1:1. Alternatively, the weight ratio of linear alkylbenzene sulfonate to ethoxylated alkyl sulfate is from 1:2 to 1:4. The alkoxylated alkyl sulfate may be derived from synthetic alcohols or natural alcohols, or a blend thereof, depending on the desired average alkyl carbon chain length and average degree of branching. Preferably, the synthetic alcohols are prepared by the Ziegler process, the OXO process, the modified OXO process, the Fischer-Tropsch process, the Guerbet process, or a combination thereof. Preferably, the naturally derived alcohols are derived from natural oils, preferably coconut oil, palm kernel oil, or a mixture thereof.

[0045] Preferably, the laundry detergent composition comprises a nonionic surfactant in an amount of from 0% to 15% by weight of the laundry detergent composition, preferably from 0.01% to 12% by weight, more preferably from 0.1% to 10% by weight, and most preferably from 0.15% to 7% by weight. The nonionic surfactant is preferably selected from alcohol alkoxylate nonionic surfactants, including naturally derived alcohols, synthetically derived alcohol-based alcohol alkoxylate nonionic surfactants, and mixtures thereof, depending on the desired average alkyl carbon chain length and average degree of branching. The alcohol alkoxylate nonionic surfactant may be a primary or secondary alcohol alkoxylate nonionic surfactant, preferably a primary alcohol alkoxylate nonionic surfactant. The synthetically derived alcohol alkoxylate nonionic surfactants include Ziegler-synthesized alcohol alkoxylates, oxo-synthesized alcohol alkoxylates, modified oxo-process-synthesized alcohol alkoxylates, Fischer-Tropsch-synthesized alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. The alkoxylated chain may be a mixed alkoxylated chain containing ethoxy, propoxy, and / or butoxy units, or may be a pure ethoxylated alkyl chain, preferably a pure ethoxylated alkyl chain.

[0046] Preferably, the liquid laundry detergent composition comprises a soap, preferably a fatty acid salt, more preferably an amine-neutralized fatty acid salt, in an amount between 1.5% and 20%, more preferably between 2% and 15%, even more preferably between 3% and 10%, and most preferably between 4% and 8% by weight of the laundry detergent composition, wherein preferably the amine is an alkanolamine, more preferably selected from monoethanolamine, diethanolamine, triethanolamine or mixtures thereof, more preferably monoethanolamine.

[0047] Preferably, the laundry detergent composition comprises a non-aqueous solvent, preferably wherein the non-aqueous solvent is selected from ethanol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, ethylene glycol, polyethylene glycol, polypropylene glycol or mixtures thereof, preferably wherein the polypropylene glycol has a molecular weight of 400. Preferably, the liquid laundry detergent composition comprises a non-aqueous solvent in an amount between 10% and 40%, preferably between 15% and 30% by weight of the liquid laundry detergent composition. Without being bound by theory, the non-aqueous solvent ensures an appropriate level of film plasticization, so that the film is not too brittle and not too "floppy". Without being bound by theory, having the correct degree of plasticization will also promote film dissolution when exposed to water during the washing process.

[0048] Preferably, the liquid laundry detergent composition comprises water in an amount between 1% and 20%, preferably between 5% and 15% by weight of the liquid laundry detergent composition.

[0049] Preferably, the laundry detergent composition comprises a component selected from the list consisting of cationic polymers, polyester terephthalate polymers, amphiphilic graft copolymers, alkoxylated (preferably ethoxylated) polyethyleneimine polymers, carboxymethyl cellulose, enzymes, bleaches or mixtures thereof.

[0050] Preferably, the laundry detergent composition comprises an unencapsulated fragrance.

[0051] The laundry detergent composition may comprise auxiliary components, wherein the auxiliary components are selected from color-toning dyes, aesthetic dyes, builders, preferably citric acid, chelating agents, cleaning polymers, dispersants, dye transfer inhibitor polymers, optical brighteners, light blockers, antifoaming agents, preservatives, antioxidants or mixtures thereof. Preferably, the chelating agent is selected from aminocarboxylate chelating agents, aminophosphonate chelating agents or mixtures thereof.

[0052] Preferably, the laundry detergent composition has a pH between 6 and 10, more preferably between 6.5 and 8.9, and most preferably between 7 and 8, wherein the pH of the laundry detergent composition is measured when diluted to 10% in softened water at 20 °C.

[0053] Liquid laundry detergent compositions can be Newtonian or non - Newtonian. Preferably, the liquid laundry detergent composition is non - Newtonian. Without being bound by theory, non - Newtonian liquids have different properties from Newtonian liquids. More specifically, the viscosity of a non - Newtonian liquid depends on the shear rate, while a Newtonian liquid has a constant viscosity independent of the applied shear rate. The reduction in viscosity when shear is applied to a non - Newtonian liquid is considered to be further beneficial for the dissolution of the liquid detergent. The liquid laundry detergent compositions described herein can have any suitable viscosity, depending on factors such as the formulation ingredients and the purpose of the composition. According to the methods described herein, when Newtonian, the composition can have a viscosity value of from 100 cP to 3,000 cP, or from 200 cP to 2,000 cP, or from 300 cP to 1,000 cP at a shear rate of 20 s⁻¹ and a temperature of 20 °C. According to the methods described herein, when non - Newtonian, the composition can have a high - shear viscosity value of from 100 cP to 3,000 cP, or from 300 cP to 2,000 cP, or from 500 cP to 1,000 cP at a shear rate of 20 s⁻¹ and a temperature of 20 °C, and a low - shear viscosity value of from 500 cP to 100,000 cP, or from 1,000 cP to 10,000 cP, or from 1,300 cP to 5,000 cP at a shear rate of 1 s⁻¹ and a temperature of 20 °C. Methods for measuring viscosity are known in the art. According to the present disclosure, a rotational rheometer (e.g., TA instruments AR550) is used to perform the viscosity measurement. The instrument includes a 40 mm 2° or 1° conical clamp with a gap of about 50 μm - 60 μm for isotropic liquids, or a 40 mm flat steel plate with a 1000 μm gap for liquids containing particles. A procedure involving a conditioning step, a peak - hold, and a continuous ramp step is used for the measurement. The conditioning step involves setting the measurement temperature at 20 °C, performing a 10 - second pre - shear at a shear rate of 10 s⁻¹, and equilibrating for 60 seconds at the selected temperature. The peak - hold involves applying a shear rate of 0.05 s⁻¹ at 20 °C for 3 minutes and sampling every 10 seconds. The continuous ramp step is performed at 20 °C at a shear rate from 0.1 s⁻¹ to 1200 s⁻¹ for 3 minutes to obtain the full flow characteristics.

[0054] Capsule

[0055] The laundry detergent composition contains capsules, where the capsules have a core and a shell, and where the shell surrounds the core.

[0056] The laundry detergent composition preferably contains capsules in an amount of from 0.05% to 20%, more preferably from 0.05% to 10%, even more preferably from 0.1% to 5%, and most preferably from 0.2% to 3% by weight of the laundry detergent composition.

[0057] The core contains a hydrophobic material, preferably the hydrophobic material contains at least one perfume ingredient. The core is described in more detail below.

[0058] The laundry detergent composition may contain perfume-containing capsules as the sole source of perfume ingredients, or may contain perfume-containing capsules in combination with perfume freely added to the laundry detergent composition. The laundry detergent composition may contain a sufficient amount of capsules to provide about 0.05% to about 10%, or about 0.1% to about 5%, or about 0.1% to about 3% of perfume ingredients by weight of the laundry detergent composition. When discussing the amount or weight percentage of capsules herein, it means the sum of the shell material and the core material.

[0059] The capsules may have an average shell thickness of 10 nm to 10,000 nm, preferably 170 nm to 1000 nm, more preferably 300 nm to 500 nm.

[0060] The capsules may have an average volume-weighted capsule diameter of 0.1 microns to 300 microns, preferably 10 microns to 200 microns, more preferably 10 microns to 50 microns. It has been advantageously found that large capsules (e.g., an average diameter of 10 μm or greater) can be provided according to the embodiments herein without sacrificing the overall stability of the capsules and / or while maintaining good burst strength.

[0061] The average volume-weighted diameter of the capsules is between 1 micron and 200 microns, preferably between 1 micron and 10 microns, more preferably between 2 microns and 8 microns. The shell thickness can be 1 nm to 10000 nm, 1 nm to 1000 nm, 10 nm to 200 nm. The capsules may have an average volume-weighted diameter between 1 micron and 10 microns and a shell thickness between 1 nm and 200 nm. It has been found that capsules having an average volume-weighted diameter between 1 micron and 10 microns and a shell thickness between 1 nm and 200 nm have higher burst strength.

[0062] Without being bound by theory, it is believed that higher burst strength provides better durability during the washing process, where the process may cause premature rupture of mechanically weak capsules due to mechanical constraints in the washing machine.

[0063] Capsules having an average volume-weighted diameter between 1 micron and 10 microns and a shell thickness between 10 nm and 200 nm provide only resistance to mechanical constraints when prepared with a specifically selected silica precursor. The precursor may have a molecular weight between 2 kDa and 5 kDa, even more preferably between 2.5 kDa and 4 kDa. In addition, the concentration of the precursor needs to be carefully selected, where the concentration is 20% to 60% by weight of the oil phase used during encapsulation, preferably 40% to 60% by weight.

[0064] Without being bound by theory, it is believed that precursors of higher molecular weight have a much slower migration time from the oil phase to the water phase. The slower migration time is thought to be caused by a combination of the following three phenomena: diffusion, partitioning, and reaction kinetics. This phenomenon is important in the case of small-sized capsules because the total surface area between the oil and water in the system increases as the capsule diameter decreases. The higher surface area results in a higher migration of the precursor from the oil phase to the water phase, which in turn reduces the polymerization yield at the interface. Therefore, precursors of higher molecular weight are required to mitigate the effect of the increased surface area and to obtain the capsules according to the present invention.

[0065] It has surprisingly been found that, in addition to the inorganic shell, the volume core-shell ratio can play a role in ensuring the physical integrity of the capsules. A shell that is too thin compared to the overall size of the capsule (core:shell ratio > 98:2) tends to lack self-integrity. On the other hand, an extremely thick shell relative to the capsule diameter (core:shell ratio < 80:20) tends to have a higher shell permeability in a surfactant-rich matrix. Although one might intuitively think that a thick shell would result in a lower shell permeability (since this parameter affects the average diffusion path of the active substance through the shell), it has surprisingly been found that the capsules of the present invention having a shell with a thickness above a threshold have a higher shell permeability. It is believed that this upper threshold depends in part on the capsule diameter. The volume core-shell ratio is determined according to the method provided in the "Test Methods" section below.

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

[0067] It may be desirable to have a specific combination of these capsule properties. For example, the capsules can have a volume core-shell ratio of from about 99:1 to about 50:50 and have an average volume-weighted capsule diameter of from about 0.1 μm to about 200 μm and an average shell thickness of from about 10 nm to about 10,000 nm. The capsules can have a volume core-shell ratio of from about 99:1 to about 50:50 and have an average volume-weighted capsule diameter of from about 10 μm to about 200 μm and an average shell thickness of from about 170 nm to about 10,000 nm. The capsules can have a volume core-shell ratio of from about 98:2 to about 70:30 and have an average volume-weighted capsule diameter of from about 10 μm to about 100 μm and an average shell thickness of from about 300 nm to about 1000 nm.

[0068] The methods according to the present disclosure can produce capsules having a low coefficient of variation of the capsule diameter. Control of the capsule size distribution can beneficially allow the population to have an improved and more uniform burst strength. The capsule population can have a coefficient of variation of the capsule diameter of 40% or less, preferably 30% or less, more preferably 20% or less.

[0069] In order for capsules containing nuclear materials to function in consumer product applications such as liquid detergents or liquid fabric softeners and to be cost-effective, they should: i) resist the spread of the nucleus (e.g., low leakage or permeability) during the shelf life of the liquid product; ii) have the ability to deposit on the target surface during application (e.g., a washing machine cycle); and iii) be able to release the nuclear material by mechanical shell rupture at the appropriate time and location to provide the intended beneficial effect to the end consumer.

[0070] The capsules described herein may have an average rupture strength of from 0.1 MPa to 10 MPa, preferably from 0.25 MPa to 5 MPa, more preferably from 0.25 MPa to 3 MPa. Entirely inorganic capsules have traditionally had poor rupture strength, whereas for the capsules described herein, the rupture strength of the capsules can be greater than 0.25 MPa, thus providing improved stability and triggered release of the beneficial agent at a specified amount of rupture stress.

[0071] The nucleus can be oil-based or the nucleus can be water-based. Preferably, the nucleus is oil-based. The nucleus can be liquid at the temperature at which it is used to formulate the product. The nucleus can be liquid at and near room temperature.

[0072] The nucleus preferably comprises a fragrance raw material. Based on the total weight of the nucleus, the nucleus can contain from about 1 wt% to 100 wt% of the fragrance. Preferably, the nucleus can contain from about 50 wt% to 100 wt% of the fragrance based on the total weight of the nucleus, more preferably from 80 wt% to 100 wt% of the fragrance based on the total weight of the nucleus. Generally, higher levels of fragrance are preferred in order to increase delivery efficiency.

[0073] The fragrance raw material can comprise one or more, preferably two or more fragrance raw materials. As used herein, the term "fragrance raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mol, and which can be used alone or in combination with other fragrance raw materials to impart an odor, aroma, essence, or fragrance. Typical PRMs include, among others, alcohols, ketones, aldehydes, esters, ethers, nitrites, and olefins, such as terpenes.

[0074] PRMs can be characterized by their boiling point (B.P.) measured at atmospheric pressure (760 mm Hg), and their octanol / water partition coefficient (P), which can be described by logP and is determined according to the test method described in the test methods section. Based on these properties, PRMs can be classified as first quadrant, second quadrant, third quadrant, or fourth quadrant fragrances, as detailed below. Fragrances having multiple PRMs from different quadrants may be desirable, for example, to provide aromatic beneficial effects at different points of contact during normal use.

[0075] A fragrance raw material having a boiling point (B.P.) below about 250 °C and a logP of less than about 3 is referred to as a first quadrant fragrance raw material. The first quadrant fragrance raw materials are preferably limited to less than 30% of the fragrance composition. A fragrance raw material having a B.P. above about 250 °C and a logP greater than about 3 is referred to as a fourth quadrant fragrance raw material, a fragrance raw material having a B.P. above about 250 °C and a logP of less than about 3 is referred to as a second quadrant fragrance raw material, and a fragrance raw material having a B.P. below about 250 °C and a logP greater than about 3 is referred to as a third quadrant fragrance raw material.

[0076] Preferably, the capsule contains a fragrance. Preferably, the fragrance of the capsule comprises a mixture of at least 3, or even at least 5, or at least 7 fragrance raw materials. The fragrance of the capsule may comprise at least 10 or at least 15 fragrance raw materials. The mixture of fragrance raw materials may provide a more complex and desired aesthetics, and / or better fragrance performance or persistence, for example, at multiple contact points. However, it may be desirable to limit the number of fragrance raw materials in the fragrance to reduce or limit the formulation complexity and / or cost.

[0077] The fragrance may comprise at least one fragrance raw material of natural origin. Such components may be desirable for sustainability / environmental reasons. The fragrance raw materials of natural origin may include natural extracts or essences, which may comprise a mixture of PRMs. Such natural extracts or essential oils may include orange oil, lemon oil, rose extract, lavender, musk, pogostemon cablin, balsam essence, sandalwood oil, pine oil, cedar, etc.

[0078] In addition to the fragrance raw materials, the core may further comprise a pre-fragrance, which may contribute to improving the persistence of the freshness benefit. The pre-fragrance may comprise a non-volatile material that is released or converted into a fragrance material, for example, by simple hydrolysis, or may be a pH-triggered pre-fragrance (e.g., triggered by a pH drop), or may be an enzyme-released pre-fragrance, or a light-triggered pre-fragrance. Depending on the selected pre-fragrance, the pre-fragrance may exhibit different release rates.

[0079] The core of the encapsulation of the present disclosure may comprise core modifiers, such as distribution modifiers and / or density modifiers. In addition to the fragrance, the core may further comprise core modifiers in an amount greater than 0% to 80%, preferably greater than 0% to 50%, more preferably greater than 0% to 30% based on the total core weight. The distribution modifiers may include materials selected from the following: vegetable oils, modified vegetable oils, mono-esters, di-esters, and tri-esters of C4-C 24 fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The distribution modifiers may preferably include isopropyl myristate or consist of isopropyl myristate. The modified vegetable oils may be esterified and / or brominated. The modified vegetable oils may preferably include castor oil and / or soybean oil.

[0080] The shell contains an inorganic material in an amount between 90% and 100% by weight of the shell, preferably between 95% and 100%, more preferably between 99% and 100%. Preferably, the inorganic material in the shell includes a material selected from metal oxides, metalloid oxides, metals, minerals, or mixtures thereof. Preferably, the inorganic material in the shell contains a material selected from SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, clay, gold, silver, iron, nickel, copper, or mixtures thereof. More preferably, the inorganic material in the shell includes a material selected from SiO2, TiO2, Al2O3, CaCO3, or mixtures thereof, and most preferably SiO2.

[0081] The shell may include a first shell component. The shell preferably includes 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 contain an inorganic material.

[0082] The inorganic shell may include a first shell component that includes a condensation layer surrounding the core and may also include a nanoparticle layer surrounding the condensation layer. The inorganic shell may also include a second shell component surrounding the first shell component. The first shell component contains an inorganic material, preferably a metal / metalloid oxide, more preferably SiO2, TiO2, and Al2O3, or mixtures thereof, and even more preferably SiO2. The second shell component contains an inorganic material, preferably a material selected from the group consisting of metal / metalloid oxides, metals, and minerals, and preferably a material selected from the following list: SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, clay, gold, silver, iron, nickel, and copper, or mixtures thereof, and even more preferably selected from SiO2 and CaCO3, or mixtures thereof. Preferably, the second shell component material has the same type of chemical properties as the first shell component to maximize chemical compatibility.

[0083] 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 selected from formula (I), formula (II), and mixtures thereof, where formula (I) is (M v O z Y n ) w , and where formula (II) is (M v O z Y n R 1 p ) wPreferably, the precursor contains only the formula (I) and does not contain the compound according to the formula (II), for example, in order to reduce the organic content of the capsule shell (i.e., without R 1 group). The formula (I) and (II) are described in more detail below.

[0084] One or more precursors may have the formula (I):

[0085] (M v O z Y n ) w (Formula I),

[0086] wherein M is one or more of silicon, titanium and aluminum, v is the valence number of M and is 3 or 4, z is from 0.5 to 1.6, preferably from 0.5 to 1.5, each Y is independently selected from -OH, -OR 2 , -NH2, -NHR 2 , -N(R 2 )2, wherein R 2 is C1 to C 20 alkyl, C1 to C 20 alkylene, C6 to C 22 aryl, or a 5-12 membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N and S, R 3 is H, C1 to C 20 alkyl, C1 to C 20 alkylene, C6 to C 22 aryl, or a 5-12 membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N and S, n is from 0.7 to (v - 1), and w is from 2 to 2000.

[0087] One or more precursors may have the formula (I), wherein M is silicon. It is possible that Y is -OR 2 . It is possible that n is from 1 to 3. It may be preferred that Y is -OR 2 and n is from 1 to 3. It is possible that n is at least 2, one or more of Y is -OR 2 , and one or more of Y is -OH.

[0088] R 2 can be C1 to C 20 alkyl. R 2 can be C6 to C 22 aryl. R 2 can be one or more of C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl and C8 alkyl. R 2 can be C1 alkyl. R 2 can be C2 alkyl. R 2 can be C3 alkyl. R2 may be a C4 alkyl group.

[0089] It is possible that z is from 0.5 to 1.3, or from 0.5 to 1.1, from 0.5 to 0.9, or from 0.7 to 1.5, or from 0.9 to 1.3, or from 0.7 to 1.3.

[0090] Preferably, M is silicon, v is 4, each Y is -OR 2 , n is 2 and / or 3, and each R 2 is a C2 alkyl group.

[0091] The precursor may comprise a polyalkoxysilane (PAOS). The precursor may comprise a polyalkoxysilane (PAOS) synthesized by a hydrolysis process.

[0092] The precursor may alternatively or also comprise one or more of the compounds of formula (II):

[0093] (M v O z Y n R 1 p ) w (Formula II),

[0094] wherein M is one or more of silicon, titanium and aluminum, v is the valence number of M and is 3 or 4, z is from 0.5 to 1.6, preferably from 0.5 to 1.5, each Y is independently selected from -OH, -OR 2 , -NH2, -NHR 2 , -N(R 2 )2, wherein R 2 is selected from C1 to C 20 alkyl, C1 to C 20 alkylene, C6 to C 22 aryl, or a 5-12 membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N and S, R 3 is H, C1 to C 20 alkyl, C1 to C 20 alkylene, C6 to C 22 aryl, or a 5-12 membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N and S; n is from 0 to (v - 1); each R 1 is independently selected from: C1 to C 30 alkyl; C1 to C 30 alkylene; C1 to C substituted by a member selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -C(O)OH, -C(O)O-alkyl, -C(O)O-aryl, -C(O)O-heteroaryl and mixtures thereof 30alkyl; and C1 to C substituted by a member selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -C(O)OH, -C(O)O-alkyl, -C(O)O-aryl, and -C(O)O-heteroaryl 30 alkylene; and p is a number greater than zero and up to pmax, where pmax = 60 / [9*Mw(R 1 )+8], where Mw(R 1 ) is the molecular weight of the R 1 group, and where w is from 2 to 2000.

[0095] R 1 may be C1 to C alkyl substituted by one to four groups independently selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H (i.e., C(O)OH), -C(O)O-alkyl, -C(O)O-aryl, and -C(O)O-heteroaryl. 30 alkyl. R 1 may be C1 to C alkylene substituted by one to four groups independently selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, -C(O)O-alkyl, -C(O)O-aryl, and -C(O)O-heteroaryl. 30 alkylene.

[0096] As described above, to reduce or even eliminate the organic content in the first shell member, it may be preferable to reduce or even eliminate the presence of the compound according to formula (II) having the R1 group. The precursor, the condensation layer, the first shell member, and / or the shell may be free of the compound according to formula (II).

[0097] The precursor of formula (I) and / or (II) may be characterized by one or more physical properties, namely, molecular weight (Mw), degree of branching (DB), and polydispersity index (PDI) of the molecular weight distribution. It is believed that selecting a specific Mw and / or DB can be used to obtain capsules that maintain their mechanical integrity after drying on the surface and have low shell permeability in a surfactant-based matrix. The precursor of formula (I) and (II) may be characterized by having a DB of 0 to 0.6, preferably 0.1 to 0.5, more preferably 0.19 to 0.4, and / or an Mw of 600 Da to 100,000 Da, preferably 700 Da to 60,000 Da, more preferably 1000 Da to 30,000 Da. This characteristic provides useful properties of the precursor to obtain the capsules of the present invention. The precursor of formula (I) and / or (II) may have a PDI of 1 to 50.

[0098] A condensed layer containing a metal / semimetal oxide can be formed from the condensation product of a precursor that includes at least one compound of formula (I) and / or at least one compound of formula (II), optionally in combination with one or more monomer precursors of a metal / semimetal oxide, where the metal / semimetal oxide includes TiO2, Al2O3, and SiO2, preferably SiO2. The monomer precursor of the metal / semimetal oxide can include a compound of the formula M(Y) V-n R n where M, Y, and R are as defined in formula (II), and n can be an integer from 0 to 3. The monomer precursor of the metal / semimetal oxide can preferably be in the form where M is silicon, where the compound has the general formula Si(Y) 4-n R n , where Y and R are as defined for formula (II) and n can be an integer from 0 to 3. Examples of such monomers are TEOS (tetraethoxysilane), TMOS (tetramethoxysilane), TBOS (tetrabutoxysilane), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). These are not intended to limit the range of monomers that can be used, and it will be apparent to those skilled in the art what are suitable monomers that can be used in combination herein.

[0099] The first shell member can include an optional layer of nanoparticles. The layer of nanoparticles contains nanoparticles. The nanoparticles of the layer of nanoparticles can be one or more of SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, clay, silver, gold, and copper. Preferably, the layer of nanoparticles can contain SiO2 nanoparticles.

[0100] The nanoparticles can have an average diameter of 1 nm to 500 nm, preferably 50 nm to 400 nm.

[0101] The pore size of the capsule can be adjusted by varying the shape of the nanoparticles and / or by using a combination of different nanoparticle sizes. For example, non-spherical irregular nanoparticles can be used because they can have improved packing when forming the layer of nanoparticles, which is believed to result in a denser shell structure. This can be advantageous when limited permeability is desired. The nanoparticles used can have a more regular shape, such as spherical. Any conceivable nanoparticle shape can be used herein.

[0102] The nanoparticles can be substantially free of hydrophobic modification. The nanoparticles can be substantially free of organic compound modification. The nanoparticles can contain organic compound modification. The nanoparticles can be hydrophilic.

[0103] The nanoparticles may comprise surface modifications such as, but not limited to, linear or branched C1 to C 20 alkyl groups, surface amino groups, surface methacryloyl groups, surface halogens or surface thiols. These surface modifications enable organic molecules to be covalently bound to the surface of the nanoparticles. When inorganic nanoparticles are disclosed for use in this document, this means including any of the above surface modifications or not including the above surface modifications without explicitly stating so.

[0104] The capsules of the present disclosure can be defined as including a substantially inorganic shell, which substantially inorganic shell includes a first shell component and a second shell component. Substantially inorganic means that the first shell component may contain up to 10 wt% or up to 5 wt% of organic content, preferably up to 1 wt% of organic content, as defined later in the calculation of organic content. It may be preferred that the first shell component, the second shell component, or both contain no more than about 5 wt%, preferably no more than about 2 wt%, more preferably about 0 wt% of organic content, depending on the case, based on the weight of the first or shell component.

[0105] While the first shell component can be used to construct a mechanically stable scaffold or framework, it can also provide low shell permeability in liquid products containing surfactants (such as laundry detergents, shower gels, cleaners, etc.) (see Surfactants in Consumer Products, J. Falbe, Springer-Verlag). The second shell component can greatly reduce the shell permeability, which improves the impermeability of the capsules in surfactant-based matrices. The second shell component can also greatly improve the mechanical properties of the capsules, such as capsule burst force and burst strength. Without being bound by theory, it is believed that the second shell component contributes to the densification of the entire shell by depositing precursors in the pores remaining in the first shell component. The second shell component also adds an additional inorganic layer to the surface of the capsule. These improved shell permeability and mechanical properties provided by the second shell component only occur when used in combination with the first shell component as defined in the present invention.

[0106] The capsules of the present disclosure can be formed by first mixing a hydrophobic material with any of the precursors of the condensation layer as defined above to form an oil phase, where the oil phase may comprise an oil base and / or an oil-soluble precursor. Then the precursor / hydrophobic material mixture is used as the dispersed phase or as the continuous phase combined with water, where in the former case an O / W (oil-in-water) emulsion is formed, and in the latter case a W / O (water-in-oil) emulsion is formed once the two phases are mixed and homogenized by methods known to those skilled in the art. Preferably, an O / W emulsion is formed. The nanoparticles can be present in the aqueous phase and / or the oil phase, regardless of the desired emulsion type. The oil phase may comprise an oil-based core modifier and / or an oil-based beneficial agent as well as the precursor of the condensation layer. Suitable core materials for use in the oil phase were earlier described herein.

[0107] Once any emulsion is formed, the following steps can be carried out:

[0108] (a) The nanoparticles migrate to the oil / water interface, thereby forming a nanoparticle layer.

[0109] (b) The precursor of the condensation layer containing the metal / metalloid oxide precursor will start to undergo hydrolysis / condensation reaction with water at the oil / water interface, thereby 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.

[0110] Based on the total weight of the oil phase, the precursor for forming the condensation layer can be present in an amount of 1 wt% to 50 wt%, preferably 10 wt% to 40 wt%.

[0111] The oil phase composition can include any compound as defined in the core part above. Before emulsification, the oil phase can contain 10 wt% to about 99 wt% of the beneficial agent.

[0112] In the method for preparing capsules according to the present disclosure, the oil phase can be the dispersed phase, and the continuous water (or aqueous) phase can include water, an acid or a base, and nanoparticles. At least when the oil phase and the water phase are mixed together, the water (aqueous) phase can have a pH of 1 to 11, preferably 1 to 7. The acid can be a strong acid. The strong acid can include one or more of HCl, HNO3, H2SO4, HBr, HI, HClO4, and HClO3, preferably HCl. The acid can be a weak acid. The weak acid can be acetic acid or HF. The concentration of the acid in the continuous water phase 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 a hydroxide, such as sodium hydroxide and ammonia. For example, the mineral 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 and their concentration ranges listed above is not meant to limit the scope of the present invention, and other suitable acids and bases that allow control of the pH of the continuous phase are contemplated herein.

[0113] In the method of preparing the 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 initiated with an aqueous phase at an acidic or neutral pH, and then a base can be added during the process to increase the pH value. Alternatively, the method can be initiated with an aqueous phase at a basic or neutral pH, and then an acid can be added during the process to decrease the pH value. Additionally, the method can be initiated with an aqueous phase at an acidic or neutral pH, and then an acid can be added during the process to further decrease the pH value. Further, the method can be initiated with an aqueous phase at a basic or neutral pH, and then a base can be added during the process to further increase the pH value. Any suitable pH change can be used. Additionally, any suitable combination of an acid and a base can be used in the method at any time to achieve the desired pH. Any of the above nanoparticles 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.

[0114] 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.

[0115] The second shell component can be formed by blending 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) as defined above, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). The second shell component precursor can further include one or more of the Si(Y) 4-n R n type silane monomers, where 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 were given earlier in this paragraph, and these are not intended to limit the scope of the monomers that can be used. The second shell component precursor can include silicates, titanates, aluminates, zirconates, and / or zincates. The second shell component precursor can include carbonates and calcium salts. The second shell component precursor can include salts of iron, silver, copper, nickel, and / or gold. The second shell component precursor can include zinc, zirconium, silicon, titanium, and / or aluminum alkoxides. The second shell component precursor can include one or more of silicate solutions such as sodium silicate, tetraol silicon solution, iron sulfate salt and iron nitrate salt, titanium alcohol solution, triol aluminum solution, diol zinc solution, zirconium alcohol solution, calcium salt solution, carbonate solution. The second shell component containing CaCO3 can be obtained from the combined use of a calcium salt and a carbonate. The second shell component containing CaCO3 can be obtained from a calcium salt without adding a carbonate by in-situ generating carbonate ions from CO2.

[0116] The second shell component precursor may comprise any suitable combination of any of the compounds listed above.

[0117] The solution of the second shell component precursor may be added dropwise to the capsule comprising the first shell component. The solution of the second shell component precursor and the capsule may be mixed together for 1 minute to 24 hours. The solution of the second shell component precursor and the capsule may be mixed together at room temperature or at an elevated temperature such as 20 °C to 100 °C.

[0118] Based on the total weight of the solution of the second shell component precursor, the second shell component precursor solution may comprise from 1 wt% to 50 wt% of the second shell component precursor.

[0119] The capsule having the first shell component may 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 may be a strong acid. The strong acid may include one or more of HCl, HNO3, H2SO4, HBr, HI, HClO4 and HClO3, preferably HCl. In other embodiments, the acid may be a weak acid. In an embodiment, the weak acid may be acetic acid or HF. The concentration of the acid in the second shell component precursor solution may be 10 -7 M to 5M. The base may be an inorganic base or an organic base, preferably an inorganic base. The inorganic base may be a hydroxide, such as sodium hydroxide and ammonia. For example, the mineral 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 enumerated above is not meant to limit the scope of the invention, and other suitable acids and bases that allow control of the pH of the second shell component precursor solution are contemplated herein.

[0120] The method of forming the second shell component may include a change in pH during the method. For example, the process of forming the second shell component may be initiated at an acidic or neutral pH, and then a base may be added during the process to increase the pH. Alternatively, the process of forming the second shell component may be initiated at a basic or neutral pH, and then an acid may be added during the process to decrease the pH. Additionally, the process of forming the second shell component may be initiated at an acidic or neutral pH, and an acid may be added during the process to further decrease the pH. Additionally, the process of forming the second shell component may be initiated at a basic or neutral pH, and a base may be added during the process to further increase the pH. Any suitable pH change may be used. Additionally, any suitable combination of acid and base may be used in the solution of the second shell component precursor at any time to achieve the desired pH. The method of forming the second shell component may include maintaining a stable pH with a maximum deviation of + / - 0.5 pH units during the process. For example, the process of forming the second shell component may be maintained at a basic, acidic, or neutral pH. Alternatively, the process of forming the second shell component may be maintained within a specific pH range by controlling the pH using an acid or a base. Any suitable pH range may be used. Additionally, any suitable combination of acid and base may be used in the solution of the second shell component precursor at any time to maintain the stable pH within the desired range.

[0121] Whether preparing an oil-based core or an aqueous core, the emulsion can be cured under conditions that cause the precursor to solidify, thereby forming a shell surrounding the core.

[0122] The reaction temperature for curing can be increased to increase the rate of obtaining cured capsules. The curing process can cause condensation of the precursor. The curing process can be completed at room temperature or above room temperature. The curing process can be carried out at a temperature of 30 °C to 150 °C, preferably 50 °C to 120 °C, more preferably 80 °C to 100 °C. The curing process can be completed within any suitable time period to enable the capsule shell to be strengthened by condensation of the precursor material. The curing process can be carried out for 1 minute to 45 days, preferably 1 hour to 7 days, more preferably 1 hour to 24 hours. The capsule is considered cured when it no longer collapses. The determination of capsule collapse is described in detail below. During the curing step, it is believed that hydrolysis of the Y moiety (from formula (I) and / or (II)) occurs, followed by subsequent condensation of the -OH group with another -OH group or another moiety of type Y (where the two Y moieties are not necessarily the same). The hydrolyzed precursor moiety will initially condense with the surface moiety of the nanoparticle (provided they contain such moieties). As the shell formation proceeds, the precursor moiety will react with the pre-formed shell.

[0123] The emulsion can be cured such that condensation of the shell precursor occurs. The emulsion can be cured such that condensation of the shell precursor occurs by reaction with the nanoparticles. Examples of the hydrolysis and condensation steps of the silica-based shell described herein are shown below:

[0124] Hydrolysis: ≡Si-OR + H2O → ≡Si-OH + ROH

[0125] Condensation: ≡Si-OH + ≡Si-OR → ≡Si-O-Si≡ + ROH

[0126] ≡Si-OH + ≡Si-OH → ≡Si-O-Si≡ + H2O.

[0127] For example, when using the precursors of formula (I) or (II), the hydrolysis and condensation steps are described below:

[0128] Hydrolysis: ≡M-Y + H2O → ≡M-OH + YH

[0129] Condensation: ≡M-OH + ≡M-Y → ≡M-O-M≡ + YH

[0130] ≡M-OH + ≡M-OH → ≡M-O-M≡ + H2O.

[0131] The capsules can be provided as a slurry composition (or simply referred to as "slurry" herein). The result of the method described herein can be a slurry containing the capsules. The slurry can be formulated into a product, such as a consumer product.

[0132] Method for manufacturing water-soluble unit-dose product

[0133] Those skilled in the art will know the known techniques and methods for preparing liquid laundry detergent compositions and water-soluble unit dose articles.

[0134] Method of use

[0135] Another aspect of the present invention is a method for washing fabrics, the method comprising the steps of: diluting the water-soluble unit dose article according to the present invention 200 to 3000 times, preferably 300 to 2000 times with water to prepare a washing liquid, and contacting the fabric to be treated with the washing liquid.

[0136] The washing liquid can contain water having any hardness preferably varying between 0 gpg and 40 gpg.

[0137] Preferably, the washing solution contains polyvinyl alcohol between 0.01 ppm and 100 ppm, preferably between 0.1 ppm and 10 ppm, and capsules between 1 ppm and 1000 ppm, preferably between 10 ppm and 100 ppm. The weight ratio of the capsules to polyvinyl alcohol in the washing solution is preferably from 1:1 to 100:1, preferably 10:1 to 50:1.

[0138] Test method

[0139] It should be understood that the test methods disclosed in the test method section of the present application should be used to determine the corresponding parameter values of the subject matter claimed by the applicant as claimed and described herein.

[0140] Method for determining logP

[0141] Calculate the logarithm (logP) of the octanol / water partition coefficient of each PRM in the tested spice mixture. Use the Consensus logP Computational Model version 14.02 (Linux) purchased from Advanced Chemistry Development Inc. (ACD / Labs) (Toronto, Canada) to calculate the logP of individual PRMs to provide a dimensionless logP value. The Consensus logP Computational Model of ACD / Labs is part of the ACD / Labs model suite.

[0142] Average shell thickness measurement

[0143] The capsule shell, including a first shell component and a second shell component, when present, is measured in nanometers on a delivery capsule containing twenty beneficial agents using a focused ion beam scanning electron microscope (FIB-SEM; FEI Helios Nanolab 650) or an equivalent. Samples are prepared by diluting a small amount (20 μL) of the liquid capsule dispersion with distilled water (1:10). The suspension is then deposited on an ethanol-cleaned aluminum rod and transferred to a carbon coater (Leica EM ACE600 or equivalent). The sample is dried in the coater under vacuum (vacuum level: 1 0-5 mbar). Next, 25 nm - 50 nm of carbon is rapidly deposited onto the sample to deposit a conductive carbon layer on the surface. The aluminum rod is then transferred to the FIB-SEM to prepare a cross-section of the capsule. Using the cross-section cleaning mode, the cross-section is prepared by ion milling at an acceleration voltage of 30 kV with an emission current of 2.5 nA. Images are acquired in immersion mode (hold time approximately 10 μs) at 5.0 kV and 100 pA with a magnification of approximately 10,000.

[0144] Images of the fractured shell are acquired in the form of cross-sectional views of 20 beneficial delivery capsules selected in a random manner unbiased by their size to form a representative sample presenting the capsule size distribution. Using calibrated microscope software, at 3 different random positions, the shell thickness of each of the 20 capsules is measured by drawing a measurement line perpendicular to the tangent of the outer surface of the capsule shell. Sixty independent thickness measurements are recorded and used to calculate the average thickness.

[0145] Average value and coefficient of variation of volume-weighted capsule diameter

[0146] Determine the capsule size distribution by single particle optical sensing (SPOS) (also known as optical particle counting (OPC)) using an AccuSizer 780AD instrument or equivalent and the accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, U.S.A.) or equivalent. The instrument is configured with the following conditions and selections: flow rate = 1 mL / sec; lower size threshold = 0.50 μm; sensor model = LE400-05SE or equivalent; auto dilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 mL; maximum coincidence = 9200. Start the measurement by flushing the sensor with water until the background count is less than 100 to bring it to a cold state. Introduce the sample in suspension of the delivery capsules and adjust the density of the capsules with DI water by auto dilution as needed to obtain a capsule count of at most 9200 capsules / mL. Analyze the suspension over a 60-second period. The size range used is from 1 μm to 493.3 μm.

[0147] Volume distribution:

[0148]

[0149]

[0150]

[0151] Where:

[0152] CoV v – Coefficient of variation of the volume-weighted size distribution

[0153] σ v – Standard deviation of the volume-weighted size distribution

[0154] μ v – Mean value of the volume-weighted size distribution

[0155] d i – Diameter in fraction i

[0156] x i,v – Frequency in fraction i (corresponding to diameter i) of the volume-weighted size distribution

[0157]

[0158] Volume core-shell ratio evaluation

[0159] The volume core-shell ratio is determined as follows and depends on the average shell thickness as measured by the shell thickness testing method. The volume core-shell ratio of the capsules whose average shell thickness is measured is calculated by the following formula:

[0160]

[0161] where the thickness is the average shell thickness of the capsule population measured by FIBSEM, and D 胶囊 is the average volume-weighted diameter of the capsule population measured by optical particle counting.

[0162] The nuclear weight percentage can be calculated by using the following formula to convert this ratio into a core-shell ratio fractional value:

[0163]

[0164] And the shell percentage can be calculated based on the following formula: % shell = 100 - % core.

[0165] Degree of branching method

[0166] The degree of branching of the precursor is determined as follows: The degree of branching is measured using (29Si) nuclear magnetic resonance spectroscopy (NMR).

[0167] Sample preparation

[0168] Each sample is diluted to a 25% solution using deuterated benzene (benzene-D6 “100%” (D, 99.96%, purchased from Cambridge Isotope Laboratories Inc., Tewksbury, MA, or equivalent). 0.015 M chromium(III) acetylacetonate (99.99% purity, purchased from Sigma-Aldrich, St. Louis, MO, or equivalent) is added as a paramagnetic relaxation reagent. If glass NMR tubes (Wilmed-LabGlass, Vineland, NJ or equivalent) are used for analysis, blank samples must also be prepared by filling the NMR tubes with the same type of deuterated solvent used to dissolve the samples. The same glass tubes must be used to analyze the blanks and the samples.

[0169] Sample analysis

[0170] The degree of branching is determined using a Bruker 400 MHz nuclear magnetic resonance spectroscopy (NMR) instrument or equivalent. The standard silicon (29Si) method is used (e.g., from Bruker, with default parameter settings of at least 1000 scans and a relaxation time of 30 seconds.

[0171] Sample treatment

[0172] Use system software suitable for NMR spectroscopy such as MestReNova version 12.0.4 - 22023 (purchased from Mestrelab Research) or equivalent to store and process samples. Apply phase adjustment and background correction. There is a large broad signal extending from -70 ppm to -136 ppm, which is the result of using a glass NMR tube and the glass present in the probe housing. This signal is suppressed by subtracting the spectrum of a blank sample from the spectrum of the synthesized sample, provided that the same tube and the same method parameters are used to analyze the blank and the sample. To further account for any minor differences in data collection, tubes, etc., the area outside the peaks of the region of interest should be integrated and normalized to a consistent value. For example, for all blanks and samples, integrate from -117 ppm to -115 ppm and set the integrated value to 4.

[0173] The resulting spectra yield up to five main peak areas. The first peak (Q0) corresponds to unreacted TAOS. The second set of peaks (Q1) corresponds to end groups. The next set of peaks (Q2) corresponds to linear groups. The next broad set of peaks (Q3) is the semi - dendritic unit. The last broad set of peaks (Q4) is the dendritic unit. When analyzing PAOS and PBOS, each set falls within a defined ppm range. Representative ranges are described in the table below:

[0174] Group ID Number of bridging oxygens per silicon ppm range Q0 0 -80 to -84 Q1 1 -88 to -91 Q2 2 -93 to -98 Q3 3 -100 to -106 Q4 4 -108 to -115

[0175] The polyoxymethylsilanes have different chemical shifts for Q0 and Q1, overlapping signals for Q2, and unchanged Q3 and Q4, as shown in the table below:

[0176] Group ID Number of bridging oxygens per silicon ppm range Q0 0 -78 to -80 Q1 1 -85 to -88 Q2 2 -91 to -96 Q3 3 -100 to -106 Q4 4 -108 to -115

[0177] The ppm ranges shown in the table above may not apply to all monomers. Other monomers may cause changes in chemical shifts; however, the correct assignment of Q0 - Q4 should not be affected.

[0178] Using MestReNova, each set of peaks is integrated, and the degree of branching can be calculated by the following formula:

[0179]

[0180] Method for determining molecular weight and polydispersity index

[0181] The molecular weight (polystyrene equivalent weight - average molecular weight (Mw)) and polydispersity index (Mw / Mn) of the condensation layer precursors described herein are determined using size - exclusion chromatography with refractive index detection. Mn is the number - average molecular weight.

[0182] Sample preparation

[0183] Weigh the sample and then dilute it to a target concentration of 10 mg / mL with the solvent used in the instrument system. For example, weigh 50 mg of polyalkoxysilane into a 5 mL volumetric flask, dissolve it and dilute it to volume with toluene. After the sample has been dissolved in the solvent, pass it through a 0.45 um nylon filter and load it into the instrument's autosampler.

[0184] Sample analysis

[0185] Use an HPLC system with an autosampler (e.g., Waters 2695 HPLC separation module, Waters Corporation, Milford MA, or equivalent) connected to a refractive index detector (e.g., Wyatt 2414 refractive index detector, Santa Barbara, CA, or equivalent) for polymer analysis. Separation is carried out on three chromatographic columns, each 7.8 mm I.D.×300 mm long, packed with 5 μm polystyrene-divinylbenzene medium, connected in series, which have molecular weight cut-offs of 1 kDa, 10 kDa, and 60 kDa respectively. Suitable chromatographic columns are TSK Gel G1000HHR, G2000HHR, and G3000HHR columns (purchased from TOSOH Bioscience, King of Prussia, PA) or equivalents. Protect the analytical columns with a 6 mm I.D.×40 mm long 5 μm polystyrene-divinylbenzene guard column (e.g., TSKgel Guardcolumn HHR-L, TOSOH Bioscience, or equivalent). Pump toluene (HPLC grade or equivalent) isocratically at 1.0 mL / min while maintaining the columns and detector at 25 °C. Inject 100 μL of the prepared sample for analysis. Use software with GPC calculation capabilities (e.g., ASTRA version 6.1.7.17 software, purchased from Wyatt Technologies, Santa Barbara, CA, or equivalent) to store and process the sample data.

[0186] Use ten or more narrow-disperse polystyrene standards with known molecular weights (in the range of approximately 0.250 kDa - 70 kDa) (e.g., Standard ReadyCal Set, (e.g., Sigma-Aldrich Corporation, PN 76552, or equivalent)) and use a third-order fit of the Mp vs. retention time curve to calibrate the system.

[0187] Using the system software, calculate and record the weight-average molecular weight (Mw) and the polydispersity index (Mw / Mn).

[0188] Method for calculating organic content in the first shell component

[0189] As used herein, the definition of the organic portion in the inorganic shell of the capsule according to the present disclosure: via hydrolysis of the M-X bond of the inorganic precursor that attaches the portion to the metal or metalloid M, and under specific reaction conditions, any portion X that cannot be cleaved from the metal precursor bearing the metal M (where M belongs to the group of metals and metalloids, and X belongs to the group of non-metals) will be considered organic. When exposed to neutral pH distilled water for a duration of 24 hours without stirring, a minimum hydrolysis degree of 1% is set as the reaction condition.

[0190] This method allows one to calculate the theoretical organic content assuming complete conversion of all hydrolyzable groups. Thus, it allows one to evaluate the theoretical organic percentage of any silane mixture, and the result represents only the precursor mixture itself, rather than the actual organic content in the first shell component. Therefore, when a certain percentage of the organic content of the first shell component is disclosed anywhere in this document, it should be understood to include any mixture of unhydrolyzed precursors or prepolymerized precursors, and the theoretical organic content calculated according to the following is lower than the disclosed amount.

[0191] Examples of silanes (but not limited to; see the general formula at the end of this section):

[0192] Consider a mixture of silanes, where the mole fraction of each is Y i , and where i is the ID number of each silane. The mixture can be represented as follows:

[0193] Si(XR) 4-n R n

[0194] where XR is a hydrolyzable group under the conditions mentioned in the above definition, and R i ni is non-hydrolyzable under the above conditions, and n i = 0, 1, 2, or 3.

[0195] This silane mixture will produce a shell with the following general formula:

[0196]

[0197] Then, the weight percentage of the organic portion as previously defined can be calculated as follows:

[0198] 1) Find the mole fraction of each precursor (including the nanoparticles)

[0199] 2) Determine the general formula of each precursor (including the nanoparticles)

[0200] 3) Calculate the general formula of the precursor and nanoparticle mixture based on the mole fraction

[0201] 4) Convert the silane into the reacted form (all hydrolyzable groups are converted into oxygen groups)

[0202] 5) Calculate the weight ratio of the organic part relative to the total mass (assuming the framework is 1 mole of Si)

[0203] Example :

[0204]

[0205] To calculate the general formula of the mixture, multiply each atomic exponent in each chemical formula by their respective mole fractions. Then, for the mixture, when similar exponents occur (usually for ethoxy groups), take the sum of the fractional exponents.

[0206] Note: According to the calculation method (the sum of all mole fractions of Si is 1), the sum of all Si fractions in the general formula of the mixture will always add up to 1.

[0207] SiO 1*0.57+2*0.25 (OEt) 2*0.57+4*0.07+2*0.10 Me 2*0.10

[0208] SiO 1.07 (OEt) 1.62 Me 0.20

[0209] To convert the unreacted chemical formula into the reacted chemical formula, simply divide the exponents of all hydrolyzable groups by 2 and then add them together (if applicable, together with any pre-existing oxygen groups) to obtain the fully reacted silane.

[0210] SiO 1.88 Me 0.20

[0211] In this case, the expected result is SiO 1.9 Me 0.2 , because the sum of all exponents must conform to the following formula:

[0212] A + B / 2 = 2,

[0213] where A is the exponent of the oxygen atom and B is the sum of all non-hydrolyzable exponents. Small errors may occur due to rounding during the calculation and should be corrected. Then readjust the exponents on the oxygen atoms to satisfy the chemical formula.

[0214] Therefore, the final chemical formula is SiO 1.9 Me 0.2 , and the weight ratio of the organic matter is calculated as follows:

[0215] Weight ratio = (0.20 * 15) / (28 + 1.9 * 16 + 0.20 * 15) = 4.9%

[0216] General case:

[0217] The above chemical formulas can be generalized by considering the valence of the metal or metalloid M, thus giving the following modified chemical formulas:

[0218]

[0219] And using a similar method, but considering the valence V of the corresponding metal.

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

[0221] Example

[0222] For a liquid laundry detergent composition comprising a silica shell-based fragrance capsule according to the present invention suitable for water-soluble unit dose articles, the effect of the presence and absence of a polyvinyl alcohol water-soluble film on the wet fabric fragrance headspace performance (in nmol / L) on cotton and polyester fabrics is evaluated, and according to the test methods described herein, the above effect is compared with the effect for a liquid laundry detergent composition that is the same but variably contains a polyacrylate shell-based fragrance capsule outside the scope of the present invention.

[0223] Starting materials :

[0224] Liquid detergent composition

[0225] A liquid detergent composition having the formulation provided in Table 1 is prepared on a laboratory scale by conventionally mixing the respective starting materials at room temperature in a batch-type process. Example 1 of the present invention contains a silica shell-based fragrance capsule according to the present invention, while Comparative Example 1 contains a polyacrylate shell-based fragrance capsule outside the scope of the present invention.

[0226] Table 1: Liquid detergent composition

[0227]

[0228] (1) Lutensit Z96: Zwitterionic ethoxylated quaternized sulfated hexamethylenediamine, from BASF

[0229] (2) Details: See the following fragrance capsule section

[0230] (3) Percentage of encapsulated perfume %

[0231] Fragrance capsule

[0232] Synthesize two perfume capsules in each liquid detergent composition such as those in Table 1 according to the following synthetic route.

[0233] Fragrance capsule based on silica shell

[0234] Prepare the oil phase by mixing a non-hydrolyzable precursor with a perfume composition (one part non-hydrolyzable precursor to two parts perfume composition) and homogenizing (or even dissolving if all compounds are miscible). Prepare the aqueous phase by adding 1.25 wt% Aerosil 300 (purchased from Evonik) to an aqueous 0.1 M HCl solution and dispersing it in an ultrasonic bath for at least 30 minutes. Once each phase is prepared separately, combine them (one part oil phase to four parts water) and disperse the oil phase into the aqueous phase at 13400 rpm / minute using an IKA ultra-turrax S25N-10G mixing tool. Once the emulsification step is complete, cure the resulting emulsion with the following temperature profile: 4 h at 22 °C, 16 h at 50 °C, and 96 h at 70 °C. To deposit the second shell component, the capsules are post-treated with a second shell component solution: dilute the slurry 2-fold in 0.1 M HCl and treat it with a controlled addition (40 μL / min, 0.16 mL / g slurry) of a 10 wt% aqueous sodium silicate solution at 22 °C using a suspended magnetic stirring reactor at 250 rpm. Maintain the pH at pH 7 using 1 M HCl (aqueous solution). After the injection of the second shell component solution is complete, centrifuge the capsules at 2500 rpm for 10 minutes and redisperse them in deionized water. According to the present disclosure, the resulting capsules comprise a first and a second silica-based shell component, with an average size of 29.22 μm and a CoV of 38%.

[0235] Non-hydrolytic precursor synthesis

[0236] Under a nitrogen atmosphere, 1000 g of tetraethyl orthosilicate (TEOS, purchased from Sigma Aldrich) was added to a clean, dry round-bottom flask equipped with a stir bar and distillation apparatus. 490 mL of acetic anhydride (purchased from Sigma Aldrich) and 5.8 g of tetra(trimethylsilyloxy)titanium (purchased from Gelest) were added and the contents of the flask were stirred at 135 °C for 28 h. During this time, ethyl acetate formed by the reaction of ethoxysilyl groups with acetic anhydride was distilled off. The reaction flask was cooled to room temperature and placed on a rotary evaporator (Buchi RotovaporR110) used in conjunction with a water bath and a vacuum pump (Welch 1402DuoSeal) to remove any residual solvents and volatile compounds. The resulting polyethoxysilane (PEOS) was a yellow viscous liquid with the following specifications found in Table 2. The ratio of TEOS to acetic anhydride can be varied to control the parameters presented in Table 2.

[0237] Table 2.

[0238] Parameters of PEOS Results Degree of branching (DB) 0.26 Molecular weight (Mw) 1.2 Polydispersity index (PDI) 3.9

[0239] Fragrance capsule based on polyacrylate shell

[0240] A set of perfume capsules comprising a polyacrylate shell encapsulating the same perfume composition as the silica shell-based perfume capsules described above was prepared according to the encapsulant, which was prepared according to the process disclosed in U.S. Publication No. 2011 / 0268802.

[0241] Non-hydrolytic PEOS synthesis:

[0242] Under a nitrogen atmosphere, 1000 g of TEOS (purchased from Sigma Aldrich) was added to a clean, dry round-bottom flask equipped with a stir bar and distillation equipment. Next, 564 grams of acetic anhydride (purchased from Sigma Aldrich) and 5.9 grams of titanium(IV) bis(trimethylsilanolate) (purchased from Gelest, Sigma Aldrich) were added, and the contents of the flask were heated to 135 °C with stirring. The reaction temperature was maintained at 135 °C with vigorous stirring for 30 hours, during which the organic esters formed by the reaction of alkoxysilyl groups with acetic anhydride and additional organic esters formed by the condensation of silyl acetate groups with other alkoxysilyl groups, which occurs during the formation of polyethoxysilane (PEOS), were distilled off. The reaction flask was cooled to room temperature and placed on a rotary evaporator (Buchi Rotovapor R110) used in conjunction with a water bath and a vacuum pump (Welch 1402 DuoSeal) to remove any residual solvent. The degree of branching (DB), molecular weight (Mw), and polydispersity index (PDI) of the synthesized PEOS polymer were 0.42, 2.99, and 2.70, respectively.

[0243] Capsule synthesis :

[0244] Five batches were prepared following the procedure below, and after the curing step, the 5 batches were combined to produce a combined slurry.

[0245] The oil phase was prepared by mixing 3 g of the PEOS precursor synthesized above with 2 g of a beneficial agent and / or core modifier (here, a flavor oil) and homogenizing (or even dissolving if all compounds are miscible). The aqueous phase was prepared by mixing 0.5 g of NaCl, 3.5 grams of Aerosil 300 pyrogenic silica from Evonik, and 96 grams of deionized water to make 100 grams of the aqueous phase. The pyrogenic silica was dispersed in the aqueous phase at 20000 rpm for 15 min using an IKA ultra-turrax (S25N).

[0246] Once the phases were prepared separately, 5 g of the oil phase was dispersed into 16 g of the aqueous phase at 25000 rpm for 5 minutes using an IKA Ultra-Turrax mixer (S25N-10g) to achieve the desired average oil droplet diameter. Then the pH was adjusted to 1 using 0.1 M HCl added dropwise. Once the emulsification step was complete, the resulting emulsion was left to stand at room temperature for 4 hours without stirring and then at 90 °C for 16 hours until sufficient curing occurred to prevent the capsules from collapsing. After the curing step, the five batches were combined to obtain a combined capsule slurry.

[0247] To deposit the second shell component, the combined capsule slurry is subjected to a post-treatment with the second shell component solution. 50 g of the combined slurry is diluted with 50 g of 0.1 M HCl (aqueous solution). The pH is adjusted to 7 using 1 M NaOH (aqueous solution) added dropwise. Then, at room temperature, the diluted slurry is treated by the controlled addition (40 μL / min) of the second shell component precursor solution (20 mL of 15 wt% sodium silicate (aqueous solution)) using a suspended magnetic stirrer reactor at 300 rpm. The pH is kept constant at pH 7 by the continuous injection of 1.6 M HCl (aqueous solution) and 1 M NaOH (aqueous solution). The capsules are then centrifuged at 2500 rpm every 10 minutes. The supernatant is discarded and the capsules are redispersed in deionized water.

[0248] To test whether the capsules collapse, the slurry is diluted 10-fold in deionized water. A few drops of the subsequent dilution are added to a microscope slide and allowed to dry overnight at room temperature. The next day, the dried capsules are observed by transmitted light under an optical microscope (without using a cover slip) to evaluate whether the capsules maintain their spherical shape. The capsules are still present after drying and do not collapse. The measured average volume-weighted diameter of the capsules is 5.3 μm and the CoV is 46.2%. The percentage of organic matter content in the shell is 0%.

[0249] Polyvinyl alcohol film

[0250] The polyvinyl alcohol used is a polyvinyl alcohol homopolymer / anionic polyvinyl alcohol copolymer blend, such as obtained from MonoSol and used in Ariel 3-in-1 Pods, commercially available in the UK in July 2020.

[0251] Test method for wet fabric fragrance headspace performance:

[0252] The wet fabric perfume headspace performance of the inventive and comparative compositions (e.g., Table 1) is tested in the presence and absence of a polyvinyl alcohol-based film. The washed fabric is analyzed by GCMS in the wet stage to obtain the wet fabric headspace (WFHS) of each perfume ingredient.

[0253] Preparation of fabric samples

[0254] The method of treating fabrics includes using a commercial washing machine, such as a Miele Honeycomb Care W1724, or other similar machines with standard machine settings (cotton short cycle program at 40 °C, 1200 rpm for 1 hour and 14 minutes, using water with a hardness of 2.5 mmol / L). The fabric composition in the washing machine consists of terry cotton and polyester test fabrics, as well as a standard ballast consisting of a mixture of polyethylene cotton and cotton, totaling 3 kg. A water-soluble polyvinyl alcohol polymer and a detergent treatment agent are delivered to the drum of the machine at the detergent level: 22.6 g of the detergent composition (with and without the water-soluble polyvinyl alcohol film), and the water-soluble polyvinyl alcohol film (0.03 g) is administered as a similar Figure 1 empty 3-compartment unit dose product, for example, similar to the unit dose product design commercially available in the UK in July 2020.

[0255] Headspace analysis

[0256] Immediately after the washing cycle, headspace analysis of the fragrance is performed on the wet fabric tracer. Six replicates of each type of tracer for each washing test are analyzed by rapid headspace GC / MS. A 4 cm × 4 cm aliquot of the fabric tracer is transferred to a 25 mL headspace vial. The fabric sample is equilibrated at 65 °C for 10 minutes. The headspace above the fabric is sampled for 5 minutes via the SPME (50 / 30 μm DVB / Carboxen / PDMS) method. Subsequently, the SPME fiber is thermally desorbed immediately into the GC. The analytes are analyzed by rapid GC / MS in the full scan mode. The total headspace response (expressed in nmol / L) above the test group is calculated using ion extraction of specific masses of the fragrance raw materials.

[0257] Test results

[0258] Table 3 summarizes the total fragrance headspace response relative to the wet terry cotton tracer and the single variable headspace loss / increase effect of adding polyvinyl alcohol for the silica shell capsules according to the present invention and polyacrylate shell capsules outside the scope of the present invention. Table 4 summarizes the total headspace response relative to the wet polyester fabric tracer and the single variable headspace loss / gain effect of adding polyvinyl alcohol for the silica shell capsules according to the present invention and polyacrylate shell capsules outside the scope of the present invention.

[0259] When combined with silica shell capsules, the data clearly show that the PVA film has a positive fragrance headspace effect on the terry cotton fabric tracer headspace (+56% total headspace), while when combined with polyacrylate shell capsules, it shows a negative effect on it (-16% total headspace). When combined with silica shell capsules, the PVA film has been found to have a neutral effect on the polyester fabric tracer (+1% total headspace), while when combined with polyacrylate shell capsules, a negative effect on it (-23% total headspace) is again observed. As a final result, although the silica-based fragrance capsules according to the invention inherently have lower performance in terms of wet-phase fragrance headspace compared to polyacrylate-based fragrance capsules, due to the surprising opposite synergistic PVA wet-phase fragrance headspace effect, when formulating these fragrance capsules according to the invention within a water-soluble PVA film containing unit-dose articles, this inherent wet-phase fragrance headspace performance gap has been significantly reduced (-27% vs. -61% on cotton, -8% vs. -31% on polyester).

[0260] Table 3. Total wet fabric headspace on cotton fabric (in nmol / L) 。

[0261]

[0262] Table 4. Total wet fabric headspace on polyester fabric (in nmol / L) 。

[0263]

Claims

1. A water-soluble unit dose product, wherein the water-soluble unit dose product comprises a water-soluble polyvinyl alcohol film and a laundry detergent composition, wherein the water-soluble polyvinyl alcohol film encapsulates the laundry detergent composition, wherein the laundry detergent composition comprises capsules, wherein the capsules have a core and a shell, and wherein the shell surrounds the core; wherein the core comprises a hydrophobic material, and wherein the hydrophobic material comprises at least one perfume raw material; wherein the shell comprises an inorganic material between 90% and 100% by weight of the shell, and the inorganic material comprises SiO2.

2. The water-soluble unit dose product according to claim 1, wherein the shell comprises (a) a first shell component, the first shell component comprising a condensation layer and a nanoparticle layer, wherein the condensation layer comprises a condensation product of a precursor, and wherein the nanoparticle layer comprises inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer, and (b) a second shell component, the second shell component surrounding the first shell component, wherein the second shell component surrounds the nanoparticle layer.

3. The water-soluble unit dose product according to claim 2, wherein the capsules are characterized by one or more of the following: (a) An average volume-weighted capsule diameter of 10 µm to 200 µm; (b) An average shell thickness of 170 nm to 1000 nm; (c) A volume core / shell ratio of 50:50 to 99:1; (d) The first shell component comprises an organic content of no more than 5% by weight of the first shell component; or (e) A mixture thereof.

4. The water-soluble unit dose product according to claim 2, wherein the precursor comprises at least one compound selected from formula (I), formula (II), or a mixture thereof, where formula (I) is (M v O z Y n ) w , where formula (II) is (M v O z Y n R 1 p ) w , wherein for formula (I), formula (II), or a mixture thereof: each M is independently selected from silicon, titanium, and aluminum, v is the valence number of M and is 3 or 4, z is from 0.5 to 1.6, Each Y is independently selected from -OH, -OR 2 , halogen , -NH2, -NHR 2 , -N(R 2 )2 and , wherein R 2 is C1 to C 20 alkyl, C1 to C 20 alkylene, C6 to C 22 aryl or a 5- to 12-membered heteroaryl, wherein the heteroaryl contains 1 to 3 ring heteroatoms selected from O, N, and S; wherein R 3 is H, C1 to C 20 alkyl, C1 to C 20 alkylene, C6 to C 22 aryl or a 5- to 12-membered heteroaryl, wherein the heteroaryl contains 1 to 3 ring heteroatoms selected from O, N, and S; w is from 2 to 2000; wherein for formula (I), n is from 0.7 to (v - 1); and wherein for formula (II), n is from 0 to (v - 1); Each R 1 is independently selected from: C1 to C 30 alkyl; C1 to C 30 alkylene; C1 to C substituted by a member selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -CO2H, -C(O)-alkyl, -C(O)O-aryl and -C(O)O-heteroaryl 30 alkyl; and C1 to C substituted by a member selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -C(O)OH, -C(O)O-alkyl, -C(O)O-aryl and -C(O)O-heteroaryl 30 alkylene; and p is a number greater than zero and up to pmax, where pmax = 60 / [9*Mw(R 1 ) + 8], where Mw(R 1 ) is the molecular weight of the R 1 group.

5. The water-soluble unit dose product according to claim 4, wherein the precursor comprises any one of the following; a. At least one compound according to formula (I); or b. At least one compound according to formula (II).

6. The water-soluble unit dose product according to claim 4, wherein one or both of the compounds of formula (I) and formula (II) are characterized by one or more of the following: (a) A polystyrene equivalent weight average molecular weight (Mw) determined by size exclusion chromatography with refractive index detection of 700 Da to 30,000 Da; (b) Use of 0.2 to 0.6 29 Degree of branching measured by Si nuclear magnetic resonance spectroscopy; (c) A molecular weight polydispersity index determined by size exclusion chromatography with refractive index detection of 1 to 20; or (d) A mixture thereof.

7. The water-soluble unit dose product according to claim 4, wherein for formula (I), formula (II), or both, M is silicon.

8. The water-soluble unit dose article according to claim 4, wherein for formula (I), formula (II), or both, Y is OR, where R is selected from a methyl group, an ethyl group, a propyl group, or a butyl group.

9. The water-soluble unit dose article according to claim 2, wherein the inorganic nanoparticles of the first shell member comprise at least one of metal nanoparticles, mineral nanoparticles, metal oxide nanoparticles, or semi-metal oxide nanoparticles, or a mixture thereof.

10. The water-soluble unit dose article according to claim 9, wherein the inorganic nanoparticles comprise one or more materials selected from SiO2, TiO2, Al2O3, Fe2O3, Fe3O4, CaCO3, clay, silver, gold, copper, or a mixture thereof.

11. The water-soluble unit dose article according to claim 9, wherein the inorganic nanoparticles comprise one or more materials selected from SiO2, CaCO3, Al2O3, clay, or a mixture thereof.

12. The water-soluble unit dose article according to claim 2, wherein the inorganic second shell member comprises at least one of SiO2, TiO2, Al2O3, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, iron, silver, nickel, gold, copper, clay, or a mixture thereof.

13. The water-soluble unit dose article according to claim 1, wherein the laundry detergent composition comprises the capsules in an amount of 0.05% to 20% by weight of the laundry detergent composition.

14. The water-soluble unit dose article according to claim 1, wherein the laundry detergent composition is a liquid laundry detergent composition, and the liquid laundry detergent composition comprises water in an amount between 1% and 20% by weight of the liquid laundry detergent composition.

15. The water-soluble unit dose article according to claim 1, wherein the laundry detergent composition comprises unencapsulated perfume.

16. The water-soluble unit dose article according to claim 1, wherein the water-soluble polyvinyl alcohol film comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer, or a blend of a polyvinyl alcohol homopolymer and / or a polyvinyl alcohol copolymer.

17. The water-soluble unit dose article according to claim 16, wherein the polyvinyl alcohol copolymer is an anionic polyvinyl alcohol copolymer.

18. The water-soluble unit dose article according to claim 16, wherein the water-soluble polyvinyl alcohol film comprises an anionic polyvinyl alcohol copolymer selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers.

19. The water-soluble unit dose article according to claim 18, wherein the anionic polyvinyl alcohol copolymer is selected from carboxylated anionic polyvinyl alcohol copolymers.

20. The water-soluble unit dose article according to claim 16, wherein the water-soluble polyvinyl alcohol film comprises a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer.

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